Advanced Aberration-corrected STEM Techniques for Atomic Imaging of Zeolites-confined Single Molecules: From Ex situ toIn situ

doi:10.1007/s40242-024-4222-2

高等学校化学研究 ›› 2025, Vol. 41 ›› Issue (2): 196-210.doi: 10.1007/s40242-024-4222-2

Advanced Aberration-corrected STEM Techniques for Atomic Imaging of Zeolites-confined Single Molecules: From Ex situ toIn situ

WANG Guowei¹, XIONG Hao², WEI Fei^1,2, CHEN Xiao^1,2

1. Ordos Laboratory, Ordos 017000, P. R. China;
2. Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, P. R. China

收稿日期:2024-11-07 接受日期:2024-12-04 出版日期:2025-04-01 发布日期:2025-03-31
通讯作者: CHEN Xiao,chenx123@mail.tsinghua.edu.cn E-mail:chenx123@mail.tsinghua.edu.cn
基金资助:
This work was supported by the National Key Research and Development Program of China (Nos. 2020YFB0606401 and 2018YFB0604801), the National Natural Science Foundation of China (Nos. 22238004, 22275110, 22322203, 223B2205), the Tsinghua-Toyota Joint Research Fund, the National Postdoctoral Program for Innovative Talent and Shuimu Scholar from Tsinghua University, and the Key Research and Development Program of Inner Mongolia and Ordos, China.

Advanced Aberration-corrected STEM Techniques for Atomic Imaging of Zeolites-confined Single Molecules: From Ex situ toIn situ

WANG Guowei¹, XIONG Hao², WEI Fei^1,2, CHEN Xiao^1,2

1. Ordos Laboratory, Ordos 017000, P. R. China;
2. Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, P. R. China

Received:2024-11-07 Accepted:2024-12-04 Online:2025-04-01 Published:2025-03-31
Contact: CHEN Xiao,chenx123@mail.tsinghua.edu.cn E-mail:chenx123@mail.tsinghua.edu.cn
Supported by:
This work was supported by the National Key Research and Development Program of China (Nos. 2020YFB0606401 and 2018YFB0604801), the National Natural Science Foundation of China (Nos. 22238004, 22275110, 22322203, 223B2205), the Tsinghua-Toyota Joint Research Fund, the National Postdoctoral Program for Innovative Talent and Shuimu Scholar from Tsinghua University, and the Key Research and Development Program of Inner Mongolia and Ordos, China.

摘要/Abstract

摘要： Zeolites are a class of inorganic microporous crystalline materials with ordered pore channels, unique shape selectivity, adjustable acidity and alkalinity, and high stability and have been widely used in gas adsorption and heterogeneous catalysis. The size of the zeolite pore structure determines its molecular sieving properties. Therefore, flexibly adjusting the zeolite pore structure and the host-guest interactions with guest molecules to control diffusion or reaction pathways is crucial for designing novel zeolites. Observing the real movement behavior of small molecules and changes in the local structure of the zeolite framework at the micro-nano scale is of great significance. Recently, emerging scanning transmission electron microscopy (STEM) imaging techniques, such as integrated differential phase contrast/optimum bright-field STEM (iDPC/OBF-STEM) and 4D-STEM ptychography have shown great potential for atomic resolution characterization of zeolites, since these are greatly advantageous for imaging electron beam-sensitive materials and light elements. This review first introduces the structural characteristics and applications of zeolites. Secondly, we discuss the application of three emerging imaging techniques in atomic imaging of zeolites. Thirdly, we focus on using iDPC-STEM imaging technology to observe the host-guest interactions between zeolites and single molecules (e.g., benzene, p-xylene, and pyridine). Furthermore, we explore the adsorption-desorption behavior of single molecules in zeolites using in situ iDPC-STEM imaging technology. Finally, we discuss the current challenges and future prospects of advanced TEM characterization techniques in the imaging of zeolite-confined single molecule.

关键词: Zeolite, Integrated differential phase contrast/optimum bright-field STEM, 4D-STEM ptychography, Single-molecule imaging, In situ TEM

Abstract: Zeolites are a class of inorganic microporous crystalline materials with ordered pore channels, unique shape selectivity, adjustable acidity and alkalinity, and high stability and have been widely used in gas adsorption and heterogeneous catalysis. The size of the zeolite pore structure determines its molecular sieving properties. Therefore, flexibly adjusting the zeolite pore structure and the host-guest interactions with guest molecules to control diffusion or reaction pathways is crucial for designing novel zeolites. Observing the real movement behavior of small molecules and changes in the local structure of the zeolite framework at the micro-nano scale is of great significance. Recently, emerging scanning transmission electron microscopy (STEM) imaging techniques, such as integrated differential phase contrast/optimum bright-field STEM (iDPC/OBF-STEM) and 4D-STEM ptychography have shown great potential for atomic resolution characterization of zeolites, since these are greatly advantageous for imaging electron beam-sensitive materials and light elements. This review first introduces the structural characteristics and applications of zeolites. Secondly, we discuss the application of three emerging imaging techniques in atomic imaging of zeolites. Thirdly, we focus on using iDPC-STEM imaging technology to observe the host-guest interactions between zeolites and single molecules (e.g., benzene, p-xylene, and pyridine). Furthermore, we explore the adsorption-desorption behavior of single molecules in zeolites using in situ iDPC-STEM imaging technology. Finally, we discuss the current challenges and future prospects of advanced TEM characterization techniques in the imaging of zeolite-confined single molecule.

Key words: Zeolite, Integrated differential phase contrast/optimum bright-field STEM, 4D-STEM ptychography, Single-molecule imaging, In situ TEM

WANG Guowei, XIONG Hao, WEI Fei, CHEN Xiao. Advanced Aberration-corrected STEM Techniques for Atomic Imaging of Zeolites-confined Single Molecules: From Ex situ toIn situ[J]. 高等学校化学研究, 2025, 41(2): 196-210.

参考文献

[1] Zhou W., Cheng K., Kang J., Zhou C., Subramanian V., Zhang Q., Wang Y., Chem. Soc. Rev., 2019, 48, 3193.
[2] Sun Q., Xie Z., Yu J., Natl. Sci. Rev., 2018, 5, 542.
[3] Qin Z., Lakiss L., Tosheva L., Gilson J. P., Vicente A., Fernandez C., Valtchev V., Adv. Funct. Mater., 2014, 24, 257.
[4] Martinez C., Corma A., Coord. Chem. Rev., 2011, 255, 1558.
[5] Chu K., Wang Y., Liu W., Bu L., Huang Y., Guo N., Qu L., Sang J., Li Y., Su X., Zhang X., Chem. Res. Chinese Universities, 2024, 40, 1151.
[6] Liu P., Wu Q., Chen Z., Xiao F., Chem. Res. Chinese Universities, 2024, 40, 646.
[7] Qu Z., Zhang T., Yin X., Zhang J., Xiong X., Sun Q., Chem. Res. Chinese Universities, 2023, 39, 870.
[8] Li Y., Yu J. H., Chem. Rev., 2014, 114, 7268.
[9] Li C., Moliner M., Corma A., Angew. Chem. Int. Ed. Engl., 2018, 57, 15330.
[10] Sachse A., Garcia-Martinez J., Chem. Mater., 2017, 29, 3827.
[11] Dusselier M., Davis M. E., Chem. Rev., 2018, 118, 5265.
[12] Li J., Cormab A., Yu J., Chem. Soc. Rev., 2015, 44, 7112.
[13] Přech J., Pizarro P., Serrano D. P., Čejka J., Chem. Soc. Rev., 2018, 47, 8263.
[14] Breck D. W. (Union Carbide Corporation), Crystalline Zeolite Y, US 3130007, 1964.
[15] Weitkamp J., Solid State Ionics, 2000, 131, 175.
[16] Argauer R. J., Landolt G. R. (Mobil Oil Corporation), Crystalline Zeolite ZSM-5 and Method of Preparing the Same, US 3702886, 1972.
[17] Cundy C. S., Cox P. A., Chem. Rev., 2003, 103, 663.
[18] Koempel H., Liebner W., Studies in Surface Science and Catalysis, 2007, 167, 261.
[19] Tian P., Wei Y., Ye M., Liu Z., ACS Catal., 2015, 5, 1922.
[20] Yang J., Pan X., Jiao F., Li J., Bao X., Chem. Commun., 2017, 53, 11146.
[21] Zhao B., Zhai P., Wang P., Li J., Li T., Peng M., Zhao M., Hu G., Yang Y., Li Y. W., Zhang Q., Fan W., Ma D., Chem, 2017, 3, 323.
[22] Su J., Zhou H., Liu S., Wang C., Jiao W., Wang Y., Liu C., Ye Y., Zhang L., Zhao Y., Liu H., Wang D., Yang W., Xie Z., He M., Nat. Commun., 2019, 10, 1297.
[23] Ni Y., Chen Z., Fu Y., Liu Y., Zhu W., Liu Z., Nat. Commun., 2018, 9, 3457.
[24] Li Z., Qu Y., Wang J., Liu H., Li M., Miao S., Li C., Joule, 2019, 3, 570.
[25] Wang S., Zhang L., Zhang W., Wang P., Qin Z., Yan W., Dong M., Li J., Wang J., He L., Olsbye U., Fan W., Chem, 2020, 6, 3344.
[26] Kim J., Kim W., Seo Y., Kim J., Ryoo R., J. Catal., 2013, 301, 187.
[27] Hengsawad T., Srimingkwanchai C., Butnark S., Resasco D. E., Jongpatiwut S., Ind. Eng. Chem. Res., 2018, 57, 1429.
[28] Meng J., Li C., Chen X., Song C., Liang C., Micropor. Mesopor. Mater., 2020, 309, 110565.
[29] Ye X., Schmidt J. E., Wang R. P., van Ravenhorst I. K., Oord R., Chen T., de Groot F., Meirer F., Weckhuysen B. M., Angew. Chem. Int. Ed., 2020, 59, 15610.
[30] Negri C., Selleri T., Borfecchia E., Martini A., Lomachenko K. A., Janssens T. V. W., Cutini M., Bordiga S., Berlier G., J. Am. Chem. Soc., 2020, 142, 15884.
[31] Csicsery S. M., Zeolites, 1984, 4, 202.
[32] Smit B., Maesen T. L., Nature, 2008, 451, 671.
[33] Haw J. F., Song W., Marcus D. M., Nicholas J. B., Acc. Chem. Res., 2003, 36, 317.
[34] Kärger J., Vasenkov S., Auerbach S. M., Handbook of Zeolite Science and Technology, CRC Press, Boca Raton, 2003, 446.
[35] Bhan A., Iglesia E., Acc. Chem. Res., 2008, 41, 559.
[36] Katada N., Suzuki K., Noda T., Sastre G., Niwa M., J. Phys. Chem. C, 2009, 113,19208.
[37] Bnmner G. O., Meier W. M., Nature, 1989, 337, 146.
[38] Baerlocher C., McCusker L. B., Olson D. H., Atlas of Zeolite Framework Types, Elsevier, Netherlands, 2007.
[39] Barrer R. M., Zeolites, 1981, 1, 130.
[40] Li J., Corma A., Yu J., Chem. Soc. Rev., 2015, 44, 7112.
[41] Li Y., Yu J., Chem. Rev., 2014, 114, 7268.
[42] Weisz P., Frilette V., J. Phys. Chem., 1960, 64, 382.
[43] Derouane E. G., Studies in Surface Science and Catalysis, 1980, 5.
[44] Hereijgers B. P., Bleken F., Nilsen M. H., Svelle S., Lillerud K. P., Bjørgen M., Weckhuysen B. M., Olsbye U., J. Catal., 2009, 264, 77.
[45] Zhang J., Qian W., Kong C., Wei F., ACS Catal., 2015, 5, 2982.
[46] Fraenkel D., Levy M., J. Catal., 1989, 118, 10.
[47] Chen Q., Liu J., Yang B., Nat. Commun., 2021, 12, 3725.
[48] Mirth G., Cejka J., Lercher J., J. Catal., 1993, 139, 24.
[49] Qin Z., Shen B., Yu Z., Deng F., Zhao L., Zhou S., Yuan D., Gao X., Wang B., Zhao H., Liu H., J. Catal., 2013, 298, 102.
[50] Tarach K., Góra-Marek K., Tekla J., Brylewska K., Datka J., Mlekodaj K., Makowski W., López M. C. I., Triguero J. M., Rey F., J. Catal., 2014, 312, 46.
[51] Lin Q., Gao Z. R., Lin C., Zhang S., Chen J., Li Z., Liu X., Fan W., Li J., Chen X., Camblor M. A., Chen F., Science, 2021, 374, 1605.
[52] Li Y., Yu J., Chem. Rev., 2014, 114, 7268.
[53] Morishita S., Ishikawa R., Kohno Y., Sawada H., Shibata N., Ikuhara Y., Microscopy, 2018, 67, 46.
[54] Wang S. X., Wang L. M., Ewing R. C., J. Nucl. Mater., 2000, 278, 233.
[55] Ugurlu O., Haus J., Gunawan A. A., Thomas M. G., Maheshwari S., Tsapatsis M., Mkhoyan K. A., Phys. Rev. B, 2011, 83, 113408.
[56] Menter J. W., Adv. Phys., 1958, 7, 299.
[57] Bursill L. A., Lodge E. A., Thomas J. M., Nature, 1980, 286, 111.
[58] Haider M., Uhlemann S., Schwan E., Rose H., Kabius B., Urban K., Nature, 1998, 392, 768.
[59] Li C., Zhang Q., Mayoral A., ChemCatChem, 2020, 12, 1248.
[60] O’Leary C. M., Allen C. S., Huang C., Kim J. S., Liberti E., Nellist P. D., Kirkland A. I., Appl. Phys. Lett., 2020, 116, 124101.
[61] Shen B., Chen X., Cai D., Xiong H., Liu X., Meng C., Han Y., Wei F., Adv. Mater., 2020, 32, e1906103.
[62] Zhou Y., Dong Z., Terasaki O., Ma Y., Acc. Mater. Res., 2022, 3, 110.
[63] Wang L., Jiang Y., Zhou Y., Shi R., Hosokawa F., Terasaki O., Zhang Q., Part. Part. Syst. Charact., 2023, 40, 2200122.
[64] Shen B., Chen X., Shen K., Xiong H., Wei F., Nat. Commun., 2020, 11, 2692.
[65] Shibata N., Findlay S. D., Kohno Y., Sawada H., Kondo Y., Ikuhara Y., Nat. Phys., 2012, 8, 611.
[66] Shen B., Chen X., Cai D., Xiong H., Liu X., Meng C., Han Y., Wei F., Adv. Mater., 2020, 32, 1906103.
[67] Shen B., Chen X., Fan X., Xiong H., Wang H., Qian W., Wang Y., Wei F., Nat. Commun., 2021, 12, 2212.
[68] Rose H., Ultramicroscopy, 1977, 2, 251.
[69] Ooe K., Seki T., Ikuhara Y., Shibata N., Ultramicroscopy, 2021, 220, 113133.
[70] Shen B., Wang H., Xiong H., Chen X., Bosch E. G. T., Lazić I., Qian W., Wei F., Nature, 2022, 607, 703.
[71] Shen B., Chen X., Wang H., Xiong H., Bosch E. G. T., Lazić I., Cai D., Qian W., Jin S., Liu X., Han Y., Wei F., Nature, 2021, 592, 541.
[72] Xiong H., Liu Z., Chen X., Wang H., Qian W., Zhang C., Zheng A., Wei F., Science, 2022, 376, 491.
[73] Ooe K., Seki T., Yoshida K., Kohno Y., Ikuhara Y., Shibata N., Sci. Adv., 2023, 9, eadf6865.
[74] Shamzhy M., Opanasenko M., Concepción P., Martínez A., Chem. Soc. Rev., 2019, 48, 1095.
[75] Cornelius M.L. U., Price L., Wells S. A., Petrik L. F., Sartbaeva A., Zeitschrift für Krist. Cryst. Mater., 2019, 234, 461.
[76] Mayoral A., Zhang Q., Zhou Y., Chen P., Ma Y., Monji T., Losch P., Schmidt W., Schüth F., Hirao H., Yu J., Terasaki O., Angew. Chem. Int. Ed., 2020, 59, 19510.
[77] Hoppe W., Acta Cryst., 1969, 25, 495.
[78] Hoppe W., Strube G., Acta Cryst., 1969, 25, 502.
[79] Hoppe W., Acta Cryst., 1969, 25, 508.
[80] Dong Z., Zhang E., Jiang Y., Zhang Q., Mayoral A., Jiang H., Ma Y., J. Am. Chem. Soc., 2023, 145, 6628.
[81] Sha H., Cui J., Li J., Zhang Y., Yang W., Li Y., Yu R., Sci. Adv., 2023, 9, eadf1151.
[82] Zhang H., Li G., Zhang J., Zhang D., Chen Z., Liu X., Guo P., Zhu Y., Chen C., Liu L., Guo X., Han Y., Science, 2023, 380, 633.
[83] Bhan A., Iglesia E., Acc. Chem. Res., 2008, 41, 559.
[84] Katada N., Suzuki K., Noda T., Sastre G., Niwa M., J. Phys. Chem. C, 2009, 113, 19208.
[85] Kokotailo G. T., Lawton S. L., Olson D. H., Meier W. M., Nature, 1978, 272, 437.
[86] Lazic I., Bosch E. G. T., Lazar S., Ultramicroscopy, 2016, 160, 265.
[87] Lazić I., Bosch E. G. T., Adv. Imag. Elect. Phys., 2017, 199, 75.
[88] Yucelen E., Lazic I., Bosch E. G. T., Sci. Rep., 2018, 8, 2676.
[89] Jae J., Tompsett G. A., Foster A. J., Hammond K. D., Auerbach S. M., Lobo R. F., Huber G. W., J. Catal., 2011, 279, 257.
[90] Bereciartua P. J., Cantín Á., Corma A., Jorda J. L., Palomino M., Rey F., Valencla S., Corcoran Jr. E. W., Kortunov P., Ravikovitch P. I., Burton A., Yoon C., Wang Y., Paur C., Guzman J., Bishop A. R., Casty G. L., Science, 2017, 358,1068.
[91] Wang Z., Lobo R. F., Lambros J., Micropor. Mesopor. Mater., 2003, 57, 1.
[92] Li Z., Johnson M. C., Sun M., Ryan E. T., Earl D. J., Maichen W., Martin J. I., Li S., Lew C. M., Wang J., Deem M. W., Davis M. E., Yan Y., Angew. Chem. Int. Ed., 2006, 45, 6329.

Advanced Aberration-corrected STEM Techniques for Atomic Imaging of Zeolites-confined Single Molecules: From Ex situ toIn situ

Advanced Aberration-corrected STEM Techniques for Atomic Imaging of Zeolites-confined Single Molecules: From Ex situ toIn situ

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	XU Jing, ZHANG Rui, WANG Ke, WANG Xiao, SONG Shuyan, ZHANG Hongjie. Co-loading Pd and CeO₂ on Silicalite-1 as High-performance Catalyst for Methane Dry Reforming Reaction[J]. 高等学校化学研究, 2025, 41(1): 15-20.
[2]	HU Chao, FU Wenhua, YUAN Zhiqing, LIU Chuang, WANG Zhendong, YANG Weimin. Direct Synthesis of UOS Zeolite Using a Simple and Commercially Available Organic Structure-directing Agent[J]. 高等学校化学研究, 2025, 41(1): 113-120.
[3]	SHEN Xueyuan, QI Guodong, LIANG Jiawei, WANG Ruichen, XU Jun, DENG Feng. Unveiling the Mechanism of Glycerol Oxidation to Lactic Acid on Pt/Sn-MFI Zeolite: an In situ Solid-state NMR Study[J]. 高等学校化学研究, 2024, 40(6): 935-942.
[4]	HUANG Yitong, WANG Yaquan, LIU Wenrong, BU Lingzhen, QU Liping, CHU Kailiang, GUO Niandong, ZHANG Xian, SU Xuemei, LI Yaoning, SANG Juncai. Synthesis of LSX Using Seed-iteration Approach with High N₂ Adsorption Capacity for Air Separation[J]. 高等学校化学研究, 2024, 40(6): 1192-1200.
[5]	LIU Pei, WU Qinming, CHEN Zhenghai, XIAO Feng-Shou. Recent Advances in the Synthesis of Zeolites from Solid Wastes[J]. 高等学校化学研究, 2024, 40(4): 646-656.
[6]	ZHENG Mingdan, CHEN Ya, LIU Zhan, LYU Jiamin, YE Bo, SUN Ming-Hui, CHEN Li-Hua, SU Bao-Lian. Hierarchically Macroporous Zeolite ZSM-5 Microspheres for Efficient Catalysis[J]. 高等学校化学研究, 2024, 40(4): 704-711.
[7]	HAN Xiaoyang, XIA Huicong, TU Weifeng, WEI Yifan, XUE Dongping, LI Minhan, YAN Wenfu, ZHANG Jia-Nan, HAN Yi-Fan. Zeolite-confined Fe-site Catalysts for the Hydrogenation of CO₂ to Produce High-value Chemicals[J]. 高等学校化学研究, 2024, 40(1): 78-95.
[8]	QU Ziqiang, ZHANG Tianjun, YIN Xichen, ZHANG Junyi, XIONG Xiaoyun, and SUN Qiming. Zeolite-encaged Ultrasmall Pt-Zn Species with Trace Amount of Pt for Efficient Propane Dehydrogenation[J]. 高等学校化学研究, 2023, 39(6): 870-876.
[9]	XIAO Peiwen, LI Hui, WANG Pingmei, LIU Bolun, JING Wendan, HE Lipeng, WANG Runwei, HAN Xue, ZHANG Zongtao, QIU Shilun, LUO Jianhui. Functionalized Hierarchical ZSM-5 Zeolites for the Viscosity Reduction of Heavy Oil at Low Temperature[J]. 高等学校化学研究, 2022, 38(4): 1083-1088.
[10]	LIU Yifeng, WANG Liang, and XIAO Feng-Shou. Selective Oxidation of Methane into Methanol Under Mild Conditions[J]. 高等学校化学研究, 2022, 38(3): 671-676.
[11]	CHENG Dajun, and MENG Xiangju. Recent Advances of Beta Zeolite in the Volatile Organic Compounds(VOCs) Elimination by the Catalytic Oxidations[J]. 高等学校化学研究, 2022, 38(3): 716-722.
[12]	MI Zhenrui, LU Tingting, ZHANG Jia-Nan, XU Ruren, YAN Wenfu. Synthesis of Pure Silica Zeolites[J]. 高等学校化学研究, 2022, 38(1): 9-17.
[13]	LI Jun, RONG Huazhen, CHEN Cong, LI Ziyi, ZUO Jiayu, WANG Wenjian, LIU Xinjian, GUAN Yixing, YANG Xiong, LIU Yingshu, ZOU Xiaoqin, ZHU Guangshan. Synthesis Optimization of SSZ-13 Zeolite Membranes by Dual Templates for N₂/NO₂ Separation[J]. 高等学校化学研究, 2022, 38(1): 250-256.
[14]	LUAN Huimin, WU Qinming, ZHANG Jian, WANG Yeqing, MENG Xiangju, XIAO Feng-Shou. Sustainable Synthesis of Core-Shell Structured ZSM-5@Silicalite-1 Zeolite[J]. 高等学校化学研究, 2022, 38(1): 136-140.
[15]	SHI Chao, WANG Jiaze, LI Lin, LI Yi. High-throughput Screening of Aluminophosphate Zeolites for Adsorption Heat Pump Applications[J]. 高等学校化学研究, 2022, 38(1): 161-166.