电子束敏感材料的原子尺度结构研究

doi:10.7503/cjcu20200548

摘要/Abstract

摘要：

分子筛和金属有机骨架(MOF)材料以其独特的孔道和骨架结构在催化、储能、干燥及净化和吸附分离等领域有着广泛应用, 对其结构的原子尺度表征对于深入理解其构效关系具有重要意义. 但其大孔道结构和有机骨架使得它们对电子束辐照极为敏感, 在常规透射电镜成像模式下结构会很快被破坏变为非晶, 从而无法获得孔道和骨架的原子排列信息. 最近发展起来的基于积分差分相位衬度扫描透射电子显微(iDPC-STEM)技术在电子敏感材料和轻元素组分成像方面展现出明显优势, 使得对多孔骨架材料及烃池物种的表征成为了可能. 本文综述了本课题组近期利用该技术对分子筛和MOF材料原子尺度结构方面的研究. 将iDPC-STEM技术应用到ZSM-5分子筛催化剂中, 实现了对该分子筛的原子级骨架结构的成像分析. 在MOF体系中, 利用该技术观察到MIL-101骨架内部有机连接体与金属节点的配位方式, 在此基础上解析了MIL-101结构中有机配体的连接和金属节点的苯环结构, 并观察了MOF的原子级表面、界面和缺陷等局域结构特征. 最后对iDPC-STEM技术在原子尺度成像方面的应用潜力进行了总结与展望.

关键词: 透射电子显微镜, 积分差分相位衬度, 金属有机骨架, 分子筛

Abstract:

Molecular sieves and metal organic framework （MOF） materials are widely used in the fields of catalysis， energy storage， drying， purification， and adsorption separation due to their unique pores and framework structures. The atomic scale characterization of their structures is significance for a deep understanding of their structure-activity relationships. However， their large pore structure and organic framework make them extremely sensitive to electron beam. The structure will be quickly destroyed and become amorphous in the conventional transmission electron microscope imaging mode， and the atomic arrangement information of the pores and framework cannot be obtained. The recently developed scanning transmission electron microscopy technology based on integrated differential phase contrast （iDPC-STEM） has shown obvious advantages in imaging of beam sensitive materials and light element components， making the characterization of porous framework materials and hydrocarbon pool species become possible. This article reviews our research group’s recent research on molecular sieve and MOF material atomic structure using this technology. The iDPC-STEM technology was applied to the ZSM-5 molecular sieve catalyst for methanol conversion to realize the imaging analysis of the atomic-level framework structure of the molecular sieve. In the MOF system， the coordination mode of the organic linker and the metal node in the MIL-101 framework was observed using this technology. On this basis， the benzene ring structure of the organic link and the metal node was analyzed， and the atomic-level surface， interface and defects and other local structural features of the MOF were observed. Finally， the application potential of iDPC-STEM technology in atomic scale imaging is summarized and prospected.

Key words: Transmission electron microscopy（TEM）, Integrated differential phase contrast, Metal organic framework（MOF）, Molecular sieve

中图分类号:

O766+.1

TrendMD:

陈晓, 申博渊, 熊昊, 魏飞. 电子束敏感材料的原子尺度结构研究. 高等学校化学学报, 2021, 42(1): 133.

CHEN Xiao, SHEN Boyuan, XIONG Hao, WEI Fei. Atomic Scale Structure of Beam Sensitive Materials. Chem. J. Chinese Universities, 2021, 42(1): 133.

图/表 22

Fig.2 Atomic resolution iDPC‐STEM imaging of the [010] projection of ZSM‐5[40](A, B) Magnified iDPC‐STEM images of ZSM‐5 showing the atomic‐resolution straight channels as the elliptical Si10‐rings; (C, D) profile analysis of three structural units on the framework marked as three colored frames in (B); (E) intensity profiles exhibit the contrasts and projected distances between different atoms; (F) integration mapping of the projected electrostatic potential in ZSM‐5 framework from the [010] projection.Copyright 2020, Wiley?VCH.

Fig.3 iDPC‐STEM image (A) and detailed analysis(B1―B3, C) from the [100] direction[40]The imaged structure is consistent with the structural model and calculated electrostatic potential(B1—B3). The intensity profiles (C) show the detailed atomic position of each element.Copyright 2020, Wiley?VCH.

Fig.4 iDPC‐STEM image from [001] projection of ZSM?5[40](A—C) iDPC‐STEM image and detailed analysis (B1—B3, C) from the [001] direction. Especially, the intensity profiles (C) show the capacity of iDPC‐STEM for imaging light O bridges, where the positions of four O atoms are clearly marked.Copyright 2020, Wiley?VCH .

Fig.5 iDPC?STEM image from [102] projection of ZSM?5（A―C）[40]The higher‐index surface was found out to give a more obvious imaging of O bridges as shown in the profile analysis.Copyright 2020, Wiley?VCH.

Fig.8 iDPC‐STEM imaging of the (010) interfaces between ZSM‐5 particles[40](A) HAADF‐STEM image of assembled ZSM‐5 particles. These particles were stacked from the [010] direction, and their flat (010) surfaces were in close contact with each other; (B, C) iDPC‐STEM images of the (010) interfaces in the areas marked in (A); (D, E) Zoom‐in interface areas of iDPC‐STEM images marked in (B,C); (F,G) FFT patterns corresponding to (B), (F) and (C), (G), respectively. FFT pattern of adjacent particles shows single set of diffraction spots indicating the coherent alignment of ZSM‐5 lattices by the interactions between these (010) surfaces.Copyright 2020, Wiley‐VCH.

Fig.9 Designed scheme of the silica deposition process and the results of TEM images[11](A) Designed scheme of the silica deposition process. Aberration-corrected HRTEM images of pristine ZSM-5(ZSM-5-P): (100) surface(B) and (010) surface(C). Aberration-corrected HRTEM images of coked ZSM-5-P (ZSM-CP): (100) surface(D) and (010) surface(E). Image of surface-selective coated ZSM-5 after the reaction (coked ZSM-5-OC): aberration-corrected STEM image of the (010) surface(F). (G) Aberration-corrected HRTEM image of the (100) surface.Copyright 2019, Royal Society of Chemistry.

Fig.10 Comparison of the catalytic performance of various ZSM?5 catalysts in the MTO reaction[11](A) The carbon?based yield of different species (methanol conversion remains at 100%); (B) olefins, aromatics and paraffin selectivity, (TOS=9 h); (C) lifetime test of ZSM?5?OC(WHSV=1 h-1, reaction temperature: 500 °C, the N2 flow rate is 30 SCCM). Mass balance (outlet carbon/inlet carbon) was kept at about 98%.Copyright 2019, Royal Society of Chemistry.

Fig.11 Methanol conversion and aromatic selectivity of UZ?5 and UZ5 samples as a function of time?on?stream[9,10](A) Methanol conversion and aromatic selectivity of pristine and aging samples as a function of time?on?stream (reaction temperature: 475 ℃, reaction pressure: atmospheric pressure, WHSV: 0.8 h-1 ); (B) turnover frequencies (TOFs) to different products vs. acid density.Copyright 2016, Royal Society of Chemistry.

Fig.13 SEM(A) and ADF?STEM(B) images of MIL?101[43](A) SEM image showing the octahedral shape of a MIL?101 crystal. Scale bar: 200 nm; (B) ADF?STEM image of MIL?101 from the <110> projection.Copyright 2020, Nature Publishing Group.

Fig.14 iDPC?STEM imaging of MIL?101 [110] projection with an ultrahigh resolution(A, B) and the corresponding FFT pattern of image(C)[43]The corresponding FFT showing an information transfer up to 1.8 ?.Copyright 2020, Nature Publishing Group.

Fig.15 Imaging the atomic MIL?101 lattice in the averaged iDPC?STEM image(A) and the corresponding model structure(B)[43](A, B) The red and blue circles indicate two types of cages with 29 and 34 ? sizes, respectively.Copyright 2020, Nature Publishing Group.

Fig.16 Detailed structure observation and strength profile analysis of MIL?101[43](A) Imaging the super tetrahedrons formed by Cr nodes and BDC linkers; (B) imaging the structure in 29 ? cage in the MIL?101; (C) profile analysis of image(exp) and simulation(sim) of the detailed structures in the blue frame in (B), which helps to resolve the Cr columns in the frameworks.Copyright 2020, Nature Publishing Group.

Fig.17 Two different {111} surface analysis of MIL?101 crystal[43](A, C) Two types of surface terminations with two types of cages exposed on the {111} surfaces. (B, D) Structures of single unit cells at two types of surface terminations and the corresponding structural models, respectively.Copyright 2020, Nature Publishing Group.

Fig.20 iDPC?STEM image showing the terminations of a corner in the octahedral MIL?101 crystal[43]The 34 ? cages (marked by the blue circles) were exposed at this corner.Copyright 2020, Nature Publishing Group.

Fig.21 Observation and analysis of MIL?101 twin interface structure[43](A) ADF?STEM image of a twin?crystal of MIL?101; (B) ADF?STEM image of the {111} interface marked as the red frame in image (A); (C) iDPC?STEM image of the {111} interface marked as the blue frame in image (A). The structural model of the twin?plane interface imaged in image (C).Copyright 2020, Nature Publishing Group.

Fig.22 Observation and analysis of mismatch defect structure at MIL?101 twin interface[43](A) ADF?STEM image of a MIL?101 crystal; (B, C) iDPC?STEM images showing the defects in this MIL?101 crystal. Copyright 2020, Nature Publishing Group.

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