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
The structure transformation of metal-organic frameworks(MOFs)is significant for expanding the MOF family and exploring new MOF properties;however,it remains a significant challenge.In this work,we showcase the struct...The structure transformation of metal-organic frameworks(MOFs)is significant for expanding the MOF family and exploring new MOF properties;however,it remains a significant challenge.In this work,we showcase the structure transformation of an Hf-based MOF.This MOF,with different phases denoted as Hf-SDC(face-centered cubic(fcc))and Hf-SDC(hexagonal closepacked(hcp)),was successfully synthesized under controlled synthesis conditions.Interestingly,we demonstrated that the obtained two different phase MOFs can be further transformed to amorphous Hf-SDC-Br(am)and semi-crystalline Hf-SDC-Br(sc)through a simple bromination reaction,which converts the rigid-C=C-bonds into flexible-C(Br)-C(Br)-bonds.Specifically,the three-dimensional fcc topology could no longer be maintained,and the interlayer order of the hcp topology was disrupted,resulting in the amorphous Hf-SDC-Br(am)and semi-crystalline Hf-SDC-Br(sc),respectively.Finally,as a proof-of-concept application,the semicrystalline Hf-SDC-Br(sc)was used as a support to load with Pd nanoparticles,yielding a Pd/Hf-SDC-Br(sc)catalyst.Benefiting from the Br-Pd interaction and the retained partial structural order that facilitates mass transport of reactants,Pd/Hf-SDC-Br(sc)exhibited excellent catalytic performance in the conversion of vanillin to 2-methoxy-4-methylphenol,with a record turnover frequency of 1021 h−1.This work demonstrates the feasibility of the structure transformation of MOF through simple chemical reaction and highlights the importance of the structure transformation of MOFs for advanced catalysis.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support from the National Key Research and Development Program of China(No.2024YFA1510103)the National Natural Science Foundation of China(Nos.22473083 and 22509146).
文摘The structure transformation of metal-organic frameworks(MOFs)is significant for expanding the MOF family and exploring new MOF properties;however,it remains a significant challenge.In this work,we showcase the structure transformation of an Hf-based MOF.This MOF,with different phases denoted as Hf-SDC(face-centered cubic(fcc))and Hf-SDC(hexagonal closepacked(hcp)),was successfully synthesized under controlled synthesis conditions.Interestingly,we demonstrated that the obtained two different phase MOFs can be further transformed to amorphous Hf-SDC-Br(am)and semi-crystalline Hf-SDC-Br(sc)through a simple bromination reaction,which converts the rigid-C=C-bonds into flexible-C(Br)-C(Br)-bonds.Specifically,the three-dimensional fcc topology could no longer be maintained,and the interlayer order of the hcp topology was disrupted,resulting in the amorphous Hf-SDC-Br(am)and semi-crystalline Hf-SDC-Br(sc),respectively.Finally,as a proof-of-concept application,the semicrystalline Hf-SDC-Br(sc)was used as a support to load with Pd nanoparticles,yielding a Pd/Hf-SDC-Br(sc)catalyst.Benefiting from the Br-Pd interaction and the retained partial structural order that facilitates mass transport of reactants,Pd/Hf-SDC-Br(sc)exhibited excellent catalytic performance in the conversion of vanillin to 2-methoxy-4-methylphenol,with a record turnover frequency of 1021 h−1.This work demonstrates the feasibility of the structure transformation of MOF through simple chemical reaction and highlights the importance of the structure transformation of MOFs for advanced catalysis.
