Calixarene-Functionalized Stable Bismuth Oxygen Clusters for Specific CO 2 -to-HCOOH Electroreduction

作者：Jingwen Shi, Shengnan Sun, Jiang Liu, Jiang Liu, Qian Niu, Long‐Zhang Dong, Qing Huang, Jing-Jing Liu, Jing-Jing Liu, Rui Wang, Zhifeng Xin, Dongdi Zhang, Jingyang Niu, Ya‐Qian Lan · 发表于：ACS Catalysis · 年份：2022 · DOI：10.1021/acscatal.2c02715 · 被引用次数：82 · 研究领域：CO2 Reduction Techniques and Catalysts、Covalent Organic Framework Applications、Metal-Organic Frameworks: Synthesis and Applications

Designing and synthesizing well-defined crystalline catalysts for long-term electrocatalytic conversion of CO 2 to specific products remain a great challenge. In this work, two very stable crystalline bismuth oxygen clusters functionalized by hydrophobic p - tert -butylthiacalix[4]arene ligand, Bi 3 and Bi 14, were constructed and treated as catalysts for efficient electrochemical CO 2 reduction. Sandwich-type Bi 3 with synergistic bi-bismuth exhibits a remarkable performance for CO 2 -to-HCOOH conversion with a faradaic efficiency (FE HCOOH ) of 96.47% at −1.3 V (vs reversible hydrogen electrode) and durability over 27.5 h, while rodlike Bi 14 with a monobismuth active site reached a maximum FE HCOOH of 92.76% at −1.2 V with durability over 23.9 h. Density functional theory calculation proves that adjacent double active bismuth atoms in Bi 3 are more beneficial to stabilize the *OCHO intermediate and then promote the electrocatalytic reduction of CO 2 to HCOOH than Bi 14 with a single active site. This work represents the report of stable crystalline bismuth-oxo cluster catalysts for specific electrocatalytic CO 2 reduction conversion.