SSZ-13分子筛上甲醇转化过程中甲氧基物种的生成与活性研究

doi:10.11938/cjmr20222983

波谱学杂志 ›› 2022, Vol. 39 ›› Issue (4): 439-447.doi: 10.11938/cjmr20222983

SSZ-13分子筛上甲醇转化过程中甲氧基物种的生成与活性研究

覃瑞^1,²,王超²,王强²,胡敏^2,³,李金林^1,*(),徐君^2,*(),邓风²

1. 中南民族大学, 催化转化与能源材料化学教育部重点实验室, 催化材料科学湖北省重点实验室, 湖北武汉 430074
2. 中国科学院精密测量科学与技术创新研究院, 武汉物理与数学研究所, 波谱与原子分子物理国家重点实验室, 武汉磁共振中心, 湖北武汉 430071
3. 中国科学院大学, 北京 100049

收稿日期:2022-03-15 出版日期:2022-12-05 发布日期:2022-04-28
通讯作者: 李金林,徐君 E-mail:lij@mail.scuec.edu.cn;xujun@wipm.ac.cn
基金资助:
国家自然科学基金资助项目(22072165);国家自然科学基金资助项目(21991092);国家自然科学基金资助项目(U1932218);国家自然科学基金资助项目(21733013);国家自然科学基金资助项目(22061130202);湖北省自然科学基金资助项目(2021CFA021)

Formation and Reactivity of Surface Methoxy Species in Methanol Conversion over SSZ-13 Zeolite

Rui QIN^1,²,Chao WANG²,Qiang WANG²,Min HU^2,³,Jin-lin LI^1,*(),Jun XU^2,*(),Feng DENG²

1. Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education & Hubei Key Laboratory of Catalysis and Materials Science, South-Central Minzu University, Wuhan 430074, China
2. National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, China
3. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2022-03-15 Online:2022-12-05 Published:2022-04-28
Contact: Jin-lin LI,Jun XU E-mail:lij@mail.scuec.edu.cn;xujun@wipm.ac.cn

摘要/Abstract

摘要：

本文使用固体核磁共振（NMR）技术研究了SSZ-13分子筛上甲醇制烯烃反应过程中表面甲氧基物种的生成以及反应活性.通过二维¹³C-²⁷Al HMQC NMR方法确证了甲醇在分子筛骨架Brønsted酸位上生成的甲氧基物种，以及在Lewis酸位上生成的另外一种表面甲氧基物种.¹³C NMR结合气相色谱-质谱（GC-MS）实验结果表明，这两种甲氧基物种在甲醇制烯烃反应中均具有较高的反应活性，既可以导致烃池物种的生成，也可以参与烃池反应生成碳氢化合物.

关键词: SSZ-13分子筛, 固体核磁共振, 甲醇转化, 表面物种, 反应机理

Abstract:

The formation and reactivity of surface methoxy species in methanol reaction over SSZ-13 zeolite were investigated by using solid-state nuclear magnetic resonance (NMR) technique. The surface methoxy species bound to Brønsted acid sites was identified by two-dimensional ¹³C-²⁷Al heteronuclear multiple quantum coherence (HMQC) NMR experiment. The formation of another surface methoxy species bound to Lewis acid sites was also observed. The combination of ¹³C NMR and gas chromatography-mass spectrometry (GC-MS) showed that the two kinds of surface methoxy species possess high reactivity, contributing to the formation of hydrocarbon pool species and hydrocarbons via the hydrocarbon pool mechanism.

Key words: SSZ-13 zeolite, solid-state nuclear magnetic resonance, methanol conversion, surface species, reaction mechanism

中图分类号:

O482.53

覃瑞,王超,王强,胡敏,李金林,徐君,邓风. SSZ-13分子筛上甲醇转化过程中甲氧基物种的生成与活性研究[J]. 波谱学杂志, 2022, 39(4): 439-447.

Rui QIN,Chao WANG,Qiang WANG,Min HU,Jin-lin LI,Jun XU,Feng DENG. Formation and Reactivity of Surface Methoxy Species in Methanol Conversion over SSZ-13 Zeolite[J]. Chinese Journal of Magnetic Resonance, 2022, 39(4): 439-447.

图/表 4

参考文献 48

1	CHANG C D, SILVESTRI A J The conversion of methanol and other O-compounds to hydrocarbons over zeolite catalysts[J]. J Catal, 1977, 47 (2):249-259. doi: 10.1016/0021-9517(77)90172-5
2	CHANG C D Hydrocarbons from methanol[J]. Catal Rev, 1983, 25 (1):1-118. doi: 10.1080/01614948308078874
3	HAW J F, SONG W, MARCUS D M, et al The mechanism of methanol to hydrocarbon catalysis[J]. Acc Chem Res, 2003, 36 (5):317-326. doi: 10.1021/ar020006o
4	OLSBYE U, SVELLE S, BJ RGEN M, et al Conversion of methanol to hydrocarbons: How zeolite cavity and pore size controls product selectivity[J]. Angew Chem Int Ed, 2012, 51 (24):5810-5831. doi: 10.1002/anie.201103657
5	ILIAS S, BHAN A Mechanism of the catalytic conversion of methanol to hydrocarbons[J]. ACS Catal, 2013, 3 (1):18-31. doi: 10.1021/cs3006583
6	WANG C, XU J, DENG F Mechanism of methanol-to-hydrocarbon reaction over zeolites: A solid-state NMR perspective[J]. ChemCatChem, 2020, 12 (4):965-980. doi: 10.1002/cctc.201901937
7	MOLE T, BETT G, SEDDON D Conversion of methanol to hydrocarbons over ZSM-5 zeolite: An examination of the role of aromatic hydrocarbons using 13carbon- and deuterium-labeled feeds[J]. J Catal, 1983, 84 (2):435-445. doi: 10.1016/0021-9517(83)90014-3
8	HAW J F, NICHOLAS J B, SONG W, et al Roles for cyclopentenyl cations in the synthesis of hydrocarbons from methanol on zeolite catalyst HZSM-5[J]. J Am Chem Soc, 2000, 122 (19):4763-4775. doi: 10.1021/ja994103x
9	SONG W G, HAW J F, NICHOLAS J B, et al Methylbenzenes are the organic reaction centers for methanol-to-olefin catalysis on HSAPO-34[J]. J Am Chem Soc, 2000, 122 (43):10726-10727. doi: 10.1021/ja002195g
10	ARSTAD B, KOLBOE S Methanol-to-hydrocarbons reaction over SAPO-34. Molecules confined in the catalyst cavities at short time on stream[J]. Catal Lett, 2001, 71 (3-4):209-212.
11	SVELLE S, BJ RGEN M, KOLBOE S, et al Intermediates in the methanol-to-hydrocarbons (MTH) reaction: A gas phase study of the unimolecular reactivity of multiply methylated benzenium cations[J]. Catal Lett, 2006, 109 (1-2):25-35. doi: 10.1007/s10562-006-0052-8
12	ILIAS S, BHAN A The mechanism of aromatic dealkylation in methanol-to-hydrocarbons conversion on H-ZSM-5: What are the aromatic precursors to light olefins?[J]. J Catal, 2014, 311, 6-16. doi: 10.1016/j.jcat.2013.11.003
13	SUN X Y, MUELLER S, SHI H, et al On the impact of co-feeding aromatics and olefins for the methanol-to-olefins reaction on HZSM-5[J]. J Catal, 2014, 314, 21-31. doi: 10.1016/j.jcat.2014.03.013
14	YARULINA I, DE WISPELAERE K, BAILLEUL S, et al Structure–performance descriptors and the role of Lewis acidity in the methanol-to-propylene process[J]. Nat Chem, 2018, 10 (8):804-812. doi: 10.1038/s41557-018-0081-0
15	ST CKER M Methanol-to-hydrocarbons: catalytic materials and their behavior[J]. Micropor Mesopor Mat, 1999, 29 (1-2):3-48. doi: 10.1016/S1387-1811(98)00319-9
16	LIU Y, M LLER S, BERGER D, et al Formation mechanism of the first carbon–carbon bond and the first olefin in the methanol conversion into hydrocarbons[J]. Angew Chem Int Ed, 2016, 55 (19):5723-5726. doi: 10.1002/anie.201511678
17	CHOWDHURY A D, HOUBEN K, WHITING G T, et al Initial carbon–carbon bond formation during the early stages of the methanol-to-olefin process proven by zeolite-trapped acetate and methyl acetate[J]. Angew Chem Int Ed, 2016, 55 (51):15840-15845. doi: 10.1002/anie.201608643
18	WANG C, CHU Y Y, XU J, et al Extra-framework aluminum-assisted initial C−C bond formation in methanol-to-olefins conversion on zeolite H-ZSM-5[J]. Angew Chem Int Ed, 2018, 57 (32):10197-10201. doi: 10.1002/anie.201805609
19	LESTHAEGHE D, VAN SPEYBROECK V, MARIN G B, et al Understanding the failure of direct C-C coupling in the zeolite-catalyzed methanol-to-olefin process[J]. Angew Chem Int Ed, 2006, 45 (11):1714-1719. doi: 10.1002/anie.200503824
20	MARCUS D M, MCLACHLAN K A, WILDMAN M A, et al Experimental evidence from H/D exchange studies for the failure of direct C-C coupling mechanisms in the methanol-to-olefin process catalyzed by HSAPO-34[J]. Angew Chem Int Ed, 2006, 45 (19):3133-3136. doi: 10.1002/anie.200504372
21	SONG W g, MARCUS D M, FU H, et al An oft-studied reaction that may never have been: Direct catalytic conversion of methanol or dimethyl ether to hydrocarbons on the solid acids HZSM-5 or HSAPO-34[J]. J Am Chem Soc, 2002, 124 (15):3844-3845. doi: 10.1021/ja016499u
22	HUTCHINGS G J, GOTTSCHALK F, HUNTER R Hydrocarbon formation from methylating agents over the zeolite catalyst ZSM-5. Comments on the mechanism of carbon?carbon bond and methane formation[J]. J Chem Soc, Farady Trans, 1987, 83 (3):571-583. doi: 10.1039/f19878300571
23	WU X Q, XU S T, ZHANG W N, et al Direct mechanism of the first carbon–carbon bond formation in the methanol-to-hydrocarbons process[J]. Angew Chem Int Ed, 2017, 56 (31):9039-9043. doi: 10.1002/anie.201703902
24	DESSAU R M, LAPIERRE R B On the mechanism of methanol conversion to hydrocarbons over HZSM-5[J]. J Catal, 1982, 78 (1):136-141. doi: 10.1016/0021-9517(82)90292-5
25	MOLE T, WHITESIDE J A, SEDDON D Aromatic co-catalysis of methanol conversion over zeolite catalysts[J]. J Catal, 1983, 82 (2):261-266. doi: 10.1016/0021-9517(83)90192-6
26	DAHL I, KOLBOE S On the reaction mechanism for propene formation in the MTO reaction over SAPO-34[J]. Catal Lett, 1993, 20 (3-4):329-336. doi: 10.1007/BF00769305
27	XU S T, ZHENG A M, WEI Y X, et al Direct observation of cyclic carbenium ions and their role in the catalytic cycle of the methanol-to-olefin reaction over chabazite zeolites[J]. Angew Chem Int Ed, 2013, 52 (44):11564-11568. doi: 10.1002/anie.201303586
28	SVELLE S, JOENSEN F, NERLOV J, et al Conversion of methanol into hydrocarbons over zeolite H-ZSM-5: Ethene formation is mechanistically separated from the formation of higher alkenes[J]. J Am Chem Soc, 2006, 128 (46):14770-14771. doi: 10.1021/ja065810a
29	BJORGEN M, SVELLE S, JOENSEN F, et al Conversion of methanol to hydrocarbons over zeolite H-ZSM-5: On the origin of the olefinic species[J]. J Catal, 2007, 249 (2):195-207. doi: 10.1016/j.jcat.2007.04.006
30	YU B W, LOU C Y, ZHANG W N, et al Insight into the dual cycle mechanism of methanol-to-olefins reaction over SAPO-34 molecular sieve by isotopic tracer studies[J]. Chem Res Chinese U, 2020, 36 (6):1203-1208. doi: 10.1007/s40242-020-0216-x
31	MCCANN D M, LESTHAEGHE D, KLETNIEKS P W, et al A complete catalytic cycle for supramolecular methanol-to-olefins conversion by linking theory with experiment[J]. Angew Chem Int Ed, 2008, 47 (28):5179-5182. doi: 10.1002/anie.200705453
32	WANG C, XU J, QI G D, et al Methylbenzene hydrocarbon pool in methanol-to-olefins conversion over zeolite H-ZSM-5[J]. J Catal, 2015, 332, 127-137. doi: 10.1016/j.jcat.2015.10.001
33	WANG C, CHU Y Y, ZHENG A M, et al New insight into the hydrocarbon-pool chemistry of the methanol-to-olefins conversion over zeolite H-ZSM-5 from GC-MS, solid-state NMR spectroscopy, and DFT calculations[J]. Chem Eur J, 2014, 20 (39):12432-12443. doi: 10.1002/chem.201403972
34	WANG W, SEILER M, HUNGER M Role of surface methoxy species in the conversion of methanol to dimethyl ether on acidic zeolites investigated by in situ stopped-flow MAS NMR spectroscopy[J]. J Phys Chem B, 2001, 105 (50):12553-12558. doi: 10.1021/jp0129784
35	WANG W, BUCHHOLZ A, SEILER M, et al Evidence for an initiation of the methanol-to-olefin process by reactive surface methoxy groups on acidic zeolite catalysts[J]. J Am Chem Soc, 2003, 125 (49):15260-15267. doi: 10.1021/ja0304244
36	COMAS-VIVES A, VALLA M, COP RET C, et al Cooperativity between Al sites promotes hydrogen transfer and carbon–carbon bond formation upon dimethyl ether activation on alumina[J]. ACS Cent Sci, 2015, 1 (6):313-319. doi: 10.1021/acscentsci.5b00226
37	DEIMUND M A, HARRISON L, LUNN J D, et al Effect of heteroatom concentration in SSZ-13 on the methanol-to-olefins reaction[J]. ACS Catal, 2016, 6 (2):542-550. doi: 10.1021/acscatal.5b01450
38	赵星岭, 齐国栋, 王强, 等 Ga改性Ga/ZSM-5分子筛的结构、性质及其催化丙烷芳构化的固体核磁共振波谱研究[J]. 高等学校化学学报, 2020, 41 (12):2681-2689.
	ZHAO X L, QI G D, WANG Q, et al Structure, nature and activity of ga species for propane aromatization in Ga/ZSM-5 revealed by solid-state NMR spectroscopy[J]. Chem J Chinese U, 2020, 41 (12):2681-2689.
39	ZHOU X, WANG C, CHU Y Y, et al Mechanistic insight into ethanol dehydration over sapo-34 zeolite by solid-state NMR spectroscopy[J]. Chem Res Chinese U, 2022, 38 (1):155-160. doi: 10.1007/s40242-022-1450-1
40	齐国栋, 叶晓栋, 徐君, 等分子筛上糖类催化转化的核磁共振研究[J]. 高等学校化学学报, 2021, 42 (1):148-164.
	QI G D, YE X D, XU J, et al Progress in NMR studies of carbohydrates conversion on zeolites[J]. Chem J Chinese U, 2021, 42 (1):148-164.
41	WANG W, HUNGER M Reactivity of surface alkoxy species on acidic zeolite catalysts[J]. Acc Chem Res, 2008, 41 (8):895-904. doi: 10.1021/ar700210f
42	LI S H, LAFON O, WANG W Y, et al Recent advances of solid-state nmr spectroscopy for microporous materials[J]. Adv Mater, 2020, 32 (44):2002879. doi: 10.1002/adma.202002879
43	QI G D, WANG Q, XU J, et al Solid-state NMR studies of internuclear correlations for characterizing catalytic materials[J]. Chem Soc Rev, 2021, 50 (15):8382-8399. doi: 10.1039/D0CS01130D
44	RAVI M, SUSHKEVICH V L, VAN BOKHOVEN J A Towards a better understanding of Lewis acidic aluminium in zeolites[J]. Nat Mater, 2020, 19 (10):1047-1056. doi: 10.1038/s41563-020-0751-3
45	PHUNG T K, BUSCA G On the Lewis acidity of protonic zeolites[J]. App Catal A: Gen, 2015, 504, 151-157. doi: 10.1016/j.apcata.2014.11.031
46	LESTHAEGHE D, VANDER MYNSBRUGGE J, VANDICHEL M, et al Full theoretical cycle for both ethene and propene formation during methanol-to-olefin conversion in H-ZSM-5[J]. ChemCatChem, 2011, 3 (1):208-212. doi: 10.1002/cctc.201000286
47	LIU Y, KIRCHBERGER F M, M LLER S, et al Critical role of formaldehyde during methanol conversion to hydrocarbons[J]. Nat Commun, 2019, 10 (1):1462. doi: 10.1038/s41467-019-09449-7
48	ARORA S S, NIESKENS D L S, MALEK A, et al Lifetime improvement in methanol-to-olefins catalysis over chabazite materials by high-pressure H₂ co-feeds[J]. Nat Catal, 2018, 1 (9):666-672. doi: 10.1038/s41929-018-0125-2

[1]	曾姝, 徐舒涛, 魏迎旭, 刘中民. H-SSZ-13分子筛催化乙醇脱水制乙烯反应的原位固体核磁共振研究[J]. 波谱学杂志, 2022, 39(2): 123-132.
[2]	陈翰迪,孔海宇,赵侦超,张维萍. 固体核磁共振结合密度泛函理论计算研究SSZ-39分子筛的钠离子落位与铝分布[J]. 波谱学杂志, 2021, 38(4): 543-551.
[3]	杨文杰,黄骏. 基于固体核磁共振技术的固体酸结构、酸性及活性分析[J]. 波谱学杂志, 2021, 38(4): 460-473.
[4]	夏锡锋,张文静,林芝晔,柯晓康,温玉洁,王芳,陈俊超,彭路明. 氧化物纳米材料表面结构与性质的固体核磁共振波谱研究[J]. 波谱学杂志, 2021, 38(4): 533-542.
[5]	王永祥,王强,徐君,夏清华,邓风. 六氟硅酸铵后处理对H-ZSM-5分子筛酸性影响的固体NMR研究[J]. 波谱学杂志, 2021, 38(4): 514-522.
[6]	王子春,黄骏,姜怡娇. 五配位铝强化硅铝固体酸的固体核磁共振研究[J]. 波谱学杂志, 2021, 38(4): 552-570.
[7]	史朝为,石攀,田长麟. 非天然氨基酸在蛋白质动态特性核磁共振研究中的应用[J]. 波谱学杂志, 2021, 38(4): 523-532.
[8]	肖瑶,夏长久,易先锋,刘凤庆,刘尚斌,郑安民. 固体核磁共振技术在锡硅分子筛表征中的应用[J]. 波谱学杂志, 2021, 38(4): 571-584.
[9]	高树树,徐舒涛,魏迎旭,刘中民. 固体核磁共振技术在甲醇制烯烃反应中的应用[J]. 波谱学杂志, 2021, 38(4): 433-447.
[10]	陈欣,付颖懿,岳斌,贺鹤勇. 固体核磁共振技术研究金属氧化物类固体酸催化剂的酸碱性[J]. 波谱学杂志, 2021, 38(4): 491-502.
[11]	张之杰, 李端秀, 罗春, 仇汝臣, 邓宗武, 张海禄. 晶体学辅助的2-吡啶甲酸固体¹³C化学位移理论计算归属[J]. 波谱学杂志, 2020, 37(1): 67-75.
[12]	雷振宇, 梁欣苗, 雷友义, 杨丽, 冯继文. 固体核磁共振技术在锂/钠离子电池碳负极中的应用及研究进展[J]. 波谱学杂志, 2020, 37(1): 28-39.
[13]	魏令, 张善民. 利用相位步进脉冲消除探头¹³C NMR背景信号[J]. 波谱学杂志, 2020, 37(1): 123-130.
[14]	高秀枝, 张翊, 王秀梅, 张智华, 徐广通. NMR研究超稳Y分子筛水热老化过程中结构与酸性的变化[J]. 波谱学杂志, 2020, 37(1): 95-103.
[15]	冯宗静, 杜亚平, 罗锋, 徐骏. 通过超宽¹³⁹La固体核磁共振波谱研究层状La(OH)₂NO₃[J]. 波谱学杂志, 2020, 37(1): 76-85.

SSZ-13分子筛上甲醇转化过程中甲氧基物种的生成与活性研究

Formation and Reactivity of Surface Methoxy Species in Methanol Conversion over SSZ-13 Zeolite

RichHTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 4

参考文献 48

相关文章 15

编辑推荐

Metrics

本文评价