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 funct...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.展开更多
In this study, inhibition of tall oil fatty acid hydrodeoxygenation(HDO) activity due to addition of rosin acid over sulfided Ni Mo/Al_2O_3 was investigated. Oleic acid and abietic acid were used as model compounds fo...In this study, inhibition of tall oil fatty acid hydrodeoxygenation(HDO) activity due to addition of rosin acid over sulfided Ni Mo/Al_2O_3 was investigated. Oleic acid and abietic acid were used as model compounds for fatty acid and rosin acid respectively in tall oil. After completion of each HDO experiment,the Ni Mo catalysts were recovered and used again under the same conditions. The results showed that the oleic acid HDO activity of sulfided catalysts was inhibited by addition of abietic acid due to competitive adsorption and increased coke deposition. The rate of carbon deposition on the catalysts increased when abietic acid was added to oleic acid feed. Moreover, the coke was in a more advanced form with higher stability for the catalysts exposed to both oleic acid and abietic acid. Furthermore, a clear correlation between the rate of coke formation and concentration of abietic acid was observed.展开更多
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)+2 种基金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。
文摘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.
基金Formas (Contracts: 239-2012-1584 and 239-2014-164) and Preem for the financial support
文摘In this study, inhibition of tall oil fatty acid hydrodeoxygenation(HDO) activity due to addition of rosin acid over sulfided Ni Mo/Al_2O_3 was investigated. Oleic acid and abietic acid were used as model compounds for fatty acid and rosin acid respectively in tall oil. After completion of each HDO experiment,the Ni Mo catalysts were recovered and used again under the same conditions. The results showed that the oleic acid HDO activity of sulfided catalysts was inhibited by addition of abietic acid due to competitive adsorption and increased coke deposition. The rate of carbon deposition on the catalysts increased when abietic acid was added to oleic acid feed. Moreover, the coke was in a more advanced form with higher stability for the catalysts exposed to both oleic acid and abietic acid. Furthermore, a clear correlation between the rate of coke formation and concentration of abietic acid was observed.
