文献类型：期刊文献

英文题名：Surface hydroxyl group dominating aerobic oxidation of methane below room temperature

作者：Yu, Baiyang[1,2];Cheng, Lu[3,4];Wu, Jiaju[1,2];Yang, Bing[5];Li, Hong[5];Xu, Jing[6];Zhang, Ying[1,2];Pan, Chengsi[1,2];Cao, Xiao-Ming[3,4,7];Zhu, Yongfa[8];Lou, Yang[1,2]

机构：[1]Jiangnan Univ, Sch Chem & Mat Engn, Key Lab Synthet & Biol Colloids, Minist Educ, Wuxi 214122, Jiangsu, Peoples R China;[2]Jiangnan Univ, Int Joint Res Ctr Photorespons Mol & Mat, Wuxi 214122, Jiangsu, Peoples R China;[3]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Res Inst Ind Catalysis, Shanghai 200237, Peoples R China;[5]Dalian Inst Chem Phys, CAS Key Lab Sci & Technol Appl Catalysis, 457 Zhongshan Rd, Dalian 116023, Peoples R China;[6]Jiangnan Univ, Sch Food Sci & Technol, Wuxi 214122, Jiangsu, Peoples R China;[7]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, Shanghai 200240, Peoples R China;[8]Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China

年份：2024

卷号：17

期号：21

起止页码：8127

外文期刊名：ENERGY & ENVIRONMENTAL SCIENCE

收录：;EI(收录号：20244117172481);WOS:【SCI-EXPANDED(收录号:WOS:001318606900001)】；

基金：This project was supported financially by the National Key R&D Program of China (2021YFB3501900), the National Natural Science Foundation of China (U21A20326, 22172065, and 22022302), the NSFC Center for Single-Atom Catalysis (22388102), the Natural Science Foundation of Jiangsu Province (BK20211239), the Jiangsu Specially-Appointed Professor (1046010241211400), the Dalian Institute of Chemical Physics (DICP I202107) and the CAS Project for Young Scientists in Basic Research (YSBR-022).

语种：英文

外文关键词：Free radical reactions - Free radicals - Hydrogen bonds

摘要：Direct oxidation of methane (DOM) using molecular oxygen (O2) and hydrogen (H2) is currently considered to be triggered by in situ produced H2O2 or free hydroxyl radicals ((OH)-O-center dot). However, the role of the surface hydroxyl group in the DOM that is in situ formed from O2 and H2 has long been ignored. Herein, we provide experimental evidence that DOM using H2 and O2 over titanium silicate-supported single Pd atoms coated with an ultrathin N-doped carbon (Pd1/TS-1@CN) catalyst is dominated by a surface hydroxyl group instead of H2O2 or free (OH)-O-center dot. Furthermore, the direct bonding between Pd atoms with the pyrrolic nitrogen of the coating layers reinforces the bonding strength of Pd1 and framework oxygen, forming a unique N1-Pd1-O2 configuration that considerably boosts the stability of isolated Pd active sites and their capability to stably generate a surface hydroxyl group from H2 and O2. Therefore, Pd1/TS-1@CN yields a liquid oxygenate productivity of 647 mu mol gcat-1 h-1 with 100% selectivity at 15 degrees C and high stability over 30 cycles with no activity loss. Our findings regarding the catalytic role of the surface hydroxyl group in DOM and its stabilization strategy open up a new avenue for designing advanced catalysts for the DOM using O2 under mild reaction conditions. Titanium silicate-supported single Pd atoms coated with ultrathin N-doped carbon (Pd1/TS-1@CN) as an efficient and stable catalyst enabling direct oxidation of methane to value-added products with 100% selectivity by O2 and H2 at 15 degrees C.