Isolated Rhodium Atoms Activate Porous TiO2 for Enhanced Electrocatalytic Conversion of Nitrate to Ammonia
Abstract The direct electrochemical reduction of nitrate to ammonia is an efficient and environmentally friendly technology, however, developing electrocatalysts with high activity and selectivity remains a great challenge. Single‐atom catalysts demonstrate unique properties and exceptional performa...
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Wiley
2025-01-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202411705 |
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| author | Zhi Liang Zhao Shaoxuan Yang Shensong Wang Zhe Zhang Liang Zhao Qi Wang Xinyi Zhang |
| author_facet | Zhi Liang Zhao Shaoxuan Yang Shensong Wang Zhe Zhang Liang Zhao Qi Wang Xinyi Zhang |
| author_sort | Zhi Liang Zhao |
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| description | Abstract The direct electrochemical reduction of nitrate to ammonia is an efficient and environmentally friendly technology, however, developing electrocatalysts with high activity and selectivity remains a great challenge. Single‐atom catalysts demonstrate unique properties and exceptional performance across a range of catalytic reactions, especially those that encompass multi‐step processes. Herein, a straightforward and cost‐effective approach is introduced for synthesizing single‐atom dispersed Rh on porous TiO2 spheres (Rh1‐TiO2), which functions as an efficient electrocatalyst for the electroreduction of NO3− to NH3. The synthesized Rh1‐TiO2 catalyst achieve a maximum NH3 Faradaic efficiency (FE) of 94.7% and an NH3 yield rate of 29.98 mg h−1 mgcat−1 at −0.5 V versus RHE in a 0.1 M KOH+0.1 M KNO3 electrolyte, significantly outperforming not only undoped TiO2 but also Ru, Pd, and Ir single‐atom doped titania catalysts. Density functional theory calculations reveal that the incorporation of Rh single atom significantly enhances charge transfer between adsorbed NO3− and the active site. The Rh atoms not only serve as the highly active site for electrochemical nitrate reduction reaction (NO3RR), but also activates the adjacent Ti sites through optimizating the electronic structure, thereby reducing the energy barrier of the rate‐limiting step. Consequently, this results in a substantial enhancement in electrochemical NO3RR performance. Furthermore, this synthetic method has the potential to be extended to other single‐atom catalysts and scaled up for commercial applications. |
| format | Article |
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| institution | Kabale University |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Wiley |
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| spelling | doaj-art-729a75da48424d3daff2eac078c5f06e2025-01-13T15:29:43ZengWileyAdvanced Science2198-38442025-01-01122n/an/a10.1002/advs.202411705Isolated Rhodium Atoms Activate Porous TiO2 for Enhanced Electrocatalytic Conversion of Nitrate to AmmoniaZhi Liang Zhao0Shaoxuan Yang1Shensong Wang2Zhe Zhang3Liang Zhao4Qi Wang5Xinyi Zhang6National energy key laboratory for new hydrogen‐ammonia energy technologies Foshan Xianhu Laboratory Foshan 528200 P. R. ChinaNational energy key laboratory for new hydrogen‐ammonia energy technologies Foshan Xianhu Laboratory Foshan 528200 P. R. ChinaHubei Key Laboratory of Micro‐Nanoelectronic Materials and Devices School of Microelectronics Hubei University Wuhan 430062 P. R. ChinaCollege of Physics Science and Technology & Microelectronics Industry Research Institute Yangzhou University Jiangsu 225009 P. R. ChinaCollege of Physics Science and Technology & Microelectronics Industry Research Institute Yangzhou University Jiangsu 225009 P. R. ChinaDepartment of Materials Science and Engineering City University of Hong Kong Kowloon Hong Kong 999077 P. R. ChinaNational energy key laboratory for new hydrogen‐ammonia energy technologies Foshan Xianhu Laboratory Foshan 528200 P. R. ChinaAbstract The direct electrochemical reduction of nitrate to ammonia is an efficient and environmentally friendly technology, however, developing electrocatalysts with high activity and selectivity remains a great challenge. Single‐atom catalysts demonstrate unique properties and exceptional performance across a range of catalytic reactions, especially those that encompass multi‐step processes. Herein, a straightforward and cost‐effective approach is introduced for synthesizing single‐atom dispersed Rh on porous TiO2 spheres (Rh1‐TiO2), which functions as an efficient electrocatalyst for the electroreduction of NO3− to NH3. The synthesized Rh1‐TiO2 catalyst achieve a maximum NH3 Faradaic efficiency (FE) of 94.7% and an NH3 yield rate of 29.98 mg h−1 mgcat−1 at −0.5 V versus RHE in a 0.1 M KOH+0.1 M KNO3 electrolyte, significantly outperforming not only undoped TiO2 but also Ru, Pd, and Ir single‐atom doped titania catalysts. Density functional theory calculations reveal that the incorporation of Rh single atom significantly enhances charge transfer between adsorbed NO3− and the active site. The Rh atoms not only serve as the highly active site for electrochemical nitrate reduction reaction (NO3RR), but also activates the adjacent Ti sites through optimizating the electronic structure, thereby reducing the energy barrier of the rate‐limiting step. Consequently, this results in a substantial enhancement in electrochemical NO3RR performance. Furthermore, this synthetic method has the potential to be extended to other single‐atom catalysts and scaled up for commercial applications.https://doi.org/10.1002/advs.202411705ammonia synthesiselectrocatalysisnitrate reduction reactionsingle atom catalysts |
| spellingShingle | Zhi Liang Zhao Shaoxuan Yang Shensong Wang Zhe Zhang Liang Zhao Qi Wang Xinyi Zhang Isolated Rhodium Atoms Activate Porous TiO2 for Enhanced Electrocatalytic Conversion of Nitrate to Ammonia Advanced Science ammonia synthesis electrocatalysis nitrate reduction reaction single atom catalysts |
| title | Isolated Rhodium Atoms Activate Porous TiO2 for Enhanced Electrocatalytic Conversion of Nitrate to Ammonia |
| title_full | Isolated Rhodium Atoms Activate Porous TiO2 for Enhanced Electrocatalytic Conversion of Nitrate to Ammonia |
| title_fullStr | Isolated Rhodium Atoms Activate Porous TiO2 for Enhanced Electrocatalytic Conversion of Nitrate to Ammonia |
| title_full_unstemmed | Isolated Rhodium Atoms Activate Porous TiO2 for Enhanced Electrocatalytic Conversion of Nitrate to Ammonia |
| title_short | Isolated Rhodium Atoms Activate Porous TiO2 for Enhanced Electrocatalytic Conversion of Nitrate to Ammonia |
| title_sort | isolated rhodium atoms activate porous tio2 for enhanced electrocatalytic conversion of nitrate to ammonia |
| topic | ammonia synthesis electrocatalysis nitrate reduction reaction single atom catalysts |
| url | https://doi.org/10.1002/advs.202411705 |
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