Interface tuning of Cu+/CuO by zirconia for dimethyl oxalate hydrogenation to ethylene glycol over Cu/SiO2 catalyst  

作　　者：Yujun Zhao Huanhuan Zhang Yuxi Xu Shengnian Wang Yan Xu Shengping Wang Xinbin Ma 

机构地区：[1]Key Laboratory for Green Chemical Technology of Ministry of Education,Collaborative Innovation Center of Chemical Science and Engineering,School of Chemical Engineering and Technology,Tianjin University,Tianjin 300072,China [2]Chemical Engineering,Institute for Micromanufacturing.Louisiana Tech University,Ruston,LA 71272,USA

出　　处：《Journal of Energy Chemistry》2020年第10期248-256,共9页能源化学（英文版）

基　　金：financial support from the National Natural Science Foundation of China(21878227,U1510203)。

摘　　要：An efficient ZrO2-doped Cu/SiO2 catalyst was fabricated through hydrolysis precipitation method(HP)and used to produce ethylene glycol(EG)through dimethyl oxalate(DMO)hydrogenation.The states for zirconia on copper catalyst and roles in DMO hydrogenation were investigated through various characterization tools,including N2 physical adsorption,XRD,H2-TPR,Methyl glycolate-TPD-MS,XPS,XAES as well.Compared with common ammonia evaporation and co-precipitation methods used in catalyst preparation,this HP method is found to effectively suppress the agglomeration and further size growth of copper nanoparticles by enhancing the interactions between copper and zirconia species.More importantly,uniform distribution of ZrO2 dopant is achieved due to the pseudo-homogeneous reactions in the mixing step of catalyst preparation.A proper amount of zirconium dopant helps achieve the desirable proportion of Cu+/(Cu++CuO)for surface copper species,especially promotes the production of Cu+species originated from Cu-ZrO2 species at the interface of copper and zirconia particles.In comparison with Cu+species formed from copper phyllosilicates reduction,the Cu+sites derived from Cu-ZrO2 species show higher adsorption ability of MG,an important intermediate species in ethylene glycol production.These adsorbed MG molecules further react with atomic hydrogen shifted from adjacent metallic copper surface,leading to a higher catalytic behavior.For the EG production via DMO hydrogenation,the turnover frequency(TOF)normalized by CuO species on CuZr/SiO2 catalyst is 1.8 times than that of traditional Cu/SiO2 counterpart.Due to the enhanced synergy effect between Cu+and Cuo active sites,a lower activation energy of ester hydrogenation on this ZrO2-doped Cu/SiO2 catalyst is believed to be responsible for the significant improvement.

关 键 词：Copper ZIRCONIA HYDROGENATION Ethylene glycol 

分 类 号：TQ223.162[化学工程—有机化工] TQ426