Stabilization of Pd0 by Cu Alloying : Theory-Guided Design of Pd3Cu Electrocatalyst for Anodic Methanol Carbonylation
© 2024 Wiley‐VCH GmbH..
Electrocatalytic carbonylation of CO and CH3OH to dimethyl carbonate (DMC) on metallic palladium (Pd) electrode offers a promising strategy for C1 valorization at the anode. However, its broader application is limited by the high working potential and the low DMC selectivity accompanied with severe methanol self-oxidation. Herein, our theoretical analysis of the intermediate adsorption interactions on both Pd0 and Pd4+ surfaces revealed that inevitable reconstruction of Pd surface under strongly oxidative potential diminishes its CO adsorption capacity, thus damaging the DMC formation. Further theoretical modeling indicates that doping Pd with Cu not only stabilizes low-valence Pd in oxidative environments but also lowers the overall energy barrier for DMC formation. Guided by this insight, we developed a facile two-step thermal shock method to prepare PdCu alloy electrocatalysts for DMC. Remarkably, the predicted Pd3Cu demonstrated the highest DMC selectivity among existing Pd-based electrocatalysts, reaching a peaked DMC selectivity of 93% at 1.0 V versus Ag/AgCl electrode. (Quasi) in-situ spectra investigations further confirmed the predicted dual role of Cu dopant in promoting Pd-catalyzed DMC formation.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - year:2024 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - (2024) vom: 12. Apr., Seite e202401311 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Shi, Yunru [VerfasserIn] |
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| Links: |
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| Themen: |
Dimethyl carbonate (DMC) * electrocatalytic carbonylation * Pd * valence state controlling * Cu doping |
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| Anmerkungen: |
Date Revised 12.04.2024 published: Print-Electronic Citation Status Publisher |
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| doi: |
10.1002/anie.202401311 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM370958071 |
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| 245 | 1 | 0 | |a Stabilization of Pd0 by Cu Alloying |b Theory-Guided Design of Pd3Cu Electrocatalyst for Anodic Methanol Carbonylation |
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| 520 | |a Electrocatalytic carbonylation of CO and CH3OH to dimethyl carbonate (DMC) on metallic palladium (Pd) electrode offers a promising strategy for C1 valorization at the anode. However, its broader application is limited by the high working potential and the low DMC selectivity accompanied with severe methanol self-oxidation. Herein, our theoretical analysis of the intermediate adsorption interactions on both Pd0 and Pd4+ surfaces revealed that inevitable reconstruction of Pd surface under strongly oxidative potential diminishes its CO adsorption capacity, thus damaging the DMC formation. Further theoretical modeling indicates that doping Pd with Cu not only stabilizes low-valence Pd in oxidative environments but also lowers the overall energy barrier for DMC formation. Guided by this insight, we developed a facile two-step thermal shock method to prepare PdCu alloy electrocatalysts for DMC. Remarkably, the predicted Pd3Cu demonstrated the highest DMC selectivity among existing Pd-based electrocatalysts, reaching a peaked DMC selectivity of 93% at 1.0 V versus Ag/AgCl electrode. (Quasi) in-situ spectra investigations further confirmed the predicted dual role of Cu dopant in promoting Pd-catalyzed DMC formation | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a dimethyl carbonate (DMC) * electrocatalytic carbonylation * Pd * valence state controlling * Cu doping | |
| 700 | 1 | |a Hu, Yi-Fan |e verfasserin |4 aut | |
| 700 | 1 | |a Ye, Jinyu |e verfasserin |4 aut | |
| 700 | 1 | |a Zhong, Gang |e verfasserin |4 aut | |
| 700 | 1 | |a Xia, Chungu |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Zhi-Pan |e verfasserin |4 aut | |
| 700 | 1 | |a Huang, Yang |e verfasserin |4 aut | |
| 700 | 1 | |a He, Lin |e verfasserin |4 aut | |
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