Electrifying HCOOH synthesis from CO2 building blocks over Cu-Bi nanorod arrays

• 成果类型: Article
• 署名作者: Zhang, Guiru; Tan, Bing; Mok, Dong Hyeon; Liu, Huiya; Ni, Baoxin; Zhao, Gui; Ye, Ke; Huo, Shengjuan; Miao, Xiaohe; Liang, Zheng; Liu, Xi; Chen, Liwei; Zhang, Zemin; Cai, Wen Bin; Back, Seoin; Jiang, Kun
• 署名单位: Shanghai Jiao Tong University; Lanzhou University; Sogang University; Shanghai Jiao Tong University; Shanghai Jiao Tong University; Shanghai Jiao Tong University; Shanghai University; Westlake University; Shanghai Jiao Tong University; Ningxia University; Fudan University
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-10907
• DOI: 10.1073/pnas.2400898121
• 发表日期: 2024-07-16
• 关键词: formic-acid; electrochemical reduction; carbon-dioxide; formate; electroreduction; electrolysis; selectivity; conversion; hydrogen; surface

摘要

Precise electrochemical synthesis of commodity chemicals and fuels from CO2 2 building blocks provides a promising route to close the anthropogenic carbon cycle, in which renewable but intermittent electricity could be stored within the greenhouse gas molecules. Here, we report state- of- the- art CO2- 2- to- HCOOH- HCOOH valorization performance over a multiscale optimized Cu-Bi cathodic architecture, delivering a formate Faradaic efficiency exceeding 95% within an aqueous electrolyzer, a C- basis HCOOH purity above 99.8% within a solid- state electrolyzer operated at 100 mA cm-2 -2 for 200 h and an energy efficiency of 39.2%, as well as a tunable aqueous HCOOH concentration ranging from 2.7 to 92.1 wt%. Via a combined two-- dimensional reaction phase diagram and finite element analysis, we highlight the role of local geometries of Cu and Bi in branching the adsorption strength for key intermediates like *COOH and *OCHO for CO2 2 reduction, while the crystal orbital Hamiltonian population analysis rationalizes the vital contribution from moderate binding strength of 11 2 (O,O)- OCHO on Cu- doped Bi surface in promoting HCOOH electrosynthesis. The findings of this study not only shed light on the tuning knobs for precise CO2 2 valorization, but also provide a different research paradigm for advancing the activity and selectivity optimization in a broad range of electrosynthetic systems.