Switching Electrocatalytic Hydrogen Evolution Pathways through Electronic Tuning of Copper Porphyrins
© 2024 Wiley-VCH GmbH..
The electronic structure of metal complexes plays key roles in determining their catalytic features. However, controlling electronic structures to regulate reaction mechanisms is of fundamental interest but has been rarely presented. Herein, we report electronic tuning of Cu porphyrins to switch pathways of the hydrogen evolution reaction (HER). Through controllable and regioselective β-oxidation of Cu porphyrin 1, we synthesized analogues 2-4 with one or two β-lactone groups in either a cis or trans configuration. Complexes 1-4 have the same Cu-N4 core site but different electronic structures. Although β-oxidation led to large anodic shifts of reductions, 1-4 displayed similar HER activities in terms of close overpotentials. With electrochemical, chemical and theoretical results, we show that the catalytically active species switches from a CuI species for 1 to a Cu0 species for 4. This work is thus significant to present mechanism-controllable HER via electronic tuning of catalysts.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:63 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - 63(2024), 13 vom: 22. März, Seite e202401074 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Peng, Xinyang [VerfasserIn] |
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| Links: |
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| Themen: |
Copper Porphyrin |
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| Anmerkungen: |
Date Revised 18.03.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/anie.202401074 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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NLM368011658 |
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| 520 | |a © 2024 Wiley-VCH GmbH. | ||
| 520 | |a The electronic structure of metal complexes plays key roles in determining their catalytic features. However, controlling electronic structures to regulate reaction mechanisms is of fundamental interest but has been rarely presented. Herein, we report electronic tuning of Cu porphyrins to switch pathways of the hydrogen evolution reaction (HER). Through controllable and regioselective β-oxidation of Cu porphyrin 1, we synthesized analogues 2-4 with one or two β-lactone groups in either a cis or trans configuration. Complexes 1-4 have the same Cu-N4 core site but different electronic structures. Although β-oxidation led to large anodic shifts of reductions, 1-4 displayed similar HER activities in terms of close overpotentials. With electrochemical, chemical and theoretical results, we show that the catalytically active species switches from a CuI species for 1 to a Cu0 species for 4. This work is thus significant to present mechanism-controllable HER via electronic tuning of catalysts | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Copper Porphyrin | |
| 650 | 4 | |a Electronic Tuning | |
| 650 | 4 | |a Hydrogen Evolution | |
| 650 | 4 | |a Molecular Electrocatalysis | |
| 650 | 4 | |a Reaction Mechanism | |
| 700 | 1 | |a Zhang, Mengchun |e verfasserin |4 aut | |
| 700 | 1 | |a Qin, Haonan |e verfasserin |4 aut | |
| 700 | 1 | |a Han, Jinxiu |e verfasserin |4 aut | |
| 700 | 1 | |a Xu, Yuhan |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Wenzi |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Xue-Peng |e verfasserin |4 aut | |
| 700 | 1 | |a Zhang, Wei |e verfasserin |4 aut | |
| 700 | 1 | |a Apfel, Ulf-Peter |e verfasserin |4 aut | |
| 700 | 1 | |a Cao, Rui |e verfasserin |4 aut | |
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