The Key Steps and Distinct Performance Trends of Pyrrolic vs. Pyridinic M-N-C Catalysts in Electrocatalytic Nitrate Reduction
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| Main Authors: | , , , , , , , , , |
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| Format: | Preprint |
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2024
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| _version_ | 1866908976612900864 |
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| author | Jiang, Qiuling Gu, Mingyao Wang, Tianyi Liu, Fangzhou Yang, Xin Zhang, Di Wu, Zhijian Wang, Ying Wei, Li Li, Hao |
| author_facet | Jiang, Qiuling Gu, Mingyao Wang, Tianyi Liu, Fangzhou Yang, Xin Zhang, Di Wu, Zhijian Wang, Ying Wei, Li Li, Hao |
| contents | Electrochemical nitrate reduction reaction(NO3RR)offers a sustainable route for ambient ammonia synthesis. While metal-nitrogen-carbon (M-N-C) single-atom catalysts have emerged as promising candidates for NO3RR, the structure-activity relations underlying their catalytic behavior remain to be elucidated. Through systematic analysis of reported experimental data and pH-field coupled microkinetic modelling on a reversible hydrogen electrode (RHE) scale, we reveal that the coordination-dependent activity originates from distinct scaling relations governed by metal-intermediate interactions. M-N-Pyrrolic catalysts demonstrate higher turnover frequencies for ammonia production, whereas M-N-Pyridinic catalysts exhibit broader activity ranges across the activity volcano plot. Meanwhile, the adsorption and protonation of nitrate, which is a step often dismissed and/or assumed to be simultaneous in many previous reports, is identified to be the rate-determining step (RDS) in NO3RR. Remarkably, our subsequent experimental validation confirms the theoretical predictions under both neutral and alkaline conditions. This study offers a comprehensive mechanistic framework for interpreting the electrocatalytic activity of M-N-C catalysts in NO3RR, showing that a classical thermodynamic limiting-potential model is not sufficiently accurate to capture the RDS and the catalytic performance trends of different materials (even on M-N-Pyrrolic and M-N-Pyridinic catalysts). These findings provide brand new insights into the reaction mechanism of NO3RR and establish fundamental design principles for electrocatalytic ammonia synthesis. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2412_19615 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | The Key Steps and Distinct Performance Trends of Pyrrolic vs. Pyridinic M-N-C Catalysts in Electrocatalytic Nitrate Reduction Jiang, Qiuling Gu, Mingyao Wang, Tianyi Liu, Fangzhou Yang, Xin Zhang, Di Wu, Zhijian Wang, Ying Wei, Li Li, Hao Chemical Physics Materials Science Electrochemical nitrate reduction reaction(NO3RR)offers a sustainable route for ambient ammonia synthesis. While metal-nitrogen-carbon (M-N-C) single-atom catalysts have emerged as promising candidates for NO3RR, the structure-activity relations underlying their catalytic behavior remain to be elucidated. Through systematic analysis of reported experimental data and pH-field coupled microkinetic modelling on a reversible hydrogen electrode (RHE) scale, we reveal that the coordination-dependent activity originates from distinct scaling relations governed by metal-intermediate interactions. M-N-Pyrrolic catalysts demonstrate higher turnover frequencies for ammonia production, whereas M-N-Pyridinic catalysts exhibit broader activity ranges across the activity volcano plot. Meanwhile, the adsorption and protonation of nitrate, which is a step often dismissed and/or assumed to be simultaneous in many previous reports, is identified to be the rate-determining step (RDS) in NO3RR. Remarkably, our subsequent experimental validation confirms the theoretical predictions under both neutral and alkaline conditions. This study offers a comprehensive mechanistic framework for interpreting the electrocatalytic activity of M-N-C catalysts in NO3RR, showing that a classical thermodynamic limiting-potential model is not sufficiently accurate to capture the RDS and the catalytic performance trends of different materials (even on M-N-Pyrrolic and M-N-Pyridinic catalysts). These findings provide brand new insights into the reaction mechanism of NO3RR and establish fundamental design principles for electrocatalytic ammonia synthesis. |
| title | The Key Steps and Distinct Performance Trends of Pyrrolic vs. Pyridinic M-N-C Catalysts in Electrocatalytic Nitrate Reduction |
| topic | Chemical Physics Materials Science |
| url | https://arxiv.org/abs/2412.19615 |