Catalysis Communications 10 (2009) 11741177

Contents lists available at ScienceDirect

Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Inuence of Au promoter on hydrodesulfurization activity of thiophene over sulded AuNi/SiO2 bimetallic catalysts
Zhanghuai Suo *, Aihua Lv, Hongying Lv, Mingshan Jin, Tao He
Institute of Applied Catalysis, Yantai University, 32 Qingquan Road, Yantai City, Shandong Province 264005, PR China

a r t i c l e

i n f o

a b s t r a c t
AuNi/SiO2 bimetallic catalysts with high performance on hydrodesulfurization (HDS) were prepared through consecutive impregnation route. The activities of the catalysts with different metal loading were estimated by thiophene HDS. The activity is affected by nickel and gold loadings as well as the catalyst pretreatment. It is found the presence of Au can partly inhibit the formation of nickel sulde phase and signicantly increase the HDS activity of Ni/SiO2 catalyst. The sulded catalysts show higher activity than reduced or oxidized catalysts. Synergetic effect between gold and nickel species is preferable for high activity with low metal loadings. 2009 Elsevier B.V. All rights reserved.

Article history: Received 4 November 2008 Received in revised form 12 January 2009 Accepted 15 January 2009 Available online 20 January 2009 Keywords: Gold Nickel Silica Bimetallic catalyst Thiophene Hydrodesulfurization

1. Introduction Sulfur in transportation fuels remains one of major sources of air pollution. With increasing emphasis on environmental protection, strict legislation has been imposed on sulfur level in diesel [14]. Therefore, it is urgent for reners and scientists to develop new HDS catalysts with high activity and selectivity. In order to nd catalysts for HDS of fuel with high activity and selectivity, many researches have been performed during the two decades [57]. Using of noble metal-based catalyst is particularly interesting due to their high performance in HDS [810]. Using gold in catalysis was inspired by the nding of its high activity through Harutas work for low-temperature CO oxidation [11]. Gold has advantages of its strong afnity to sulfur compounds and good sulfur tolerance [1214]. Based on the knowledge, Venezia et al. [15,16] applied gold catalyst in hydrodesulfurization, claiming that the benecial effect of gold was present in supported AuPd bimetallic HDS catalyst. The recent work of these authors also reported the inuence of gold promoter on HDS activity over supported cobalt catalyst [17]. The result shows that the AuCo bimetallic catalyst promotes thiophene HDS activity as compared with the monometallic cobalt catalyst. Herein, Au promoted Ni catalyst was applied in HDS reaction for the rst time. The aim of present work is to show the inuence of gold promoter on HDS of thiophene activity over supported nickel

and the synergetic effect between gold and nickel species are also addressed. 2. Experimental 2.1. Preparation of catalysts Ni/SiO2 catalysts with Ni loading of 1.0, 2.5, 5.0, 7.5, and 10wt% respectively, were prepared by incipient wetness impregnation of SiO2 (Qingdao Ocean Chemical Co., Ltd.; SSA = 420.7 m2/g; dP = 4.88 nm) with an aqueous solution of nickel nitrate followed by drying overnight at 100 C and calcination in air for 4 h at 400 C. 1%Au/SiO2 catalyst was prepared by incipient wetness technique using aqueous solution of chloroauric acid (HAuCl43H2O). After impregnating overnight and drying for 5 h at 60 C, the sample immersed in dilute ammonia solution to remove chloride ions adsorbed on the surface and then dried at 60 C for 5 h. Finally, the sample was calcined in air at 400 C for 4 h. The actual loading of Au is 0.98%, as determined by AAS. AuNi/SiO2 catalysts were prepared by consecutive impregnation method. The Ni/SiO2 samples obtained were used to impregnate with gold salt solution to obtain AuNi/SiO2 catalysts as in preparation procedure of Au/SiO2. 2.2. Characterization of catalysts The surface areas and pore volumes were determined with NOVA 3000e automatic analyzer by low-temperature nitrogen

* Corresponding author. Tel.: +86 0535 6902514; fax: +86 0535 6902233. E-mail address: zhsuo@ytu.edu.cn (Z. Suo). 1566-7367/$ - see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.catcom.2009.01.019

Z. Suo et al. / Catalysis Communications 10 (2009) 11741177

1175

adsorption using the BET and the BJH equations, respectively. The crystalline phases of all samples were identied by X-ray diffraction (XRD) in a Shimadzu-6100 diffractometer using Cu Ka radiation. Standard JCPDS les were employed to identify the phases. The H2-TPR proles of sulded Ni/SiO2 and sulded AuNi/SiO2 samples were obtained using 10% H2/N2 gases from room temperature up to 900 C with heating rate of 20 C/min. The Ni 2p and Au 4f XPS studies of sulded Ni/SiO2 and sulded AuNi/SiO2 samples were performed in a VG ESCALAB 210 X-ray photoelectron spectrometer. The binding energy was determined utilizing Si 2p line as a reference with energy of 103.4 eV. 2.3. HDS activity The HDS activities of thiophene over all samples were tested in a continuous ow x-bed microreactor. The feed gases are 1 vol% thiophene in hexane with liquid hourly space velocity (LHSV) of 3.6 h1 and H2 ow rate of 50 ml/min. The reaction operates at atmospheric pressure and reaction temperature of 340 C. Prior to the catalytic activity evaluation, the catalysts were sulded in situ at 340 C for 4 h in a continuous stream of 3 vol% CS2/hexane. The activity was determined after 60 min on stream. The reaction products were analyzed by on line gas chromatography with FID detector and a graphitized carbon black column. 3. Results and discussion The textural properties of sulded Ni/SiO2 and sulded AuNi/ SiO2 catalysts are listed in Table 1. It is shown that the surface areas and pore volumes of all samples decrease with increasing Ni loading, while the average pore diameter changes slightly. On the other hand, addition of gold to supported nickel catalyst makes the surface area and the pore volume decrease. However, the average pore diameter of nickel catalyst does not change distinctly with addition of gold, which agrees with the result of Venezia et al. [17]. This is due to their different chemistry of synthesis, which may result in the partial coating of Ni/SiO2 surface by Au or blocking of large pore of SiO2. The XRD diffraction lines of nickel sulde phase can not be found in sulded Ni/SiO2 samples with Ni loadings of 2.5% and below. For the samples with higher Ni loadings, the diffraction lines at 2h = 21.1, 31.5, 38.7, 50.6 and 55.7 are attributed to nickel sulde (Ni3S2) phase according to JCPDS standard (300863), being in agreement with the result from Le et al. [18]. XRD patterns of sulded 1%AuNi/SiO2 catalysts are presented in Fig. 1. Metallic gold phase is observed for all samples, indicating that Au0 is main phase after the samples were calcined in air at 400 C for 4 h. The diffraction lines of nickel sulde are difcult to be observed in all gold-containing samples except for 1%Au10%Ni/SiO2 catalyst,

Ni3S2 Ni3S2 Au
0

Au

Ni3S2 Ni3S2 1%Au-10%Ni/SiO2 10%Ni/SiO2 1%Au-7.5%Ni/SiO2 7.5%Ni/SiO2 1%Au-5%Ni/SiO2 5%Ni/SiO2

Intensity/a.u.
10

20

30

2 Theta / o

40

50

60

70

80

Fig. 1. XRD patterns of sulded Ni/SiO2 and sulded AuNi/SiO2 catalysts.

suggesting the presence of gold can partly inhibit the formation of nickel sulde phase. H2-TPR proles of oxidized Ni/SiO2, Au/SiO2 and oxidized Au Ni/SiO2 samples show that no reduction in Au/SiO2 sample occurs between 25 C and 800 C. The reduction peak of Ni/SiO2 sample appeared at 429 C was attributed to the reduction of NiO phase. When metallic Au was added to Ni/SiO2, the maximum reduction temperature was increased to 454 C, leading to the conclusion that the presence of Au increases the reduction of NiO phase. This can be explained that stronger NiO bond in AuNi/SiO2 catalysts results in higher reduction temperature. Chin et al. found that addition of Au signicantly reduced the total amount of H2 chemisorbed on AuNi/MgAl2O4 catalysts [19]. There are two reduction peaks in the TPR proles of sulded Ni/ SiO2 and sulded AuNi/SiO2 catalysts (Fig. 2). For sulded Ni/SiO2 the low-temperature peak (Tmax 250 C) is attributed to the supercial reduction of sulfur with anionic vacancies and the high-temperature peak (Tmax 357 C) arises from the reduction of the bulk suldes [20,21]. With the inclusion of gold in the sulded Ni/ SiO2, the two maximum reduction peaks decrease to 226 C and 338 C, respectively, indicating that the presence of Au is preferable for the reduction of nickel sulde phase, being in agreement with Yuans work on co-impregnated NiAu/SiO2 [22].

226 C sulfided Au-Ni/SiO2

338 C

Table 1 Textural property of sulded Ni/SiO2 and sulded AuNi/SiO2 catalysts. Catalyst sample 1%Ni/SiO2 0.5%Au1%Ni/SiO2 1%Au1%Ni/SiO2 1.5%Au1%Ni/SiO2 2.5%Ni/SiO2 1%Au2.5%Ni/SiO2 5%Ni/SiO2 1%Au5%Ni/SiO2 7.5%Ni/SiO2 1%Au7.5%Ni/SiO2 10%Ni/SiO2 1%Au10%Ni/SiO2 SBET (m /g) 392.5 380.6 366.9 351.0 385.7 355.3 372.8 333.9 363.8 319.1 355.4 304.5
2

H2 consumption

250 C 357 C sulfided Ni/SiO2

o

Vp (cm /g) 1.01 0.97 0.92 0.86 0.90 0.88 0.89 0.88 0.86 0.83 0.84 0.76

Rp (nm) 4.85 3.30 3.30 3.30 3.32 3.29 3.32 3.31 3.29 3.28 3.27 3.24

50

100

150

200

250

300
o

350

400

450

Temperature

Fig. 2. H2-TPR proles of sulded 7.5%Ni/SiO2 and sulded 1%Au7.5%Ni/SiO2 catalysts.

1176

Z. Suo et al. / Catalysis Communications 10 (2009) 11741177

Ni 2p

1/2

Ni 2p 3/2

Au-Ni/SiO

Ni/SiO 2

840

850

860

870

880

890

Binding Energy/eV
Fig. 3. Ni 2p XPS spectra of sulded 7.5%Ni/SiO2 and sulded 1%Au7.5%Ni/SiO2 catalysts.

50 45

Thiophene conversion/ %

40 35

1%Au-Ni/SiO2

er HDS activity than Ni/SiO2. For example, 36.5% conversion of thiophene is obtained when addition of 1%Au to sulded 1% Ni/SiO2. For sulded AuNi/SiO2 catalyst, the HDS activity is found to be sensitive to its chemical state. The sulded catalyst shows higher activity than the oxidized or the reduced catalysts. On the other hand, the activity is also affected by suldation temperature and suldation time of AuNi/SiO2 catalyst. When suldation temperature increases from 250 C to 450 C, thiophene conversion is found to increase from 45.2% to 60.4% and the activity is increased to maximum at suldation for 2 h. When Au is added to Ni/SiO2, the elevated activity is found. The improvement is more notable at Ni loading of 5% or lower, as shown in Fig. 4. Their dependences of HDS activities on Au loading are also found. These results show that the synergy effect between gold and nickel is signicant for HDS activity with low Ni loadings. This view can be supported by the work of Pinzn et al. using Pt Mo bimetallic HDS catalysts, in which the enhanced HDS activities are due to an improved dispersion of the active species on the support, which was reached at low metal contents and a specic atomic ratio [23]. There is an increase of Nisulde dispersion at low loadings and this would be supported by the shift of the XPS signals of Ni in the presence of Au, as given by Venezia et al. [17]. Chin et al also provided some consistent evidences of a signicant interaction between gold atoms and reduced Ni crystallites on AuNi/ MgAl2O4 [19]. 4. Conclusions

Intensity/a.u.

30 25 20 15 10 5 0 0 1 2 3 4 5 6 7 8

Ni/SiO2

10

Ni loading/ %
Fig. 4. Effect of Ni loading on HDS activity over sulded Ni/SiO2 and sulded AuNi/ SiO2 catalysts.

This work shows the potential uses of gold promoter on HDS over sulded Ni/SiO2 catalyst. It is found that the presence of Au inhibits the formation of nickel sulde. NiO is the main phase on the surface, while the main nickel sulde phase exists in the bulk of sulde Ni/SiO2 and AuNi/SiO2. Moreover, the HDS activity of the bimetallic AuNi catalyst is sensitive to its reduction temperature of the sulfur species and chemical state. The sulded catalysts show higher activity than the oxidized and the reduced catalysts. Further, the synergy effect between gold and nickel is more significant for HDS activity of the catalysts with low metal loadings. Acknowledgements This work was nancially supported by the National Science Foundation of China (NSFC NO. 20473070). References
[1] R.T. Yang, A.J. Hernandez-Maldonado, F.H. Yang, Science 301 (2003) 7981. [2] D.D. Whitehurst, T. Isoda, I. Mochida, Advances in Catalysis, vol. 42, Academic Press Inc., San Diego, 1998, pp. 345471. [3] H.Y. Lv, J.B. Gao, Z.X. Jiang, F. Jing, Y.X. Yang, G. Wang, C. Li, Journal of Catalysis 239 (2006) 369375. [4] B.C. Gates, H. Topsoe, Polyhedron 16 (1997) 32133217. [5] C.S. Song, X.L. Ma, Applied Catalysis B 41 (2003) 207. [6] E.J.M. Hensen, D.G. Poduval, J.A.R. van Veen, Industrial and Engineering Chemistry Research 46 (2007) 42024211. [7] A. Hynaux, C. Sayag, S. Suppan, J. Trawczynski, M. Lewandowski, A. Szymanska-Kolasa, G. Djega-Mariadassou, Applied Catalysis B 72 (2007) 62 70. a, M. Zdraz il, Journal of Catalysis 232 (2005) 447 [8] Z.E. Vt, D. Gulkov, L.E. Kaluz 455. [9] D. Perez-Martinez, S.A. Giraldo, A. Centeno, Applied Catalysis A 315 (2006) 35 43. [10] M.M. Hossain, Chemical Engineering Journal 123 (2006) 1523. [11] M. Haruta, N. Yamada, T. Kobayashi, S. Lijima, Journal of Catalysis 115 (1989) 301309. [12] Marie-Christine Daniel, Didier Astruc, Chemical Review 104 (2004) 293 346. [13] A.M. Venezia, V. La Parola, V. Nicol, G. Deganello, Journal of Catalysis 212 (1) (2002) 5662. [14] A.M. Venezia, R. Murania, G. Pantaleo, G. Deganello, Journal of Catalysis 251 (1) (2007) 94102.

The Ni 2p XPS spectra of sulded Ni/SiO2 and sulded AuNi/ SiO2 samples are shown in Fig. 3. For sulded Ni/SiO2, the binding energies of Ni 2p1/2 and Ni 2p3/2 are 873.7 eV and 855.0 eV, which are attributed to Ni2+ species [18]. For sulded AuNi/SiO2 they are shifted to 872.5 eV and 854.3 eV due to the perturbation of gold to nickel. The negative shift is identiable of low-valence nickel species which is superior to the formation of surface sulde. It can be concluded from its XRD and XPS results that NiO is the main phase on the surface of Ni/SiO2 and AuNi/SiO2, meanwhile, nickel sulde phase is the main phase in the bulk of sulde Ni/SiO2 and AuNi/ SiO2. The binding energies of Au 4f5/2 and Au 4f7/2 appear at 87.1 eV and 83.8 eV, respectively, for sulded AuNi/SiO2, which are attributed to metallic gold, indicating that metallic gold present in surface and bulk of the catalyst along with its XRD and TPR results. The HDS activities of Au/SiO2, Ni/SiO2 and AuNi/SiO2 samples were evaluated in order to estimate the inuence of Au promoter on the nickel catalyst. The activity of Au/SiO2 is found to be low although thiophene conversion increases from 2.9% at 0.5% Au loading to 6.8% at 1.5% Au loading. As shown in Fig. 4, the activity of sulded Ni/SiO2 changes greatly with Ni loading, thiophene conversion is 6.1% at 1% Ni loading and amounts to 32.6% at 7.5% Ni loading. Due to the presence of Au, sulded AuNi/SiO2 gives high-

Z. Suo et al. / Catalysis Communications 10 (2009) 11741177 [15] A.M. Venezia, V. La Parola, V. Nicoli, G. Deganello, Journal of Catalysis 212 (2002) 5662. [16] A.M. Venezia, V. La Parola, G. Deganello, B. Pawelec, J.L.G. Fierro, Journal of Catalysis 215 (2003) 317325. [17] A. Venezia, R. Murania, G. Pantaleo, G. Deganello, Gold Bulletin 40 (2007) 130 134. [18] Z. Le, P. Afanasiev, D. Li, X. Long, M. Vrinat, Catalysis Today 130 (2008) 2431. [19] Y.-H.C. Chin, D.L. King, H.-S. Roh, Y. Wang, S.M. Heald, Journal of Catalysis 244 (2006) 153162.

1177

[20] C. Calais, N. Matsubayashi, C. Geantet, Y. Yoshimura, H. Shimada, A. Nishijima, M. Lacroix, M.E. Breysse, Journal of Catalysis 174 (1998) 130 141. [21] P.J. Mangnus, A. Riezebos, A.D.V. Langeveld, J.A. Moulijn, Journal of Catalysis 151 (1995) 178191. [22] G. Yuan, J.L. Lopez, C. Loius, L. Delannoy, M.A. Keane, Catalysis of Communication 6 (2005) 555562. n, A. Centeno, S.A. Giraldo, Applied Catalysis A: General 302 (2006) [23] M.H. Pinzo 118126.