Microporous and Mesoporous Materials 89 (2006) 158163 www.elsevier.

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Gold nano-particles stabilized in mesoporous MCM-48 as active CO-oxidation catalyst

M. Bandyopadhyay a, O. Korsak a, M.W.E. van den Berg b, W. Gru nert b, c d d a,* A. Birkner , W. Li , F. Schu th , H. Gies
a

Institut fu r Geologie, Mineralogie und Geophysik, Lehrstuhl Kristallographie, Fakulta t fu r Chemie, Ruhr-Universita t Bochum, Universita tsstr., D-44780 Bochum, Germany b Lehrstuhl fu r Technische Chemie, Ruhr-Universita t Bochum, Universita tsstr., D-44780 Bochum, Germany c Lehrstuhl fu r Physikalische Chemie 1, Ruhr-Universita t Bochum, Universita tsstr., D-44780 Bochum, Germany d MPI fu r Kohlenforschung, Kaiser-Wilhelmplatz 1, D-45470 Mu hlheim, Germany Received 31 May 2005; received in revised form 15 September 2005; accepted 18 September 2005 Available online 28 November 2005

Abstract Gold in nano-crystal size is known as highly active CO-oxidation catalyst. Using simple deposition techniques gold has been deposited as $3 nm particles inside the channels of mesoporous silicaTiO2MCM-48. In the presence of gold nano-particles the catalyst converts CO to CO2 at 50% level at 20 C. The composite is stable against sintering up to at least 200 C. XANES and EXAFS conrm the coexistence of elementary and ionic gold during the catalytic activity. 2005 Elsevier Inc. All rights reserved.
Keywords: Au/TiO2MCM-48; Au/TiO2; CO oxidation; Au XANES; Au EXAFS

1. Introduction Gold is thought to be the noblest of all metals [1]. Ground breaking work by Haruta et al. [24], showed that gold as catalyst exhibits considerable activity when it is highly dispersed on metal oxides supports [57]. Two dierent classes of oxides could be used for the support [8]. Active supports, such as TiO2 and Fe2O3, which can be easily reduced, or inert supports, like Mg(OH)2, Al2O3, and silica. These supports can also give active catalysts, typically when some reducible elements are also introduced [9], although in some cases even for Au on the unmodied support material, low-temperature CO-oxidation activity has been reported. For all catalytic applications it is important that the small gold particles are highly dispersed on the oxide support [7]. Au/oxides catalysts have been widely

Corresponding author. E-mail address: hermann.gies@rub.de (H. Gies).

applied to many important chemical reactions such as CO oxidation [2], hydrogenation of unsaturated hydrocarbons [10], reduction of NOx [11], epoxidation of C3H6 [12], selective CO oxidation in a hydrogen-rich steam [13], combustion of methane [14], etc. Recently, Hua et al. [15] have used Au/iron oxide catalysts for the water gas shift reaction. The catalytic performances of dierent systems with gold on oxide supports is strongly inuenced by the preparation method, the specic synthesis parameters such as light protection, the Au particle size, and more [5,9,16]. The depositionprecipitation (DP) process is considered to be the best method to synthesize highly active gold catalysts [17] because of the good control of the particle size by adjustment of pH during particle formation. In addition, some other methods like chemical vapor deposition [18] (CVD) or co-sputtering [19] are widely used for catalyst formation. An extensive study on Au/Al2O3 catalyst prepared by both DP and CVD methods reveals that nely dispersed Au/Al2O3 with Au particle size <5 nm can be

1387-1811/$ - see front matter 2005 Elsevier Inc. All rights reserved. doi:10.1016/j.micromeso.2005.09.029

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easily prepared by the CVD method, whereas the traditional DP method leads to formation of larger gold particles (>7 nm) on the Al2O3 support [20]. A series of active Au/TiO2, Au/Co3O4, Au/ZrO2 catalysts were studied leading to the conclusion that, with similar gold particle sizes, Au/TiO2 is the most active system. However, a draw back of all nano-dispersed Au on oxide supports is its ready aggregation to larger particles already at moderate temperatures, usually at $60 C. In addition to zeolites, M41S [21] materials are thought to be particularly useful as carriers or matrices for functional molecules or nano-particles because of their high thermal and chemical stability. Their mesoporous structure could be explored as a host or matrix to immobilize catalytically active species on or for providing nano-size connement inside the pore system [2226]. Some literature is available on highly dispersed metal nano-particles on SBA-15 type material [27,28]. Recently, we reported on the deposition of Ti salts within the pore system of cubic MCM-48 and their subsequent decomposition to Ti-oxide clusters [26]. The use of MCM-48 with quantum-sized titania particles inside the porous matrix as a support for Au particles is the main interest of our present study. Here we have explored the use of TiO2/MCM-48 as a matrix for the formation of thermally stable nano-sized gold metal particles and the use of the composite as CO-oxidation catalyst. 2. Experimental 2.1. Synthesis TiMCM-48 was prepared by a post-synthetic wet impregnation method according to the literature procedure [26]. In a typical synthesis procedure 500 mg of the standard MCM-48, which was dried overnight in vacuum at 180 C, was reacted with 200 ml of solution of tetrabutylorthotitanate (Merck) in dry acetone (0.05 m). The mixture was stirred for 6 h at room temperature. As tetrabutylorthotitanate is moisture sensitive, the whole procedure was carried out in dry N2 atmosphere. Finally, the solid was ltered o carefully, washed with acetone, dried at room temperature and then calcined at 300 C for 5 h. For successive impregnations the respective procedure was repeated several times. Three times impregnated TiO2/MCM-48 containing $15 wt.% titania was used for Au loading. The depositionprecipitation method was chosen for gold insertion [29]. During catalyst preparation 100 ml of an aqueous solution of HAuCl4 3H2O (Aldrich, 8 wt.% Au with respect to support) was heated at 70 C. The initial pH was around 2.5. The pH was adjusted to neutral value 7 by drop-wise addition of dilute NaOH. After that 0.1 g of TiMCM-48 was dispersed in the solution. The pH of the solution became 56 and the pH was then readjusted to 7 again by addition of NaOH. The suspension was stirred for 1 h at same temperature. Finally the solid was ltered, washed with water, and freeze-dried overnight under

vacuum. The whole procedure was carried out in absence of light. 2.2. Characterization X-ray powder diraction experiments were carried out using a Siemens D5000 diractometer, which was operating in transmission mode (modied Debye Scherrer geometry) ). with monochromated CuKa1 radiation (k = 1.54059 A For long exposure times, a Huber Guinier imaging plate camera G670 was also used with CuKa1 radiation. In both cases the sample was loaded in a glass capillary. A Hitachi H-8100 scanning and transmission electron microscope operating at accelerating voltages up to 200 kV with a single crystal LaB6 lament was used for the TEM studies. The specimens were prepared by placing a drop of the dilute solution of the calcined powder samples in ethanol on a carbon-coated copper grid. The samples were allowed to dry at room temperature. X-ray absorption spectra (Au LIII-edge at 11 919.0 eV) were measured at Hasylab X1 station (Hamburg, Germany). This beamline was equipped with a Si(3 1 1) double-crystal monochromator that was used detuned to 50% of the maximum intensity in order to exclude higher harmonics present in the X-ray beam. The samples were mixed with polyethylene and pressed into wafers of sucient thickness. The spectra l(k) were measured in transmission mode using ionization chambers, with the sample wafer at liquid nitrogen temperature. A gold metal foil (between the second and the third ionization chamber) was measured at the same time for energy calibration purposes. Data treatment was carried out using the software package VIPER [30]. For background subtraction a Victoreen polynomial was tted to the pre-edge region. A smooth atomic background l0(k), was evaluated using smoothed cubic splines. The radial distribution function FT[k2v(k)] was obtained by Fourier transformation of the k2-weighted experimental function v(k) = (l(k) l0(k))/l0(k) multiplied by a Bessel window. 2.3. Catalytic activity measurements For the CO oxidation reaction a plug-ow reactor with inner diameter of 4.5 mm was used. Measurements were carried out under dynamic conditions while ramping the temperature. The heating rate during these experiments was 2 C/min. The reaction gas contained 1% CO, 20% O2 and N2 as balance which was passed over 50 mg of the catalyst (Au/Ti/MCM-48) with a ow rate of 67 ml/min, corresponding to a space velocity of 80,000 ml/h gcat. 3. Results and discussion The gold particles were introduced into the mesoporous TiO2/MCM-48 matrix using the DP method. After three impregnation runs the nal Au content amounted to

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$3 wt.% Upon loading with gold the colour of the white sample changed to grayish. Low-angle powder XRD patterns show that the parent structure of the mesoporous host is maintained after loading with titania and consecutively with Au (Fig. 1(a) and (b)). However, because of the strong reduction of scattering contrast between wall and pore due the impregnation of nano-particles [31], the resulting X-ray diraction signal from the mesoporous car-

rier MCM-48 is only very weak. The high angle shoulder in the (2 1 1)-peak originating from the (2 2 0)-peak can just be seen. For the conrmation of the analysis complementary information from TEM-experiments is needed and will be discussed later on. In addition, a strong contribution of the nano-particles to the SAXS-signal can be seen in the low angle region. In the wide-angle XRD pattern given in Figs. 1 and 2, there are clear signals of gold metal at

240000

Au/TiO2-MCM-48

210000

180000

Intensity (counts)

150000

120000

90000

60000

30000

0 2 8 14 20 26 32 38 44 50 56 62

a
240000

2 () Au/TiO2-MCM-48

210000

180000

Intensity (counts)

150000

120000

90000

60000

30000

0 2 3 4 5 6 7 8 9 10 11 12

2 ()

Fig. 1. XRD diagram of Au/TiO2MCM-48 showing (a) the complete pattern up to 62 2h and (b) the low angle part between 2 and 12 2h. The insert in (a) is enlarged by a factor of 50 and clearly shows the diraction pattern of nano-particles of gold. In (b) the diraction pattern still shows the integrity of the MCM-48 mesoporous support. Because of the considerable decrease of scattering contrast through TiO2 and Au loading, only weak signals are seen. At $2.64 2h the major signal appears, at $3.04 2h the typical shoulder of MCM-48 material can be seen, and, nally, at $3.65 2h a very weak signal of the second set of signals shows up.

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Fig. 2. Powder XRD patterns of Ti impregnated (blue) and Ti/Au impregnated MCM-48 (red). The st maximum at ca. 23 2h is due to the amorphous silica matrix, the following 4 maxima can be indexed as (1 1 1), (2 0 0), (2 2 0) and (3 1 1) for fcc gold metal. (For interpretation of the references in colour in this gure legend, the reader is referred to the web version of this article.)

around 38.3, 44.4, 64.7, 78.0 2h. Using the Scherrer formula for an estimation of the particle size, the peak half width of all reections gave an averaged value of around for metallic gold. Thus, the particles are small enough 27 A to t inside the porous matrix of TiO2/MCM-48 as the [26]. However, pore diameter of TiMCM-48 is 2829 A as obvious from the unusual shape of the diraction signal, there is signal overlap from particles of dierent size. Few larger particles contribute to the generally very broad signal giving a rather sharp and high signal on a broad base leading to an overestimation of the particle size, since the FWHM is measured to small. To conrm the interpretation of the XRD experiments, complementary TEM studies were carried out. First, the integrity of every sample was

checked with TEM together with its qualitative titania and gold content using EDX. The results of the analyses always showed the typical lattice fringes of the well ordered and well maintained silica host structure of MCM-48. The TEM image (Fig. 3) also shows uniform and highly dispersed gold particles inside the channel system. The XAS spectra of the Au LIII-edge can be seen in Fig. 4. Model analysis of the rst coordination sphere around the central gold atom yields a AuAu coordination number of 7.6 0.2 (see Table 1). By assuming spherically shaped Au particles, the apparent crystallite size can be estimated from the coordination number derived from EXAFS data, as shown by Borowski [32]. Doing so, appar are found. ent crystallite sizes ranging from 11 to 12 A

Fig. 3. TEM image and EDX analysis of the Au/TiO2MCM-48 composites freshly prepared.

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(a)

(b)

(raw)

(d)

FT ( ), absolute FT (), imaginary part fitted

(k)k2)

Normalised absorption (-)

0.2 FT ((k)k2)

-1 4 1 6 8 10 12 14 16

k, eV

Au Foil Au/TiO2 @ MCM-48

(c)

BFT fitted

(k)k2)

0
-1

-1

11900

11950 E, eV

12000

12050

10

12

14

16

k, eV

r,

Fig. 4. k2-weighted Au LIII-edge absorption spectra of Au/TiO2-MCM-48, showing (a) the XANES compared to Au-foil, (b) the measured v(k), (c) the model v(k) and (d) the Fourier transform and model Fourier transform.

Table 1 Parameters of the model t of the Au-EXAFS ) No. Element R (A CN 1 2 3 O Cl Au 1.913 0.019 2.400 0.023 2.852 0.002 0.3 0.1 0.3 0.2 7.6 0.2

100

2) 10 r (A
3 2

CO Conversion %

1.0 0.0 10.0 1.1 5.9 0.1

80 60 40 20 0 -40 -30 -20 -10 0 10 20

black-first red-second blue-third

The table lists the Au-element distance, coordination number, and Debye Waller factor.

Fitting the data with models containing just AuAu-contributions were unsuccessful. The XANES shown in Fig. 4(a) show that the measured Au foil diers somewhat from the sample measured. From this, and the non-zero intensity in the Fourier transform of the Au LIII-edge at lower distance than AuAu it can be concluded that a light atom must be present near the gold. The model shown in Table 1 incor and a chlorine atom at porates an oxygen atom at 1.91 A . The correlation coecient for this model was 7.6. 2.40 A It was the best t thus far, however, a possible Ti contribution should be further investigated. Using the freshly prepared sample in a CO-oxidation experiment, the conversion set in at $30 C reaching 50% conversion at 20 C (Fig. 5). In consecutive runs the temperature for 50% conversion remained almost constant. After a short recovery period after the second run, the 50% conversion temperature for a third cycle was again lower than for the 2nd cycle, at $20 C. In additional experiments, which were conducted after storing the freshly prepared sample in the dark for one week, similar values for the conversion were obtained. It is important to mention that only those samples were active which have been synthesized under protection from daylight. Those which were exposed to daylight were active only with 50% conversion at $160 C. In attempts to increase the dispersion of gold inside the mesoporous channels by controlling the

Temp. oC

Fig. 5. CO-conversion as function of temperature. Three consecutive runs are shown. The fresh sample (black) showed the best performance, in the second run (red) the 50% conversion temperature increased, however, after a recovery period, the 50% conversion temperature dropped again showing that the catalyst is still very active. (For interpretation of the references in colour in this gure legend, the reader is referred to the web version of this article.)

pH even more precisely, a sample has been synthesized with a 50% conversion temperature around 30 C reecting the increased activity of the composite material. EXAFSand XANES-studies in operando are currently carried out. In order to determine the thermal stability of the nanoconned gold particles the sample was heated to $200 C and studied with X-ray diraction, TEM and CO-oxidation catalysis. Dierent from gold nano-particles deposited on dense supports, the nano-particles located in the conning pore system are stable towards sintering up to at least 200 C. There was no dierence in particle distribution and particle size of the deposited gold before and after catalysis and heating. In catalysis-runs the heat treated

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sample showed the same activity at similar temperatures as the freshly prepared sample. This shows that the structural and electronic properties of the gold particles relevant for catalysis are not changed and an active form of the gold particles is preserved inside the nano-conning MCM-48 support. In conclusion, the study shows that gold nano-particles can be deposited inside mesoporous titania-modied MCM-48. The composite is catalytically active even at temperatures as low as 30 C. In the active catalyst, both, metallic and ionic Au was observed. If the Au ions detected are relevant for the CO oxidation activity is subject to ongoing research. The encapsulation in mesoporous MCM-48 prevents the gold nano-particles from sintering up to at least 200 C without apparent loss in catalytic activity, a temperature which would lead to the deactivation of the catalyst deposited on a bulk TiO2 powder. Besides CO-oxidation, other gold-catalyzed reactions should also be feasible, e.g. the epoxidation of alkenes in gas phase. In addition, it would be interesting the take advantage of the size selectivity of the mesoporous support for the catalytic reaction. Studies concerning these properties are currently carried out. References
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