中国科学技术大学孟征团队报道了含镍双（二亚胺）单元的导电金属-有机框架的固态电化学二氧化碳捕获。相关研究成果于2024年11月19日发表在国际顶尖学术期刊《美国化学会杂志》。

该文首次实现了导电金属有机框架（MOF）Ni₃（2,3,6,7,10,11-六亚氨基三联苯）₂（Ni₃（HITP）₂）与镍双（二亚胺）（Ni-BDI）单元的集成，用于高效的固态电化学二氧化碳（CO₂）捕获。使用Ni₃（HITP）₂作为工作电极组装的电化学电池，可以通过电位控制可逆地捕获和释放CO₂。实现了96%的高容量利用率和98%的法拉第效率。

该材料还表现出优异的电化学稳定性，在50个捕获-释放循环中保持其容量，并抵抗一般干扰，包括O₂、H₂O、NO₂和SO₂。当二氧化碳浓度低至1%时，产能利用率可达35%。捕获浓度在1%至100%范围内的二氧化碳需要极低的能耗，仅为30.5-72.4 kJ mol^-1。

结合光谱实验和计算方法的研究表明，CO₂捕获和释放机制涉及MOF中Ni-BDI单元的N原子，在单电子氧化还原反应中可逆的氨基甲酸酯形成。

附：英文原文

Title: Solid-State Electrochemical Carbon Dioxide Capture by Conductive Metal–Organic Framework Incorporating Nickel Bis(diimine) Units

Author: Jinxin Liu, Mingyu Yang, Xinyi Zhou, Zheng Meng

Issue&Volume: November 19, 2024

Abstract: This paper presents the first implementation of electrically conductive metal–organic framework (MOF) Ni3(2,3,6,7,10,11-hexaiminotriphenylene)2 (Ni3(HITP)2) integrated with nickel bis(diimine) (Ni-BDI) units for efficient solid-state electrochemical carbon dioxide (CO2) capture. The electrochemical cell assembled using Ni3(HITP)2 as working electrodes can reversibly capture and release CO2 through potential control. A high-capacity utilization of 96% and a Faraday efficiency of 98% have been achieved. The material also exhibits excellent electrochemical stability with its capacity maintained during 50 capture–release cycles and resistance to general interferences, including O2, H2O, NO2, and SO2. Capacity utilization of up to 35% is obtained at CO2 concentrations as low as 1%. The capture of CO2 at concentrations ranging from 1% to 100% requires exceptionally low energy consumption of only 30.5–72.4 kJ mol–1. Studies combining spectroscopic experiments and computational approaches reveal that the CO2 capture and release mechanism involves reversible carbamate formation on the N atom of the Ni-BDI unit in the MOF upon its one-electron redox reaction.

DOI: 10.1021/jacs.4c10654

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c10654