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Monitoring Activation Intermediates via Operando Target-Specific NMR Enables Selective C-N Coupling for Urea
Hang Zhou1, Zejiang Huang1, Jian Guan2
1Physics Department & Shanghai Key Laboratory of Magnetic Resonance, School of Physics, Institute of Magnetic Resonance and Molecular Imaging in Medicine, East China Normal University, North Zhongshan Road 3663, Shanghai 200062, P. R. China.
Abstract:
Electrocatalytic urea synthesis from CO2 and NO3- offers a sustainable nitrogen-carbon route but faces challenges from complex electron transfer and side reactions. Here, we design a SnO2/CuOx heterojunction catalyst with an optimized Sn:Cu ratio of 1:5.5, denoted as m-SnO2/CuOx, to promote C-N coupling by balancing *CO and *NH2OH adsorption. The m-SnO2/CuOx interface enables selective N-terminal hydrogenation of *NO to *NH2OH while suppressing the hydrogen evolution reaction and NH3 formation. In situ infrared spectroscopy reveals the site-specific activation of CO2 on SnO2 and NO3- on CuOx. Operando 1H, 13C, 15N, and 17O NMR confirms that *NH2OH couples with *CO via the *H2NCHO intermediate to form urea. Density functional theory calculations indicate that interfacial charge redistribution lowers energy barriers and stabilizes intermediates. The optimized catalyst delivers a urea yield of 215 mmol g-1 h-1 and a Faradaic efficiency of 72.18%. This study underscores the role of rational catalyst design, together with operando insights, in advancing efficient electrocatalytic urea production.
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