Converting carbohydrates into 5-hydroxymethylfurfural(5-HMF) is an attractive and promising route for value-added utilization of agricultural and forestry biomass resource. As an important platform compound, 5-HMF pos...Converting carbohydrates into 5-hydroxymethylfurfural(5-HMF) is an attractive and promising route for value-added utilization of agricultural and forestry biomass resource. As an important platform compound, 5-HMF possesses high active furan structure with hydroxymethyl and aldehyde group for production of various bio-chemicals and materials, meanwhile, which suffer from low stability and poor yield during the industrial biorefinery process. Hence, selective production of 5-HMF with high-yield and low-cost has attracted extensive attention from scientific and industrial researchers. This review sorted and described the latest advanced research on solvent and catalyst system, as well as energy field effect for production of 5-HMF with different feedstock in detail, emphatically discussing the solvent effect and its synergistic effect with other aspects. Besides, the future prospects and challenges for production of 5-HMF from carbohydrates were also presented, which provide a profound insight into industrial 5-HMF process with economic and environmental feature.展开更多
2,5-Furandicarboxylic acid(FDCA)is a promising biomass-derived polymeric monomer that serves as an attractive alternative to terephthalic acid derived from fossil resources.However,the green and efficient production o...2,5-Furandicarboxylic acid(FDCA)is a promising biomass-derived polymeric monomer that serves as an attractive alternative to terephthalic acid derived from fossil resources.However,the green and efficient production of FDCA through the oxidation of 5-hydroxymethylfurfural(HMF)and its derivatives is still rudimentary under base-free conditions.In this work,oxygen-vacancy-rich Mn Oxwas prepared and displayed a strong adsorption and anchoring ability to Ru species that mainly exposed the(210)plane of RuO_(2),bringing about highly dispersed and active interfacial Ru-O-Mn structures.Experimental results and density functional theory calculations confirm that these above features greatly facilitate the adsorption/activation of oxygen and the dehydrogenation-oxidation of HMF/5-methoxymethylfurfural(MMF),which enables an efficient FDCA production under base-free and mild conditions.Notably,a desirable FDCA yield of 86.56%was still obtained from concentrated HMF(10 wt%)under base-free conditions over oxygen-vacancy-rich Mn Oxsupported Ru Ox(1.0 MPaO_(2),120℃,6 h).This work delineates a facile catalyst preparation strategy for HMF/MMF oxidation,and might open a new avenue for the green synthesis of FDCA under base-free conditions.展开更多
Biomass,derived from plant photosynthesis that captures carbon dioxide to form carbohydrates,offers vast renewable reserves.The electrooxidation of biomass,coupled with the hydrogen evolution reaction,enables the simu...Biomass,derived from plant photosynthesis that captures carbon dioxide to form carbohydrates,offers vast renewable reserves.The electrooxidation of biomass,coupled with the hydrogen evolution reaction,enables the simultaneous production of biomass-based plastic monomers and green hydrogen,attracting significant scholarly interest.However,ambiguity remains regarding the adsorption mechanism at the catalyst surface(Langmuir-Hinshelwood or Eley-Rideal)and the adsorbed substrate groups.To address this,we prepared a Ni/Co electrode for the electrooxidation of 5-hydroxymethylfurfural(HMF)into 2,5-furandicarboxylic acid(FDCA)through a corrosion reaction and electro-reduction pathway.HMF conversion reached 100.00%,FDCA yield reached 96.82%,and Faradic efficiency(FE)reached 92.14%.Meaningfully,utilizing in-situ spectroscopy and electrochemical methods,this work provided valuable insights into active sites and catalyst surface adsorption.展开更多
Highly-efficient oxidation of 5-hydroxymethylfurtural(HMF) to 2,5-furandicarboxylic acid(FDCA) at low temperature with air as the oxidant is still challenging.Herein,inspired by the respirato ry electron transport cha...Highly-efficient oxidation of 5-hydroxymethylfurtural(HMF) to 2,5-furandicarboxylic acid(FDCA) at low temperature with air as the oxidant is still challenging.Herein,inspired by the respirato ry electron transport chain(ETC) of living cells mediated by electron carriers,we constructed artificial ETCs and transformed liquid flow fuel cells(LFFCs) to flexible reactors for efficient oxidation of HMF to produce FDCA under mild conditions.This LFFC reactor employed an electrodeposition modified nickel foam as an anode to promote HMF oxidation and(VO_(2))_(2)SO_(4) as a cathode electron carrier to facilitate the electron transfer to air.The reaction rate could be easily controlled by selecting the anode catalyst,adjusting the external loading and changing the cathodic electron carrier or oxidants.A maximal power density of 44.9 mW cm^(-2) at room temperature was achieved,while for FDCA production,short-circuit condition was preferred to achieve quick transfer of electrons.For a single batch operation with 0.1 M initial HMF,FDCA yield reached 97.1%.By fed-batch operation,FDCA concentration reached 144.5 g L^(-1) with a total yield of 96%.Ni^(2+)/Ni^(3+) redox couple was the active species mediating the electron transfer,while both experimental and DFT calculation results indicated that HMFCA pathway was the preferred reaction mechanism.展开更多
High-efficient production of 5-hydroxymethylfurfural(HMF),a“sleeping giant”in sustainable chemistry,from cellulose depends significantly on the effective separation of cellulose from lignocellulosic biomass.Herein,w...High-efficient production of 5-hydroxymethylfurfural(HMF),a“sleeping giant”in sustainable chemistry,from cellulose depends significantly on the effective separation of cellulose from lignocellulosic biomass.Herein,we report the fractional separation of wheat straw cellulose(WSC)from wheat straw under solvothermal conditions using a mixed solvent of γ-valerolactone(GVL)and H_(2)O as the separating solvent,wherein the impacts of fractional separation parameters(solvent composition,temperature,and time)on removals of lignin and hemicellulose as well as purity and recovery of cellulose were studied by a Box-Behnken Design of response surface method.The optimization of the solvothermal parameters enabled an optimal fractional separation condition(V_(GVL):~60.0%,T:205℃,t:~1.7 h)that led to a higher purity(89.4%)and recovery(86.7%)of cellulose in WSC.A further correlation of the removals of lignin and hemicellulose as well as purity and recovery of cellulose with the yield of HMF excluded an independent influence of the above factors.Instead,a comprehensive contribution of high fractional separation efficiency(defined as the product of cellulose purity and recovery)and low crystallinity of WSC was found to improve the HMF yield.However,the heat-and freeze-dryings of WSC after the solvothermal separation were found to lower the HMF molar yield because it re-improved the crystallinity of WSC.A high HMF molar yield of 58.6%was achieved after reacting wet-WSC in a mixed solvent of 1,4-dioxane and H_(2)O at 180℃for 20 min,which was 1.5 fold higher than that from microcrystalline cellulose.This work highlights the importance of enhancing the fractional separation efficiency of cellulose from lignocellulosic biomass while avoiding the drying process for future HMF biorefinery.展开更多
With the continuous improvement of solar energy production capacity,how to effectively use the electricity generated by renewable solar energy for electrochemical conversion of biomass is a hot topic.Electrochemical c...With the continuous improvement of solar energy production capacity,how to effectively use the electricity generated by renewable solar energy for electrochemical conversion of biomass is a hot topic.Electrochemical conversion of 5-hydroxymethylfurfural(HMF)to biofuels and value-added oxygenated commodity chemicals provides a promising and alternative pathway to convert re-newable electricity into chemicals.Although nickel-based eletrocatalysts are well-known for HMF oxidation,their relatively low intrinsic activity,poor conductivity and stability still limit the poten-tial applications.Here,we report the fabrication of a freestanding nickel-based electrode,in which Ni(OH)_(2) species were in-situ constructed on Ni foam(NF)support using a facile ac-id-corrosion-induced strategy.The Ni(OH)2/NF electrocatalyst exhibits stable and efficient electro-chemical HMF oxidation into 2,5-furandicarboxylic acid(FDCA)with HMF conversion close to 100% with high Faraday efficiency.In-situ formation strategy results in a compact interface between Ni(OH)_(2) and NF,which contributes to good conductivity and stability during electrochemical reac-tions.The superior performance benefits from dynamic cyclic evolution of Ni(OH)_(2) to NiOOH,which acts as the reactive species for HMF oxidation to FDCA.A scaled-up device based on a continu-ous-flow electrolytic cell was also established,giving stable operation with a high FDCA production rate of 27 mg h^(-1)cm^(−2).This job offers a straightforward,economical,and scalable design strategy to design efficient and durable catalysts for electrochemical conversion of valuable chemicals.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
Renewable resources based polymers provides a sustainable alternative to petroleum derived polymeric materials.As a part of our series on synthesis of vanillin based renewable polymers,we report the synthesis of poly(...Renewable resources based polymers provides a sustainable alternative to petroleum derived polymeric materials.As a part of our series on synthesis of vanillin based renewable polymers,we report the synthesis of poly(hydrovanilloin-furfural)[poly(HVL-Fur)]and poly(hydrovanilloin–5-hydromethylfurfural)[poly(HVL-5-HMF)].Vanillin was dimerized to a mixtures of meso/DL-hydrovanilloins with 94%meso product by electrochemical reductive coupling in aqueous sodium hydroxide using lead electrodes in quantitative yield.Then sodium hydroxide catalyzed condensation of hydrovanilloin with furfural in water at 80℃for 72 h was used to synthesize poly(HVL-Fur)with Mw=8600 g mol^(−1),PDI=1.28 in 78%yield.Similarly,condensation of hydrovanilloin with 5-hydroxymethylfurfural at 80℃for 48 h produced poly(HVL-5-HMF)with Mw=12,100 g mol−1,PDI=1.27 in 68%yield.poly(HVL-Fur)and poly(HVL-5-HMF)showed similar Tg values of 59℃and 60℃,respectively;whereas melting behaviors are dissimilar with Tm 171℃–173℃and 148℃–182℃,respectively.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
The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical in...The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical industry.Here,we precisely constructed carbon nitride supported Pd-based catalysts by a simple impregnation-reduction method.By changing the reduction temperature,catalysts with different oxidation state could be precisely constructed.Moreover,the important correlation between the ratio of Pd^(0)/Pd^(2+)and catalytic activity is revealed during the selective hydrogenation of HMF.The Pd/g—C_(3)N_(4)—300 catalyst with a Pd^(0)/Pd^(2+)ratio of 3/2 showed the highest catalytic activity,which could get 96.9%5-hydroxymethylfurfural conversion and 90.3%2,5-dihydroxymethylfuran selectivity.Further density functional theory calculation revealed that the synergistic effect between Pd0and Pd2+in Pd/g—C_(3)N_(4)—300 system could boost the adsorption of the substrate and the dissociation of hydrogen.In this work,we highlight the important correlation between metal oxidation state and catalytic activity,which provides valuable insights for the rational design of precious metal catalysts for hydrogenation reactions.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
[Objectives]To explore the effect of storage time on pH and 5-hydroxymethylfurfural content in Jiulongteng honey.[Methods]The pH of Jiulongteng honey was determined by neutralization titration with sodium hydroxide st...[Objectives]To explore the effect of storage time on pH and 5-hydroxymethylfurfural content in Jiulongteng honey.[Methods]The pH of Jiulongteng honey was determined by neutralization titration with sodium hydroxide standard solution.The content of 5-hydroxymethylfurfural in Jiulongteng honey was determined by HPLC.Chromatographic conditions:ZORBAX SB-C 18 column(250 mm×4.6 mm,5μm)from Agilent Co.,Ltd.,acetonitrile-0.1%formic acid solution(5:95)as mobile phase,flow rate of 0.8 mL/min,5-hydroxymethylfurfural detection wavelength of 284 nm,guanosine detection wavelength of 254 nm.[Results]The pH of 12 batches of Jiulongteng honey was 3.70-3.84 in the new honey stage,3.92-4.05 in the old honey stage 1,and 4.25-4.53 in the old honey stage 2;5-hydroxymethylfurfural was not detected in the new honey stage,5-hydroxymethylfurfural was detected in FM-001 in the old honey stage 1,and 5-hydroxymethylfurfural was detected in most samples in the old honey stage 2.[Conclusions]The pH and 5-hydroxymethylfurfural content of 12 batches of Jiulongteng honey met the requirements within 3 years of storage.There was no 5-hydroxymethylfurfural in Jiulongteng honey,but with the extension of storage time,the detection amount of 5-hydroxymethylfurfural increased significantly even if Jiulongteng honey was stored at low temperature.Therefore,5-hydroxymethylfurfural can be used as an important indicator of honey freshness.展开更多
The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventio nal thermocatalytic route for the production of high-value-added chemicals from biomass resources.In virtue of the wide poten...The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventio nal thermocatalytic route for the production of high-value-added chemicals from biomass resources.In virtue of the wide potential window with promising Faradic efficiency(FE) towards BHMF,Cu-based electrode has been in the center of investigation.However,its structure-activity relationship remains ambiguous and its intrinsic catalytic activity is still unsatisfactory.In this work,we develop a two-step oxidation-reduction strategy to reconstruct the surface atom arrangement of the Cu foam(CF).By combination of multiple quasi-situ/in-situ techniques and density functional theory(DFT) calculation,the critical factor that governs the reaction is demonstrated to be facet effect of the metallic Cu crystal:Cu(110) facet accounts for the most favorable surface with enhanced chemisorption with reactants and selective production of BHMF,while Cu(100) facet might trigger the accumulation of the by-product 5,5'-bis(hydroxy methy)hydrofurion(BHH).With the optimized composition of the facets on the reconstructed Cu(OH)_(2)-ER/CF,the performance could be noticeably enhanced with a BHMF FE of 92.3% and HMF conversion of 98.5% at a potential of -0.15 V versus reversible hydrogen electrode(vs.RHE) in 0.1 M KOH solution.This work sheds light on the incomplete mechanistic puzzle for Cu-catalyzed electrochemical hydrogenation of HMF to BHMF,and provides a theoretical foundation for further precise design of highly efficient catalytic electrodes.展开更多
Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of met...Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of metal oxide modified MO_(x)-Au/TiO_(2)(M=Fe,Co,Ni)catalysts with low Au loading amount of 0.5 wt%were synthesized.Addition of transition metal oxides promotes electron transfer and generation of the Au^(δ-)-O_(v)-Ti^(3+)interface.A combination study reveals that the dual-active site(Au^(δ-)-O_(v)-Ti^(3+))governs the catalytic performance of the ratedetermining step,namely hydroxyl group oxidation.Au^(δ-) site facilitates chemisorption and activation of O_(2) molecules.At the same time,O_(v)-Ti^(3+) site acts as the role of“killing two birds with one stone”:enhancing adsorption of both reactants,accelerating the activation and dissociation of H_(2)O,and facilitating activation of the adsorbed O_(2).Besides,superoxide radicals instead of base is the active oxygen species during the rate-determining step.On this basis,a FDCA yield of 71.2% was achieved under base-free conditions,complying with the“green chemistry”principle.This work provides a new strategy for the transition metal oxides modification of Au-based catalysts,which would be constructive for the rational design of other heterogeneous catalysts.展开更多
食品加工过程中的美拉德反应有助于形成一些热诱导毒性产物,包括晚期糖基化终末产物(advanced glycation end products,AGEs)和5-羟甲基糠醛(5-hydroxymethylfurfural,5-HMF)。食源性AGEs在体内的积累和循环与糖尿病并发症的发生有关,...食品加工过程中的美拉德反应有助于形成一些热诱导毒性产物,包括晚期糖基化终末产物(advanced glycation end products,AGEs)和5-羟甲基糠醛(5-hydroxymethylfurfural,5-HMF)。食源性AGEs在体内的积累和循环与糖尿病并发症的发生有关,同时可能诱发氧化应激、炎症和动脉粥样硬化。5-HMF的代谢物5-磺基氧甲基糠醛(5-sulfooxymethylfurfural,5-SMF)有潜在基因毒性和致癌性。如何控制热加工食品中这些危害物的形成已成为食品行业的关注焦点。本文从美拉德反应和焦糖化反应两条途径探究了AGEs和5-HMF的形成机理,并对近5年二者的检测方法进行了综述,阐述了各类方法的优缺点,以期为建立二者的通用检测方法奠定基础。在此基础上,从削减前体物质的供给、阻断中间体的转化,以及去除已经生成的AGEs和5-HMF这3个方面着手,综述了近年来相应所采用的抑制策略,以期为AGEs和5-HMF在食品中的控制及热加工食品质量与安全管理提供理论依据。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
This study investigated the conversion of sugars into furan derivatives,specifically 2,5-dimethylfuran,through catalytic processes using bibliographic analysis.This method evaluates scientific outcomes and impact with...This study investigated the conversion of sugars into furan derivatives,specifically 2,5-dimethylfuran,through catalytic processes using bibliographic analysis.This method evaluates scientific outcomes and impact within a specific field by analyzing data such as publication trends,references,collaborative models,leading authors,and institutions.The study utilized data fromthe reliable Scopus database and conducted analysis using the visualization of similarity(VOS)viewer program to gain in-depth insights into the current state of research on this topic.The findings revealed that“5 hydroxymethyl furfural”was the most used keyword,followed by“biomass”and“catalysis.”The research trend remained stable and popular from 2006 to 2022,with a decline beginning in 2023.The growing number of publications indicates increasing interest and importance of these topics.Notably,China led in the number of publications,with 80%more than the second-rankedUnited States,followed closely by India in the third place.The study also highlighted citation linkages between authors and countries,providing a comprehensive overview of research on converting sugars to furan derivatives,particularly 2,5-dimethylfuran,through catalytic processes.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
基金supported by the National Nature Science Foundation of China (32222058, 32001274)the Youth Talent Support Program for Science & Technology Innovation of National Forestry and Grassland (2019132603) for financial support。
文摘Converting carbohydrates into 5-hydroxymethylfurfural(5-HMF) is an attractive and promising route for value-added utilization of agricultural and forestry biomass resource. As an important platform compound, 5-HMF possesses high active furan structure with hydroxymethyl and aldehyde group for production of various bio-chemicals and materials, meanwhile, which suffer from low stability and poor yield during the industrial biorefinery process. Hence, selective production of 5-HMF with high-yield and low-cost has attracted extensive attention from scientific and industrial researchers. This review sorted and described the latest advanced research on solvent and catalyst system, as well as energy field effect for production of 5-HMF with different feedstock in detail, emphatically discussing the solvent effect and its synergistic effect with other aspects. Besides, the future prospects and challenges for production of 5-HMF from carbohydrates were also presented, which provide a profound insight into industrial 5-HMF process with economic and environmental feature.
基金the funding supported by the National Natural Science Foundation of China(22378338,22078275)the Natural Science Foundation of Fujian Province of China(2021H0009)the Fundamental Research Funds for the Central Universities(20720220065)。
文摘2,5-Furandicarboxylic acid(FDCA)is a promising biomass-derived polymeric monomer that serves as an attractive alternative to terephthalic acid derived from fossil resources.However,the green and efficient production of FDCA through the oxidation of 5-hydroxymethylfurfural(HMF)and its derivatives is still rudimentary under base-free conditions.In this work,oxygen-vacancy-rich Mn Oxwas prepared and displayed a strong adsorption and anchoring ability to Ru species that mainly exposed the(210)plane of RuO_(2),bringing about highly dispersed and active interfacial Ru-O-Mn structures.Experimental results and density functional theory calculations confirm that these above features greatly facilitate the adsorption/activation of oxygen and the dehydrogenation-oxidation of HMF/5-methoxymethylfurfural(MMF),which enables an efficient FDCA production under base-free and mild conditions.Notably,a desirable FDCA yield of 86.56%was still obtained from concentrated HMF(10 wt%)under base-free conditions over oxygen-vacancy-rich Mn Oxsupported Ru Ox(1.0 MPaO_(2),120℃,6 h).This work delineates a facile catalyst preparation strategy for HMF/MMF oxidation,and might open a new avenue for the green synthesis of FDCA under base-free conditions.
基金the financial support from the National Natural Science Foundation of China(22072170)the Zhejiang Provincial Key Research and Development Program(2021C03170)the Ningbo Science and Technology Bureau(2019B10096)。
文摘Biomass,derived from plant photosynthesis that captures carbon dioxide to form carbohydrates,offers vast renewable reserves.The electrooxidation of biomass,coupled with the hydrogen evolution reaction,enables the simultaneous production of biomass-based plastic monomers and green hydrogen,attracting significant scholarly interest.However,ambiguity remains regarding the adsorption mechanism at the catalyst surface(Langmuir-Hinshelwood or Eley-Rideal)and the adsorbed substrate groups.To address this,we prepared a Ni/Co electrode for the electrooxidation of 5-hydroxymethylfurfural(HMF)into 2,5-furandicarboxylic acid(FDCA)through a corrosion reaction and electro-reduction pathway.HMF conversion reached 100.00%,FDCA yield reached 96.82%,and Faradic efficiency(FE)reached 92.14%.Meaningfully,utilizing in-situ spectroscopy and electrochemical methods,this work provided valuable insights into active sites and catalyst surface adsorption.
基金supported by the National Key R&D Program of China(2022YFA2105900)the National Natural Science Foundation of China(22178197)。
文摘Highly-efficient oxidation of 5-hydroxymethylfurtural(HMF) to 2,5-furandicarboxylic acid(FDCA) at low temperature with air as the oxidant is still challenging.Herein,inspired by the respirato ry electron transport chain(ETC) of living cells mediated by electron carriers,we constructed artificial ETCs and transformed liquid flow fuel cells(LFFCs) to flexible reactors for efficient oxidation of HMF to produce FDCA under mild conditions.This LFFC reactor employed an electrodeposition modified nickel foam as an anode to promote HMF oxidation and(VO_(2))_(2)SO_(4) as a cathode electron carrier to facilitate the electron transfer to air.The reaction rate could be easily controlled by selecting the anode catalyst,adjusting the external loading and changing the cathodic electron carrier or oxidants.A maximal power density of 44.9 mW cm^(-2) at room temperature was achieved,while for FDCA production,short-circuit condition was preferred to achieve quick transfer of electrons.For a single batch operation with 0.1 M initial HMF,FDCA yield reached 97.1%.By fed-batch operation,FDCA concentration reached 144.5 g L^(-1) with a total yield of 96%.Ni^(2+)/Ni^(3+) redox couple was the active species mediating the electron transfer,while both experimental and DFT calculation results indicated that HMFCA pathway was the preferred reaction mechanism.
基金supported by the National Natural Science Foundation of China(22378277)the 111 project(B17030)the Basal Research Fund of the Central University(2016SCU04B06).
文摘High-efficient production of 5-hydroxymethylfurfural(HMF),a“sleeping giant”in sustainable chemistry,from cellulose depends significantly on the effective separation of cellulose from lignocellulosic biomass.Herein,we report the fractional separation of wheat straw cellulose(WSC)from wheat straw under solvothermal conditions using a mixed solvent of γ-valerolactone(GVL)and H_(2)O as the separating solvent,wherein the impacts of fractional separation parameters(solvent composition,temperature,and time)on removals of lignin and hemicellulose as well as purity and recovery of cellulose were studied by a Box-Behnken Design of response surface method.The optimization of the solvothermal parameters enabled an optimal fractional separation condition(V_(GVL):~60.0%,T:205℃,t:~1.7 h)that led to a higher purity(89.4%)and recovery(86.7%)of cellulose in WSC.A further correlation of the removals of lignin and hemicellulose as well as purity and recovery of cellulose with the yield of HMF excluded an independent influence of the above factors.Instead,a comprehensive contribution of high fractional separation efficiency(defined as the product of cellulose purity and recovery)and low crystallinity of WSC was found to improve the HMF yield.However,the heat-and freeze-dryings of WSC after the solvothermal separation were found to lower the HMF molar yield because it re-improved the crystallinity of WSC.A high HMF molar yield of 58.6%was achieved after reacting wet-WSC in a mixed solvent of 1,4-dioxane and H_(2)O at 180℃for 20 min,which was 1.5 fold higher than that from microcrystalline cellulose.This work highlights the importance of enhancing the fractional separation efficiency of cellulose from lignocellulosic biomass while avoiding the drying process for future HMF biorefinery.
文摘With the continuous improvement of solar energy production capacity,how to effectively use the electricity generated by renewable solar energy for electrochemical conversion of biomass is a hot topic.Electrochemical conversion of 5-hydroxymethylfurfural(HMF)to biofuels and value-added oxygenated commodity chemicals provides a promising and alternative pathway to convert re-newable electricity into chemicals.Although nickel-based eletrocatalysts are well-known for HMF oxidation,their relatively low intrinsic activity,poor conductivity and stability still limit the poten-tial applications.Here,we report the fabrication of a freestanding nickel-based electrode,in which Ni(OH)_(2) species were in-situ constructed on Ni foam(NF)support using a facile ac-id-corrosion-induced strategy.The Ni(OH)2/NF electrocatalyst exhibits stable and efficient electro-chemical HMF oxidation into 2,5-furandicarboxylic acid(FDCA)with HMF conversion close to 100% with high Faraday efficiency.In-situ formation strategy results in a compact interface between Ni(OH)_(2) and NF,which contributes to good conductivity and stability during electrochemical reac-tions.The superior performance benefits from dynamic cyclic evolution of Ni(OH)_(2) to NiOOH,which acts as the reactive species for HMF oxidation to FDCA.A scaled-up device based on a continu-ous-flow electrolytic cell was also established,giving stable operation with a high FDCA production rate of 27 mg h^(-1)cm^(−2).This job offers a straightforward,economical,and scalable design strategy to design efficient and durable catalysts for electrochemical conversion of valuable chemicals.
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funded by United States National Science Foundation(NSF)Grant HRD-1036593USDA-NIFA Grant 12684238:Award No.2020-65209-31474United States Department of Energy Grant DE-SC0023345.
文摘Renewable resources based polymers provides a sustainable alternative to petroleum derived polymeric materials.As a part of our series on synthesis of vanillin based renewable polymers,we report the synthesis of poly(hydrovanilloin-furfural)[poly(HVL-Fur)]and poly(hydrovanilloin–5-hydromethylfurfural)[poly(HVL-5-HMF)].Vanillin was dimerized to a mixtures of meso/DL-hydrovanilloins with 94%meso product by electrochemical reductive coupling in aqueous sodium hydroxide using lead electrodes in quantitative yield.Then sodium hydroxide catalyzed condensation of hydrovanilloin with furfural in water at 80℃for 72 h was used to synthesize poly(HVL-Fur)with Mw=8600 g mol^(−1),PDI=1.28 in 78%yield.Similarly,condensation of hydrovanilloin with 5-hydroxymethylfurfural at 80℃for 48 h produced poly(HVL-5-HMF)with Mw=12,100 g mol−1,PDI=1.27 in 68%yield.poly(HVL-Fur)and poly(HVL-5-HMF)showed similar Tg values of 59℃and 60℃,respectively;whereas melting behaviors are dissimilar with Tm 171℃–173℃and 148℃–182℃,respectively.
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.
基金supported by the National Key Research and Development Program of China(2021YFA1500500)。
文摘The highly selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dihydroxymethylfuran is an important reaction in the field of biomass hydrogenation,because it is a bridge between biomass resources and chemical industry.Here,we precisely constructed carbon nitride supported Pd-based catalysts by a simple impregnation-reduction method.By changing the reduction temperature,catalysts with different oxidation state could be precisely constructed.Moreover,the important correlation between the ratio of Pd^(0)/Pd^(2+)and catalytic activity is revealed during the selective hydrogenation of HMF.The Pd/g—C_(3)N_(4)—300 catalyst with a Pd^(0)/Pd^(2+)ratio of 3/2 showed the highest catalytic activity,which could get 96.9%5-hydroxymethylfurfural conversion and 90.3%2,5-dihydroxymethylfuran selectivity.Further density functional theory calculation revealed that the synergistic effect between Pd0and Pd2+in Pd/g—C_(3)N_(4)—300 system could boost the adsorption of the substrate and the dissociation of hydrogen.In this work,we highlight the important correlation between metal oxidation state and catalytic activity,which provides valuable insights for the rational design of precious metal catalysts for hydrogenation reactions.
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Supported by Young and Middle-aged Teachers Scientific Research Basic Ability Improvement Project in Universities of Guangxi in 2020 (2020 KY07040)School-level Scientific Research Project of Guangxi University of Chinese Medicine in 2021 (2021MS010).
文摘[Objectives]To explore the effect of storage time on pH and 5-hydroxymethylfurfural content in Jiulongteng honey.[Methods]The pH of Jiulongteng honey was determined by neutralization titration with sodium hydroxide standard solution.The content of 5-hydroxymethylfurfural in Jiulongteng honey was determined by HPLC.Chromatographic conditions:ZORBAX SB-C 18 column(250 mm×4.6 mm,5μm)from Agilent Co.,Ltd.,acetonitrile-0.1%formic acid solution(5:95)as mobile phase,flow rate of 0.8 mL/min,5-hydroxymethylfurfural detection wavelength of 284 nm,guanosine detection wavelength of 254 nm.[Results]The pH of 12 batches of Jiulongteng honey was 3.70-3.84 in the new honey stage,3.92-4.05 in the old honey stage 1,and 4.25-4.53 in the old honey stage 2;5-hydroxymethylfurfural was not detected in the new honey stage,5-hydroxymethylfurfural was detected in FM-001 in the old honey stage 1,and 5-hydroxymethylfurfural was detected in most samples in the old honey stage 2.[Conclusions]The pH and 5-hydroxymethylfurfural content of 12 batches of Jiulongteng honey met the requirements within 3 years of storage.There was no 5-hydroxymethylfurfural in Jiulongteng honey,but with the extension of storage time,the detection amount of 5-hydroxymethylfurfural increased significantly even if Jiulongteng honey was stored at low temperature.Therefore,5-hydroxymethylfurfural can be used as an important indicator of honey freshness.
基金supported by the National Natural Science Foundation of China (21808035, 21901040)the Natural Science Foundation of Fujian Province (2019J05058, 2021J05216, 2022J01922)+3 种基金the Fujian Provincial Department of Finance (GY-Z220231)the fund of the State Key Laboratory of Catalysis in DICP (N-22-08)the Fujian Fishery Disaster Reduction Center (GY-H-22146)College Student Innovation and Entrepreneurship Training Program (x202110388068)。
文摘The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventio nal thermocatalytic route for the production of high-value-added chemicals from biomass resources.In virtue of the wide potential window with promising Faradic efficiency(FE) towards BHMF,Cu-based electrode has been in the center of investigation.However,its structure-activity relationship remains ambiguous and its intrinsic catalytic activity is still unsatisfactory.In this work,we develop a two-step oxidation-reduction strategy to reconstruct the surface atom arrangement of the Cu foam(CF).By combination of multiple quasi-situ/in-situ techniques and density functional theory(DFT) calculation,the critical factor that governs the reaction is demonstrated to be facet effect of the metallic Cu crystal:Cu(110) facet accounts for the most favorable surface with enhanced chemisorption with reactants and selective production of BHMF,while Cu(100) facet might trigger the accumulation of the by-product 5,5'-bis(hydroxy methy)hydrofurion(BHH).With the optimized composition of the facets on the reconstructed Cu(OH)_(2)-ER/CF,the performance could be noticeably enhanced with a BHMF FE of 92.3% and HMF conversion of 98.5% at a potential of -0.15 V versus reversible hydrogen electrode(vs.RHE) in 0.1 M KOH solution.This work sheds light on the incomplete mechanistic puzzle for Cu-catalyzed electrochemical hydrogenation of HMF to BHMF,and provides a theoretical foundation for further precise design of highly efficient catalytic electrodes.
基金support of State Key Laboratory of Chemical Engineering (No.SKL-ChE-20A02)the support of International Clean Energy Talent Program by China Scholarship Council.
文摘Despite wide applications of noble metal-based catalysts in 5-hydroxymethylfurfural(HMF)oxidation,promoting the catalytic performance at low loading amounts still remains a significant challenge.Herein,a series of metal oxide modified MO_(x)-Au/TiO_(2)(M=Fe,Co,Ni)catalysts with low Au loading amount of 0.5 wt%were synthesized.Addition of transition metal oxides promotes electron transfer and generation of the Au^(δ-)-O_(v)-Ti^(3+)interface.A combination study reveals that the dual-active site(Au^(δ-)-O_(v)-Ti^(3+))governs the catalytic performance of the ratedetermining step,namely hydroxyl group oxidation.Au^(δ-) site facilitates chemisorption and activation of O_(2) molecules.At the same time,O_(v)-Ti^(3+) site acts as the role of“killing two birds with one stone”:enhancing adsorption of both reactants,accelerating the activation and dissociation of H_(2)O,and facilitating activation of the adsorbed O_(2).Besides,superoxide radicals instead of base is the active oxygen species during the rate-determining step.On this basis,a FDCA yield of 71.2% was achieved under base-free conditions,complying with the“green chemistry”principle.This work provides a new strategy for the transition metal oxides modification of Au-based catalysts,which would be constructive for the rational design of other heterogeneous catalysts.
文摘食品加工过程中的美拉德反应有助于形成一些热诱导毒性产物,包括晚期糖基化终末产物(advanced glycation end products,AGEs)和5-羟甲基糠醛(5-hydroxymethylfurfural,5-HMF)。食源性AGEs在体内的积累和循环与糖尿病并发症的发生有关,同时可能诱发氧化应激、炎症和动脉粥样硬化。5-HMF的代谢物5-磺基氧甲基糠醛(5-sulfooxymethylfurfural,5-SMF)有潜在基因毒性和致癌性。如何控制热加工食品中这些危害物的形成已成为食品行业的关注焦点。本文从美拉德反应和焦糖化反应两条途径探究了AGEs和5-HMF的形成机理,并对近5年二者的检测方法进行了综述,阐述了各类方法的优缺点,以期为建立二者的通用检测方法奠定基础。在此基础上,从削减前体物质的供给、阻断中间体的转化,以及去除已经生成的AGEs和5-HMF这3个方面着手,综述了近年来相应所采用的抑制策略,以期为AGEs和5-HMF在食品中的控制及热加工食品质量与安全管理提供理论依据。
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supported by National Research Council of Thailand(NRCT)contract no.N42A671047 and Chiang Mai University(CMU).
文摘This study investigated the conversion of sugars into furan derivatives,specifically 2,5-dimethylfuran,through catalytic processes using bibliographic analysis.This method evaluates scientific outcomes and impact within a specific field by analyzing data such as publication trends,references,collaborative models,leading authors,and institutions.The study utilized data fromthe reliable Scopus database and conducted analysis using the visualization of similarity(VOS)viewer program to gain in-depth insights into the current state of research on this topic.The findings revealed that“5 hydroxymethyl furfural”was the most used keyword,followed by“biomass”and“catalysis.”The research trend remained stable and popular from 2006 to 2022,with a decline beginning in 2023.The growing number of publications indicates increasing interest and importance of these topics.Notably,China led in the number of publications,with 80%more than the second-rankedUnited States,followed closely by India in the third place.The study also highlighted citation linkages between authors and countries,providing a comprehensive overview of research on converting sugars to furan derivatives,particularly 2,5-dimethylfuran,through catalytic processes.
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.