The biomass electrochemical oxidation coupled with hydrogen evolution reaction has received widespread attention due to its carbon-neutral and sustainable properties.The electrosynthesis of 2,5-furanodicarboxylic acid...The biomass electrochemical oxidation coupled with hydrogen evolution reaction has received widespread attention due to its carbon-neutral and sustainable properties.The electrosynthesis of 2,5-furanodicarboxylic acid(FDCA)from 5-hydroxymethylfurfural(HMF)oxidation is one of the most promising means for the production of bioplastic monomers.In this work,we constructed a novel P-doped Ni_(3)S_(2)and Ni heterojunction on nickel foam(P-Ni_(3)S_(2)/Ni/NF)using electrodeposition methods and thermal sulfuration techniques as a bifunctional catalyst for the simultaneous anodic oxidation of HMF to FDCA(HMFOR)and the cathodic hydrogen evolution reaction(HER).On one hand,the synergistic promotion of P doping and the heterojunction of Ni_(3)S_(2)and Ni accelerated electron transfer,and on the other hand,the structure of three-dimensional microsphere stacking on NF surface to form macropores enhances the exposure of catalytically active sites.The prepared P-Ni_(3)S_(2)/Ni/NF exhibited remarkable performance with high HMF conversion(99.2%),FDCA yield(98.1%),and Faraday efficiency(98.8%),and excellent stability with good product selectivity for 7 consecutive cycles,which stands at a higher level than majority of previously published electrocatalysts.Furthermore,P-Ni_(3)S_(2)/Ni/NF also shows a significant response in HER.By using HMFOR and HER as the anodic reaction and cathodic reaction,respectively,the biomass upgrading and hydrogen production can be carried out simultaneously.The synthesized P-Ni_(3)S_(2)/Ni/NF only need a voltage of 1.31V to achieve a current density of 10mA/cm^(2)in a two-electrode system of HMFOR and HER,which is much lower than that of 1.48 V in OER and HER process,thus potentially reducing the cost of this process.展开更多
In this work,nickel foam supported CeO_(2)-modified CoBDC(BDC stands for terephthalic acid linker)metal-organic frameworks(NF/CoBDC@CeO_(2)) are prepared by hydrothermal and subsequent impregnation methods,which can b...In this work,nickel foam supported CeO_(2)-modified CoBDC(BDC stands for terephthalic acid linker)metal-organic frameworks(NF/CoBDC@CeO_(2)) are prepared by hydrothermal and subsequent impregnation methods,which can be further transformed to NF/CoOOH@CeO_(2) by reconstruction during the electrocatalytic test.The obtained NF/CoOOH@CeO_(2) exhibits excellent performance in electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF) because the introduction of CeO_(2) can optimize the electronic structure of the heterointerface and accelerate the accumulation of ^(*)OH.It requires only a potential of 1.290 V_(RHE) to provide a current density of 50 mA cm^(-2) in 1.0 M KOH+50 mM HMF,which is 222 mV lower than that required in 1,0 M KOH(1.512 V_(RHE)).In addition,density-functional theory calculation results demonstrate that CeO_(2) biases the electrons to the CoOOH side at the heterointerface and promotes the adsorption of ^(*)OH and ^(*)HMF on the catalyst surface,which lower the reaction energy barrier and facilitate the electrocata lytic oxidation process.展开更多
The unique properties of metal oxide surfaces,crystal surfaces and defects play vital roles in biomass upgrading reactions.In this work,hierarchical porous bowl-shaped ZrO_(2)(HB-ZrO_(2))with mixed crystal phase was d...The unique properties of metal oxide surfaces,crystal surfaces and defects play vital roles in biomass upgrading reactions.In this work,hierarchical porous bowl-shaped ZrO_(2)(HB-ZrO_(2))with mixed crystal phase was designed and employed as the support for loading AuPd bimetal with different proportions to synthesize AuPd/HB-ZrO_(2) catalysts.The effects of surface chemistry,oxygen defects,bimetal interaction and metal-support interaction of AuPd/HB-ZrO_(2) on catalytic performance for the selective oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA)were systematically investigated.The Au 2 Pd1/HB-ZrO_(2) catalyst afforded a satisfactory FDCA yield of 99.9%from HMF oxidation using O_(2) as the oxidant in water,accompanied with an excellent FDCA productivity at 97.6 mmol g^(−1) h^(−1).This work offers fresh insights into rationally designing efficient catalysts with oxygen-rich defects for the catalytic upgrading of biomass platform chemicals.展开更多
The electrochemical coupling of biomass oxidation and nitrogen conversion presents a potential strategy for high value-added chemicals and nitrogen cycling.Herein,in this work,CuO/Co_(3)O_(4)with heterogeneous interfa...The electrochemical coupling of biomass oxidation and nitrogen conversion presents a potential strategy for high value-added chemicals and nitrogen cycling.Herein,in this work,CuO/Co_(3)O_(4)with heterogeneous interface is successfully constructed as a bifunctional catalyst for the electrooxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and the electroreduction of nitrate to ammonia(NH_(3)).The open-circuit potential spontaneous experiment shows that more 5-hydroxymethylfurfural molecules are adsorbed in the Helmholtz layer of the CuO/Co_(3)O_(4)composite,which certifies that the CuO/Co_(3)O_(4)heterostructure is conducive to the kinetic adsorption of 5-hydroxymethylfurfural.In situ electrochemical impedance spectroscopy further shows that CuO/Co_(3)O_(4)has faster reaction kinetics and lower reaction potential in oxygen evolution reaction and 5-hydroxymethylfurfural electrocatalytic oxidation.Moreover,CuO/Co_(3)O_(4)also has a good reduction effect on NO_(3)^(-).The ex-situ Raman spectroscopy shows that under the reduction potential,the metal oxide is reduced,and the generated Cu_(2)O can be used as a new active site for the reaction to promote the electrocatalytic conversion of NO_(3)^(-)to NH_(3) synthesis.This work provides valuable guidance for the synthesis of value-added chemicals by 5-hydroxymethylfurfural electrocatalytic oxidation coupled with NO_(3)^(-)while efficiently producing NH_(3).展开更多
Electrocatalytic conversion of biomass-derived compounds and nitrate pollutants offers a promising route toward sustainable chemical synthesis and environmental remediation.In this work,a bifunctional NiO-NiCoP cataly...Electrocatalytic conversion of biomass-derived compounds and nitrate pollutants offers a promising route toward sustainable chemical synthesis and environmental remediation.In this work,a bifunctional NiO-NiCoP catalyst with a well-defined heterogeneous interface is synthesized via a low-temperature co-precipitation,annealing and phosphidation process to enable the coupled electrocatalytic 5-hydroxymethylfurfural oxidation reaction(HMFOR) and nitrate reduction reaction(NO_(3)^(-)RR).X-ray photoelectron spectroscopy(XPS),high-resolution transmission electron microscopy(HRTEM),open-circuit potential(OCP),and in-situ electrochemical impedance spectroscopy(in-situ EIS) confirm the formation of the heterogeneous interface,which facilitates electron redistribution,enhances charge transfer,and optimizes reactant adsorption.The catalyst exhibits excellent HMFOR activity,achieving 99.46% HMF conversion,97.23% 2,5-furandicarboxylic acid(FDCA) yield,and 97.62% Faradaic efficiency(FE) at 1.40 V vs.RHE.For NO_(3)^(-)RR,nearly 100% FE and an NH_(3) yield of 8.82 mg h^(-1)cm^(-2)are obtained at-0.40 V vs.RHE.In a paired HMFOR//NO_(3)^(-)RR electrolyzer,the NiO-NiCoP catalyst demonstrates superior current density,product selectivity,and long-term stability compared to conventional oxygen evolution reaction//hydrogen evolution reaction(OER//HER) systems.At 1.60 V,the HMFOR//NO_(3)^(-)RR system achieved a maximum HMF conversion of 95.84%,an FDCA yield of94.83%,and a FE of 89.53%,while at 1.90 V,it reached a maximum NH_(3) yield of 32.50 mg h^(-1)cm^(-2)with an FE of 94.63%.This study underscores the catalytic advantages of heterogeneous interface engineering and provides a viable strategy for integrated biomass valorization and nitrogen-cycle remediation.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
NiMo catalyst exhibits excellent catalytic performance in the electrooxidation of 5-hydroxymethylfurfural(HMF)to produce high-value 2,5-furandicarboxylic acid(FDCA).Although metallic nickel is known to undergo reconst...NiMo catalyst exhibits excellent catalytic performance in the electrooxidation of 5-hydroxymethylfurfural(HMF)to produce high-value 2,5-furandicarboxylic acid(FDCA).Although metallic nickel is known to undergo reconstruction into high-valent species during the reaction,the dynamic evolution of molybdenum components in NiMo catalyst and their mechanistic roles in catalytic reaction remain unclear.In this study,the structural evolution of NiMo alloy during HMF electrooxidation is systematically investigated.Operando analyses reveal that under anodic polarization,molybdenum undergoes oxidative dissolution in the form of MoO_(4)^(2-),concurrently driving the generation of high-valent Ni^(3+)species.Meanwhile,the dissolved MoO_(4)^(2-)re-adsorbs on the catalyst surface,forming a unique interfacial structure with Ni^(3+).Electrochemical results demonstrate that this surface structure facilitates a synergistic effect between the MoO_(4)^(2-)and high-valent Ni^(3+),enhancing the adsorption and activation of HMF molecules.Therefore,the NiMo alloy exhibits excellent catalytic performance,with a high FDCA selectivity of 99.0%.This study provides new insights into the relationship between the catalyst reconstruction process and enhancement of catalytic performance.展开更多
The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products,making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire ...The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products,making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire process.To achieve the efficient selective oxidation of HMF to FDCA,a series of NiCo_(2)O_(4)catalysts with different morphologies,such as flaky,echinoids,pompon and corolla,were prepared and characterized by XRD,SEM,TEM,BET,XPS,and FTIR.Among the four catalysts,flaky NiCo_(2)O_(4)exhibited the most excellent catalytic activity and stability,with a FDCA yield of 60.1%within 12 h at 80℃without alkali participation.The excellent performance of flaky NiCo_(2)O_(4)catalyst is attributed to the oxygen vacancies and acid sites generated by the exposed(400)facets.The oxygen vacancies and acid sites on the catalyst surface can precisely adsorb-CHO and-CH_(2)-OH of HMF,respectively,and this synergistic effect promotes the efficient production of FDCA.This work is of great significance for fundamentally study the effect of micro-topography or crystal-plane reaction properties on surfaces.展开更多
Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear s...Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear structure-activity relationship at the atomic level.In this work,we have successfully synthesized atomically precise Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)clusters(PET:2-phenylethanethiol)for HMFOR.Ni^(2+)and S_(2)-with atomic ratio of 1:2 was mainly existed in Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)to form Ni-S bond.The electrochemical test results have suggested both Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)displayed outstanding electrocatalytic ability for HMFOR.The Ni_(6)(PET)_(12)exhibited better electrocatalytic ability than Ni_(4)(PET)_(8)with higher current density,lower overpotential and faster reaction kinetics.The superior electrochemical ability of Ni_(6)(PET)_(12)may be due to the enhanced adsorption towards HMF molecule with strong interaction towards hydroxyl group and furan ring.Moreover,it found that the Ni^(2+)species in Ni_(6)(PET)_(12)could rapidly oxidized into Ni^(3+)species,which could spontaneously capture electron and proton from HMF for oxidation.The theoretical calculation demonstrated that the Ni_(6)(PET)_(12)process lower free energy barrier than Ni_(4)(PET)_(8)to display excellent electrocatalytic performance.This work is of great significance for designing efficient electrocatalysts for HMFOR.展开更多
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
Photocatalytic activation of C-H bonds is versatile but challenging for undergoing oriented conversion processes.Herein,a spatially site-isolated heterojunction(ZS-Vs/ZIS)of ZnIn2S4 with strong Lewis acidity(ZIS)and Z...Photocatalytic activation of C-H bonds is versatile but challenging for undergoing oriented conversion processes.Herein,a spatially site-isolated heterojunction(ZS-Vs/ZIS)of ZnIn2S4 with strong Lewis acidity(ZIS)and ZnS with S-vacancy(ZS-Vs)is constructed for activating α-C‒H bond and forming·O_(2)^(-)to cleave the C-H bond,respectively.ZS-Vs/ZIS displays outstanding performance in visible-light partial photooxidation of bio-based 5-hydroxymethylfurfural(HMF)to 2,5-diformylfuran(DFF)in an unprecedented yield of 95.7%at 25°C.In-situ experiments and calculations reveal that Zn sites of ZIS serve as hole enrichment to adsorb HMF for α-C‒H activation via ligand-to-metal charge transfer.Shallow trap states introduced by S-vacancy in ZS-Vs act as an electron pool to realize directed O_(2) activation into·O_(2)^(-)for breaking pre-activated α-C‒H bond in HMF to exclusively give DFF.Moreover,ZS-Vs/ZIS has good recyclability and universality in the photooxidation of various alcohols to carbonyls(86.4-95.6%yields).The synergistic C-H activation/breaking strategy exhibits high potential in targeted photocatalytic transformations.展开更多
The photocatalytic selective oxidation of biomass-derived 5-hydroxymethylfurfural(HMF)offers a sustainable alternative to thermal catalysis.However,the efficiency of this process is significantly limited by inadequate...The photocatalytic selective oxidation of biomass-derived 5-hydroxymethylfurfural(HMF)offers a sustainable alternative to thermal catalysis.However,the efficiency of this process is significantly limited by inadequate light absorption efficiency and the rapid recombination of photogenerated charge carriers in conventional photocatalysts.Herein,we developed a Co_(3)O_(4)/ZnIn_(2)S_(4)(Co_(3)O_(4)/ZIS)photocatalyst,in which Co_(3)O_(4)functions as a multifunctional cocatalyst.This photocatalyst significantly enhances the chemisorption and activation of HMF molecules through interfacial oxygen-hydroxyl interactions.Additionally,the incorporation of narrow-band gap Co_(3)O_(4)broadens the optical absorption range of the composite photocatalyst.Besides,integrating Co_(3)O_(4)with ZnIn_(2)S_(4)leads to a 5.9-fold increase in charge separation efficiency compared to pristine ZnIn_(2)S_(4).The optimized Co_(3)O_(4)/ZIS-3 photocatalyst(3 wt% Co_(3)O_(4)loading)exhibits exceptional selectivity and yield for 2,5-diformylfuran(DFF)under visible light irradiation,achieving 70.4%DFF selectivity with a 5.4-fold enhancement compared to pristine ZnIn_(2)S_(4).Scavenger experiments and electron spin resonance(ESR)spectroscopy indicate that superoxide radicals(O_(2)^(-))and h^(+)are the main active species driving the photocatalytic oxidation of HMF.Molecular simulations reveal that the activation of HMF and the transformation of the intermediate^(*)MF to^(*)DFF are more favorable over the Co_(3)O_(4)/ZIS composite due to lower activation barriers compared to those over ZnIn_(2)S_(4).Through this work,we aim to design highly efficient and affordable photocatalysts for biomass valorization and contribute valuable insights into the mechanisms of photocatalytic oxidation of HMF.展开更多
5-Hydroxymethylfurfural(HMF)and its oxidation derivatives have emerged as a bridge between biomass resources and the future energy industry.These renewable biomass resources can be transformed into a variety of value-...5-Hydroxymethylfurfural(HMF)and its oxidation derivatives have emerged as a bridge between biomass resources and the future energy industry.These renewable biomass resources can be transformed into a variety of value-added chemicals,thereby addressing the challenges posed by diminishing fossil fuel reserves and environmental concerns.The immobilization of catalysts represents an innovative method for the sustainable and efficient synthesis of HMF and its oxidation derivatives.This method not only enhances the yield and selectivity of the products but also allows for the optimization of the catalytic performance of immobilized catalysts through the strategic design of their supports.In this review,we provide an overview of the recent advancements in the technology of immobilized catalyst and its application in the synthesis of HMF and its oxidation derivatives,with a particular focus on the preparation and catalytic characteristics of these immobilized catalysts.Furthermore,we discuss potential future directions for the development of immobilized catalysts,including the preparation of high-performance immobilized catalysts,the exploration of their growth and catalytic mechanisms,and the economic implications of raw material utilization.This area of research presents both significant promise and considerable challenges.展开更多
Concurrent activation of lattice oxygen(O_L)and molecular oxygen(O_(2))is crucial for the efficient catalytic oxidation of biomass-derived molecules over metal oxides.Herein,we report that the introduction of ultralow...Concurrent activation of lattice oxygen(O_L)and molecular oxygen(O_(2))is crucial for the efficient catalytic oxidation of biomass-derived molecules over metal oxides.Herein,we report that the introduction of ultralow-loading of Ru single atoms(0.42 wt%)into Mn_(2)O_(3)matrix(0.4%Ru-Mn_(2)O_(3))greatly boosts its catalytic activity for the aerobic oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA).The FDCA productivity over the 0.4%Ru-Mn_(2)O_(3)(5.4 mmol_(FDCA)g_(cat)h^(-1))is 4.9 times higher than the Mn_(2)O_(3).Especially,this FDCAproductivity is also significantly higher than that of existing Ru and Mn-based catalysts.Experimental and theoretical investigations discovered that the Ru single atom facilitated the formation of oxygen vacancy(O_(v))in the catalyst,which synergistically weakened the Mn-O bond and promoted the activation of O_L.The co-presence of Ru single atoms and O_(v)also promote the adsorption and activation of both O_(2)and HMF.Consequently,the dehydrogenation reaction energy barrier of the rate-determining step was reduced via both the O_L and chemisorbed O_(2)dehydrogenation pathways,thus boosting the catalytic oxidation reactions.展开更多
The electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR) represents a promising route for biomass valorization,yet its efficiency is often limited by suboptimal adsorption configurations of reaction intermediat...The electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR) represents a promising route for biomass valorization,yet its efficiency is often limited by suboptimal adsorption configurations of reaction intermediates on conventional catalysts.Herein,we demonstrate that Ce doping effectively modulates both geometric and electronic structures of CuO to achieve exceptional HMFOR performance.The designed Ce-CuO catalyst exhibits remarkable activity and selectivity,achieving nearquantitative FDCA Faradaic efficiency(98.4%) with substantially enhanced production rates(67.0 μmol cm^(-2)h^(-1)) compared to pristine CuO(87.3%,54.0 μmol cm^(-2)h^(-1)),while maintaining over 90% FDCA Faradaic efficiency over 8 cycles.Comprehensive in-situ/ex-situ spectroscopic characterization and theoretical calculations reveal that Ce incorporation induces electron transfer to Cu sites and triggers the coordination geometric restructuring,while simultaneously optimizing the geometric matching between active sites and reaction intermediates.This dual modulation enables key intermediates to adopt thermodynamically favorable adsorption configurations with significantly reduced steric hindrance,thereby lowering the energy barrier of the rate-determining step from 0.99 to 0.46 eV.This work establishes geometric configuration engineering through rational dopant incorporation as a crucial design strategy beyond conventional electronic structure modulation for advanced electrocatalysts in biomass conversion and other complex electrochemical transformations.展开更多
Catalytic oxidation of biomass-derived 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA,an alternative bioplastic monomer to petroleum-derived terephthalic acid),has been identified as an important bioma...Catalytic oxidation of biomass-derived 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA,an alternative bioplastic monomer to petroleum-derived terephthalic acid),has been identified as an important biomass conversion reaction in bio-based polyester industry.However,it is still challenging to acquire a high FDCA yield from the selective oxidation of HMF at low temperatures.Herein,a ternary metal-based catalyst was prepared by loading AuPdPt noble metal nanoparticles on the oxygen-rich vacancy titanium dioxide layer deposited on natural clay mineral halloysite nanotubes(HNTs),and the catalytic activity was examined for air-oxidation of HMF to FDCA in water at ambient temperature(30℃).By adjusting the Au/Pd/Pt ratio,a 93.6%FDCA yield was achieved with the optimal Au_(0.5)Pd_(0.2)Pt_(0.3)/TiO_(2)@HNTs catalyst,which revealed an impressive FDCA formation rate of 67.58 mmol g^(-1)h^(-1)and an excellent TOF value of 17.54 h^(-1)under normal air pressure at 30℃,surpassing the performance of mono-and bimetallic-based catalysts.Theoretical calculation and catalytic performance study clarified the structure-activity relationship.It was found that the ternary metal and oxygen vacancies revealing synergistic enhancement of ambient temperature catalyzed HMF air-oxidation via electronic structure tuning and adsorption intensification.DFT and kinetics study demonstrated that the presence of ternary metal significantly improved the adsorption capacity of substrate and enhanced the rate-determining step of the key intermediate 5-hydroxymethyl-2-furanocarboxylic acid(HMFCA)oxidation when compared to mono-and bimetal.Additionally,the TiO_(2)@HNTs support with high oxygen vacancy concentration facilitated the adsorption of oxygen,synergistically working with the ternary metal to activate and low the energy barriers for the generation of superoxide radical,thus enhancing the FDCA formation.This work offers a novel strategy for designing ternary metal-based catalysts for low-energy catalytic oxidation reactions.展开更多
Balancing the adsorption of OH⁻and 5-hydroxymethylfurfural(HMF)is crucial in optimizing the competing HMF oxidation reaction and oxygen evolution reaction,especially given the polymerization tendency of HMF in alkalin...Balancing the adsorption of OH⁻and 5-hydroxymethylfurfural(HMF)is crucial in optimizing the competing HMF oxidation reaction and oxygen evolution reaction,especially given the polymerization tendency of HMF in alkaline solutions.Herein,we present an innovative approach for rapidly synthesizing a NiFe bimetallic metalorganic framework(MOF)induced by electron-withdrawing carbon quantum dot(EW-CQD)via electron beam irradiation within 2 min.EW-CQD serve as structural regulators,expanding the NiFe-MOF interlayer spacing,increasing reactive site availability,and more effectively balancing the adsorption of OH6(-) and HMF,thereby significantly boosting the oxidation activity of HMF.The resulting EW-CQD-MOF exhibits a low potential of 1.36 V vs.RHE at 10 mA cm^(-2)and maintains excellent durability over 120 h.Comprehensive in situ characterization elucidates the HMF oxidation reaction pathway,showing high selectivity towards 2,5-furandicarboxylic acid(FDCA)under ambient conditions,with an impressive HMF conversion rate of 94%and FDCA selectivity of 96%within 6 h.These findings underscore the critical role of structural optimization and adsorption balance in catalytic performance enhancement and offer valuable insights for designing high-efficiency catalysts,advancing sustainable catalytic processes.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
Fossil fuel depletion and environmental deterioration have created an urgent need to develop renewable and clean energy.Biomass,a sustainable organic carbon source,can meet the huge demand for energy and chemicals.Amo...Fossil fuel depletion and environmental deterioration have created an urgent need to develop renewable and clean energy.Biomass,a sustainable organic carbon source,can meet the huge demand for energy and chemicals.Among them,5-hydroxymethylfurfural(HMF)is an important biomass-derived platform molecule,which can be converted into various high-value chemicals.One of its oxidation products,2,5-furandicarboxylic acid(FDCA),is expected to replace terephthalic acid as a raw material for the synthesis of bio-based degradable plastics.The electrooxidation of HMF emerges as a promising green route for preparing FDCA due to its advantages of mild conditions,fast reaction rate,and high selectivity.The theoretical potential of the HMF electrooxidation reaction(HMFOR,0.3 V vs.reversible hydrogen electrode,RHE)is also lower than that of the oxygen evolution reaction(OER,1.23 V vs.RHE).Coupling anodic HMFOR with cathodic hydrogen evolution reaction(HER)is expected to simultaneously produce valuable FDCA and reduce the cell voltage of hydrogen(H2)evolution.However,the construction of efficient and stable bifunctional catalysts for HMFOR-assisted H2 production is still challenging.In this study,Co-doped Ni-Mo-O porous nanorods grown on a nickel foam(Co-NiMoO/NF)is prepared by simple hydrothermal and calcination methods for both HMFOR and HER.Results of electrocatalytic studies indicate that Co-NiMoO/NF exhibits enhanced performance for HMFOR(E10/100=1.31/1.37 V vs.RHE)and HER(E−10/−100=−35/−123 mV vs.RHE)and shows durable HMFOR/HER stability.In particular,Co-NiMoO/NF maintains high FDCA selectivity(~99.2%)and Faradaic efficiency(~95.7%)for 40 successive cycles at 1.36 V vs.RHE for HMFOR.Conversely,Co-NiMoO/NF maintains stable operation at−200 mA∙cm^(−2)for 50 h with no significant activity attenuation for HER.When coupled as a bifunctional electrode for overall HMF splitting,Co-NiMoO/NF reaches an electric flux of 50 mA∙cm^(−2)at 1.48 V,which is 290 mV lower than that of the overall water splitting.This confirms that the HMFOR-assisted H2 production over Co-NiMoO/NF significantly reduces the energy consumption.Moreover,the two-electrode system maintains good FDCA selectivity(97.6%)for 10 cycles at 1.45 V,implying good stability of HMFOR-assisted H2 evolution.The remarkable catalytic performance of Co-NiMoO/NF could be due to the introduction of Co,which optimizes the electronic structure of Ni-Mo-O and adsorption behaviors of the reactants,thereby enhancing the intrinsic activity and stability of the catalyst.Meanwhile,the porous nanorod structure enhanced the mass transport of substrates and desorption of bubbles,thereby elevating the HMFOR/HER kinetics.This study provides useful insights for designing efficient and durable bifunctional catalysts for HMFOR and HER.展开更多
Electrocatalytic 5-hydroxymethylfurfural oxidation reaction(HMFOR)provides a promising strategy to convert biomass derivative to highvalue-added chemicals.Herein,a cascade strategy is proposed to construct Pd-NiCo_(2)...Electrocatalytic 5-hydroxymethylfurfural oxidation reaction(HMFOR)provides a promising strategy to convert biomass derivative to highvalue-added chemicals.Herein,a cascade strategy is proposed to construct Pd-NiCo_(2)O_(4)electrocatalyst by Pd loading on Ni-doped Co3O4 and for highly active and stable synergistic HMF oxidation.An elevated current density of 800 mA cm^(-2)can be achieved at 1.5 V,and both Faradaic efficiency and yield of 2,5-furandicarboxylic acid remained close to 100%over 10 consecutive electrolysis.Experimental and theoretical results unveil that the introduction of Pd atoms can modulate the local electronic structure of Ni/Co,which not only balances the competitive adsorption of HMF and OH-species,but also promote the active Ni^(3+)species formation,inducing high indirect oxidation activity.We have also discovered that Ni incorporation facilitates the Co2+pre-oxidation and electrophilic OH*generation to contribute direct oxidation process.This work provides a new approach to design advanced electrocatalyst for biomass upgrading.展开更多
基金financially supported by Natural Science Foundation of Shandong Province(No.ZR2024QB415)。
文摘The biomass electrochemical oxidation coupled with hydrogen evolution reaction has received widespread attention due to its carbon-neutral and sustainable properties.The electrosynthesis of 2,5-furanodicarboxylic acid(FDCA)from 5-hydroxymethylfurfural(HMF)oxidation is one of the most promising means for the production of bioplastic monomers.In this work,we constructed a novel P-doped Ni_(3)S_(2)and Ni heterojunction on nickel foam(P-Ni_(3)S_(2)/Ni/NF)using electrodeposition methods and thermal sulfuration techniques as a bifunctional catalyst for the simultaneous anodic oxidation of HMF to FDCA(HMFOR)and the cathodic hydrogen evolution reaction(HER).On one hand,the synergistic promotion of P doping and the heterojunction of Ni_(3)S_(2)and Ni accelerated electron transfer,and on the other hand,the structure of three-dimensional microsphere stacking on NF surface to form macropores enhances the exposure of catalytically active sites.The prepared P-Ni_(3)S_(2)/Ni/NF exhibited remarkable performance with high HMF conversion(99.2%),FDCA yield(98.1%),and Faraday efficiency(98.8%),and excellent stability with good product selectivity for 7 consecutive cycles,which stands at a higher level than majority of previously published electrocatalysts.Furthermore,P-Ni_(3)S_(2)/Ni/NF also shows a significant response in HER.By using HMFOR and HER as the anodic reaction and cathodic reaction,respectively,the biomass upgrading and hydrogen production can be carried out simultaneously.The synthesized P-Ni_(3)S_(2)/Ni/NF only need a voltage of 1.31V to achieve a current density of 10mA/cm^(2)in a two-electrode system of HMFOR and HER,which is much lower than that of 1.48 V in OER and HER process,thus potentially reducing the cost of this process.
基金National Key Research and Development Program of China (2021YFB3500700)National Natural Science Foundation of China (51802015)Fundamental Research Funds for the Central Universities (FRF-EYIT-23-07)。
文摘In this work,nickel foam supported CeO_(2)-modified CoBDC(BDC stands for terephthalic acid linker)metal-organic frameworks(NF/CoBDC@CeO_(2)) are prepared by hydrothermal and subsequent impregnation methods,which can be further transformed to NF/CoOOH@CeO_(2) by reconstruction during the electrocatalytic test.The obtained NF/CoOOH@CeO_(2) exhibits excellent performance in electrocatalytic oxidation of 5-hydroxymethylfurfural(HMF) because the introduction of CeO_(2) can optimize the electronic structure of the heterointerface and accelerate the accumulation of ^(*)OH.It requires only a potential of 1.290 V_(RHE) to provide a current density of 50 mA cm^(-2) in 1.0 M KOH+50 mM HMF,which is 222 mV lower than that required in 1,0 M KOH(1.512 V_(RHE)).In addition,density-functional theory calculation results demonstrate that CeO_(2) biases the electrons to the CoOOH side at the heterointerface and promotes the adsorption of ^(*)OH and ^(*)HMF on the catalyst surface,which lower the reaction energy barrier and facilitate the electrocata lytic oxidation process.
基金financially supported by the Natural Science Foundation of Jiangsu Province(No.BK20200917)the China Postdoctoral Science Foundation(No.2021M701474)+1 种基金Youth Talent Cultivation Plan of Jiangsu UniversityCollaborative Innovation Center for Water Treatment Technology and Materials.
文摘The unique properties of metal oxide surfaces,crystal surfaces and defects play vital roles in biomass upgrading reactions.In this work,hierarchical porous bowl-shaped ZrO_(2)(HB-ZrO_(2))with mixed crystal phase was designed and employed as the support for loading AuPd bimetal with different proportions to synthesize AuPd/HB-ZrO_(2) catalysts.The effects of surface chemistry,oxygen defects,bimetal interaction and metal-support interaction of AuPd/HB-ZrO_(2) on catalytic performance for the selective oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA)were systematically investigated.The Au 2 Pd1/HB-ZrO_(2) catalyst afforded a satisfactory FDCA yield of 99.9%from HMF oxidation using O_(2) as the oxidant in water,accompanied with an excellent FDCA productivity at 97.6 mmol g^(−1) h^(−1).This work offers fresh insights into rationally designing efficient catalysts with oxygen-rich defects for the catalytic upgrading of biomass platform chemicals.
基金the support received from the National Natural Science Foundation of China(Grant No.22372012,22261160640,and 22002009)the Natural Science Foundation of Hunan Province(Grant No.2023JJ20037 and 2021JJ40565)the Scientific Research Project of Hunan Provincial Department of Education(Grant No.22B0293)
文摘The electrochemical coupling of biomass oxidation and nitrogen conversion presents a potential strategy for high value-added chemicals and nitrogen cycling.Herein,in this work,CuO/Co_(3)O_(4)with heterogeneous interface is successfully constructed as a bifunctional catalyst for the electrooxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid and the electroreduction of nitrate to ammonia(NH_(3)).The open-circuit potential spontaneous experiment shows that more 5-hydroxymethylfurfural molecules are adsorbed in the Helmholtz layer of the CuO/Co_(3)O_(4)composite,which certifies that the CuO/Co_(3)O_(4)heterostructure is conducive to the kinetic adsorption of 5-hydroxymethylfurfural.In situ electrochemical impedance spectroscopy further shows that CuO/Co_(3)O_(4)has faster reaction kinetics and lower reaction potential in oxygen evolution reaction and 5-hydroxymethylfurfural electrocatalytic oxidation.Moreover,CuO/Co_(3)O_(4)also has a good reduction effect on NO_(3)^(-).The ex-situ Raman spectroscopy shows that under the reduction potential,the metal oxide is reduced,and the generated Cu_(2)O can be used as a new active site for the reaction to promote the electrocatalytic conversion of NO_(3)^(-)to NH_(3) synthesis.This work provides valuable guidance for the synthesis of value-added chemicals by 5-hydroxymethylfurfural electrocatalytic oxidation coupled with NO_(3)^(-)while efficiently producing NH_(3).
基金the support received from the National Natural Science Foundation of China (22372012,22261160640,22002009)the Natural Science Foundation of Hunan Province (2023JJ20037)the Science and Technology Innovation Program of Hunan Province (2024RC3177)。
文摘Electrocatalytic conversion of biomass-derived compounds and nitrate pollutants offers a promising route toward sustainable chemical synthesis and environmental remediation.In this work,a bifunctional NiO-NiCoP catalyst with a well-defined heterogeneous interface is synthesized via a low-temperature co-precipitation,annealing and phosphidation process to enable the coupled electrocatalytic 5-hydroxymethylfurfural oxidation reaction(HMFOR) and nitrate reduction reaction(NO_(3)^(-)RR).X-ray photoelectron spectroscopy(XPS),high-resolution transmission electron microscopy(HRTEM),open-circuit potential(OCP),and in-situ electrochemical impedance spectroscopy(in-situ EIS) confirm the formation of the heterogeneous interface,which facilitates electron redistribution,enhances charge transfer,and optimizes reactant adsorption.The catalyst exhibits excellent HMFOR activity,achieving 99.46% HMF conversion,97.23% 2,5-furandicarboxylic acid(FDCA) yield,and 97.62% Faradaic efficiency(FE) at 1.40 V vs.RHE.For NO_(3)^(-)RR,nearly 100% FE and an NH_(3) yield of 8.82 mg h^(-1)cm^(-2)are obtained at-0.40 V vs.RHE.In a paired HMFOR//NO_(3)^(-)RR electrolyzer,the NiO-NiCoP catalyst demonstrates superior current density,product selectivity,and long-term stability compared to conventional oxygen evolution reaction//hydrogen evolution reaction(OER//HER) systems.At 1.60 V,the HMFOR//NO_(3)^(-)RR system achieved a maximum HMF conversion of 95.84%,an FDCA yield of94.83%,and a FE of 89.53%,while at 1.90 V,it reached a maximum NH_(3) yield of 32.50 mg h^(-1)cm^(-2)with an FE of 94.63%.This study underscores the catalytic advantages of heterogeneous interface engineering and provides a viable strategy for integrated biomass valorization and nitrogen-cycle remediation.
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supported by the Natural Science Foundation of Guangxi Zhuang(2022JJD120011)the National Natural Science Foundation of China(22479031,22162004)the Project for Enhancing Young and Middle-aged Teacher's Research Basis Ability in Colleges of Guangxi(2025KY0040).
文摘NiMo catalyst exhibits excellent catalytic performance in the electrooxidation of 5-hydroxymethylfurfural(HMF)to produce high-value 2,5-furandicarboxylic acid(FDCA).Although metallic nickel is known to undergo reconstruction into high-valent species during the reaction,the dynamic evolution of molybdenum components in NiMo catalyst and their mechanistic roles in catalytic reaction remain unclear.In this study,the structural evolution of NiMo alloy during HMF electrooxidation is systematically investigated.Operando analyses reveal that under anodic polarization,molybdenum undergoes oxidative dissolution in the form of MoO_(4)^(2-),concurrently driving the generation of high-valent Ni^(3+)species.Meanwhile,the dissolved MoO_(4)^(2-)re-adsorbs on the catalyst surface,forming a unique interfacial structure with Ni^(3+).Electrochemical results demonstrate that this surface structure facilitates a synergistic effect between the MoO_(4)^(2-)and high-valent Ni^(3+),enhancing the adsorption and activation of HMF molecules.Therefore,the NiMo alloy exhibits excellent catalytic performance,with a high FDCA selectivity of 99.0%.This study provides new insights into the relationship between the catalyst reconstruction process and enhancement of catalytic performance.
基金supported by the Swedish Energy Agency(P47500-1)the National Key R&D Program of China(2020YFA0710200)+2 种基金the National Natural Science Foundation of China(22378401 and U22A20416)the financial support from STINT(CH2019-8287)financial support from the European Union and Swedish Energy Agency(P2020-90066).
文摘The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products,making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire process.To achieve the efficient selective oxidation of HMF to FDCA,a series of NiCo_(2)O_(4)catalysts with different morphologies,such as flaky,echinoids,pompon and corolla,were prepared and characterized by XRD,SEM,TEM,BET,XPS,and FTIR.Among the four catalysts,flaky NiCo_(2)O_(4)exhibited the most excellent catalytic activity and stability,with a FDCA yield of 60.1%within 12 h at 80℃without alkali participation.The excellent performance of flaky NiCo_(2)O_(4)catalyst is attributed to the oxygen vacancies and acid sites generated by the exposed(400)facets.The oxygen vacancies and acid sites on the catalyst surface can precisely adsorb-CHO and-CH_(2)-OH of HMF,respectively,and this synergistic effect promotes the efficient production of FDCA.This work is of great significance for fundamentally study the effect of micro-topography or crystal-plane reaction properties on surfaces.
基金supported by National Natural Science Foundation of China(No.22102155)the China Postdoctoral Science Foundation(Nos.2021M692909 and 2022T150587).
文摘Nickel sulfide exhibits excellent catalytic activity in the electrochemical 2,5-hydroxymethylfurfural oxidation reaction(HMFOR).However,due to the polydispersity of nanoparticles,it is difficult to establish a clear structure-activity relationship at the atomic level.In this work,we have successfully synthesized atomically precise Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)clusters(PET:2-phenylethanethiol)for HMFOR.Ni^(2+)and S_(2)-with atomic ratio of 1:2 was mainly existed in Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)to form Ni-S bond.The electrochemical test results have suggested both Ni_(6)(PET)_(12)and Ni_(4)(PET)_(8)displayed outstanding electrocatalytic ability for HMFOR.The Ni_(6)(PET)_(12)exhibited better electrocatalytic ability than Ni_(4)(PET)_(8)with higher current density,lower overpotential and faster reaction kinetics.The superior electrochemical ability of Ni_(6)(PET)_(12)may be due to the enhanced adsorption towards HMF molecule with strong interaction towards hydroxyl group and furan ring.Moreover,it found that the Ni^(2+)species in Ni_(6)(PET)_(12)could rapidly oxidized into Ni^(3+)species,which could spontaneously capture electron and proton from HMF for oxidation.The theoretical calculation demonstrated that the Ni_(6)(PET)_(12)process lower free energy barrier than Ni_(4)(PET)_(8)to display excellent electrocatalytic performance.This work is of great significance for designing efficient electrocatalysts for HMFOR.
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(22478087,22368014)Guizhou Provincial S&T Project(GCC[2023]011,ZK[2022]011)Guizhou Provincial Higher Education Institution Program(Qianjiaoji[2023]082).
文摘Photocatalytic activation of C-H bonds is versatile but challenging for undergoing oriented conversion processes.Herein,a spatially site-isolated heterojunction(ZS-Vs/ZIS)of ZnIn2S4 with strong Lewis acidity(ZIS)and ZnS with S-vacancy(ZS-Vs)is constructed for activating α-C‒H bond and forming·O_(2)^(-)to cleave the C-H bond,respectively.ZS-Vs/ZIS displays outstanding performance in visible-light partial photooxidation of bio-based 5-hydroxymethylfurfural(HMF)to 2,5-diformylfuran(DFF)in an unprecedented yield of 95.7%at 25°C.In-situ experiments and calculations reveal that Zn sites of ZIS serve as hole enrichment to adsorb HMF for α-C‒H activation via ligand-to-metal charge transfer.Shallow trap states introduced by S-vacancy in ZS-Vs act as an electron pool to realize directed O_(2) activation into·O_(2)^(-)for breaking pre-activated α-C‒H bond in HMF to exclusively give DFF.Moreover,ZS-Vs/ZIS has good recyclability and universality in the photooxidation of various alcohols to carbonyls(86.4-95.6%yields).The synergistic C-H activation/breaking strategy exhibits high potential in targeted photocatalytic transformations.
基金financially supported by the National Key Research and Development Program of China(No.2022YFB3805400)the National Natural Science Foundation of China(No.22178297,No.22478327)+3 种基金the Science and Technology Innovation Program of Hunan Province(No.2024RC9009)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDC04010100)the Provincial Natural Science Foundation of Hunan(No.2024JJ5371)the Scientific Research Fund of Hunan Provincial Education Department(No.24A0107)。
文摘The photocatalytic selective oxidation of biomass-derived 5-hydroxymethylfurfural(HMF)offers a sustainable alternative to thermal catalysis.However,the efficiency of this process is significantly limited by inadequate light absorption efficiency and the rapid recombination of photogenerated charge carriers in conventional photocatalysts.Herein,we developed a Co_(3)O_(4)/ZnIn_(2)S_(4)(Co_(3)O_(4)/ZIS)photocatalyst,in which Co_(3)O_(4)functions as a multifunctional cocatalyst.This photocatalyst significantly enhances the chemisorption and activation of HMF molecules through interfacial oxygen-hydroxyl interactions.Additionally,the incorporation of narrow-band gap Co_(3)O_(4)broadens the optical absorption range of the composite photocatalyst.Besides,integrating Co_(3)O_(4)with ZnIn_(2)S_(4)leads to a 5.9-fold increase in charge separation efficiency compared to pristine ZnIn_(2)S_(4).The optimized Co_(3)O_(4)/ZIS-3 photocatalyst(3 wt% Co_(3)O_(4)loading)exhibits exceptional selectivity and yield for 2,5-diformylfuran(DFF)under visible light irradiation,achieving 70.4%DFF selectivity with a 5.4-fold enhancement compared to pristine ZnIn_(2)S_(4).Scavenger experiments and electron spin resonance(ESR)spectroscopy indicate that superoxide radicals(O_(2)^(-))and h^(+)are the main active species driving the photocatalytic oxidation of HMF.Molecular simulations reveal that the activation of HMF and the transformation of the intermediate^(*)MF to^(*)DFF are more favorable over the Co_(3)O_(4)/ZIS composite due to lower activation barriers compared to those over ZnIn_(2)S_(4).Through this work,we aim to design highly efficient and affordable photocatalysts for biomass valorization and contribute valuable insights into the mechanisms of photocatalytic oxidation of HMF.
文摘5-Hydroxymethylfurfural(HMF)and its oxidation derivatives have emerged as a bridge between biomass resources and the future energy industry.These renewable biomass resources can be transformed into a variety of value-added chemicals,thereby addressing the challenges posed by diminishing fossil fuel reserves and environmental concerns.The immobilization of catalysts represents an innovative method for the sustainable and efficient synthesis of HMF and its oxidation derivatives.This method not only enhances the yield and selectivity of the products but also allows for the optimization of the catalytic performance of immobilized catalysts through the strategic design of their supports.In this review,we provide an overview of the recent advancements in the technology of immobilized catalyst and its application in the synthesis of HMF and its oxidation derivatives,with a particular focus on the preparation and catalytic characteristics of these immobilized catalysts.Furthermore,we discuss potential future directions for the development of immobilized catalysts,including the preparation of high-performance immobilized catalysts,the exploration of their growth and catalytic mechanisms,and the economic implications of raw material utilization.This area of research presents both significant promise and considerable challenges.
基金financially supported by National Natural Science Foundation of China(22208137 and 22068022)Yunnan Fundamental Research Projects(202101BE070001-033,202401AT070825,202201BE070001007 and 202301AV070005)。
文摘Concurrent activation of lattice oxygen(O_L)and molecular oxygen(O_(2))is crucial for the efficient catalytic oxidation of biomass-derived molecules over metal oxides.Herein,we report that the introduction of ultralow-loading of Ru single atoms(0.42 wt%)into Mn_(2)O_(3)matrix(0.4%Ru-Mn_(2)O_(3))greatly boosts its catalytic activity for the aerobic oxidation of 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA).The FDCA productivity over the 0.4%Ru-Mn_(2)O_(3)(5.4 mmol_(FDCA)g_(cat)h^(-1))is 4.9 times higher than the Mn_(2)O_(3).Especially,this FDCAproductivity is also significantly higher than that of existing Ru and Mn-based catalysts.Experimental and theoretical investigations discovered that the Ru single atom facilitated the formation of oxygen vacancy(O_(v))in the catalyst,which synergistically weakened the Mn-O bond and promoted the activation of O_L.The co-presence of Ru single atoms and O_(v)also promote the adsorption and activation of both O_(2)and HMF.Consequently,the dehydrogenation reaction energy barrier of the rate-determining step was reduced via both the O_L and chemisorbed O_(2)dehydrogenation pathways,thus boosting the catalytic oxidation reactions.
基金supported by the National Natural Science Foundation of China (22379071)the Jiangsu Provincial Major Science and Technology Program (BG2024011)+2 种基金the support from the Nanjing “U35” Talent Foundation-Strengthening Projectthe National and Local Joint Engineering Research Center of Biomedical Functional Materialsthe Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘The electrochemical oxidation of 5-hydroxymethylfurfural(HMFOR) represents a promising route for biomass valorization,yet its efficiency is often limited by suboptimal adsorption configurations of reaction intermediates on conventional catalysts.Herein,we demonstrate that Ce doping effectively modulates both geometric and electronic structures of CuO to achieve exceptional HMFOR performance.The designed Ce-CuO catalyst exhibits remarkable activity and selectivity,achieving nearquantitative FDCA Faradaic efficiency(98.4%) with substantially enhanced production rates(67.0 μmol cm^(-2)h^(-1)) compared to pristine CuO(87.3%,54.0 μmol cm^(-2)h^(-1)),while maintaining over 90% FDCA Faradaic efficiency over 8 cycles.Comprehensive in-situ/ex-situ spectroscopic characterization and theoretical calculations reveal that Ce incorporation induces electron transfer to Cu sites and triggers the coordination geometric restructuring,while simultaneously optimizing the geometric matching between active sites and reaction intermediates.This dual modulation enables key intermediates to adopt thermodynamically favorable adsorption configurations with significantly reduced steric hindrance,thereby lowering the energy barrier of the rate-determining step from 0.99 to 0.46 eV.This work establishes geometric configuration engineering through rational dopant incorporation as a crucial design strategy beyond conventional electronic structure modulation for advanced electrocatalysts in biomass conversion and other complex electrochemical transformations.
基金supported by the National Natural Science Foundation of China(22478167,22278419)the College Students Innovative Practice Plan of Jiangsu University(202410299160Y)+2 种基金the Youth Talent Cultivation Plan of Jiangsu Universitythe Key Core Technology Research(Social Development)Foundation of Suzhou(2023ss06)Collaborative Innovation Center for Water Treatment Technology and Materials and the Special Fund of Henan Key Laboratory of Water Pollution Control and Rehabilitation Technology(CJSZ2024010).
文摘Catalytic oxidation of biomass-derived 5-hydroxymethylfurfural(HMF)to 2,5-furandicarboxylic acid(FDCA,an alternative bioplastic monomer to petroleum-derived terephthalic acid),has been identified as an important biomass conversion reaction in bio-based polyester industry.However,it is still challenging to acquire a high FDCA yield from the selective oxidation of HMF at low temperatures.Herein,a ternary metal-based catalyst was prepared by loading AuPdPt noble metal nanoparticles on the oxygen-rich vacancy titanium dioxide layer deposited on natural clay mineral halloysite nanotubes(HNTs),and the catalytic activity was examined for air-oxidation of HMF to FDCA in water at ambient temperature(30℃).By adjusting the Au/Pd/Pt ratio,a 93.6%FDCA yield was achieved with the optimal Au_(0.5)Pd_(0.2)Pt_(0.3)/TiO_(2)@HNTs catalyst,which revealed an impressive FDCA formation rate of 67.58 mmol g^(-1)h^(-1)and an excellent TOF value of 17.54 h^(-1)under normal air pressure at 30℃,surpassing the performance of mono-and bimetallic-based catalysts.Theoretical calculation and catalytic performance study clarified the structure-activity relationship.It was found that the ternary metal and oxygen vacancies revealing synergistic enhancement of ambient temperature catalyzed HMF air-oxidation via electronic structure tuning and adsorption intensification.DFT and kinetics study demonstrated that the presence of ternary metal significantly improved the adsorption capacity of substrate and enhanced the rate-determining step of the key intermediate 5-hydroxymethyl-2-furanocarboxylic acid(HMFCA)oxidation when compared to mono-and bimetal.Additionally,the TiO_(2)@HNTs support with high oxygen vacancy concentration facilitated the adsorption of oxygen,synergistically working with the ternary metal to activate and low the energy barriers for the generation of superoxide radical,thus enhancing the FDCA formation.This work offers a novel strategy for designing ternary metal-based catalysts for low-energy catalytic oxidation reactions.
基金funded by Shanghai Pujiang Program(21PJD022)Hunan Provincial Natural Science Foundation(2023JJ60522).
文摘Balancing the adsorption of OH⁻and 5-hydroxymethylfurfural(HMF)is crucial in optimizing the competing HMF oxidation reaction and oxygen evolution reaction,especially given the polymerization tendency of HMF in alkaline solutions.Herein,we present an innovative approach for rapidly synthesizing a NiFe bimetallic metalorganic framework(MOF)induced by electron-withdrawing carbon quantum dot(EW-CQD)via electron beam irradiation within 2 min.EW-CQD serve as structural regulators,expanding the NiFe-MOF interlayer spacing,increasing reactive site availability,and more effectively balancing the adsorption of OH6(-) and HMF,thereby significantly boosting the oxidation activity of HMF.The resulting EW-CQD-MOF exhibits a low potential of 1.36 V vs.RHE at 10 mA cm^(-2)and maintains excellent durability over 120 h.Comprehensive in situ characterization elucidates the HMF oxidation reaction pathway,showing high selectivity towards 2,5-furandicarboxylic acid(FDCA)under ambient conditions,with an impressive HMF conversion rate of 94%and FDCA selectivity of 96%within 6 h.These findings underscore the critical role of structural optimization and adsorption balance in catalytic performance enhancement and offer valuable insights for designing high-efficiency catalysts,advancing sustainable catalytic processes.
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.
文摘Fossil fuel depletion and environmental deterioration have created an urgent need to develop renewable and clean energy.Biomass,a sustainable organic carbon source,can meet the huge demand for energy and chemicals.Among them,5-hydroxymethylfurfural(HMF)is an important biomass-derived platform molecule,which can be converted into various high-value chemicals.One of its oxidation products,2,5-furandicarboxylic acid(FDCA),is expected to replace terephthalic acid as a raw material for the synthesis of bio-based degradable plastics.The electrooxidation of HMF emerges as a promising green route for preparing FDCA due to its advantages of mild conditions,fast reaction rate,and high selectivity.The theoretical potential of the HMF electrooxidation reaction(HMFOR,0.3 V vs.reversible hydrogen electrode,RHE)is also lower than that of the oxygen evolution reaction(OER,1.23 V vs.RHE).Coupling anodic HMFOR with cathodic hydrogen evolution reaction(HER)is expected to simultaneously produce valuable FDCA and reduce the cell voltage of hydrogen(H2)evolution.However,the construction of efficient and stable bifunctional catalysts for HMFOR-assisted H2 production is still challenging.In this study,Co-doped Ni-Mo-O porous nanorods grown on a nickel foam(Co-NiMoO/NF)is prepared by simple hydrothermal and calcination methods for both HMFOR and HER.Results of electrocatalytic studies indicate that Co-NiMoO/NF exhibits enhanced performance for HMFOR(E10/100=1.31/1.37 V vs.RHE)and HER(E−10/−100=−35/−123 mV vs.RHE)and shows durable HMFOR/HER stability.In particular,Co-NiMoO/NF maintains high FDCA selectivity(~99.2%)and Faradaic efficiency(~95.7%)for 40 successive cycles at 1.36 V vs.RHE for HMFOR.Conversely,Co-NiMoO/NF maintains stable operation at−200 mA∙cm^(−2)for 50 h with no significant activity attenuation for HER.When coupled as a bifunctional electrode for overall HMF splitting,Co-NiMoO/NF reaches an electric flux of 50 mA∙cm^(−2)at 1.48 V,which is 290 mV lower than that of the overall water splitting.This confirms that the HMFOR-assisted H2 production over Co-NiMoO/NF significantly reduces the energy consumption.Moreover,the two-electrode system maintains good FDCA selectivity(97.6%)for 10 cycles at 1.45 V,implying good stability of HMFOR-assisted H2 evolution.The remarkable catalytic performance of Co-NiMoO/NF could be due to the introduction of Co,which optimizes the electronic structure of Ni-Mo-O and adsorption behaviors of the reactants,thereby enhancing the intrinsic activity and stability of the catalyst.Meanwhile,the porous nanorod structure enhanced the mass transport of substrates and desorption of bubbles,thereby elevating the HMFOR/HER kinetics.This study provides useful insights for designing efficient and durable bifunctional catalysts for HMFOR and HER.
基金financially supported by Key Research and Development Projects of Sichuan Province (2023YFG0222)“Tianfu Emei” Science and Technology Innovation Leader Program in Sichuan Province (2021)+3 种基金University of Electronic Science and Technology of China Talent Start-up Funds (A1098 5310 2360 1208)the Youth Innovation Promotion Association of CAS (2020458)National Natural Science Foundation of China (21464015, 21472235, 52122212, 12274391, 223210001)Beijing Natural Science Foundation (IS23045)
文摘Electrocatalytic 5-hydroxymethylfurfural oxidation reaction(HMFOR)provides a promising strategy to convert biomass derivative to highvalue-added chemicals.Herein,a cascade strategy is proposed to construct Pd-NiCo_(2)O_(4)electrocatalyst by Pd loading on Ni-doped Co3O4 and for highly active and stable synergistic HMF oxidation.An elevated current density of 800 mA cm^(-2)can be achieved at 1.5 V,and both Faradaic efficiency and yield of 2,5-furandicarboxylic acid remained close to 100%over 10 consecutive electrolysis.Experimental and theoretical results unveil that the introduction of Pd atoms can modulate the local electronic structure of Ni/Co,which not only balances the competitive adsorption of HMF and OH-species,but also promote the active Ni^(3+)species formation,inducing high indirect oxidation activity.We have also discovered that Ni incorporation facilitates the Co2+pre-oxidation and electrophilic OH*generation to contribute direct oxidation process.This work provides a new approach to design advanced electrocatalyst for biomass upgrading.
