REVIEW ARTICLE

Solid-state NMR for metal-containing zeolites: from active sites to reaction mechanism

  • Xingling Zhao 1,2 ,
  • Jun Xu , 1,3 ,
  • Feng Deng , 1
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  • 1. National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, CAS Key Laboratory of Magnetic Resonance in Biological Systems, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China
  • 2. University of Chinese Academy of Sciences, Beijing 100049, China
  • 3. Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, Wuhan 430074, China

Received date: 19 Apr 2019

Accepted date: 04 Jul 2019

Published date: 15 Apr 2020

Copyright

2020 Higher Education Press and Springer-Verlag GmbH Germany, part of Springer Nature

Abstract

Metal-containing zeolite catalysts have found a wide range of applications in heterogeneous catalysis. To understand the nature of metal active sites and the reaction mechanism over such catalysts is of great importance for the establishment of structure-activity relationship. The advanced solid-state NMR (SSNMR) spectroscopy is robust in the study of zeolites and zeolite-catalyzed reactions. In this review, we summarize recent developments and applications of SSNMR for exploring the structure and property of active sites in metal-containing zeolites. Moreover, detailed information on host-guest interactions in the relevant zeolite catalysis obtained by SSNMR is also discussed. Finally, we highlight the mechanistic understanding of catalytic reactions on metal-containing zeolites based on the observation of key surface species and active intermediates.

Cite this article

Xingling Zhao , Jun Xu , Feng Deng . Solid-state NMR for metal-containing zeolites: from active sites to reaction mechanism[J]. Frontiers of Chemical Science and Engineering, 2020 , 14(2) : 159 -187 . DOI: 10.1007/s11705-019-1885-1

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 21622311, 21473245, 21603265, 21733013, 21773296), Key Program for Frontier Science of the Chinese Academy of Sciences (Grant No. QYZDB-SSW-SLH027) and Hubei Provincial Natural Science Foundation (Grant No. 2017CFA032).
1
Jacobs P, Flanigen E M, Jansen J, van Bekkum H. Introduction to Zeolite Science and Practice. Amsterdam: Elsevier, 2001, 11–67

2
IZA Structure Commission Website

3
Almutairi S M T, Mezari B, Filonenko G A, Magusin P C M M, Rigutto M S, Pidko E A, Hensen E J M. Influence of extraframework aluminum on the Brønsted acidity and catalytic reactivity of faujasite zeolite. ChemCatChem, 2013, 5(2): 452–466

4
Wang Q L, Giannetto G, Guisnet M. Dealumination of zeolites III. Effect of extra-framework aluminum species on the activity, selectivity, and stability of Y-zeolites in n-heptane cracking. Journal of Catalysis, 1991, 130(2): 471–482

5
Li S H, Zheng A M, Su Y C, Zhang H L, Chen L, Yang J, Ye C H, Deng F. Brønsted/Lewis acid synergy in dealuminated HY zeolite: A combined solid-state NMR and theoretical calculation study. Journal of the American Chemical Society, 2007, 129(36): 11161–11171

6
Vogt E T C, Weckhuysen B M. Fluid catalytic cracking: Recent developments on the grand old lady of zeolite catalysis. Chemical Society Reviews, 2015, 44(20): 7342–7370

7
Ennaert T, Van Aelst J, Dijkmans J, De Clercq R, Schutyser W, Dusselier M, Verboekend D, Sels B F. Potential and challenges of zeolite chemistry in the catalytic conversion of biomass. Chemical Society Reviews, 2016, 45(3): 584–611

8
Corma A, Nemeth L T, Renz M, Valencia S. Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer-Villiger oxidations. Nature, 2001, 412(6845): 423–425

9
Holm M S, Saravanamurugan S, Taarning E. Conversion of sugars to lactic acid derivatives using heterogeneous zeotype catalysts. Science, 2010, 328(5978): 602–605

10
Moliner M, Roman-Leshkov Y, Davis M E. Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water. Proceedings of the National Academy of Sciences of the United States of America, 2010, 107(14): 6164–6168

11
Roman-Leshkov Y, Moliner M, Labinger J A, Davis M E. Mechanism of glucose isomerization using a solid Lewis acid catalyst in water. Angewandte Chemie International Edition, 2010, 49(47): 8954–8957

12
Taarning E, Osmundsen C M, Yang X B, Voss B, Andersen S I, Christensen C H. Zeolite-catalyzed biomass conversion to fuels and chemicals. Energy & Environmental Science, 2011, 4(3): 793–804

13
Nikolla E, Roman-Leshkov Y, Moliner M, Davis M E. “One-Pot” synthesis of 5-(hydroxymethyl)furfural from carbohydrates using tin-beta zeolite. ACS Catalysis, 2011, 1(4): 408–410

14
Bermejo-Deval R, Assary R S, Nikolla E, Moliner M, Roman-Leshkov Y, Hwang S J, Palsdottir A, Silverman D, Lobo R F, Curtiss L A, Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites. Proceedings of the National Academy of Sciences of the United States of America, 2012, 109(25): 9727–9732

15
Kubicka D, Kubickova I, Cejka J. Application of molecular sieves in transformations of biomass and biomass-derived feedstocks. Catalysis Reviews, 2013, 55(1): 1–78

16
Dapsens P Y, Mondelli C, Perez-Ramirez J. Design of Lewis-acid centres in zeolitic matrices for the conversion of renewables. Chemical Society Reviews, 2015, 44(20): 7025–7043

17
Luo H Y, Lewis J D, Roman-Leshkov Y. Lewis acid zeolites for biomass conversion: Perspectives and challenges on reactivity, synthesis, and stability. Annual Review of Chemical and Biomolecular Engineering, 2016, 7(1): 663–692

18
Smeets P J, Woertink J S, Sels B F, Solomon E I, Schoonheydt R A. Transition-metal ions in zeolites: Coordination and activation of oxygen. Inorganic Chemistry, 2010, 49(8): 3573–3583

19
Kosinov N, Liu C, Hensen E J M, Pidko E A. Engineering of transition metal catalysts confined in zeolites. Chemistry of Materials, 2018, 30(10): 3177–3198

20
Singh J, Lamberti C, van Bokhoven J A. Advanced X-ray absorption and emission spectroscopy: in situ catalytic studies. Chemical Society Reviews, 2010, 39(12): 4754–4766

21
Bordiga S, Groppo E, Agostini G, van Bokhoven J A, Lamberti C. Reactivity of surface species in heterogeneous catalysts probed by in situ X-ray absorption techniques. Chemical Reviews, 2013, 113(3): 1736–1850

22
Sushkevich V L, Palagin D, Ranocchiari M, van Bokhoven J A. Selective anaerobic oxidation of methane enables direct synthesis of methanol. Science, 2017, 356(6337): 523–527

23
Newton M A, Knorpp A J, Pinar A B, Sushkevich V L, Palagin D, van Bokhoven J A. On the mechanism underlying the direct conversion of methane to methanol by copper hosted in zeolites; braiding Cu K-Edge XANES and reactivity studies. Journal of the American Chemical Society, 2018, 140(32): 10090–10093

24
Grundner S, Markovits M A C, Li G, Tromp M, Pidko E A, Hensen E J M, Jentys A, Sanchez-Sanchez M, Lercher J A. Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol. Nature Communications, 2015, 6(1): 1–9

25
Almutairi S M T, Mezari B, Magusin P C M M, Pidko E A, Hensen E J M. Structure and reactivity of Zn-modified ZSM-5 zeolites: The importance of clustered cationic Zn complexes. ACS Catalysis, 2012, 2(1): 71–83

26
Groothaert M H, van Bokhoven J A, Battiston A A, Weckhuysen B M, Schoonheydt R A. Bis(mu-oxo)dicopper in Cu-ZSM-5 and its role in the decomposition of NO: A combined in situ XAFS, UV-Vis-Near-IR, and kinetic study. Journal of the American Chemical Society, 2003, 125(25): 7629–7640

27
Smeets P J, Groothaert M H, Schoonheydt R A. Cu based zeolites: A UV-vis study of the active site in the selective methane oxidation at low temperatures. Catalysis Today, 2005, 110(3-4): 303–309

28
Snyder B E R, Vanelderen P, Bols M L, Hallaert S D, Bottger L H, Ungur L, Pierloot K, Schoonheydt R A, Sels B F, Solomon E I. The active site of low-temperature methane hydroxylation in iron-containing zeolites. Nature, 2016, 536(7616): 317–321

29
Fitzgerald J J. Solid-State NMR Spectroscopy of Inorganic Materials. Washington: American Chemical Society, 1999, 2–120

30
Qi G D, Wang Q, Xu J, Trebosc J, Lafon O, Wang C, Amoureux J P, Deng F. Synergic effect of active sites in zinc-modified ZSM-5 zeolites as revealed by high-field solid-state NMR spectroscopy. Angewandte Chemie International Edition, 2016, 55(51): 15826–15830

31
Gao P, Wang Q, Xu J, Qi G D, Wang C, Zhou X, Zhou X L, Feng N D, Liu X L, Deng F. Bronsted/Lewis acid synergy in methanol-to-aromatics conversion on Ga-modified ZSM-5 zeolites, as studied by solid-state NMR spectroscopy. ACS Catalysis, 2018, 8(1): 69–74

32
Qi G D, Wang Q, Xu J, Wu Q M, Wang C, Zhao X L, Meng X J, Xiao F S, Deng F. Direct observation of tin sites and their reversible interconversion in zeolites by solid-state NMR spectroscopy. Communications Chemistry, 2018, 1(1): 1–7

33
Qi G D, Wang Q, Chu Y Y, Xu J, Zheng A M, Su J H, Chen J F, Wang C, Wang W Y, Gao P, Room temperature stable zinc carbonyl complex formed in zeolite ZSM-5 and its hydrogenation reactivity: A solid-state NMR study. Chemical Communications, 2015, 51(44): 9177–9180

34
Li S H, Li J, Zheng A M, Deng F. Solid-state NMR characterization of the structure and catalytic reaction mechanism of solid acid catalysts. Acta Physico-Chimica Sinica, 2017, 33(2): 270–282 (in Chinese)

35
Hunger M. Brønsted acid sites in zeolites characterized by multinuclear solid-state NMR spectroscopy. Catalysis Reviews, 1997, 39(4): 345–393

36
Jiang Y J, Huang J, Dai W L, Hunger M. Solid-state nuclear magnetic resonance investigations of the nature, property, and activity of acid sites on solid catalysts. Solid State Nuclear Magnetic Resonance, 2011, 39(3-4): 116–141

37
Zheng A M, Huang S J, Wang Q, Zhang H L, Deng F, Liu S B. Progress in development and application of solid-state NMR for solid acid catalysis. Chinese Journal of Catalysis, 2013, 34(3): 436–491

38
Gutmann T, Grunberg A, Rothermel N, Werner M, Srour M, Abdulhussain S, Tan S L, Xu Y P, Breitzke H, Buntkowsky G. Solid-state NMR concepts for the investigation of supported transition metal catalysts and nanoparticles. Solid State Nuclear Magnetic Resonance, 2013, 55-56: 1–11

39
Zheng A M, Li S H, Liu S B, Deng F. Acidic properties and structure-activity correlations of solid acid catalysts revealed by solid-state NMR spectroscopy. Accounts of Chemical Research, 2016, 49(4): 655–663

40
Blasco T. Insights into reaction mechanisms in heterogeneous catalysis revealed by in situ NMR spectroscopy. Chemical Society Reviews, 2010, 39(12): 4685–4702

41
Zhang W P, Xu S T, Han X W, Bao X H. In situ solid-state NMR for heterogeneous catalysis: A joint experimental and theoretical approach. Chemical Society Reviews, 2012, 41(1): 192–210

42
Dedecek J, Sobalik Z, Wichterlova B. Siting and distribution of framework aluminium atoms in silicon-rich zeolites and impact on catalysis. Catalysis Reviews, 2012, 54(2): 135–223

43
Huang J, Jiang Y, Marthala V R R, Thomas B, Romanova E, Hunger M. Characterization and acidic properties of aluminum-exchanged zeolites X and Y. Journal of Physical Chemistry C, 2008, 112(10): 3811–3818

44
Deng F, Yue Y, Ye C H. 1H/27Al TRAPDOR NMR studies on aluminum species in dealuminated zeolites. Solid State Nuclear Magnetic Resonance, 1998, 10(3): 151–160

45
Deng F, Yue Y, Ye C H. Observation of nonframework Al species in zeolite beta by solid-state NMR spectroscopy. Journal of Physical Chemistry B, 1998, 102(27): 5252–5256

46
Jiao J, Altwasser S, Wang W, Weitkamp J, Hunger M. State of aluminum in dealuminated, nonhydrated zeolites Y investigated by multinuclear solid-state NMR spectroscopy. Journal of Physical Chemistry B, 2004, 108(38): 14305–14310

47
Hunger M, Horvath T. Multi-nuclear solid-state NMR-study of the local-structure of siohal groups and their interaction with probe-molecules in dehydrated faujasite, mordenite and zeolite ZSM-5. Berichte Der Bunsen-Gesellschaft-Physical Chemistry Chemical Physics, 1995, 99(11): 1316–1320

48
Jiao J, Kanellopoulos J, Wang W, Ray S S, Foerster H, Freude D, Hunger M. Characterization of framework and extra-framework aluminum species in non-hydrated zeolites Y by 27Al spin-echo, high-speed MAS, and MQMAS NMR spectroscopy at B0= 9.4 to 17.6 T. Physical Chemistry Chemical Physics, 2005, 7(17): 3221–3226

49
Medek A, Harwood J S, Frydman L. Multiple-quantum magic-angle spinning NMR: A new method for the study of quadrupolar nuclei in solids. Journal of the American Chemical Society, 1995, 117(51): 12779–12787

50
Kentgens A P M, Iuga D, Kalwei M, Koller H. Direct observation of Brønsted acidic sites in dehydrated zeolite H-ZSM5 using DFS-enhanced 27Al MQMAS NMR spectroscopy. Journal of the American Chemical Society, 2001, 123(12): 2925–2926

51
Brown S P, Spiess H W. Advanced solid-state NMR methods for the elucidation of structure and dynamics of molecular, macromolecular, and supramolecular systems. Chemical Reviews, 2001, 101(12): 4125–4155

52
Li S H, Huang S J, Shen W L, Zhang H L, Fang H J, Zheng A M, Liu S B, Deng F. Probing the spatial proximities among acid sites in dealuminated H-Y zeolite by solid-state NMR spectroscopy. Journal of Physical Chemistry C, 2008, 112(37): 14486–14494

53
Yu Z W, Li S H, Wang Q, Zheng A M, Jun X, Chen L, Deng F. Bronsted/Lewis acid synergy in H-ZSM-5 and H-MOR zeolites studied by 1H and 27Al DQ-MAS solid-state NMR spectroscopy. Journal of Physical Chemistry C, 2011, 115(45): 22320–22327

54
Yu Z W, Wang Q, Chen L, Deng F. Bronsted/Lewis acid sites synergy in H-MCM-22 zeolite studied by 1H and 27Al DQ-MAS NMR spectroscopy. Chinese Journal of Catalysis, 2012, 33(1): 129–139

55
Wang Q, Hu B, Lafon O, Trebosc J, Deng F, Amoureux J P. Double-quantum homonuclear NMR correlation spectroscopy of quadrupolar nuclei subjected to magic-angle spinning and high magnetic field. Journal of Magnetic Resonance (San Diego, Calif.), 2009, 200(2): 251–260

56
Yu Z W, Zheng A M, Wang Q A, Chen L, Xu J, Amoureux J P, Deng F. Insights into the dealumination of zeolite HY revealed by sensitivity-enhanced 27Al DQ-MAS NMR spectroscopy at high field. Angewandte Chemie International Edition, 2010, 49(46): 8657–8661

57
Zheng A M, Liu S B, Deng F. Acidity characterization of heterogeneous catalysts by solid-state NMR spectroscopy using probe molecules. Solid State Nuclear Magnetic Resonance, 2013, 55�?6: 12–27

58
Biaglow A I, Gorte R J, Kokotailo G T, White D. A probe of Brønsted site acidity in zeolites: 13C chemical-shift of acetone. Journal of Catalysis, 1994, 148(2): 779–786

59
Barich D H, Nicholas J B, Xu T, Haw J F. Theoretical and experimental study of the 13C chemical shift tensors of acetone complexed with Brønsted and Lewis acids. Journal of the American Chemical Society, 1998, 120(47): 12342–12350

60
Yang J, Janik M J, Ma D, Zheng A M, Zhang M J, Neurock M, Davis R J, Ye C H, Deng F. Location, acid strength, and mobility of the acidic protons in Keggin 12-H3PW12O40: A combined solid-state NMR spectroscopy and DFT quantum chemical calculation study. Journal of the American Chemical Society, 2005, 127(51): 18274–18280

61
Fang H J, Zheng A M, Chu Y Y, Deng F. 13C chemical shift of adsorbed acetone for measuring the acid strength of solid acids: A theoretical calculation study. Journal of Physical Chemistry C, 2010, 114(29): 12711–12718

62
Gabrienko A A, Arzumanov S S, Freude D, Stepanov A G. Propane aromatization on Zn-modified zeolite BEA studied by solid-state NMR in situ. Journal of Physical Chemistry C, 2010, 114(29): 12681–12688

63
Fricke R, Kosslick H, Lischke G, Richter M. Incorporation of gallium into zeolites: Syntheses, properties and catalytic application. Chemical Reviews, 2000, 100(6): 2303–2405

64
Wang L S, Tao L X, Xie M S, Xu G F, Huang J S, Xu Y D. Dehydrogenation and aromatization of methane under nonoxidizing conditions. Catalysis Letters, 1993, 21(1-2): 35–41

65
Spivey J J, Hutchings G. Catalytic aromatization of methane. Chemical Society Reviews, 2014, 43(3): 792–803

66
Yang J, Ma D, Deng F, Luo Q, Zhang M J, Bao X H, Ye C H. Solid state 13C NMR studies of methane dehydroaromatization reaction on Mo/HZSM-5 and W/HZSM-5 catalysts. Chemical Communications, 2002, (24): 3046–3047

67
Karakaya C, Kee R J. Progress in the direct catalytic conversion of methane to fuels and chemicals. Progress in Energy and Combustion Science, 2016, 55: 60–97

68
Kosinov N, Coumans F J A G, Uslamin E A, Wijpkema A S G, Mezari B, Hensen E J M. Methane dehydroaromatization by Mo/HZSM-5: Mono- or bifunctional catalysis? ACS Catalysis, 2017, 7(1): 520–529

69
Zheng H, Ma D, Bao X H, Hu J Z, Kwak J H, Wang Y, Peden C H F. Direct observation of the active center for methane dehydroaromatization using an ultrahigh field 95Mo NMR spectroscopy. Journal of the American Chemical Society, 2008, 130(12): 3722–3723

70
Hensen E J M, Garcia-Sanchez M, Rane N, Magusin P C M M, Liu P H, Chao K J, van Santen R A. In situ GaK edge XANES study of the activation of Ga/ZSM-5 prepared by chemical vapor deposition of trimethylgallium. Catalysis Letters, 2005, 101(1-2): 79–85

71
Filek U, Bressel A, Sulikowski B, Hunger M. Structural stability and Brønsted acidity of thermally treated AlPW12O40 in comparison with H3PW12O40. Journal of Physical Chemistry C, 2008, 112(49): 19470–19476

72
Zheng A M, Zhang H L, Chen L, Yue Y, Ye C H, Deng F. Relationship between 1H chemical shifts of deuterated pyridinium ions and Brønsted acid strength of solid acids. Journal of Physical Chemistry B, 2007, 111(12): 3085–3089

73
Fraissard J, Ito T. 129Xe-NMR study of adsorbed xenon a new method for studying zeolites and metal-zeolites. Zeolites, 1988, 8(5): 350–361

74
Li X J, Zhang W P, Liu S L, Xu L Y, Han X W, Bao X H. The role of alumina in the supported Mo/Hbeta-Al2O3 catalyst for olefin metathesis: A high-resolution solid-state NMR and electron microscopy study. Journal of Catalysis, 2007, 250(1): 55–66

75
Xu J, Zheng A M, Wang X M, Qi G D, Su J H, Du J F, Gan Z H, Wu J F, Wang W, Deng F. Room temperature activation of methane over Zn modified H-ZSM-5 zeolites: Insight from solid-state NMR and theoretical calculations. Chemical Science (Cambridge), 2012, 3(10): 2932–2940

76
Daniel C, Elbaraoui A, Aguado S, Springuel-Huet M A, Nossov A, Fontaine J P, Topin S, Taffary T, Deliere L, Schuurman Y, Xenon capture on silver-loaded zeolites: Characterization of very strong adsorption sites. Journal of Physical Chemistry C, 2013, 117(29): 15122–15129

77
Xu S T, Zhang W P, Liu X C, Han X W, Bao X H. Enhanced in situ continuous-flow MAS NMR for reaction kinetics in the nanocages. Journal of the American Chemical Society, 2009, 131(38): 13722–13727

78
Moliner M. State of the art of Lewis acid-containing zeolites: Lessons from fine chemistry to new biomass transformation processes. Dalton Transactions (Cambridge, England), 2014, 43(11): 4197–4208

79
Corma A, Domine M E, Nemeth L, Valencia S. Al-free Sn-beta zeolite as a catalyst for the selective reduction of carbonyl compounds (Meerwein-Ponndorf-Verley reaction). Journal of the American Chemical Society, 2002, 124(13): 3194–3195

80
Boronat M, Concepcion P, Corma A, Renz M, Valencia S. Determination of the catalytically active oxidation Lewis acid sites in Sn-beta zeolites, and their optimisation by the combination of theoretical and experimental studies. Journal of Catalysis, 2005, 234(1): 111–118

81
Bermejo-Deval R, Gounder R, Davis M E. Framework and extraframework tin sites in zeolite beta react glucose differently. ACS Catalysis, 2012, 2(12): 2705–2713

82
Bermejo-Deval R, Orazov M, Gounder R, Hwang S J, Davis M E. Active sites in Sn-beta for glucose isomerization to fructose and epimerization to mannose. ACS Catalysis, 2014, 4(7): 2288–2297

83
Rossini A J, Zagdoun A, Lelli M, Lesage A, Copéret C, Emsley L. Dynamic nuclear polarization surface enhanced NMR spectroscopy. Accounts of Chemical Research, 2013, 46(9): 1942–1951

84
Gunther W R, Michaelis V K, Caporini M A, Griffin R G, Roman-Leshkov Y. Dynamic nuclear polarization NMR enables the analysis of Sn-beta zeolite prepared with natural abundance 119Sn precursors. Journal of the American Chemical Society, 2014, 136(17): 6219–6222

85
Wolf P, Valla M, Rossini A J, Comas-Vives A, Nunez-Zarur F, Malaman B, Lesage A, Emsley L, Coperet C, Hermans I. NMR signatures of the active sites in Sn-beta zeolite. Angewandte Chemie International Edition, 2014, 53(38): 10179–10183

86
Kolyagin Y G, Yakimov A V, Tolborg S, Vennestrom P N R, Ivanova I I. Application of 119Sn CPMG MAS NMR for fast characterization of Sn sites in zeolites with natural 119Sn isotope abundance. Journal of Physical Chemistry Letters, 2016, 7(7): 1249–1253

87
Kolyagin Y G, Yakimov A V, Tolborg S, Vennestrom P N R, Ivanova I I. Direct observation of tin in different T-sites of Sn-BEA by one- and two-dimensional 119Sn MAS NMR spectroscopy. Journal of Physical Chemistry Letters, 2018, 9(13): 3738–3743

88
Wolf P, Valla M, Nunez-Zarur F, Comas-Vives A, Rossini A J, Firth C, Kallas H, Lesage A, Emsley L, Coperet C, Correlating synthetic methods, morphology, atomic-level structure, and catalytic activity of Sn-beta catalysts. ACS Catalysis, 2016, 6(7): 4047–4063

89
Josephson T R, Jenness G R, Vlachos D G, Caratzoulas S. Distribution of open sites in Sn-beta zeolite. Microporous and Mesoporous Materials, 2017, 245: 45–50

90
Jiao J, Kanellopoulos J, Wang W, Ray S S, Foerster H, Freude D, Hunger M. Characterization of framework and extra-framework aluminum species in non-hydrated zeolites Y by 27Al spin-echo, high-speed MAS, and MQMAS NMR spectroscopy at B0= 9.4 to 17.6 T. Physical Chemistry Chemical Physics, 2005, 7(17): 3221–3226

91
Jiao J, Wang W, Sulikowski B, Weitkamp J, Hunger M. 29Si and 27Al MAS NMR characterization of non-hydrated zeolites Y upon adsorption of ammonia. Microporous and Mesoporous Materials, 2006, 90(1): 246–250

92
Li S, Pourpoint F, Trébosc J, Zhou L, Lafon O, Shen M, Zheng A, Wang Q, Amoureux J P, Deng F. Host-guest interactions in dealuminated HY zeolite probed by 13C-27Al solid-state NMR spectroscopy. Journal of Physical Chemistry Letters, 2014, 5(17): 3068–3072

93
Corma A, Garcia H. Supramolecular host-guest systems in zeolites prepared by ship-in-a-bottle synthesis. European Journal of Inorganic Chemistry, 2004, 2004(6): 1143–1164

94
Haw J, Marcus D. Well-defined (supra)molecular structures in zeolite methanol-to-olefin catalysis. Topics in Catalysis, 2005, 34(1-4): 41–48

95
Song W, Fu H, Haw J F. Supramolecular origins of product selectivity for methanol-to-olefin catalysis on HSAPO-34. Journal of the American Chemical Society, 2001, 123(20): 4749–4754

96
Wang C, Wang Q, Xu J, Qi G D, Gao P, Wang W Y, Zou Y Y, Feng N D, Liu X L, Deng F. Direct detection of supramolecular reaction centers in the methanol-to-olefins conversion over zeolite H-ZSM-5 by 13C-27Al solid-state NMR spectroscopy. Angewandte Chemie International Edition, 2016, 55(7): 2507–2511

97
Pourpoint F, Trebosc J, Gauvin R M, Wang Q, Lafon O, Deng F, Amoureux J P. Measurement of aluminum-carbon distances using S-RESPDOR NMR experiments. ChemPhysChem, 2012, 13(16): 3605–3615

98
Wang C, Xu J, Wang Q, Zhou X, Qi G D, Feng N D, Liu X L, Meng X J, Xiao F S, Deng F. Host-guest interactions and their catalytic consequences in methanol to olefins conversion on zeolites studied by 13C-27Al double-resonance solid-state NMR spectroscopy. ACS Catalysis, 2017, 7(9): 6094–6103

99
Sazama P, Wichterlova B, Dedecek J, Tvaruzkova Z, Musilova Z, Palumbo L, Sklenak S, Gonsiorova O. FTIR and 27Al MAS NMR analysis of the effect of framework Al- and Si-defects in micro- and micro-mesoporous H-ZSM-5 on conversion of methanol to hydrocarbons. Microporous and Mesoporous Materials, 2011, 143(1): 87–96

100
Schallmoser S, Ikuno T, Wagenhofer M F, Kolvenbach R, Haller G L, Sanchez-Sanchez M, Lercher J A. Impact of the local environment of Bronsted acid sites in ZSM-5 on the catalytic activity in n-pentane cracking. Journal of Catalysis, 2014, 316: 93–102

101
Wang C, Chu Y Y, Xu J, Wang Q, Qi G D, Gao P, Zhou X, Deng F. Extra-framework aluminum-assisted initial C-C bond formation in methanol-to-olefins conversion on zeolite H-ZSM-5. Angewandte Chemie International Edition, 2018, 57(32): 10197–10201

102
Groothaert M H, Smeets P J, Sels B F, Jacobs P A, Schoonheydt R A. Selective oxidation of methane by the bis(mu-oxo)dicopper core stabilized on ZSM-5 and mordenite zeolites. Journal of the American Chemical Society, 2005, 127(5): 1394–1395

103
Snyder B E R, Bols M L, Schoonheydt R A, Sels B F, Solomon E I. Iron and copper active sites in zeolites and their correlation to metalloenzymes. Chemical Reviews, 2018, 118(5): 2718–2768

104
Kolyagin Y G, Ivanova I I, Ordomsky V V, Gedeon A, Pirogov Y A. Methane activation over Zn-modified MFI zeolite: NMR evidence for Zn-methyl surface species formation. Journal of Physical Chemistry C, 2008, 112(50): 20065–20069

105
Kazansky V B, Subbotina I R, Rane N, van Santen R A, Hensen E J M. On two alternative mechanisms of ethane activation over ZSM-5 zeolite modified by Zn2+ and Ga1+ cations. Physical Chemistry Chemical Physics, 2005, 7(16): 3088–3092

106
Kazansky V B, Borovkov V Y, Serikh A I, van Santen R A, Anderson B G. Nature of the sites of dissociative adsorption of dihydrogen and light paraffins in ZnHZSM-5 zeolite prepared by incipient wetness impregnation. Catalysis Letters, 2000, 66(1-2): 39–47

107
Pidko E A, Xu J, Mojet B L, Lefferts L, Subbotina I R, Kazansky V B, van Santen R A. Interplay of bonding and geometry of the adsorption complexes of light alkanes within cationic faujasites. Combined spectroscopic and computational study. Journal of Physical Chemistry B, 2006, 110(45): 22618–22627

108
Kazansky V B, Serykh A I, Pidko E A. DRIFT study of molecular and dissociative adsorption of light paraffins by HZSM-5 zeolite modified with zinc ions: Methane adsorption. Journal of Catalysis, 2004, 225(2): 369–373

109
Biscardi J A, Meitzner G D, Iglesia E. Structure and density of active Zn species in Zn/H-ZSM5 propane aromatization catalysts. Journal of Catalysis, 1998, 179(1): 192–202

110
Kolyagin Y G, Ordomsky V V, Khimyak Y Z, Rebrov A I, Fajula F, Ivanova I I. Initial stages of propane activation over Zn/MFI catalyst studied by in situ NMR and IR spectroscopic techniques. Journal of Catalysis, 2006, 238(1): 122–133

111
Kolyagin Y G, Ivanova I I, Pirogov Y A. 1H and 13C MAS NMR studies of light alkanes activation over MFI zeolite modified by Zn vapour. Solid State Nuclear Magnetic Resonance, 2009, 35(2): 104–112

112
Barbosa L, Zhidomirov G M, van Santen R A. Theoretical study of methane adsorption on Zn(II) zeolites. Physical Chemistry Chemical Physics, 2000, 2(17): 3909–3918

113
Pidko E A, van Santen R A. Activation of light alkanes over zinc species stabilized in ZSM-5 zeolite: A comprehensive DFT study. Journal of Physical Chemistry C, 2007, 111(6): 2643–2655

114
Benco L, Bucko T, Hafner J, Toulhoat H. Periodic DFT calculations of the stability of Al/Si substitutions and extraframework Zn2+ cations in mordenite and reaction pathway for the dissociation of H2 and CH4. Journal of Physical Chemistry B, 2005, 109(43): 20361–20369

115
Frash M V, van Santen R A. Activation of ethane in Zn-exchanged zeolites: A theoretical study. Physical Chemistry Chemical Physics, 2000, 2(5): 1085–1089

116
Ono Y. Transformation of lower alkanes into aromatic hydrocarbons over ZSM-5 zeolites. Catalysis Reviews, 1992, 34(3): 179–226

117
Bhan A, Delgass W N. Propane aromatization over HZSM-5 and Ga/HZSM-5 catalysts. Catalysis Reviews, 2008, 50(1): 19–151

118
Meriaudeau P, Naccache C. The role of Ga2O3 and proton acidity on the dehydrogenating activity of Ga2O3-HZSM-5 catalysts: Evidence of a bifunctional mechanism. Journal of Molecular Catalysis, 1990, 59(3): L31–L36

119
Derouane E G, Hamid S B A, Ivanova I I, Blom N, Hojlundnielsen P E. Thermodynamic and mechanistic studies of initial-stages in propane aromatization over Ga-modified H-ZSM-5 catalysts. Journal of Molecular Catalysis, 1994, 86(1-3): 371–400

120
Price G L, Kanazirev V, Dooley K M, Hart V I. On the mechanism of propane dehydrocyclization over cation-containing, proton-poor MFI zeolite. Journal of Catalysis, 1998, 173(1): 17–27

121
Anunziata O A, Pierella L B. Nature of the active sites in H-ZSM-11 zeolite modified with Zn2+ and Ga3+. Catalysis Letters, 1993, 19(2): 143–151

122
Derouane E G, He H Y, Derouane-Abd Hamid S B, Ivanova I I. In situ MAS NMR investigations of molecular sieves and zeolite-catalyzed reactions. Catalysis Letters, 1999, 58(1): 1–19

123
Shubin A A, Zhidomirov G M, Kazansky V B, van Santen R A. DFT cluster modeling of molecular and dissociative hydrogen adsorption on Zn2+ ions with distant placing of aluminum in the framework of high-silica zeolites. Catalysis Letters, 2003, 90(3): 137–142

124
Barbosa L A M M, van Santen R A. Influence of zeolite framework geometry structure on the stability of the [ZnOZn]2+ cluster by periodical density functional theory. Journal of Physical Chemistry B, 2003, 107(19): 4532–4536

125
Wu J F, Wang W D, Xu J, Deng F, Wang W. Reactivity of C1 surface species formed in methane activation on Zn-modified H-ZSM-5 zeolite. Chemistry (Weinheim an der Bergstrasse, Germany), 2010, 16(47): 14016–14025

126
Gabrienko A A, Arzumanov S S, Toktarev A V, Danilova I G, Prosvirin I P, Kriventsov V V, Zaikovskii V I, Freude D, Stepanov A G. Different efficiency of Zn2+ and ZnO species for methane activation on Zn-modified zeolite. ACS Catalysis, 2017, 7(3): 1818–1830

127
Wang X M, Qi G D, Xu J, Li B J, Wang C, Deng F. NMR-spectroscopic evidence of intermediate-dependent pathways for acetic acid formation from methane and carbon monoxide over a ZnZSM-5 zeolite catalyst. Angewandte Chemie International Edition, 2012, 51(16): 3850–3853

128
Choudhary V R, Mondal K C, Mulla S A R. Simultaneous conversion of methane and methanol into gasoline over bifunctional Ga-, Zn-, In-, and/or Mo-modified ZSM-5 zeolites. Angewandte Chemie International Edition, 2005, 44(28): 4381–4385

129
Wang X M, Xu J, Qi G D, Li B J, Wang C, Deng F. Alkylation of benzene with methane over ZnZSM-5 zeolites studied with solid-state NMR spectroscopy. Journal of Physical Chemistry C, 2013, 117(8): 4018–4023

130
Luzgin M V, Rogov V A, Arzumanov S S, Toktarev A V, Stepanov A G, Parmon V N. Understanding methane aromatization on a Zn-modified high-silica zeolite. Angewandte Chemie International Edition, 2008, 47(24): 4559–4562

131
Wang X M, Xu J, Qi G D, Wang C, Wang W Y, Gao P, Wang Q, Liu X L, Feng N D, Deng F. Carbonylation of ethane with carbon monoxide over Zn-modified ZSM-5 zeolites studied by in situ solid-state NMR spectroscopy. Journal of Catalysis, 2017, 345: 228–235

132
Chang C D, Silvestri A J. Conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts. Journal of Catalysis, 1977, 47(2): 249–259

133
Ono Y, Adachi H, Senoda Y. Selective conversion of methanol into aromatic-hydrocarbons over zinc-exchanged ZSM-5 zeolites. Journal of the Chemical Society-Faraday Transactions 1, 1988, 84: 1091–1099

134
Inoue Y, Nakashiro K, Ono Y. Selective conversion of methanol into aromatic-hydrocarbons over silver-exchanged ZSM-5 zeolites. Microporous Materials, 1995, 4(5): 379–383

135
Zeng D F, Yang J, Wang J Q, Xu J, Yang Y X, Ye C H, Deng F. Solid-state NMR studies of methanol-to-aromatics reaction over silver exchanged HZSM-5 zeolite. Microporous and Mesoporous Materials, 2007, 98(1-3): 214–219

136
Conte M, Lopez-Sanchez J A, He Q, Morgan D J, Ryabenkova Y, Bartley J K, Carley A F, Taylor S H, Kiely C J, Khalid K, Modified zeolite ZSM-5 for the methanol to aromatics reaction. Catalysis Science & Technology, 2012, 2(1): 105–112

137
Choudhary V R, Kinage A K. Methanol-to-aromatics conversion over H-Gallosilicate (MFI): Influence of Si/Ga ratio, degree of H+ exchange, pretreatment conditions, and poisoning of strong acid sites. Zeolites, 1995, 15(8): 732–738

138
Bjorgen M, Svelle S, Joensen F, Nerlov J, Kolboe S, Bonino F, Palumbo L, Bordiga S, Olsbye U. Conversion of methanol to hydrocarbons over zeolite H-ZSM-5: On the origin of the olefinic species. Journal of Catalysis, 2007, 249(2): 195–207

139
Svelle S, Joensen F, Nerlov J, Olsbye U, Lillerud K P, Kolboe S, Bjorgen M. Conversion of methanol into hydrocarbons over zeolite H-ZSM-5: Ethene formation is mechanistically separated from the formation of higher alkenes. Journal of the American Chemical Society, 2006, 128(46): 14770–14771

140
Westgard Erichsen M, Svelle S, Olsbye U. The influence of catalyst acid strength on the methanol to hydrocarbons (MTH) reaction. Catalysis Today, 2013, 215: 216–223

141
Freeman D, Wells R P K, Hutchings G J. Conversion of methanol to hydrocarbons over Ga2O3/H-ZSM-5 and Ga2O3/WO3 catalysts. Journal of Catalysis, 2002, 205(2): 358–365

142
Haw J F, Nicholas J B, Song W G, Deng F, Wang Z K, Xu T, Heneghan C S. Roles for cyclopentenyl cations in the synthesis of hydrocarbons from methanol on zeolite catalyst HZSM-5. Journal of the American Chemical Society, 2000, 122(19): 4763–4775

143
Dai W L, Wang C M, Dyballa M, Wu G J, Guan N J, Li L D, Xie Z K, Hunger M. Understanding the early stages of the methanol-to-olefin conversion on H-SAPO-34. ACS Catalysis, 2015, 5(1): 317–326

144
Wang C, Yi X F, Xu J, Qi G D, Gao P, Wang W Y, Chu Y Y, Wang Q, Feng N D, Liu X L, Experimental evidence on the formation of ethene through carbocations in methanol conversion over H-ZSM-5 zeolite. Chemistry–A European Journal. 2015, 21(34): 12061–12068

145
Xu S T, Zheng A M, Wei Y X, Chen J R, Li J Z, Chu Y Y, Zhang M Z, Wang Q Y, Zhou Y, Wang J B, Direct observation of cyclic carbenium ions and their role in the catalytic cycle of the methanol-to-olefin reaction over chabazite zeolites. Angewandte Chemie International Edition, 2013, 52(44): 11564–11568

146
Wang C, Xu J, Qi G D, Gong Y J, Wang W Y, Gao P, Wang Q, Feng N D, Liu X L, Deng F. Methylbenzene hydrocarbon pool in methanol-to-olefins conversion over zeolite H-ZSM-5. Journal of Catalysis, 2015, 332: 127–137

147
Wang C, Sun X Y, Xu J, Qi G D, Wang W Y, Zhao X L, Li W Z, Wang Q, Deng F. Impact of temporal and spatial distribution of hydrocarbon pool on methanol conversion over H-ZSM-5. Journal of Catalysis, 2017, 354: 138–151

148
Wang J B, Wei Y X, Li J Z, Xu S T, Zhang W N, He Y L, Chen J R, Zhang M Z, Zheng A M, Deng F, Direct observation of methylcyclopentenyl cations (MCP+) and olefin generation in methanol conversion over TON zeolite. Catalysis Science & Technology, 2016, 6(1): 89–97

149
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, A mechanistic study of methanol-to-aromatics reaction over Ga-modified ZSM-5 zeolites: Understanding the dehydrogenation process. ACS Catalysis, 2018, 8(10): 9809–9820

150
Xiao D, Xu S T, Brownbill N J, Paul S, Chen L H, Pawsey S, Aussenac F, Su B L, Han X W, Bao X H, Fast detection and structural identification of carbocations on zeolites by dynamic nuclear polarization enhanced solid-state NMR. Chemical Science (Cambridge), 2018, 9(43): 8184–8193

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