Advances in Post-Synthetic Ligand Insertion Engineering for Zirconium-Based Metal-Organic Frameworks★

doi:10.6023/A26010026

Acta Chimica Sinica ›› 2026, Vol. 84 ›› Issue (5): 709-722.DOI: 10.6023/A26010026 Previous Articles Next Articles

Review

锆基金属-有机框架的合成后配体插入工程研究进展^★

李颖果^a^,^*^,^†(), 岳小艺^a^,^†, 付萌萌^a, 于超^a, 巩伟^b^,^*()

^a 江苏科技大学环境与化学工程学院镇江 212100
^b 上海交通大学化学化工学院化学生物协同物质创制全国重点实验室上海 200240

投稿日期:2026-01-26 发布日期:2026-03-03
通讯作者: 李颖果, 巩伟

作者简介:

李颖果, 博士, 讲师, 硕士研究生导师. 2022年获上海交通大学博士学位, 同年9月加入江苏科技大学. 主要研究方向为金属/共价-有机功能材料的设计合成与应用开发, 包括金属-有机大环(metallacycle)、分子笼(cage)、索烃(catenane)及框架材料(MOF/COF)的构筑, 及其在分离、催化等领域的性能研究. 以第一作者/通讯作者身份在J. Am. Chem. Soc.、Nat. Commun.、Angew. Chem. Int. Ed. 等国际顶级学术期刊上发表论文20余篇.

岳小艺, 江苏科技大学环境与化学工程学院在读硕士研究生, 目前主要研究方向为多孔材料化学.

付萌萌, 江苏科技大学环境与化学工程学院在读硕士研究生, 目前主要研究方向为多孔材料化学和微流控技术.

于超, 博士, 教授, 硕士研究生导师. 2015年6月博士毕业于南京工业大学, 同年11月进入布朗大学化学系及工程系从事博士后研究工作. 2020年加入江苏科技大学环境与化学工程学院工作. 主要从事功能纳米结构材料的基础研究和应用工作, 在Nat. Commun.、Matter、J. Am. Chem. Soc.、Angew. Chem. Int. Ed.、Adv. Energ. Mater.、Adv. Funct. Mater.、Chem. Eng. J.、Rare Met.等国际权威期刊共发表各类文章40篇.

巩伟, 博士, 上海交通大学化学化工学院长聘(教轨)副教授, 博士生导师, 国家自然科学基金青年科学基金B类(原优秀青年科学基金)获得者. 2019年获上海交通大学博士学位, 2020~2022年期间在美国德克萨斯大学圣安东尼奥分校和西北大学从事访问学者研究. 目前主要从事新型高稳定晶态多孔框架材料的创制及其在吸附分离、催化以及能源领域的基础研究. 以第一作者/通讯作者身份在J. Am. Chem. Soc., Chem, Angew. Chem. Int. Ed., Nat. Commun.等国际顶级学术期刊上发表论文30余篇. 担任Chin. J. Struc. Chem., Chin. Chem. Lett., 以及Nano-Micro Lett.等杂志青年编委.

^†共同第一作者

★ 框架材料化学专辑.

基金资助:
国家自然科学基金(52003121); 国家自然科学基金(22208133); 国家自然科学基金(22301111); 国家自然科学基金(22522108); 国家自然科学基金(22301176); 国家自然科学基金(52373213)

Advances in Post-Synthetic Ligand Insertion Engineering for Zirconium-Based Metal-Organic Frameworks^★

Yingguo Li^a^,^*(), Xiaoyi Yue^a, Mengmeng Fu^a, Chao Yu^a, Wei Gong^b^,^*()

^a School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212100, China
^b State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2026-01-26 Published:2026-03-03
Contact: Yingguo Li, Wei Gong
About author:
^†The authors contributed equally to this work.
★ For the VSI “Chemistry of Framework Materials”.
Supported by:
National Natural Science Foundation of China(52003121); National Natural Science Foundation of China(22208133); National Natural Science Foundation of China(22301111); National Natural Science Foundation of China(22522108); National Natural Science Foundation of China(22301176); National Natural Science Foundation of China(52373213)

Zirconium-based metal-organic frameworks (Zr-MOFs) have attracted significant attention due to their remarkable chemical stability and highly tunable topological architectures. Post-synthetic ligand insertion engineering offers an important functionalization strategy capable of achieving precise design and modulation of the structure and function of the resulting Zr-MOFs, at the molecular level. This review systematically summarizes recent advances of ligand insertion within Zr-MOFs, with a focus on two dominant approaches of ligand installation and ligand exchange. It outlines the evolution from early-stage pendant-group modifications to the recent development of sequential ligand installation, elucidating the mechanisms, applicable scopes, and performance enhancements of these methods in areas such as gas adsorption/separation and heterogeneous catalysis, etc. Special emphasis is placed on how sequential ligand installation enables precise and stepwise incorporation of functional linkers through pre-engineered structural vacancies, thereby allowing atomic-scale modulation of pore microenvironments and enabling function enhancement. Finally, future challenges and prospects in scalable synthesis, multifunctional integration, and practical applications are discussed, providing theoretical guidelines for the rational design of high-performance Zr-MOFs materials.

Key words: zirconium-based metal-organic frameworks, post-synthetic ligand insertion, ligand installation, ligand exchange, microenvironment modulation

Cite this article

Yingguo Li, Xiaoyi Yue, Mengmeng Fu, Chao Yu, Wei Gong. Advances in Post-Synthetic Ligand Insertion Engineering for Zirconium-Based Metal-Organic Frameworks^★[J]. Acta Chimica Sinica, 2026, 84(5): 709-722.

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Fig. & Tab. 11

Figure 1. Schematic illustration of ligand installation in Zr-MOFs. Left: sequential installation of multidentate carboxylic acids; right: capping installation of monodentate carboxylic acids

Figure 3. (a) Conformation of BPDC in the fcu structure. (b) Conformation of Me2-BPDC in the bcu structure. (c, e) fcu structure formed with BPDC. (d, f) bcu structure formed with Me2-BPDC. Reprinted with permission from ref. [60]. Copy right © 2015 American Chemical Society

Figure 4. Single crystal structures of (a) PCN-609 and its derivatives (b) PCN-609-BDC, (c) PCN-609-BPDC, (d) PCN-609-TPDC, (e) PCN-609-BDC-BPDC, (f) PCN-609-BDC-TPDC, (g) PCN-609-BPDC-TPDC and (h) PCN-609-BDC-BPDC-TPDC. Reprinted with permission from ref. [64]. Copy right © 2018 American Chemical Society

Figure 6. (a) Representations and (b) structures of PCN-700-Me2 with different linkers installed. Insets: photos of the microscope view of the corresponding single crystal. Reprinted with permission from ref. [80]. Copy right © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 7. (a) Generation of multivariate MOF catalysts via the DSI approach from proto-LIFM-28 showing their interconversion toward different catalytic purposes. The molecular structures of the inserted functional spacers are illustrated for crystal structures, in which the ArSO3H group is simplified as an orange ball and Zr6-clusters are shown as purple polyhedrons. Reprinted with permission from ref. [82]. Copy right © 2019 American Chemical Society. (b) Post-synthetic variable-spacer installation (PVSI) demonstration by spacer H2L5. Elastic deformation occurring in the c-axis is controllable by spacers of different lengths. Reprinted with permission from ref. [86]. Copy right © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 8. (a) Construction methods of MOF-based enantioselective sensing materials. Reprinted with permission from ref. [89]. Copy right © 2024 American Chemical Society. (b) The linker, H2BCMTC, was installed as a capping linker into an existing MOF framework, Zr6(Me2BPDC)4, to make new Zr-MOF. Reprinted with permission from ref. [90]. Copy right © 2018 American Chemical Society

Figure 9. (a) Postsynthetic activation of Zr6-BTB through formate exchange and triflation to strongly Lewis acidic Zr6OTf-BTB. (b) PXRD patterns of Zr6-BTB (red), Zr6OTf-BTB (blue), and the recovered MOF after MCR (green) compared with the simulated PXRD pattern (black). (c) TEM image of Zr6OTf-BTB. (d) HR-TEM image of Zr6OTf-BTB. (e, f) AFM topographies and height profiles of Zr6-BTB and Zr6OTf-BTB. (g) Fluorescence spectra of Zr6OTf-BTB-(NMA) (blue), Zr6-BTB-(NMA) (red), and free NMA. (h) Fitting of Zr6OTf-BTB EXAFS data at the Zr K-edge. Reprinted with permission from ref. [95]. Copy right © 2021 American Chemical Society

Figure 11. (a) Schematic representation of the PSE approach. (b) Asymmetric organic transformations catalyzed by UiO-68-M and UiO-68-M-M'. Reprinted with permission from ref. [110]. Copy right © 2018 American Chemical Society. (c) Synthesis of UiO-66-CAT via PSD and PSE. Reprinted with permission from ref. [111]. Copy right © 2014 American Chemical Society

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锆基金属-有机框架的合成后配体插入工程研究进展^★

Advances in Post-Synthetic Ligand Insertion Engineering for Zirconium-Based Metal-Organic Frameworks^★

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锆基金属-有机框架的合成后配体插入工程研究进展★

Advances in Post-Synthetic Ligand Insertion Engineering for Zirconium-Based Metal-Organic Frameworks★

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锆基金属-有机框架的合成后配体插入工程研究进展^★

Advances in Post-Synthetic Ligand Insertion Engineering for Zirconium-Based Metal-Organic Frameworks^★