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![Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F55858.jpg&w=3840&q=50)
Protein Film Infrared Electrochemistry Demonstrated for Study of H2 Oxidation by a [NiFe] Hydrogenase
Published on: December 4, 2017
Proton-Feeding Dual-N Claw Sites in a Copper-Covalent Organic Framework Promote Hydrogenation Kinetics for
Tang Wang1,2, Bowen Song3, Yu Zhou1
1College of Materials Science and Engineering, College of Environment, State Key Laboratory of Advanced Separation Membrane Materials, Zhejiang Key Laboratory of Low-carbon Control Technology for Industrial Pollution, Zhejiang University of Technology, Hangzhou 310014, China.
Abstract:
The electrocatalytic conversion of nitrate to ammonia offers a sustainable solution for both environmental remediation and green energy production, yet its complex proton-coupled electron transfer kinetics poses a grand challenge for catalyst design. Herein, we demonstrate a proton-feeding dual-nitrogen claw site (DNCS) within a copper-covalent organic framework (DNCS-CuCOF) that captures and supplies localized protons to nitrogenous intermediates on the Cu center, enabling efficient hydrogenation. Compared with pristine CuCOF, DNCS-CuCOF maintains structural stability and exhibits significantly enhanced electrocatalytic performance, achieving a high Faradaic efficiency of 94% and an ammonia yield of 10.6 mg h-1 mgcat-1 at -0.8 V vs RHE. In-situ characterizations and density functional theory calculations reveal that the DNCS, by supplying localized protons, accelerates proton transfer kinetics and reduces the energy barrier for the rate-limiting step (*NO → *NHO) via an N-site-assisted Langmuir-Hinshelwood mechanism. This work establishes a new design principle of atomically precise innovation-engineering by creating localized proton feeding, offering a versatile platform for advancing electrocatalysis.
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