Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction

作者：Weng, Zhe; Wu, Yueshen; Wang, Maoyu; Jiang, Jianbing; Yang, Ke; Huo, Shengjuan; Wang, Xiao-Feng; Ma, Qing; Brudvig, Gary W.; Batista, Victor S.; Liang, Yongye^*; Feng, Zhenxing^*; Wang, Hailiang^*

来源：Nature Communications, 2018, 9(1): 415.

DOI：10.1038/s41467-018-02819-7

• RAY-ABSORPTION SPECTROSCOPY
• CO2 REDUCTION
• ELECTROCATALYTIC REDUCTION
• SURFACE RECONSTRUCTION
• ORGANIC FRAMEWORKS
• METAL
• ELECTROREDUCTION
• SIZE
• NANOPARTICLES
• SELECTIVITY

Restructuring-induced catalytic activity is an intriguing phenomenon of fundamental importance to rational design of high-performance catalyst materials. We study three copper-complex materials for electrocatalytic carbon dioxide reduction. Among them, the copper(II) phthalocyanine exhibits by far the highest activity for yielding methane with a Faradaic efficiency of 66% and a partial current density of 13 mA cm(-2) at the potential of -1.06 V versus the reversible hydrogen electrode. Utilizing in-situ and operando X-ray absorption spectroscopy, we find that under the working conditions copper(II) phthalocyanine undergoes reversible structural and oxidation state changes to form similar to 2 nm metallic copper clusters, which catalyzes the carbon dioxide-to-methane conversion. Density functional calculations rationalize the restructuring behavior and attribute the reversibility to the strong divalent metal ion-ligand coordination in the copper(II) phthalocyanine molecular structure and the small size of the generated copper clusters under the reaction conditions.

• 出版日期2018-1-29
• 单位上海大学; 西北大学; 南方科技大学; 南华大学