格式化
铋
金属有机骨架
傅里叶变换红外光谱
电化学
电导率
化学
催化作用
材料科学
无机化学
物理化学
化学工程
电极
有机化学
吸附
工程类
作者
Zengqiang Gao,Man Hou,Yongxia Shi,Li Li,Qisheng Sun,Shuyuan Yang,Zhiqiang Jiang,Wenjuan Yang,Zhicheng Zhang,Wenping Hu
出处
期刊:Chemical Science
[The Royal Society of Chemistry]
日期:2023-01-01
卷期号:14 (25): 6860-6866
被引量:13
摘要
Bismuth-based metal-organic frameworks (Bi-MOFs) have received attention in electrochemical CO2-to-formate conversion. However, the low conductivity and saturated coordination of Bi-MOFs usually lead to poor performance, which severely limits their widespread application. Herein, a conductive catecholate-based framework with Bi-enriched sites (HHTP, 2,3,6,7,10,11-hexahydroxytriphenylene) is constructed and the zigzagging corrugated topology of Bi-HHTP is first unraveled via single-crystal X-ray diffraction. Bi-HHTP possesses excellent electrical conductivity (1.65 S m-1) and unsaturated coordination Bi sites are confirmed by electron paramagnetic resonance spectroscopy. Bi-HHTP exhibited an outstanding performance for selective formate production of 95% with a maximum turnover frequency of 576 h-1 in a flow cell, which surpassed most of the previously reported Bi-MOFs. Significantly, the structure of Bi-HHTP could be well maintained after catalysis. In situ attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirms that the key intermediate is *COOH species. Density functional theory (DFT) calculations reveal that the rate-determining step is *COOH species generation, which is consistent with the in situ ATR-FTIR results. DFT calculations confirmed that the unsaturated coordination Bi sites acted as active sites for electrochemical CO2-to-formate conversion. This work provides new insights into the rational design of conductive, stable, and active Bi-MOFs to improve their performance towards electrochemical CO2 reduction.
科研通智能强力驱动
Strongly Powered by AbleSci AI