Ammonia (NH3) is an essential agriculture fertilizer and a promising hydrogen carrier, making its sustainable production a priority. Photocatalytic NO3− reduction offers an efficient, light-driven pathway towards NH3 synthesis, addressing both energy and environmental challenges. In this study, we explore Cu3Nx cluster incorporated TiO2 nanosheet catalysts, where sub-nanometric Cu3Nx clusters enhance NH3 production by increasing active site accessibility, stabilizing Cu+ states, and enabling efficient electron–hole separation. Consequently, the CN0.3 catalyst (Cu3Nx size = 0.3 nm) demonstrates an NH3 production rate 158 times higher than that of pristine TiO2 nanosheets, with excellent stability and an apparent quantum yield of 14.2 % at 330 nm. Density functional theory calculations further reveal that Cu3Nx stabilizes NO3− adsorption, lowers the energy barrier for the rate-determining deoxygenation step, and facilitates effective charge transfer. Our findings highlight the potential of Cu3Nx/TiO2 as a robust candidate for efficient photocatalytic NH3 synthesis and underscore the potential of sub-nanometric metal-nitride clusters in photocatalysis.
Tailoring Cu3Nx clusters on TiO2 nanosheets to the sub-nanometric scale for enhancing NH3 photosynthesis
發布日期：2025/06/18
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Ammonia (NH3) is an essential agriculture fertilizer and a promising hydrogen carrier, making its sustainable production a priority. Photocatalytic NO3− reduction offers an efficient, light-driven pathway towards NH3 synthesis, addressing both energy and environmental challenges. In this study, we explore Cu3Nx cluster incorporated TiO2 nanosheet catalysts, where sub-nanometric Cu3Nx clusters enhance NH3 production by increasing active site accessibility, stabilizing Cu+ states, and enabling efficient electron–hole separation. Consequently, the CN0.3 catalyst (Cu3Nx size = 0.3 nm) demonstrates an NH3 production rate 158 times higher than that of pristine TiO2 nanosheets, with excellent stability and an apparent quantum yield of 14.2 % at 330 nm. Density functional theory calculations further reveal that Cu3Nx stabilizes NO3− adsorption, lowers the energy barrier for the rate-determining deoxygenation step, and facilitates effective charge transfer. Our findings highlight the potential of Cu3Nx/TiO2 as a robust candidate for efficient photocatalytic NH3 synthesis and underscore the potential of sub-nanometric metal-nitride clusters in photocatalysis.