基于过饱和策略的MOFs晶面可控合成用于理解本征晶面效应

doi:10.1016/S1872-2067(25)64719-X

催化学报 ›› 2025, Vol. 73: 153-158.DOI: 10.1016/S1872-2067(25)64719-X

基于过饱和策略的MOFs晶面可控合成用于理解本征晶面效应

刘利芳^a^,^c, 肖晔珺^b, 郭向阳^a, 金盛烨^b, 章福祥^a()

^a中国科学院大连化学物理研究所, 催化基础国家重点实验室, 洁净能源国家实验室, 能源材料化学协同创新中心, 辽宁大连 116023
^b中国科学院大连化学物理研究所, 分子反应动力学国家重点实验室, 能源材料化学协同创新中心, 辽宁大连 116023
^c中国科学院大学材料科学与光电子工程中心, 北京 100049

收稿日期:2025-02-27 接受日期:2025-03-31 出版日期:2025-06-18 发布日期:2025-06-12
通讯作者: *电子信箱: fxzhang@dicp.ac.cn (章福祥).
基金资助:
国家自然科学基金(21925206);国家自然科学基金(22261160369);国家自然科学基金(22303105);大连市支持高层次人才创新创业项目(2020RD06);辽宁省振兴人才计划(XLYC1807241);辽宁省自然科学基金(2023-MS-002)

Facets-controllable synthesis of metal-organic frameworks via one supersaturation strategy to insight intrinsic facets effect

Lifang Liu^a^,^c, Yejun Xiao^b, Xiangyang Guo^a, Shengye Jin^b, Fuxiang Zhang^a()

^aState Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, The Collaborative Innovation Centre of Chemistry for Energy Materials (iChEM), Dalian National Laboratory for Clean Energy, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bState Key Laboratory of Molecular Reaction Dynamics and Dynamics Research Center for Energy and Environmental Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^cCenter of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China.

Received:2025-02-27 Accepted:2025-03-31 Online:2025-06-18 Published:2025-06-12
Contact: *E-mail: fxzhang@dicp.ac.cn (F. Zhang).
Supported by:
National Natural Science Foundation of China(21925206);National Natural Science Foundation of China(22261160369);National Natural Science Foundation of China(22303105);Dalian Supports High-Level Talent Innovation and Entrepreneurship Projects(2020RD06);Liaoning Revitalization Talents Program(XLYC1807241);Natural Science Foundation of Liaoning Province(2023-MS-002)

摘要/Abstract

摘要：

晶面调控的无机半导体因其显著的晶面效应在光催化及光电领域备受关注, 金属有机框架(MOFs)材料因其结构可设计等优势作为极具潜力的光催化材料, 其晶面效应对其催化性能的影响存在显著争议, 例如, NH₂-MIL-125(Ti)的{001}与{111}晶面在光催化产氢中的作用机制存在矛盾结论, 本征晶面效应研究对于理解构效关系具有重要科学意义. 传统晶面调控方法多依赖封端剂诱导特定晶面生长, 但这些封端剂的残留可能改变材料表面局域化学环境, 导致对晶面效应的误判. 开发一种无封端剂晶面可控合成方法, 不仅为准确理解MOFs晶面特性提供了新方法, 也为解决光催化材料晶面效应争议提供了概念性证明.

本工作通过概念验证性示例, 阐明无封端剂条件下过饱和度调控的合成策略在揭示本征晶面效应中的关键作用. 首先基于过饱和度的晶面调控策略, 在无封端剂条件下精准制备了{001}、{111}和{100}不同暴露晶面的NH₂-MIL-125(Ti); 通过调节溶剂组成、添加碱及前驱体浓度实现晶面的精准调控. 为系统解析封端剂对晶面效应的影响, 制备了传统封端剂(乙酸、CTAB)作用下的相似{001}和{111}晶面暴露的对照样品; 结果表明, 对照组样品表面存在封端剂残留. 随后对系列样品进行了光催化分解水产氢实验; 结果表明, 本征晶面样品活性呈火山型曲线, 与对照组样品的晶面暴露比与活性顺序不同, 这表明封端剂对光催化活性具有显著调控作用, 致使传统研究中对本征晶面效应的认知存在差异. 最后通过多维度表征揭示了局部表面结构环境改变、表面润湿性、电荷分离效率等特性对晶面效应的影响. 无机半导体和MOFs光催化剂, 过往研究中晶面效应结论的相互矛盾性, 本质源于合成过程封端剂的干扰作用, 建立的无封端剂干扰的晶面调控体系为揭示真实晶面功能差异提供了研究范式.

综上, 本研究发展的无封端剂过饱和合成策略, 为MOFs晶面工程提供了普适性方法, 揭示了本征晶面效应受封端剂干扰的影响机制. 未来可进一步结合原位表征与理论计算, 建立晶面与活性构效关系的定量模型. 本工作不仅有望推动MOFs光催化剂的精准设计, 也为其他晶面材料的研究提供了重要参考.

关键词: 金属有机框架, 晶面可控合成, 过饱和度, 本征晶面效应, 光催化剂

Abstract:

The facets effect on the catalytic properties of inorganic compounds and metal-organic frameworks (MOFs) has been widely demonstrated, but the intrinsic facets effect free of interference of capping agents has not been discussed. Here we give a proof-of-concept illustration on the intrinsic facets effect by employing the popularly investigated NH₂-MIL-125(Ti) MOFs with {001}, {111} and {100} facets controllably exposed as model photocatalysts, which were synthesized via a simple supersaturation strategy free of any capping agents. Compared to conventional synthetic routes with capping agents employed, the NH₂-MIL-125(Ti) MOFs obtained in this work exhibit remarkably different physical and chemical properties such as surface wettability, charge separation as well as trend of facets effect on photocatalytic water splitting performance. The main reason has been unraveled to originate from unavoidable residue/influence of capping agents during the conventional facets-controlled synthetic routes leading to changed local surface structural environment as well as distinct charge separation property. Our results demonstrate the importance and feasibility of facets-controllable synthesis free of capping agents in getting insight into the intrinsic facets effect of MOFs-related materials.

Key words: Metal-organic framework, Facets-controllable synthesis, Supersaturation, Intrinsic facets effect, Photocatalyst

刘利芳, 肖晔珺, 郭向阳, 金盛烨, 章福祥. 基于过饱和策略的MOFs晶面可控合成用于理解本征晶面效应[J]. 催化学报, 2025, 73: 153-158.

Lifang Liu, Yejun Xiao, Xiangyang Guo, Shengye Jin, Fuxiang Zhang. Facets-controllable synthesis of metal-organic frameworks via one supersaturation strategy to insight intrinsic facets effect[J]. Chinese Journal of Catalysis, 2025, 73: 153-158.

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图/表 5

Scheme 1. Schematic illustration for the synthesis NH2-MIL-125(Ti) of supersaturation-dependent facets evolution.

Fig. 1. SEM images of NH2-MIL-125(Ti) samples with different facets exposed under different preparative conditions. (a1)-(a4) Different volume ratios of DMF and MeOH are 9:1, 6:1, 4.5:1, and 1:1, respectively. Adding NaOH (aq, pH = 8): 1 μL (b1), 2 μL (b2), 4 μL (b3), and CH3COONa (4 mg) (b4). Changing the amount of Ti(C3H7O)4: 90 μL (c1), 100 μL (c2), 101 μL (c3), and 102 μL (c4).

Fig. 2. Comparison of the photocatalytic hydrogen evolution activity of the series samples prepared by different strategies: supersaturation strategy (a), capping agents (b,c), the photocatalytic reaction conditions of all the samples remain consistent.

Fig. 3. Comparison of structure properties of Ti111-OH, Ti111-OH-AA, and Ti111-OH-CTAB samples. (a) IR spectra; (b) Contact angle measurement; (c) X-ray photoelectron spectroscopy.

Fig. 4. UV-vis diffuse reflectance spectra (a), electrochemical impedance spectroscopy (b), and Comparison of normalized TA kinetics (c) of typical samples.

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基于过饱和策略的MOFs晶面可控合成用于理解本征晶面效应

Facets-controllable synthesis of metal-organic frameworks via one supersaturation strategy to insight intrinsic facets effect

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