Zn-induced electron-rich Sn catalysts enable highly efficient CO2 electroreduction to formate

Xingxing Tan; Shunhan Jia; Xinning Song; Xiaodong Ma; Jiaqi Feng; Libing Zhang; Limin Wu; Juan Du; Aibing Chen; Qinggong Zhu; Xiaofu Sun; Buxing Han

doi:10.1039/d3sc02790b

Zn-induced electron-rich Sn catalysts enable highly efficient CO₂ electroreduction to formate

Chem Sci. 2023 Jul 10;14(30):8214-8221. doi: 10.1039/d3sc02790b. eCollection 2023 Aug 2.

Authors

Xingxing Tan^{1

2}, Shunhan Jia^{1

2}, Xinning Song^{1

2}, Xiaodong Ma^{1

2}, Jiaqi Feng¹, Libing Zhang^{1

2}, Limin Wu^{1

2}, Juan Du³, Aibing Chen³, Qinggong Zhu^{1

2}, Xiaofu Sun^{1

2}, Buxing Han^{1

2

4}

Affiliations

¹ Beijing National Laboratory for Molecular Sciences, Key Laboratory of Colloid and Interface and Thermodynamics, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences Beijing 100190 P. R. China sunxiaofu@iccas.ac.cn hanbx@iccas.ac.cn.
² School of Chemical Sciences, University of Chinese Academy of Sciences Beijing 100049 P. R. China.
³ College of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology Shijiazhuang 050018 P. R. China.
⁴ Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University Shanghai 200062 P. R. China.

Abstract

Renewable-energy-driven CO₂ electroreduction provides a promising way to address the growing greenhouse effect issue and produce value-added chemicals. As one of the bulk chemicals, formic acid/formate has the highest revenue per mole of electrons among various products. However, the scaling up of CO₂-to-formate for practical applications with high faradaic efficiency (FE) and current density is constrained by the difficulty of precisely reconciling the competing intermediates (*COOH and HCOO*). Herein, a Zn-induced electron-rich Sn electrocatalyst was reported for CO₂-to-formate with high efficiency. The faradaic efficiency of formate (FE_formate) could reach 96.6%, and FE_formate > 90% was maintained at formate partial current density up to 625.4 mA cm^-1. Detailed study indicated that catalyst reconstruction occurred during electrolysis. With appropriate electron accumulation, the electron-rich Sn catalyst could facilitate the adsorption and activation of CO₂ molecules to form a intermediate and then promoted the carbon protonation of to yield a HCOO* intermediate. Afterwards, the HCOO* → HCOOH* proceeded via another proton-coupled electron transfer process, leading to high activity and selectivity for formate production.