1. Atmospheric Pressure Ammonia Synthesis on AuRu Catalysts Enabled by Plasmon-Controlled Hydrogenation and Nitrogen-species Desorption
- Author
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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., Majumdar, Arun, Bao, Junwei Lucas, and Dionne, Jennifer A.
- Subjects
Physics - Chemical Physics - Abstract
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 $\mu$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., Comment: 21 pages, 4 figures, journal article submission soon
- Published
- 2024