Stabilizing *CO2 Intermediates at the Acidic Interface using Molecularly Dispersed Cobalt Phthalocyanine as Catalysts for CO2 Reduction

Feng，Shijia1; Wang，Xiaojun1,2; Cheng，Dongfang4; Luo，Yao3; Shen，Mengxin1; Wang，Jingyang1; Zhao，Wei1; Fang，Susu3; Zheng，Hongzhi1; Ji，Liyao1; Zhang，Xing1; Xu，Weigao3; Liang，Yongye6; Sautet，Philippe4,5; Zhu，Jia1,2

2024-02-19

10.1002/anie.202317942

Angewandte Chemie - International Edition   影响因子和分区

1433-7851

1521-3773

CO electroreduction (COR) operating in acidic media circumvents the problems of carbonate formation and CO crossover in neutral/alkaline electrolyzers. Alkali cations have been universally recognized as indispensable components for acidic COR, while they cause the inevitable issue of salt precipitation. It is therefore desirable to realize alkali-cation-free COR in pure acid. However, without alkali cations, stabilizing *CO intermediates by catalyst itself at the acidic interface poses as a challenge. Herein, we first demonstrate that a carbon nanotube-supported molecularly dispersed cobalt phthalocyanine (CoPc@CNT) catalyst provides the Co single-atom active site with energetically localized d states to strengthen the adsorbate-surface interactions, which stabilizes *CO intermediates at the acidic interface (pH=1). As a result, we realize CO conversion to CO in pure acid with a faradaic efficiency of 60 % at pH=2 in flow cell. Furthermore, CO is successfully converted in cation exchanged membrane-based electrode assembly with a faradaic efficiency of 73 %. For CoPc@CNT, acidic conditions also promote the intrinsic activity of COR compared to alkaline conditions, since the potential-limiting step, *CO to *COOH, is pH-dependent. This work provides a new understanding for the stabilization of reaction intermediates and facilitates the designs of catalysts and devices for acidic COR.

Acidic Interface CO2 Adsorption, Stabilizing *CO2 Intermediates CO2 Reduction Molecularly Dispersed Catalyst

SCI ; EI

英语

其他

CHEMISTRY

2-s2.0-85182429668

Scopus

1.National Laboratory of Solid State Microstructures,Collaborative Innovation Center of Advanced Microstructures,College of Engineering and Applied Sciences,Nanjing University,Nanjing,Jiangsu,210023,China
2.School of Sustainable Energy and Resources,Nanjing University,Suzhou,215163,China
3.Key Laboratory of Mesoscopic Chemistry of Ministry of Education,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing,210023,China
4.Department of Chemical and Biomolecular Engineering,University of California,Los Angeles,Los Angeles,90095,United States
5.Department of Chemistry and Biochemistry,University of California,Los Angeles,Los Angeles,90095,United States
6.Department of Materials Science and Engineering,Guangdong Provincial Key Laboratory of Energy Materials for Electric Power,Southern University of Science and Technology,Shenzhen,China

Feng，Shijia,Wang，Xiaojun,Cheng，Dongfang,et al. Stabilizing *CO2 Intermediates at the Acidic Interface using Molecularly Dispersed Cobalt Phthalocyanine as Catalysts for CO2 Reduction[J]. Angewandte Chemie - International Edition,2024,63(8).

Feng，Shijia.,Wang，Xiaojun.,Cheng，Dongfang.,Luo，Yao.,Shen，Mengxin.,...&Zhu，Jia.(2024).Stabilizing *CO2 Intermediates at the Acidic Interface using Molecularly Dispersed Cobalt Phthalocyanine as Catalysts for CO2 Reduction.Angewandte Chemie - International Edition,63(8).

Feng，Shijia,et al."Stabilizing *CO2 Intermediates at the Acidic Interface using Molecularly Dispersed Cobalt Phthalocyanine as Catalysts for CO2 Reduction".Angewandte Chemie - International Edition 63.8(2024).