Tuning Nitrate Electroreduction on Pt Single Crystals via Bulk Pd Alloying: A Combined Kinetic and DFT Approach
[EN] The electrochemical nitrate reduction reaction (NO3RR) offers a strategy for nitrogen cycle remediation and decentralized ammonia production, offering a potential alternative to the energy-intensive Haber-Bosch process. In this study, we employ PtPd bulk alloy single-crystal electrodes (Pt100-x...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | Universitat Politècnica de València (UPV) |
| Repositorio: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia |
| Idioma: | inglés |
| OAI Identifier: | oai:riunet.upv.es:10251/226362 |
| Acceso en línea: | https://riunet.upv.es/handle/10251/226362 |
| Access Level: | acceso abierto |
| Palabra clave: | Nitrate reduction Nitric oxide reduction Pt single crystals PtPd bulk alloy single-crystals Ammonia production |
| Sumario: | [EN] The electrochemical nitrate reduction reaction (NO3RR) offers a strategy for nitrogen cycle remediation and decentralized ammonia production, offering a potential alternative to the energy-intensive Haber-Bosch process. In this study, we employ PtPd bulk alloy single-crystal electrodes (Pt100-x Pd x (hkl)) to investigate how Pd incorporation influences NO3RR on well-defined Pt(111) and Pt(100) surfaces. By combining systematic electrochemical measurements with density functional theory (DFT) calculations, we uncover how Pd modulates surface reactivity and alters the reaction pathway. Our results show that Pd significantly enhances NO3RR activity, particularly on Pt(100), where Pt93Pd7(100) exhibits a 13-fold increase in current density compared to pure Pt(100). On Pt(111), Pd addition introduces a distinct reduction feature associated with nitric oxide adsorption at mixed Pt-Pd hollow sites, indicating a modified pathway that mitigates surface poisoning and promotes product desorption. DFT calculations further reveal that isolated Pd atoms embedded in the Pt(100) matrix stabilize nitrite adsorption and lower the activation barrier for nitrate reduction by approximately 0.15 eV. In contrast, excessive Pd content disrupts favorable adsorption geometries, leading to reduced catalytic performance. These findings highlight the critical role of atomic-scale surface composition and ensemble effects in tuning catalytic activity. This work provides fundamental insights into the design of bimetallic electrocatalysts for efficient and selective nitrate reduction, with broader implications for ammonia production and environmental remediation. |
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