Biomass conversion offers an efficient approach to alleviate the energy and environmental issues.Electrochemical oxidation of 5-hydroxymethylfurfural(HMF)has attracted tremendous attention in the latest few years for ...Biomass conversion offers an efficient approach to alleviate the energy and environmental issues.Electrochemical oxidation of 5-hydroxymethylfurfural(HMF)has attracted tremendous attention in the latest few years for the mild synthesis conditions and high conversion efficiency to obtain 2,5-furan dicarboxylic acid(FDCA),but there still remain problems such as limited yield,short cycle life,and ambiguous reaction mechanism.Despite many reviews highlighting a variety of electrocatalysts for electrochemical oxidation of HMF,a detailed discussion of the structural modulation of catalyst and the underlying catalytic mechanism is still lacking.We herein provide a comprehensive summary of the recent development of electrochemical oxidation of HMF to FDCA,particularly focusing on the mechanism studies as well as the advanced strategies developed to regulate the structure and optimize the performance of the electrocatalysts,including heterointerface construction,defect engineering,single-atom engineering,and in situ reconstruction.Experimental characterization techniques and theoretical calculation methods for mechanism and active site studies are elaborated,and challenges and future directions of electrochemical oxidation of HMF are also prospected.This review will provide guidance for designing advanced catalysts and deepening the understanding of the reaction mechanism beneath electrochemical oxidation of HMF to FDCA.展开更多
The hydrogenolysis of carbon–oxygen bonds is an important model reaction in upgrading biomass‐derived furanic compounds to transportation fuels.One of these model reactions,namelyconversion of5‐hydroxymethylfurfura...The hydrogenolysis of carbon–oxygen bonds is an important model reaction in upgrading biomass‐derived furanic compounds to transportation fuels.One of these model reactions,namelyconversion of5‐hydroxymethylfurfural(HMF)to the gasoline additive2,5‐dimethylfuran(DMF),isespecially attractive.In this study,bimetallic Cu‐Co catalysts supported on CeO2,ZrO2,and Al2O3were used for the selective hydrogenolysis of HMF to DMF.The structures of the fresh and usedcatalysts were studied using X‐ray diffraction,the Brunauer‐Emmett‐Teller method,transmissionelectron microscopy,temperature‐programmed reduction by H2,temperature‐programmed desorptionof NH3,and CHNS analysis.The structures were correlated with the catalytic activities.TheCu‐Co/CeO2catalyst produced mainly2,5‐bis(hydroxymethyl)furan via reduction of C=O bonds onlarge Cu particles.The Cu‐Co/Al2O3catalyst gave the best selectivity for DMF,as a result of a combinationof highly dispersed Cu,mixed copper–cobalt oxides,and suitable weak acidic sites.Cu‐Co/ZrO2had low selectivity for DMF and produced a combination of variousover‐hydrogenolysis products,including2,5‐dimethyltetrahydrofuran and5,5‐oxybis(methylene)‐bis(2‐methylfuran),because of the presence of strong acidic sites.The reaction pathways and effectsof various operating parameters,namely temperature,H2pressure,and time,were studied to enableoptimization of the selective conversion of HMF to DMF over the Cu‐Co/Al2O3catalyst.展开更多
Using natural resources to construct electrocatalysts for biomass conversion and elucidating their catalytic mechanisms are of great significance,but have remained challenging.Here,a series of two-dimensional(2D)bioma...Using natural resources to construct electrocatalysts for biomass conversion and elucidating their catalytic mechanisms are of great significance,but have remained challenging.Here,a series of two-dimensional(2D)biomass-based Pb/PbO@C nanoparticles catalysts with Pb/PbO anchored on carbon nanosheets were synthesized using natural-derived humate as the precursor.By adjusting the carbonization temperature,an electron-deficient Pb0/Pb^(2+)dual-center-site catalyst can be achieved.The optimized Pb/PbO@C catalyst showed an excellent performance for the electrochemical hydrogenation of 5 hydroxymethylfurfural(HMF)to high value-added 2,5 bis(hydroxymethyl)furan(BHMF),with high Faradaic efficiency(FE:91.9%)and selectivity(Sel:89.7%),achieving comparable performance to those of the reported noble metal-based electrocatalysts.Mechanism study revealed that the electron-deficient Pb^(0)/Pb^(2+)dual-center-site provided abundant Lewis acidic sites and promoted the dissociation of water to the active hydrogen(H^(*))species,thus enhancing the adsorption of HMF on Pb^(2+)sites and the coverage of H^(*)species on Pb0 sites.The high coverage of H*species and the synergistic effect of dual-center sites substantially promoted the binding of H*and HMF to form H-HMF^(*)and inhibited the recombination of H^(*)species,thereby accelerating the reaction kinetics of HMF reduction.展开更多
Solar light driven hydrogen production from water splitting and oxidation of biomass-derivatives is attractive for the conversion of solar energy to high value-added chemicals.The fabrication of heterostructure photoc...Solar light driven hydrogen production from water splitting and oxidation of biomass-derivatives is attractive for the conversion of solar energy to high value-added chemicals.The fabrication of heterostructure photocatalysts with matched band structure between two semiconductors is a promising approach for efficient photocatalysis.In this work,a novel In_(2)O_(3)/In_(2)S_(3)heterostructured hollow fiber photocatalyst was successfully fabricated through two-step ion exchange and chemical bath deposition methods,where the In_(2)S_(3)nanoparticles(NPs)anchored on the surface of In_(2)O_(3)hollow fibers via strong interfacial interaction between the In_(2)O_(3)(222)and In_(2)S_(3)(220)facets.The photocatalyst was used for efficient visible-light-driven photocatalytic hydrogen production integrated with selective oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-diformylfuran(DFF).Compared with pristine In_(2)O_(3)and In_(2)S_(3),the optimal In_(2)O_(3)/In_(2)S_(3)heterostructure exhibits an enhanced photocatalytic hydrogen pro-duction rate(111.2μmol h^(-1)g^(-1)),HMF conversion efficiency(56%)and DFF selectivity(68%)under visible light irradiation.The experimental and theoretical investigations illustrate the phase interface between well matched In_(2)O_(3)(222)and In_(2)S_(3)(220)facets gives rise to facilitated photogenerated charge separation and transfer.This study presents the development of high-performance heterostructured photocatalysts for high efficient hydrogen production coupled with biomass oxidation.展开更多
The synthesis of biomass-derived monomers has received great attention in recent years,motivated by the depletion of fossil fuels and environmental issues.Moreover,the intrinsic functionality within the biomass or bio...The synthesis of biomass-derived monomers has received great attention in recent years,motivated by the depletion of fossil fuels and environmental issues.Moreover,the intrinsic functionality within the biomass or biomass-derived chemicals has great potential to produce new types of monomers containing multiple acid or alcohol groups,thereby leading to materials with novel properties.Given their versatile functional groups and easy production from cellulose/hemicellulose,furfural and hydroxymethylfurfural were regarded as very important biomass-derived platform chemicals through which multiple monomers can be produced via heterogeneous catalysis.In the current review,recent development in heterogeneous catalysis for the production of 6 bio-based monomers,furfuryl alcohol,2,5-bis(hydroxymethyl)furan,2,5-bis-(hydroxymethyl)tetrahydrofuran,1,5-pentanediol,1,6-hexanediol,and 2,5-furandicarboxylic acid,from furfural and hydroxymethylfurfural is reviewed and summarized.The major challenge is how to efficiently and selectively convert specific functional group(s)in furfural and hydroxymethylfurfural during the production of these monomers.Additionally,catalyst stability issues need to be addressed due to necessity of using hot water as reaction medium and high tendency of carbonaceous deposit formation on catalyst surface.The current review mainly focuses on efforts of catalytic site design and modification,including selection of metal/support,use of synergy between metal and support,tuning metal size,use of inverse catalysts,adding catalytic promoters,constructing bimetallic sites,etc.,to realize efficient,selective and stable production of bio-based monomers from furfural and hydroxymethylfurfural.展开更多
The selective oxidation of 2,5‐bis(hydroxymethyl)furan(BHMF)in this work was proven as a promising route to produce 2,5‐furandicarboxylic acid(FDCA),an emerging bio‐based building‐block with wide application.Under...The selective oxidation of 2,5‐bis(hydroxymethyl)furan(BHMF)in this work was proven as a promising route to produce 2,5‐furandicarboxylic acid(FDCA),an emerging bio‐based building‐block with wide application.Under ambient pressure,the modified carbon nanotube‐supported Pd‐based catalysts demonstrate the maximum FDCA yield of 93.0%with a full conversion of BHMF after 60 min at 60°C,much superior to that of the traditional route using 5‐hydroxymethylfurfural(HMF)as substrates(only a yield of 35.7%).The participation of PdH_(x) active species with metallic Pd can be responsible for the encouraging performance.Meanwhile,a possible reaction pathway proceeding through 2,5‐diformylfuran(DFF)and 5‐formyl‐2‐furancarboxylic acid(FFCA)as process intermediates is suggested for BHMF route.The present work may provide new opportunities to synthesize other high value‐added oxygenates by using BHMF as an alternative feedstock.展开更多
Phosphorylated mesoporous carbons （PMCs） were investigated as catalysts in the dehydration of fructose to hydroxymethylfurfural （HMF）. The acidic PMCs show better selectivity to HMF compared to sulfonated carbon c...Phosphorylated mesoporous carbons （PMCs） were investigated as catalysts in the dehydration of fructose to hydroxymethylfurfural （HMF）. The acidic PMCs show better selectivity to HMF compared to sulfonated carbon catalyst （SC） despite lower activity. The concentration of P-O groups on the PMC was correlated with the activity/selectivity of the catalysts; the higher the P-O concentration, the higher the activity. However, the higher the P-O content, the lower the selectivity to HME Indeed, a lower concentration of the P-O groups minimized the degradation of HMF to levulinic acid and the formation of by-products, such as humines. Stability tests showed that these systems deactivate due to the formation of humines and water insoluble by-products derived from the dehydration of fructose which blocked the catalytically active sites.展开更多
An insight into chemical composition,nutritional value and potential health risk of increasingly popular bilberry and black chokeberry commercial juices was provided,based on HPLC-UV(anthocyanins and non-anthocyanin p...An insight into chemical composition,nutritional value and potential health risk of increasingly popular bilberry and black chokeberry commercial juices was provided,based on HPLC-UV(anthocyanins and non-anthocyanin phenolics;patulin;hydroxymethylfurfural),AAS(minerals)and ICP-MS(trace elements)analyses.Delfinidin(in bilberry)and cyanidin glycosides(in bilberry and chokeberry)were the most abundantly present anthocyanins,chlorogenic acid dominated among non-anthocyanin polyphenols,while mineral composition revealed high K and desirable low Na content.A glass of blueberry/black chockeberry juice(200 mL)per day could provide up to 63.5/27.0 mg of anthocyanins,147.2/314.0 mg of polyphenols,almost 50%of Mg(the only mineral satisfying the requirement for a nutritional claim)and,in case of chokeberry,20%of Mn adequate intake.No health risk was observed related to any of the investigated toxicants.Despite indications of a possible benefitial role for health,observed compositional variations precluded positioning of berry juices as functional foods.The labelling could help specialist in nutrition and functional foods as well as health-conscious consumers seeking foods with reliable quantity of dietary valuable phytochemicals and minerals.Sufficiently characterised food has been one of the prerequisites for the approval of a health claim,along with sufficiently defined and substantiated claimed effect.展开更多
基金National Natural Science Foundation of China(22272150,22302177)Major Program of Zhejiang Provincial Natural Science Foundation of China(LD22B030002)+2 种基金Zhejiang Provincial Ten Thousand Talent Program(2021R51009)Public Technology Application Project of Jinhua City(2022-4-067)Self Designed Scientific Research of Zhejiang Normal University(2021ZS0604)。
文摘Biomass conversion offers an efficient approach to alleviate the energy and environmental issues.Electrochemical oxidation of 5-hydroxymethylfurfural(HMF)has attracted tremendous attention in the latest few years for the mild synthesis conditions and high conversion efficiency to obtain 2,5-furan dicarboxylic acid(FDCA),but there still remain problems such as limited yield,short cycle life,and ambiguous reaction mechanism.Despite many reviews highlighting a variety of electrocatalysts for electrochemical oxidation of HMF,a detailed discussion of the structural modulation of catalyst and the underlying catalytic mechanism is still lacking.We herein provide a comprehensive summary of the recent development of electrochemical oxidation of HMF to FDCA,particularly focusing on the mechanism studies as well as the advanced strategies developed to regulate the structure and optimize the performance of the electrocatalysts,including heterointerface construction,defect engineering,single-atom engineering,and in situ reconstruction.Experimental characterization techniques and theoretical calculation methods for mechanism and active site studies are elaborated,and challenges and future directions of electrochemical oxidation of HMF are also prospected.This review will provide guidance for designing advanced catalysts and deepening the understanding of the reaction mechanism beneath electrochemical oxidation of HMF to FDCA.
文摘The hydrogenolysis of carbon–oxygen bonds is an important model reaction in upgrading biomass‐derived furanic compounds to transportation fuels.One of these model reactions,namelyconversion of5‐hydroxymethylfurfural(HMF)to the gasoline additive2,5‐dimethylfuran(DMF),isespecially attractive.In this study,bimetallic Cu‐Co catalysts supported on CeO2,ZrO2,and Al2O3were used for the selective hydrogenolysis of HMF to DMF.The structures of the fresh and usedcatalysts were studied using X‐ray diffraction,the Brunauer‐Emmett‐Teller method,transmissionelectron microscopy,temperature‐programmed reduction by H2,temperature‐programmed desorptionof NH3,and CHNS analysis.The structures were correlated with the catalytic activities.TheCu‐Co/CeO2catalyst produced mainly2,5‐bis(hydroxymethyl)furan via reduction of C=O bonds onlarge Cu particles.The Cu‐Co/Al2O3catalyst gave the best selectivity for DMF,as a result of a combinationof highly dispersed Cu,mixed copper–cobalt oxides,and suitable weak acidic sites.Cu‐Co/ZrO2had low selectivity for DMF and produced a combination of variousover‐hydrogenolysis products,including2,5‐dimethyltetrahydrofuran and5,5‐oxybis(methylene)‐bis(2‐methylfuran),because of the presence of strong acidic sites.The reaction pathways and effectsof various operating parameters,namely temperature,H2pressure,and time,were studied to enableoptimization of the selective conversion of HMF to DMF over the Cu‐Co/Al2O3catalyst.
基金This work was supported by the National Natural Science Foundation of China(Nos.22225501 and 52073173)the Key Research Projects of Universities in Henan Province(No.23A530005)+2 种基金the National Key Laboratory of Biobased Transport Fuel Technology(No.KFKT2022002)of ChinaProgram of Shanghai Academic/Technology Research Leader(No.23XD1431700)Shanghai Engineering Research Center of Specialized Polymer Materials for Aerospace(No.18DZ2253500).
文摘Using natural resources to construct electrocatalysts for biomass conversion and elucidating their catalytic mechanisms are of great significance,but have remained challenging.Here,a series of two-dimensional(2D)biomass-based Pb/PbO@C nanoparticles catalysts with Pb/PbO anchored on carbon nanosheets were synthesized using natural-derived humate as the precursor.By adjusting the carbonization temperature,an electron-deficient Pb0/Pb^(2+)dual-center-site catalyst can be achieved.The optimized Pb/PbO@C catalyst showed an excellent performance for the electrochemical hydrogenation of 5 hydroxymethylfurfural(HMF)to high value-added 2,5 bis(hydroxymethyl)furan(BHMF),with high Faradaic efficiency(FE:91.9%)and selectivity(Sel:89.7%),achieving comparable performance to those of the reported noble metal-based electrocatalysts.Mechanism study revealed that the electron-deficient Pb^(0)/Pb^(2+)dual-center-site provided abundant Lewis acidic sites and promoted the dissociation of water to the active hydrogen(H^(*))species,thus enhancing the adsorption of HMF on Pb^(2+)sites and the coverage of H^(*)species on Pb0 sites.The high coverage of H*species and the synergistic effect of dual-center sites substantially promoted the binding of H*and HMF to form H-HMF^(*)and inhibited the recombination of H^(*)species,thereby accelerating the reaction kinetics of HMF reduction.
基金supported by the Natural Science Foundation of Shandong Province(ZR2021QB022)National Natural Science Foundation of China(52102362,52302272,22376110)+1 种基金Taishan Scholar Program of Shandong Province(ts201712030,tstp20230665)Technology Support Program for Youth Innovation Team of Shandong Universities(2023KJ225).
文摘Solar light driven hydrogen production from water splitting and oxidation of biomass-derivatives is attractive for the conversion of solar energy to high value-added chemicals.The fabrication of heterostructure photocatalysts with matched band structure between two semiconductors is a promising approach for efficient photocatalysis.In this work,a novel In_(2)O_(3)/In_(2)S_(3)heterostructured hollow fiber photocatalyst was successfully fabricated through two-step ion exchange and chemical bath deposition methods,where the In_(2)S_(3)nanoparticles(NPs)anchored on the surface of In_(2)O_(3)hollow fibers via strong interfacial interaction between the In_(2)O_(3)(222)and In_(2)S_(3)(220)facets.The photocatalyst was used for efficient visible-light-driven photocatalytic hydrogen production integrated with selective oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-diformylfuran(DFF).Compared with pristine In_(2)O_(3)and In_(2)S_(3),the optimal In_(2)O_(3)/In_(2)S_(3)heterostructure exhibits an enhanced photocatalytic hydrogen pro-duction rate(111.2μmol h^(-1)g^(-1)),HMF conversion efficiency(56%)and DFF selectivity(68%)under visible light irradiation.The experimental and theoretical investigations illustrate the phase interface between well matched In_(2)O_(3)(222)and In_(2)S_(3)(220)facets gives rise to facilitated photogenerated charge separation and transfer.This study presents the development of high-performance heterostructured photocatalysts for high efficient hydrogen production coupled with biomass oxidation.
基金supported by the National Natural Science Foundation of China(22008074,22008072,21991103)Natural Science Foundation of Shanghai(20ZR1415700)China Postdoctoral Science Foundation(2020M671025,2019TQ0093).
文摘The synthesis of biomass-derived monomers has received great attention in recent years,motivated by the depletion of fossil fuels and environmental issues.Moreover,the intrinsic functionality within the biomass or biomass-derived chemicals has great potential to produce new types of monomers containing multiple acid or alcohol groups,thereby leading to materials with novel properties.Given their versatile functional groups and easy production from cellulose/hemicellulose,furfural and hydroxymethylfurfural were regarded as very important biomass-derived platform chemicals through which multiple monomers can be produced via heterogeneous catalysis.In the current review,recent development in heterogeneous catalysis for the production of 6 bio-based monomers,furfuryl alcohol,2,5-bis(hydroxymethyl)furan,2,5-bis-(hydroxymethyl)tetrahydrofuran,1,5-pentanediol,1,6-hexanediol,and 2,5-furandicarboxylic acid,from furfural and hydroxymethylfurfural is reviewed and summarized.The major challenge is how to efficiently and selectively convert specific functional group(s)in furfural and hydroxymethylfurfural during the production of these monomers.Additionally,catalyst stability issues need to be addressed due to necessity of using hot water as reaction medium and high tendency of carbonaceous deposit formation on catalyst surface.The current review mainly focuses on efforts of catalytic site design and modification,including selection of metal/support,use of synergy between metal and support,tuning metal size,use of inverse catalysts,adding catalytic promoters,constructing bimetallic sites,etc.,to realize efficient,selective and stable production of bio-based monomers from furfural and hydroxymethylfurfural.
文摘The selective oxidation of 2,5‐bis(hydroxymethyl)furan(BHMF)in this work was proven as a promising route to produce 2,5‐furandicarboxylic acid(FDCA),an emerging bio‐based building‐block with wide application.Under ambient pressure,the modified carbon nanotube‐supported Pd‐based catalysts demonstrate the maximum FDCA yield of 93.0%with a full conversion of BHMF after 60 min at 60°C,much superior to that of the traditional route using 5‐hydroxymethylfurfural(HMF)as substrates(only a yield of 35.7%).The participation of PdH_(x) active species with metallic Pd can be responsible for the encouraging performance.Meanwhile,a possible reaction pathway proceeding through 2,5‐diformylfuran(DFF)and 5‐formyl‐2‐furancarboxylic acid(FFCA)as process intermediates is suggested for BHMF route.The present work may provide new opportunities to synthesize other high value‐added oxygenates by using BHMF as an alternative feedstock.
基金supported by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT-Battelle,LLC, for the U. S. Department of Energy (GMV). TEM studies were performed through Oak Ridge National Laboratory’s Center for Nanophase Materials Science (CNMS) which is sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, U. S. Department of Energy
文摘Phosphorylated mesoporous carbons （PMCs） were investigated as catalysts in the dehydration of fructose to hydroxymethylfurfural （HMF）. The acidic PMCs show better selectivity to HMF compared to sulfonated carbon catalyst （SC） despite lower activity. The concentration of P-O groups on the PMC was correlated with the activity/selectivity of the catalysts; the higher the P-O concentration, the higher the activity. However, the higher the P-O content, the lower the selectivity to HME Indeed, a lower concentration of the P-O groups minimized the degradation of HMF to levulinic acid and the formation of by-products, such as humines. Stability tests showed that these systems deactivate due to the formation of humines and water insoluble by-products derived from the dehydration of fructose which blocked the catalytically active sites.
文摘An insight into chemical composition,nutritional value and potential health risk of increasingly popular bilberry and black chokeberry commercial juices was provided,based on HPLC-UV(anthocyanins and non-anthocyanin phenolics;patulin;hydroxymethylfurfural),AAS(minerals)and ICP-MS(trace elements)analyses.Delfinidin(in bilberry)and cyanidin glycosides(in bilberry and chokeberry)were the most abundantly present anthocyanins,chlorogenic acid dominated among non-anthocyanin polyphenols,while mineral composition revealed high K and desirable low Na content.A glass of blueberry/black chockeberry juice(200 mL)per day could provide up to 63.5/27.0 mg of anthocyanins,147.2/314.0 mg of polyphenols,almost 50%of Mg(the only mineral satisfying the requirement for a nutritional claim)and,in case of chokeberry,20%of Mn adequate intake.No health risk was observed related to any of the investigated toxicants.Despite indications of a possible benefitial role for health,observed compositional variations precluded positioning of berry juices as functional foods.The labelling could help specialist in nutrition and functional foods as well as health-conscious consumers seeking foods with reliable quantity of dietary valuable phytochemicals and minerals.Sufficiently characterised food has been one of the prerequisites for the approval of a health claim,along with sufficiently defined and substantiated claimed effect.
