{"title":"Asymmetrically Steering Excited-State Reaction Channels for Ambient N <sub><b>2</b></sub> Catalytic Oxidation.","authors":"Jiabao Lv, Pu Guo, Shanzhi Liu, Yaqi Peng, Lujie Liu, Jian Wu, Xiaodong Li, Zhifu Qi, Songqiang Zhu, Liang Wang, Angjian Wu, Jianping Xiao, Jianhua Yan","doi":"10.1021/jacsau.5c00767","DOIUrl":null,"url":null,"abstract":"<p><p>Precise control of catalytic reactions in the excited state is challenging, as the highly reactive chemical environment strengthens both forward and reverse reactions simultaneously. Here, we propose a strategy to asymmetrically regulate the reaction channels via the physical mixing of the model catalyst Co<sub>3</sub>O<sub>4</sub>/Al<sub>2</sub>O<sub>3</sub> with 13X zeolite, enabling efficient plasma-driven N<sub>2</sub> oxidation with minimized reverse reaction kinetics. <i>In situ</i> characterization combined with molecular dynamics simulations reveals that the diffusion of the product NO is selectively accelerated through Na<sup>+</sup>-mediated transport channels. This promotes NO turnover on octahedral Co<sup>3+</sup> active sites, thereby unidirectionally shifting the reaction equilibrium. Thus, we demonstrate N<sub>2</sub> oxidation performance under ambient conditions that surpasses the efficiency of thermochemical conversion at 1,800 K, achieving more than a 3-fold improvement in the N<sub>2</sub> conversion rate compared to the conventional plasma-catalysis system. This work provides an approach to orderly modulate heterogeneous catalytic reactions in the excited state.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 9","pages":"4398-4407"},"PeriodicalIF":8.7000,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12457990/pdf/","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"JACS Au","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1021/jacsau.5c00767","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/9/22 0:00:00","PubModel":"eCollection","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Precise control of catalytic reactions in the excited state is challenging, as the highly reactive chemical environment strengthens both forward and reverse reactions simultaneously. Here, we propose a strategy to asymmetrically regulate the reaction channels via the physical mixing of the model catalyst Co3O4/Al2O3 with 13X zeolite, enabling efficient plasma-driven N2 oxidation with minimized reverse reaction kinetics. In situ characterization combined with molecular dynamics simulations reveals that the diffusion of the product NO is selectively accelerated through Na+-mediated transport channels. This promotes NO turnover on octahedral Co3+ active sites, thereby unidirectionally shifting the reaction equilibrium. Thus, we demonstrate N2 oxidation performance under ambient conditions that surpasses the efficiency of thermochemical conversion at 1,800 K, achieving more than a 3-fold improvement in the N2 conversion rate compared to the conventional plasma-catalysis system. This work provides an approach to orderly modulate heterogeneous catalytic reactions in the excited state.