A modeling strategy investigation for selective hydrodeoxygenation biomass upgrading of vanillin via metal supported on pyridinic and pyrrolic nitrogen-doped carbon catalysts  

作　　者：Yi Xiao Li Liu Wei-Bin Zhang Li-Li Han 

机构地区：[1]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou,350002,China [2]Laboratory of New Energy and Materials,Xinjiang Institute of Engineering,Ürümqi,830091,China [3]Institute of Physics and Electronic Information,Yunnan Normal University,Kunming,650500,China

出　　处：《Rare Metals》2024年第12期6460-6472,共13页稀有金属(英文版)

基　　金：financially supported by the National Key R&D Program of China(No.2022YFA1505700);the National Natural Science Foundation of China(Nos.22205232,51971157 and 21601187);the Natural Science Foundation of Fujian Province(No.2023J01310231);XinJiang Tianshan Talent Program(No.2022SNGGNT104);support by High-performance Computing Platform of Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China。

摘　　要：To extend the practical application of biomass upgrading conversion to liquid fuel,it is crucial to develop highly catalytic and reversible nonprecious metal catalysts.Herein,we propose a high-throughput density functional theory(DFT)approach to design a high-efficiency catalyst for the selective electrocatalytic upgrading of vanillin via hydrodeoxygenation(HDO).The optimal pyridinic and pyrrolic nitrogen carbon transition metal(TM)-based monolayers exhibit excellent activity for producing2-methoxy-4-methylphenol(MMP)from vanillin.The pyridinic and pyrrolic nitrogen carbon substrates can provide unique sites to support TM atoms,and TM-pyridinic or pyrrolic N moieties serve as catalytic activity sites for the electrocatalytic upgrading of vanillin.Our DFT calculations suggest that the pyridinic N@TM(TM=Zr,Ru,Rh,Os and Ir)and pyrrolic N@TM(TM=Rh and Os)catalysts possess high activity for MMP synthesized from vanillin,and they have a relatively small limiting potential(U_(L))of the rate-determining step.A new route reaction path was used to explore the activity of metal nitrogendoped carbon catalysts,finding that a single metal atom through strong electron correlation between metal and N_(4)C_(8)sites can improve the activity of the vanillin HDO process.Our results show that pyridinic N@Ir and pyrrolic N@Rh with limiting potential(U_(L))of 0.04 and 0.29 V are the most preferable candidate catalysts for the vanillin HDO process.The high stability and relatively low|U_(L)|for vanillin electrocatalytic upgrading are the best candidate electrocatalysts.This work proposes new ideas for designing and developing novel catalysts for selective HDO of biomass under real conditions.

关 键 词：VANILLIN Biomass upgrading Pyridinic and pyrrolic nitrogen carbon metal-based catalysts Selective hydrodeoxygenation(HDO) Dominant metal environment 

分 类 号：TQ426[化学工程]