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Journal of the European Ceramic Society 35 (2015) 3119–3125

Hydrothermal synthesis of boehmite in cellular alumina monoliths for

catalytic and separation applications
Nuno M.D. Vitorino a,∗ , Andrei V. Kovalevsky a , João C.C. Abrantes a,b , J.R. Frade a
a Aveiro Institute of Materials CICECO-DEMaC, University of Aveiro, 3810 Aveiro, Portugal
bUIDM, ESTG, Polytechnic Institute of Viana do Castelo, 4900 Viana do Castelo, Portugal
Received 5 March 2015; received in revised form 22 April 2015; accepted 24 April 2015
Available online 12 May 2015

Abstract
For the first time, controlled hydrothermal functionalization was performed in porous cellular ␣-Al2 O3 ceramics, targeting potential separation and
catalytic processes for sustainable chemistry applications. Growth of micro-nano hierarchical structures of boehmite (␥-AlOOH) with high aspect
ratio was assessed by SEM/EDS/XRD/FTIR. The pH and precursors concentration determine the growth mechanism and final functionalization
level. The obtained results anticipate strategies for promoting formation of boehmite at the pores surfaces and tuning its morphology, including
pre-treatments of the cellular matrix to increase the concentration of the surface defects and preliminary saturation of the pores with appropriate
precursors to achieve uniform functionalization. Thus grown boehmite structures can be easily converted to ␥-Al2 O3 by thermal treatment while
retaining the former distribution and aspect ratio, opening new possibilities for preparation of ␥-Al2 O3 supported catalysts.
© 2015 Elsevier Ltd. All rights reserved.

Keywords: Boehmite; Cellular alumina monoliths; Hydrothermal synthesis; ␥-Alumina

1. Introduction encouraging the design of cheap, environmentally-safe and

Functional materials with controlled dimensionality and
morphology are recognized as an essential part of numerous
engineering solutions for energy, food, water and environmen-
tal problems. Those possessing large surface areas, tunable
pore size, appropriate thermal stability and tailored acid/basic
functionalities, allowing modification with catalytically active
species, are of particular interest for both technology and fun-
damental research. Transition aluminas, being already known
and quite mature materials, are one of the most frequently
used catalyst supports [1,2], especially the ␥-alumina polymorph
which contributes significantly to performance of supported cat-
alysts in a variety of industries, with emphasis on petroleum,
automotive sectors [1,3]. Therefore, reasonable improvements
in relevant alumina properties and/or working concepts for
catalytic applications are extremely challenging and expected
to contribute significantly to green sustainable chemistry,
∗ Corresponding author. Tel.: +351 258 819 700.
E-mail address: nuno.vitorino@ua.pt (N.M.D. Vitorino).
effective systems and processes.
A well-established route to induce the ␥-alumina poly-
morph is based on dehydration of boehmite (AlOOH) at
400–1000 ◦ C [4–7]. Nanostructured boehmite itself repre-
sents an interesting material for designing superhydrophobic
and self-cleaning surfaces for adhesion and surface oxida-
tion prevention, self-cleaning of windshields, antibiofouling
paints, etc. [8–10]. Boehmite is also known for a fairly
rare combination of superhydrophobicity, superoleophilicity
and relatively good thermal stability [11], very promising
for filtration or separation. Most commonly the nanostruc-
tured boehmite is synthesized by hydrothermal processes in
various conditions and based on different synthesis strate-
gies, as summarized in Table 1. As shown, these strategies
are designed to yield boehmite particles of different shapes,
seeking requirements of diverse applications. Boehmite can
be then converted into ␥-alumina powder with corresponding
particle morphologies. For many catalytic applications alumina-
based supports with narrow pore size distribution, uniform
pore structure with appropriate pore volume are highly desired
[12]. Furthermore, as an ultimate goal one may consider 3D

http://dx.doi.org/10.1016/j.jeurceramsoc.2015.04.040
0955-2219/© 2015 Elsevier Ltd. All rights reserved.
3120 N.M.D. Vitorino et al. / Journal of the European Ceramic Society 35 (2015) 3119–3125

Table 1
Literature data on the conditions of the hydrothermal synthesis of nanostructured boehmite.
Precursors Hydrothermal conditions Boehmite features Ref.

Temperature (◦ C) Time (h)

Al(NO3 )3 •9H2 O; NaHCO3 200 24 2D particles with 8 ␮m diameter (low Al concentration, 0.1 M) [19]
1D wire-like particles with 10 ␮m length (high Al concentration, 0.2 M)
Al(NO3 )3 •9H2 O; NH3 160 24 Nanotubes with ∼500 nm length and ∼20–40 nm diameter [20]
Camphorsulfonic acid
NaAlO2 ; urea 160 3 Flower-like boehmite nanostructures on quartz surface [21]
180
200
NH4 Al(SO4 )2 •12H2 O; Urea 150 12 Flower-like boehmite structures [7]
Al(OH)3 160 0.17 Plate-like boehmite particles with average particle size in range 4–25 ␮m [22]
220 1.33
300 2
AlCl3 ; NaOH; CTAB 160 12 Leaf-like boehmite nanosheets with aspect ratio of 2 and 60–90 nm of thickness [4]
AlCl3 ; C2 H6 O (ethanol) 200 72 Flowerlike nanoarchitetures [23]
Al(NO3 )3 •9H2 O; 200 24 Cantaloupe-like and hollow microspherical superstructures [24]
C6 H5 Na3 O7 •2H2 O
Al2(SO4)3•18H2 O 165 3 Hollow core/shell and hollow microspheres [25]
Urea
sodium tartrate
Al(NO3 )3 •9H2 O, urea and 180 3 The morphology evolves from singe nanoflakes, nanoflakes assemblies, and [26]
KAl(SO4 )2 flower-like structures to hollow microspheres with increasing of KAl(SO4 )2
12H2 O
Al2 (SO4 )3 •18H2O; NH3 165 24 Nanorods-like structure [27]

hierarchical structures, which are ordered in all appropriate
length scales, from molecular to nano and macro [13–15]. In
particular, the incorporation of macropores into mesoporous
architectures can minimize diffusion barriers and potentially
enhance the distribution of active sites during modification
with catalyst [13]. On the other hand, such hierarchical struc-
tures are expected to tackle the challenges of the filtering
applications, especially those demanding high medium flow
rates.
Synthesis of mesoporous aluminas with narrow pore size
distribution represents an interesting and challenging approach
for the fabrication of catalyst supports [1], especially in the
view of great advancements, realized for mesostructured forms
of silica [14,16]. For those applications dealing with high
medium flow rates and significant pressure changes (filtering of
water/oil emulsions, combustion, and other catalytic reactions
with volume change), introduction of larger pores is essential to
support a reasonable performance, along with providing suffi-
cient mechanical strength and appropriate interconnectivity of
the pores. Recently a new facile method for processing of highly
porous cellular alumina ceramics by emulsification of the liq-
uid paraffin in ceramic suspensions was developed in our group
[17,18]. The approach allows fine 3D-tuning of cavities shape
and interconnectivity between pores, and results in mechanically
strong ceramics (compressive strength of 10–40 MPa), with a
clear potential for further improvement. Thus, to benefit from
the synergy of simple and flexible processing, well-tunable pore
structure and mechanical resistance, the present work focuses on
the bulk modification of the monolithic cellular ceramics with
boehmite/␥-alumina nanostructures via hydrothermal treatment.
Thus modified monoliths are attractive for variety of catalytic
applications, considering that nanostructured boehmite at the
surface of the pores can be further functionalized by impregna-
tion with various precursors, containing transition metal cations
(Ni2+ , Cu2+ , Fe2+/3+ , Co2+/3+ , etc.) and converted to ␥-alumina-
supported catalytic layers. Those functionalities can represent a
particular interest for performing catalytic combustion in mono-
liths, where inherent porous microstructure may be adjusted for
efficient gas and thermal transport. To our best knowledge, the
described strategy represents a first attempt for in situ functional-
ization of porous ceramic monoliths in hydrothermal conditions.
2. Experimental
Porous alumina monoliths were prepared by emulsification
of molten paraffin (Merck 1.07337.2500) in aqueous alumina
(Alcoa CT3000) suspension (50% vol. of solids content, sta-
bilized with a viscosity close to 0.5 Pa s using Dolapix PC-67
(10% vol.)). Paraffin was melted at 80 ◦ C, prior to addition
of the alumina suspension in volume ratio paraffin:suspension
1.5:1, followed by addition of an anionic surfactant (sodium
lauryl sulphate, Sigma-Aldrich L-6026) as emulsification agent
(6% related to the emulsion volume), and collagen (OXOID
LP0008) as shape stabilizer. Emulsification was promoted by
mechanical stirring at 1000 rpm for 10 min, while maintaining
temperature at 80 ◦ C, to avoid paraffin solidification. After dry-
ing, the resulting ceramic emulsions was sintered at 1550 ◦ C for
3 h with heating rate 0f 5 ◦ C min−1 , and a dwell of 2 h at 200 ◦ C
to allow paraffin volatilization. Additional details about cellu-
lar alumina monoliths preparation can be founded in our recent
papers [17,18,28].
The 0.5 cm thick alumina monoliths (∅ 2 cm), sintered at
1550 ◦ C for 2 h, with ∼60–70% porosity were subjected to
hydrothermal synthesis in a 100 ml Teflon-lined stainless steel
 N.M.D. Vitorino et al. / Journal of the European Ceramic Society 35 (2015) 3119–3125
Table 2
Sample denominations, concentration of precursors, pH and phase composition of the modified monoliths, estimated by XRD analysis.
Sample denomination Precursor concentrations, M
c(Al(NO3 )3 c(NaHCO3 )
Al05Na05 0.5 0.5
Al01Na05 0.1
Al005Na025 0.05 0.25
Al001Na005 0.01 0.05
Al0001Na0005 0.001 0.005
Al1Na05 1 0.5
Al005Na05 0.05
Al001Na05 0.01
autoclave, with an aqueous solution fraction of 40% at room tem-
perature. Hydrothermal treatments were performed at 190 ◦ C for
19 h, using various concentration of Al(NO3 )3 •9H2 O (Sigma
Aldrich BCBH6623V) and NaHCO3 (Merck K25746929 843).
The pH of solutions was assessed in ambient conditions by
after dissolving the precursors and boiling for 1 h under con-
tinuous stirring, in order to assess possible effects of basicity
on boehmite formation. Still, one should not exclude significant
shifts in pH values as hydrothermal synthesis progresses. The
concentration of precursors for various treatments and corre-
sponding values of pH are given in Table 2. After hydrothermal
treatment the samples were washed by repeated immersions
in deionized water to remove residual precursors, and dried
at 100 ◦ C. Possibilities for conversion of boehmite to ␥-Al2 O3
were studied at 400–700 ◦ C.
Phase composition of dried modified monoliths, was studied
by XRD (Bruker D8 Advance DaVinci, in 10–90◦ 2θ range with
a step of 0.02◦ and a residence time of 0.5 s), after crushing the
monolith to powder. Diffraction patterns were analyzed using
ICDD (International Centre of Diffraction Data, PDF 4) in EVA
(Bruker) software. The phase content was evaluated by Rietveld
analysis, using Topas software (Bruker). The microstructure
and phases distribution in monoliths was assessed by electron
microscopy (SEM-Hitachi SU1510), and energy dispersive X-
Ray spectroscopy (EDS – Bruker Quantax 200), using fracture
surfaces.
The quantification of boehmite was also performed by visual
counting the specific number of its clusters, to assess the mor-
phology of the synthesized phase. For this quantification, a set
5–10 SEM micrographs, which corresponded to various vol-
ume parts of samples, prepared in the same conditions, was
selected; the results, obtained for each micrograph, were then
averaged. The areas, used for calculations, were additionally
mapped by EDS, to avoid confusion between boehmite clusters
and remaining traces of spurious phases such as nitrite, nitratine
and nahcolite.
3. Results and discussion
Typical SEM micrograph of the sintered ceramic mono-
liths (Fig. 1A) shows well-defined cellular structure with
nearly bimodal cell size distribution and good interconnec-
tivity between pores, as previously observed in [17,18]. The
3121
pH Phase composition of monoliths (% wt.)
Al3+ /HCO3 − molar ratio ␣-Alumina Boehmite
1 3.34 99.1 0.9
0.2 8.51 99.5 0.5
8.09 99.8 0.2
8.20 100 0
8.64 100 0
2 2.63 95.5 4.5
0.1 8.36 99.2 0.8
0.02 8.54 100 0
cited works already demonstrated high flexibility of the devel-
oped processing route for tuning microstructural features, with
emphasis on cell size distribution, thickness of the cell walls,
size of interconnecting windows, percolation of open poros-
ity, and appropriate mechanical strength, aiming to match
requirements of various applications. The monoliths with shown
microstructure (Fig. 1A) were thus selected as model monoliths,
to demonstrate the concept of in situ hydrothermal func-
tionalization of ␣-alumina cellular ceramics with open cell
microstructures.
The phase composition of the cellular monoliths after
performing hydrothermal synthesis is shown in Fig. 2, and cor-
responding phase fractions are listed in Table 2. Two phases
were unambiguously detected by XRD, including the support-
ing ␣-Al2 O3 as a main component and hydrothermally induced
boehmite. Additional peaks of minor intensity may be attributed
to remaining traces of reactant (NaHCO3 ) or sodium-containing
byproducts (nitrite Na2 CO3 and nitratine NaNO3 ). Broader
peaks shape indicates nanostructuring in synthesized boehmite,
which is typical for hydrothermally-grown phases. FTIR results
also confirm presence of boehmite in modified cellular mono-
liths (Fig. 3), ascribed as in Refs. [20,29]. The spectrum shows
a large band around 3400 cm−1 , assigned to the (Al)O–H vibra-
tions, whereas the small band at 1065 cm−1 is attributed to
the Al–O–H symmetric and asymmetric modes of boehmite.
The torsional boehmite modes at 798 and 652 cm−1 are also
observed in the spectrum. The weak band at 1636 cm−1 corre-
sponds to the stretching and bending modes of adsorbed water.
The band at 1382 cm−1 , growing upon increasing the concentra-
tion of precursors, may be attributed to the stretching vibration of
C O and C–O bonds of CO3 2− ion [30], indicating that a part
of carbonate-based residuals is still trapped inside the highly
porous cellular monolith even after repeated washing.
The results of combined SEM/EDS analysis (Fig. 1B–D)
clearly confirm microstructural changes in hydrothermally-
modified cellular ceramics, if compared to non-modified one
(Fig. 1A). As a unique difference observed is the formation
of rods/fibres and flower-like clusters, one should attribute
those structures to boehmite grown during the hydrothermal
treatment, in accordance with XRD and FTIR results. EDS
inspection also suggests that the fibres are mainly composed
of aluminium cations and do not result from precipitation of any
sodium-containing species (Fig. 4). As a known morphological
3122 N.M.D. Vitorino et al. / Journal of the European Ceramic Society 35 (2015) 3119–3125

Fig. 1. SEM micrographs of the fractured non-modified cellular ceramics (A) and hydrothermally-modified Al1Na05 (B), Al1Na05 (C) and Al005Na05 (D) samples.

feature, boehmite crystals form aggregates with nanorod- and Al0001Na0005

nanowire-type structures having high aspect ratio, which have
been reported by hydrothermal synthesis in acidic to moderately
Transmitance (a.u.)

Al01Na05
basic conditions [31–33]. The thickness of boehmite nanorods,
grown in the pores of cellular monoliths, is ∼100–500 nm, Al1Na05
i.e. one order of magnitude thicker than in above cited Refs.
[31–33], and with high aspect ratio. Note that the used range Al2O3 monolith

652
of pH of the precursor’s solution (Table 2) is favourable for
1065
1382
1636
3445

development of elongated architectures, while at pH ≥ 10.5 one

798

observed the formation of nanoplates and flake-type boehmite

particles [32,33]. In the present work pH was determined by 4000 3500 3000 2500 2000 1500 1000 500
Wave number / cm-1
changes in Al(NO3 )3 and NaHCO3 concentrations, which can be
Fig. 3. FTIR spectra of the powdered hydrothermally-modified and non-
modified cellular ceramics samples.

Fig. 2. XRD patterns of the powdered Al1Na05 and Al0001Na0005 samples. Fig. 4. EDS map of the fracture of Al005Na05 sample.
 N.M.D. Vitorino et al. / Journal of the European Ceramic Society 35 (2015) 3119–3125
understood considering two main reactions with opposite effects
on acidity/bacicity:
Al3+ + 3H2 O  Al(OH)3 + 3H+
− −
HCO3 + H2 O  H2 CO3 + OH
Low Al3+ /HCO3 − ratio (0.02–0.2) results in slightly basic
conditions (Table 2), facilitating the formation of colloidal dis-
persion of Al(OH)3 particles, which eventually may be converted
to boehmite according to the reaction:
Al(OH)3 → AlOOH + H2 O
Thus, one may expect rather massive formation of boehmite
when shifting to more basic conditions. However, the estimates
of the boehmite fraction from XRD data (Table 2) suggest
higher modification of the cellular monoliths in acidic condi-
tions, which correspond to the excess of the Al(NO3 )3 . As the
precursors/products residues were mostly washed out from the
pores after the hydrothermal treatment, one may assume that
lower pH might be more favourable for improved bonding of
boehmite particles to the monolith walls and further growth
with preferential fibre-like orientation. Firstly, acidic conditions
may contribute by protonation of the surface oxygen ions in the
monolith, thus creating the conditions for further stacking of
AlOOH layers along b-axis through the formation of hydrogen
bonds. Secondly, preferential growth of boehmite nanostructures
with high aspect ratio was shown to be facilitated by selective
adsorption of anionic groups (i.e. NO3 − ) in acidic conditions
on the (0 1 0) and (0 0 1) facets of boehmite, terminating fur-
ther progress in these directions, while allowing the growth
along (1 0 0) plane [29,32,33]. This mechanism is expected to
be relevant for the whole studied pH range (Table 2), taking
into account that isoelectric point of boehmite corresponds to
9.1–9.2 [32,34] and further dissolution of aluminium hydrox-
ides in more basic conditions is rather relevant at pH > 8.6,
in accordance with Pourbaix diagrams [35]. Still, one should
not exclude presence of specific local pH conditions inside the
pores of ceramic monolith during hydrothermal treatment, also
provided by diffusion limitations for precursors and resulting
products. Indeed, further studies are required for detailed infor-
mation on these mechanisms of hydrothermal synthesis inside
porous ceramics, as compared to traditional approaches. From
the other hand, the concentration of aluminium precursor in solu-
tion during hydrothermal treatment appears to be quite important
factor for the surface modification of cellular ceramics, as the
highest fractions of boehmite were observed for samples with
notations Al1Na05 and Al05Na05.
The morphological features of hydrothermally-induced
boehmite in the pores are expected to be affected by presence
of surface defects and dangling bonds, which may energeti-
cally favour the nucleation and growth processes. The results,
presented in Fig. 5, show a clear tendency for the amount of
boehmite clusters to saturate for higher modification levels. The
number of clusters drastically increases only for low modifi-
cation level, while further increase in boehmite content results
in formation of hierarchical structures, including larger clusters
and flower-like architectures (Fig. 5), rather than appearance
3123
(1)
(2)
(3)
Fig. 5. Dependence of the area-specific number of boehmite clusters on the
modification level of the cellular ceramics. Top left image shows an example of
SEM image for visual quantification.
of new nucleation sites. This implies that further improve-
ment in modification level may be achieved by appropriate
pre-treatments of the cellular monoliths, to increase the con-
centration of surface defects, favourable for nucleation. For
the latter, one might consider hydrothermal pre-treatment in
strongly alkaline or acidic conditions, or even high-temperature
annealing in reducing atmospheres.
Particular attention should be given to the obvious specifics
of the hydrothermally-induced modification in porous cellular
ceramics, including different conditions for the reaction at the
surface of the sample and inside the pores. The results, presented
in this work, describe the “bulk situation” extending over a layer
thickness of at least 1–2 mm apart from the surface, i.e. on a dis-
tance of around two orders of magnitude larger than the average
pore size. Within these boundaries, the results of SEM/XRD
analysis confirmed nearly equal level of modification, while
at the surface the concentration of boehmite was found to be
around 10 times higher. Although one may consider further
improvement of the hydrothermal reactor in order to facilitate the
diffusion inside pores (i.e., rotation/shaking and/or application
of ultrasound, etc.), more feasible approach may include several
pre-impregnation of the sample with corresponding solution of
the precursors under vacuum, each followed by a drying step.
The latter is expected to be more important for the case of thick
monoliths, considering intermediate and large-scale separation
and catalytic applications.
Finally, depending on the target application, the boehmite
may be converted to ␥-Al2 O3 by controlled thermal treat-
ment, as demonstrated by the XRD and SEM results shown
in Fig. 6. It should be noticed that the nanostructural fea-
tures of boehmite are nearly retained in resulting ␥-Al2 O3 ,
with some reduction in fibres size. The optimal temperature
range for conversion corresponds to 670–800 K, typical for
this phase transformation [5]; further heating results in rever-
sion to ␣-Al2 O3 . As a feasible strategy for producing cellular
␥-alumina supported catalysts, one may thus consider a two-
steps modification approach, including simultaneous growth
3124 N.M.D. Vitorino et al. / Journal of the European Ceramic Society 35 (2015) 3119–3125
Fig. 6. Examples of the XRD patterns for the powders, obtained from Al1Na05
samples after annealing at 773 and 973 K for 2 h. The inset shows the depen-
dence of the ␥-alumina content on the annealing temperature, estimated from
XRD data. The SEM images correspond to the fractured ceramic samples after
annealing at 773 and 973 K.
and functionalization of boehmite in the solution, containing
appropriate precursors, under hydrothermal conditions, fol-
lowed by thermal treatment to form target supported-catalyst
structure.
4. Conclusions
Nanostructured boehmite (␥-AlOOH) having rods/fibre-
and flower like morphology was successfully synthesized by
hydrothermal treatment at 463 K for 19 h at the pore surfaces
of the cellular ␣-Al2 O3 monoliths, using aqueous solution of
Al(NO3 )3 ·9H2 O and NaHCO3 precursors. The amount of the
boehmite formed was mainly determined by the concentration
of precursors, with a maximum of ∼4.5% from the total weight
of the porous alumina matrix. Within the studied range, the pH
showed a minor effect on the morphology and modification level,
with apparently more facile surface attachment of the boehmite
particles in acidic conditions. The general mechanism of the pro-
cess includes initial nucleation, followed by preferential growth
of the clusters and their transformation into more complicated
hierarchical structures. In thus modified porous ceramics, the
boehmite can be transformed into ␥-alumina phase by a deli-
cate thermal treatment, while retaining favourable micro- and
nanostructural features.
Acknowledgements
This work was developed in the scope of the project CICECO-
Aveiro Institute of Materials (Ref. FCT UID/CTM/50011/2013,
PTDC/CTM-ENE/2073/2012 and PEst-C/CTM/LA0011/2013,
and grants SFRH/BPD/99367/2013 and IF/00302/2012),
financed by national funds through the FCT/MEC and when
applicable co-financed by FEDER under the PT2020 Partnership
Agreement.
SEM facilities were funded by FEDER Funds through
QREN – Aviso SAIECT-IEC/2/2010, Operação NORTE-07-
0162-FEDER-000050.
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