Catalysis Communications 12 (2011) 332336

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Catalysis Communications
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c a t c o m

Short Communication

Preparation of highly loaded and dispersed Ni/SiO2 catalysts

Mingwei Xue, Shenghua Hu, Hui Chen, Yuchuan Fu , Jianyi Shen
Lab of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China

a r t i c l e

i n f o

a b s t r a c t
A highly loaded and dispersed Ni/SiO2B catalyst was prepared by the precipitation method with an n-butanol drying process. Drying with n-butanol signicantly increased the surface area of the catalyst as well as the reducibility and dispersion of supported nickel, leading to the high active nickel surface area (66 m2/gcatalyst). In addition, the surface acidity of the Ni/SiO2-B catalyst was signicantly enhanced, as probed by the microcalorimetric adsorption of ammonia. Accordingly, this catalyst adsorbed great amount of toluene with the high initial heat of about 140 kJ/mol, and exhibited high activity for the hydrogenation of toluene to methyl cyclohexane. 2010 Elsevier B.V. All rights reserved.

Article history: Received 11 June 2010 Received in revised form 21 September 2010 Accepted 4 October 2010 Available online 21 November 2010 Keywords: Ni/SiO2 catalyst Drying with n-butanol Active metal surface area Microcalorimetric adsorption Surface acidity Hydrogenation of toluene

1. Introduction Ni/SiO2 catalysts are often used for industrial hydrogenation processes, such as hydrogenation of olens and aromatics, methane reforming, watergas shift reaction, and so on due to their high activity and economics. It is well known that the hydrogenation activity depends on the number of surface active nickel atoms, which in turn depend on the loading, reducibility and dispersion. Higher loading, reducibility and dispersion lead to the more surface active nickel atoms, but these parameters are usually contradictory and special preparation techniques are required to maximize these parameters simultaneously. Different preparation methods have been employed, including precipitation [1], incipient wetness impregnation [2,3], ion-exchange [4], homogeneous depositionprecipitation [2,3,510] and solgel techniques [11,12]. It is usually difcult to prepare highly loaded and dispersed nickel catalysts with a simple method. Precipitation is a frequently used method for the preparation of supported metal catalysts. However, the precipitated small particles may agglomerate during the drying process owing to the removal of water of high surface tension. Such coagulations may be avoided in the supercritical uid drying process, by removing water at low surface tension conditions. However, the supercritical uid process is expensive and hazardous [13]. Alternatively, a solvent (usually n-butanol) replacing technique of drying may be used to effectively reduce the possibility of formation of chemical bonds between particles and thus to prevent the formation of hard agglomerates [1416].

In our previous work [1719], high surface area VOx, VAgO and Ni/MgO catalysts were prepared by using n-butanol to replace water in the samples during the drying process so that water may be removed from the solution of n-butanol, rather than removed directly from the samples. In this way, the catalysts with high surface areas were prepared. In this work, we extended the technique to the preparation of 60%Ni/ SiO2 catalysts. 2. Experimental 2.1. Preparation of catalysts Ni/SiO2 with 60% Ni by weight was prepared by the precipitation method. Specically, an aqueous solution containing the required amount of nickel nitrates was precipitated at 353 K with a solution containing sodium silicate and a slightly excess of sodium carbonate. The nal pH was maintained at about 9 and a green precipitate was formed. It was then ltered and washed thoroughly with de-ionized water. The lter cake was evenly divided into two parts. One was directly dried at 353 K for 12 h and then at 393 K for another 12 h. This sample was denoted as Ni/SiO2. Another part was added into 200 g nbutanol and heated at 353 K for 12 h during which water and n-butanol were evaporated and could be collected. The collected mixture contained about 195 g n-butanol and 60 g H2O. The sample was then further dried at 393 K for 12 h and denoted as Ni/SiO2B. 2.2. Characterization of catalysts

Corresponding author. Tel./fax: +86 25 83594305. E-mail address: jyshen@nju.edu.cn (J. Shen). 1566-7367/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.catcom.2010.10.002

X-ray diffraction (XRD) patterns were collected at ambient atmosphere by an X'TRA diffractometer with a Cu K radiation

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( = 1.5418 ). The applied voltage and current were 40 kV and 40 mA, respectively. The surface areas and pore sizes were measured by the Gemini V analyzer. Experiments were performed at 77.3 K using N2 as an adsorbate. The samples were degassed at 573 K for 1 h before the measurements. The chemical compositions of catalysts were analyzed by an ARL9800 X-ray uorescence spectrometer (XRF). Transmission electron microscopic measurements (TEM) were carried out using a JEOL electron microscope (JEM-2010), with an accelerating voltage of 200 keV. The catalysts were usually reduced in owing H2 at 673 K for 2 h. Reduced catalysts were passivated in N2 containing about 0.1% O2 at room temperature for 48 h before the BET, XRD and TEM measurements. Temperature programmed reduction (TPR) was performed by using a quartz U-tube reactor loaded with about 50 mg of a sample. A mixture of N2 and H2 (5.13% H2 by volume) was used as the reacting agent and the ow rate was maintained at 40 ml/min. The temperature was raised at a programmed rate of 10 K/min from 303 to 1273 K. H2 and O2 adsorptions were performed on the home-made volumetric adsorption system at room temperature and 673 K, respectively. The catalyst was reduced in H2 at 673 K for 2 h and evacuated at 673 K for 1 h before the measurements. After cooling the catalyst to room temperature, doses of H2 were admitted sequentially and coverage of H2 was measured until the equilibrium pressure (PH2) reached about 50 kPa. An isotherm (coverage versus PH2) was then obtained. The uptake of H2 for the saturation coverage of hydrogen on a nickel surface was determined by extrapolating the coverage of isotherm to PH2 =0. The surface area of metallic nickel was calculated by the uptake of H2 assuming the molar ratio of H/Nisurf = 1 and a surface area of 6.5 2 for a Ni atom [20]. Microcalorimetric adsorption of NH3 and toluene was performed on a TianCalvet heat-ux apparatus. A C-80 calorimeter (Setaram, France) was connected to a volumetric system equipped with a Baratron capacitance manometer (USA) for the pressure measurement and gas handling. Prior to the microcalorimetric adsorption, the samples were typically reduced in H2 at 673 K for 2 h followed by the evacuation at the same temperature for 1 h. 2.3. Hydrogenation of toluene The catalytic hydrogenation experiments were performed at atmospheric pressure in a continuous down-ow xed-bed microreactor. The catalyst was reduced in owing H2 at 673 K for 2 h before the reaction. An n-hexane solution containing toluene (toluene: n-hexane=1:2 w/w) with H2 was fed into the reactor for the hydrogenation reactions. The reaction was performed at 423 K with the weight hourly space velocity (WHSV) of toluene from 28 to 106 h1. 3. Results and discussion 3.1. Textural and structural properties of catalysts Table 1 summarizes the chemical compositions, specic surface areas and pore structural parameters of the Ni/SiO2 and Ni/SiO2-B
Table 1 Surface area and pore structure of the 60%Ni/SiO2 and 60%Ni/SiO2B catalysts. Catalyst Ni loading by XRF (wt%) 59.4 58.1 Surface area (m2/g) Dried 105 142 Calcined 248 574 Reduced 141 373 Pore size (nm) Reduced 2 2 Pore volume (cm3/g) Reduced 0.13 0.51

( (
Intensity (a.u.)

) Ni2(OH)2CO3.H2O, ( ) Ni ) Nickel hydrosilicate

Ni/SiO2 Ni/SiO2-B Ni/SiO2 (R) Ni/SiO2-B (R)

20

30

40

50

60

70

80

2 theta (degree)
Fig. 1. XRD patterns of the 60%Ni/SiO2 and 60%Ni/SiO2B catalysts after drying and reduction in H2 at 673 K (with R in parentheses), respectively.

catalysts. The results from XRF showed that the loadings of nickel were 59.4% and 58.1% for the Ni/SiO2 and Ni/SiO2B, respectively. Thus the compositions of catalysts analyzed were close to the values desired (60%). The data in Table 1 showed that the treatment with nbutanol signicantly increased the surface areas of catalysts. For example, the surface area was 141 and 373 m2/g for the reduced Ni/ SiO2 and Ni/SiO2B, respectively. The pore volume was also increased signicantly from 0.13 to 0.51 cm3/g for the reduced catalysts. Fig. 1 shows the X-ray diffraction patterns for the Ni/SiO2 and Ni/ SiO2B catalysts after drying at 393 K and reduction in H2 at 673 K. After dried at 393 K, the two catalysts exhibited broad and weak peaks around 24, 36 and 63, probably belonging to basic nickel carbonate and nickel hydrosilicate [21]. No distinct XRD peaks were observed for silica in the two catalysts. After reduction at 673 K, two broad diffraction peaks around 44 and 52 for metallic Ni were detected for the two catalysts. These diffraction peaks were weaker for Ni/SiO2B than for Ni/SiO2, indicating the more highly dispersed metallic Ni in Ni/SiO2B than in Ni/SiO2. The average particle sizes of metallic nickel were calculated to be 6.3 and 3.4 nm, respectively, in the Ni/SiO2 and Ni/SiO2B, according to the Scherrer equation.

3.2. Reducibility and dispersion of supported nickel Fig. 2 shows the TPR proles for the Ni/SiO2 and Ni/SiO2B catalysts. It is seen that the Ni/SiO2 began to reduce at about 680 K with a broad reduction peak with a maximum around 821 K, while the Ni/ SiO2B began to reduce at about 620 K with a relatively narrower

821
H2 consumption

Ni/SiO2 712

Ni/SiO2-B
400 600 800 1000 1200

Ni/SiO2 Ni/SiO2-B

T (K)
Fig. 2. TPR proles of the 60%Ni/SiO2 and 60%Ni/SiO2B catalysts.

The catalysts were dried at 393 K, followed by calcination in N2 at 673 K or by reduction in H2 at 673 K for 2 h.

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Table 2 Chemisorption of H2 and O2 on the 60%Ni/SiO2 and 60%Ni/SiO2B catalysts reduced at 673 K. Catalyst Ni/SiO2 Ni/SiO2B H2 ads. (mol/g) 476 848 O2 ads. (mol/g) 2350 2646 Ni surf. area (m2/g-cat.) 37 66 d (nm) 5.1 3.2 Disp. (%) 20 32 Redu. (%) 54 61

3.3. Microcalorimetric adsorption of NH3 and toluene The results of microcalorimetric adsorption of NH3 on the Ni/SiO2 and Ni/SiO2B catalysts were shown in Fig. 4. Fig. 4(a) showed that SiO2 possessed only weak surface acidity with the adsorption heat lower than 20 kJ/mol. The Ni/SiO2B evacuated at 673 K displayed strong surface acidity with the initial heat of 160 kJ/mol and coverage of 1200 ml/g. The strong acidity may be assigned to the nickel hydrosilicate, since both SiO2 and NiO processed weak surface acidity (the initial heat of ammonia adsorption on NiO was lower than 40 kJ/ mol [23]). The initial heat for the adsorption of ammonia on the reduced Ni/SiO2B was almost not changed. On the other hand, the Ni/ SiO2 evacuated at 673 K showed the relatively weaker surface acidity with the initial heat of about 90 kJ/mol for the adsorption of ammonia. The initial heat was increased to about 120 kJ/mol for the reduced Ni/ SiO2, which might be due to the dissociative adsorption of NH3 on the metallic Ni [24,25]. This phenomenon was not observed for the reduced Ni/SiO2B probably owing to its strong surface acidity that generated higher heat than that for the adsorption of ammonia on metallic nickel. Fig. 4(b) presents the microcalorimetric adsorption of toluene on the Ni/SiO2 and Ni/SiO2B catalysts. The initial heat and coverage for the adsorption of toluene over SiO 2 B was 63 kJ/mol and 1100 mol/g, respectively. The initial heat and coverage were increased to 84 kJ/mol and 1800 mol/g, respectively, on the Ni/ SiO2B, due to its stronger surface acidity. The initial heat was increased to 140 kJ/mol on the reduced Ni/SiO2B, much higher than that on the un-reduced catalyst, indicating the adsorption of toluene on the surface of metallic nickel [25]. The adsorption heat was dropped rapidly with the increase of coverage of toluene, indicating that only a small amount of toluene could be adsorbed on some highly active metallic nickel sites and generated the high heat. The initial heat for the adsorption of toluene was also higher over the reduced Ni/SiO2 than the un-reduced Ni/SiO2B.

Notes: Reduction degree (Redu.) was calculated according to the uptake of O2. Average diameter (d) and dispersion (Disp.) of supported nickel particles were calculated according to the uptake of H2 and the amount of reduced nickel.

peak with a maximum around 712 K. Thus, the treatment with nbutanol favored the reduction of supported nickel species. The adsorption of H2 and O2 on the reduced catalysts was carried out at room temperature and 673 K, respectively, according to which the dispersion, reducibility and nickel surface area of supported nickel could be derived [20,22]. Table 2 summarizes the information obtained by the adsorption of H2 and O2. According to O2 uptakes, the degrees of reduction were found to be 54% and 61% for the Ni/SiO2 and Ni/SiO2-B catalysts, respectively, suggesting that the n-butanol treatment increased the reducibility of nickel, consistent with the TPR results. In addition, the n-butanol treatment signicantly increased the dispersion of Ni from 20% to 32%, probably due to the increased surface area of the catalyst. The H2 uptake was measured to be 476 and 848 mol/g for the Ni/SiO2 and Ni/SiO2B, corresponding to the active nickel surface area of 37 and 66 m2/g-catalyst, respectively. The average particle sizes of reduced Ni were then calculated to be 5.1 and 3.2 nm for the Ni/SiO2 and Ni/SiO2-B, respectively, in agreement with the results of XRD and TEM. Fig. 3 displays TEM images for the Ni/SiO2 and Ni/SiO2B reduced in H2 at 673 K. The images showed that the size distribution of nickel particles was quite uniform in the two samples. The Ni particles were obviously smaller in Ni/SiO2B than in Ni/SiO2.

Fig. 3. TEM images of the 60%Ni/SiO2 (a and b) and 60%Ni/SiO2B (c and d) reduced in H2 at 673 K.

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(a)
160

(a)
Adsorption at 423 K
Ni/SiO2-B Ni/SiO2-B (R) Ni/SiO2 Conversion (%)
80 100

(b)
Ni/SiO2-B
0.12

Differential heat (kJ/mol)

120

Ni/SiO2-B
0.08

SiO2-B
80

60

40

TOF (s-1)
0.04

Ni/SiO2 (R)

40 20 0 0 400 800 1200

Ni/SiO2

Ni/SiO2

0 40 80 120

0.00 40 80 120

Coverage of NH3 (mol/g)

WHSV (h-1)

WHSV (h-1)

(b)
160

Differential heat (kJ/mol)

120

Adsorption at 303 K

Ni/SiO2-B Ni/SiO2-B (R) Ni/SiO2 (R) SiO2-B

Fig. 5. Conversion (a) and TOF (b) of toluene versus WHSV of toluene on the 60%Ni/SiO2 and 60%Ni/SiO2B catalysts reduced in H2 at 673 K. Reaction conditions: P = 1 atm, T = 423 K and H2/toluene = 5 (molar ratio).

4. Conclusions Ni/SiO2 catalysts with the high loading (60% by weight) were prepared by the precipitation method. It was found that a drying process with n-butanol signicantly increased the surface area of catalyst due to the removal of water at the condition of low surface tension of n-butanol. In addition, the number of surface active nickel sites was also signicantly increased due to the improvement of reducibility and dispersion of supported nickel. The reduced nickel particles on the SiO2 support could be as small as 4 nm, even at the high loading of 60 wt.%. Such a catalyst possessed high active nickel surface area and thus was highly active for the hydrogenation of toluene to methyl cyclohexane. It is interesting to note that the surface acidity was also signicantly increased for the 60%Ni/SiO2B prepared with the treatment of nbutanol, which favored the adsorption and hydrogenation of toluene. Acknowledgements

80

40

0 0 400 800 1200 1600

Coverage of toluene (mol/g)

Fig. 4. Differential heats vs. coverage for the adsorption of NH3 (a) and toluene (b) on the 60%Ni/SiO2 and 60%Ni/SiO2B catalysts after evacuation at 673 K or reduction in H2 at 673 K (with R in parentheses).

3.4. Catalytic hydrogenation of toluene Fig. 5 presents the results of hydrogenation of toluene at 423 K on the Ni/SiO2 and Ni/SiO2B catalysts. Methyl cyclohexane was found to be the only product. The conversion of toluene was 32% over the Ni/ SiO2 at the WHSV of toluene of 28 h1, while it was 100% over the Ni/ SiO2B at the same reaction conditions. Thus, Ni/SiO2B was much more active than Ni/SiO2 for the hydrogenation of toluene, apparently due to the much higher active nickel surface area on Ni/SiO2B than on Ni/SiO2. Since the uptake of H2 measured the number of active sites of surface nickel, the activity could be expressed in turnover frequency (TOF) as shown in Fig. 5(b). The TOF of toluene for Ni/SiO2 was relative steady around 0.02 s1, while it increased to about 0.11 s1 with the increase of WHSV for Ni/SiO2B. The higher activity of Ni/SiO2B could not be ascribed to its higher active nickel surface area only, since the TOF of toluene for Ni/SiO2B was also signicantly increased. Studies have shown that the activity of aromatic hydrogenation depended not only on the amounts of accessible active metal sites, but also on the surface acid-base properties [2426]. The surface acidity favored the adsorption of toluene since toluene can be taken as a Lewis base due to the enriched electron density on the aromatic ring. This has been proved by the results of microcalorimetric adsorption of toluene presented above. So the higher activity may also be due to the stronger surface acidity of Ni/SiO2-B.

Financial supports from NSFC (21073089), MSTC (2005CB221400) and Jiangsu Province, China (BE2009145) are acknowledged. References
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