Local Chemical Environment Dependent Nitrate-Reduction-to-Ammonia Performance on Cu-Based Electrocatalysts
The active component of copper-based materials for electrocatalytic nitrate reduction to ammonia (NRA) remains unclear due to the susceptibility of oxidation of copper. Using density functional theory calculations, NRA pathways are evaluated on low-index crystal surfaces Cu2O (111), CuO (111), and Cu (111) at different pH. Cu2O (111), with abundant undercoordinated Cu atoms on the surface, shows easier adsorption of NO3- than Cu (111) or CuO (111). NRA on CuO (111) is hindered by the large ΔG of adsorption of NO3- and hydrogenation of *NO. Thus, Cu (111) and Cu2O (111) contribute most to the NRA activity while CuO (111) is inert. Three key steps of NRA on copper-based catalysts are identified: adsorption of NO3-, *NO → *NOH/*NHO, and *NH3 desorption, as the three can be rate-determining steps depending on the local environment. Moreover, previous experimentally detected NH2OH on copper-based catalysts may come from the NRA on Cu2O (111) as the most probable pathway on Cu2O (111) is NO3- → *NO3 → *NO2 → *NO → *NHO → *NHOH → *NH2OH → *NH2 → *NH3 → *NH3(g). At high reduction potential, CuOx would be reduced into Cu, so the effective active substance for NRA in a strong reduction environment is Cu.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:15 |
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| Enthalten in: |
The journal of physical chemistry letters - 15(2024), 12 vom: 28. März, Seite 3258-3266 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Hu, Tao [VerfasserIn] |
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| Links: |
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| Themen: |
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| Anmerkungen: |
Date Revised 28.03.2024 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.1021/acs.jpclett.3c03462 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM369784499 |
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| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a The active component of copper-based materials for electrocatalytic nitrate reduction to ammonia (NRA) remains unclear due to the susceptibility of oxidation of copper. Using density functional theory calculations, NRA pathways are evaluated on low-index crystal surfaces Cu2O (111), CuO (111), and Cu (111) at different pH. Cu2O (111), with abundant undercoordinated Cu atoms on the surface, shows easier adsorption of NO3- than Cu (111) or CuO (111). NRA on CuO (111) is hindered by the large ΔG of adsorption of NO3- and hydrogenation of *NO. Thus, Cu (111) and Cu2O (111) contribute most to the NRA activity while CuO (111) is inert. Three key steps of NRA on copper-based catalysts are identified: adsorption of NO3-, *NO → *NOH/*NHO, and *NH3 desorption, as the three can be rate-determining steps depending on the local environment. Moreover, previous experimentally detected NH2OH on copper-based catalysts may come from the NRA on Cu2O (111) as the most probable pathway on Cu2O (111) is NO3- → *NO3 → *NO2 → *NO → *NHO → *NHOH → *NH2OH → *NH2 → *NH3 → *NH3(g). At high reduction potential, CuOx would be reduced into Cu, so the effective active substance for NRA in a strong reduction environment is Cu | ||
| 650 | 4 | |a Journal Article | |
| 700 | 1 | |a Wang, Mengting |e verfasserin |4 aut | |
| 700 | 1 | |a Ren, Lijun |e verfasserin |4 aut | |
| 700 | 1 | |a Li, Chang Ming |e verfasserin |4 aut | |
| 700 | 1 | |a Guo, Chunxian |e verfasserin |4 aut | |
| 773 | 0 | 8 | |i Enthalten in |t The journal of physical chemistry letters |d 2010 |g 15(2024), 12 vom: 28. März, Seite 3258-3266 |w (DE-627)NLM195788362 |x 1948-7185 |7 nnns |
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