Zhiqiang Peng, Jianglan Liu, Xiao-Yi Yang, Shengfa Ye, Xuebin Jiang, Bin Chen, Rong-Zhen Liao, Chen-Ho Tung, Wenguang Wang, Li-Zhu Wu
{"title":"Synergistic Iron-Molybdenum Effects for Selective Electrocatalytic Reduction of Nitrite to Nitric Oxide.","authors":"Zhiqiang Peng, Jianglan Liu, Xiao-Yi Yang, Shengfa Ye, Xuebin Jiang, Bin Chen, Rong-Zhen Liao, Chen-Ho Tung, Wenguang Wang, Li-Zhu Wu","doi":"10.1021/jacs.5c07512","DOIUrl":null,"url":null,"abstract":"<p><p>We report an efficient bimetallic Mo(IV)Fe(II) electrocatalyst that achieves highly selective nitrite-to-NO reduction. This catalyst demonstrates exceptional performance, with a record turnover frequency (TOF) of ∼10<sup>3</sup> s<sup>-1</sup> and a Faradaic efficiency of 93.8%. Mechanistic studies integrating experimental and DFT analyses reveal that the Mo(IV) center preferentially binds NO over the Fe(II) site, preventing the catalytic cycle from terminating at a stable ferrous nitrosyl species. The synergistic interplay between the Fe and Mo centers enhances nitrite dynamic coordination and facilitates reductive N-O bond cleavage, highlighting the critical role of bimetallic synergism in lowering energy barriers and driving demanding exergonic reaction steps involving electron and proton transfer.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":"24014-24022"},"PeriodicalIF":14.4000,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.5c07512","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/6/26 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
We report an efficient bimetallic Mo(IV)Fe(II) electrocatalyst that achieves highly selective nitrite-to-NO reduction. This catalyst demonstrates exceptional performance, with a record turnover frequency (TOF) of ∼103 s-1 and a Faradaic efficiency of 93.8%. Mechanistic studies integrating experimental and DFT analyses reveal that the Mo(IV) center preferentially binds NO over the Fe(II) site, preventing the catalytic cycle from terminating at a stable ferrous nitrosyl species. The synergistic interplay between the Fe and Mo centers enhances nitrite dynamic coordination and facilitates reductive N-O bond cleavage, highlighting the critical role of bimetallic synergism in lowering energy barriers and driving demanding exergonic reaction steps involving electron and proton transfer.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.