生物炭表面NO吸附特性的量子化学研究  

Quantum chemical study on the adsorption characteristic of NO on the surface of biochar

作　　者：朱世遥 薛婕雯 张雨轩 陈斌[1,3] 武卫东[1] ZHU Shi-Yao;XUE Jie-Wen;ZHANG Yu-Xuan;CHEN Bin;WU Wei-Dong(University of Shanghai for Science and Technology,Shanghai 200093,China;School of Urban Railway Transportation,Shanghai University of Engineering Science,Shanghai 201620,China;School of Mechanical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China)

机构地区：[1]上海理工大学,上海200093 [2]上海工程技术大学城市轨道交通学院,上海201620 [3]上海交通大学机械与动力工程学院,上海200240

出　　处：《原子与分子物理学报》2025年第5期7-16,共10页Journal of Atomic and Molecular Physics

基　　金：国家自然科学基金(52176016);上海市科技带头人(21XD1433400)。

摘　　要：生物炭表面具有丰富的官能团,通过化学吸附可以与一氧化氮(NO)分子形成稳定化学键,廉价易得且环境适应性强,具有广阔的应用前景.然而,当前对生物炭表面NO吸附特性的研究大多仍停留在宏观层面,缺乏深入的微观机制解析.本文基于密度泛函理论,深入研究了生物炭表面一氧化氮(NO)的吸附转化路径,从分子层面揭示了生物炭对NO的吸附特性.研究结果显示,N-down型吸附构型的能量普遍低于O-down型吸附构型,是较为可能的吸附构型,并且含氧原子的官能团在NO的吸附和氨(NH_(3))的形成过程中扮演着关键角色.此外,通过对N-down型构型的进一步分析发现,在与活性位点结合后,NO将优先取代羟基,最终在生物质焦炭表面转化为NH_(3).同时,基于变分过渡态理论(CVT)计算了反应速率,发现NO优先反应的途径将受到不同区域内反应速率的限制.本文通过量子化学方法深入揭示了生物炭表面NO吸附特性的微观机制,为优化生物炭在NO治理中的应用提供了理论支持.Biochar possesses abundant surface functional groups,which can form stable chemical bonds with nitric oxide(NO)molecules through chemical adsorption,making it inexpensive,readily available,and environmentally adaptable with broad application prospects.However,current research on the adsorption characteristics of NO on biochar surfaces mostly remains at the macroscopic mechanism,lacking in-depth analysis of the underlying microscopic mechanism.In this study,based on density functional theory,the adsorption and transformation pathways of nitric oxide(NO)on biochar surfaces are investigated,and the adsorption property of biochar towards NO is revealed.The results show that the energy of the N-down adsorption configuration is generally lower than that of the O-down adsorption configuration,making it a more probable adsorption structure,with oxygen-containing functional groups playing a crucial role in the NO adsorption and the formation of ammonia(NH_(3)).Furthermore,further analysis of the N-down configuration reveals that NO will preferentially replace hydroxyl groups after binding to active sites,ultimately converting to NH_(3) on the surface of biochar.Additionally,reaction rates were calculated using the canonical variational transition state theory(CVT),indicating that the pathway favored by NO will be limited by reaction rates in different regions.This study employs quantum chemical methods to comprehensively elucidate the microscopic mechanisms of NO adsorption on biochar surfaces,providing theoretical support for optimizing the application of biochar in NO control.

关 键 词：吸附 生物炭 密度泛函理论 

分 类 号：O561[理学—原子与分子物理]