Details

Autor(en) / Beteiligte

• Feng, Shijia
• Wang, Xiaojun
• Cheng, Dongfang
• Luo, Yao
• Shen, Mengxin
• Wang, Jingyang
• Zhao, Wei
• Fang, Susu
• Zheng, Hongzhi
• Ji, Liyao
• Zhang, Xing
• Xu, Weigao
• Liang, Yongye
• Sautet, Philippe
• Zhu, Jia

Titel

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

Ist Teil von

• Angewandte Chemie, 2024-02, Vol.136 (8), p.n/a

Ort / Verlag

Weinheim: Wiley Subscription Services, Inc

Erscheinungsjahr

2024

Quelle

Wiley-Blackwell Journals

Beschreibungen/Notizen

• CO2 electroreduction (CO2R) operating in acidic media circumvents the problems of carbonate formation and CO2 crossover in neutral/alkaline electrolyzers. Alkali cations have been universally recognized as indispensable components for acidic CO2R, while they cause the inevitable issue of salt precipitation. It is therefore desirable to realize alkali‐cation‐free CO2R in pure acid. However, without alkali cations, stabilizing *CO2 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 *CO2 intermediates at the acidic interface (pH=1). As a result, we realize CO2 conversion to CO in pure acid with a faradaic efficiency of 60 % at pH=2 in flow cell. Furthermore, CO2 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 CO2R compared to alkaline conditions, since the potential‐limiting step, *CO2 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 CO2R. Without the assistance of metal cations, CoPc@CNT itself stabilizes *CO2 intermediates at the acidic interface, and thus enables CO2 conversion in pure acid, even at pH=1. As for Au/Ag, CO2 adsorption step is completely suppressed by the high coverage of H, causing only hydrogen evolution reaction to occur.