Microporous Metal‐Containing Hydrogen‐Bonded Organic Frameworks with Benchmark C <sub>2</sub> H <sub>2</sub> Storage Density for Efficient C <sub>2</sub> H <sub>2</sub> /C <sub>2</sub> H <sub>4</sub> and C <sub>2</sub> H <sub>2</sub> /CO <sub>2</sub> Separations

J Jiali Fu Q Qingxue Hui Y Yu‐Hao Gu (State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University Nanjing China) Q Qi Ding H Haoning Xu (State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 China) B Biao Yang (State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, School of Chemical Engineering) C Chengyu Huangfu (State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 China) Q Qingqing Wang (Institute of Immunology, Zhejiang University School of Medicine) X Xin‐Li Liu (State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 China) X Xin‐Yi Wang (Fujian Provincial Key Laboratory of Advanced Inorganic Oxygenated‐Materials Fujian Provincial Key Laboratory of Cancer Metastasis Chemoprevention and Chemotherapy College of Chemistry Fuzhou University Fuzhou Fujian 350108 P.R. China) Y Youting Wu (Key Laboratory of Mesoscopic Chemistry of MOE School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 China) X Xingbang Hu (MOE Key Laboratory of Mesoscopic Chemistry, Nanjing University, Nanjing, Jiangsu 210023, China) S Shuai Yuan (State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering) Z Zhaoqiang Zhang (State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering)

Abstract

Abstract Separation of C 2 H 2 from industrially important gas pairs using energy‐efficient adsorptive techniques with multifunctional porous materials remains a significant yet challenging issue. Here, we report the highly efficient separation of C 2 H 2 /CO 2 and C 2 H 2 /C 2 H 4 mixtures with isostructural metal‐containing hydrogen‐bonded organic frameworks (M–HOFs), which feature micropore channels decorated with high‐density and uncoordinated carboxyl groups. Single‐crystal X‐ray diffraction analysis reveals that each free carboxyl group is capable of trapping one C 2 H 2 molecule through hydrogen bonding. This endows the M–HOFs with excellent C 2 H 2 capture capability, achieving a benchmark storage density of 396.0 mg cm −3 , while simultaneously demonstrating remarkable selectivity over C 2 H 4 (420–97) and CO 2 (188–53). Breakthrough experiments confirm that binary gas mixtures can be efficiently separated by M–HOFs, where an impressive C 2 H 4 productivity (137.4 mol kg −1 ) is realized in the separation of C 2 H 2 /C 2 H 4 (1/99), and an outstanding separation factor (17) is achieved for C 2 H 2 /CO 2 (50/50) splitting. Coupled with their superior chemical stability, these M–HOFs display tremendous potential for practical applications.

Article Details

Volume / Issue Vol. 64, Issue 48
Published November 24, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (14)

J

Jiali Fu

Q

Qingxue Hui

Y

Yu‐Hao Gu

State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University Nanjing China

Q

Qi Ding

H

Haoning Xu

State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 China

B

Biao Yang

State Key Laboratory of Fine Chemicals, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, School of Chemical Engineering

C

Chengyu Huangfu

State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 China

Q

Qingqing Wang

Institute of Immunology, Zhejiang University School of Medicine

X

Xin‐Li Liu

State Key Laboratory of Coordination Chemistry School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 China

X

Xin‐Yi Wang

Fujian Provincial Key Laboratory of Advanced Inorganic Oxygenated‐Materials Fujian Provincial Key Laboratory of Cancer Metastasis Chemoprevention and Chemotherapy College of Chemistry Fuzhou University Fuzhou Fujian 350108 P.R. China

Y

Youting Wu

Key Laboratory of Mesoscopic Chemistry of MOE School of Chemistry and Chemical Engineering Nanjing University Nanjing 210023 China

X

Xingbang Hu

MOE Key Laboratory of Mesoscopic Chemistry, Nanjing University, Nanjing, Jiangsu 210023, China

S

Shuai Yuan

State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of MOE, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering

Z

Zhaoqiang Zhang

State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering