Stabilizing copper sites in coordination polymers toward efficient electrochemical C-C coupling

Yongxiang Liang, Jiankang Zhao, Yu Yang, Sung Fu Hung, Jun Li, Shuzhen Zhang, Yong Zhao, An Zhang, Cheng Wang, Dominique Appadoo, Lei Zhang, Zhigang Geng*, Fengwang Li*, Jie Zeng*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

Electroreduction of carbon dioxide with renewable electricity holds promise for achieving net-zero carbon emissions. Single-site catalysts have been reported to catalyze carbon-carbon (C-C) coupling—the indispensable step for more valuable multi-carbon (C2+) products—but were proven to be transformed in situ to metallic agglomerations under working conditions. Here, we report a stable single-site copper coordination polymer (Cu(OH)BTA) with periodic neighboring coppers and it exhibits 1.5 times increase of C2H4 selectivity compared to its metallic counterpart at 500 mA cm−2. In-situ/operando X-ray absorption, Raman, and infrared spectroscopies reveal that the catalyst remains structurally stable and does not undergo a dynamic transformation during reaction. Electrochemical and kinetic isotope effect analyses together with computational calculations show that neighboring Cu in the polymer provides suitably-distanced dual sites that enable the energetically favorable formation of an *OCCHO intermediate post a rate-determining step of CO hydrogenation. Accommodation of this intermediate imposes little changes of conformational energy to the catalyst structure during the C-C coupling. We stably operate full-device CO2 electrolysis at an industry-relevant current of one ampere for 67 h in a membrane electrode assembly. The coordination polymers provide a perspective on designing molecularly stable, single-site catalysts for electrochemical CO2 conversion.

Original languageEnglish
Article number474
JournalNature Communications
Volume14
Issue number1
DOIs
StatePublished - Dec 2023

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