A covalent molecular design enabling efficient CO2 reduction in strong acids

Qiang Zhang (Co-first Author), Charles B. Musgrave III (Co-first Author), Yun Song, Jianjun Su, Libei Huang, Le Cheng, Geng Li, Yong Liu, Yinger Xin, Qiushi Hu, Ge Ye, Hanchen Shen, Xue Wang, Ben Zhong Tang*, William A. Goddard III*, Ruquan Ye*

*Corresponding author for this work

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

41 Citations (Scopus)
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Abstract

Molecular complexes are an important class of catalysts for the electrochemical carbon dioxide reduction reaction (CO2RR). However, selective CO2RR in strong acids remains challenging due to competition with the hydrogen evolution reaction. Peripheral functionalization is effective for tailoring the intrinsic activity of molecular catalysts, mostly attributed to the inductive effect or to stabilization of reaction intermediates. Here we report that peripheral functionalization of immobilized molecular complexes with quaternary ammonium groups can regulate the catalytic activity by tuning the mass distribution surrounding the active sites, enabling high-performance CO2RR in strong acids. The positively charged and hydrophobic alkylammonium groups affect the migration of water and hydronium in the double layer, while their immobilized configuration enables a stable cationic layer, inhibiting the hydrogen evolution reaction over extended potential windows. Dodecyl ammonium-functionalized cobalt phthalocyanine and tin porphyrin suppress the hydrogen Faradaic efficiency to <10% in pH ~0.5 media, while providing a single-pass conversion efficiency up to ~85%. The selectivity can be maintained at 90% even in Li+ solutions, which often exhibit poor proton shielding. Our study underscores the role of second-sphere structure for selective molecular electrochemistry. © The Author(s), under exclusive licence to Springer Nature Limited 2024.

Original languageEnglish
JournalNature Synthesis
Online published25 Jun 2024
DOIs
Publication statusOnline published - 25 Jun 2024

Funding

This work was supported by the Guangdong Basic and Applied Basic Research Fund (2024A1515030164 and 2022A1515011333), the Hong Kong Research Grant Council (11309723), the State Key Laboratory of Marine Pollution (SKLMP/SCRF/0060) and the Shenzhen Science and Technology Program (JCYJ20220818101204009). B.Z.T. acknowledges support from Shenzhen Key Laboratory of Functional Aggregate Materials (ZDSYS20211021111400001), the Science Technology Innovation Commission of Shenzhen Municipality (KQTD20210811090142053 and JCYJ20220818103007014) and the Innovation and Technology Commission (ITC-CNERC14SC01). C.B.M. and W.A.G. acknowledge support from the Liquid Sunlight Alliance, which is supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Fuels from Sunlight Hub under award number DE-SC0021266.

Publisher's Copyright Statement

  • COPYRIGHT TERMS OF DEPOSITED POSTPRINT FILE: This version of the article has been accepted for publication, after peer review (when applicable) and is subject to Springer Nature’s AM terms of use, but is not the Version of Record and does not reflect post-acceptance improvements, or any corrections. The Version of Record is available online at: https://doi.org/10.1038/s44160-024-00588-4.

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