Enhanced selectivity of catalytic hydrogenation of halogenated nitroaromatics by interfacial effects  

界面效应对卤代硝基芳烃催化加氢选择性的提升

作　　者：HUANG Rui LIU Shengjie WU Qingyuan ZHENG Nanfeng 黄睿;刘圣杰;吴庆远;郑南峰(厦门大学化学化工学院,新基石科学实验室,固体表面物理化学国家重点实验室,能源材料化学协同创新中心,纳米材料制备技术国家地方联合工程研究中心,厦门361005;福建省能源材料科学与技术创新实验室(IKKEM),厦门361002)

机构地区：[1]New Cornerstone Science Laboratory,State Key Laboratory for Physical Chemistry of Solid Surfaces,Collaborative Innovation Center of Chemistry for Energy Materials,National&Local Joint Engineering Research Center of Preparation Technology of Nanomaterials,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,Fujian 361005,China [2]Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM),Xiamen,Fujian 361002,China

出　　处：《无机化学学报》2025年第1期201-212,共12页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.92261207,22388102);新基石科学基金;中国博士后科学基金(No.2023M732946);国家资助博士后研究人员计划(No.GZB20230380)资助。

摘　　要：The highly selective catalytic hydrogenation of halogenated nitroaromatics was achieved by employing Pd‑based catalysts that were co‑modified with organic and inorganic ligands.It was demonstrated that the catalysts contained Pd species in mixed valence states,with high valence Pd at the metal‑support interface and zero valence Pd at the metal surface.While the strong coordination of triphenylphosphine(PPh3)to Pd0 on the Pd surface prevents the adsorption of halogenated nitroaromatics and thus dehalogenation,the coordination of sodium metavanadate(NaVO3)to high‑valence Pd sites at the interface helps to activate H2 in a heterolytic pathway for the selective hydrogenation of nitro‑groups.The excellent catalytic performance of the interfacial active sites enables the selective hydrogenation of a wide range of halogenated nitroaromatics.采用有机配体和无机配体共修饰的Pd基催化剂实现了卤代硝基芳烃的高选择性催化加氢。研究表明催化剂包含混合价态的Pd物质,金属-载体界面处的Pd为高价态,金属表面的Pd为零价态。三苯基膦强配位在零价Pd表面,阻止卤代硝基芳烃的吸附,从而防止脱卤反应的发生。偏钒酸钠配位在界面高价Pd物质处,有利于氢气异裂活化,并实现硝基的高选择性加氢。界面活性位点的优异催化性能使其能够对多种卤代硝基芳烃进行选择性加氢。

关 键 词：halogenated nitroaromatic heterogeneous catalysis HYDROGENATION selectivity control interfacial effect 

分 类 号：O643.38[理学—物理化学]