Non-contact biomimetic mechanism for selective hydrogenation of nitroaromatics on heterogeneous metal nanocatalysts

作     者：Wenting Zhou Laiyang Li Ruixuan Qin Jiaxin Zhu Shengjie Liu Shiguang Mo Zaifa Shi Huihuang Fang Pengpeng Ruan Jun Cheng Gang Fu Nanfeng Zheng Wenting Zhou;Laiyang Li;Ruixuan Qin;Jiaxin Zhu;Shengjie Liu;Shiguang Mo;Zaifa Shi;Huihuang Fang;Pengpeng Ruan;Jun Cheng;Gang Fu;Nanfeng Zheng

作者机构：State Key Laboratory for Physical Chemistry of Solid SurfacesCollaborative Innovation Center of Chemistry for Energy Materialsand Department of ChemistryCollege of Chemistry and Chemical EngineeringXiamen UniversityXiamen 361005China Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM)Xiamen 361005China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2022年第65卷第4期

页      面：726-732页

核心收录：

学科分类：081702[工学-化学工艺] 081705[工学-工业催化] 08[工学] 0817[工学-化学工程与技术] 

基　　金：supported by the National Key Research and Development Program of China(2017YFA0207302) the National Nature Science Foundation of China(21890752,21731005,22072116,92045303) support from the Tencent Foundation through the XPLORER PRIZE the XAFS Station(BL14W1)of the Shanghai Synchrotron Radiation Facility(SSRF) 

主　　题：hydrogenation catalysis nitroaromatics proton/electron separation non-contact hydrogenation biomimetic mechanism 

摘      要：While the enzymatic reduction of unsaturated compounds usually has high specificity,highly selective reduction processes are hardly realized by heterogeneous industrial catalysts,which is critical for the green production of many fine ***,we report an unexpected discovery of a biomimetic behavior of dicyandiamide(DICY)-modified Pt nanocatalysts for the green hydrogenation of a wide range of *** demonstrate that the surface modification by DICY not only prevents the direct contact of nitroaromatic reactants with Pt surface but also induces an effective non-contact hydrogenation mechanism mediated by protons and *** such a process,the DICY layer serves as a“semi-permeable membraneto allow the permeation of H_(2) molecules for being activated into electrons and protons at the Pt-DICY *** the generation of separated protons and electrons,the nitro group with strong electrophilic properties can be hydrogenated through the electron transfer followed by the proton transfer,which is facilitated by the hydrogen bonding network formed by protonated *** unique mechanism makes it highly directional toward the hydrogenation of nitro groups without side *** to its capability to largely eliminate the waste generation,the developed Pt-DICY catalysts have been successfully applied for the green industrial production of many important aniline intermediates.