过渡金属氧化物修饰的Rh催化四氢糠醇氢解反应的密度泛函理论研究  

The Role of MO(M=Re, Mo, W) in Rh(111) Catalysts for the Hydrogenolysis of Tetrahydrofurfuryl Alcohol to Pentanediols: Insights from DFT Studies

作　　者：王萌菲 金冰冰 马雨欣 赵一鸣 关静 Wang Mengfei;Jin Bingbing;Ma Yuxin;Zhao Yiming;Guan Jing(School of Environmental and Municipal Engineering,Qingdao University of Technology,Qingdao 266033,China)

机构地区：[1]青岛理工大学环境与市政工程学院,山东青岛266033

出　　处：《广东化工》2021年第15期78-81,共4页Guangdong Chemical Industry

基　　金：山东省大学生创新训练项目(No.S202010429227)。

摘　　要：过渡金属氧化物MOx(M=Re,Mo,W)修饰的Rh基催化剂,可将四氢糠醇(THFA)呋喃环中的C-O键打开并加氢获得戊二醇。本论文采用密度泛函理论(DFT)计算,研究了MOx/Rh(111)催化剂表面THFA氢解生成1,5-戊二醇和1,2-戊二醇的热力学过程,重点考察了ReOx、MoOx、WOx调变催化剂活性和选择性的作用机制。结果表明,在修饰催化剂上反应遵循直接氢解机理,1,5-戊二醇为主要产物。与单金属Rh基催化剂相比,修饰催化剂上1,5-戊二醇选择性的提高可主要归因于Rh-M协同催化的氢解反应过程,其中Rh(111)表面解离吸附的氢原子优先进攻醇盐中间体上空间位阻较大的次级CH-O键。此外,MoOx和WOx作为修饰组分更有利于四氢糠醇氢解获得1,5-戊二醇。The furan ring of tetrahydrofurfuryl alcohol(THFA) can open to form pentanediols using MOx-modified Rh catalysts(M=Re, Mo, W). The thermodynamics of THFA hydrogenolysis to produce 1,5-pentanediol(1,5-PeD) and 1,2-pentanediol(1,2-PeD) over ReOx/Rh(111), MoOx/Rh(111) and WOx/Rh(111)surfaces were studied using density functional theory(DFT) calculations, with a special focus on the mechanism of MOx in controlling the activity and selectivity of the reactions. A direct hydrogenolysis mechanism was proposed for the MOx-modified Rh catalysts, and these catalysts favor the production of 1,5-PeD. The synergy between the oxide modifier(MOx) and the surfaces of Rh metal, may be the key to the high 1,5-PeD selectivity on the modified catalysts, where the H atom preferentially attacks the more sterically hindered secondary CH-O bond rather than the less sterically hindered primary CH2-O moiety on alkoxide species. In addition, from the comparative thermodynamic profiles, we found that 1,5-PeD is favored to form when MoOx or WOx was used as modified component, indicating that the promoting effect of MoOx or WOx was more remarkable in terms of high activity than ReOx. Our theoretical results give a good explanation for the experimental fact that 1,5-PeD was the dominant product observed on prompted Rh/SiO2.

关 键 词：金属氧化物 四氢糠醇 氢解开环 戊二醇 密度泛函理论 

分 类 号：TQ[化学工程]