Y. Li et al. / Journal of Catalysis 286 (2012) 124–136
135
(1) The better dispersion of the active metals, which is neces-
Acknowledgments
sary for the creation of a larger number of accessible active
sites. The dispersion of oxidic W and Ni species increases
with the incorporation of aluminum into the SBA-15 sup-
port, as shown by the wide-range XRD characterization
results in Fig. 9B. In addition, the homogenous distribution
of WS2 crystals (Fig. 13B) was obtained due to the strong
interaction of oxidic W and Ni species with Al–OH on the
support, as confirmed by the H2-TPR characterization results
in Fig. 12.
This work was financially supported by the National Basic Re-
search Program of China (the 973 Program) (Grant
2010CB226901), the National Natural Science Foundation of China
(Grants 20573021 and 20825621), the Ministry of Education of
China (Grant 20060246010), and the Society of Technical Commu-
nication (Shanghai) (Grant 08DZ2270500).
Appendix A. Supplementary material
(2) The short length and increased stacking layers of WS2 slabs,
which favor the formation of more type II active phase. In
the NiW/Al-SBA-15 catalyst, Ni–W–S phases consist mostly
of short slabs (ꢀ5 nm) of two layers, as shown by the HRTEM
images in Fig. 13B. On one hand, for a large sulfur-containing
molecule such as DBT, a lower degree of stacking of sulfide
Supplementary data associated with this article can be found, in
References
slabs, as in the case of the NiW/c-Al2O3 catalyst, hampers
the planar adsorption of the molecule through its aromatic
rings and thereby decreases the HDS activity [48]; on the
other hand, a very high degree of stacking sulfide slabs, as
observed for the weakly interacting support SBA-15, reduces
the number of corner sites, which are necessary for sulfur
elimination via the perpendicular adsorption of the mole-
cule through the S atom [45].
[1] D.Y. Zhao, J.L. Feng, Q.S. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka, G.D.
Stucky, Science 279 (1998) 548.
[2] D.Y. Zhao, Q.S. Huo, J.L. Feng, B.F. Chmelka, G.D. Stucky, J. Am. Chem. Soc. 120
(1998) 6024.
[3] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, T.W.
Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgins, J.L. Schlenkert, J.
Am. Chem. Soc. 114 (1999) 10834.
[4] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359 (1992)
710.
[5] A. Corma, Chem. Rev. 97 (1997) 2373.
[6] Q.F. Tan, Y. Fan, H.Y. Liu, T.C. Song, G. Shi, B.J. Shen, X.J. Bao, AIChE J. 54 (2008)
1850.
(3) The more and stronger B acid sites and enhanced L acid sites,
which favor the hydrogenolysis/isomerization and hydroge-
nation ability of the catalyst and enhance the HDS activity.
Solis et al. [55] considered that the enhanced DBT HDS activ-
ity of metal sulfides over acidic supports is partly related to
the improvement in their hydrogenation property due to
electronic effects of the acidity on the metal sulfide phase;
Gallezot et al. [56] reported that both B and L acid sites
can be used as the potential electron acceptors and the
resulting electron-deficient metal clusters can promote the
[7] L.Y. Lizama, T.E. Klimova, J. Mater. Sci. 44 (2009) 6617.
[8] G.M. Kumaran, S. Garg, K. Soni, M. Kumar, L.D. Sharma, G.M. Dhar, K.S.R. Rao,
Appl. Catal. A Gen. 305 (2006) 123.
[9] A. Olivas, T.A. Zepeda, Catal. Today 143 (2009) 120.
[10] G.M. Esquivel, J. Ramírez, A. Gutiérrez-Alejandre, Catal. Today 148 (2009) 36.
[11] X. Li, A.J. Wang, M. Egorova, R. Prins, J. Catal. 250 (2007) 283.
[12] Y.Y. Sun, R. Prins, Angew. Chem. Int. Ed. 47 (2008) 8478.
[13] F. Hoffmann, M. Cornelius, J. Morell, M. Fröba, Angew. Chem. Int. Ed. 45 (2006)
3216.
[14] B. Dragoi, E. Dumitriu, C. Guimon, A. Auroux, Micropor. Mesopor. Mater. 121
(2009) 7.
[15] H.M. Kao, C.C. Ting, S.W. Chao, J. Mol. Catal. A Chem. 235 (2005) 200.
[16] S. Sumiya, Y. Oumi, T. Uozumi, T. Sano, J. Mater. Chem. 11 (2001) 1111.
[17] Z.H. Luan, E.M. Maes, P.A.W. Van der Heide, D.Y. Zhao, R.S. Czernuszewicz, L.
Kevan, Chem. Mater. 11 (1999) 3680.
p
adsorption of DBT via its aromatic rings which is the pre-
requisite for the HYD pathway. The NiW/Al-SBA-15 catalyst
has the highest amount of B acid sites that are expected to
enhance the hydrogenolysis and isomerization ability of
the catalyst, and truly the DBT HDS products contain the
highest amount of DDS pathway product BP and the further
isomerization products CPMB, CPCH, and CPMCH, as shown
in Table 5. It is the perfect combination of the good disper-
sion and suitable stacking of metal sulfide crystals and the
enhanced B and L acid sites that endows the NiW/Al-SBA-
15 catalyst with the best DBT HDS activity.
[18] A. Campos, L. Martins, L. Deoliveira, C. Dasilva, M. Wallau, E. Urquietagonzalez,
Catal. Today 107–108 (2005) 759.
[19] R. Mokaya, J. Phys. Chem. B 104 (2000) 8279.
[20] Y.D. Xia, R. Mokaya, Micropor. Mesopor. Mater. 74 (2004) 179.
[21] D.H. Pan, P. Yuan, L.Z. Zhao, N. Liu, L. Zhou, G.F. Wei, J. Zhang, Y.C. Ling, Y. Fan,
B.Y. Wei, H. Liu, C.Z. Yu, X.J. Bao, Chem. Mater. 21 (2009) 5413.
[22] L.L. Hench, J.K. West, Chem. Rev. 90 (1990) 33.
[23] X.Y. Lin, Y. Fan, Z.H. Liu, G. Shi, H.Y. Liu, X.J. Bao, Catal. Today 125 (2007) 185.
[24] H. Wang, Y. Fan, G. Shi, H.Y. Liu, X.J. Bao, J. Catal. 260 (2008) 119.
[25] H.S. Joo, J.A. Guin, Fuel Process. Technol. 49 (1996) 137.
[26] S. Brunauer, P.H. Emmett, E. Teller, J. Am. Chem. Soc. 60 (1938) 309.
[27] E.P. Barrett, L.G. Joyner, P.P. Halenda, J. Am. Chem. Soc. 73 (1951) 373.
[28] G. Berhault, M.P. De Ia Rosa, A. Mehta, M.J. Yácaman, R.R. Chianelli, Appl. Catal.
A Gen. 345 (2008) 80.
4. Conclusions
[29] E.J.M. Hensen, P.J. Kooyman, Y. van der Meer, A.M. van der Kraan, V.H.J. de
Beer, J.A.R. van Veen, R.A. van Santen, J. Catal. 199 (2001) 224.
[30] Y. Liu, W.Z. Zhang, T.J. Pinnavaia, Angew. Chem. Int. Ed. 40 (2001) 1255.
[31] S.Q. Zeng, J. Blanchard, M. Breysse, Y.H. Shi, X.T. Su, H. Nie, D.D. Li, Appl. Catal.
A Gen. 298 (2006) 88.
[32] S.Q. Zeng, J. Blanchard, M. Breysse, Y.H. Shi, X.T. Su, H. Nie, D.D. Li, Micropor.
Mesopor. Mater. 85 (2005) 297.
[33] A. Sampieri, S. Pronier, S. Brunet, X. Carrier, C. Louis, J. Blanchard, K. Fajerwerg,
M. Breysse, Micropor. Mesopor. Mater. 130 (2010) 130.
[34] X.D. Li, M.J. Edirisinghe, Chem. Mater. 16 (2004) 1111.
[35] T. Kataoka, J.A. Dumesic, J. Catal. 112 (1988) 66.
[36] P. Rayo, J. Ramírez, M.S. Rana, J. Ancheyta, A. Aguilar-Elguézabal, Ind. Eng.
Chem. Res. 48 (2009) 1242.
[37] V. Sundaramurthy, I. Eswaramoorthi, A.K. Dalai, J. Adjaye, Micropor. Mesopor.
Mater. 111 (2008) 560.
[38] D. Li, A. Nishijima, D.E. Morris, G.D. Guthrie, J. Catal. 188 (1999) 111.
[39] T. Klimova, J. Reyes, O. Gutiérrez, L. Lizama, Appl. Catal. A Gen. 335 (2008) 159.
[40] L. Vradman, M.V. Landau, M. Herskowitz, V. Ezersky, M. Talianker, S. Nikitenko,
Y. Koltypin, A. Gedanken, J. Catal. 213 (2003) 163.
[41] M.Y. Sun, D. Nicosia, R. Prins, Catal. Today 86 (2003) 173.
[42] D.C. Vermaire, P.C.V. Berge, J. Catal. 116 (1989) 309.
[43] H. Topsøe, B.S. Clausen, F.E. Massoth, Hydrotreating Catalysis—Science and
Technology, Springer, Berlin, 1996.
In conclusion, highly ordered and highly hydrothermally stable
Al-SBA-15 materials have been prepared by adjusting pH and
increasing temperature during the hydrothermal treatment pro-
cess. Using such a method, almost all Al species have been success-
fully introduced into SBA-15. Thus-obtained Al-SBA-15 has
uniformly distributed mesopores, high hydrothermal stability,
and medium B/L acidity. Using Al-SBA-15 as support, a NiW/Al-
SBA-15 catalyst was prepared and showed much higher DBT
HDS activity than SBA-15 and Al2O3 supported catalysts because
of the perfect combination of the better dispersion and higher
stacking of Ni–W–S phases on the support and the participation
of B and L acid sites. This study opens a new route to the introduc-
tion of Al and other heteroatoms into mesoporous silica materials
with various mesostructures and demonstrates the potential of
mesostructured silicoaluminate Al-SBA-15 with high aluminum
loading and suitable B and L acidity as support for deep HDS
catalysts.