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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 language | English |
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Journal | Nature Synthesis |
Online published | 25 Jun 2024 |
DOIs | |
Publication status | Online 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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GRF: Steering the Local Environment of Ultrathin Covalent Organic Polymers for Efficient Electroreduction of CO2 to Methanol
YE, R. (Principal Investigator / Project Coordinator) & YAKOBSON, B. I. (Co-Investigator)
1/11/23 → …
Project: Research