摘要
The one-step conversion of ethanol to 1,3-butadiene has achieved a breakthrough with the development of beta zeolite supported dual metal catalysts.However,the reaction mechanism from ethanol to butadiene is complex and has not yet been fully elucidated,and no catalyst screening effort has been done based on central metal atoms.In this work,density functional theory(DFT)calculations were employed to study the mechanism of one-step conversion of ethanol to butadiene over ZnY/BEA catalyst.The results show that ethanol dehydrogenation prefers to proceed on Zn site with a reaction energy of 0.77 eV in the rate-determining step,and the aldol condensation to produce butadiene prefers to proceed on Y site with a reaction energy of 0.69 eV in the rate-determining step.Based on the mechanism revealed,six elements were selected to replace Y for screening superior combination of Zn-M/BEA(M=Sn,Nb,Ta,Hf,Zr,Ti;BEA:beta polymorph A)for this reaction.As a result,Zn-Y/BEA(0.69 eV)is proven to be the most preferring catalyst compared with the other six ones,and Zn-Zr/BEA(0.85 eV),Zn-Ti/BEA(0.87 eV),and Zn-Sn/BEA(0.93 eV)can be potential candidates for the conversion of ethanol to butadiene.This work not only provides mechanistic insights into one-step catalytic conversion of ethanol to butadiene over Zn-Y/BEA catalyst but also offers more promising catalyst candidates for this reaction.
基金
This work was supported by the National Natural Science Foundation of China(No.22078257,No.22038011,and No.22108213)
the National Key R&D Program of China(No.2020YFA0710000)
the China Postdoctoral Science Foundation(No.2018T111034 and No.2021M692548)
the Rising Star Program in Science and Technology of Shaanxi Province(No.2020KJXX-079).Chun-Ran Chang also acknowledges the support from the K.C.Wong Education Foundation.The calculations were performed by using the HPC Platform at Xi’an Jiaotong University。
作者简介
Authors to whom correspondence should be addressed:杨东元.E-mail:yangdongyuan@sxycpc.com;Authors to whom correspondence should be addressed:常春然.E-mail:changcr@mail.xjtu.edu.cn。
