Surface segregation is ubiquitous in multi-component materials and is of great important for catalysis but little is known on the surface structure under graphene encapsulation.Here,we show that the graphene encapsula...Surface segregation is ubiquitous in multi-component materials and is of great important for catalysis but little is known on the surface structure under graphene encapsulation.Here,we show that the graphene encapsulated CoCu performs well for the electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF)to2,5-furandicarboxylic acid(FDCA)with the onset potential before 1.23 VRHEand a nearly 100%selectivity of FDCA under 1.4 VRHE.From the experimental results,the unprecedented catalytic performance was attributed to local structural distortion and sub-nanometer lattice composition of the CoCu surface.We accurately show the dispersed Cu doped Co_(3)O_(4) nano-islands with a lot of edge sites on the bimetallic Co-Cu surface.While,the gradient components effectively facilitate the establishment of built-in electric field and accelerate the charge transfer.Theoretical and experimental results reveal that the surface Co and neighbouring Cu atoms in sub-nanometer lattice synergistically promote the catalysis of HMF.This work offers new insights into surface segregation in tuning the element spatial distribution for catalysis.展开更多
The electrochemical oxidation of 5-hydroxymethylfurfural(HMF) represents a significant avenue for sustainable chemical synthesis, owing to its potential to generate high-value derivatives from biomass feedstocks. Tran...The electrochemical oxidation of 5-hydroxymethylfurfural(HMF) represents a significant avenue for sustainable chemical synthesis, owing to its potential to generate high-value derivatives from biomass feedstocks. Transition metal catalysts offer a cost-effective alternative to precious metals for catalyzing HMF oxidation, with transition bimetallic catalysts emerging as particularly promising candidates. In this review, we delve into the intricate reaction pathways and electrochemical mechanisms underlying HMF oxidation, emphasizing the pivotal role of transition bimetallic catalysts in enhancing catalytic efficiency. Subsequently, various types of transition bimetallic catalysts are explored, detailing their synthesis methods and structural modulation strategies. By elucidating the mechanisms behind catalyst modification and performance enhancement, this review sets the stage for upcoming advancements in the field, ultimately advancing the electrochemical HMF conversion and facilitating the transition towards sustainable chemical production.展开更多
Co-based catalysts are promising alternatives to precious metals for the selective and effective oxidation of 5-hydroxymethylfurfural(HMF)to the higher value-added 2,5-furandicarboxylic acid(FDCA).However,these cataly...Co-based catalysts are promising alternatives to precious metals for the selective and effective oxidation of 5-hydroxymethylfurfural(HMF)to the higher value-added 2,5-furandicarboxylic acid(FDCA).However,these catalysts still suffer from unsatisfactory activity and poor selectivity.A series of N-doped carbon-supported Co-based dual-metal nanoparticles(NPs)have been designed,among which the Co-Cu_(1.4)-CN_(x) exhibits enhanced HMF oxidative activity,achieving FDCA formation rates 4 times higher than that of pristine Co-CN_(x),with 100%FDCA selectivity.Density functional theory(DFT)calculations evidenced that the increased electron density on Co sites induced by Cu can mediate the positive electronegativity offset to downshift the dband center of Co-Cu_(1.4)-CN_(x),thus reducing the energy barriers for the conversion of HMF to FDCA.Such findings will support the development of superior non-precious metal catalysts for HMF oxidation.展开更多
基金supported by the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(Grant No.:22122901,21902047)the Provincial Natural Science Foundation of Hunan(2020JJ5045,2021JJ20024,2021RC3054)。
文摘Surface segregation is ubiquitous in multi-component materials and is of great important for catalysis but little is known on the surface structure under graphene encapsulation.Here,we show that the graphene encapsulated CoCu performs well for the electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF)to2,5-furandicarboxylic acid(FDCA)with the onset potential before 1.23 VRHEand a nearly 100%selectivity of FDCA under 1.4 VRHE.From the experimental results,the unprecedented catalytic performance was attributed to local structural distortion and sub-nanometer lattice composition of the CoCu surface.We accurately show the dispersed Cu doped Co_(3)O_(4) nano-islands with a lot of edge sites on the bimetallic Co-Cu surface.While,the gradient components effectively facilitate the establishment of built-in electric field and accelerate the charge transfer.Theoretical and experimental results reveal that the surface Co and neighbouring Cu atoms in sub-nanometer lattice synergistically promote the catalysis of HMF.This work offers new insights into surface segregation in tuning the element spatial distribution for catalysis.
基金Hubei Provincial Natural Science Foundation of China (2023AFB0049)Scientific Research Fund Project of Wuhan Institute of Technology (K202232 and K2023028)Graduate Education Innovation Fund of Wuhan Institute of Technology (CX2023091)。
文摘The electrochemical oxidation of 5-hydroxymethylfurfural(HMF) represents a significant avenue for sustainable chemical synthesis, owing to its potential to generate high-value derivatives from biomass feedstocks. Transition metal catalysts offer a cost-effective alternative to precious metals for catalyzing HMF oxidation, with transition bimetallic catalysts emerging as particularly promising candidates. In this review, we delve into the intricate reaction pathways and electrochemical mechanisms underlying HMF oxidation, emphasizing the pivotal role of transition bimetallic catalysts in enhancing catalytic efficiency. Subsequently, various types of transition bimetallic catalysts are explored, detailing their synthesis methods and structural modulation strategies. By elucidating the mechanisms behind catalyst modification and performance enhancement, this review sets the stage for upcoming advancements in the field, ultimately advancing the electrochemical HMF conversion and facilitating the transition towards sustainable chemical production.
基金the National Natural Science Foundation of China(Nos.51902281,51801075,and 82160421)the Natural Science Foundation of Jiangsu Province(No.BK20211322)the Scientific and Technological Projects of Henan Province(No.212102210293).
文摘Co-based catalysts are promising alternatives to precious metals for the selective and effective oxidation of 5-hydroxymethylfurfural(HMF)to the higher value-added 2,5-furandicarboxylic acid(FDCA).However,these catalysts still suffer from unsatisfactory activity and poor selectivity.A series of N-doped carbon-supported Co-based dual-metal nanoparticles(NPs)have been designed,among which the Co-Cu_(1.4)-CN_(x) exhibits enhanced HMF oxidative activity,achieving FDCA formation rates 4 times higher than that of pristine Co-CN_(x),with 100%FDCA selectivity.Density functional theory(DFT)calculations evidenced that the increased electron density on Co sites induced by Cu can mediate the positive electronegativity offset to downshift the dband center of Co-Cu_(1.4)-CN_(x),thus reducing the energy barriers for the conversion of HMF to FDCA.Such findings will support the development of superior non-precious metal catalysts for HMF oxidation.
