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| Natura: | Preprint |
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2024
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| Accesso online: | https://arxiv.org/abs/2410.01300 |
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| _version_ | 1866916420654202880 |
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| author | Yuan, Lin Bourgeois, Briley B. Begin, Elijah Zhang, Yirui Dai, Alan X. Cheng, Zhihua McKeown-Green, Amy S. Xue, Zhichen Cui, Yi Xu, Kun Wang, Yu Jones, Matthew R. Cui, Yi Majumdar, Arun Bao, Junwei Lucas Dionne, Jennifer A. |
| author_facet | Yuan, Lin Bourgeois, Briley B. Begin, Elijah Zhang, Yirui Dai, Alan X. Cheng, Zhihua McKeown-Green, Amy S. Xue, Zhichen Cui, Yi Xu, Kun Wang, Yu Jones, Matthew R. Cui, Yi Majumdar, Arun Bao, Junwei Lucas Dionne, Jennifer A. |
| contents | Ammonia is a key component of fertilizer and a potential clean fuel and hydrogen carrier. The Haber-Bosch process for ammonia synthesis consumes more than half of industrial hydrogen and contributes up to ~3% of global greenhouse gas emissions. Light-driven reactions via surface plasmon resonances offer a less energy-intensive pathway for ammonia production by altering reaction intermediates. Here, we report gold-ruthenium plasmonic bimetallic alloys for ammonia synthesis at room temperature and pressure, driven by visible light. We use colloidal synthesis to create AuRu$_x$ alloys (x=0.1, 0.2, 0.3) and disperse these nanoparticles on MgO supports for gas-phase ammonia synthesis. We observe a ~60 $μ$mol/g/h reactivity and ~0.12% external quantum efficiency on a AuRu$_0$$_.$$_2$ sample under 100 mW/cm$^2$ visible light. In-situ diffuse reflective infrared Fourier transform spectroscopic measurements show that hydrogenation of nitrogen adsorbates is accelerated under light compared to thermocatalysis. Combining wavelength-dependent reactivity and spectroscopic findings with semi-classical electromagnetic modeling, we show plasmonic bimetallic alloys expedite ammonia synthesis by aiding hydrogenation of adsorbed nitrogen species via plasmon-mediated hot electrons. Quantum mechanical calculations reveal hydrogen-assisted N$_2$ splitting in the excited state is key to activating the reaction under ambient conditions. Therefore, light or H$_2$ alone cannot dissociate N$_2$ -- the key bottleneck to breaking N$_2$'s triple bond. Our findings are consistent with recent hypotheses on how nitrogenase enzymes catalyze ammonia production at mild conditions and provide insights for sustainable photochemical transformations. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2410_01300 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Atmospheric Pressure Ammonia Synthesis on AuRu Catalysts Enabled by Plasmon-Controlled Hydrogenation and Nitrogen-species Desorption Yuan, Lin Bourgeois, Briley B. Begin, Elijah Zhang, Yirui Dai, Alan X. Cheng, Zhihua McKeown-Green, Amy S. Xue, Zhichen Cui, Yi Xu, Kun Wang, Yu Jones, Matthew R. Cui, Yi Majumdar, Arun Bao, Junwei Lucas Dionne, Jennifer A. Chemical Physics Ammonia is a key component of fertilizer and a potential clean fuel and hydrogen carrier. The Haber-Bosch process for ammonia synthesis consumes more than half of industrial hydrogen and contributes up to ~3% of global greenhouse gas emissions. Light-driven reactions via surface plasmon resonances offer a less energy-intensive pathway for ammonia production by altering reaction intermediates. Here, we report gold-ruthenium plasmonic bimetallic alloys for ammonia synthesis at room temperature and pressure, driven by visible light. We use colloidal synthesis to create AuRu$_x$ alloys (x=0.1, 0.2, 0.3) and disperse these nanoparticles on MgO supports for gas-phase ammonia synthesis. We observe a ~60 $μ$mol/g/h reactivity and ~0.12% external quantum efficiency on a AuRu$_0$$_.$$_2$ sample under 100 mW/cm$^2$ visible light. In-situ diffuse reflective infrared Fourier transform spectroscopic measurements show that hydrogenation of nitrogen adsorbates is accelerated under light compared to thermocatalysis. Combining wavelength-dependent reactivity and spectroscopic findings with semi-classical electromagnetic modeling, we show plasmonic bimetallic alloys expedite ammonia synthesis by aiding hydrogenation of adsorbed nitrogen species via plasmon-mediated hot electrons. Quantum mechanical calculations reveal hydrogen-assisted N$_2$ splitting in the excited state is key to activating the reaction under ambient conditions. Therefore, light or H$_2$ alone cannot dissociate N$_2$ -- the key bottleneck to breaking N$_2$'s triple bond. Our findings are consistent with recent hypotheses on how nitrogenase enzymes catalyze ammonia production at mild conditions and provide insights for sustainable photochemical transformations. |
| title | Atmospheric Pressure Ammonia Synthesis on AuRu Catalysts Enabled by Plasmon-Controlled Hydrogenation and Nitrogen-species Desorption |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2410.01300 |