Iodine Dopants Facilitate Tandem Catalysis via Transformation Adsorption Behavior for Efficient Electrochemical Nitrate Reduction Reaction

作者：Zhijie Cui, Honghai Wang, Chunli Li, Wenchao Peng, Jiapeng Liu · 发表于：ACS Nano · 年份：2025 · DOI：10.1021/acsnano.5c08871 · 被引用次数：31 · 研究领域：Ammonia Synthesis and Nitrogen Reduction、Advanced Photocatalysis Techniques、Caching and Content Delivery

Electrochemical nitrate reduction reaction (NO 3 RR) has great potential for simultaneously achieving nitrate-rich wastewater treatment and ammonia (NH 3 ) synthesis. Given that the NO 3 RR process encompasses distinct steps of deoxygenation and hydrogenation, the active sites of most catalysts frequently demonstrate similar adsorption behavior. In this work, the second-shell iodine-doped modified cobalt single atoms (I-CoN 4 ) and cobalt atomic clusters (Co AC) anchored on nitrogen-doped carbon (Co SAAC/INC) are synthesized through a mild etching synchronization doping strategy. In the neutral electrolyte, Co SAAC/INC exhibits a high NH 3 yield rate of 18.64 mg h –1 mg cat –1 at −0.7 V versus reversible hydrogen electrode (vs RHE) and a satisfactory FE of 97.2% at −0.6 V vs RHE. Combining in situ electrochemical Fourier infrared spectroscopy, online differential electrochemical mass spectrometry, confirmatory experiments, and density functional theory calculations demonstrates that second-shell iodine heteroatom doping effectively regulates the electronic structure of CoN 4 site and induced the favorable adsorption from H 2 O/*H to NO 3 –, while the adjacent Co AC site accelerates the dissociation of H 2 O and provides abundant active hydrogen (H ads ) for the subsequent hydrogenation step, thus constructing the tandem catalytic sites with I-CoN 4 site to promote NO 3 RR. Furthermore, the Zn-NO 3 – battery with Co SAAC/INC as the cathode shows high power density (15.41 mW cm...