Catalysis Communications 20 (2012) 611

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Catalysis Communications
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Short Communication

A highly dispersed nickel supported catalyst for dry reforming of methane

Xiangyu Lv a, Jian-Feng Chen a, b, 1, Yisheng Tan c, Yi Zhang a, b,
a b c

State Key Laboratory of OrganicInorganic Composites, Department of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China Research Centre of the Ministry of Education for High Gravity Engineering and Technology, Beijing University of Chemical Technology, Beijing 100029, China State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Science, Taiyuan, 030001, China

a r t i c l e

i n f o

a b s t r a c t
The modication of silica support using ethylene glycol (EG) signicantly modied surface properties of silica support, resulting in the decreased decomposition temperature of impregnated nickel nitrate and the enhanced metalsupport interaction. The catalyst prepared by modied silica support realized excellent stability and two times higher catalytic activity than the catalyst obtained from non modied silica support in dry reforming of CH4, since its highly dispersed supported nickel and strong nickelsilica interaction. The properties of silica supports, catalyst precursors and catalysts were characterized by TG-DSC, FT-IR, XRD, H2 chemisorption, O2 titration, TPR and TEM. 2012 Elsevier B.V. All rights reserved.

Article history: Received 7 December 2011 Received in revised form 5 January 2012 Accepted 7 January 2012 Available online xxxx Keywords: Reforming of methane Dispersion Nickel Silica Modication

1. Introduction During the past decade, there has been increasing global concern over the rise in carbon dioxide emissions from different sources into the atmosphere. Recently, there have been many attempts to reduce the concentration of CO2 and CH4 in the atmosphere through their utilization. Dry reforming of methane is of particular interest because it uses two greenhouse effect pollutant gases. Series of catalysts have been investigated for the dry reforming of methane [16], including supported noble metal catalysts such as Rh, Ru, and Ir [712], due to its high activity and stability. However, considering the limited resources, numerous researches focused on non-noble metal catalysts, particularly the developing of Ni-based catalysts [1315]. A large number of publications indicate that supported nickel catalysts exhibited high catalytic activity in dry reforming of methane. However, the greatest problem of nickel-based catalysts is the deactivation due to carbon deposition and Ni particle sintering [15]. The activity and stability of the Ni-based catalysts are affected by various factors, such as additives [10,11], the active component [16] and method of dealing with supports [14,17]. Generally, the nature of the support seriously affects the properties of catalysts via adjusting the interaction between the supported metal and support to reduce carbon deposition and metal sintering [18,19]. It is believed

that improving the dispersion of supported nickel and increasing the thermal stability of the Ni/SiO2 are the effective method. In the present work, the silica support was modied by ethylene glycol (EG) at room temperature before impregnation of nickel precursor. The results showed that the modied silica support signicantly enhanced the dispersion and interaction between the supported nickel and support, contributing to high activity and excellent coke resistance in dry reforming of methane.

2. Experimental Commercially available silica gel (pore volume 1.061 ml/g, pore diameter 6.7 nm, BET = 451 m 2/g) was used as support in this study. The silica gel was treated with ethylene glycol (EG) before the impregnation of Ni precursor, for 1 h at room temperature by incipientwetness impregnation method. And then, the samples were dried in air at 373 K for 12 h. The details of pretreatment were reported elsewhere [20]. Then the aqueous solution of nickel nitrate was impregnated onto pretreated silica support by incipient-wetness impregnation method. After that, the sample was dried over night at 373 K, following calcination at 673 K for 2 h. This catalyst was marked as Ni/SiO2-EG. As comparison, Ni/SiO2 was also prepared by the same method using non-pretreated silica support. The loading of nickel were 10 wt.% for all catalysts. The loading of nickel was determined by XRF, which are 9.83 wt.% for Ni/SiO2 and 9.76 wt.% for Ni/SiO2-EG. For characterization of reduced catalysts, the catalysts were passivated by 1% oxygen in nitrogen at room temperature to protect the reduced nickel after reduction.

Corresponding author at: State Key Laboratory of OrganicInorganic Composites, Department of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China. Tel.: +86 10 64447274; fax: +86 10 64423474. E-mail address: yizhang@mail.buct.edu.cn (Y. Zhang). 1 Tel.: + 86 10 64447274; fax: + 86 10 64423474. 1566-7367/$ see front matter 2012 Elsevier B.V. All rights reserved. doi:10.1016/j.catcom.2012.01.002

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C and Ni Ni C and Ni NiO C

d c
NiO NiO

b
NiO

a
50 60 70 80

20

30

40

2theta (degree)

Ni

Fig. 1. XRD patterns of passivated catalysts: (a) Ni/SiO2-EG; (b) Ni/SiO2, and two used catalysts: (c) Ni/SiO2-EG (d) Ni/SiO2. TEM images of two passivated catalysts: (e) Ni/SiO2-EG; (f) Ni/SiO2. TEM images of two used catalysts: (g) Ni/SiO2-EG; (h) Ni/SiO2.

An X-ray diffractometer (XRD, SHIMADZU XRD-6000) was used to detect supported nickel crystalline size of the passivated catalysts. The crystalline average size was calculated by L = K/(2)cos 0, where L is the crystalline size, K is a constant (K = 0.9), is the wavelength of X-ray (CuK = 0.154 nm), and (2) is the width of the peak at half height. TEM images of the passivated catalysts were determined by a Hitachi H-800 microscope. The specimen was prepared by ultrasonically suspending the catalyst powder in ethanol. A drop of the suspension was deposited on a carbon-enhanced copper grid and dried in air. Chemisorption experiments were carried out in a static volumetric glass high-vacuum system (Quantachrome Autosorb-1, Yuasa Ionics). Research grade gases (H2: 99.9995%) were used without further purication. Before adsorption of H2, the catalysts, which were previously reduced by H2 and passivated, were treated in H2 at 673 K for 1 h,

followed by evacuation. H2 adsorption isotherms were measured at room temperature. The dispersion and particle size of supported Ni were calculated by hydrogen chemisorption data.

Table 1 The various properties of two catalysts. Catalysts Dispersiona (%) 15.2 30.8 Reduction degreeb (%) 54.5 29.3 Particle size (nm) Haa 7.5 3.2 XRD 12 N.A. TEMc 17 3.8

Ni/SiO2 Ni/SiO2-EG

a Determined by hydrogen chemisorption; dispersion of reduced Ni particles: amount ratio of H2 consumption to O2 consumption, assuming H/Nisurface = 1 and total reduced Ni = 2 (O2 consumption). b Calculated by oxygen titration. c From TEM images of used catalysts.

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Temperature-programmed reduction (TPR) experiments were carried out in a quartz tube reactor using 0.2 g calcined catalysts. The reducing gas, a mixture of 5% H2 diluted by N2, was fed via a mass ow controller at 50 cm 3/min and the temperature was increased from 323 K until 1073 K at a rate of 8 K/min. The efuent of reactor passed through a 5 A molecular sieve trap to remove produced water, before reaching TCD. FT-IR spectra of pretreated silica support were collected on a Nexus 470 FT-IR spectrometer equipped with a diffuse reectance attachment and MCT detector. The dried pretreated-silica powder of 14 mg was contained in a cell with a ZnSe window. In-situ absorbance spectra were obtained using 32 scans at 2 cm 1 resolution. Before collection of spectra, the sample was treated in situ in a He stream owing at 50 ml/min at 393 K for 2 h. The spectra were obtained at room temperature under the He stream. The reduction degree of catalysts was determined by oxygen titration at 673 K using 2% O2 in nitrogen by pulse method. The passivated catalysts of about 0.1 g were re-reduced by hydrogen at 673 K for 1 h, and then the whole system was purged by helium stream of 25 cm3/min for 1 h in order to remove the hydrogen absorbed on the catalyst surface. The oxygen pulses were introduced into the reactor by a six-port valve to re-oxidize the catalysts at 673 K. The reduction degree was calculated by assuming stoichiometric conversion of metallic Ni to NiO, from the consumed oxygen of the pulses. Thermo gravimetric thermal analysis (TG-DSC) was carried out from 323 K and 1073 K at a heating rate of 10 K min 1 to determine the decomposition temperature of impregnated nickel nitrate and carbon deposition of used catalysts. The catalysts were tested using a xed-bed quartz reactor with an inner diameter of 10 mm. The 100 mg catalysts were loaded into reactor and reduced by hydrogen at 673 K for 10 h and then purged by N2. The dry reforming of methane reaction was carried out at 1023 K under atmospheric pressure (Ar/CH4/CO2 = 4/48/48, Ar is inner reference, GHSV = 21000 cm 3 g 1 h 1). The products were analyzed by on-line gas chromatograph equipped with a thermal conductivity detector (TCD). 3. Results and discussion The supported nickel particle size of two catalysts was detected by XRD. The XRD patterns of various passivated catalysts are shown

in Fig. 1a and b. The nickel peaks of Ni/SiO2-EG catalyst were too broad and weak to calculate the crystalline size. On the other hand, the Ni/SiO2 catalyst, prepared by non pretreated silica support, exhibits sharp and strong nickel peaks, and the crystalline size is 12 nm as compared in Table 1. The particle size of two catalysts was also determined by hydrogen chemisorption, as 3.2 nm for Ni/ SiO2-EG and 7.5 nm for Ni/SiO2 respectively. Fig. 1 also shows the TEM images of two supported catalysts. Ni/SiO2-EG catalyst exhibited remarkable smaller particle size and distributed homogeneously (Fig. 1e). However, for Ni/SiO2, larger support nickel oxide particle aggregated into even larger clusters on the silica surface (Fig. 1f). It is proved that the pretreated silica support by EG extremely enhanced the dispersion of supported nickel. It was reported that there were two kinds of silanol groups on silica surface, H-bonded SiOH and isolated (non-H-bonded) SiOH [21,22]. The supported metal species interacted with H-bonded SiOH resulting in large supported metal particle, and H-bonded SiOH was easier to be removed than isolated SiOH by calcination of silica support [23]. It is believed that the pretreatment of silica by EG adjusted the surface properties of silica support, contributing to formation of smaller supported nickel particle. The surface properties of pretreated silica support were determined by FT-IR. The FTIR spectra of two silica supports are shown in Fig. 2. As reported [24], the bond at 3743 cm 1 is the non-Hbonded O\H, and the broad band from 3700 cm 1 to 3200 cm 1 is the H-bonded O\H. As shown in Fig. 2, the O\H bands, both of non-H-bonded and H-bonded one, on the surface of pretreated silica signicantly decreased, however, C\H bands were detected, indicating that the pretreatment of silica supports by EG decreased the coverage of OHs and formed oxyls groups on surface of pretreated silica supports. On the other hand, for pretreated silica support, Si\OH band and Si\H band appears at 856 cm 1 and 628 cm 1, meanwhile, the Si\O\Si band (1085, 815, 505 cm 1) of pretreated silica become strong, indicating that pretreatment by EG signicantly modied surface properties of silica support. Because the supported metal species interacting with H-bonded SiOH formed large supported metal particle [23], the lower coverage of H-bonded SiOHs of pretreated silica could contribute to forming smaller supported nickel particle to realize high dispersion of supported nickel. On the other hand, EG pre-treatment of silica supports decreased the coverage of OHs and enhanced the Si\O\Si band of silica surface to increase

(2)

SiO 2

Si-OH bending
(1)

SiO 2 -EG

Si-H stretching C-H stretching OH C-H bending Si-O-Si symmetric stretching OH

Si-O-Si bending Si-O-Si asymmetric stretching

4000

3600

3200

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wavenumber (cm-1)
Fig. 2. FT-IR spectra for different SiO2 support: (1) EG pretreated SiO2 and (2) non pretreated SiO2.

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negative charge on the pretreated silica surface, contributing to increased supported nickel and silica interaction resulting in higher supported nickel dispersion [25]. From these ndings, it is proved that the pretreatment of silica support by EG signicantly improved the dispersion of the supported Ni. Generally, the dispersion of supported metal strongly depends on oxidative pretreatment of catalyst precursor. As reported [26], the signicantly higher cobalt dispersion is found in the catalyst prepared via low-temperature cobalt nitrate decomposition. In this study, the decomposition of impregnated nickel nitrate was studied by TG-DSC. The weight loss at low temperature (b 400 K) should be attributed to removing of water. As shown in Fig. 3A and B, there

are two exothermic peaks for both of two catalyst precursors when nickel nitrate was decomposed. For Ni/SiO2-EG catalyst precursor, the peaks locate at 480 K and 525 K, lower than that of Ni/SiO2 catalyst precursor as 530 K and 543 K. As reference, the EG pretreated silica support and non pretreated silica support were also detected by TG-DSC at the same conditions. As shown in Fig. 3C, the adsorbed EG exothermically decomposes at 535 K, which is higher than the decomposition temperature of impregnated nickel nitrate for Ni/ SiO2-EG catalyst precursor. The non pretreated silica support did not exhibit obvious weight lost as shown in Fig. 3D. Based on these, it is considered that the heat released from thermal decomposing of nickel nitrate was quickly absorbed by the adsorbed EG on silica

100 exc

0.6 0.4

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0.6 0.4 0.2

95 0.2

DSC/uv/mg

DSC/uv/mg

TG (%)

TG (%)

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Temperature (K)
1 0 -1 -2

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TG/%

94 92 90 88 -3 -4

TG/%

94 92 90 88 -3 -4

86 -5 300 330 360 390 420 450 480 510 540 570 600 630 660

-5 86 300 340 380 420 460 500 540 580 620 660

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Temperature (K)
4 exc 2 0

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4 2 0

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TG (%)

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Fig. 3. TG-DSC curves of decomposition of impregnated nickel nitrate after drying: (A) Ni/SiO2-EG; (B) Ni/SiO2; (C) EG pretreated silica support; (D) non pretreated silica support, and two used catalysts: (E) Ni/SiO2-EG catalyst; (F) Ni/SiO2 catalyst.

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surface to supply energy for decomposition, decreasing the decomposition temperature both of nickel nitrate and adsorbed EG. The lower decomposition temperature was efciently prevented the aggregation of nickel oxide, resulting in highly dispersed nickel oxide. The reduction performance of various catalysts was determined by temperature-programmed reduction (TPR). As shown in Fig. 4, only one peak exists for the Ni/SiO2 catalyst, which locates at 673 K. For Ni/SiO2-EG catalyst, the reduction performance was quite different from the Ni/SiO2 catalyst. The H2 consumption peak is very broad, which locates from 573 K to 993 K. The broad hydrogen consumption peak of Ni/SiO2-EG catalyst should be attributed to the reduction of various Ni species, including Ni hydrosilicates [27]. It is considered that the hard be reduced Ni species are formed via strong interaction between supported nickel and silica support. Comparing the reduction degrees of two catalysts, which were calculated by oxygen titration at 673 K, the reduction degree of Ni/SiO2-EG catalyst (29.3%) was much lower than that of Ni/SiO2 (54.5%), as shown in Table 1, indicating that Ni/SiO2-EG catalyst was hard to be reduced under reduction conditions during the catalyst preparation, according to the TPR results. The broad and higher temperature reduction peak of Ni/SiO2-EG catalyst indicates that the modied silica support increased the nickelsilica interaction, contributing to the decreased reducibility and the increased dispersion of supported nickel. To investigate the promotional effects of ethylene glycol modication, the Ni/SiO2-EG catalyst, prepared by EG pretreated silica support, was applied to dry reforming of CH4. As shown in Fig. 5A, Ni/SiO2-EG catalyst realized 72% CH4 conversion after 9 h, which is two times higher than that of Ni/SiO2 catalyst, prepared by non pretreated silica support. Besides the higher activity, Ni/SiO2-EG catalyst is much stable than Ni/SiO2 catalyst, whose conversion of CH4 decreased from 45% to 33% after 9 h reaction. The conversion of CO2 was slightly higher than that of CH4 for two catalysts due to the reverse water gas shift reaction. The performance of CO2 conversion is similar to CH4 conversion for two catalysts, as shown in Fig. 5B. The H2/CO ratio is 0.82 for Ni/SiO2-EG and 0.79 for Ni/SiO2 respectively. According to Norval et al. [28], for reforming of methane, the number of active sites is usually less than the total number of surface metallic atoms. Active sites sometimes are crystalline defects and/or edges of metal particles. Less metal density and better metal dispersion may lead to more active sites on the catalyst surface. Segner et al. [29] reported that the activation of CO2 is structuresensitive, and small particle size promotes its activation. Therefore, the Ni/SiO2-EG catalyst exhibited higher activity in dry reforming reaction due to its higher dispersion of supported nickel. Carbon deposition was the key problem for the reforming reaction, which could lead to catalyst deactivation, blockaded the pores of the catalyst support, and covered the metal active component [2].

A
conversion of CH4 (%)

90 80 70 60 50 40 30 1 2 3 4 5 6 7 8 9

Time on stream (h)

B
conversion of CO2 (%)

90 80 70 60 50 40 30 1 2 3 4 5 6 7 8 9

Time on stream (h)

Fig. 5. The conversions of CH4 (A) and CO2 (B) of different catalysts: () Ni/SiO2-EG catalyst () Ni/SiO2 catalyst; Reaction conditions: P = atmospheric pressure, T = 1023 K, CO2/CH4 = 1:1, GHSV= 21,000 cm3 g 1 h 1.

consumption (a.u)

H2

The carbon deposition of two used catalysts was determined by TGDSC, as shown in Fig. 3E and F. The weight loss of carbon deposition for used Ni/SiO2 catalyst, located around 773973 K, is 55%, which is 2 times higher than that of Ni/SiO2-EG catalyst. As the metalsupport interaction was one of the important factors that affected carbon deposition in dry methane reforming [19,30], it is considered the Ni/SiO2-EG catalyst realized less carbon deposition due to stronger interaction of metal and support, as proved by TPR, contributing to good reaction stability. Meanwhile, according to the coke formation mechanism [31,32], the coke was easily formed on the surface of larger sized Ni particles [14]. Therefore, the smaller supported Ni particles of Ni/SiO2-EG catalyst reduced carbon deposition and promoted CO2 activation to remove the deposited carbon, resulting in not only high activity but also stability in dry reforming of methane. On the other hand, because the sintering of the supported Ni particles strongly inuences the stability of catalyst during reaction [15], the used catalysts were also detected by XRD and TEM, as shown in Fig. 1c, d, and g, h. The XRD patterns of two used catalysts illustrated that the Ni sintering of Ni/SiO2-EG catalyst was much less than that of Ni/SiO2 catalyst as stronger interaction between the supported Ni and silica support. The NiO was found in patterns of used catalysts, since the water, which formed from reverse water gas shift reaction, oxidized the supported nickel during the reaction. Furthermore, TEM images of used catalysts clearly proved the severe sintering and carbon deposition of Ni/SiO2 catalyst, as compared in Table 1 and Fig. 3g, h. Base on illustrated above, Ni/SiO2-EG catalyst realized excellent stability in dry reforming of methane. 4. Conclusion In conclusion, EG pretreated silica support was applied to prepare the Ni supported catalyst, which exhibited higher activity and excellent stability in dry reforming of methane. Since the EG pretreatment

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Temperature (K)
Fig. 4. The H2-TPR proles for different catalysts: (a) Ni/SiO2-EG catalyst and (b) Ni/SiO2 catalyst.

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signicantly modied the surface properties of silica support, the decomposition temperature of impregnated nickel nitrate was decreased and the Nisilica interaction was enhanced, resulting in high dispersion of supported Ni, as illustrated in graphic abstract. The smaller Ni particle size and strong Nisupport interaction formed more active sits, reduced carbon deposition and nickel sintering, contributing to high activity and excellent stability of Ni/SiO2-EG catalyst in dry reforming of methane. Acknowledgment Financial support from the National Natural Science Foundation of China (No. 51174259, No. 21121064 and No. 20990221), National 863 program of China (No. 2009AA033301), and the Foundation of State Key Laboratory of Coal Conversion (No. 10-11-902-1) is greatly appreciated. References
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