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
It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for elec...It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for electrocatalytic HMF oxidative reaction(e-HMFOR)have been facing low Faradaic efficiency(FE)and high water splitting voltage.Herein,we propose a strategy of the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction by constructing a Co-Ni paired site,where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site,thus giving the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction superior electrocata lytic performances for e-HMFOR and water splitting.By optimizing conditions,the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction has high conversion of 99.7%,high selectivity of 99.9%,and high FE of 98.4%at 1.3 V,as well as low cell voltage of 1.31 V at 10 mA cm^(-2)in 1 M KOH+0.1 M HMF.This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H_(2)in an economical manner.展开更多
Electrocatalytic conversion of renewable biomass is emerging as a promising route for sustainable chemical production;hence it urgently calls for developing efficient electrocatalysts with low potentials and high curr...Electrocatalytic conversion of renewable biomass is emerging as a promising route for sustainable chemical production;hence it urgently calls for developing efficient electrocatalysts with low potentials and high current densities.Herein,a Pr-doped Co(OH)_(2)hexagonal sheet(Pr/Co=1/9,in mole)is synthesized by electrodeposition as highly performant catalyst for 5-hydroxymethylfurfural(HMF)oxidation reaction(HMFOR)to produce 2,5-furandicarboxylic acid(FDCA).This novel and low-cost catalyst possesses a rather low onset potential of 1.05 V(vs.RHE)and requires only 1.10 V(vs.RHE)to reach a current density of 10 mA cm^(-2)for HMFOR,significantly outperforming Co(OH)_(2)benchmark(i.e.,210 mV higher to reach10 m A cm^(-2)).The origin of Pr promotion effect as well as the evolution of CoOOH catalytic sites and HMFOR process has been deeply elucidated by physical characterizations,kinetic experiments,in situ electrochemical techniques,and theoretical calculations.The unique Pr-ameliorated CoOOH active centers enable 100%conversion of HMF,99.6%selectivity of FDCA,and 99.7%Faraday efficiency,with a superior cycling durability toward HMFOR.This can be one of the most outstanding results for Co-based HMFOR catalysts to date in the literature.Thereby this work can help open up new horizons for constructing novel and efficient Co-based electrocatalysts by the utilization of lanthanide elements.展开更多
Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,...Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.展开更多
N-substituted furfurylamines(FAs)are valuable precursors for producing pharmacologically active compounds and polymers.However,enzymatic synthesis of the type of chemicals is still in its infancy.Here we report an imi...N-substituted furfurylamines(FAs)are valuable precursors for producing pharmacologically active compounds and polymers.However,enzymatic synthesis of the type of chemicals is still in its infancy.Here we report an imine reductase from Streptomyces albidoflavus(SaIRED)for the reductive amination of biobased furans.A simple,fast and interference-resistant high-throughput screening(HTS)method was developed,based on the coloration reaction of carbonyl compounds with 2,4-dinitrophenylhydrazine.The reductive amination activity of IREDs can be directly indicated by a colorimetric assay.With the reductive amination of furfural with allylamine as the model reaction,SaIRED with the activity of 4.8 U mg^(-1) was subjected to three rounds of protein engineering and screening by this HTS method,affording a high-activity tri-variant I127V/D241A/A242T(named M3,20.2 U mg^(-1)).The variant M3 showed broad substrate scope,and enabled efficient reductive amination of biobased furans with a variety of amines including small aliphatic amines and sterically hindered amines,giving the target FAs in yields up to>99%.In addition,other variants were identified for preparative-scale synthesis of commercially interesting amines such as N-2-(methylsulfonyl)ethyl-FA by the screen method,with isolated yields up to 87%and turnover numbers up to 9700 for enzyme.Gram-scale synthesis of N-allyl-FA,a valuable building block and potential polymer monomer,was implemented at 0.25 mol L^(-1) substrate loading by a whole-cell catalyst incorporating variant M3,with 4.7 g L^(-1) h^(-1) space-time yield and 91%isolated yield.展开更多
Co_(3)O_(4)possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural(HMF).However,the enrichment and activation effects of Co_(3)O_(4)o...Co_(3)O_(4)possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural(HMF).However,the enrichment and activation effects of Co_(3)O_(4)on OH-and HMF are weak,which limits its further application.Metal defect engineering can regulate the electronic structure,optimize the adsorption of intermediates,and improve the catalytic activity by breaking the symmetry of the material,which is rarely involved in the upgrading of biomass.In this work,we prepare Co_(3)O_(4)with metal defects and load the precious metal platinum at the defect sites(PtVco).The results of in-situ characterizatio ns,electrochemical measurements,and theoretical calculations indicate that the reduction of Co-Co coordination number and the formation of Pt-Co bond induce the decrease of electron filling in the antibonding orbitals of Co element.The resulting upward shift of the d-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH species,thus exhibiting excellent HMF oxidation activity(including a lower onset potential(1.14 V)and 19 times higher current density than pure Co_(3)O_(4)at 1.35 V).In summary,this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail,provides a new option for improving the HMF oxidation activity of cobalt-based materials,broadens the application field of metal defect based materials,and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.展开更多
Imine reductases(IREDs)have been extensively used for the imine reduction and reductive amination to access various amines.However,poor activity and severe substrate/product inhibition limit their widespread applicati...Imine reductases(IREDs)have been extensively used for the imine reduction and reductive amination to access various amines.However,poor activity and severe substrate/product inhibition limit their widespread application in industry.Herein,an engineered IRED from Streptomyces viridochromogenes was developed through four rounds of directed evolution.The engineered SvIRED displayed a significant increase in specific activity to 136.8 U mg^(-1),the highest reported for an IRED to date.Molecular dynamics simulations elucidated the surge in specific activity during mutations.The best mutant can also catalyse the reductive coupling of aldehyde homologs and primary amines with up to 66.9 U mg^(-1).Additionally,we established an in-situ product adsorption system using resin,which significantly alleviated substrate/product inhibition and enhanced substrate loading to 100 g L^(-1).Under optimal conditions,a wide range of chiral 2-aryl-pyrrolidines were successfully produced at high substrate loadings(50-100 g L^(-1))with enantiomeric excess over 99%.The usefulness of this biocatalytic system was further demonstrated by preparation of pharmaceutically relevant chiral 2-aryl pyrrolidines,particularly the decagram-scale synthesis of the key chiral aticaprant intermediate with 90%isolated yield,>99%ee,and 438 g L^(-1) d^(-1) space-time yield.展开更多
Electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR),featuring favorable thermodynamics,presents a promising alternative to the conventional oxygen evolution reaction for energy-saving hydrogen(H_(2))production...Electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR),featuring favorable thermodynamics,presents a promising alternative to the conventional oxygen evolution reaction for energy-saving hydrogen(H_(2))production coupled with biomass upgrading.However,the multiple proton-coupled electron transfer steps in HMFOR result in sluggish kinetics,highlighting the development of highly efficient electrocatalysts.Herein,a high-entropy amorphous MoCrCoNiZn-S grown on nickel foam(HEAS@NF)is constructed via a metal organic framework-derived strategy to efficiently convert HMF to 2,5-furandicarboxylic acid(FDCA).The abundant active sites on the HEAS@NF facilitate the structural evolution to oxyhydroxides that possess strong reducibility for HMF dehydrogenation,leading to superior HMFOR performance compared to sulfides with fewer metal elements.In situ electrochemical impedance spectroscopy results confirm significantly favored kinetics to HMFOR over OER on the HEAS@NF,resulting in a remarkable98%HMF conversion,with FDCA yield and Faradaic efficiency of 98%and 94%even at a concentrated 100 mM HMF.A two-electrode flow electrolyzer equipped with the bifunctional HEAS@NF enables simultaneous cathodic H2and anodic FDCA production with an electricity saving of 10.8%.This study presents an effective strategy to inspire the exploration of high-entropy catalysts for biomass-assisted H2production.展开更多
Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via lo...Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.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.
基金supported by the National Natural Science Foundation of China(22302019)the Changzhou Sci&Tech Program(CJ20220214).
文摘It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for electrocatalytic HMF oxidative reaction(e-HMFOR)have been facing low Faradaic efficiency(FE)and high water splitting voltage.Herein,we propose a strategy of the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction by constructing a Co-Ni paired site,where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site,thus giving the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction superior electrocata lytic performances for e-HMFOR and water splitting.By optimizing conditions,the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction has high conversion of 99.7%,high selectivity of 99.9%,and high FE of 98.4%at 1.3 V,as well as low cell voltage of 1.31 V at 10 mA cm^(-2)in 1 M KOH+0.1 M HMF.This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H_(2)in an economical manner.
基金National Natural Science Foundation of China(No.22272149,22062025)Yunnan University’s Research Innovation Fund for Graduate Students(No.KC-23234085)+1 种基金Workstation of Academician Chen Jing of Yunnan Province(No.202105AF150012)Free Exploration Fund for Academician(No.202405AA350001)。
文摘Electrocatalytic conversion of renewable biomass is emerging as a promising route for sustainable chemical production;hence it urgently calls for developing efficient electrocatalysts with low potentials and high current densities.Herein,a Pr-doped Co(OH)_(2)hexagonal sheet(Pr/Co=1/9,in mole)is synthesized by electrodeposition as highly performant catalyst for 5-hydroxymethylfurfural(HMF)oxidation reaction(HMFOR)to produce 2,5-furandicarboxylic acid(FDCA).This novel and low-cost catalyst possesses a rather low onset potential of 1.05 V(vs.RHE)and requires only 1.10 V(vs.RHE)to reach a current density of 10 mA cm^(-2)for HMFOR,significantly outperforming Co(OH)_(2)benchmark(i.e.,210 mV higher to reach10 m A cm^(-2)).The origin of Pr promotion effect as well as the evolution of CoOOH catalytic sites and HMFOR process has been deeply elucidated by physical characterizations,kinetic experiments,in situ electrochemical techniques,and theoretical calculations.The unique Pr-ameliorated CoOOH active centers enable 100%conversion of HMF,99.6%selectivity of FDCA,and 99.7%Faraday efficiency,with a superior cycling durability toward HMFOR.This can be one of the most outstanding results for Co-based HMFOR catalysts to date in the literature.Thereby this work can help open up new horizons for constructing novel and efficient Co-based electrocatalysts by the utilization of lanthanide elements.
基金China Postdoctoral Science Foundation (2023M733451)Dalian Innovation Team in Key Areas(2020RT06)Engineering Research Center for Key Aromatic Compounds and LiaoNing Key Laboratory,Liaoning Provincial Natural Science Foundation (Doctoral Research Start-up Fund 2024-BSBA-37)。
文摘Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.
文摘N-substituted furfurylamines(FAs)are valuable precursors for producing pharmacologically active compounds and polymers.However,enzymatic synthesis of the type of chemicals is still in its infancy.Here we report an imine reductase from Streptomyces albidoflavus(SaIRED)for the reductive amination of biobased furans.A simple,fast and interference-resistant high-throughput screening(HTS)method was developed,based on the coloration reaction of carbonyl compounds with 2,4-dinitrophenylhydrazine.The reductive amination activity of IREDs can be directly indicated by a colorimetric assay.With the reductive amination of furfural with allylamine as the model reaction,SaIRED with the activity of 4.8 U mg^(-1) was subjected to three rounds of protein engineering and screening by this HTS method,affording a high-activity tri-variant I127V/D241A/A242T(named M3,20.2 U mg^(-1)).The variant M3 showed broad substrate scope,and enabled efficient reductive amination of biobased furans with a variety of amines including small aliphatic amines and sterically hindered amines,giving the target FAs in yields up to>99%.In addition,other variants were identified for preparative-scale synthesis of commercially interesting amines such as N-2-(methylsulfonyl)ethyl-FA by the screen method,with isolated yields up to 87%and turnover numbers up to 9700 for enzyme.Gram-scale synthesis of N-allyl-FA,a valuable building block and potential polymer monomer,was implemented at 0.25 mol L^(-1) substrate loading by a whole-cell catalyst incorporating variant M3,with 4.7 g L^(-1) h^(-1) space-time yield and 91%isolated yield.
基金financially supported by the Natural Science Foundation of Shandong Province(ZR2023QB235,ZR202111240183,ZR2021QF120)the Postdoctoral Science Foundation of China(2022M711956)the Taishan Scholar Program of Shandong Province(tsqnz20231216).
文摘Co_(3)O_(4)possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural(HMF).However,the enrichment and activation effects of Co_(3)O_(4)on OH-and HMF are weak,which limits its further application.Metal defect engineering can regulate the electronic structure,optimize the adsorption of intermediates,and improve the catalytic activity by breaking the symmetry of the material,which is rarely involved in the upgrading of biomass.In this work,we prepare Co_(3)O_(4)with metal defects and load the precious metal platinum at the defect sites(PtVco).The results of in-situ characterizatio ns,electrochemical measurements,and theoretical calculations indicate that the reduction of Co-Co coordination number and the formation of Pt-Co bond induce the decrease of electron filling in the antibonding orbitals of Co element.The resulting upward shift of the d-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH species,thus exhibiting excellent HMF oxidation activity(including a lower onset potential(1.14 V)and 19 times higher current density than pure Co_(3)O_(4)at 1.35 V).In summary,this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail,provides a new option for improving the HMF oxidation activity of cobalt-based materials,broadens the application field of metal defect based materials,and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.
文摘Imine reductases(IREDs)have been extensively used for the imine reduction and reductive amination to access various amines.However,poor activity and severe substrate/product inhibition limit their widespread application in industry.Herein,an engineered IRED from Streptomyces viridochromogenes was developed through four rounds of directed evolution.The engineered SvIRED displayed a significant increase in specific activity to 136.8 U mg^(-1),the highest reported for an IRED to date.Molecular dynamics simulations elucidated the surge in specific activity during mutations.The best mutant can also catalyse the reductive coupling of aldehyde homologs and primary amines with up to 66.9 U mg^(-1).Additionally,we established an in-situ product adsorption system using resin,which significantly alleviated substrate/product inhibition and enhanced substrate loading to 100 g L^(-1).Under optimal conditions,a wide range of chiral 2-aryl-pyrrolidines were successfully produced at high substrate loadings(50-100 g L^(-1))with enantiomeric excess over 99%.The usefulness of this biocatalytic system was further demonstrated by preparation of pharmaceutically relevant chiral 2-aryl pyrrolidines,particularly the decagram-scale synthesis of the key chiral aticaprant intermediate with 90%isolated yield,>99%ee,and 438 g L^(-1) d^(-1) space-time yield.
基金financially supported by the National Natural Science Foundation of China(No.22275138 and 22271219)
文摘Electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR),featuring favorable thermodynamics,presents a promising alternative to the conventional oxygen evolution reaction for energy-saving hydrogen(H_(2))production coupled with biomass upgrading.However,the multiple proton-coupled electron transfer steps in HMFOR result in sluggish kinetics,highlighting the development of highly efficient electrocatalysts.Herein,a high-entropy amorphous MoCrCoNiZn-S grown on nickel foam(HEAS@NF)is constructed via a metal organic framework-derived strategy to efficiently convert HMF to 2,5-furandicarboxylic acid(FDCA).The abundant active sites on the HEAS@NF facilitate the structural evolution to oxyhydroxides that possess strong reducibility for HMF dehydrogenation,leading to superior HMFOR performance compared to sulfides with fewer metal elements.In situ electrochemical impedance spectroscopy results confirm significantly favored kinetics to HMFOR over OER on the HEAS@NF,resulting in a remarkable98%HMF conversion,with FDCA yield and Faradaic efficiency of 98%and 94%even at a concentrated 100 mM HMF.A two-electrode flow electrolyzer equipped with the bifunctional HEAS@NF enables simultaneous cathodic H2and anodic FDCA production with an electricity saving of 10.8%.This study presents an effective strategy to inspire the exploration of high-entropy catalysts for biomass-assisted H2production.
基金the National Nature Science Foundation of China for Excellent Young Scientists Fund(32222058)Fundamental Research Foundation of CAF(CAFYBB2022QB001).
文摘Developing biomass platform compounds into high value-added chemicals is a key step in renewable resource utilization.Herein,we report porous carbon-supported Ni-ZnO nanoparticles catalyst(Ni-ZnO/AC)synthesized via low-temperature coprecipitation,exhibiting excellent performance for the selective hydrogenation of 5-hydroxymethylfurfural(HMF).A linear correlation is first observed between solvent polarity(E_(T)(30))and product selectivity within both polar aprotic and protic solvent classes,suggesting that solvent properties play a vital role in directing reaction pathways.Among these,1,4-dioxane(aprotic)favors the formation of 2,5-bis(hydroxymethyl)furan(BHMF)with 97.5%selectivity,while isopropanol(iPrOH,protic)promotes 2,5-dimethylfuran production with up to 99.5%selectivity.Mechanistic investigations further reveal that beyond polarity,proton-donating ability is critical in facilitating hydrodeoxygenation.iPrOH enables a hydrogen shuttle mechanism where protons assist in hydroxyl group removal,lowering the activation barrier.In contrast,1,4-dioxane,lacking hydrogen bond donors,stabilizes BHMF and hinders further conversion.Density functional theory calculations confirm a lower activation energy in iPrOH(0.60 eV)compared to 1,4-dioxane(1.07 eV).This work offers mechanistic insights and a practical strategy for solvent-mediated control of product selectivity in biomass hydrogenation,highlighting the decisive role of solvent-catalyst-substrate interactions.
