Pulse Electrolysis Turns on CO2 Methanation through N-Confused Cupric Porphyrin
© 2024 Wiley-VCH GmbH..
Breaking the D4h symmetry in the square-planar M-N4 configuration of macrocycle molecular catalysts has witnessed enhanced electrocatalytic activity, but at the expense of electrochemical stability. Herein, we hypothesize that the lability of the active Cu-N3 motifs in the N-confused copper (II) tetraphenylporphyrin (CuNCP) could be overcome by applying pulsed potential electrolysis (PPE) during electrocatalytic carbon dioxide reduction. We find that applying PPE can indeed enhance the CH4 selectivity on CuNCP by 3 folds to reach the partial current density of 170 mA cm-2 at >60 % Faradaic efficiency (FE) in flow cell. However, combined ex situ X-ray diffraction (XRD), transmission electron microscope (TEM), and in situ X-ray absorption spectroscopy (XAS), infrared (IR), Raman, scanning electrochemical microscopy (SECM) characterizations reveal that, in a prolonged time scale, the decomplexation of CuNCP is unavoidable, and the promoted water dissociation under high anodic bias with lowered pH and enriched protons facilitates successive hydrogenation of *CO on the irreversibly reduced Cu nanoparticles, leading to the improved CH4 selectivity. As a key note, this study signifies the adaption of electrolytic protocol to the catalyst structure for tailoring local chemical environment towards efficient CO2 reduction.
| 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), 12 vom: 18. März, Seite e202315922 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Hua, Wei [VerfasserIn] |
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| Links: |
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| Themen: |
Electrocatalytic CO2 reduction |
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| Anmerkungen: |
Date Revised 11.03.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1002/anie.202315922 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| 520 | |a Breaking the D4h symmetry in the square-planar M-N4 configuration of macrocycle molecular catalysts has witnessed enhanced electrocatalytic activity, but at the expense of electrochemical stability. Herein, we hypothesize that the lability of the active Cu-N3 motifs in the N-confused copper (II) tetraphenylporphyrin (CuNCP) could be overcome by applying pulsed potential electrolysis (PPE) during electrocatalytic carbon dioxide reduction. We find that applying PPE can indeed enhance the CH4 selectivity on CuNCP by 3 folds to reach the partial current density of 170 mA cm-2 at >60 % Faradaic efficiency (FE) in flow cell. However, combined ex situ X-ray diffraction (XRD), transmission electron microscope (TEM), and in situ X-ray absorption spectroscopy (XAS), infrared (IR), Raman, scanning electrochemical microscopy (SECM) characterizations reveal that, in a prolonged time scale, the decomplexation of CuNCP is unavoidable, and the promoted water dissociation under high anodic bias with lowered pH and enriched protons facilitates successive hydrogenation of *CO on the irreversibly reduced Cu nanoparticles, leading to the improved CH4 selectivity. As a key note, this study signifies the adaption of electrolytic protocol to the catalyst structure for tailoring local chemical environment towards efficient CO2 reduction | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a Electrocatalytic CO2 reduction | |
| 650 | 4 | |a In situ electrochemical spectrometry | |
| 650 | 4 | |a Methanation | |
| 650 | 4 | |a N-confused copper tetraphenylporphyrin | |
| 650 | 4 | |a Pulsed potential electrolysis | |
| 700 | 1 | |a Liu, Tingting |e verfasserin |4 aut | |
| 700 | 1 | |a Zheng, Zhangyi |e verfasserin |4 aut | |
| 700 | 1 | |a Yuan, Huihong |e verfasserin |4 aut | |
| 700 | 1 | |a Xiao, Long |e verfasserin |4 aut | |
| 700 | 1 | |a Feng, Kun |e verfasserin |4 aut | |
| 700 | 1 | |a Hui, Jingshu |e verfasserin |4 aut | |
| 700 | 1 | |a Deng, Zhao |e verfasserin |4 aut | |
| 700 | 1 | |a Ma, Mutian |e verfasserin |4 aut | |
| 700 | 1 | |a Cheng, Jian |e verfasserin |4 aut | |
| 700 | 1 | |a Song, Daqi |e verfasserin |4 aut | |
| 700 | 1 | |a Lyu, Fenglei |e verfasserin |4 aut | |
| 700 | 1 | |a Zhong, Jun |e verfasserin |4 aut | |
| 700 | 1 | |a Peng, Yang |e verfasserin |4 aut | |
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