Structure， Nature and Activity of Ga Species for Propane Aromatization in Ga/ZSM-5 Revealed by Solid-state NMR Spectroscopy

doi:10.7503/cjcu20200474

Abstract

Abstract:

A series of Ga-modified ZSM-5 zeolites were prepared by different methods. The structure and aci-dity of these catalysts were characterized by solid-state NMR（ssNMR）. The catalytic reactions for propane aromatization were also investigated. With the help of ⁷¹Ga NMR and trimethylphosphine（TMP） probe 1D ³¹P and 2D ¹H-³¹P HETCOR NMR， it was found that the Ga₂O₃/ZSM-5 sample prepared by physical mixing only contains Ga₂O₃ species with weak Lewis acidity， and the samples prepared by impregnation（Ga/ZSM-5-ox） and impregnation followed by reduction-oxidation treatment（Ga/ZSM-5-redox） contain both highly dispersed ga- llium clusters and cationic Ga species. Cationic Ga species was favored on Ga/ZSM-5-IE prepared by ion exchange. Both dispersed gallium clusters and cationic Ga exhibited stronger Lewis acidity. The results of propane aromatization over Ga-modified ZSM-5 showed that the speciation and acidity of Ga have significant effect on the propane conversion. The conversion and selectivity to aromatics followed the order of Ga/ZSM-5-IE > Ga/ZSM-5-redox > Ga/ZSM-5-ox > Ga₂O₃/ZSM-5 > H-ZSM-5. The synergic active sites composed of Br?nsted acid site（BAS） and Lewis acid sites（cationic Ga and dispersed Ga species） on Ga/ZSM-5 zeolite were identified by 2D ¹H-³¹P HETCOR NMR spectroscopy， which were correlated to the catalytic activity.

Key words: Metal-modified zeolite, Active site, Structural characterization, Propane aromatization, Solid-state NMR

CLC Number:

O643

TrendMD:

ZHAO Xingling, QI Guodong, WANG Qiang, CHU Yueying, GAO Wei, LI Shenhui, XU Jun, DENG Feng. Structure， Nature and Activity of Ga Species for Propane Aromatization in Ga/ZSM-5 Revealed by Solid-state NMR Spectroscopy[J]. Chem. J. Chinese Universities, 2020, 41(12): 2681.

Figures/Tables 8

References 31

1	Guisnet M.， Gnep N. S.， Alario F.， Appl. Catal. A⁃Gen.， 1992， 89（1）， 1—30
2	Bhan A.， Delgass W. N.， Catal. Rev.， 2008， 50（1）， 19—151
3	Hagen A.， Roessner F.， Catal. Rev.， 2000， 42（4）， 403—437
4	Ono Y.， Catal. Rev.， 1992， 34（3）， 179—226
5	Meriaudeau P.， Naccache C.， J. Catal.， 1995， 157（2）， 283—288
6	Biscardi J. A.， Meitzner G. D.， Iglesia E.， J. Catal.， 1998， 179（1）， 192—202
7	Meriaudeau P.， Naccache C.， Catal. Rev.， 1997， 39（1/2）， 5—48
8	Mowry J. R.， Anderson R. F.， Johnson J. A.， Oil & Gas J.， 1985， 83（48）， 128—131
9	Biscardi J. A.， Iglesia E.， Catal. Today， 1996， 31（3/4）， 207—231
10	Gnep N. S.， Doyemet J. Y.， Guisnet M.， J. Mol. Catal.， 1988， 45（3）， 281—284
11	Gnep N. S.， Doyemet J. Y.， Seco A. M.， Ribeiro F. R.， Guisnet M.， Appl. Catal.， 1988， 43（1）， 155—166
12	Lukyanov D. B.， Gnep N. S.， Guisnet M. R.， Ind. Eng. Chem. Res.， 1995， 34（2）， 516—523
13	Schreiber M. W.， Plaisance C. P.， Baumgartl M.， Reuter K.， Jentys A.， Bermejo⁃Deval R.， Lercher J. A.， J. Am. Chem. Soc.， 2018， 140（14）， 4849—4859
14	Kwak B. S.， Sachtler W. M. H.， J. Catal.， 1994， 145（2）， 456—463
15	Buckles G. J.， Hutchings G. J.， Catal. Today， 1996， 31（3/4）， 233—246
16	Gnep N. S.， Doyemet J. Y.， Guisnet M.， Stud. Surf. Sci. Catal，1989， 46， 153—162
17	Rodrigues V. D.， Eon J. G.， Faro A. C.， J. Phys. Chem. C， 2010， 114（10）， 4557—4567
18	Nowak I.， Quartararo J.， Derouane E. G.， Vedrine J. C.， Appl. Catal. A⁃Gen.， 2003， 251（1）， 107—120
19	Al⁃Yassir N.， Akhtar M. N.， Al⁃Khattaf S.， J. Porous Mat.， 2012， 19（6）， 943—960
20	Meriaudeau P.， Naccache C.， Catal. Today， 1996， 31（3/4）， 265—273
21	Fricke R.， Kosslick H.， Lischke G.， Richter M.， Chem. Rev.， 2000， 100（6）， 2303—2405
22	Vosmerikova L. N.， Volynkina A. N.， Zaikovskii V. I.， Vosmerikov A. V.， Key Eng. Mater.， 2015， 670， 15—20
23	Larsen F. H.， Jakobsen H. J.， Ellis P. D.， Nielsen N. C.， J. Phys. Chem. A， 1997， 101（46）， 8597—8606
24	Occelli M. L.， Schwering G.， Fild C.， Eckert H.， Auroux A.， Iyer P. S.， Micropor. Mesopor. Mat.， 2000， 34（1）， 15—22
25	Pal P.， Quartararo J.， Abd Hamid S.， Derouane E.， Vedrine J.， Magusin P.， Anderson B.， Can. J. Chem.， 2005， 83（6/7）， 574— 580
26	Gao P.， Wang Q.， Xu J.， Qi G. D.， Wang C.， Zhou X.， Zhou X. L.， Feng N. D.， Liu X. L.， Deng F.， ACS Catal.， 2018， 8（1）， 69— 74
27	Zhao X. L.， Xu J.， Chu Y. Y.， Qi G. D.， Wang Q.， Gao W.， Li S. H.， Feng N. D.， Deng F.， ChemCatChem， 2020， 12（15）， 3380—3889
28	Chu Y. Y.， Yu Z. W.， Zheng A. M.， Fang H. J.， Zhang H. L.， Huang S. J.， Liu S. B.， Deng F.， J. Phys. Chem. C， 2011， 115（15）， 7660—7667
29	Kitagawa H.， Sendoda Y.， Ono Y.， J. Catal.， 1986， 101（1）， 12—18
30	Derouane E. G.， Hamid S. B. A.， Ivanova I. I.， Blom N.， Hojlundnielsen P. E.， J. Mol. Catal.， 1994， 86（1—3）， 371—400
31	Gao P.， Xu J.， Qi G. D.， Wang C.， Wang Q.， Zhao Y. X.， Zhang Y. H.， Feng N. D.， Zhao X. L.， Li J. L.， Deng F.， ACS Catal.， 2018， 8（10）， 9809—9820

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