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Series Editors:
Professor George A. Kraus, Department of Chemistry, Iowa State University,
Ames, Iowa, USA
Professor Andrzej Stankiewicz, Delft University of Technology, The Netherlands
Professor Peter Siedl, Federal University of Rio de Janeiro, Brazil
Professor Yuan Kou, Peking University, China
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Edited by
Brian Trewyn
Colorado School of Mines, USA
Email: btrewyn@mines.edu
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Dedication
vii
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viii
Dedication
protocols for MSNs but also demonstrated the applications of this interesting
class of nanomaterials in including heterogeneous catalysis, renewable energy,
biosensing, and nanomedicine. He is still frequently cited and the techniques
we developed together are still visible in the current literature today.
Victor was profoundly interested in focusing research time and eort on
exploring heterogeneous catalysis, specifically those supported on MSNs.
He developed novel methods to eectively control the pore environment to
tune catalytic properties. He also developed a bifunctional mesoporous
calcium-silicate mixed-oxide heterogeneous catalyst for the cooperative
and economic conversion of bio-based high-free-fatty-acid feedstocks into
biodiesel, and founded a startup company, Catilin, to bring this technology
to the market. Shortly after his death, Catilin merged with a multinational
catalyst company, Albemarle.
One characteristic that comes to mind when I think about Victor was his
generosity with his time and knowledge. He always answered the door to his
oce with a smile on his face and was sincerely happy to see you. He played the
role of an important father figure for those of us working in his research group.
Along with his astounding intelligence, Victor had a very clever sense of humor
and knew exactly when a mood needed lightening with a joke. He allowed and
often encouraged us to pursue our own ideas in the research laboratory,
oering both financial and intellectual support to them. This exemplary
attitude extended outside our laboratory, frequently inviting other students to
group meetings and into the lab, openly discussing research ideas and goals.
His positive attitude rubbed o on the people around him, often turning a gray
day sunny; even when every reaction failed, Victor would find the silver lining
and you would leave his oce feeling much better than when you arrived. If
you ever had the opportunity to meet Victor and spend even a little bit of time
with him, I am sure you understand what I mean his smile was contagious.
Victor made a number of significant accomplishments in his brief
scientific career, holding an impressive number of professional honors. In
addition to his appointment as the John D. Corbett Professor in Chemistry
that he received shortly prior to his passing, Victor was recognized for his
outstanding research contributions with a National Science Foundation
CAREER Award, the LAS Award for Early Achievements in Research, an
Outstanding Technology Development Award from the Federal Laboratory
Consortium, and the ISU Award for Mid-Career Achievement in Research. He
was also very proud to serve on the Editorial Advisory Board of Advanced
Functional Materials.
I will never forget the time I spent with Victor, first as a graduate student
in his research group (one of his first) and later as a research scientist
assisting him in running his group. Today I have my own research group in
the chemistry department at the Colorado School of Mines and hope to be a
fraction as successful as he was in the short time he spent on earth.
I frequently find myself thinking What would Victor do in this situation?,
thankful to have known such a great man.
Brian Trewyn
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Contents
Chapter 1 Synthesis of Multi-functionalized Mesoporous
Silica Nanoparticles for Cellulosic Biomass
Conversion
Kevin C.-W. Wu
1.1
1.2
Introduction
1.1.1 Background of Cellulosic Biomass
Conversion
1.1.2 Cellulosic Conversion in Ionic Liquid
Systems
1.1.3 Enzyme-assisted Cellulose Conversion
1.1.4 Production of 5-Hydroxymethylfurfural from
Cellulosic Conversion
1.1.5 Mesoporous Catalysts from Cellulosic
Conversion
Cellulase-immobilized Mesoporous Silica
Nanocatalysts for Ecient Cellulose-to-glucose
Conversion
1.2.1 Optimization of Reaction Conditions
1.2.2 Characterization of Mesoporous Silica
Nanomaterials
1.2.3 Cellulase Immobilization
1.2.4 Cellulose Hydrolysis by using
Cellulase-immobilized MSN
1
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Contents
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1.3
Introduction
Synthesis and Structural Aspects of Mesoporous
Silica
2.2.1 Functionalization Techniques for
Mesoporous Silica
2.3 Single-site Heterogeneous Catalysts
2.3.1 Examples of Single-site Catalysts
2.3.2 Surface Distribution of Immobilized Species
2.4 Conclusion
References
Chapter 3 Supported Metal Catalysts for Green Reactions
K. Hara, H. Kobayashi, T. Komanoya, S.-J. Huang, M. Pruski
and A. Fukuoka
3.1
Introduction
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3.2
Introduction
History of Zeolites
Conventional Zeolites
4.3.1 Structures
4.3.2 Synthesis
4.3.3 Role of Organic Structure-directing Agents
4.3.4 Role of Inorganic Species
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Contents
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5.1
Introduction
Previous Work using Mesoporous Materials
6.2.1 StructureActivity Studies of Mesoporous
Sulfonic Acids
6.2.2 Catalysis of Organic Reactions
6.2.3 Lin Group Contributions
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CHAPTER 1
Synthesis of Multi-functionalized
Mesoporous Silica
Nanoparticles for Cellulosic
Biomass Conversion
KEVIN C.-W. WU
Department of Chemical Engineering, National Taiwan University, No. 1,
Sec. 4, Roosevelt Road, Taipei 10617, Taiwan
Email: kevinwu@ntu.edu.tw
1.1 Introduction
1.1.1
The usage of fossil fuels causes serious problems like the energy crisis and
global warming. In order to solve these problems, so far much attention has
been paid to the development of renewable energies such as solar or wind
energy. Biofuel produced from biomass is one of the potential alternatives.
First-generation biofuels (i.e. biodiesel) produced from corn and soybean oil
have proved that biomass-to-biofuel conversion is possible; however, the use
of edible agriculture as a source will cause other problems such as food
deficiency.1 Therefore, second-generation biofuels generated from nonedible lignocellulosic biomass have attracted more attention recently.
Lignocellulosic (or so-called wood-based) biomass consists of three
major components: cellulose (41%), hemicellulose (28%), and lignin (27%).2
Generally, cellulose and hemicellulose can be used to produce bioethanol,
RSC Green Chemistry No. 33
Heterogeneous Catalysis for Todays Challenges: Synthesis, Characterization and Applications
Edited by Brian Trewyn
r The Royal Society of Chemistry 2015
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Chapter 1
1.1.2
Recently, ionic liquids (ILs) have attracted a lot of attention and have been
utilized as solvents for the degradation of the lignocellulosic biomass.1014
The importance of ionic liquids in cellulose dissolution has been emphasized in several reviews.1517 ILs are a kind of novel green solvent. They
are organic salts with relatively low melting points. In other words, ILs
usually appear as crystals under normal conditions; however, they can be
melted and dissociated into two ionic parts at relatively high temperatures
(usually less than 100 1C). In contrast to other crystalline salts (e.g. NaCl),
the attractive characteristic of ILs is that they can transform into a
liquid phase.
The utilization of ILs for the dissolution of lignocellulose started in early
2000. Numerous papers have been published on controlling the viscosity and
polarity of ionic liquids by varying their ionic structures.16,17 The main focus
of these papers was the solubility of the synthesized ILs toward dierent
carbohydrates such as glucose, sucrose, amylose, cellulose, and so on. In
2002, Rogers et al. reported that cellulose could be dissolved in ILs at
100 1C.10 The solubility of cellulose in ionic liquids results from its anions.
It can disrupt the hydrogen bonds between polysaccharide chains of
cellulose and then dissolve it.18 This discovery started a new pathway to deal
with cellulose at low temperatures and ambient pressure.
In 2007, Zhang and his co-workers discovered that CrCl2 in [EMIM]Cl
(1-ethyl-3-methylimidazolium chloride, an imidazolium-type ionic liquid)
can eciently catalyze the glucose-to-HMF conversion.19 HMF is a
promising platform chemical because it can further transform to a widely
used biofuel called 2,5-dimethylfuran (DMF)20 and other useful materials.21
Since then, many have worked on the production of HMF from cellulose or
glucose in ionic liquid systems. Binder and Raines combined HCl, CrCl2 or
CrCl3, DMA/LiCl and [EMIM]Cl to convert cellulose to HMF;13 Zhang and
his co-workers used CrCl2/CuCl2 as catalysts in [EMIM]Cl;14 Han and his
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1.1.3
In recent decades, cellulase was broadly studied for the hydrolysis of cellulose.2731 Cellulase is a mixture of enzymes containing three main components: (1) endo-1,4-beta-D-glucanase (EG) which randomly cleaves the
cellulose chain to lower the crystallinity; (2) cellobiohydrolase (CBH) which
degrades cellulose by releasing cellobiose units; (3) beta-glucosidase which
hydrolyzes cellobiose and other oligomers to get glucose units. To date, the
reaction conditions and the hydrolytic processes of hydrolyzing cellulose by
using free cellulase have been optimized with a glucose yield as high as
70%.29 However, one critical problem when using cellulase as a catalyst is
the easy deactivation of cellulase by environmental factors (e.g., temperature), which greatly hinder its practical use in industry.32,33 In order to
overcome such diculties, the immobilization of cellulase onto solid
materials is a feasible way to enhance its stability.
Many research papers have demonstrated that immobilizing cellulase
onto organic and inorganic materials could improve the stability and
reusability of cellulase without reducing its catalytic ability.3441 Among the
host materials, mesoporous silica materials have gained much attention
because of their large specific surface area, high mechanical strength, and
tunable surface functionality.34,35 Recently, Sakaguchi et al. studied the encapsulation of cellulase by using mesoporous silica SBA-15 with various pore
sizes as hosts.36 They found that the enzymatic activity of cellulase strongly
depended on the pore size of SBA-15. The best performance of cellulase
could be obtained when using SBA-15 with pore diameter around 8.9 nm.
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Chapter 1
1.1.4
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Dierent solvents have been used in the fructose-to-HMF conversion because of the contrast between water-soluble reactants (e.g., fructose and
glucose) and organic-solvent-soluble products (e.g., HMF). The careful selection of solvents can promote the preferential reaction and enhance
product yield. The Dumesic group studied the eects of solvents on the
dehydration of fructose in biphasic systems, and demonstrated the catalytic
ability of dimethylsulfoxide (DMSO), which is able to suppress the undesired
side reactions eectively.55 Recently, ILs have been widely used as both
catalysts and solvents for producing HMF from lignocelluloses because of
their comparatively higher catalytic activity and adjustable composition.56
However, despite the excellent activity and recyclability of ILs, their potential
is restricted to laboratory-scale experiments due to high costs. Therefore, a
low-price solvent with the desired properties (e.g., high boiling point and low
viscosity) such as DMSO can have more potential in industrial applications.
In recent years, several groups have reported the production of HMF from
fructose in DMSO-based reaction systems via homogeneous and heterogeneous catalysts, including acids, salts, and metal ions.57 The Dumesic
group has investigated the catalytic capabilities of various homogeneous
mineral acids.58 Recently, Wang et al. used carbon-based p-toluenesulfonic
acid (TsOH) at 130 1C for 1.5 h resulting in a 91.2% yield of HMF.59 Although
these pioneering studies showed high yields of HMF, harsher reaction
conditions are always needed in such homogeneous catalytic systems. From
economic and sustainable viewpoints, scientists have turned to heterogeneous solid catalysts and mild reaction conditions. For example, the
Sidhpuria group immobilized ILs onto silica particles as an ecient heterogeneous catalyst for fructose-to-HMF conversion with a yield of 63% in a
DMSO system.60
1.1.5
Mesoporous silica nanoparticles (MSNs) have attracted a great deal of attention in the field of catalysis because of their high surface area and controllable pore size. In addition, abundant SiOH groups on the surface of
MSNs provide the possibility of further functionalization with other organic
groups.61 For example, the Lin group has used a co-condensation method to
functionalize MSNs with a general acid (i.e., a ureidopropyl (UDP) group) and
a base (i.e., a 3-[2-(2-aminoethylamino)ethylamino]-propyl (AEP) group) as a
cooperative acidbase catalyst for aldol, Henry, and cyanosilylation reactions.62 We also have used a grafting method to functionalize MSNs with
several metalhistidine complexes for H2O2-assisted tooth bleaching. However,
the conventional MSNs synthesized from the cationic surfactant cetyltrimethylammonium bromide (CTAB) exhibit a pore size of around 2 nm. For
several catalytic reactions involving large molecules (e.g., proteins or cellulose),
this pore size is too small to allow the reactants to diuse into the mesopores,
thus losing the advantage of high surface area inside the MSNs. Therefore, the
synthesis of MSNs with pore sizes large than 10 nm is highly desirable.
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Chapter 1
The MSNs with large pore sizes can be synthesized through two approaches: (1) using high-molecular-weight surfactants as templates; and (2)
adding hydrophobic additives as swelling agents. For example, the Zhao
group succeeded in synthesising mesoporous silica with an ultra-large pore
size of approximately 37.0 nm by using a high-molecular-weight surfactant
(poly(ethylene oxide)-b-poly(methyl methacrylate); PEO-b-PMMA).63 The
same group has also reported the addition of 1,3,5-trimethylbenzene (TMB)
as a swelling agent to synthesize mesoporous silica with a large pore of 25.4
nm (as denoted as FDU-12).63,64 The Lu group has functionalized FDU-12
materials with phenyl, thiol, amino, and vinyl groups and studied the eect
of these functional groups on the immobilization ecacy of an enzyme (i.e.,
cellulase).65 Despite these pioneering studies, researchers have not yet
utilized large-pored MSNs with various functional groups for cellulosic
conversion in ionic liquid systems. In general, cellulosic conversion involves
three main reactions: (1) cellobiose-to-glucose depolymerization, (2) glucoseto-fructose isomerization, (3) fructose-to-HMF dehydration. These reactions
need acid, base, and acid catalysts, respectively, as illustrated in Scheme 1.1.
Consequently, to synthesize large-pored MSNs with both acid and base
functionalities as a new cooperative solid catalyst would be helpful for
one-pot cellulose-to-HMF conversion.
Scheme 1.1
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(a)
(b)
(c)
Figure 1.1
Optimization of reaction conditions for cellulase-assisted celluloseto-glucose conversion: (a) reaction temperature; (b) cellulase amount;
(c) reaction time.
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Chapter 1
1.2.2
The morphology and porous properties of the synthesized MSNs with two
dierent pore sizes (NB these are referred to as large-pore MSNs (LPMSNs)
and small-pore MSNs (SPMSNs) hereafter) are characterized with scanning
electron microscopy (SEM) and nitrogen adsorptiondesorption isotherms.
The SEM images in Figure 1.2a and b show the uniform and spherical
morphology for both LPMSNs and SPMSNs with diameters around 600 and
150 nm, respectively. In Figure 1.2c and d, LPMSNs and SPMSNs exhibit type
III and type IV nitrogen adsorptiondesorption isotherms, respectively. The
type III isotherm of LPMSNs exhibits prominent adsorption at high relative
pressures (P/P0), which is indicative of adsorption in macropores. In contrast, the type IV isotherm of SPMSNs has been widely shown to occur in a
typical mesoporous material with a two-dimensional hexagonal structure.
The BrunauerEmmettTeller (BET) specific surface areas for LPMSNs and
SPMSNs are 262.6 and 820.1 m2 g1, respectively. In addition, the pore-size
distribution calculated from the BarrettJoynerHalenda (BJH) method
clearly shows that LPMSNs exhibit a broad pore size around 2040 nm while
SPMSNs exhibit a narrow pore size around 25 nm, as depicted in Figure 1.2e
and f, respectively. The structural properties of LPMSNs and SPMSNs are
summarized in Table 1.1.
In addition to pore size and surface area, the surface functionality of the
MSN also aects the immobilization of cellulase. We qualitatively and
quantitatively study the functional groups on the SPMSNs and LPMSNs by
29
Si and 13C solid-state nuclear magnetic resonance (NMR). Because the
synthetic methods for SPMSNs and LPMSNs are dierent, the organic
functional groups and their amounts on the surface of the prepared materials are dierent. As shown in the 29Si NMR spectra (Figure 1.3a), LPMSNs
exhibited Q3, Q4, T3 and T2 bonds, indicating that there are SiOH and
SiOC bonds in the material. Because we added 3-aminopropyltrimethoxysilane (APTMS) during the synthesis of LPMSN, the SiOC bonds should be
due to the presence of APTMS. On the other hand, SPMSN exhibited only Q3
and Q4 peaks that represent the presence of SiOSi and SiOH bonds, as
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(a)
(b)
(c)
(d)
(e)
(f)
Figure 1.2
Table 1.1
Sample
SPMSN
LPMSN
TESP-SA
LPMSN
a
Particle
size/nm
Specific
surface
area/m2 g1
Pore
size/nm
R grafted/
mmol g1
OH residues/
mmol g1
ca. 150
ca. 600
ca. 600
820.1
262.6
N.D.
25
2040
N.D.
N.D.
1.06
1.49
9.89
6.12
4.37
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10
Chapter 1
(a)
(b)
(c)
(d)
Figure 1.3
29
Si solid-state NMR spectra of (a) LPMSN and (b) SPMSN. 13C solid-state
NMR spectra of (c) LPMSN and (d) TESP-SA-functionalized LPMSN.
shown in Figure 1.3b. These two materials were used as hosts for physical
adsorption of cellulase. For chemically binding cellulase, we further functionalize LPMSN with carboxyl groups by reacting LPMSN with an organosilane 3-triethoxysilylpropyl succinic acid anhydride (TESP-SA). Based on
the 13C NMR spectra of LPMSN and TESP-SA-functionalized LPMSN in
Figure 1.3c and d, respectively, we could conclude that the TESP-SA was
successfully grafted onto the surface of LPMSN. The TESP-SA-functionalized
LPMSN should exhibit two functional groups, i.e., the amino group from
APTMS and the carboxyl group from TESP-SA, on its surfaces. The amounts
of the functional groups on the SPMSN, LPMSN, and TESP-SA-functionalized
LPMSN were calculated and summarized in Table 1.1.
1.2.3
Cellulase Immobilization
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Table 1.2
Sample
Cellulase/mg
Free cellulase
Cellulase-adsorbed
SPMSN
Cellulase-adsorbed
LPMSN
Cellulase-linked
TESP-SA LPMSN
a
11
4.5
14.6
Glucose
yield (%)
before
Glucose
yield (%)
after
85.86
53.39
(24.89)a
4.59
(24.89)a
10.64
(42.71)a
82.15
23.4
33.3
(46.14)a
77.89
19.2
83.79
Percentage
lost (%)
37.78
83.30
86.56
4.61
Yield of cellobiose.
SPMSN (i.e., 25 nm) made the diusion of cellulase into the pore dicult
due to the large size of cellulase (around 8 nm). Therefore, a pore size larger
than 8 nm in MSNs is essential for the immobilization of cellulase. In
addition, although the amount of cellulase chemically bonded with TESP-SAfunctionalized LPMSN was less than that of cellulase-adsorbed LPMSN, the
amount was still larger than 4.5 mg which had been considered to be the
minimum amount for maximum glucose production under optimal reaction
conditions.
Another factor aecting the immobilization of cellulase is surface charge.
The surface charges of cellulase and SPMSN at pH 4.8 are both negative
(6.7 and 14.8 mV, respectively). Therefore, the electrostatic interaction
between SPMSN and cellulase was negligible. The surface charge of LPMSN
is around zero (1.0 mV) because of the existence of both SiOH and SiNH2
groups. Therefore, in addition to the larger pore size of LPMSN, the increased adsorption amount in the case of cellulase-adsorbed LPMSN also
resulted from the electrostatic interaction between cellulase and SiNH2
groups of LPMSN. It is worth noting that the surface charge of TESP-SAfunctionalized LPMSN was negative (40.5 mV) owing to the existence of
carboxylic acid groups in TESP-SA. Therefore the immobilized cellulase
amount in this case was less than that of cellulase-adsorbed LPMSN. However, we have confirmed that the immobilized cellulases here were covalently
linked with TESP-SA-functionalized LPMSN by 13C NMR, and such chemically linked cellulases could avoid the problem of cellulase detachment,
resulting in excellent stability (see discussion below).
1.2.4
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12
Figure 1.4
Chapter 1
Yields of glucose for free cellulase, cellulase-adsorbed SPMSN, cellulaseadsorbed LPMSN, and cellulase-linked TESP-SA-functionalized LPMSN
of LPMSN and TESP-SA-functionalized LPMSN. Glucose_before indicates that the catalysts were used immediately after preparation.
Glucose_after indicates that the catalysts were used after aging at
room temperature for 23 days.
in the MSN materials are all larger than 4.5 mg, their glucose yields were all
less than 85% at the same optimal reaction conditions. As shown in
Figure 1.4 and Table 1.2, the glucose yields for cellulase-adsorbed SPMSN,
cellulase-adsorbed LPMSN, and cellulase-linked TESP-SA LPMSN were
33.30%, 77.89%, and 83.79%, respectively. It is clearly seen that the cellulase
chemically bonded with TESP-SA functionalized LPMSN exhibited almost
the same activity with free cellulase. For the case of cellulase-adsorbed
SPMSN, the glucose yield was the smallest, which might be due to the formation of a byproduct (i.e., cellobiose with yield of 46.14%). Because the
cellulase-adsorbed LPMSN catalyst still exhibited a respectable glucose yield
of 77.89%, we suggest that the low glucose yield for cellulase-adsorbed
SPMSN was due to the small pore size. When the pore size of MSN was small,
not only could cellulase not be adsorbed in the pores but also the pre-treated
cellulose could not diuse into the pores. This result again proved the significance of suitable pore size when using MSN materials as hosts.
One may be concerned that the chemically linked cellulase will lose its
activity due to the change of its conformation via covalent binding. The Lu
group has utilized amino-group-functionalized mesoporous silica materials
to immobilize cellulase and found that the activity of the immobilized cellulase decreased although the amount of immobilized material was large, as
compared to free cellulase.35 They suggested that the amino group of the
materials would bind to the catalytic domains of the cellulase, thereby
reducing its catalytic ability. In contrast to their result, our data indicated
that the activity of chemically linked cellulase was similar with that of free
cellulase. We conclude that the carboxylic-group-functionalized LPMSN used
in this study would bind with the cellulose binding domains (not catalytic
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13
1.3 Conversion and Kinetics Study of Fructose-to-5Hydroxymethylfurfural (HMF) using Sulfonic and
Ionic Liquid Groups Bi-functionalized MSNs as
Recyclable Solid Catalysts in DMSO Systems
1.3.1
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14
Scheme 1.2
Chapter 1
the Brij-97 solution with stirring at room temperature. After stirring for
30 min, organosilanes (i.e., MPTMS and CPTES) were added to the reaction
system along with TEOS, and the whole system, with a composition (in
molar ratios) of water: Brij-97 : TEOS : MPTMS : CPTES 433 : 0.293 : 1 : 0.009 :
0.009, was prepared and kept stirred for 24 h at room temperature. The
mixture was subsequently heated at 100 1C overnight. Finally, the precipitated solid was collected by filtration and washed sequentially with water
and methanol. It is worth noting that the template can be extracted by this
washing step. To further convert the thiol group of (MP CP)-MSN to a
sulfonic group, the (MP CP)-MSN was oxidized in an H2O2 solution with a
composition of (MP CP)-MSN : H2O : MeOH : H2O2 0.5 g : 10 ml : 10 ml :
10 ml. After reaction at room temperature overnight, the obtained sample
(i.e., (HSO3 CP)-MSN) was washed and dried in vacuum. To further functionalize the (HSO3 CP)-MSN with ionic liquid, the (HSO3 CP)-MSN
sample and solid imidazole were degassed for 3 h before the addition of
anhydrous benzene and chlorobutane with the molar ratio of imidazole :
chlorobutane 1 : 2. After one day of reflux, the product (i.e., (HSO3 ILs)MSN) was collected through filtration and washed with anhydrous benzene.
Finally, the (HSO3 ILs)-MSN sample was immersed in CrCl2 solution, and
the whole mixture was kept stirred overnight. CrCl2 can be physically
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1.3.2
The morphology and porous properties of the series of synthesized bifunctionalized MSN were characterized with SEM and nitrogen adsorption
desorption isotherms. The SEM image shows an uniform and spherical
morphology for bi-functionalized MSN with particle size of sub-microns. In
addition, the bi-functionalized MSNs exhibit a type IV nitrogen adsorption
desorption isotherm, indicating multilayer adsorption by capillary condensation. Moreover, the results of BET specific surface area and pore-size
distribution calculated from the BJH method are listed in Table 1.3 together
with other structural properties of bi-functionalized MSNs.
Next, we qualitatively and quantitatively investigated the functional
groups on the bi-functionalized MSN using 29Si and 13C solid-state NMR.
The 13C NMR spectrum contains ten identified signals, and these results
evidenced the successful grafting of the organosilane MPTMS and ILs on the
MSN. Additionally, we further quantified the amounts of each functional
group on the MSN by 29Si NMR. There were Qn and Tn peaks, which represents the relative amount of silica framework and their covalent bonding
with organosilanes. The amounts of functional groups are summarized in
Table 1.3. In addition, results of element analysis indicated the presence of
the sulfonic acid (S, around 2.3%) and ionic liquid (N, around 1.7%).
1.3.3
In order to demonstrate the eect of bi-functionalized MSN on the fructoseto-HMF conversion, the reaction was executed without catalysts (blank
sample), with MSN and bi-functionalized MSN. The result including the
ecacy of fructose conversion, HMF yield, and selectivity is depicted in
Figure 1.5a. The cases labeled blank (no catalyst) and MSN (with nonfunctionalized MSN as the catalyst) showed low conversion (around 25%)
and almost no HMF yield, indicating that the dehydration of fructose to
generate HMF was dicult to achieve in such reaction conditions (i.e.,
DMSO solvent, 90 1C, 3 h). In contrast, with the same reaction conditions,
Table 1.3
Physical properties
Functionalization
Specific
surface
Pore
area/m2 g1 size/nm
Particle
size/nm
Number
of SiOH/
mmol g1
Functional
group/mmol
g1
Elemental
analysis
N% C% H%
98.0
400
6.12
1.06
1.7
4.4
S%
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16
Chapter 1
1.3.4
Kinetic Study
We further study the kinetics of the fructose-to-HMF conversion and compare the rate constants, reaction orders, and activation energies for the
systems with and without bi-functionalized MSN catalysts. First, we
(a)
Figure 1.5
(b)
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(a)
Figure 1.6
17
(b)
(a) Eect of reaction time and catalyst on the yield of HMF. (b) The
kinetics profiles of HMF decomposition in DMSO at dierent temperatures. Diamonds: 120 1C; squares: 140 1C.
conducted two reaction systems (i.e., with and without catalyst) at the same
reaction temperature (i.e., 90 1C) but for dierent reaction time periods.
We observed the variation of HMF yields with reaction time and the data is
shown as Figure 1.6a. The reaction rates of both cases are initially higher but
tend to be almost constant after a time-span, indicating that the reactants
have already run out, resulting in no more HMF being produced. However,
adding our synthesized catalysts, [HSO3 (ILs/CrCl2)]-MSN, obviously accelerates the generation of HMF to some extent. Three hours later, there is
about 73.4% of HMF, which is nearly three times larger than the percentage
in blank (25.3%). That is to say, our material has an eect on the catalytic
fructose conversion.
For the purpose of identifying the relationships between kinetic parameters (such as rate constants, reaction orders, and activation energies)
and the addition of the bi-functionalized catalyst, we further comprehensively constructed the kinetics profiles at dierent temperatures for systems
with and without [HSO3 (ILs/CrCl2)]-MSN (Figure 1.6a). We supposed that
the ultimate product of fructose dehydration is HMF only, i.e. we did not
take other by-products into account. Besides, we assumed the degradation of
HMF would not occur under our designed condition (90 1C, 06 h). This
hypothesis can be supported by the test results of HMF decomposition, as
shown in Figure 1.6b. In this experiment, HMF is considered as the reactant,
placed in an identical environment as before. From the data shown, we can
see that the apparent decay of HMF (15.18%) could be noticed only under
sucient reaction temperature and time (140 1C, 6 h), which is very far from
our practical operating conditions. That is to say, in our milder conditions
(90 1C, 3 h), the decomposition of HMF is negligible and this outcome
bolsters the previous model we have set up.
In Figure 1.7, we analyzed the kinetics profiles in order to systematically
understand the shifts of each kinetics parameter caused by the catalysts.
Referring to the previous published research,54 we assumed that the
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transformation of fructose is a 1st order process and that the reaction rate
could be expressed as follows:
dHMF
dfructose
kfructose
dt
dt
dHMF
dfructose
kfructose
dt
dt
where [ ] means the molar concentration of each chemical and k is the rate
constant for fructose conversion at a certain temperature. Next, we transformed this equation into a numerical form and made the [fructose] in terms
of conversion X, i.e. [fructose]t [fructose]t0 (1 X). After the subsequent
integral calculation, the original equation will become:
ln(1 X) kt C
where t is the reaction time and C is an arbitrary constant. Therefore, we
plotted a figure with ln(1 X) as the y-axis and t as the x-axis, fitting the
data linearly, and evaluated reaction constants from the slopes. As shown in
Figure 1.7, there is an obvious increase of k in the presence of bi-functionalized MSNs, confirming their ability to promote this reaction. Next, we
calculated the activation energy (Ea) of each system from rate constants we
obtained by the Arrhenius equation. The Ea values of systems with and
without catalysts are 67.5 and 80.05 kJ mol1, respectively. This fact indicated that our addition of [HSO3 (ILs/CrCl2)]-MSN has altered the reaction
route to a certain degree, consequently lowering the activation energy and
leading to a higher reaction rate.
(a)
Figure 1.7
(b)
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To functionalize LPMSN with acid and base groups, the organosilane, i.e.,
MPTMS and APTMS, was grafted onto the surface of LPMSN. Typically, 1 g of
LPMSN in a two-necked round-bottom flask was degassed in vacuum at
110 1C for 3 h. After that, dried toluene (40 mL) was injected into the flask
under nitrogen atmosphere, followed by injecting organosilanes. The
amount of organosilane used was 1.3 times the amount of silanol group
on the LPMSN that was previously calculated by solid-state NMR (i.e.,
6 mmol g1). Then, the mixture was heated and refluxed at 110 1C for 24 h.
Finally, the acid- and/or base-functionalized LPMSN was collected by
filtration, washed with toluene several times in order to remove the
residual reactant, and dried in vacuum. The resulting samples were called
LPMSN-NH2 and LPMSN-SH. Then, the LPMSN-SH was oxided to become
LPMSN-SO3H by modifying a published procedure.67 Typically, 0.5 g
of LPMSN-SH was added to the mixture of hydrogen peroxide (10 mL),
deionized water (10 mL), and methanol (10 mL). The mixture was stirred
at room temperature for 12 h. After that, the resulting precipitate was collected by filtration, washed with deionized water several times and dried in
vacuum. The resulting sample was named LPMSN-SO3H. LPMSN-SO3H
and LPMSN-NH2 are used as acid and base solid catalysts, respectively,
in this study. For preparation of bi-functionalized LPMSN exhibiting
both acid and base groups (denoted as LPMSN-Both), APTMS was grafted
onto the pre-synthesized LPMSN-SO3H using the same grafting process
described above.
1.4.2
The cellulosic conversion includes pre-treatment and reaction. For pretreatment, cellulose (15 mg) was added into [EMIM]Cl (150 mL), and the
whole mixture was heated at 120 1C for 0.5 h with stirring for dissolution of
cellulose. For reaction, LPMSN-based catalysts (4 mg) and water (16.67 mL)
were added to the cellulose/[EMIM]Cl solution while keeping heating
at 120 1C for another 3 h. All reactions were repeated three times and
the average yields of products were obtained. After the optimization of the
reaction conditions beforehand, the amount of catalyst was determined as
4 mg. The conversion process for cellobiose, glucose and fructose was the
same as that for cellulose except for exclusion of the pre-treatment step.
When using glucose and fructose as reactants, water did not be added into
the reaction systems.
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1.4.3
Figure 1.8
(b)
13
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Samples
LPMSN
LPMSNNH2
LPMSNSO3H
LPMSNBoth
21
Pore
size/nm
Acidity/pKa
Functional
group/mmol g1
Hydroxy
group/mmol g1
233.2
166.3
31.4
32.2
2.04.8
9.315
1.06
1.67
6.12
5.28
170.0
28.1
0.82.0
1.35
5.14
63.0
26.7
7.79.3
2.32
2.51
1.4.4
Fructose (15 mg) and LPMSN-based catalysts (4 mg) were added into
[EMIM]Cl (150 mL), and the whole mixture was heated at 120 1C for 3 h. As
shown in Figure 1.9a, the yields of HMF converted from fructose with the
presence of four LPMSN-based catalysts were similar with each other (in
the range around 6670%). It has been considered that an acid catalyst is
necessary for the dehydration of fructose to produce HMF. However, we
suggested that fructose could be easily converted into 5-HMF in the ILs
system with a high temperature (120 1C) because such conditions (ILs and
high temperature) favor dehydration. Therefore, there is no dierence
between all LPMSN-based catalysts. Other groups have also reported similar
findings.
The yields of HMF converted from glucose with the presence of four
LPMSN-based catalysts are shown in Figure 1.9b. It can be clearly seen that
the cases with LPMSN-Both and LPMSN-NH2 catalysts exhibited the highest
yield around 13%, in contrast to that of LPMSN-SO3H (ca. 10%) and LPMSN
(ca. 7%). The conversion of glucose to HMF involves two steps: isomerization
of glucose to fructose and dehydration of fructose to HMF. In general, base
catalysts are helpful for isomerization of glucose to fructose.51 From the
result of fructose-to-HMF conversion, we have confirmed that four dierent
LPMSN catalysts had a similar eect on the dehydration of fructose to HMF;
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(a)
(c)
Figure 1.9
Chapter 1
(b)
(d)
in other words, HMF can be easily converted from fructose in our reaction
system. Therefore, the high HMF yields for the cases using LPMSN-Both and
LPMSN-NH2 indicate that base catalysts indeed promote the production of
fructose converted from glucose, and the glucose-to-fructose conversion can
be regarded as the rate-determining step in the glucose-to-HMF conversion.
To stimulate the structure of pre-hydrolyzed cellulose, we used cellobiose
as the reactant and studied its conversion with the presence of LPMSN-based
catalysts. The yields of glucose and HMF converted from cellobiose are
shown in Figure 1.9c. It can be seen that the LPMSN-SO3H exhibited the
highest yields of both glucose and HMF (25.6 and 18.9%, respectively). The
cellobiose-to-HMF conversion contains three steps: hydrolysis of cellobioseto-glucose, isomerization of glucose-to-fructose and dehydration of fructose
to HMF. Because acid catalysts can facilitate the first step, we suggest that it
is the reason why the highest yield of glucose appeared in the case of
LPMSN-SO3H. In addition, it can also be proposed that the cellobiose-toglucose is the rate-determining step of the three reactions. Therefore, catalysts with stronger acidity (i.e., LPMSN-SO3H and LPMSN) would favor the
production of glucose that was then converted to HMF, resulting high yields
of glucose and HMF.
We further directly used pre-hydrolyzed cellulose as the reactant and
performed the cellulose-to-HMF conversion in ionic liquid system with the
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Figure 1.10
23
1.5 Conclusions
In this chapter, we have demonstrated the successful synthesis of multifunctionalized MSNs as eective, reliable, and re-usable solid catalysts for
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24
Chapter 1
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
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25
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Chapter 1
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CHAPTER 2
2.1 Introduction
Rapid increases in the cost of feedstock chemicals, precious metals, and
recent environmental concerns about chemical waste have caused a shift
from homogeneous catalysis to heterogeneous catalysis where stability and
recyclability are clear advantages. The times of utilizing stoichiometric
reagents for organic chemical transformations to convert starting reagents to
products are long gone. Today, optimized catalysts are critical to maximize
product yield and minimize the thermal and capital expenses that contribute
to increased chemical costs. Many highly ecient and selective catalysts
have been developed in the last three decades establishing the field of
catalysis. Among these, homogeneous catalysts, mainly organometallic,
enjoyed a substantial growth and were used with diverse reactive reagents to
produce a large number of fine chemicals. The significant drawbacks of
homogeneous catalysis include challenging molecular synthesis, diculty in
separating and recycling, and poor thermal stability to name a few. The
advantages of homogeneous catalysis are the feasibility of following
reactions via spectroscopic methods to gain an understanding of the real
y
28
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29
Figure 2.1
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Chapter 2
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Table 2.1
31
Pore size/nm
Method
25
47
58
28
420
411
1027
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32
Chapter 2
The pore diameter also expanded when other substances were incorporated
that can be solubilized in the micelle core. For example, super critical (sc)
carbon dioxide was used as a swelling agent for tuning the pore size during
silicate hydrolysis for hexagonal mesoporous silica.34 It was also discovered
that incorporation of a specific concentration of metallic nanoparticles in
the system where P123 was used as the surfactant and tetraethyl orthosilicate (TEOS) as the silica source could also expand the mesochannels.35
Additionally, the pore size can be tailored by changing the initial synthesis
temperature and hydrothermal treatment conditions.27,36 Carrying out the
synthesis at a low temperature (B25 1C) showed that the combination of
pluronic block copolymers with the appropriate swelling agents form
mesoporous silica with an unusually large pore size.37 Lowering the initial
temperature from 2540 1C to 15 1C in the synthesis of FDU-12 templated by
F127 in the presence of TMB led to a doubling of the pore diameter to
27 nm.36 Hydrothermal temperature can significantly aect pore size; the
pore sizes of SBA-15 can be altered from 4.6 nm to 10 nm and from 9.5 nm to
11.4 nm by increasing the hydrothermal temperature from 70 to 130 1C and
by increasing the time from 6 h to 4 days.3841 Similar trends were seen for
mesoporous silicates with body centered cubic Im3m mesostructures and for
cubic bicontinuous Ia3d mesostructures when using F127 and the triblock
copolymer P123 as a template with butanol as a co-solute, respectively.42,43
Increasing the hydrothermal treatment conditions from 45 1C and 24 h to
100 1C and 48 h resulted in SBA-16 with larger mesopores, thinner pore
walls, and reduced intrawall micropores. The pore sizes of mesoporous silica
with Ia3d symmetry could be tuned from 4 to 10 nm by increasing the
hydrothermal temperature from 65 to 130 1C.42
2.2.1
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(a)
(b)
Scheme 2.1
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34
Chapter 2
2.3.1
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(CH3O)3Si(CH2)3SH
(STMOS)
+
Si(OCH2CH3)4
35
1) CTAB,NaOH,H2O
(TEOS)
2) APTMOS, toluene
(CH2)3NH2
(CH2)3NH2
3) H2O2,CH3COOH
4) CTAB removal
5) 150 oC, 0.1 mmHg
H2N(H2C)3
H2N(H2C)3
SAMSN-AP
Scheme 2.2
Table 2.2
Cascade reaction consisting of acid-catalyzed hydrolysis and basecatalyzed Henry reaction. Reaction conditions: catalyst, 100 mg
(1.5 mmol); H2O, 1.5 mmol; CH3NO2, 1 ml; 80 1C; 24 h.
OCH3
OCH3
O2N
NO2
CHO
Base
Acid
O2N
H 2O
O2N
CH3NO2
Entry
Catalysta
Bb (%)
Cb (%)
Conv. of Ab (%)
1
2
3
4
5
6
7
8
9
10
SAMSN-AP
APMSN-SA
SAMSN/APMSN
SAMSN
APMSN
SAMSN-AP/AP
SAMSN-AP/PTSA
APMSN-SA/AP
APMSN-SA/PTSA
MSN
2.3
1.9
4.5
100
0
0
100
0
100
0
97.7
98.1
95.5
0
0
0
0
0
0
0
100
100
100
100
0
0
100
0
100
0
a
b
and 13C and 29Si solid-state NMR spectroscopy. Organic functional group
loading was quantified via elemental analysis. The activity for a one-pot
reaction sequence involving acid-catalyzed hydrolysis of an acetal followed
by a subsequent base-catalyzed Henry reaction was tested as shown in
Table 2.2.
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36
Chapter 2
Both bifunctional materials, SAMSN-AP and APMSN-SA, gave 100% conversion of A and a very high yield of the desired product C by catalyzing the
reaction in a cascade fashion. The catalytic activity for the same reaction was
similar for physically mixed APMSN and SAMSN (see entry 3 in Table 2.2).
However, when a single functionality was incorporated on the MSN surface
(either acid or base) there was a lack of measured product C formation.
SAMSN-AP or APMSN-SA when combined with the homogeneous analogues
of sulfonic acid (PTSA) and propylamine (AP) gave no product C either, since
the free acid and base molecules neutralized the corresponding heterogeneous base or acid. These catalysts were recyclable up to five times with a
negligible decrease in catalytic activity. The kinetics of the catalysts were
studied as well: incorporating both acidic and basic groups introduced by
the co-condensation method showed better reactivity (TOF, turnover
frequency) than the analogous catalysts where grafting was used to tether the
same groups onto the external surface of the MSNs (Figure 2.2a). These
results indicate that diusion limitations during the catalytic cycle might be
minimized and the dispersion or surface coverage of the catalytic sites might
play a role in the activity. To investigate this, a series of catalytic reactions were
run using MSN-based catalysts with five dierent concentrations of amines
(Figure 2.2b). The catalytic activity by measuring TOF decreased steeply as the
surface coverage of the catalysts increased, showing a direct relationship
between the catalysts activity and the catalyst coverage on the MSN surface.
Rothenberg et al. also used MSN to support two antagonistic functional
groups:50 they reported the synthesis of MSN-supported catalysts with
site-isolated amine and phosphotungstic acid groups. Amine groups were
attached to SBA-15 using the grafting method and the resulting material was
then treated with a methanolic solution of the phosphotungstic acid
(H3PW12O40) which led to a bifunctional (acidbase) catalyst as shown in
Scheme 2.3.
This bifunctional catalyst demonstrated high conversion and yield for
the acid-catalyzed deacetalization of benzaldehyde dimethylacetal followed
Figure 2.2
(a) Turnover frequency of the acid and base catalysts located on either
the internal or external surfaces of SAMSN-AP and APMSN-SA. (b) Fitted
curve of base activity versus base concentration on the APMSN surface.
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Scheme 2.3
37
SB
SAB
OCH3
OCH3
SAB,H2O
-2CH3OH
CHO
NC
CN
2.SAB,CH2CN2
-H2O
Scheme 2.4
by the base-catalyzed Henry reaction between 4-benzaldehyde and nitromethane, and base-catalyzed aldol condensation of 4-benzaldehyde and
malononitrile as shown in Scheme 2.4.
The catalyst activity for the tandem reaction was governed by the tunable
ratio of aminopropyl (AP) groups and phosphotungstic acid (HPW) groups
on the MSN support. When the AP/HPW ratio on MSN was tuned to 2 : 1, half
of the total amine on the MSN surface was used for immobilizing polyacids
whereas a ratio of 1 : 1 stopped the reaction sequence at step 1 with the
formation of benzaldehyde as all the AP groups of the MSNs were used for
polyacid immobilization, leading to only acidic sites being present on the
MSN catalyst surface.
Asefa et al. developed MSN-based bifunctional, highly ecient catalysts
for the Henry reaction.5153 The catalysts were prepared by post-synthetic
grafting of 3-APTMS on MCM-41-type mesoporous silica materials at
elevated temperature in ethanol and toluene and were labeled as AP-E1,
AP-T1, and AP-T2 as described in Scheme 2.5.
The organoamine loading was the highest for AP-T2 (4.3 mmol g1)
followed by AP-T1 (4.1 mmol g1), and AP-E1 had the lowest loading of
1.3 mmol g1. Catalytic studies for the Henry reaction showed that AP-E1
was a superior catalyst to AP-T1 and AP-T2. Taking into consideration the
fact that AP-E1 had the lowest density of catalytically active organoamine
groups of the three catalysts synthesized, it was thought that surface silanol
groups activated the carbonyl group of benzaldehyde to facilitate the
nitroaldol reaction as shown in Scheme 2.6. Grafting additional organic
groups led to significantly reduced catalytic eciency indicating the
importance of well-isolated active sites and silanol groups for improved
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38
Chapter 2
AP-E1
AP-T1,AP-T2
Scheme 2.5
(a)
AP-E1
O
O O O OO
O
Si
Si
Si
Si Si
O
O O
O HO O
O O
O
O
H
O
Si T2
O Si O
Si T3 H
O
H
O
CH2NO2
H
CH2NO2
H
N
+
2
NH3
AP-T1,AP-T2
O O O O O O O Si O
Si
Si
Si
Si
Si
OO
O
O
OO O
O O
O
Si T3
O HO
HO
Si T2 Si T3
Si T2
O
H 2N
H 3N
H2N
H 3N
CH2NO2
HO
HO
O
HO
Scheme 2.6
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O
O
S
O
Si(OEt)3
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N
H
O
S
(EtO)3Si
Figure 2.3
NH
Si(OEt)3
S
(EtO)3Si
Si(OEt)3
S
Si(OEt)3
O
O
N
H
Si(OEt)3
(EtO)3Si
N
H
Si(OEt)3
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40
Chapter 2
(a)
NH2
(b)
SH
NO2
S
O2N
COOH
HOOC
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Si
O O OH
S
Si
HO O O
3-S
O
HOOC
COOH
O2N
O2N
S
S
S
S
Si
OH
Si
O
HO O O
Scheme 2.7
NH2
N
S
Si
O O OH
Si
Si
OH
HO O O O O
grafted onto the surface of two dierently functionalized MSNs, 8 and 9, but
with the same surface distribution and active sites; the uniformity between
the two surfaces was achieved by the synthesis of 9 directly by thermal
deprotection of 8. An increase in thiolamine pairing was seen in material 10
over 11 which has contributed to a greater tendency of carbamate silane
precursor 2 to condense on the MSN surface next to xanthate silane
precursor 1 as compared to the condensation of 2 next to tethered
mercaptopropyl groups (formed after thermal deprotection of 1 on the surface) as illustrated in Scheme 2.8. In contrast, the condensation tendency
shown by xanthate silane 1 next to carbamate silane 2 and primary amine
(formed by thermal deprotection of 2 on the surface) was the same. Thiol
amine pairing was also dierent based on the sequence of grafting, material
with 1 grafted first followed by 2 showed dierent pairing as compared to
the case when 2 was grafted before 1. Such dependences indicated a nonrandom distribution of imprints on the surface possibly driven by kinetic
phenomena or specific interactions between the surface species.
Cooperative heterogeneous catalysis is a remarkable concept; supporting
dierent functionalities on a heterogeneous support which may work
together in a cooperative way either to alter the reaction characteristics or to
assist in performing several steps of a reaction sequence. One of the reactions where this concept has been applied is the synthesis of bisphenols.
Bisphenol A (BPA) and bisphenol Z (BPZ) are important feedstocks in the
08:23:58.
Published on 22 June 2015 on http://pubs.rsc.org | doi:1
S
S
(EtO)3Si
NH
O
O
S
NH
S
O
O
S
NH
O
O
SH
NH2
N2, 250 oC
NH
SH
NH2
NH2
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
Si
10
N2,250oC
O
O
HS
O
NH
HS
SH
(EtO)3Si
HS
NH
HS
SH
NH
Si
Si
Si
Si
NH
Si
Si
Si
Si
Scheme 2.8
HS
Si
Si
Si
NH2
HS
o
N2, 250 C
HS
NH2
SH
NH2
Si
Si
Si
Si
Si
Si
11
Interactions during condensation between carbamate 2 and immobilized xanthate 1 and mercaptopropyl species on
homologous surfaces 8 and 9 influenced the distribution of species on the final surfaces 10 and 11.
41
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42
Chapter 2
OH
OH
HO
HO
+
OH
o, p' isomer
08:23:58.
Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00028
Bisphenol A
(p, p' isomer)
HO
OH
HO
OH
+
+
OH
Bisphenol Z
(p, p' isomer)
Scheme 2.9
o, p' isomer
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43
OH
OH
S
08:23:58.
Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00028
SH
1
EtO
OEt
OEt
Si
SH
O
S
S
OH
S
O
S
S
EtO
OMe
Si
OMe
MeO
Si OEt
OEt
EtO
Table 2.3
Si OEt
OEt
Si
MeO
Bis-silane
Scheme 2.10
Cl
O S O
OMe
OMe
Material
SBETa/m2 g1
Dpb/nm
SBA-15
SBA-g3
SBA-A
SBA-AT-p
SBA-AT-r
SBA-T
860
230
6.3
5.8
430
6.0
H1 c/mmol g1
0.20
0.21
0.13
SHd/mmol g1
SH/H1
0.19
0.12
0.32
0.90
0.92
that silanes are covalently bound to the surface at two points. The
confirmation that both the trialkoxysilane groups of 3 are attached to the
surface was deduced by the absence of T0 peaks, which would have appeared
at 41 ppm. Thermogravimetric analysis (TGA) in air was used for the
quantitative determination of the organic content of SBA-g3. After the
introduction of bis-silane 3 to the silica surface, deprotection was carried out
in one step using aqueous tris(2-carboxyethyl)phosphine hydrochloride
(TCEP HCl) leading to SBA-AT-p (Scheme 2.11).
The success of the deprotection step was confirmed using 13C CP/MAS
NMR spectroscopy. A comparison of 29Si CP/MAS NMR spectrum of SBA-AT-p
with SBA-g3 showed an increase in T3 signal due to further condensation of
alkoxysilane moieties in the aqueous condition used for deprotection, but T2
still remained the most intense peak. The surface area of SBA-AT-p increased
to 430 m2 g1 from 230 m2 g1 for SBA-g3 probably due to the removal of
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44
Chapter 2
O
S
S
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Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00028
EtO
Si
O
SH
TCEP.HCl
H2O
O
HO
OMe
Si
EtO
Si
O
O
S
O
Si
OMe
O
SBA-g3
Scheme 2.11
SBA-AT-p
mercaptoethanol and also unblocking of some blocked pore openings. SBAAT-p was characterized for acid content and thiol content and the values are
shown in Table 2.3. Notably, the acid/thiol ratio was close to 1 in support of
this co-catalyst functionalization method.
For catalytic studies, catalysts containing (i) only thiol (SBA-T), (ii) only
arylsulfonic acid (SBA-A), and (iii) randomly distributed arylsulfonic acid and
thiol groups (SBA-AT-r) were also prepared as illustrated in Scheme 2.12.
The catalytic activity of various materials was tested for the synthesis of
bisphenols A and Z. For bisphenol A, the catalysts having both the thiol and
acid groups in close proximity on the same silica support for both organized
(SBA-AT-p) as well as randomly distributed (SBA-AT-r) exhibited similar activity but a remarkable advantage of the paired catalyst over the randomly
distributed catalyst was the selectivity (isomer ratio of 19.3 versus 15.2).
SBA-T was inactive for the catalysis of bisphenol A synthesis as there was no
acid group present, SBA-A showed some activity but low selectivity due to
absence of thiol sites, a physical mixture of SBA-A and SBA-T demonstrated
low activity and selectivity as the acid and thiol groups are unable to interact
except at the outer catalytic sites whereas PTSA was able to interact with
surface bound thiols by entering the pores. For bisphenol Z, a similar trend
was seen but the selectivity using SBA-T-p was more than three times higher
than the selectivity observed for SBA-AT-r. These data suggests that catalytic
cooperativity for the synthesis of bisphenol Z was more dependent on
acid/thiol distance than for bisphenol A.
The thermolytic molecular precursor (TMP) method is a unique and
ecient approach to attain single-site catalysts developed by Tilley et al. This
method was first used to synthesize non-mesostructured homogeneous
mixed elemental oxides, for example ZrO2 4SiO2 was prepared by thermally
decomposing Zr[OSi(OtBu)3] with the elimination of alkene and water as
shown in the following equation:58
D
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SH
SBA-15
Toluene
Si OMe
MeO OMe
HO
08:23:58.
Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00028
MPTMS
Si
O
O
SBA-T
O
O S O
O
O S O
OH
O S O
TCEP.HCl
H2 O
SBA-15
Toluene
MeO
45
Si
OMe
OMe
HO
Si
O
O
HO
SBA-g4
O
O S O
S
S
S
S
SBA-15
Toluene
Si
O
O
SBA-A
O
O S O
OH
O S O
HS
TCEP.HCl
H2O
Si
OMe
MeO OMe
Scheme 2.12
MeO
Si
OMe
OMe
HO
Si
O
O
HO
SBA-g2,4
Si
O
O
HO
Si
O
O
HO
Si
O
O
SBA-AT-r
Synthesis of SBA-T, SBA-A, and SBA-AT-r. Top: grafting 3-mercaptopropyltrimethoxysilane (MPTMS) onto SBA-15 generated SBA-T, containing only thiol sites. Middle: grafting sulfonate ester precursor 4
generated intermediate SBA-g4, which was hydrolyzed to SBA-A, containing only acid sites. Bottom: grafting both disulfide 2 and sulfonate
ester 4 generates intermediate SBA-g2, 4 which was deprotected to
form SBA-AT-r, containing randomly distributed acid and thiol sites.
aqueous solvents.59 Tilley et al. also covalently attached well-defined oxygenrich organometallic molecular precursors onto the mesoporous silica
support using post-synthetic grafting; this approach not only controlled the
structure of the catalytic site on the molecular level but also led to an
excellent spectroscopic model for the catalytic active sites.6065 Tilley and
Rioux et al. recently reported Pd(II) centers supported on mesoporous silica
using the TMP method,66 where two novel tris(t-butoxy)siloxy palladium(II)
complexes of the form (4,4 0 -di-tert-butyl-2,2 0 -bipyridyl)Pd-[OSi(OtBu)3](R)
(where R OSi(OtBu)3 for complex 1 and R CH3 for complex 2) were
synthesized as shown in Scheme 2.13.
The structures of the complexes 1 and 2 were characterized using 1H, 13C,
29
Si NMR spectroscopy, and X-ray analysis: the latter showed that both
structures were found to have slightly distorted cis square planar geometry
around the Pd center. The thermal decomposition behaviors of the complexes were studied using TGA and dierential scanning calorimetry (DSC).
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Chapter 2
Cl
Pd
Cl
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Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00028
2KOSi(O Bu)3
CH2Cl2, 25 C,16 h
-2KCl
N
Pd
N
OSi(O Bu)3
t
OSi(O Bu)3
(1)
N
Pd
N
CH3
I
+ 2HOSi(OtBu)3
+ Ag2O
Pd
N
CH3
t
OSi(O Bu)3
(2)
Scheme 2.13
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47
+ HOSi(OtBu)3
N
N
08:23:58.
Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00028
Pd
25 C, 16 h
+ SBA-15
R
t
Pd
OH
R
OH OH
OSi(O Bu)3
R = OSi(OtBu)3 or CH3
Scheme 2.14
Table 2.4
Nitrogen porosity and palladium loading data for the PdSBA15 materials.
Material
Pd content (wt%)
[ICP-OES]a
Pd coverage/
nm2
SBET b/
m2 g1
rP c/
nm
Vpore, avg d/
cm3 g1
SBA15
Pd(1)SBA15
Pd(2)SBA15
1.89
1.90
0.16
0.16
666
458
467
2.8
2.8
2.8
0.685
0.500
0.504
Average value of triplicates with relative standard deviations o4% in all cases.
Specific surface area using the BET method.
c
Average pore diameter.
d
Average pore volume.
b
(A)
(A)
(B)
(B)
Figure 2.4
(1) DR UV-Vis spectra for (A) complex 1 and Pd(1)SBA15, and (B) complex
2 and Pd(2)SBA15. (2) XANES (A) and extended EXAFS (B) region of Pd
K-edge for complex 1 and Pd(1)SBA15 at room temperature.
grafting and the grafted materials exhibited reduced surface areas and
pore volumes as compared to SBA-15. The properties of the two catalysts and
SBA-15 are shown in Table 2.4.
FTIR spectroscopy showed several analogous peaks contributed to the
t
Bu2-bpy ligand structure for both the Pd(1)SBA15 and Pd(2)SBA15 materials
suggesting intactness of the (tBu2bpy)Pd core after grafting. DR UV-Vis
analysis for the surface structure (Figure 2.4) showed strong high energy
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48
Chapter 2
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49
Si(OEt)3
S
O
N
08:23:58.
Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00028
Figure 2.5
Scheme 2.15
[Cu(CH3CN)4]PF6
CH3CN
Cu12 +
SBA-15,70 oC
Overnight
N
N Cu
N
N OTf
II
Fe
N
Fe
OTf
N
CuI
phenanthroline 1 and 2 were used for elemental tagging for ligand identification via ICP analysis (Figure 2.5).
Trialkoxysilyl groups enabled immobilization to mesoporous silica for
ligand 1. Ligand 1 was tethered on SBA-15-type mesoporous silica using two
methods: metal templating and random ligand grafting. The materials were
named T, CuIIT, FeIIT, G, CuIIG and FeIIG where T is the material prepared by
metal-templating method (discussed below) and G stands for materials
prepared by random ligand grafting. Procedures shown in Schemes 2.15 and
2.16 outline the preparation steps of dierent materials studied.
1. Metal templating. This was achieved using the following steps and is
shown in Scheme 2.15.
(a) Formation of thermodynamically stable [Cu12]1.
(b) Covalent attachment to mesoporous silica using post-synthetic
grafting method.
(c) Removal of Cu atom template using EDTA.
(d) Metalation of immobilized metal templated 1 with Fe(OTf)2 to form
the final catalyst.
2. Random ligand grafting. It involves two steps as shown in
Scheme 2.16.
(a) Covalent attachment of ligand 1 on SBA-15.
(b) Metalation of immobilized grafted ligand.
An equal loading of ligand 1 was achieved by both the random ligand
grafting and metal-templating methods. As shown in Table 2.5, the template
material proved better in that it achieved a 2 : 1 ratio of ligand : metal as
calculated by ICP analysis, thus ensuring the presence of active catalytic
species in the desired form. The ligand : metal ratio was 2.9 : 1 for FeIIcoordinated grafted materials, implying the formation of either a highly stable
FeII-(tris-1) complex or loss of loosely associated FeII ions upon washing.
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Chapter 2
Si(OEt)3
N
S
08:23:58.
Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00028
O
N
SBA-15, 70 C
Table 2.5
CH3CN, Overnightt
Fe(OTf)2
OTf
OTf
MeOH,Overnight
Scheme 2.16
Fe
Material
Loading of ligand
1/mmol g1] ( 0.01)
Metal loading/mmol
g1 ( 0.002)
T
CuIIT
FeIIT
G
CuIIG
FeIIG
0.11
0.11
0.11
0.10
0.10
0.10
0.001
0.052
0.055
0.00
0.055
0.035
2.1 : 1
2.0 : 1
1.7 : 1
2.9 : 1
Table 2.6
Substrate
[Fe23](OTf)2
Vinylcyclohexane
1-Octene
Allyl acetate
2-Cyclohexen-1-one
85
80
25
15
60 (65)
65 (80)
15 (40)
o5 (o5)
(90)
(95)
(70)
(85)
60 (65)
75 (95)
20 (45)
0 (0)
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Si(OEt)3
S
SBA-15
N N
O
O
08:23:58.
Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00028
[Mn(CF3SO3)2]
Covalent
attachment
Cu
Grafted Material
G
Cu
Cu
Dematalation
Mn
MnIIG
Mn
Templated Material
T
Scheme 2.17
Mn
Mn
Random grafting
Mn
MnIIT
Knowing that 20 is twice the distance between the silicon atom and
center of two coordinating N atoms of the ligand in an extended alkyl chain
conformation, a ligand loading of greater than 0.30 mmol g1 was calculated
to be unfavorable for site isolation.
Metal templating with ligand loadings of 0.3, 0.11 and 0.025 mmol g1 led
to a ratio of 2 : 1 of S (from ligand) : metal whereas for grafted ligand
materials the ratio varied randomly. The coordination environments of
CuIIG and CuIIT complexes were analyzed using X-band EPR spectroscopy
which showed that coordination environments of templated materials
(CuIIT) were more similar to the organometallic complex in the
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52
Table 2.7
Chapter 2
II
08:23:58.
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Yield ( 3%)
Selectivity ( 3%)
[MnII(Phen)2]21
[MnII(Phen)1]21
[MnII(2)2]21
[MnII(2)1]21
MnIIT (0.30)
MnIIT (0.11)
MnIIT (0.025)
MnIIG (0.30)
MnIIG (0.11)
MnIIG (0.025)
95
72
80
73
97
98
98
80
83
72
72
72
85
73
97
98
98
84
83
72
homogeneous state than the grafted materials (CuIIG). For catalytic activity
examination, epoxidation of vinyl cyclohexane was used as a test reaction
and all the catalysts and controls were tested for it (Table 2.7).
The most reactive and selective catalyst was MnIIT. The reactivity and selectivity of MnIIT did not vary with ligand loading. A lower epoxide selectivity
for MnIIG was observed and it was similar to the homogeneous catalyst when
1 equiv. of 2 or 1,10-phenanthroline (phen) for 1 equiv. of MnII was used for
the catalyst synthesis. The kinetics while using similar MnIIT loading was
much faster (approx. 5 times) than MnIIG for epoxidation of 1-octene. Results
indicate that both catalysts, MnIIT and MnIIG, have a broad substrate scope
for the epoxidation reaction: a high yield was demonstrated for trisubstituted
electron-rich olefins for both whereas [MnII(2)2]21 completely oxidized trisubstituted olefins. Also, MnIIT led to no isomerization of cis-olefins and a
very ecient formation of epoxides a, b-unsaturated ketones and esters.
With ecient heat control of the reaction, MnIIT could be recycled five
times without any significant change in the percent yield, the amount of
oxidant needed and the Mn content of the catalysts. However, in the random
grafting sample, MnIIG showed that the ligand content attached to the solid
support remained the same but metal leaching occurred which led to a loss
of reactivity.
Stack et al. reported the synthesis of mesoporous silica functionalized
with azide groups with various loadings, which could be easily controlled
by varying the ratio of 3-azidopropyltriethoxysilane (3-AzPTES) added
during the synthesis using the co-condensation method.70,71 The idea of
using the co-condensation method was to avoid clustering of the ligand
sites. The hybrid azidopropyl mesoporous silica were labeled SBA-15-N3-x
(x is the mole percentage of the 3-AzPTES used during the synthesis; the
sum of the total mole percentage with TEOS is 100). Four strategically
important alkyne-terminated organic compounds were attached using
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53
R
08:23:58.
Published on 22 June 2015 on http://pubs.rsc.org | doi:10.1039/9781849737494-00028
N3
N
N N
N3
Si(OEt)3 + Si(OEt)4
(100-x %)
(x %)
SBA-15-N3-x
R
Click
SBA-15-N3-x
N
Fe
R=
Scheme 2.18
Fc
Pyrene
TPA
N
Cl
Fe
Ph
Ph
Ph
FeTPP
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54
Chapter 2
Figure 2.6
interaction and an increase in excimer fluorescence. A direct dependence of increased loading with increased excimer detected was observed (Figure 2.6).
2. SBA-15-TPA-x dioxygen adduct monomer/dimer of CuTPA complexes.
Oxygenation of [CuI(TPA)]1 in homogeneous solutions generated
uniquely colored species depending on the dioxygen adduct formed.
The monomeric superoxo complex was green whereas the dicopper
complex, formed by rapid oxidation of [CuI(TPA)]1, was purple. CuTPA
complexes supported on SBA-15 were treated with dioxygen and the
results were compared with that of the analogous homogeneous complexes. Similar results were observed for supported CuTPA complexes
and the site-isolated loadings on heterogeneous support led to the
formation of stable reactive monomeric species; these monomeric
species were highly unstable in the homogeneous state. The variously
loaded SBA-15-[CuI(TPA)]1-x showed dierent results. Materials with
high loading turned purple due to densely packed complexes leading
to the formation of trans-peroxo complexes whereas materials with
low loading, where adequate site isolation was possible, showed the
formation of green copper superoxide complexes.
2.3.2
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(a)
(b)
Figure 2.7
55
(c)
Graphical representations of theoretical surface distributions: (a) clustered, (b) uniform, and (c) random.
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Chapter 2
08:23:58.
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2.4 Conclusion
In this review, we outlined the common strategies of surface functionalization of mesoporous silica materials and summarized recent developments in single-site heterogeneous catalysis. Single-site heterogeneous
catalysis is defined as using supported active catalysts that are independent
and have no measurable interaction with one another. We focused on a
limited number of recent publications that have been central to the development and understanding of the physical characteristics of these
catalysts. Herein, we described publications that used clever molecular
designs to control the amount of space between the supported active
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57
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42. T.-W. Kim, F. Kleitz, B. Paul and R. Ryoo, J. Am. Chem. Soc., 2005,
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45. J. M. Thomas, R. Raja and D. W. Lewis, Angew. Chem., Int. Ed., 2005,
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Angew. Chem., Int. Ed., 2011, 50(41), 96159619.
51. K. K. Sharma, A. Anan, R. P. Buckley, W. Ouellette and T. Asefa, J. Am.
Chem. Soc., 2008, 130(1), 218228.
52. K. K. Sharma and T. Asefa, Angew. Chem., Int. Ed., 2007, 46(16), 2879
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57. E. L. Margelefsky, A. Bendjeriou, R. K. Zeidan, V. Dufaud and
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58. K. W. Terry, C. G. Lugmair and T. D. Tilley, J. Am. Chem. Soc., 1997,
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59. J. W. Kriesel, M. S. Sander and T. D. Tilley, Adv. Mater., 2001, 13(5), 331335.
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2005, 29, 37363738.
61. K. L. Fujdala, I. J. Drake, A. T. Bell and T. D. Tilley, J. Am. Chem. Soc.,
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62. K. L. Fujdala and T. D. Tilley, J. Am. Chem. Soc., 2001, 123(41), 10133
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63. D. A. Ruddy, J. Jarupatrakorn, R. M. Rioux, J. T. Miller, M. J. McMurdo,
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64. D. A. Ruddy, N. L. Ohler, A. T. Bell and T. D. Tilley, J. Catal., 2006, 238(2),
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65. D. A. Ruddy and T. D. Tilley, Chem. Commun., 2007, 32, 33503352.
66. Y.-S. Choi, E. G. Moschetta, J. T. Miller, M. Fasulo, M. J. McMurdo,
R. M. Rioux and T. D. Tilley, ACS Catal., 2011, 1(10), 11661177.
67. T. J. Terry, G. Dubois, A. Murphy and T. D. P. Stack, Angew. Chem., Int.
Ed., 2007, 46(6), 945947.
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Chapter 2
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CHAPTER 3
3.1 Introduction
Supported metal catalysts have played numerous significant roles in the
chemical industry. The current global environmental and resource problems
are motivating further research and development of supported metal catalysts. The typical general requirements expected for ideal catalysts nowadays
include high activity, selectivity, durability, recyclability, compatibility with
practical reaction conditions, broad applicability as well as cost, safety and
environmental benignness. Regardless of the presence of such multiple requirements, a number of supported metal catalysts were recently developed
and applied to a wide range of reactions.
The recent developments in supported metal catalysts were significantly
enhanced with the aid of newly established methodologies in novel materials synthesis as well as those in spectroscopy, microscopy and model
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Chapter 3
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3.2.2
OH
Hydrogenation
O
HO
HO
OH
OH
Sorbitol
OH
OH
OH
OH
HO
OH
Gassification
Dehydration
HO
OH
CO, CH4, H2
OH
OH
O
Glucose
Hydrogenolysis
OH
Isomerization
& dehydration
Oxidation
HO
OH
OH
Sorbitan
OH
HO
OH
Ethylene
glycol
Figure 3.1
O
OH
OH
Propylene
glycol
OH
HO
OH
HO
5-Hydroxy
methylfurfural
OH
OH
Gluconic acid
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Chapter 3
3.2.3
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3.2.4
Depolymerization of hemicellulose proceeds more rapidly than that of cellulose, yielding C5 sugars which are useful as sweeteners and potential
precursors to ethylene glycol and propylene glycol, although being more
reactive than glucose. After a patent claiming the hemicellulose conversion
via a three-step process including hydrolytic hydrogenation over RANEYs
Ni,19 one-pot hydrolytic hydrogenation of hemicellulose was recently accomplished by using a Ru/AC catalyst under 5 MPa H2, where arabitol was
obtained in a high yield from beet fiber.20 However, the catalyst durability in
the reactions using real biomass still remains as a problematic issue.
Pre-treatment to remove the deactivating components from real biomass is
thus necessary at the moment. Another recent application is the conversion
of bleached birch kraft pulp into sugar alcohols by Pt/MCM-48 catalyst.21
3.2.5
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Chapter 3
3.2.6
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67
Ru
Oligomers
O
HOOC
HO
HO
O
O
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OH2
Figure 3.2
Glucose
O
O
Ru
Ru
HO
OH2
OH2
O
Ru
O
OH2
OH
Ru
O
OH2
H
OH2
RuO2 2H2O
Main roles and possible active sites of Ru/CMK-3 catalyst for the
hydrolysis of cellulose.
the Ru/CMK-3 catalyst kept its high catalytic activity in at least five successive
reused experiments and gave no leaching of the Ru species. The Ru species
on Ru/CMK-3 catalyst before the reaction was revealed to be RuO2 2H2O,
which is produced by the reduction and re-oxidation of supported RuCl3.
The high valence of Ru species might be the origin of high catalytic activity
(Figure 3.2). Regarding the role of the carbon support, CMK-3 without Ru
gave a 16% yield of glucose and a 22% yield of oligosaccharides in the hydrolysis reaction, which indicates that the carbon support itself promotes
the hydrolysis as do the Ru species.
As described above, a mesoporous carbon CMK-3 can hydrolyze cellulose,34 which suggests that the weak acid sites such as carboxylic (pKa 4)
and phenolic groups (pKa 10) on the carbons are also eective for the
reaction. Katz et al. recently reported that silanol groups (pKa 7) on silica
can catalyze the hydrolytic reaction by attaching cellulose chains onto a
silica surface to induce strained conformations.35,36
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3.2.8
The direct formation of syngas (CO and H2) has been investigated by using
supported metal catalysts. Supported Ni catalysts were utilized for the
degradation of cellulose at ca. 900 K in the presence of water vapor to
obtain CO, H2, CH4, and CO2 with small amounts of C2 compounds.48
However, catalyst deactivation due to carbon deposition was observed. The
catalyst durability was improved by using Rh/CeO2/SiO2 catalyst, which
aorded complete conversion of cellulose to gaseous C1 products and H2 in
the presence of air and steam even at a lower reaction temperature of
773 K.49 The optimization of the reactors is also important in producing
syngas from biomass, which was shown in an example using a dual-bed
reactor for gasification of actual lignocellulosic biomass.50 Supported
metal catalysts have also been developed for the direct formation of pure
hydrogen from biomass. In order to utilize the obtained hydrogen for
polymer electrolyte fuel cells (PEFCs), it is necessary to restrict CO formation to less than 10 ppm. One accomplishment was brought about by a
Ni/TiO2 catalyst in the presence of a stoichiometric amount of NaOH,
where cellulose was directly converted to pure H2 with CO and CO2 concentrations of less than 30 ppm.51
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54
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catalytic performances. However, unprecedented support eects were recently found in the PROX reaction catalyzed by Pt catalysts supported on
mesoporous silicas, which are generally regarded as inert materials. This
chapter focuses on this promotional eect of mesoporous silica as one of the
recently found mechanistic aspects in the PROX reaction.
3.3.2
Entry
1
2
3
4
5
6
a
Catalyst
Pore
diameter/nm
Conversion (%)
at 298 K
CO
O2
1 wt% Pt/FSM-10
1 wt% Pt/FSM-16
1 wt% Pt/FSM-22
1 wt% Pt/FSM-22
5 wt% Pt/MCM41-A
5 wt% Pt/MCM41-B
1.8
2.7
4.0
7.0
2.9
2.8
42
95
100
96
100
10
25
56
100
55
100
5
Reaction conditions: 0.20 g catalyst, flow rate 40 ml min1, CO 1%, O2 1%, N2 5%, H2 93%.
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Chapter 3
(a)
(b)
OH OH
Si
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Figure 3.3
Si
Pt
OH
Si
O
Si
Pt
O
Si
Si
Si
OH
O
Si
Si
Si
3.4.2
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Silylating reagent
DFT pore
diametera/nm
Silylation
densityb/mmol g1
TMSOTf
4.6
0.31 ( 0.05)
TMCS
4.6
0.06 ( 0.01)
BSA
4.6
0.09 ( 0.01)
MeSi(OEt)3
4.2
1.04 ( 0.10)
a
b
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Chapter 3
Figure 3.4
3.5 Conclusions
Increasing demand from society has been promoting continuous advances
in supported metal catalysts. Such developments include extensive applications in bioindustry as well as the utilization of novel catalyst components
to exhibit uniquely required catalytic performances. These accomplishments
were achieved with the aid of advances in related areas of research such as
materials synthesis, spectroscopy, microscopy and model systems. However,
many challenges remain unsolved by the catalyst systems developed so far.
Apart from the conventional methodologies, a completely new design of
catalyst might be necessary for the further development of supported metal
catalysts in the near future.
References
1.
2.
3.
4.
N. Semagina and L. Kiwi-Minsker, Catal. Rev.: Sci. Eng., 2009, 51, 147.
th, ChemSusChem, 2009, 2, 1096.
R. Rinaldi and F. Schu
W. L. Faith, Ind. Eng. Chem., 1945, 37, 9.
Y.-H. P. Zhang and L. R. Lynd, Biotechnol. Bioeng., 2004, 88, 797.
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Chapter 3
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Chapter 3
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CHAPTER 4
4.1 Introduction
Zeolites are of great interest because their ordered microporous structures
combined with strong acid activity, capacity for selective sorption, thermal
and chemical resistance, and other beneficial qualities proved very useful for
practical applications with significant commercial impact.14 The ability of
zeolites to discriminate molecules based on size and shape expanded
the concept of molecular sieving and in more detail the so-called shape
selectivity. Zeolites have been used commercially as selective catalysts, e.g.
for many hydrocarbon conversions in refineries and chemical industry,
selective sorbents and ion exchangers.5,6 Zeolites have a framework
molecular structure constructed as an extended network of corner sharing
TO4 tetrahedra, with TSi, optionally substituted with heteroatoms such as
Al, which imparts strong acid character, as well as B, Fe and others.
The network is 4-connected with maximum framework density below ca.
1921 T atoms per 1 nm3.7 As elaborated below, zeolites were first recognized
as aluminosilicate minerals about 250 years ago but since about the 1940s
they have been extensively studied and developed as diverse synthetic
materials including aluminophosphates and other compositions. Recently,
novel classes of zeolites, such as mesoporous single crystals, hierarchic
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4.3.1
Structures
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Chapter 4
Figure 4.1
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81
rare (although the number of zeolites with this secondary structural unit
increased in the last years) while 4, 5 and 6 dominate and through dierent
arrangements circumscribe the bigger n-rings. A useful concept distinguishes secondary building units (SBUs), some of which were believed to
be involved in the assembly of zeolite structures during synthesis. This is
now regarded as an unlikely event in most situations since structure
building by smaller entities, mainly by addition of monomers, is considered
the predominant process. One should not rule out the possibility of a
framework assembly by bigger/extended units and in fact such a process has
been recently identified in our laboratory (vide supra).
The above general outline of concepts and issues associated with zeolite
molecular structure ought to be followed by some discussion of specific cases
or classes. However, we feel that the subject is continuously addressed in diverse reviews and the reader will be better served by being referred to these
publications.1820 Instead, we will focus here on selected aluminosilicate
structures, which we find intriguing and worth mentioning for some particular
reasons (vide infra) i.e. TUN, IMF (see Section 4.3.3 below), MSE and MCM-71.
MCM-71 is notable as one of the most recent new zeolites obtained by
an inorganic route, without a template. It is a high-Al material with onedimensional 10-ring channels having elliptical cross-sections. Its structure is
interesting as being predicted by Breck and complementing the series he
designed.17,21
MSE is the first 12 10 10-ring zeolite. Its first synthesis was attributed
to a specially designed dipositive rigid template.22 Since this first synthesis
other less elaborate and more cost eective SDAs have been identified to
aord this structure. The intersecting 12- and 10-ring channels can be
viewed as combining the pore features and high Al concentration of the most
catalytically valuable zeolites to date, i.e. FAU and MFI. Pore characteristics
of zeolites used commercially, mainly in catalysis, are given in Table 4.1
(based on ref. 23).
4.3.2
Synthesis
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Table 4.1
Chapter 4
Pore properties of synthetic zeolites used commercially.
Zeolite
IZA codea
Channel
dimensionality
Pore
opening
Pore dimensions2/nm
A
Y
ZSM-5
Beta
Mordenite
Ferrierite
MCM-22, UZM-8
SAPO-11
SSZ-13, SAPO-34
EU-1
L
ZSM-48
ZSM-23
ZSM-12
Rho
Theta-1, ZSM-22
LTA
FAU
MFI
BEA*
MOR
FER
MWW
AEL
CHA
EUO
LTL
*MRE
MTT
MTW
RHO
TON
3D
3D
3D
3D
2D
2D
2D
1D
3D
1D
1D
1D
1D
1D
3D
1D
12
12
10 10
12
12 8
10 8
2 10
10
8
10
12
10
10
12
8
10
0.41 0.41
0.74 0.74
0.53 0.56; 0.51 0.55
0.66 0.67; 0.56 0.56
0.65 0.7; 0.26 0.57
0.42 0.54; 0.35 0.48
0.55 0.40; 0.41 0.51
0.40 0.65
0.38 0.38
0.41 0.54; side pockets
0.71 0.71
0.53 0.563
0.45 0.52
0.56 0.60
0.36 0.36
0.46 0.57
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binder, very often with alumina, and formulated into larger particles. This
process is usually omitted in laboratories as it requires larger quantities
of material and specialized equipment. This is often not considered
in publications comparing the performance of laboratory samples with commercial catalysts while the dierences may be quite dramatic. As discussed in
ref. 26, the extrusion of platelet zeolite crystals, MCM-22, with alumina afforded an entire range of special crystal orientations with many fractured
fragments edge-on. On the other hand, unformulated crystals have a tendency
to agglomerate and usually expose flat surfaces when imaged in microscopy.
It must be appreciated that zeolite synthesis/formation occurs spontaneously and without human intervention when appropriate composition
and conditions are established. Arguably, the process is driven by some
self-controlling mechanism but, alas, our knowledge and understanding of
it is practically non-existent. This has not been an obstacle to impressive
expansion in both fundamental understanding and applications as well as
diversity of structures. In the long run, a greater reliance on the fundamental
knowledge of zeolite formation, especially quantitative, may be necessary to
better understand opportunities as well as limitations of zeolite synthesis.
This lack of understanding is surprising after many decades of development especially since some basic tenets are quite clear zeolite formation
begins with the nucleation of viable nuclei, i.e. ones that can grow
spontaneously. Then, as established empirically in many cases, the growth
follows the McCabe law,27 i.e. individual crystal size increases with a
constant linear rate until availability of nutrients becomes the rate limiting
factor. Initial attempts to elucidate zeolite formation focused on rationalizing the long-range order,24 which some assumed could not arise from the
attachment of small, e.g. silicate, aluminate fragments. In fact, the opposite
is the prevailing opinion right now. The nature of the nucleus has not been
resolved and is rarely considered.24,28 Some detailed proposals have often
been structure-specific and not necessarily applicable to other structures.
Ideally, one would want to relate the kinetics of crystallization to
composition, which might enable predictions including new species.
4.3.3
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Scheme 4.1
4.3.4
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Chapter 4
cations only, can be preferred to avoid the necessary ion exchange of sodium
forms to protonic ones followed by the treatment of wastewater solution.
Entirely dierent eects have been observed with inorganic species that
are supposed to be part of the framework. There is always the possibility of
isomorphic substitution, like B, Ga, and Fe for Al, or Ge for Si. The first
group of atoms carries a 3 charge and generates a negative charge of the
framework, introducing acidic properties to zeolites.17,40 The second and
particularly fruitful area resulting in numerous novel, usually extra- or largepore, structures arose from the synthesis of Ge-based zeolites.18,19 As
discussed in ref. 19 there are practical problems with Ge-based materials,
one of them being cost and availability of Ge, which is almost prohibitive
unless a really high-value application can be found. Nonetheless, the
Ge-zeolites set a new standard/frontier for more traditional compositions to
advance. The chemistry of germanosilicates in combination with appropriate SDAs oers new possibilities to synthesize novel zeolites. Another issue
with the Ge-zeolites is lower thermal and hydrothermal stability often
resulting in significant degradation upon standard treatments or activation.19
However, this apparent adversity has been turned into an opportunity
that resulted not only in novel-type materials but also the demonstration of
a new process: a 3D to 2D transformation, which will be discussed in the
following section.
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4.5 Adsorption
Zeolites have a leading role in industrial selective adsorption and separation
processes. Their benefits rely in particular on their large specific surface area
and easy modifiability through ion-exchange and molecular-sieving properties. Consequently, zeolites have found application in many industries,
particularly refining, petrochemical and chemical industries. Adsorption on
zeolites can follow several dierent pathways including ion exchange, shape
selectivity and, most importantly, equilibrium-selective adsorption.56 From
another point of view, zeolite-based adsorption applications can be divided
into impurity removal and separation processes.
The main application of zeolite ion-exchange adsorption is as additives
in laundry powders/detergents using sodium forms of zeolite A or P.57,58
Zeolites act as water softeners replacing sodium tripolyphosphate, which
was previously used but proved to be an environmentally unacceptable
component. By ion exchange, the calcium and magnesium cations, which
are responsible for water hardness hindering washing eciency and
leading to formation of carbonates,59 are removed. The ion-exchange
principle is also used in environmental remediation applications, such as
radioactive or heavy metal removal from soil and ground water. The shapeselective adsorption principle is the key to separation of n-alkanes from
i-alkanes using 5A zeolites (CaA60). Due to the suitable pore dimensions of
5A, n-alkanes readily enter the pore system, while the branched isomers are
too bulky and cannot enter the pores to be adsorbed.
Most of the zeolite adsorption applications are based on dierences in the
equilibrium selectivity of various sorbates with the adsorbent.56 Concerning
the contaminant removal, water (as moisture) is the primary concern in
many industrial applications. The activated, i.e. dehydrated, zeolites A or X
are typically used as the chosen desiccants. Generally, water removal is
operated as a pressure swing adsorption (PSA), i.e. water is removed at
elevated pressure in one adsorbent bed, while in the other bed the pressure
is decreased to regenerate the adsorbent. Very low residual humidity
(o1 ppm) can be achieved for a wide range of gases (CH4, N2, O2, H2, CO2,
SO2, H2S, NH3, HCl).61,62 Other gaseous impurities that can be removed by
using zeolites A, X or mordenite include CO2, SO2, H2S, HCl and NH3.
Table 4.2 lists characteristic applications of zeolites in adsorption and
separation processes.
Zeolites are commonly used in separations of permanent gases and
hydrocarbons. The industrial separation of permanent gases uses PSA processes and the most important ones include air separation to produce N2
and O2 (CaX, LiX, LiCaX63,64) and H2 separation from refinery o-gases (NaX,
NaA).65 The most important process, besides separation of n-alkanes from
i-alkanes due to the shape selectivity of zeolites, is isolation of p-xylene from
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Table 4.2
89
Industrial application
A (LTA)
O2/N2 separation
H2 separation from o-gases
CO2 removal
Natural gas drying
Drying of industrial gases
n-/iso-Paran separation Sorbex (Molex)
Mordenite (MOR)
O2/N2 separation
Removal of SO2
Removal of HCl
Trapping Hg vapors
Acid gases drying
X, Y (FAU)
O2/N2 separation
H2 separation from o-gases
CO2 removal
CO2/CH4 separation
Natural gas drying
Xylenes separation Sorbex (Parex)
Olefin separation Sorbex (Olex)
Removal of dioxins
4.6 Catalysis
Zeolites are now indispensable in many industrial catalytic processes,
particularly in the petroleum refining and petrochemical industries where
their application facilitated significant innovations. They have acquired this
position thanks to their unique properties including a tunable acidbasic
character, shape selectivity, ion exchangeability and large specific surface
area. Among more than 200 zeolite structures that have been discovered and
synthesized, about 20 are utilized as commercial catalysts.25 In this group,
zeolites Y (FAU), ZSM-5 (MFI), beta (BEA*), mordenite (MOR) and MCM-22
(MWW) are most extensively used. From the industrial catalysis point of
view, the most important zeolites and the processes they are applied in are
summarized in Table 4.3.
Fluid catalytic cracking (FCC) is the single most important catalytic
process using zeolites. It is consuming more zeolite volume than all
other processes altogether.5 The FCC together with hydrocracking is the key
process in a modern refinery for the conversion of vacuum distillates, i.e.
heavy oil fractions, into light products, mainly gasoline and diesel fractions.
The catalyst used in FCC has a very complex composition but the development of zeolite Y, in particular its steam pretreatment aording ultrastable
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Table 4.3
Chapter 4
Industrial catalytic processes using zeolites and zeotypes.
Catalytic process
Beta (BEA*)
Benzene alkylation
Acylation
BaeyerVilliger reaction
Erionite (ERI)
Selectoforming
Ferrierite (FER)
L (LTL)
Alkane aromatization
MCM-22 (MWW)
Benzene alkylation
Mordenite (MOR)
SAPO-11 (AEL)
SAPO-34 (CHA)
Methanol to olefins
Y (FAU)
ZSM-12 (MTW)
Aromatics alkylation
zeolite USY, has made it so that rare earth (RE)-exchanged USY is the
key component of FCC catalysts. A fresh FCC catalyst contains typically
2040 wt% of USY, the other components being matrix (includes catalytically
active binder consisting of alumina and amorphous aluminosilicate, clay)
that is responsible for pre-cracking of large feed molecules which could
not enter into USY pores, and various promoters. The role of promoters is
three-fold: protection of USY structure from vanadium, environmental protection (SOx, NOx and CO abatement) and product selectivity adjustment.
The last one may be aimed at increasing the yield of propylene, a desired
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petrochemical raw material. FCC has now become the second most
important source of propylene supplying about one third of the world propylene production. This has been enabled by the use of zeolite MFI, typically
in amounts equaling 0.53 wt% of the total FCC catalyst loading.
At the core of the FCC catalyst, there is the zeolite FAU characterized by its
unit cell size (a0) being a measure of framework aluminium content and
determining the acid site density and strength, a key property of the zeolite
for FCC.69,70 Catalyst activity as well as product yields, coke formation and
product quality (e.g. gasoline octane number) depend directly on the unit
cell dimension. The maximum activity for gas oil cracking was observed
when all framework Al atoms in the faujasite structure were isolated, i.e. at a
framework Si/Al ratio of 58 (a0 2.4362.440 nm). So far, zeolite USY with a
framework Si/Al ratio 45 was not synthesized by direct synthesis and the
dealumination of the parent zeolite Y with Si/Al of about 2.8 is the only
alternative to prepare the optimum catalyst. The dealumination helps not
only to adjust the Si/Al ratio to the optimum value range, but also aects the
catalyst performance by creating secondary mesopores and forming extraframework Al species (EFAL).71 Moreover, the dealumination of FAU zeolite
by steaming aords the ultrastable Y zeolite (USY) that has substantially
better hydrothermal stability than the parent zeolite FAU. This is essential,
particularly for the catalyst regeneration by burning o coke at temperatures
above 700 1C in the presence of steam.69 A further improvement of the
zeolite FAU stability is achieved by introducing rare earth (RE) metals, such
as lanthanum, by ion exchange. Currently, the limited availability of these
metals has led to an increased demand for low RE metals catalysts.
Besides the optimized strength and density of acid sites, shape selectivity
plays an important role in FCC catalysts that are designed accordingly. To
prevent deactivation of the active sites in zeolite Y channels that are
responsible for the optimum selectivity to light products, the catalyst
consists of an active matrix where pre-cracking takes place and where heavy
metals such as vanadium and nickel are deposited. Consequently, instead of
blocking zeolite Y pores by large feed molecules the pre-cracked molecules
enter the channel system and are further converted to gasoline and a range
of gaseous hydrocarbons. With the current shift in the demand for FCC
products, the yield of propylene is being maximized by adding a ZSM-5
additive allowing only a small range of gasoline molecules into its pores;
these are further cracked to yield gaseous products, mainly propylene and C4
olefins. Moreover, the 10-ring system of ZSM-5 eciently suppresses the
formation of carbonaceous deposits as the condensation intermediate
formation is sterically prohibited. To achieve sucient stability of ZSM-5, it
is typically treated with phosphoric acid and steaming at 800 1C to create
aluminiumphosphate complexes in the phosphorus-stabilized ZSM-5.69
Zeolite USY is at the heart of the hydrocracking process, which is another
important industrial process aimed at upgrading heavy fractions from crude
oil distillation. Unlike in FCC, this catalytic cracking is combined with deep
hydrotreating and hydrogenation. As a result the products are sulfur- and
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external surface; the lower it is, the higher the selectivity of the isomerization
to monobranched alkanes.
The main objective of light paran (C5, C6) isomerization is to maximize the
octane number of the light naphtha cut. In contrast to dewaxing, a maximum
degree of branching is desirable. The key parameter is the strength of acid
sites, as stronger acidity allows operation at lower reaction temperatures
which is beneficial from the thermodynamics point of view. Zeolites, typically
Pt/MOR, have to compete with other catalytic systems, such as chlorinatedalumina- or sulfated-zirconia-supported platinum catalysts which can be
applied at temperatures o200 1C. The operating window for Pt/MOR is around
250 1C.5 Pt/MOR has the maximum strength of Brnsted acid sites providing
the maximum isomerization activity and has a Si/Al ratio of about 10. The
dealumination of MOR decreases diusional limitations and coking rate. The
overall strength of Brnsted acid sites can be further increased by an introduction of controlled amounts of extra-framework Al by steaming and acid
leaching, which interact with Brnsted acid sites.76 While the activity of the
zeolite-based catalyst is low, resulting in a lower gain in research octane
number (ca. 10 for Pt/MOR vs. ca. 14 for Pt/chlorinated alumina), it outperforms the non-zeolite catalysts in terms of sensitivity to contaminants such
as water and small amounts of sulfur and regenerability.5 The lower activity of
Pt/MOR can be addressed by integrated separation of n- and iso-parans
using, e.g. CaA as discussed above. The process is called the total isomerization process.77 Light parans, generally C6 and C7, are alternatively
also commercially converted over a modified bifunctional zeolite L to aord
aromatics by dehydrocyclization. Typically, Pt/K-LTL or Pt/KBa-LTL zeolites are
used in processes, such as Platforming (UOP) or AROMAX (Chevron Philips).78
Unlike in isomerization, it is essential to remove any sulfur and acidity.79
Apart from the cracking process, zeolites are indispensable catalysts
for the petrochemical transformation of aromatics, in particular for the
isomerization, disproportionation and transalkylation of alkyl aromatics
(C7C9) and for the alkylation of benzene. The primary objective of the first
group of processes is to maximize the production of p-xylene and benzene,
while alkylation is targeted for the production of ethylbenzene and cumene.
The choice of catalyst for isomerization of C8 aromatics depends on the
treatment of ethylbenzene. If it is to be isomerized to xylenes (and ultimately
to p-xylene) then Pt/MOR or Pt/EU-1 (EUO) are applied; if selective dealkylation of ethylbenzene is the aim then dealuminated Pt/MFI is used.5,6 The
selectivity over Pt/MOR is generally improved by avoiding any mesoporosity
and by partial ion exchange by Na or Ca cations to decrease Brnsted acid
sites density.80 The decreased density of Brnsted acid sites limits the extent
of disproportionation reactions leading to undesired by-products, such as
trimethylbenzenes. When Pt/MFI is used as a xylene isomerization catalyst,
the formation of trimethylbenzenes is suppressed due to its transition-state
shape selectivity. The product shape selectivity of MFI to p-xylene, originating from a higher diusivity of p-xylene in comparison with m- and o-xylene
from inside zeolite pores, can be further improved by using larger zeolite
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Chapter 4
crystals, deactivating active sites on the external surface of these crystals and
reducing the size of pore windows, e.g. by coke or inorganic species
depositions.4,6
The shape selectivity of MFI in favor of the para-isomer is the key catalyst
feature used in toluene disproportionation to aord a high yield of
p-xylene.77 The intrinsic selectivity of MFI is further enhanced by suitable
catalyst design as discussed above. Toluene can be alternatively utilized as
the feedstock for transalkylation with heavier alkylaromatics (C9 and C10).
Several processes were developed (Tatoray, PX-Plus, PX-Plus-XP by UOP);
however, catalyst details were not disclosed.65
The most important processes of aromatics alkylation are the syntheses of
ethylbenzene (an intermediate of styrene production) and cumene (an intermediate of phenol production).4,81,82 Two principal technology solutions were
developed for ethylbenzene production: a vapor-phase process using MFI
catalyst (Mobil Badger process) and liquid-phase processes using MWW or
BEA* (EBMAX, Exxon Mobil and Polimeri Europa, respectively). The main
advantages of the liquid-phase process include a lower excess of benzene
needed and lower reaction temperatures.5 Nearly exclusive by-products are
diethylbenzenes that can be either recycled to the feed (gas-phase processes)
or fed into a second (transalkylation) reactor with benzene where they are
converted to ethylbenzene over the same catalyst as in the alkylation reactor.
The production of cumene by alkylation of benzene with propene is analogous
to ethylbenzene production. Several processes using dierent zeolites
are applied commercially: dealuminated mordenite (Dow), beta (Eni) and
MCM-22 (ExxonMobil).79,8183 Moreover, the dealuminated MOR (3-DMM) is
highly active and the alkylation can be operated at low temperatures, which
is beneficial for minimizing the formation of n-propylbenzene, a highly
undesirable by-product.5
Another important class of industrial technologies using zeolites or zeotypes is related to methanol as the cornerstone of C1 chemistry, which is an
alternative to the FischerTropsch synthesis (FTS) starting directly from
synthesis gas. Both FTS and methanol conversion process allow the utilization of other carbon containing feedstocks (natural gas, coal or biomass)
for the production of products obtained currently as a result of petroleum
processing. The main conversion processes include methanol-to-gasoline
(MTG), methanol-to-olefin (MTO) and methanol-to-propylene (MTP). ZSM-5
is the catalyst of choice for MTG84 and MTP77 processes, while SAPO-34
is used in the MTO process as its structure is optimal for the selective
formation of ethylene and propylene.84
4.7 Summary
Zeolites may be viewed as embodying the ultimate best of natural and synthetic inorganic compounds through a fundamental elegance and diversity
of structures combined with exceptional practical usefulness while being
environmentally benign and eventually relatively easy to manufacture. Over
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the years their properties and selective uses have been perfected to such
levels that they are hard to beat, including by other new zeolites. They provided inspiration for innovation leading to related materials like ordered
mesoporous materials, metalorganic frameworks and recently expanding
into the area originally thought to be the contradiction of zeolites i.e. 2D or
layered zeolites, which now appears to be an integral part of the family. Few
other areas of science seem to prosper so well in both improvements of the
known and advancements of the new and unknown.
Acknowledgements
This work was supported by the Czech Science Foundation Grant No. P106/
12/G015 (Centre of Excellence).
References
ejka, H. van Bekkum, A. Corma and F. Schu
th, Introduction to Zeolite
1. J. C
Science and Practice, Studies in Surface Science and Catalysis, Elsevier,
3rd revised edn, 2007, vol. 168.
2. R. Xu, W. Pang, J. Yu, Q. Huo and J. Chen, Chemistry of Zeolites and
Related Porous Materials, Wiley, Singapore, 2007.
3. S. Kulprathipanja, Zeolites in Industrial Separation and Catalysis, WileyVCH, Verlag GmbH & Co. KGaA, Weinheim, 2010.
ejka and B. Wichterlova
, Catal. Rev., 2002, 44, 375.
4. J. C
5. W. Vermeiren and J.-P. Gilson, Top. Catal., 2009, 52, 11311161.
6. T. F. Degnan, Top. Catal., 2000, 13, 349.
7. (a) C. Baerlocher, L. B. McCusker and D. H. Olson, Atlas of zeolite
framework types, Elsevier, Amsterdam, 6th revised edn, 2007; (b) IZA
Structure Commission web site.
8. J. L. Schlenker and G. H. Kuhl, in Proceedings of the 9th International
Zeolite Conference, ed. R. von Ballmoos, J. B. Higgins and M. M. J. Treacy,
Butterworth-Heinemann, Stoneham, MA, 1993, vol. 1, pp. 39.
9. K. Byrappa and M. Yoshimura, Handbook of Hydrothermal Technology,
Noyes Publications, Park Ridge, NJ, 2001, p. 333.
10. D. E. W. Vaughan, in Solid-State Supramolecular Chemistry: Two- and
Three-Dimensional Inorganic Networks, Elsevier, 1999, vol. 7, pp. 379391.
11. (a) R. M. Barrer, Zeolites and clay minerals as sorbents and molecular
sieves, Academic Press, New York, 1978; (b) R. M. Barrer, Zeolites, 1981,
1, 130; (c) R. M. Barrer, Hydrothermal chemistry of zeolites, Academic
Press, New York, 1982.
12. C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and J. S. Beck,
Nature, 1992, 359, 710.
13. Mesoporous Crystals and Related Nano-structured Materials, in Studies
in Surface Science and Catalysis, ed. O. Terasaki, Elsevier, New York, 2004,
vol. 148.
ejka, Catal. Sci. Technol., 2011, 1, 4353.
14. W. J. Roth and J. C
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CHAPTER 5
Enzyme Immobilization on
Mesoporous Silica Supports
CHENG-YU LAI* AND DANIELA R. RADU
Delaware State University, 1200 N. DuPont Highway, Dover, DE 19901, USA
*Email: cylai@desu.edu
100
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water as solvent, enzymes generate less waste. Due to their high selectivity,
shorter synthetic routes are achieved through enzymatic catalysis in comparison to traditional organic synthetic routes. Enzymatic processes can now
be carried out in organic solvents1 as well as aqueous environments, so that
non-polar organic compounds as well as water-soluble compounds can be
modified selectively and eciently. As the use of biocatalysis for industrial
chemical synthesis becomes easier, several chemical companies have begun to
increase significantly the number and sophistication of the biocatalytic processes used in their synthesis operations2 and, thus, the use of enzyme biocatalysis for industrial synthetic chemistry is on the verge of significant growth.
However, the use of enzymes in their native form is often hampered by
several limitations such as high costs, low operational stability and diculties
in recovery and reuse. Fortunately, there are many techniques available that
permit enzyme performance to be improved, involving areas of science that
have undergone impressive developments in recent years: microbiology, protein engineering, chemistry of proteins, etc. Additionally, enzyme immobilization, albeit considered old-fashioned, is a very powerful tool to improve
almost all enzyme properties, if properly designed: e.g., stability, activity, specificity and selectivity, and reduction of inhibition. Moreover, product contamination with enzymes can be minimized or completely avoided, which is
particularly critical for applications in the pharmaceutical and food industries.
Immobilization techniques have been recently revamped as new developments
within material science have highlighted the potential of a variety of organic
and inorganic materials for use as supports for enzyme immobilization.
Many catalytic supports such as resins, polymers, electropolymerized
films, solgel materials, inorganic solids such as solid and porous silica etc.,
have been explored with regard to enzyme immobilization and comprehensive reviews have been published.38
Here we outline recent advances in the area of mesoporous silica involved in
enzyme immobilization development. Mesoporous silica supports provide a
set of the most attractive features toward overcoming enzyme stability drawbacks both in biotechnology and biocatalysis applications.9 Mesoporous silica
materials are structurally robust, chemically stable over a broad pH and temperature range and benefit from flexible synthetic conditions that enable tailoring of their properties for a plethora of hostguest chemistry applications.
The large surface area and pores with an adjustable pore size, typically in
the size range of 2 to 40 nm, make them suitable for accommodating large
biomolecules, including enzymes.
Introduction
The immobilization of enzymes on a solid support is a methodology designed to overcome enzymes limitations, such as low long-term stability
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Figure 5.1
Chapter 5
Porous supports vs. solid supports for enzyme encapsulation the porous
support protects enzyme from interacting with inactivation promoters
(illustrated: gas bubbles).
Reproduced with permission from ref. 13.
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Figure 5.2
103
Two major groups of porous silica have been studied for enzyme immobilization applications, classified based on porosity order: (i) hexagonally
ordered porous silica materials (Section 5.2.2), and, (ii) hierarchically
ordered porous silica materials (Section 5.2.3). Details of both categories of
enzyme supports are presented.
5.2.2
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Table 5.1
A summary of characteristic properties of various mesoporous silica materials employed for encapsulating enzymes. Reprinted
with permission from ref. 6.
Mesoporous materials
Silica source
Template
1
CnTMA (n 1218)
MCM-48
FSM-16
Polysilicate kanemite
SBA-1
TEOS
SBA-15
SBA-16
MCF
TEOS, TMOS
TEOS
HMS
TEOS
CTAB,
C16H33(CH3)2N(CH2)(C6H5)
Gemini Cm-12-m
CnTMA1 (n 1218)
CnH2n11 N(C2H5)3X
(n 1218), 18B4-3-1
Cns1 (n 1218)
Pm, Pas, P6s, 8501500
(B01oE016),
Brij97(C1aHl5E01ol
F127, F108, or F98
F127 (EOul6PO70EO106) with
TMB
CmH2m11NH2 (m 822)
MSU-X
TEOS, TMOS
CmEOn (m 1115)
IBN-X
TEOS
PMOs
(RO3Si-R 0 -Si(OR)3
C8PhEOn, EO13P030EO13
F108, F127, P65, P123 with
FC-4 and TMB
CTAB, OTAB, CPS, P123,
F127, Brij 56, Brij 76
Pore diameter/nm
20 hex.
channels
Bicontinuous
210
24
20 hex.
channels
30 cubic
mesostructure
B4
20 hex.
channels
530
Spherical cages
Cellular foam
530
1050
Disordered
mesostructure
Disordered
mesostructure
Nanoparticle
210
520
20 or 30 hex.
220
23
215
Chapter 5
MCM-41
Description
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(a)
(d)
(b)
(e)
(c)
(f)
(g)
Figure 5.3
5.2.3
Enzyme Immobilization/Encapsulation in
Hierarchically Ordered Mesoporous Silica Materials
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Introduction
Figure 5.4
(b)
(c)
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Chemical (covalent)
binding
Entrapped CLEAs/
encapsulation
Advantages
Disadvantages
Chapter 5
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109
This general methodology translates to porous silica in physical adsorption, chemical adsorption and encapsulation or self-immobilization,
shown in Figure 5.4c. Cross-linked enzyme aggregates (CLEAs) were recently
explored as a combined cross-link/encapsulation approach. Specifically,
Mateo et al. demonstrated that a mild cross-linking upon enzyme encapsulation generated CLEAs from several enzymes (penicillin G acylase,
hydroxynitrile lyase, alcohol dehydrogenase, and two dierent nitrilases) by
precipitation and subsequent cross-linking using dextran polyaldehyde inside the silica pores.27 In most cases, higher immobilization yields were
obtained using the latter cross-linker as compared with the commonly used
glutaraldehyde. Active site titration of penicillin acylase CLEAs showed that
the higher activity originated from a significantly lower loss in active sites
using dextran polyaldehyde as a cross-linking agent. It is proposed that
macromolecular cross-linkers are too large to penetrate the protein active
site and react with catalytically essential amino acid residue.
5.3.2
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Chapter 5
5.3.3
Figure 5.5
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Introduction
5.4.2
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113
amino acids tryptophan and tyrosine absorb UV light at 280 nm. The absorbance at 200 nm is mainly due to the many peptide bonds in a protein.
However, many other substances also absorb light in this area and 200 nm is
therefore not a suitable wavelength for estimating the concentration of
proteins. Therefore measurements are normally performed at 280 nm, thus
one should be aware of the possible interference by contaminating nucleic
acids (and possibly other substances) that absorb strongly at 260 nm.
5.4.2.2
Colorimetric Assays
5.4.2.3
IR can be used to obtain information about enzymesubstrate (ES) complexes. In ES complexes there are well-organized binding modes, which are
quantifiable using infrared methods. In analyzing infrared data, it is possible to identify binding modes and heterogeneity of ES complexes.
5.4.2.4
Other Techniques
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5.4.3
Chapter 5
Enzymatic Activity
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5.4.3.1
Fluorescence Spectroscopy
5.4.3.2
UV-Vis Spectroscopy
dP
Vmax S
dt
Km S
(5:1)
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5.5 Conclusions
Porous silicas are suitable supports for the immobilization of enzymes. The
immobilization strategy must be chosen based on the enzyme and the targeted application. Physical adsorption, encapsulation, covalent binding and
recently cross-linking are the predominantly employed routes that possess
certain advantages and drawbacks. The use of tailor-made silica supports
with optimized particle size and morphology, pore diameter and surface
properties as detailed in the flowchart in Figure 5.2 will result in biocatalysts
with increased activity, higher stability and reusability. Novel surface-functionalization strategies for modification of the support properties are constantly being developed. However, until now, industrial applications exploring
the specific features of porous silica supports have not been disclosed.
Combining the knowledge generated from all presented methodologies
will aid in rationally designing biocatalyst based on enzymes immobilized in
mesoporous materials.33
References
1. A. M. Klibanov, Nature, 2001, 409, 241246.
2. A. Schmid, J. S. Dordick, B. Hauer, A. Kiener, M. Wubbolts and
B. Witholt, Nature, 2001, 409, 258268.
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CHAPTER 6
6.1 Introduction
Biodiesel is a renewable fuel that can be generated from plant oils,
rendered animal fats and industrial waste oils.1 It has evolved into a
significant industry in the midwestern United States and in Europe. In the
United States biodiesel is prepared primarily from soybean oil; in Europe,
biodiesel is generated mostly from rapeseed oil. Biodiesel has a number of
advantages over diesel fuel. Although the National Biodiesel Board
has listed a number of benefits, the most significant ones are that biodiesel
is a renewable fuel that is non-toxic, biodegradable and free of sulfurcontaining impurities.2 Biodiesel also has significant lubricity compared
to petrochemical fuels. These qualities make biodiesel especially useful
in places such as national parks, harbors and other environmentally
sensitive areas. Biodiesel is commonly sold as a mixture with petroleum
fuels: for example, B20 is a mixture of 20% biodiesel and 80%
petroleum fuel.
Biodiesel, also known as fatty acid methyl esters (FAME), is one of
the most promising alternative biofuels and is currently produced by a
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O
O C R
O
O C R
O
O C R
OH
NaOH
3 CH3OH
Scheme 6.1
O
R C O CH3
OH
OH
Biodiesel
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6.2.1
Shanks and Mbaraka have studied mesoporous silica with dierent sulfonic
acids at dierent surface concentrations.11 Chen and coworkers have studied
dual-functionalized mesoporous silica containing both sulfonic acid groups
and disulfide groups.12 Dhainaut and coworker prepared macroporous
mesoporous SBA silicas via dual templating. They cite rate enhancements for
the transesterification of bulky esters.13 Chen and coworkers utilized
mesoporous sulfonic acids with short channels and high acid capacities.
They found that these catalysts were superior to Amberlyst 15 resin.14
Yadav and Sharma used a mesoporous sulfonic acid catalyst treated with
lanthanum chloride to convert fructose into 5-hydroxymethylfurfural in good
yield.15 Karimi and coworkers utilized a phenylene-bridged mesoporous
silica catalyst to produce biodiesel.16 They attributed the enhanced yield to
the hydrophobic character of the bridged catalyst. Tang and coworkers
produced mesoporous silicas having both platinum and sulfonic acid
groups. They utilized this catalyst for a novel one-step hydrogenationesterification of acetic acid and acetaldehyde.17 Karimi and Mirzaei evaluated
a number of mesoporous sulfonic acid catalysts and correlated the improved
yields of hydroxymethylfurfural with lower surface hydrophobicity.18
6.2.2
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19
6.2.3
The Lin group had developed mesoporous silica nanomaterials with welldefined geometries. Mesoporous silica nanospheres (MSNs), as they were
named by Lins group in 2001, benefit from a facile synthetic methodology
as well as potential for tailoring their structural properties. The MSN synthesis requires the condensation of a silica source around a template. The
most studied templating reagents are cationic surfactants, which render
materials with porosities in the range of 25 nm and block co-polymers,
generating 530 nm porosities. The interior of these materials resembles a
honeycomb, with parallel channels running throughout the nanospherical
particle. The channel diameter could be fine-tuned to accommodate a large
variety of molecules, from simple organic compounds to macromolecules.
These interior structures led to the idea of converting the pores in nanoreactors, which engaged the group in a large eort toward altering pore
functionality with catalytic groups. The functional groups in the channels
could be added through either post-synthesis grafting or by in situ addition
of an organo-functionalized silane, a method also called co-condensation.
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Figure 6.1
Figure 6.2
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Figure 6.3
Chapter 6
6.2.3.1
Acid Catalyst
To address the first stage of biodiesel fabrication, the Lin group created
periodically ordered, sulfonic acid-functionalized mesoporous silicas with
pores sizes ranging from 20 to 60 and high acid-exchange capacities
(12 mequiv. of H1 (g of SiO2) 1). To do this the Lin group utilized a recently
developed synthetic method which allows the facile incorporation of various
acidic sulfonic groups to the mesoporous structures with the ability to finetune the loading of these groups.
As depicted in Scheme 6.3 the sulfonic acids are contained in the channels. The soybean oil and the solvent methanol enter the channel and
transesterification occurs in the channel. Free fatty acids also enter the
channel and are esterified with methanol.
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Scheme 6.2
Scheme 6.3
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Chapter 6
acid catalysts are the sizes of the mesopores and the pore surface
properties. These characteristics can have large eects on pore mass transfer
of reactant, product, and intermediate species. In particular, the functionalization of these derivatized mesoporous silica materials with various
surface-bound groups allows the modulation of the catalytic systems to enhance substrate selectivity by tuning substrate accessibility and pore
hydrophobicity.
Thus, to address the above toward increasing selectivity of the transesterification reactions, various functional groups have been employed in
addition to the sulfonic acid groups. The materials design involved making
the pore surface hydrophobic. The reasoning behind this step was matching
the channel hydrophobicity with the long alkyl chains in the triglycerides,
and thus, promoting their fast diusion into the channels; increasing reaction kinetics.
In preliminary investigations, the Lin group tested the catalytic activity of
the aforementioned mesoporous solid acid catalyst in comparison with
two commercially available homogeneous catalysts (sulfuric acid, H2SO4,
and p-toluene sulfonic acid, p-TSA) and an SBA-type mesoporous silica
catalyst with a propylsulfonic acid functionality (SBA-15-SO3H-P123)
also developed in the Lin group. Compared with its homogeneous counterpart, p-TSA, it showed similar reaction kinetics, indicating a fast masstransfer process for the reactants and the products to diuse in and out of
the large pores (Figure 6.4).
6.2.3.2
AcidBase Catalyst
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Figure 6.4
125
Schematic representation of the proposed catalytic system for the synthesis of methyl soyate and glycerol formation.
including homogeneous catalysts (sulfuric acid and p-TSA) and heterogeneous catalysts such as Nafions.
Following the success of acid catalyst for esterification, the Lin group also
conducted a preliminary transesterification of purified soybean oil to methyl
ester using a functionalized mesoporous solid catalyst. The resulting
nanomaterials were inexpensive to produce, were reproducible, and could be
reactivated simply by heating. A 100% conversion of the soybean oil to
methyl ester was accomplished in 20 min at 25 1C with a 5-fold excess of
methanol. The above studies suggested that a mesoporous sulfonic acid with
superbase and hydrophobic-group functionality could be employed for the
transformation of crude oil feedstocks in biodiesel from soybean oil eciently. Based on these preliminary results, there is an opportunity to design
a series of new solid catalysts with (i) higher amounts of catalytic groups,
and (ii) more reactive catalytic functionalities for both the proposed esterification and transesterification of various feedstocks.
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Figure 6.5
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Chapter 6
Scheme 6.4
6.4 Conclusions
Multifunctional mesoporous silica nanosphere catalysts have been synthesized by Lins group through simultaneous derivatization with acidcontaining aryl radicals and superbase on the surface of mesoporous silica.
The derivatization was designed to reach a complete separation of the acid
and base groups, which enables the catalyst to perform this otherwise antagonistic acidbase function. The benefit of such catalyst is the capability of
converting both free fatty acids and triglycerides in a one-pot reaction with
high yield and excellent separation which allows biodiesel fabrication in one
step. This implies a tremendous processing-costs reduction due to eliminating expensive intermediate steps. Compared with other solid acid and
solid base catalysts, the MSN catalyst materials show stable and highly efficient catalytic performance in biodiesel production with conversions
reaching 100%. The catalysts are highly ecient, environmentally friendly,
inexpensive, and easy to prepare.
References
1.
2.
3.
4.
5.
6.
7.
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Subject Index
A (LTA zeolite A), 80, 81, 82
acidbase bi-functionalized catalyst
biodiesel production, 1245
large-pore mesoporous silica
nanoparticles, 1923
acid catalyst in biodiesel production,
1224, 127
activity of enzymes (catalytic activity)
immobilized on porous silica
supports, characterization, 11215
adsorption
enzyme immobilization by,
103, 104, 107, 108, 10910
by zeolites, 889
AEL (zeolite SAPO-11), 82, 90
Alcaligenes lipase immobilization,
111
aldol reaction, 37, 120
alkylation, aromatics, 90, 93, 94
allyl acetate epoxidation, 50
aluminosilicate minerals, zeolites
as, 77, 78, 81
amino groups of amino acids and
covalent enzyme immobilization,
110
aminopropyl (AP) groups, 37, 38
3-aminopropyltrimethoxysilane
(APTMS), 8, 10, 13, 19, 20, 34, 37
APTMS (3-aminopropyltrimethoxysilane), 8, 10, 13, 19, 20, 34, 37
arenesulfonic acids in biodiesel
production, 119
arginine e-amino group and
covalent enzyme immobilization,
110
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Subject Index
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133
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134
grafting
post-synthesis, 32, 34, 3640,
42, 45, 467
biodiesel production,
1202, 124
random ligand, 49
hemicellulose, hydrolytic
hydrogenation, 65
Henry reaction, 35, 37, 38
hexagonally ordered porous silica
materials, enzyme
immobilization/encapsulation in,
1036
hierarchically ordered porous silica
materials, enzyme
immobilization/encapsulation in,
1067
highly ultrastable zeolite Y (VUSY), 92
histidine imidazole group and covalent
enzyme immobilization, 110
horseradish peroxidase, 105
hydrocarbons
zeolite USY in hydrocracking
of, 91
zeolites in separation of, 889
hydrogen
from biomass, 68
preferential oxidation of
carbon monoxide under
excess of, 6870
hydrogenation, hydrolytic
cellulose, 645
hemicellulose, 65
hydrophilic/hydrophobic volume
ratios, mesoporous silica
synthesis, 30
hydroxides, zeolite synthesis, 85
hydroxyl (OH) groups
of mesoporous silica
nanoparticles, 9, 20, 21
of serine and threonine acids
and covalent enzyme
immobilization, 110
5-hydroxymethylfurfural (HMF), 23,
46, 1324
Subject Index
IBN-X, 104
IMF (zeolite), 85
imidazole group of histidine and
covalent enzyme immobilization,
110
immobilization (on porous/
mesoporous silica supports)
enzyme, 10016
cellulose conversion, 34,
613
characterization of
catalytic activity,
11215
strategies of enzyme
immobilization,
10712
types of support used in
enzyme
immobilization, 1017
in single-site catalysis, 37, 49, 53
surface distribution of
functionalized
immobilized species,
546
indole group of tryptophan and
covalent enzyme immobilization,
110
industry, zeolites applications, 80,
904, see also bioindustry
adsorption, 88
infrared spectroscopy, enzyme
concentration in porous silica, 113
inorganic species, zeolites, 856
International Zeolite Association
(IZA) Structural Commissions
3-letter (framework type) code, 79,
82, 89, 90
ion-exchange adsorption, zeolites
in, 88
ionic liquid systems, cellulose
conversion in, 23
iron(II)/Fe(II), 48
ITQ-2 (zeolite), 87
IZA Structural Commissions 3-letter
(framework type) code, 79, 82,
89, 90
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kinetics, fructose-to-HMF
conversion, 1318, 1618
L (LTL zeolite), 82, 90, 92, 93
large-pore mesoporous silica
nanoparticles (LPMSNs), 813
acidbase bi-functionalized,
1923
large-pore zeolites, 7980
light paran isomerization, 92, 93
lignin valorization, 678
lignocellulosic biomass see biomass
Lin group, 5, 120
biodiesel production, 29,
1202, 128
lipase immobilization, 111
Lobry de BruynAlberda van
Ekenstein transformation, 4
LTA (zeolite A), 80, 81, 82
LTL (zeolite L), 82, 90, 92, 93
lysine e-amino group and covalent
enzyme immobilization, 110
manganese (Mn), 50, 51, 52, 56
MCM family of mesoporous
materials, 29, 30, 31, 37, 6970,
71, 81, 102, 104, 105
MCM-22 (MMW), 80, 81, 82, 83,
84, 86, 87, 89, 90, 94
MCM-41, 29, 31, 37, 6970, 71,
102, 104, 105
MCM-48, 29, 30, 104
MCM-56, 87
medium-pore zeolites, 7980, 845
mercaptopropyl groups, 40, 44
3-(mercaptopropyl)trimethoxysilane
(MPTMS), 14, 15, 19, 20, 34, 45
MeSi(OEt)3 (methyltriethoxysilane),
71
mesoporous carbon (CMK-3), 667
mesoporous materials in biodiesel
production, 11925, 127, 128
mesoporous silica, 160
functionalized see
functionalized mesoporous
silica
135
immobilization on see
immobilization
single-site catalysis, 2860
examples, 3454
structural aspects, 2933
pore sizes see pore sizes
synthesis, 2933
metal catalysts, supported, 6176, see
also organometallic complexes;
rare earth metal zeolites
in bioindustry, 626
metal templating, 48, 49, 51
methanol conversion, zeolites, 94
methyl ester formation, 11112, 118,
125, 126
methyltriethoxysilane (MeSi(OEt)3),
71
MFI (ZSM-5), 78, 80, 81, 82, 83, 84,
85, 89, 90, 91, 92, 934
micelles, mesoporous silica
synthesis, 29, 30, 31, 32, 103
Michaelis constant, enzymes
immobilized in porous silica,
114
microporous structure of zeolites,
77
mordenite (MOR), 80, 82, 89, 90, 92,
93, 95
MPTMS (3-(mercaptopropyl)trimethoxysilane), 14, 15, 19, 20, 34, 45
MSE (zeolite), 81
MSU-X, 104
MTT (ZSM-23), 82, 92
MTW (ZSM-12), 82, 90
Mucor niehei lipase immobilization,
111
multi-functionalized mesoporous
silica nanoparticles see
nanoparticles
multi-point vs. single-point enzyme
anchoring, 110, 111
multi-site heterogeneous catalysis
(MSHC), 33, 34
mutinaite, 78
MWW (MCM-22) zeolites, 80, 81, 82,
83, 84, 86, 87, 89, 90, 94
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nanoparticles/nanomaterials,
mesoporous silica (mesoporous
silica nanoparticles), 349, 48,
54, 120
bi-functional, 1324, 35, 36, 37
biodiesel production, 1201,
124, 125
for cellulosic biomass
conversion, 127
characterization, 8, 15, 201
enzyme immobilization, 105
Pt catalysts on, 69
surface area, 8, 9, 10, 15, 21,
29, 42
nitrogen adsorptiondesorption
isotherms, mesoporous silica
nanomaterials, 8, 15
nitrogen porosity for PdSBA15
materials, 47
NMR, mesoporous silica
nanomaterials, 810, 15
nuclear magnetic resonance (NMR),
mesoporous silica nanomaterials,
810, 15
1-octene epoxidation, 50, 52, 56
olefins, 51, 52
epoxidation, 48, 50
one-dimensionality (1D), zeolites,
79, 82
one-pot reactions
cellulose-to-HMF conversion,
1924
deacetalization, 35, 120
organic reactions in biodiesel
production, 11920
organic structure-directing agents
see structure-directing agents
organoamines, 378
organometallic complexes, 45, 46, 51
organosilanes, 10, 14, 15, 19, 20, 32
biodiesel production, 1201
in situ addition of ( cocondensation), 323, 36, 52,
71, 1201
oxidation of carbon monoxide under
excess hydrogen, preferential, 6870
Subject Index
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Subject Index