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化学进展 2022, Vol. 34 Issue (11): 2405-2416 DOI: 10.7536/PC220434 前一篇   后一篇

• 综述 •

铋基金属有机框架的合成与应用

王文婧1,2, 曾滴2, 王举雪2, 张瑜2, 张玲2,*(), 王文中2,3,*()   

  1. 1 上海师范大学化学与材料科学学院 上海 200234
    2 中国科学院上海硅酸盐研究所 上海 200050
    3 国科大杭州高等研究院化学与材料科学学院 杭州 310024
  • 收稿日期:2022-04-25 修回日期:2022-07-07 出版日期:2022-11-24 发布日期:2022-09-19
  • 通讯作者: 张玲, 王文中
  • 基金资助:
    国家自然科学基金项目(51972327); 国家自然科学基金项目(51972325); 国家自然科学基金项目(52172256)
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Synthesis and Application of Bismuth-Based Metal-Organic Framework

Wenjing Wang1,2, Di Zeng2, Juxue Wang2, Yu Zhang2, Ling Zhang2(), Wenzhong Wang2,3()   

  1. 1 College of Chemistry and Materials Science, Shanghai Normal University,Shanghai 200234, China
    2 Shanghai Institute of Ceramics, Chinese Academy of Sciences,Shanghai 200050, China
    3 School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences,Hangzhou 310024, China
  • Received:2022-04-25 Revised:2022-07-07 Online:2022-11-24 Published:2022-09-19
  • Contact: Ling Zhang, Wenzhong Wang
  • Supported by:
    National Natural Science Foundation of China(51972327); National Natural Science Foundation of China(51972325); National Natural Science Foundation of China(52172256)

金属有机框架(MOFs)材料因其丰富的拓扑结构和有序的孔洞结构被广泛关注,近年来人们按照其不同的应用前景分别进行了综述。尽管金属中心与有机框架材料的结构及性能有着密切联系,目前针对某种特定中心金属的金属有机框架材料的梳理还较少。金属铋是唯一一种具有较大丰度、低毒性的绿色重金属元素,铋基金属有机框架(Bi-MOFs)也因此在MOFs中脱颖而出,并具有广泛的应用。由于铋盐易水解的特性,在水相中合成铋基金属有机框架材料一直是一个挑战,所以对于Bi-MOFs的开发仍然处于开始阶段。本文介绍了近年来有关Bi-MOFs常用的合成配体以及一般的合成方法,综述了Bi-MOFs在光、电催化等领域的研究进展及其在药物载体、气体吸附剂及电极材料方面的应用概况。对存在的问题进行总结并提出可能的解决方法,对未来研究和应用提出展望,以推动Bi-MOFs材料的进一步研究与运用。

关键词： 金属有机框架, 铋基材料, 光催化, 电催化

Metal-organic frameworks (MOFs), featuring the ordered porous structure and abundant topology, have been widely concerned and thoroughly reviewed according to its application prospects in recent years. Although the metal center is critical to the structure and performance of MOFs, summaries of the MOFs with a specific central metal are still few at present. As the only heavy metal element with considerable abundance and low toxicity, bismuth-based metal-organic frameworks (Bi-MOFs) stand out among MOFs for its innocuousness and biocompatibility. It would be a significant direction to design legitimately, synthesize successfully, and exploit steadily the Bi-MOFs with rich structures in the current MOFs research. However, this specific type of MOFs is still in its infancy, which is limited by the flexible coordination environment and low solubility of Bi (Ⅲ) cation. The synthesis of Bi-MOFs in the aqueous solution has always been an enormous challenge resulting from the hydrolysis of the bismuth salt. Herein, this article reviews the common ligands and general synthesis methods of Bi-MOFs in recent years, focusing on its application in photocatalysis, electrocatalysis, drug carriers, gas adsorbents and electrode materials. By profusely discussing the mechanism and reaction rules in catalytic reactions, this review aims to provide rewarding references for similar catalytic reactions to improve reaction efficiency and save costs. In addition, to highlight the unique advantages of Bi-MOFs, we make detailed comparisons with traditional materials. Some expanded applications of energy storage (mainly cationic battery energy storage), adsorption separation (selective adsorption of anions and enrichment of energy gas), drug delivery (the encapsulation and release of specific drugs) are also supplemented. For consideration of existing research, our work puts forward a prospect for future pioneering research to stimulate the research progress of Bi-MOFs.

Contents

1 Introduction

2 Components and synthesis methods of Bi-MOFs

2.1 The properties of the center metal

2.2 Types of organic ligands

3 Application of Bi-MOFs

3.1 Application in catalysis

3.2 Application in chemical adsorption

3.3 Bi-MOFs as sustained-release drug carriers

3.4 Application of Bi-MOFs as sensors

3.5 Application of Bi-MOFs as battery electrode materials

4 Conclusion and outlook

Key words: metal-organic frameworks, bismuth-based materials, photocatalysis, electrocatalysis
()
图1 1,3,5-三(4-羧基苯基)苯(H3BTB)、三嗪-2,4,6-三酰三苯甲酸(H3TATB)和1,3,5-均苯三甲酸(H3BTC)结构式
Fig.1 Structure of 1,3,5-tris(4-carboxyphenyl) benzene (H3BTB), triazine-2,4,6-triacyltribenzoic acid (H3TATB) and 1,3,5-trimellitic acid (H3BTC)
图2 沿[001]方向的CAU-7-TATB的晶体结构[26]
Fig. 2 Crystal structure of CAU-7-TATB (view along [001]). Reproduced from ref 26 with permission. Copy right 2017,The Royal Society of Chemistry
图3 化合物Bi-BTC中(a) Bi3+和(b) BTC3-阴离子的配位环境 (c)中心对称二聚体{Bi2O14}和1~6个连接的BTC3-配体的多面图; (d) Bi-BTC三维结构示意图[27],Bi:绿色,O:红色,C:浅灰色,N:蓝色
Fig. 3 Coordination environment of (a) Bi3+and (b) BTC3-anions in compound Bi-BTC; (c) polyhedral view of the centrosymmetric dimeric {Bi2O14} unit and the linked 1~6 BTC3-ligands; (d) view of the 3D structure of Bi-BTC. Bi: green, O: red, C: light grey, N: blue. Reproduced from ref 27 with permission. Copyright 2017,The Royal Society of Chemistry
图4 4,4',4″,4?-(芘-1,3,6,8-四基)四苯甲酸的结构式
Fig.4 Structure of 4,4',4″,4?-(1,9-dihydropyrene- 1,3,6,8-tetrayl) tetrabenzoic acid
图5 a) Bi-mna的计算电子定位函数(ELF)图;b) Bi-mna的Fukui函数F-(r)和F+(r),等值面值为0.0015e ?-3,Bi紫、C棕、O红、N灰、H粉[8]
Fig.5 a) Calculated electron localization function (ELF) plots for Bi-mna. b) Fukui function F-(r)and F+(r) for Bi-mna. The isosurface value is 0.0015 e ?-3. Bi purple, C brown, O red, N gray, H pink[8]. Copyright 2015, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
图6 Bi-BTC催化DMF和AA制备PX的Diels-Alder反应示意图[48]
Fig.6 Schematic illustration of Bi-BTC catalyzed Diels-Alder reaction of DMF and AA to PX. Reproduced from ref 48 with permission. Copy right 2020, WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
图7 a) 在吸附 SeO 3 2 -之前CAU-17的SEM图; b) CAU-17上活性位点的吸附图; c) CAU-17在48 h内吸收 SeO x 2 -的等温线; d) CAU-17的 SeO x 2 -吸附动力学行为
Fig.7 a) SEM of CAU-17 before adsorption of SeO 3 2 -. b) Probable mechanism model for phosphate adsorption of La-CAU-17. c) Isotherm of SeO x 2 - uptaken by CAU-17 over 48 hours. d) SeO x 2 -adsorption kinetic behavior of CAU-17[57]. Copyright 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
图8 3,3',5,5'-联苯四甲酸结构式.
Fig.8 Structure of biphenyl-3,3',5,5'-tetracarboxylic acid
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摘要

铋基金属有机框架的合成与应用