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
The high-efficiency conversion of biomass resources to biofuels has attracted widespread attention, and the active sites and synergistic effect of catalysts significantly impact their surface arrangement and electroni...The high-efficiency conversion of biomass resources to biofuels has attracted widespread attention, and the active sites and synergistic effect of catalysts significantly impact their surface arrangement and electronic structure. Here, a nickel-based transition metal carbide catalyst(Ni/TMC) with high Lewis acidity was prepared by self-assembly of transition metal carbide(TMC) and nickel, which exhibited excellent performance on synergistic hydrogenation and hydrogenolysis of 5-hydroxymethylfurfural(HMF) into liquid biofuel 2,5-dimethylfuran(DMF).Notably, Ni/WC with the highest Lewis acidity(4728.3 μmol g^(-1)) can achieve 100% conversion of HMF to 97.6% yield of DMF, with a turnover frequency of up to 46.5 h^(-1). The characterization results demonstrate that the rich Lewis acid sites yielded by the synergistic effect between Ni species and TMC are beneficial for the C=O hydrogenation and C–O cleavage, thereby accelerating the process of hydrodeoxygenation(HDO). Besides, a kinetic model for the HDO of HMF to DMF process has been established based on the experimental results, which elucidated a significant correlation between the measured and the predicted data(R^(2)> 0.97). Corresponding to the adsorption configuration of Ni/WC and substrate determined by in-situ FTIR characterization, this study provides a novel insight into the selective conversion of HMF process for functional biofuel and bio-chemicals.展开更多
The electrochemical hydrogenation(ECH)of 5-hydroxymethylfurfural(HMF)to 2,5-dihydroxymethylfuran(DHMF)represents a pivotal pathway for the electrocatalytic upgrading of biomass-based organic small molecules,offering s...The electrochemical hydrogenation(ECH)of 5-hydroxymethylfurfural(HMF)to 2,5-dihydroxymethylfuran(DHMF)represents a pivotal pathway for the electrocatalytic upgrading of biomass-based organic small molecules,offering significant reductions in energy consumption while producing value-added chemicals.The conversion of HMF to DHMF is challenging due to the high reduction potential and complex intermediates of HMF ECH under neutral environment.Also,the total efficiency is hindered by sluggish anodic oxygen evolution reaction(OER)kinetics.Herein,we report a synthesis of highly alloyed Pd-Pt bimetallene(Pd3Pt1 BML)for HMF ECH coupled with formic acid oxidation reaction(FAOR).Through a combination of in-situ Raman spectroscopy,electron paramagnetic resonance analysis,and theoretical calculations,we elucidate that the HMF adsorption on Pd atoms,strategically separated by Pt atoms,is weakened compared to pure Pd surfaces.Additionally,Pt atoms serve as crucial providers of active hydrogen to neighboring Pd atoms,synergistically enhancing the reaction kinetics of HMF conversion with a Faradaic efficiency>93%.Meanwhile,the atomically dispersed Pt atoms endow Pd_(3)Pt_(1) BML with high electrochemical performance for the direct pathway of FAOR at the anode.As a result,a FAOR-assisted HMF ECH system equipped with bifunctional Pd3Pt1 BML achieves the energy-efficient conversion of HMF to DHMF at electrolysis voltage of 0.72 V at 10 mA cm^(–2).This work provides insights into the rational design of bifunctional catalysts featuring two distinct types of active sites for advanced energy electrocatalysis and ECH.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
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
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 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
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
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
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
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
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
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
BACKGROUND Most gastric cancer(GC)patients are diagnosed at middle or late stage because the symptoms in early stage are obscure,which causes higher mortality rates of GC.Helicobacter pylori(H.pylori)was identified as...BACKGROUND Most gastric cancer(GC)patients are diagnosed at middle or late stage because the symptoms in early stage are obscure,which causes higher mortality rates of GC.Helicobacter pylori(H.pylori)was identified as a class I carcinogen and leads to aberrant DNA methylation/hydroxymethylation.5-hydroxymethylcytosine(5-hmC)plays complex roles in gene regulation of tumorigenesis and can be considered as an activating epigenetic mark of hydroxymethylation.AIM To explore the association between 5-hmC levels and the progression and prognosis of GC patients with or without H.pylori infection.METHODS A retrospective cohort study was conducted to estimate the predicted value of 5-hmC level in the progression and prognosis of GC patients with different H.pylori infection status.A total of 144 GC patients were recruited.RESULTS The levels of 5-hmC were significantly decreased in tumor tissues(0.076±0.048)compared with the matched control tissues(0.110±0.057,P=0.001).A high level of 5-hmC was an independent significant favorable predictor of overall survival in GC patients(hazard ratio=0.61,95% confidence interval:0.38-0.98,P=0.040),the H.pylori-negative GC subgroup(hazard ratio=0.30,95% confidence interval:0.13-0.68,P=0.004)and the GC patients with TNM stage Ⅰ or Ⅱ(hazard ratio=0.32,95% confidence interval:0.13-0.77,P=0.011).CONCLUSION Increased 5-hmC is a favorable prognostic factor in GC,especially for H.pylori-negative subgroups.展开更多
Conversion of cellulose into platform chemical 5-hydroxymethylfurfural （HMF） in water-tetrahydrofuran （THF） co-solvents under acidic condition was studied. 38.6% of HMF was obtained with low cellulose concentratio...Conversion of cellulose into platform chemical 5-hydroxymethylfurfural （HMF） in water-tetrahydrofuran （THF） co-solvents under acidic condition was studied. 38.6% of HMF was obtained with low cellulose concentration of 2.4wt%, but levulinic acid （LA） and solid humins became the main products with high cellulose concentration. The soluble byproducts were analyzed by high performance liquid chromatography/multiple stage tandem mass spec-trometry, and chemicals with formula of C9H16O4、 C10H14O4、 C11H12O4、C12H10O5 and C12H16O8 were detected. THF could participate in the reaction via ring-opening into 1,4-butanediol followed by esterification with LA into C9H16O4 or etherification with HMF into C10H14O4. C11H12O4 was formed by esterification of HMF with LA, C12H10O5 was formed by self-etherification of HMF, while C12H16O8 was formed by acetalization of HMF with glucose. Self-etherification of HMF and etherification of HMF with 1,4-butanediol were identified as two main side reactions.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
The conversion of cellulose to 5-hydroxymethylfurfural （HMF） has been investigated by a one-pot consecutive reaction. At first, cellulose was depolymerised into glucose via a fast degradation of cellulose in molten ...The conversion of cellulose to 5-hydroxymethylfurfural （HMF） has been investigated by a one-pot consecutive reaction. At first, cellulose was depolymerised into glucose via a fast degradation of cellulose in molten ZnCI~ in the presence of hydrochloric acid, and the yield of glucose is 75% in 120 s at reaction temperature of 95 ℃. Then, DMSO was used as solvent and different kinds of metal chloride were added as catalysts, and the conversion was carried out continuously at 110-130 ℃ for 0.5-4 h. The yield of HMF was 53% when CrC13 were used as catalyst. The one-pot two steps conversion was carried out at atmosphere pressure, and it is a simple route to prepare HMF from lignocellulosic feedstock on a large scale.展开更多
In the present study, we hypothesized that 5-hydroxymethyl-2-furfural could attenuate ischemic brain damage by reducing oxidative injury. Thus, mice were subjected to bilateral common carotid artery occlusion to estab...In the present study, we hypothesized that 5-hydroxymethyl-2-furfural could attenuate ischemic brain damage by reducing oxidative injury. Thus, mice were subjected to bilateral common carotid artery occlusion to establish a model of permanent forebrain ischemia. The mice were intraperitoneally injected with 5-hydroxymethyl-2-furfura130 minutes before ischemia or 5 minutes after ischemia. The survival time of mice injected with 5-hydroxymethyl-2-furfural was longer compared with untreated mice. The mice subjected to ischemia for 30 minutes and reperfusion for 5 minutes were intraperitoneally injected with 5-hydroxymethyl-2-furfural 5 minutes prior to reperfusion, which increased superoxide dismutase content and reduced malondialdehyde content, similar to the effects of Edaravone, a hydroxyl radical scavenger used for the treatment of stroke. These findings indicate that intraperitoneal injection of 5-hydroxymethyl-2-furfural can prolong the survival of mice with permanent forebrain ischemia. This outcome may be mediated by its antioxidative effects.展开更多
In this study we report a new reaction pathway in which the hydroxyl and the aldehyde groups of 5-hydroxymethyl furfural were aminated respectively. Hydroxyl group was aminated via Ritter reaction followed by direct r...In this study we report a new reaction pathway in which the hydroxyl and the aldehyde groups of 5-hydroxymethyl furfural were aminated respectively. Hydroxyl group was aminated via Ritter reaction followed by direct reductive amination of aldehyde group. For the Ritter reaction of 5-hydroxymethyl furfural, mixture of trifluoromethane sulfonic acid and phosphoric anhydride showed good performance and the intermediate N-acyl-5-aminomethyl furfural with the highest yield of 89.1 wt% was obtained.Optimization of direct reductive amination of 2,5-bis（aminomethyl） furan was conducted and a yield of45.7 wt% was achieved. This study presents a simple way for preparing bis（amino）furans from renewable biomass based 5-hydroxymethyl furfural, which enriches the biorefinery concept from biomass.展开更多
Previous studies have shown that 5-hydroxymethylfurfural, a compound extracted from wine- processed Fructus corni, has a protective effect on hippocampal neurons. The present study was designed to explore the related ...Previous studies have shown that 5-hydroxymethylfurfural, a compound extracted from wine- processed Fructus corni, has a protective effect on hippocampal neurons. The present study was designed to explore the related mechanisms. Our study revealed that high and medium doses （10, 1 μmol/L） of 5-hydroxymethylfurfural could improve the morphology of H2O2-treated rat hippocampal neurons as revealed by inverted phase-contrast microscopy and transmission electron microscopy. MTT results showed that incubation with high and medium doses of 5-hydroxymethylfurfural caused a significant increase in the viability of neuronal cells injured by H2O2. Flow cytometry assays con- firmed that H2O2 could induce cell apoptosis, while high and medium doses of 5-hydroxymethylfurfural had a visible protective effect on apoptotic rat hippocampal neurons. Real-time PCR and western blot analysis showed that high and medium doses of 5-hydroxymethylfurfural prevented H2O2-induced up-regulation of p53, Bax and caspase-3 and an- tagonized the down-regulation of Bcl-2 induced by H2O2 treatment. These results suggested that 5-hydroxymethylfurfural could inhibit apoptosis of cultured rat hippocampal neurons injured by H2O2 via increase in Bcl-2 levels and decrease in p53, Bax and caspase-3 protein expression levels.展开更多
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.
基金Fundamental Research Foundation of CAF (CAFYBB2022QB001)National Nature Science Foundation of China for Excellent Young Scientists Fund (32222058)。
文摘The high-efficiency conversion of biomass resources to biofuels has attracted widespread attention, and the active sites and synergistic effect of catalysts significantly impact their surface arrangement and electronic structure. Here, a nickel-based transition metal carbide catalyst(Ni/TMC) with high Lewis acidity was prepared by self-assembly of transition metal carbide(TMC) and nickel, which exhibited excellent performance on synergistic hydrogenation and hydrogenolysis of 5-hydroxymethylfurfural(HMF) into liquid biofuel 2,5-dimethylfuran(DMF).Notably, Ni/WC with the highest Lewis acidity(4728.3 μmol g^(-1)) can achieve 100% conversion of HMF to 97.6% yield of DMF, with a turnover frequency of up to 46.5 h^(-1). The characterization results demonstrate that the rich Lewis acid sites yielded by the synergistic effect between Ni species and TMC are beneficial for the C=O hydrogenation and C–O cleavage, thereby accelerating the process of hydrodeoxygenation(HDO). Besides, a kinetic model for the HDO of HMF to DMF process has been established based on the experimental results, which elucidated a significant correlation between the measured and the predicted data(R^(2)> 0.97). Corresponding to the adsorption configuration of Ni/WC and substrate determined by in-situ FTIR characterization, this study provides a novel insight into the selective conversion of HMF process for functional biofuel and bio-chemicals.
文摘The electrochemical hydrogenation(ECH)of 5-hydroxymethylfurfural(HMF)to 2,5-dihydroxymethylfuran(DHMF)represents a pivotal pathway for the electrocatalytic upgrading of biomass-based organic small molecules,offering significant reductions in energy consumption while producing value-added chemicals.The conversion of HMF to DHMF is challenging due to the high reduction potential and complex intermediates of HMF ECH under neutral environment.Also,the total efficiency is hindered by sluggish anodic oxygen evolution reaction(OER)kinetics.Herein,we report a synthesis of highly alloyed Pd-Pt bimetallene(Pd3Pt1 BML)for HMF ECH coupled with formic acid oxidation reaction(FAOR).Through a combination of in-situ Raman spectroscopy,electron paramagnetic resonance analysis,and theoretical calculations,we elucidate that the HMF adsorption on Pd atoms,strategically separated by Pt atoms,is weakened compared to pure Pd surfaces.Additionally,Pt atoms serve as crucial providers of active hydrogen to neighboring Pd atoms,synergistically enhancing the reaction kinetics of HMF conversion with a Faradaic efficiency>93%.Meanwhile,the atomically dispersed Pt atoms endow Pd_(3)Pt_(1) BML with high electrochemical performance for the direct pathway of FAOR at the anode.As a result,a FAOR-assisted HMF ECH system equipped with bifunctional Pd3Pt1 BML achieves the energy-efficient conversion of HMF to DHMF at electrolysis voltage of 0.72 V at 10 mA cm^(–2).This work provides insights into the rational design of bifunctional catalysts featuring two distinct types of active sites for advanced energy electrocatalysis and ECH.
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.
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 National Natural Science Foundation of China,No.81874279Scientific and Technological Development Program of Jilin Province,No.20190201093JC and No.20200201326JC+1 种基金Jilin Province Department of Finance,No.JLSWSRCZX2020-010Youth Development Fund from First Hospital of Jilin University,No.JDYY11202021.
文摘BACKGROUND Most gastric cancer(GC)patients are diagnosed at middle or late stage because the symptoms in early stage are obscure,which causes higher mortality rates of GC.Helicobacter pylori(H.pylori)was identified as a class I carcinogen and leads to aberrant DNA methylation/hydroxymethylation.5-hydroxymethylcytosine(5-hmC)plays complex roles in gene regulation of tumorigenesis and can be considered as an activating epigenetic mark of hydroxymethylation.AIM To explore the association between 5-hmC levels and the progression and prognosis of GC patients with or without H.pylori infection.METHODS A retrospective cohort study was conducted to estimate the predicted value of 5-hmC level in the progression and prognosis of GC patients with different H.pylori infection status.A total of 144 GC patients were recruited.RESULTS The levels of 5-hmC were significantly decreased in tumor tissues(0.076±0.048)compared with the matched control tissues(0.110±0.057,P=0.001).A high level of 5-hmC was an independent significant favorable predictor of overall survival in GC patients(hazard ratio=0.61,95% confidence interval:0.38-0.98,P=0.040),the H.pylori-negative GC subgroup(hazard ratio=0.30,95% confidence interval:0.13-0.68,P=0.004)and the GC patients with TNM stage Ⅰ or Ⅱ(hazard ratio=0.32,95% confidence interval:0.13-0.77,P=0.011).CONCLUSION Increased 5-hmC is a favorable prognostic factor in GC,especially for H.pylori-negative subgroups.
基金This work was supported by the National Basic Research Program of China （No.2012CB215304）, the National Natural Science Foundation of China （No.51376185 and No.51161140331）, and the Natural Science Foundation of Guangdong Province （No.S2013010011612）.
文摘Conversion of cellulose into platform chemical 5-hydroxymethylfurfural （HMF） in water-tetrahydrofuran （THF） co-solvents under acidic condition was studied. 38.6% of HMF was obtained with low cellulose concentration of 2.4wt%, but levulinic acid （LA） and solid humins became the main products with high cellulose concentration. The soluble byproducts were analyzed by high performance liquid chromatography/multiple stage tandem mass spec-trometry, and chemicals with formula of C9H16O4、 C10H14O4、 C11H12O4、C12H10O5 and C12H16O8 were detected. THF could participate in the reaction via ring-opening into 1,4-butanediol followed by esterification with LA into C9H16O4 or etherification with HMF into C10H14O4. C11H12O4 was formed by esterification of HMF with LA, C12H10O5 was formed by self-etherification of HMF, while C12H16O8 was formed by acetalization of HMF with glucose. Self-etherification of HMF and etherification of HMF with 1,4-butanediol were identified as two main side reactions.
基金National Natural Science Foundation of China(22272150,22302177)Major Program of Zhejiang Provincial Natural Science Foundation of China(LD22B030002)+2 种基金Zhejiang Provincial Ten Thousand Talent Program(2021R51009)Public Technology Application Project of Jinhua City(2022-4-067)Self Designed Scientific Research of Zhejiang Normal University(2021ZS0604)。
文摘Biomass conversion offers an efficient approach to alleviate the energy and environmental issues.Electrochemical oxidation of 5-hydroxymethylfurfural(HMF)has attracted tremendous attention in the latest few years for the mild synthesis conditions and high conversion efficiency to obtain 2,5-furan dicarboxylic acid(FDCA),but there still remain problems such as limited yield,short cycle life,and ambiguous reaction mechanism.Despite many reviews highlighting a variety of electrocatalysts for electrochemical oxidation of HMF,a detailed discussion of the structural modulation of catalyst and the underlying catalytic mechanism is still lacking.We herein provide a comprehensive summary of the recent development of electrochemical oxidation of HMF to FDCA,particularly focusing on the mechanism studies as well as the advanced strategies developed to regulate the structure and optimize the performance of the electrocatalysts,including heterointerface construction,defect engineering,single-atom engineering,and in situ reconstruction.Experimental characterization techniques and theoretical calculation methods for mechanism and active site studies are elaborated,and challenges and future directions of electrochemical oxidation of HMF are also prospected.This review will provide guidance for designing advanced catalysts and deepening the understanding of the reaction mechanism beneath electrochemical oxidation of HMF to FDCA.
文摘The conversion of cellulose to 5-hydroxymethylfurfural （HMF） has been investigated by a one-pot consecutive reaction. At first, cellulose was depolymerised into glucose via a fast degradation of cellulose in molten ZnCI~ in the presence of hydrochloric acid, and the yield of glucose is 75% in 120 s at reaction temperature of 95 ℃. Then, DMSO was used as solvent and different kinds of metal chloride were added as catalysts, and the conversion was carried out continuously at 110-130 ℃ for 0.5-4 h. The yield of HMF was 53% when CrC13 were used as catalyst. The one-pot two steps conversion was carried out at atmosphere pressure, and it is a simple route to prepare HMF from lignocellulosic feedstock on a large scale.
基金supported by the National Basic Research Program of China (973 Program),No.2003CB517104the National Natural Science Foundation of China,No.30973513+3 种基金Beijing Municipal Science and Technology Program,No.D0206001043191the Natural Science Foundation of Beijing,No.7112061Beijing Key Foundation of Traditional Chinese Medicine,No.KJTS2011-04Beijing Health and Technical Personal of High-Level Plan,No.2009-3-66
文摘In the present study, we hypothesized that 5-hydroxymethyl-2-furfural could attenuate ischemic brain damage by reducing oxidative injury. Thus, mice were subjected to bilateral common carotid artery occlusion to establish a model of permanent forebrain ischemia. The mice were intraperitoneally injected with 5-hydroxymethyl-2-furfura130 minutes before ischemia or 5 minutes after ischemia. The survival time of mice injected with 5-hydroxymethyl-2-furfural was longer compared with untreated mice. The mice subjected to ischemia for 30 minutes and reperfusion for 5 minutes were intraperitoneally injected with 5-hydroxymethyl-2-furfural 5 minutes prior to reperfusion, which increased superoxide dismutase content and reduced malondialdehyde content, similar to the effects of Edaravone, a hydroxyl radical scavenger used for the treatment of stroke. These findings indicate that intraperitoneal injection of 5-hydroxymethyl-2-furfural can prolong the survival of mice with permanent forebrain ischemia. This outcome may be mediated by its antioxidative effects.
基金the financial support from the National Natural Science Foundation of China(no.21676223 and no.21506177)the Fujian Provincial Development and Reform Commission,China(no.2015489)+1 种基金the Natural Science Foundation of Fujian Province of China(no.2016J01077 and no.2015J05034)the Fundamental Research Funds for the Central Universities of China(nos.20720160077 and 20720160087)
文摘In this study we report a new reaction pathway in which the hydroxyl and the aldehyde groups of 5-hydroxymethyl furfural were aminated respectively. Hydroxyl group was aminated via Ritter reaction followed by direct reductive amination of aldehyde group. For the Ritter reaction of 5-hydroxymethyl furfural, mixture of trifluoromethane sulfonic acid and phosphoric anhydride showed good performance and the intermediate N-acyl-5-aminomethyl furfural with the highest yield of 89.1 wt% was obtained.Optimization of direct reductive amination of 2,5-bis（aminomethyl） furan was conducted and a yield of45.7 wt% was achieved. This study presents a simple way for preparing bis（amino）furans from renewable biomass based 5-hydroxymethyl furfural, which enriches the biorefinery concept from biomass.
基金financially supported by the National Natural Science Foundation of China,No.30772851a grant from the Six Talents Peaks Program of Jiangsu Province,Chinaa grant from the Priority Academic Program Development of Jiangsu Higher Education Institutions,PAPD(Traditional Chinese medicine combined with Western Medicine
文摘Previous studies have shown that 5-hydroxymethylfurfural, a compound extracted from wine- processed Fructus corni, has a protective effect on hippocampal neurons. The present study was designed to explore the related mechanisms. Our study revealed that high and medium doses （10, 1 μmol/L） of 5-hydroxymethylfurfural could improve the morphology of H2O2-treated rat hippocampal neurons as revealed by inverted phase-contrast microscopy and transmission electron microscopy. MTT results showed that incubation with high and medium doses of 5-hydroxymethylfurfural caused a significant increase in the viability of neuronal cells injured by H2O2. Flow cytometry assays con- firmed that H2O2 could induce cell apoptosis, while high and medium doses of 5-hydroxymethylfurfural had a visible protective effect on apoptotic rat hippocampal neurons. Real-time PCR and western blot analysis showed that high and medium doses of 5-hydroxymethylfurfural prevented H2O2-induced up-regulation of p53, Bax and caspase-3 and an- tagonized the down-regulation of Bcl-2 induced by H2O2 treatment. These results suggested that 5-hydroxymethylfurfural could inhibit apoptosis of cultured rat hippocampal neurons injured by H2O2 via increase in Bcl-2 levels and decrease in p53, Bax and caspase-3 protein expression levels.
