Applied Catalysis A: General 302 (2006) 283295 www.elsevier.

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Direct propylene epoxidation over modied Ag/CaCO3 catalysts

Jiqing Lu a, Juan J. Bravo-Suarez a, Masatake Haruta b, S. Ted Oyama a,c,*
a

Research Institute for Innovation in Sustainable Chemistry, National Institute of Advanced Industrial Science and Technology, AIST Tsukuba West, 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan b Materials Chemistry Course, Faculty of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji, 192-0397 Tokyo, Japan c Environmental Catalysis and Nanomaterials Laboratory, Department of Chemical Engineering (0211), Virginia Polytechnic Institute and State University, Blacksburg, VA 24061, USA Received 4 October 2005; received in revised form 13 January 2006; accepted 19 January 2006 Available online 7 March 2006

Abstract In this work a series of supported Ag catalysts was studied for propylene epoxidation with molecular oxygen as the oxidant. It was found that aAl2O3 and CaCO3 were suitable supports for propylene epoxidation and that on the latter Ag particles between 400 and 700 nm gave the highest selectivity to propylene oxide (PO). Ball-milling treatment of the CaCO3 catalyst and promotion with NaCl resulted in improved catalytic performance. The highest PO selectivity (45%) was obtained on a ball-milled catalyst with a silver loading of 56 wt.% supported on CaCO3 and promoted with 1 wt.% NaCl (Ag(56)NaCl(1)/CaCO3). The catalysts were tested with reactant ow rates of C3H6:O2:He = 5:10:15 cm3 min1, a gas hourly space velocity (GHSV) of 1800 h1, a reaction pressure of 0.3 MPa, and a reaction temperature of 533 K (260 8C). Addition of 500 ppm of ethyl chloride (EtCl) to the reactant gases enhanced the stability of the Ag(56)NaCl(1)/CaCO3 catalyst. X-ray diffraction (XRD) of the Ag(56) NaCl(1)/CaCO3 catalyst detected the existence of AgCl in the catalyst and ultravioletvisible (UVvis) diffuse reectance spectroscopy conrmed the presence of surface Ag+ species. Scanning electron microscopy showed a roughening of the Ag particles by the ball-milling treatment as well as by the addition of NaCl. The effect of NaCl on the enhancement of the catalytic performance was probably due to both physical and electronic changes in the properties of the catalyst. The NaCl not only helped increase the dispersion of the silver on the CaCO3 support, but also probably increased the quantity of electrophilic oxygen species favorable for epoxidation. In situ UVvis spectra suggested that the rapid reduction of Ag+ species on the surface of the Ag(56)NaCl(1)/CaCO3 catalyst could be the cause of a decline in PO selectivity observed during reaction. # 2006 Elsevier B.V. All rights reserved.
Keywords: Propylene; Epoxidation; Silver; Propylene oxide; NaCl; UVvis spectroscopy

1. Introduction Propylene oxide (PO) is an important raw material for the chemical industry, which is produced commercially by the chlorohydrin process and variations of the Halcon process [1]. The chlorohydrin process involves the stoichiometric reaction of propylene with chlorine and water, and produces a large amount of by-product salts and chlorinated organic compounds. The Halcon process utilizes hydroperoxide epoxidation reagents and produces a large quantity of coproducts (such as t-butylalcohol and styrene), whose commercial values are lower than that of PO. The deciencies in these processes have

* Corresponding author. Tel.: +1 540 231 5309; fax: +1 540 231 5022. E-mail address: oyama@vt.edu (S.T. Oyama). 0926-860X/$ see front matter # 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2006.01.023

given rise to considerable interest in the development of a direct route to PO that does not produce by-products or coproducts. Silver catalysts are well known for the epoxidation of ethylene to ethylene oxide (EO) using molecular oxygen. However, high selectivity can be obtained only with reactant olen molecules without allylic hydrogens. Molecules with allylic hydrogen atoms such as propylene are attacked by surface oxygen species, and give rise to total combustion products [24], so that epoxide selectivities are only of the order of a few percent. For this reason the development of catalysts for the direct conversion of propylene to PO using molecular oxygen remains one of the most difcult challenges in the catalysis eld. In the past several years considerable efforts have been made to improve the performance of silver catalysts for direct propylene epoxidation. Companies such as BP [5], Union

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Carbide [6] and Dow Chemical [7] have reported various modied silver catalysts for direct propylene epoxidation. Promising results were obtained by ARCO [813] with high loading silver catalysts supported on CaCO3. For example, one catalyst containing 48 wt.% Ag, 1.8 wt.% K and 0.6 wt.% Mo supported on CaCO3 gave a propylene conversion of 3.8% and a PO selectivity of 59% [12]. The effect of different promoters on propylene epoxidation has been investigated. Lu et al. [14] compared the effects of NaF, NaCl, NaBr, KF, KCl and KBr and found that NaCl and NaBr gave the best improvements. The promotion was suggested to be due to an inductive effect of the anions on the nearby oxygen atoms adsorbed on Ag. An inductive effect was also reported for an unsupported Ag catalyst modied with MoO3 [15] and a AgMoO3/ZrO2 catalyst [16]. The group of Lambert [17] studied Ag/CaCO3 catalysts promoted with K2CO3 and found that samples containing Ag crystallites of size 2040 nm gave maximum PO yields. They suggested that the optimal crystallite size was the result of a balance between exposure of low and high index planes, with low index planes enhancing epoxidation by stabilizing oxygen adatoms in the most electrophilic state, but also inhibiting desorption by interacting strongly with the product epoxide. In other work by the same group [18] the Agcatalyzed epoxidation of propylene and ethylene was investigated using an electrochemical promotion method and the state of oxygenation of the Ag subsurface region was suggested to be responsible for the very different selectivities observed in ethylene and propylene epoxidation. As mentioned earlier, the silver catalysts used for propylene epoxidation are usually supported on low surface area materials such as CaCO3. In our previous work [19], silver catalysts supported on CaCO3 with different loadings were tested for propylene and ethylene epoxidation. It was found that propylene epoxidation at 473493 K was insensitive to silver particle size, while ethylene epoxidation was mildly structuresensitive. X-ray diffraction measurements of these silver catalysts showed that the bulk of the particles consist of metallic silver, but in situ ultravioletvisible (UVvis)
Table 1 O2 chemisorption uptakes on Ag catalysts on different supports Surface area categorya H M Catalystb Ag(56)/MgO Ag(56)/CaCO3(20)MgO Ag(10)/diamond Ag(56)/a-Al2O3 Ag(56)/CeO2 Ag(56)/CaCO3(20)a-Al2O3 Ag(10)/SiC Ag(56)/SiC Ag(10)/CaCO3 Ag(56)/CaCO3 (IM) Ag(56)/CaCO3 Ag(56)/CaCO3 c H-high, M-medium, L-low. Number in parentheses indicates wt.%. Sample ball-milled for 4 h.

spectroscopy showed that, in addition to a metallic component, small particles had silver in a Ag+ state. Aside from the systems described above, few supports have been studied for PO production. This paper reports the results of a broad exploration of different supports (CaCO3, a-Al2O3, MgO, SiC, diamond, CeO2) on the propylene epoxidation and the nding that CaCO3 and a-Al2O3 are the most effective supports. The investigation also covers different additives and promoters that have been reported to be effective in the literature and characterization of samples by UVvis spectroscopy. It is found that active PO catalysts have strong plasmon resonances and a combination of Ag and Ag+ signals. Special attention is placed on studying the role of chlorine, as it is broadly used and appears to be the most effective additive. 2. Experimental 2.1. Catalyst preparation The chemicals used for catalyst preparation were ethylene diamine (WAKO, 99.0%), oxalic acid (WAKO, 98.0%), silver oxide (WAKO, 99.0%), ethanol amine (WAKO, 99.0%), CaCO3 (WAKO, 99.5%), K2CO3 (WAKO, 99.5%), ammonium molybdate (WAKO, 99.0%), NaCl (WAKO, 99.9%), RhCl3xH2O (Rare Metallic Co. Ltd., 99.9%), Ba(NO3)2 (Kishida Chemical, 99.0%), Ce(NO3)3 (Chameleon reagent, 98.0%), KCl (WAKO, 99.9%), Cu(NO3)2 (WAKO, 99.9%), (NH4)2IrCl6 (WAKO, assay in Ir 4246%), Ca(NO3)2 (WAKO, 98.5%), diamond (Aldrich, 99.9%), SiC (Strem Chemical, 99.9%), a-Al2O3 (Sumitomo Chemical, 99.5%), MgO (WAKO, 99.9%, 0.01 mm) and CeO2 (WAKO, 99.9%). Surface areas of the supports are listed in Table 1. A modied support consisting of 20 wt.% CaCO3 supported on MgO, denoted CaCO3(20) MgO, was prepared by impregnating the requisite amount of Ca(NO3)2 on the MgO, drying at 393 K (120 8C) for 12 h, and then treating with CO2 at 773 K (500 8C) for 5 h. A typical promoted Ag/CaCO3 catalyst was prepared as follows, using a method similar to that reported by ARCO [8].

Specic area of support (m2 g1) 123 65 6.4 4.8 4.4 0.1 0.7

O2 uptake (mmol g1) 23.47 8.56 5.63 6.03 9.80 7.87 0.55 0.29 1.01 0.10 4.71 5.30

Metallic surface area (m2 g1) 2.478 0.904 0.594 0.637 1.035 0.831 0.058 0.031 0.107 0.011 0.497 0.559

Dchem. (nm) 148 406 110 576 355 452 1135 12000 613 33100 738 656

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Here and elsewhere, the number in parentheses refers to the weight loading of silver or promoter on the catalyst. For a Ag(56)NaCl(1)/CaCO3 sample an amount of 15 g (250 mmol) of ethylene diamine was dissolved in 20 g of distilled deionized H2O. Then 10.1 g (112 mmol) of oxalic acid and 8.9 g (38.4 mmol) of Ag2O were slowly added under magnetic stirring until completely dissolved. After 1 h stirring, 1.8 g (29.5 mmol) of ethanolamine and 147 mg (2.51 mmol) of NaCl dissolved in 4 ml H2O were added to the solution and the mixture was stirred for another 1 h. Then 6.4 g (64 mmol) of CaCO3 was added to the solution to form a slurry. For un-ballmilled samples, the slurry was stirred for 4 h, dried at 393 K (120 8C) for 2 h, and nally calcined at 633 K (360 8C) for 3 h. Samples with other silver loadings, promoters or supports were prepared in a similar manner. For ball-milled samples, the slurry was transferred to a stainless steel milling machine (Fritsch, Model pulverisette 6) with 30 milling balls and milled for 4 h. The milled sample was then dried at 393 K (120 8C) for 2 h and calcined at 633 K (360 8C) for 3 h. An Ag(56)/ CaCO3(IM) sample was prepared by impregnating AgNO3 on the CaCO3, followed by drying at 393 K (120 8C) for 12 h and calcination at 633 K (360 8C) for 3 h. In the designation, Ag(56)/CaCO3 (IM), the number in parentheses again indicates the Ag loading in wt.%, and IM refers to impregnation. 2.2. Catalytic testing The propylene epoxidation reaction was carried out in a quartz tubular microreactor of 6 mm diameter and 180 mm length using 0.5 g catalyst of 2040 mesh size diluted with quartz sand of the same mesh size to a volume of 1 cm3. Flow rates of He (Joban Helium Supply, purity >99.9%), O2 (Hitachi Sanso, purity >99.5%) and C3H6 (Takachiho Chemical, purity >99.8%) were respectively regulated at 15, 10 and 5 cm3 min1 by mass ow meters, and the reaction pressure was set at 0.3 MPa with a back pressure regulator. Before reaction, the catalysts were pretreated with He (15 cm3 min1) at 423 K (150 8C) for 1 h. Reaction products were analyzed online using two gas chromatographs (Shimazu GC-14). Each was equipped with a ame ionization detector (FID) and a thermal conductivity detector (TCD). One had an FFAP capillary column (0.32 mm 60 m) and a Porapak Q compact column (3 mm 2 m). The other had an MS-5A 60/ 80 compact column (3 mm 2 m) and a Gaskuropak 54 84/100 compact column (3 mm 2 m). The FFAP capillary column and Porapak Q column were used to detect oxygenates (acetaldehyde, PO, acetone, propionaldehyde, acrolein, acetic acid and isopropanol) and CO2, respectively, while the MS-5A and Gaskuropak 54 84/100 were used to detect CO and hydrocarbons (propane, propylene, ethylene and ethane), respectively. Carbon balances were 100 3%. Turnover frequencies (TOF) were calculated based on surface metal sites counted by oxygen chemisorption. 2.3. Characterization X-ray diffraction patterns of samples were obtained with an X-ray diffractometer (Rigaku, RINT2000) operated at 40 kV

and 40 mA using Cu Ka monochromatized radiation (l = 0.154178 nm). Field emission scanning electron microscopy (FESEM) images of the samples were obtained in a microscope (LEO, Model 1550) operated at 15 kV. Energy dispersive spectroscopy results were obtained at 20 kV. Surface areas and oxygen uptakes reported in Table 1 were measured in a volumetric adsorption unit (Micromeritics ASAP 2020). For the chemisorption measurements, the samples were heated in owing O2 for 1 h, evacuated for 0.5 h, reduced in owing H2 for 1 h, evacuated to <1.3 mPa (10 mmHg) for 0.5 h, and dosed with O2, all at 443 K (170 8C). Silver particle size was calculated from the O2 chemisorption uptake, based on an adsorption stoichiometry of Oad/Ags = 1, where Ags represents a surface Ag atom. Dispersion for the silver samples was calculated by dividing the number of chemisorbed O atoms by the total number of Ag atoms [20 22]. If spherical Ag crystallites are assumed, the relationship between crystallite size and dispersion, D, is d (nm) = 1.34/D [23,24]. The metallic surface area was calculated according to the equation: S.A. (m2 g1) = (O2 uptake 2 106 NA)/ 1.14 1019, where NA is Avogadros constant and 1.14 1019 m2 is the surface density of silver atoms averaged for the three low index planes (1 0 0), (1 1 0) and (1 1 1). NH3 temperature programmed desorption (TPD) characterization of the supports was carried out in a ow system (BEL Japan). UVvis spectra were collected with a large compartment spectrometer (Varian Cary 5000) using a reaction chamber (Harrick Scientic, Model HVC-DRP) equipped with a praying mantis diffuse reectance attachment (DRP-XXX). Ex situ spectra were taken at room conditions (air, 298 K, 0.1 MPa) without sample pretreatment. In situ measurements were obtained after pretreatment of the catalysts in the same manner as in the reactivity studies using a pressure of 0.3 MPa, a He ow rate of 15 cm3 min1 and a temperature of 423 K (150 8C) for 1 h. After cooling to room temperature, the ow was switched to a mixture of reaction gases (C3H6 = 5 cm3 min1, O2 = 10 cm3 min1, He = 15 cm3 min1), again as used in the reactivity studies. The reaction temperature was then raised to 533 K (260 8C) at a rate of 0.17 K s1 (10 K min1) and spectra were recorded at different reaction times over the range 200 800 nm with a scan rate of 200 nm min1, an average time of 0.5 s, and a data interval of 0.333 nm. For ex situ measurements, spectra were referenced to the respective supports; for in situ measurements, spectra were referenced to CaCO3 under the same reaction conditions. Diffuse reectance spectra were analyzed using the Kubelka-Munk function, F(Ra), calculated from the absorbance data [25]. 3. Results Table 1 summarizes specic surface area and O2 chemisorption results for the different supported Ag catalysts. The supports were divided into three groups depending on the specic surface areas: high (H), medium (M) and low (L) of the supports. The O2 uptakes roughly tracked with the surface areas of the supports. However, there were exceptions; notably,

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Table 2 Propylene epoxidation over supported Ag catalysts Surface area category Catalyst Propylene conversion (%) TOF (s1) Total (10 ) H M Ag(56)/MgO Ag(56)/CaCO3(20)MgO Ag(10)/diamond Ag(56)/CeO2 Ag(56)/a-Al2O3 Ag(56)/CaCO3(20)a-Al2O3 Ag(10)/SiC Ag(56)/SiC Ag(10)/CaCO3 Ag(56)/CaCO3(IM) Ag(56)/CaCO3 Ag(56)/CaCO3 a 49.4 4.6 6.9 21.8 19.6 16.7 0.1 0.1 4.5 0.1 14.2 11.2 7.89 2.01 4.59 8.33 12.2 7.95 0.27 8.34 16.6 11.8 11.3 7.92
2

Selectivity (%) PO formation (10 ) 2.37 2.41 12.9 4.17 63.3 42.9 0 0 58.2 0 37.2 43.6
4

PO 0.3 1.2 2.8 0.5 5.2 5.4 0 0 3.5 0 3.3 5.5

Acrolein 0 0 0 0 0 0 0 0 0 0 0 0

Reaction temperature = 493 K (220 8C). a Sample ball-milled for 4 h. Reaction temperature = 453 K (180 8C).

Ag(56)/CeO2 on a medium surface area support had a high O2 uptake of 9.80 mmol g1. The O2 uptake also changed depending on the preparation method. For example, Ag(56)/ CaCO3 prepared by impregnating the Ca(NO3)2 precursor solution with CaCO3 gave an O2 uptake of 0.11 mmol g1, while the un-ball-milled and ball-milled Ag(56)/CaCO3 samples gave O2 uptakes of 4.71 and 5.30 mmol g1, respectively. The particle size calculated from the O2 uptake for a silver loading of 56 wt.% depended drastically on the support, ranging from 148 nm for Ag(56)/MgO to 33 mm for Ag(56)/CaCO3 (IM). The acidity of the supports measured by NH3-TPD was CaCO3 (0) = SiC (0) < diamond (0.3) < aAl2O3 (0.8) < MgO (1). Numbers in parentheses indicate the relative NH3 desorption amounts corrected for the surface area of the supports. Table 2 lists propylene epoxidation results on the various supported Ag catalysts. PO was the only organic product in the reaction and the only additional products were CO2 and H2O. The reactivity depended strongly on the support. For Ag on high surface area supports such as MgO, a medium turnover frequency (TOF) for total reaction of 7.89 102 s1 and a low PO selectivity of 0.3% were obtained. For Ag on medium surface area supports, the catalysts showed somewhat higher TOFs and higher selectivities, notably for the a-Al2O3 supported sample, which had a total TOF of 1.22 101 s1 at a PO selectivity of 5.2%. The CeO2-supported catalyst, however, gave low selectivity. For Ag on low surface area supports, the catalysts showed different performances. Ag supported on SiC was almost inactive, while the Ag(56)/CaCO3 catalyst gave a high total TOF of 1.13 101 s1 and a relatively moderate PO selectivity of 3.3%. Different results were obtained on the Ag(56)/CaCO3 catalysts prepared by the different methods. The Ag(56)/CaCO3 (IM) prepared by the impregnation method was almost inactive, while the Ag(56)/ CaCO3 catalyst prepared by the typical ethylene diamine method gave the results reported above. The ball-milled Ag(56)/CaCO3 catalyst gave a medium total TOF of 7.92 102 s1 and a relatively high PO selectivity of 5.5%. In general, all the unpromoted catalysts gave poor PO

selectivities of less than 6%, although the Ag(56)/CaCO3 and Ag(56)/a-Al2O3 samples gave the best performance. In order to determine the effects of promoters, we tried various salts as additives for the Ag catalysts; the results are listed in Table 3. The table is divided into two sections. The top portion shows catalysts with lower selectivity for PO than the base case of Ag(56)/CaCO3 (Table 2) which gave 5.5% PO selectivity at 11.2% propylene conversion. The bottom portion shows catalysts with higher PO selectivity. It was found that promoters such as MoO3, CuO (Cu(NO3)2 as precursor), Ce(NO3)3 and Ba(NO3)2 gave rise to an increase in conversion, but did not improve selectivity. Substances like K2CO3, Rh (RhCl3 as precursor) and Ir ((NH4)2IrCl6 as precursor) gave a negative effect compared to the unpromoted catalyst. In contrast, catalysts promoted with NaCl and KCl showed enhanced PO selectivities. Particularly, catalysts promoted with NaCl showed high PO selectivities, albeit at the expense of
Table 3 Propylene epoxidation over supported Ag catalysts with different promoters Catalyst Propylene conversion (%) 46.3 41.8 20.8 17.5 5.1 4.4 3.9 2.9 1.0 1.4 3.3 4.4 1.4 3.2 1.6 1.7 Selectivity (%) PO 4.8 2.5 3.6 4.2 2.8 3.6 3.9 0 0 39.2 30.4 30.1 15.3 13.4 7.5 5.2 Acrolein 0 0 0 0 0.3 0 0 27.9 22.7 0 0 0 0 0 0 0

Ag(14)MoO3(1)/CaCO3 Ag(56)Cu(0.04)/CaCO3 Ag(56)Ce(NO3)3(1)/CaCO3 Ag(56)Ba(NO3)2(1)/CaCO3 Ag(56)Ir(0.12)/CaCO3 Ag(56)K2CO3(1)/CaCO3 Ag(14)K2CO3(1)/CaCO3 Ag(56)Ir(0.12)/CaCO3 a Ag(14)RhCl3(1)/CaCO3 Ag(56)NaCl(1)/CaCO3 Ag(56)NaCl(1)/CaCO3(5)a-Al2O3 Ag(56)NaCl(1)/a-Al2O3 Ag(56)KCl(1)/CaCO3 Ag(56)NaCl(1)/CeO2 Ag(14)NaCl(1)/CaCO3 Ag(56)NaCl(1)/SiC

Reaction temperature = 533 K (260 8C). a Prior to reaction, the catalyst was reduced in 20 mol% H2 in He at 623 K (350 8C) for 2 h.

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Fig. 1. Propylene epoxidation on Ag(56)NaCl(x)/CaCO3 catalysts. Temperature = 533 K (260 8C).

propylene conversion. The silver catalysts promoted with 1 wt.% NaCl on the different supports showed different activities. The PO selectivity followed the order: CaCO3 > CaCO3(5)a-Al2O3 > a-Al2O3 > CeO2 > SiC, with the propylene conversion in the same range (<5%). Fig. 1 presents the effect of NaCl loading on the catalytic performance of the Ag(56)/CaCO3 catalyst. It can be seen that the unpromoted Ag(56)/CaCO3 catalyst had very high propylene conversion (60%), but low PO selectivity (<2%). Addition of NaCl to the catalyst resulted in a dramatic decline in propylene conversion (from 60 to 13%) and a substantial increase in PO selectivity (>20%). The PO selectivity passed through a maximum (40%) at a NaCl loading of 1 wt.%, then decreased with further addition of NaCl. Fig. 2 presents the XRD patterns of the Ag(56)NaCl(x)/ CaCO3 samples. For the unpromoted sample, Ag and CaCO3 were the only visible phases. For the NaCl promoted samples, peaks due to AgCl were observed in addition to the Ag and CaCO3 peaks. The intensities of the AgCl peaks became stronger and sharper with increasing NaCl loading. Fig. 3 presents the SEM images, energy dispersive spectroscopy (EDS) results and silver particle size distributions of the Ag(56)/CaCO3 (Fig. 3 (a)(c)) and the Ag(56)NaCl(1)/ CaCO3 (Fig. 3 (d)(f)) catalysts. The details of the EDS results are summarized in Table 4. The addition of NaCl increased the size of the silver particles. For the Ag(56)/CaCO3 sample, the maximum in the distribution was at 370 nm, while for the
Table 4 Energy dispersion spectroscopy results for the Ag samples (atomic percent) Element Ag(56)/CaCO3 Location 1 Ag Ca C O Na Cl 0.5 29.2 4.6 65.7 Location 2 87.0 4.0 2.0 7.0

Fig. 2. XRD patterns of Ag(56)NaCl(x)/CaCO3 catalysts.

Ag(56)NaCl(1)/CaCO3 sample, the maximum was at 800 nm. It is clear that for the unpromoted catalyst the silver particles have diverse shapes and a broad particle size, while with the addition of NaCl the silver particles become more regular in shape and the particle size distribution is shifted to larger values. Following the work reported by ARCO workers, catalysts were ball-milled to get uniform Ag particle distributions [8]. Ball-milling is an unusual procedure and it was desired to investigate the effect of ball-milling on the catalytic

Ag(56)NaCl(1)/CaCO3 Location 3 1.7 10.5 38.6 49.3 Location 1 0.6 19.9 11.8 67.7 0.06 0.03 Location 2 98.5 0 0 0.6 0.9 0.9 Location 3 2.6 16.1 24.6 56.4 0.2 0.2

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Fig. 3. Field emission scanning electron microscopy (FESEM) images, energy dispersive spectroscopy and particle size distributions of Ag(56)/CaCO3 catalysts. (a) (c) Ag(56)/CaCO3 ball-milled for 4 h; (d)(f) Ag(56)NaCl(1)/CaCO3 ball-milled for 12 h.

performance. Fig. 4 presents the results of epoxidation on Ag(56)NaCl(1)/CaCO3 with different ball-milling times. Compared to the un-ball-milled sample, the most pronounced effect for ball-milled samples was an enhancement in propylene conversion. The propylene conversion increased from less than 2% for the un-ball-milled sample to about 4% for the 12 h ballmilled sample, probably as a result of higher exposed silver area. A longer milling time of 48 h led to a decline in propylene conversion. All the samples showed similar initial PO selectivities, but then the PO selectivities declined with time

on stream. However, the decline was much slower for the 12 h ball-milled sample than for the un-ball-milled sample. Fig. 5 shows the effect of addition of the gas phase chlorine compound ethyl chloride (C2H5Cl) on propylene epoxidation. When 500 ppm C2H5Cl was co-fed in the gas stream, the stability of the catalyst was slightly enhanced. Unfortunately, attempts to make the catalyst stable by increasing the chlorine content in the feedstock were unsuccessful. Further increase in the chlorine content up to 1000 ppm resulted in a decline in both activity and selectivity.

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Fig. 4. Propylene epoxidation on Ag(56)NaCl(1)/CaCO3 catalysts with different milling time. Temperature = 533 K (260 8C).

Fig. 5. Effect of chlorine on propylene epoxidation on Ag(56)NaCl(1)/CaCO3 catalyst ball-milled for 12 h. Temperature = 533 K (260 8C).

Fig. 6 shows the UVvis spectra taken at ambient conditions of the umpromoted silver samples listed in Table 2, categorized as in the table by surface area (H, M, L). Different samples had prominent features in different energy regions. Three main features were observed: at low energies (2.43.7 eV) silver plasmon resonances, at intermediate energies (3.84.6 eV) Ag0 band transitions, and at high energies (5.46.2 eV) Ag+ band transitions [26]. Fig. 7 presents the UVvis spectra of the promoted silver samples listed in Table 3. Again, three main features are seen in different energy ranges, with different samples showing enhancement in different ranges. Fig. 8 presents the UVvis spectra for Ag(56)NaCl(x)/ CaCO3 catalysts with a NaCl loading of 06 wt.%. For the unpromoted catalyst, the plasmon resonance showed a broad asymmetric peak centered at 3.2 eV. With increase of NaCl content, the plasmon resonances became weaker and appeared to split into two regions, with a symmetric feature at around 2.9 eV and a small indistinct signal centered at 3.4 eV. Meanwhile, the intensities due to the Ag+ band transitions increased with the NaCl loading. Fig. 9 presents the UVvis spectra for the Ag(56)NaCl(1)/ CaCO3 catalysts with different ball-milling times. It is clear that the un-ball-milled sample had stronger peak intensity for Ag+ band transitions. Peak intensities for Ag+ band transitions were

similar for the samples ball-milled for 4, 12 and 48 h, respectively. Fig. 10 presents the in situ UVvis spectra for the 12 h ballmilled Ag(56)NaCl(1)/CaCO3 catalyst with time on stream at 533 K (260 8C) and 0.3 MPa in C3H6/O2/He. During the reaction, the most noticeable change in the catalyst surface detected by UVvis spectroscopy was the quick reduction of the peak due to Ag+ band transitions, which occurred rapidly up to 3 h on stream and was complete after 5 h. 4. Discussion In this work, high loading silver catalysts on different supports were prepared and employed for direct propylene epoxidation with molecular oxygen as the oxidant. A summary of the catalysts is provided in Table 1. The supports were chosen because of their potentially favorable properties in epoxidation reactions. An obvious choice was a-Al2O3 because of its use in ethylene epoxidation. Epoxides are relatively unstable and can undergo ring opening through acid- and basecatalyzed reactions [27]. Supports that do not have acidic or basic sites like SiC or diamond were of potential interest. Moreover, mildly basic oxides like CaCO3 had been reported to be effective, so MgO and CaCO3 supported on MgO were also investigated. Finally, CeO2 was tried because of its known

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Fig. 6. UVvis diffuse reectance spectra of unpromoted Ag catalysts at room conditions.(A) (a) Ag(56)/MgO, (b) Ag(56)/CaCO3(20)MgO, (c) Ag(10)/diamond, (d) Ag(56)/a-Al2O3, (e) Ag(56)/CaCO3(20)a-Al2O3. (B) (a) Ag(56)/CeO2, (b) Ag(56)/SiC, (c) Ag(10)/SiC, (d) Ag(10)/CaCO3, (e) Ag(56)/CaCO3, (f) Ag(56)/ CaCO3 ball-milled for 4 h, (g) Ag(56)/CaCO3 (IM).

Fig. 7. UVvis diffuse reectance spectra of promoted Ag catalysts at room conditions. (A) (a) Ag(14)MoO3(1)/CaCO3, (b) Ag(56)Cu(0.04)/CaCO3, (c) Ag(56) Ba(NO3)2(1)/CaCO3, (d) Ag(56)Ce(NO3)3(1)/CaCO3, (e) Ag(56)Ir(0.12)/CaCO3, (f) Ag(56)K2CO3(1)/CaCO3, (g) Ag(14)K2CO3(1)/CaCO3. (B) (a) Ag(56) NaCl(1)/CaCO3, (b) Ag(56)NaCl(1)/CaCO3(5)a-Al2O3, (c) Ag(56)NaCl(1)/a-Al2O3, (d) Ag(56)KCl(1)/CaCO3, (e) Ag(14)NaCl(1)/CaCO3, (f) Ag(56) NaCl(1)/CeO2, (g) Ag(56)NaCl(1)/SiC.

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Fig. 8. UVvis diffuse reectance spectra of un-ball-milled Ag(56)NaCl(x)/ CaCO3 catalysts at room conditions.

Fig. 10. In situ UVvis diffuse reectance spectra of the 12 h ball-milled Ag(56)NaCl(1)/CaCO3 catalyst with time on stream at 533 K and 0.3 MPa in C3H6/O2/He.

ability to store and release oxygen [28,29]. The supports could be roughly categorized according to their surface areas (Table 1). The O2 chemisorption uptakes and the silver particle sizes calculated from the uptakes tracked roughly with the surface area values (Table 1). The silver particle sizes had an inverse relation with the surface area, as expected due to better silver particle dispersion on the high surface area supports. The silver particle size also changed with the preparation method. Samples prepared using a complexation method (silver ethylene diamine) gave a silver particle size of 738 nm, while a sample that underwent ball-milling gave an even smaller silver particle size of 656 nm. This indicates that one of the effects of ball-milling is to give better silver particle dispersions.

Fig. 9. UVvis diffuse reectance spectra of Ag(56)NaCl(1)/CaCO3 catalysts ball-milled for different times at room conditions.

The various supported catalysts were tested for propylene epoxidation and the results are summarized in Table 2. The selectivities to PO are low, which is typical for unpromoted catalysts. It can be seen that the TOF for total reaction does not change much, which is probably because the total oxidation reaction occurs readily, while the TOF for PO formation changes almost 30-fold, from 2.37 104 to 6.33 103 s1. High TOF values for PO formation were obtained on catalysts supported on CaCO3 and a-Al2O3, while low TOF values were obtained on catalysts supported on MgO and CeO2. Considering that the silver particle sizes on MgO and CeO2 are 148 and 355 nm, respectively, while the silver particle sizes on CaCO3 and a-Al2O3 are 738 and 576 nm, respectively, the difference in TOF values implies that large silver particles are favorable for PO formation. This may be due to the stabilization of oxygen in low index planes, as suggested by Lambert [17]. However, considering that the PO selectivity is low on all supports and the changes in the structure of the catalysts are not large because of the limited size range, a rm conclusion cannot be reached. Moreover, the supports might also participate in the reaction. This may be the reason for the poor performance of the diamond and SiC supports. Although these materials are covalent solids and are not expected to have high intrinsic acidity or basicity, in fact, their surfaces are likely to be oxidized and the resulting functional groups could be active in decomposing PO. Pitchai et al. [30] found that the activity and selectivity of supported silver catalysts in ethylene epoxidation and combustion strongly depended on the carrier employed. All the supports they used (TiO2, Nb2O3, V2O5, SiO2, ZrO2 and SiC) except for a-Al2O3 were found to exhibit signicant activity in EO isomerization and oxidation. CaCO3 has been shown to be ineffective for the further conversion of PO to unwanted products [18], which is consistent with the nding that it gives high PO selectivity. Our results support the ndings that a-Al2O3 and CaCO3 are suitable supports for silver catalysts for propylene epoxidation.

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Various promoters were employed to investigate their effect on the catalytic performance in propylene epoxidation and the results are shown in Table 3. It is interesting that precious metals such as Rh and Ir only produce acrolein instead of PO. This result is similar to the results of Geneen et al. [31]. They found that for AgAu alloy surfaces that were rich in gold, C3H6 was selectively oxidized to acrolein and PO was produced only in trace amounts. Senkan et al. [32] investigated various metals for propylene epoxidation using a combinatorial method and reported that Rh and its combination with other metals were effective for PO formation and Ir was effective for acetone formation. In the present work, the main product on Rh was found to be acrolein. The discrepancy may be due to the method of analysis in the previous study [32] using mass spectrometry; it is difcult using this method to distinguish among PO, acrolein and acetone, because of their similar fragmentation patterns. Compounds such as K2CO3 [8,17] and MoO3 [15,16] have been reported as effective promoters for propylene epoxidation. Reduced Cu catalysts were also reported to be effective in both propylene epoxidation [33] and styrene and butadiene epoxidation [34]. Lambert et al. [34] reported extremely high selective epoxidation of styrene and butadiene on Cs-promoted Cu(1 1 1). However, Monnier et al. [35] compared butadiene epoxidation on Cu and Ag catalysts and concluded that butadiene epoxidation on Cu(1 1 1) was a Cumediated, substoichiometric reaction between adsorbed butadiene and adsorbed oxygen. This conclusion arose from the facts that, under typical reaction conditions, the metallic Cu0 surface could be easily oxidized to Cu2O by the epoxide and that the stable Cu2O phase was inactive for epoxidation. However, the promoters did not show any positive effect in the present studies, partly due to the different catalyst preparation methods. The MoO3 promotion results of the group of Lu [15,16] may have been due to the different product analysis system. Among all the promoters, NaCl was found to be the most effective (Table 3), as found previously [14]. The effect of NaCl on conversion and selectivity is dramatic (Fig. 1). Addition of just 0.2 wt.% NaCl to Ag(56)/CaCO3 lowered conversion from 60% to 5% and increased PO selectivity from 2% to 13%. The highest selectivity was obtained with a NaCl content of 1 wt.% (Fig. 1). XRD results (Fig. 2) show the presence of AgCl crystallites, with the content of AgCl increasing with the NaCl loading level. Considering that propylene conversion dramatically declined while PO selectivity rose with NaCl loading, it is reasonable to deduce that the presence of AgCl effectively suppressed the total oxidation pathway. It is already known that preadsorption of chlorine signicantly reduces the amount of oxygen adsorbed on the Ag surface [36], which leads to a decrease in the activity. The enhancing effect of chlorine for ethylene epoxidation has been studied in depth [3741] and the effect is thought to be electronic [42]. Alkali ions such as Na+ probably enhance the bond strength of chlorine to silver [4345]. Lambert et al. [18] found that promotion of Ag by K enhanced the PO selectivity. The right combination of chlorine and sodium can lead to the stabilization of a silver-oxychloride surface complex and thus

to higher coverages of weakly bound oxygen, which favors epoxidation, and lower coverages of strongly bound oxygen, which favors complete oxidation [46]. Therefore, the effect of NaCl on the catalytic performance could be due to changes in the electronic properties of the catalyst surface, inducing the adsorbed oxygen species to be more electrophilic by depleting the valence charge density on oxygen adatoms, thus favoring Oinsertion into the C C bond rather than CH cleavage and combustion. However, excessive amounts of AgCl on the surface will block the active sites [47,48], leading to a decrease in activity, while excessive amounts of alkali will increase the isomerization of the epoxide [49,50]. A nding in this study is that NaCl also has an effect on the morphology of the catalyst. Comparison of the SEM images of Ag(56)/CaCO3 and Ag(56)NaCl(1)/CaCO3 shows that the silver particles in the NaCl-containing samples are larger and more rounded (Fig. 3). This is conrmed in the particle size histograms, which show that the average particle size increases from 370 to 800 nm with the addition of NaCl. The texture of the catalyst is complicated. The high energy (20 kV) images used for the energy dispersive spectroscopy (EDS) measurements show a preponderance of structures (Fig. 3 (b) and (e)). The supports and the silver can be distinguished from their different contrast: the Ag appears bright, while the CaCO3 appears dull. For example, in the Ag(56)/CaCO3 sample the large cubic particle labeled 1 consists mainly of CaCO3, while the shiny particle labeled 2 is made up mostly of Ag (Table 4). The crystal habit of CaCO3 is cubic and matches the observed morphology. The gure also shows a third particle labeled 3, which seems to consist of an agglomerate of small CaCO3 particles, and is so conrmed by EDS. It should be mentioned that the accuracy of EDS is not high, and so considerable deviations are observed from the stoichiometric proportions expected for a compound like CaCO3. The EDS images of the Ag(56)NaCl(1)/CaCO3 sample (Fig. 3 (e)) also show that the silver particles are larger and more spherical in shape than those on the Ag(56)/CaCO3 sample. Analysis of the grayish particle labeled 1 reveals that it is mostly CaCO3 and analysis of the bright particle labeled 2 reveals that it is mostly Ag. Again the grainy material labeled 3 is shown to consist mostly of particles of CaCO3. The NaCl appears to be mostly associated with the silver particles, but is also detected on the CaCO3. It is likely that the NaCl promotes the growth of the Ag particles, perhaps by changing their surface free energy. The CaCO3-supported catalysts were prepared using a ballmilling procedure reported by ARCO researchers [8]. Ballmilling is a physical procedure by which particles in the mm range are broken up by the energy imparted in collisions with the grinding medium. The surface area of the Ag(56)NaCl(1)/ CaCO3 sample ball-milled for 12 h is 1.8 m2 g1, which is higher than the un-ball-milled sample (0.8 m2 g1). So the increase in conversion (Fig. 4) is due to an increase in surface area of the sample. The Ag(56)NaCl(1)/CaCO3 catalyst showed a slight decrease in PO selectivity with time (Fig. 4). This is probably related to a decrease in the concentration of the Ag+ species on

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the catalyst surface. There could be two forms of Ag+ species on the catalyst surface: Ag+ in Ag2O and Ag+ in AgCl. The former is due to the interaction of oxygen with the silver particles and the latter is due to the formation of AgCl during catalyst preparation, as evidenced by the XRD results (Fig. 2). Therefore, the decrease in the concentration of the Ag+ species involves the reduction of the surface Ag2O layer and the extraction of Cl from AgCl. The reduction of the surface Ag2O layer during reaction was reported in our previous work using in situ UVvis spectroscopy [19]. The loss of chlorine was found both in ethylene epoxidation [51] and in butadiene epoxidation [5254]. Monnier et al. [54] studied epoxidation of butadiene on a Ag(12)/a-Al2O3 catalyst promoted with 235 ppm Cl (CsCl as precursor) and found that the catalyst was unstable during the reaction and went through a thermal runaway without any chlorine present in the feedstream. They suggested that the thermal runaway was most likely due to the loss of surface Cl stripped by the epoxide, resulting in total combustion. Improvement of catalyst stability by the addition of organic chlorine as a co-feed gas during the reaction is well known in both ethylene [3741] and butadiene epoxidation [5254]. In the present case, the addition of 500 ppm of C2H5Cl (EtCl) did improve the PO selectivity compared to the reaction without C2H5Cl (Fig. 5). However, the improvement was small and is possibly due to the loss of Cl during the reaction, even when 500 ppm C2H5Cl was added. Since the reactivity between chlorine and the silver surface follows the trend: 1, 2dichloroethane (DCE) > 2-chlorobutane (2-CB) > 2-chloropropane (2-P) > ethyl chloride (EtCl) > vinyl chloride (VCl) > CHCl3 > CH2Cl2 [54], it is possible that the interaction between C2H5Cl and silver is not strong enough to form sufcient surface Cl species during the reaction. UVvis spectroscopy was employed to characterize the various catalysts in order to determine if there were features that could be used to distinguish between effective and ineffective PO catalysts. Fig. 6 presents the spectra for unpromoted silver catalysts categorized according to surface area. All samples show to various degrees features characteristic of different states of silver. At low energies (2.43.7 eV) are observed bands due to silver plasmon resonances, at intermediate energies (3.84.6 eV) are observed Ag0 band transitions, and at high energies (5.46.2 eV) are measured Ag+ transitions [26]. Plasmons are collective oscillations of conduction electrons in small metallic particles and give information about particle size and shape. Band transitions are due to excitations from occupied to unoccupied states and are characteristic of metallic and ionic states of silver. The high surface area materials (H) (Fig. 6 A (a) and (b)) show prominent plasmon resonances of a symmetric shape at 3.3 eV and, well developed Ag0 edges at 4 eV, and downward sloping intensity in the Ag0, Ag+ interband transition plateau at 45.5 eV. This is characteristic of well-dispersed metallic silver particles with little ionic contribution. The medium surface area materials (M) (Fig. 6 A (c)(e)) show diminished plasmon features shifted to 3.5 eV with less symmetric shapes, and again well-dened Ag0 edges and a downward sloping interband plateau. The diamondsupported sample alone has a strong feature at 2 eV, which can

be ascribed to aggregated silver particles [55]. The spectral features in these samples again indicate the presence of metallic silver particles, but the asymmetry in the plasmon region suggests that the particles are larger and more irregular in shape. The medium and low surface area materials supported on CeO2 and SiC (Fig. 6B (a)(c)) show no plasmon features and a very sharp Ag0 peak at 4 eV. This is characteristic of very large metallic silver particles. The samples supported on CaCO3 (Fig. 6B (d)(f)) show prominent plasmon features of asymmetric shape, strong Ag0 edges and a well developed plateau with a rising trailing edge at 5.4 eV. These spectral features in the samples indicate the presence of moderately large metallic particles with substantial Ag+ content. Finally, the sample of Ag/CaCO3 prepared by impregnation (Fig. 6B (g)) shows a single strong feature at 5.2 eV, indicating that the silver in this case is highly oxidized. Overall, the UVvis spectra indicate that catalysts that are most active for PO production, i.e. the Ag/CaCO3 samples, have strong intensity in all regions of the spectrum. These samples display well developed plasmon resonances indicating moderately sized silver particles and also strong interband features indicating both metallic and ionic silver. The less active catalysts tend to have strong intensity in only one or two of the regions. Fig. 7 shows the UVvis spectra of the promoted catalysts. The left panel shows the catalysts with relatively low selectivity to PO. These are all Ag/CaCO3-based catalysts and actually some have performance comparable to those of the unpromoted samples. These Ag/CaCO3 samples all have the features noted earlier for effective catalysts, namely strong plasmon resonances and well dened interband transitions. However, close examination of the spectra reveal some subtle distinctions, especially in the interband plateau region. The Ir-promoted sample is unique in having a strong metallic adsorption edge at 4.0 eV and a steeply descending plateau with no signal from ionic silver (Fig. 7A (e)). This sample had zero PO selectivity and the lack of Ag+ signal strongly correlates with this characteristic. A number of other samples show strong metal edges followed by downward sloping plateaus, namely the Ce- and Ba-promoted samples (Fig. 7A (c) and (d)). These, however, also show strong Ag+ peaks and their selectivities are moderate. Other samples, like MoO3- and K2CO3-promoted samples (Fig. 7A (a) and (f)) also show strong Ag+ features with atter plateaus and moderate PO selectivities. For the Ag(14)MoO3(1)/CaCO3 sample, the adsorption band around 5.3 eV has been assigned to 3t2 2t1 transition in tetrahedrally coordinated [MoO4] species [56]. The low silver content sample Ag(14)K2CO3(1)/CaCO3 (Fig. 8A (g)) shows a at plateau region but with a low overall intensity compared to the plasmon feature. A at plateau appears to be the distinguishing feature for high selectivity PO catalysts like Ag(56)NaCl(1)/CaCO3 (Fig. 7B (a)) and Ag(56)NaCl(1)/ CaCO3(5)a-Al2O3 (Fig. 8B (b)). This can come with moderate or reduced (Fig. 7B (c)) intensity in the Ag+ region. When the Ag+ intensity is too high (Fig. 7B (d) and (e)) or low (Fig. 7B (f) and (g)), however, the PO selectivity is low. To summarize, the best catalysts appear to have moderate plasmon signals (2.5 3.5 eV), a strong and at interband region (45.2 eV) and moderate Ag+ signal (5.26.2 eV).

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Fig. 8 shows the UVvis spectra of Ag(56)/CaCO3 samples with different NaCl contents. Clearly, the Ag+ signal at 5.4 6.0 eV increases with addition of NaCl, indicating that at least some of the intensity is due to the presence of AgCl. This is consistent with the XRD results discussed earlier that showed the formation of AgCl. It was also shown that too much NaCl resulted in a reduction of activity due to blockage of Ag site. Another characteristic revealed by the UVvis results is that with increasing NaCl the plasmon resonance becomes more symmetric, indicating that the silver particles have a more regular shape [55,5759]. This nding is also conrmed by the SEM results (Fig. 3). The UVvis results on the fresh ball-milled catalysts (Fig. 9) indicate that the surface Ag+ concentration decreased after ballmilling. As discussed earlier, excessive amounts of AgCl on the surface will block the active sites, so the decrease of the surface Ag+ concentration will create more exposed active sites, which leads to the enhancement in activity. Therefore, the increase in catalytic performance of the ball-milled Ag(56)NaCl(1)/ CaCO3 catalysts is probably due to a redistribution of surface species during ball-milling. Fig. 10 shows the UVvis spectra of the Ag(56)NaCl(1)/ CaCO3 sample taken at in situ reaction conditions with the same reactant feed mixture as used in the reactivity determinations. The high temperature (533 K) results in changes in the spectral shapes compared to the spectra obtained at room temperature (Fig. 8B (a), Figs. 9 and 10). The largest difference is the change in shape in the plateau region from at to sharply downward sloping. The gure shows a series of spectra taken as a function of reaction time, which revealed a steady decrease in intensity of the high energy (5.2 6.2 eV) peak due to Ag+ over a period of 6 h. The decrease in the peak intensity is associated with the decline in PO selectivity and increase in activity (Fig. 5) with time as discussed earlier, this is probably related to loss of chloride from the active surface and a reduction of the silver. UVvis spectroscopy is thus helpful for studying catalysts at reaction conditions and to give information about the active and selective phase. In the case of Ag/CaCO3 catalyst, this has been shown to consist of moderate-sized silver particles with substantial content of Ag+. 5. Conclusions In conclusion, various supported silver catalysts were prepared for direct propylene epoxidation. It is found that the silver catalysts supported on high surface area supports such as MgO gave low TOF values for PO formation, while the silver catalysts supported on medium surface area supports such as aAl2O3 and low surface area supports such as CaCO3 gave high TOF values for PO formation. These results implied that large silver particles are favorable for PO formation. Various promoters such as alkali and precious metals were tried on the Ag(56)/CaCO3 catalyst, among which NaCl was found to be an effective promoter for propylene epoxidation. The Ag(56) NaCl(1)/CaCO3 sample ball-milled for 12 h gives 45% PO selectivity under certain reaction conditions. Formation of

AgCl in the catalyst was evidenced by XRD and UVvis results. The effect of NaCl on the catalytic performance is probably due to changes in the electronic properties of the catalyst surface, inducing the adsorbed oxygen species to be more electrophilic, which is favorable for the epoxidation. Furthermore, the addition of chlorine in the feedstock enhanced the stability of the catalyst. In situ UVvis spectra suggest that the rapid reduction of surface Ag+ species during reaction may be the cause of instability of the catalyst. Acknowledgements The authors are grateful for nancial support from the Ministry of Economy, Trade and Industry (METI, Minimum energy chemistry project) and the National Science Foundation under grant CTS-0321979. The FE-SEM was made possible by the National Science Foundation under grant 9975678. We also thank Steve McCartney for his assistance with the SEM images. References
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