Molecularly Woven Cationic Covalent Organic Frameworks for Highly Selective Electrocatalytic Conversion of CO₂ to CO

Dagnaw, Fentahun Wondu1,2; Harrath, Karim3,4; Zheng, Tao1,2; Wu, Xu-Dong1,2; Liu, Yu-Ze1,2; Li, Rui-Qi1,2; Xie, Luo-Han1,2; Li, Zhen1,2; He, Xuezhong5; Tong, Qing-Xiao1,2; Jian, Jing-Xin1,2

2024-09-01

10.1002/advs.202408152

ADVANCED SCIENCE   影响因子和分区

2198-3844

Coupling carbon capture with electrocatalytic carbon dioxide reduction (CO2R) to yield high-value chemicals presents an appealing avenue for combating climate change, yet achieving highly selective electrocatalysts remains a significant challenge. Herein, two molecularly woven covalent organic frameworks (COFs) are designed, namely CuCOF and CuCOF+, with copper(I)-bisphenanthroline complexes as building blocks. The metal-organic helical structure unit made the CuCOF and CuCOF+ present woven patterns, and their ordered pore structures and cationic properties enhanced their CO2 adsorption and good conductivity, which is confirmed by gas adsorption and electrochemical analysis. In the electrocatalytic CO2R measurements, CuCOF+ decorated with extra ethyl groups exhibit a main CO product with selectivity of 57.81%, outperforming the CuCOF with 42.92% CO at the same applied potential of 0.8 V-RHE. After loading Pd nanoparticles, CuCOF-Pd and CuCOF+-Pd performed increased CO selectivity up to 84.97% and 95.45%, respectively. Combining the DFT theoretical calculations and experimental measurements, it is assumed that the molecularly woven cationic COF provides a catalytic microenvironment for CO2R and ensures efficient charge transfer from the electrode to the catalytic center, thereby achieving high electrocatalytic activity and selectivity. The present work significantly advances the practice of cationic COFs in real-time CO2 capture and highly selective conversion to value-added chemicals.

carbon capture CO2 reduction covalent organic frameworks electrocatalytic palladium nanoparticles

SCI

英语

其他

National Natural Science Foundation of China[52273187] ; null[2023A1515240077]

Chemistry ; Science & Technology - Other Topics ; Materials Science

Chemistry, Multidisciplinary ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary

WOS:001309548500001

WILEY

Web of Science

1.Shantou Univ Guangdong, Dept Chem Key Lab Preparat & Applicat Ordered Stru, Shantou 515063, Guangdong, Peoples R China
2.Shantou Univ, Guangdong Prov Key Lab Marine Disaster Predict & P, Shantou 515063, Guangdong, Peoples R China
3.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
4.Ganjian Innovat Acad Sci, Fundamental Sci Ctr Rare Earths, Ganzhou 431000, Peoples R China
5.Guangdong Techn Israel Inst Technol, Dept Chem Engn, Shantou 515063, Peoples R China

Dagnaw, Fentahun Wondu,Harrath, Karim,Zheng, Tao,et al. Molecularly Woven Cationic Covalent Organic Frameworks for Highly Selective Electrocatalytic Conversion of CO₂ to CO[J]. ADVANCED SCIENCE,2024.

Dagnaw, Fentahun Wondu.,Harrath, Karim.,Zheng, Tao.,Wu, Xu-Dong.,Liu, Yu-Ze.,...&Jian, Jing-Xin.(2024).Molecularly Woven Cationic Covalent Organic Frameworks for Highly Selective Electrocatalytic Conversion of CO₂ to CO.ADVANCED SCIENCE.

Dagnaw, Fentahun Wondu,et al."Molecularly Woven Cationic Covalent Organic Frameworks for Highly Selective Electrocatalytic Conversion of CO₂ to CO".ADVANCED SCIENCE (2024).