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Modulating the Electronic Structure of Cobalt in Molecular Catalysts via Coordination Environment Regulation for Highly Efficient Heterogeneous Nitrate Reduction.
- Source :
-
Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Apr 08; Vol. 63 (15), pp. e202320027. Date of Electronic Publication: 2024 Feb 21. - Publication Year :
- 2024
-
Abstract
- Ammonia (NH <subscript>3</subscript> ) is pivotal in modern industry and represents a promising next-generation carbon-free energy carrier. Electrocatalytic nitrate reduction reaction (eNO <subscript>3</subscript> RR) presents viable solutions for NH <subscript>3</subscript> production and removal of ambient nitrate pollutants. However, the development of eNO <subscript>3</subscript> RR is hindered by lacking the efficient electrocatalysts. To address this challenge, we synthesized a series of macrocyclic molecular catalysts for the heterogeneous eNO <subscript>3</subscript> RR. These materials possess different coordination environments around metal centers by surrounding subunits. Consequently, electronic structures of the active centers can be altered, enabling tunable activity towards eNO <subscript>3</subscript> RR. Our investigation reveals that metal center with an N <subscript>2</subscript> (pyrrole)-N <subscript>2</subscript> (pyridine) configuration demonstrates superior activity over the others and achieves a high NH <subscript>3</subscript> Faradaic efficiency (FE) of over 90 % within the tested range, where the highest FE of approximately 94 % is obtained. Furthermore, it achieves a production rate of 11.28 mg mg <subscript>cat</subscript> <superscript>-1</superscript> h <superscript>-1</superscript> , and a turnover frequency of up to 3.28 s <superscript>-1</superscript> . Further tests disclose that these molecular catalysts with diverse coordination environments showed different magnetic moments. Theoretical calculation results indicate that variated coordination environments can result in a d-band center variation which eventually affects rate-determining step energy and calculated magnetic moments, thus establishing a correlation between electronic structure, experimental activity, and computational parameters.<br /> (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Details
- Language :
- English
- ISSN :
- 1521-3773
- Volume :
- 63
- Issue :
- 15
- Database :
- MEDLINE
- Journal :
- Angewandte Chemie (International ed. in English)
- Publication Type :
- Academic Journal
- Accession number :
- 38317616
- Full Text :
- https://doi.org/10.1002/anie.202320027