Synergistic Iron-Molybdenum Effects for Selective Electrocatalytic Reduction of Nitrite to Nitric Oxide.

IF 14.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Journal of the American Chemical Society Pub Date : 2025-07-09 Epub Date: 2025-06-26 DOI:10.1021/jacs.5c07512
Zhiqiang Peng, Jianglan Liu, Xiao-Yi Yang, Shengfa Ye, Xuebin Jiang, Bin Chen, Rong-Zhen Liao, Chen-Ho Tung, Wenguang Wang, Li-Zhu Wu
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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.

选择性电催化还原亚硝酸盐生成一氧化氮的协同铁钼效应。
我们报道了一种高效的双金属Mo(IV)Fe(II)电催化剂,实现了高选择性亚硝酸盐到no的还原。该催化剂表现出优异的性能,具有创纪录的转换频率(TOF) ~ 103 s-1和93.8%的法拉第效率。结合实验和DFT分析的机理研究表明,Mo(IV)中心优先结合Fe(II)位点上的NO,阻止了催化循环在稳定的亚硝酸亚铁基物质上终止。Fe和Mo中心之间的协同作用增强了亚硝酸盐的动态配位,促进了还原性N-O键的裂解,突出了双金属协同作用在降低能量垒和驱动涉及电子和质子转移的高要求的exergonic反应步骤中的关键作用。
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来源期刊
CiteScore
24.40
自引率
6.00%
发文量
2398
审稿时长
1.6 months
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.
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