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
[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
Biomass conversion to value-added chemicals has received tremendous attention for solving global warming issues and fossil fuel depletion.5-Hydroxymethylfurfural(HMF)is a key bio-based platform molecule to produce man...Biomass conversion to value-added chemicals has received tremendous attention for solving global warming issues and fossil fuel depletion.5-Hydroxymethylfurfural(HMF)is a key bio-based platform molecule to produce many useful organic chemicals by oxidation,hydrogenation,polymerization,and ring-opening reactions.Among all derivatives,the oxidation product 2,5-furandicarboxylic acid(FDCA)is a promising alternative to petroleum-based terephthalic acid for the synthesis of biodegradable plastics.This review analytically discusses the recent progress in the thermocatalytic,electrocatalytic,and photocatalytic oxidation of HMF into FDCA,including catalyst screening,synthesis processes,and reaction mechanism.Rapid fundamental advances may be possible in non-precious metal and metal-free catalysts that are highly efficient under the base-free conditions,and external field-assisted processes like electrochemical or photoelectrochemical cells.展开更多
Sulfated porous carbon (PC-SO3H) catalyst was successfully synthesized from one-pot treatment of porous polydivinylbenzene in H2SO4 at 250 ℃, which exhibited very good catalytic performances in the production of 5-...Sulfated porous carbon (PC-SO3H) catalyst was successfully synthesized from one-pot treatment of porous polydivinylbenzene in H2SO4 at 250 ℃, which exhibited very good catalytic performances in the production of 5-hydroxymethylfurfural from fructose.展开更多
In the dehydration of fructose to 5-hydroxymethyl furfural(HMF),in situ produced water weakens the acid strength of the catalyst and causes the rehydration of HMF,causing unsatisfactory catalytic activity and selectiv...In the dehydration of fructose to 5-hydroxymethyl furfural(HMF),in situ produced water weakens the acid strength of the catalyst and causes the rehydration of HMF,causing unsatisfactory catalytic activity and selectivity.In this work,a class of benzenesulfonic acid-grafted metal-organic frameworks with strong acidity and hydrophobicity is obtained by the direct sulfonation method using 4-chlorobenzenesulfonic acid as sulfonating agent.The resultant MOFs have a specific surface area of greater than 250 m^(2)·g^(-1),acid density above 1.0 mmol·g^(-1),and water contact angle up to 129°.The hydrophobic MOF-PhSO_(3)H exhibits both higher catalytic activity and selectivity than MOF-SO_(3)H in the HMF synthesis due to its better hydrophobicity and olephilicity.Moreover,the catalyst has a high recycled stability.At last,fructose is completely converted,and 98.0%yield of HMF is obtained under 120℃ in a DMSO solvent system.The successful preparation of the hydrophobic acidic MOF provides a novel hydrophobic catalyst for the synthesis of HMF.展开更多
The development of high-efficiency and low-cost catalysts is very crucial for the MeerweinPonndorf-Verley (MPV) reduction of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF). In this ...The development of high-efficiency and low-cost catalysts is very crucial for the MeerweinPonndorf-Verley (MPV) reduction of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF). In this work, an amorphous and mesoporous zirconium phosphonate catalyst (Zr-DTMP), which is a zirconium-containing organic-inorganic nanohybrid, was successfully designed and synthesized by the simple assembly of zirconium tetrachloride (ZrCl4) and diethylene triaminepenta(methylene phosphonic acid)(DTMP). Satisfactorily, when Zr-DTMP was employed for the MPV reduction of HMF in the presence of 2-butanol (secBuOH), DHMF yield could be achieved as 96.5% in 3 h under a relatively mild reaction temperature of 140℃. Systematic investigations indicated that this high catalytic activity should be mainly due to the cooperative role of enhancive Lewis acid site (Zr4+) and Lewis base site (O2-) in activating the carbonyl group of HMF and dissociating the hydroxyl group of secBuOH, respectively. Additionally, Zr-DTMP showed excellent catalytic stability, when it was successively used 5 recycles, its surface characteristics and textural properties still remained almost unchanged, and so, the catalytic activity was not obviously affected. More interestingly, Zr-DTMP could also be applied for the selective reduction of other biomass-derived carbonyl compounds, such as 5-methylfurfural (MF), furfural (FF), levulinic acid (LA), ethyl levulinate (EL) and cyclohexanone (CHN), into the corresponding products with high yields, which is beneficial to the effective synthesis of various valuable bio-based chemicals.展开更多
A low-cost and easily prepared manganese carbonate(Mn CO_3) has been synthesized for catalytic conversion of 5-hydroxymethylfurfural(5-HMF) to 2,5-diformylfuran(DFF). The properties and morphology of the manganese car...A low-cost and easily prepared manganese carbonate(Mn CO_3) has been synthesized for catalytic conversion of 5-hydroxymethylfurfural(5-HMF) to 2,5-diformylfuran(DFF). The properties and morphology of the manganese carbonate were measured by SEM,XRD,TGA,BET and XPS. In this method,no harsh reaction conditions were required,and it was a simple and green process for the oxidation of 5-HMF into DFF. To achieve an optimum DFF yield,different reaction conditions,including reaction temperature,reaction time,catalyst amount,and solvents were investigated. Results from the experiments indicated that the highest DFF yield of 86.9% was obtained at 120 °C under atmospheric oxygen pressure after 6h. Finally,Mn CO_3 could be used at least five times with considerable stability.展开更多
Mesoporous Ti-Mo mixed oxides were prepared via a facile approach using stearic acid as the template, and were characterized using XRD FT-IR, nitrogen adsorption-desorption isotherm and TEM techniques. The catalytic a...Mesoporous Ti-Mo mixed oxides were prepared via a facile approach using stearic acid as the template, and were characterized using XRD FT-IR, nitrogen adsorption-desorption isotherm and TEM techniques. The catalytic activity of the prepared mesoporous Ti-Mo mixed oxides was first evaluated for the dehydration of fructose to 5-hydroxymethylfurfural(HMF), and a 50.3% yield of HMF was obtained within 60min at 120℃. Moreover, moderate yields of HMF could also be achieved from glucose and sucrose. The mesoporous catalyst could be simply separated from the reaction mixture after termination of the reaction and reused five times with no significant loss of catalytic activity.展开更多
To study the effect of adjacent hydroxyl to the active sites, several acid catalysts, i.e. substituted benzoic acids with adjacent carboxyl are employed in the fructose dehydration to 5-hydroxymethylfurfural(HMF).Expe...To study the effect of adjacent hydroxyl to the active sites, several acid catalysts, i.e. substituted benzoic acids with adjacent carboxyl are employed in the fructose dehydration to 5-hydroxymethylfurfural(HMF).Experimental results reveal that Br?nsted acid sites with adjacent carboxyl present higher catalytic ability than isolated ones. Computational results suggest that the adjacent sites lead to co-interaction on fructose, corresponding more stable transition state and faster HMF formation rate. Based on the enhancement from the adjacent sites, a novel ordered mesoporous carbon(OMC) full of carboxyls in surface is prepared and turns out to be an effective solid catalyst for HMF production from fructose derived from biomass.展开更多
A mild and simple process for the effective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) has been developed using Na NO2 as the oxidant. Some important reaction parameters were investigate...A mild and simple process for the effective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) has been developed using Na NO2 as the oxidant. Some important reaction parameters were investigated to optimize the oxidation of HMF into DFF. It was found that the reaction solvent was very crucial for this reaction. Trifluoroacetic acid was the best solvent for the oxidation of HMF into DFF by Na NO2.Under the optimal reaction condition, almost quantitative HMF conversion and high DFF yield of 90.4% were obtained after 1 h at room temperature.展开更多
Developing an efficient and easily available catalyst for the selective conversion of biomass-derived 5-hydroxymethylfurfural(HMF)into furan-2,5-dimethylcarboxylate(FDMC),a valuable biomass-based monomer,remains a hig...Developing an efficient and easily available catalyst for the selective conversion of biomass-derived 5-hydroxymethylfurfural(HMF)into furan-2,5-dimethylcarboxylate(FDMC),a valuable biomass-based monomer,remains a high demand but formidable challenge.Herein,a facile strategy for the synthesis of N-doped carbon-supported Co/Fe bimetallic catalyst(CoFe-NC)was developed,which provided an outstanding FDMC yield of 93%in a batch reactor(base-free,80℃,2 bar O_(2),4 h).Interestingly,CoFe-NC also gave a high FDMC yield of 91%under continuous-flow conditions for 80 h(5 bar O_(2),80℃,GHSV 1320 h^(-1),LHSV 0.6 h^(-1),base-free).Notably,it is the first time that a non-noble catalyst gave such a high FDMC yield under continuous-flow conditions.The introduction of Fe could greatly improve both the electron intensity of Co-N_(x)species and basicity of the catalyst,which endowed CoFe-NC with improved O_(2)activation capacity and enhanced dehydrogenation activity for the oxidation-esterification of HMF.This work delineates the efficient strategy on the construction of N-doped carbon-supported non-noble catalyst,which might open a new avenue for developing highly efficient catalyst for FDMC production.展开更多
The selective aerobic oxidation of biomass-derived 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid (FDCA, a potential renewable substitution of fossil-based terephthalic acid to produce polyethylene 2,5-furandic...The selective aerobic oxidation of biomass-derived 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid (FDCA, a potential renewable substitution of fossil-based terephthalic acid to produce polyethylene 2,5-furandicarboxylate plastic) is an appealing transformation for constructing eco-friendly and sustainable chemical processes. Au supported catalysts have showed encouraging performances for this well-received conversion, whose catalytic behavior was greatly affected by the adopted support derived from the existence of metal-support interactions. Herein, a series of Mg-Beta zeolites were hydrothermally synthesized via developed structural reconstruction, which were employed as basic supports for Au catalysts to construct bifunctional catalysts. The relationship between structure (Au particle size, basicity within zeolites and Auδ+ contents) and FDCA yield was concretely established. The conclusion was made that the utilization of Mg-Beta zeolites with strong basicity as the support could not only improve the FDCA yield but also decrease the amount of additional base. Furthermore, the possible reaction mechanism was also proposed via tracking time-dependent variations of corresponding organics and controlled experiment. This work provides some guidance for rationally designing multifunctional catalysts in the view of integrating metal catalysts with metallosilicate zeolites, which was beneficial to the catalytic upgrading of organic compounds with multiple functional groups.展开更多
Anisotropic MnO2 nanostructures,includingα-phase nanowire,α-phase nanorod,δ-phase nanosheet,α+δ-phase nanowire,and amorphous fl occule,were synthesized by a simple hydrothermal method through adjusting the pH of ...Anisotropic MnO2 nanostructures,includingα-phase nanowire,α-phase nanorod,δ-phase nanosheet,α+δ-phase nanowire,and amorphous fl occule,were synthesized by a simple hydrothermal method through adjusting the pH of the precursor solution and using diff erent counterions.The catalytic properties of the as-synthesized MnO2 nanomaterials in the selective oxidation of benzyl alcohol(BA)and 5-hydroxymethylfurfural(HMF)were evaluated.The eff ects of micromorphology,phase structure,and redox state on the catalytic activity of MnO2 nanomaterials were investigated.The results showed that the intrinsic catalytic oxidation activity was mainly infl uenced by the unique anisotropic structure and surface chemical property of MnO2.With one-dimensional and 2D structures exposing highly active surfaces,unique crystal forms,and high oxidation state of Mn,the intrinsic activities for MnO2 catalysts synthesized in pH 1,5,and 10 solutions(denoted as MnO2-pH1,MnO2-pH5,and MnO2-pH10,respectively)were twice higher than those of other MnO2 catalysts in oxidation of BA and HMF.With a moderate aspect ratio,theα+δnanowire of MnO2-pH10 exhibited the highest average oxidation state,most abundant active sites,and the best catalytic oxidation activity.展开更多
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 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.
基金supported by Chinese Academy of Sciences(QYZDB-SSW-JSC037)Natural Science Foundation of Zhejiang Province(LY19B030003,LQ19B060002)+1 种基金Ningbo Science and Technology Bureau(2018B10056,2019B10096)Fujian Institute of Innovation(FJCXY18020202)。
文摘Biomass conversion to value-added chemicals has received tremendous attention for solving global warming issues and fossil fuel depletion.5-Hydroxymethylfurfural(HMF)is a key bio-based platform molecule to produce many useful organic chemicals by oxidation,hydrogenation,polymerization,and ring-opening reactions.Among all derivatives,the oxidation product 2,5-furandicarboxylic acid(FDCA)is a promising alternative to petroleum-based terephthalic acid for the synthesis of biodegradable plastics.This review analytically discusses the recent progress in the thermocatalytic,electrocatalytic,and photocatalytic oxidation of HMF into FDCA,including catalyst screening,synthesis processes,and reaction mechanism.Rapid fundamental advances may be possible in non-precious metal and metal-free catalysts that are highly efficient under the base-free conditions,and external field-assisted processes like electrochemical or photoelectrochemical cells.
基金supported by the National Natural Science Foundation of China (U1162201)the Graduate Innovation Fund of Jilin University (20121051)
文摘Sulfated porous carbon (PC-SO3H) catalyst was successfully synthesized from one-pot treatment of porous polydivinylbenzene in H2SO4 at 250 ℃, which exhibited very good catalytic performances in the production of 5-hydroxymethylfurfural from fructose.
基金The authors appreciate support from the National Natural Science Foundation of China(21878138,21706112)the Postdoctoral Science Foundation of China(2017M622104,2018T110660)+1 种基金the Key Scientific and Technological Project of Henan Province(182102410072)the start-up funds from Nanchang University and Arizona State University.
文摘In the dehydration of fructose to 5-hydroxymethyl furfural(HMF),in situ produced water weakens the acid strength of the catalyst and causes the rehydration of HMF,causing unsatisfactory catalytic activity and selectivity.In this work,a class of benzenesulfonic acid-grafted metal-organic frameworks with strong acidity and hydrophobicity is obtained by the direct sulfonation method using 4-chlorobenzenesulfonic acid as sulfonating agent.The resultant MOFs have a specific surface area of greater than 250 m^(2)·g^(-1),acid density above 1.0 mmol·g^(-1),and water contact angle up to 129°.The hydrophobic MOF-PhSO_(3)H exhibits both higher catalytic activity and selectivity than MOF-SO_(3)H in the HMF synthesis due to its better hydrophobicity and olephilicity.Moreover,the catalyst has a high recycled stability.At last,fructose is completely converted,and 98.0%yield of HMF is obtained under 120℃ in a DMSO solvent system.The successful preparation of the hydrophobic acidic MOF provides a novel hydrophobic catalyst for the synthesis of HMF.
基金financially supported by the National Natural Science Foundation of China (21506071)the Special Foundation of Jiangsu Collaborative Innovation Center of Regional Modern Agriculture and Environmental Protection (HSXT2-316)
文摘The development of high-efficiency and low-cost catalysts is very crucial for the MeerweinPonndorf-Verley (MPV) reduction of biomass-derived 5-hydroxymethylfurfural (HMF) into 2,5-dihydroxymethylfuran (DHMF). In this work, an amorphous and mesoporous zirconium phosphonate catalyst (Zr-DTMP), which is a zirconium-containing organic-inorganic nanohybrid, was successfully designed and synthesized by the simple assembly of zirconium tetrachloride (ZrCl4) and diethylene triaminepenta(methylene phosphonic acid)(DTMP). Satisfactorily, when Zr-DTMP was employed for the MPV reduction of HMF in the presence of 2-butanol (secBuOH), DHMF yield could be achieved as 96.5% in 3 h under a relatively mild reaction temperature of 140℃. Systematic investigations indicated that this high catalytic activity should be mainly due to the cooperative role of enhancive Lewis acid site (Zr4+) and Lewis base site (O2-) in activating the carbonyl group of HMF and dissociating the hydroxyl group of secBuOH, respectively. Additionally, Zr-DTMP showed excellent catalytic stability, when it was successively used 5 recycles, its surface characteristics and textural properties still remained almost unchanged, and so, the catalytic activity was not obviously affected. More interestingly, Zr-DTMP could also be applied for the selective reduction of other biomass-derived carbonyl compounds, such as 5-methylfurfural (MF), furfural (FF), levulinic acid (LA), ethyl levulinate (EL) and cyclohexanone (CHN), into the corresponding products with high yields, which is beneficial to the effective synthesis of various valuable bio-based chemicals.
基金supported by the Natural Science Foundation of Tianjin (No. 16JCYBJC19600)the National Natural Science Foundation of China (No. 21621004)the Beiyang Young Scholar of Tianjin University (2012)
文摘A low-cost and easily prepared manganese carbonate(Mn CO_3) has been synthesized for catalytic conversion of 5-hydroxymethylfurfural(5-HMF) to 2,5-diformylfuran(DFF). The properties and morphology of the manganese carbonate were measured by SEM,XRD,TGA,BET and XPS. In this method,no harsh reaction conditions were required,and it was a simple and green process for the oxidation of 5-HMF into DFF. To achieve an optimum DFF yield,different reaction conditions,including reaction temperature,reaction time,catalyst amount,and solvents were investigated. Results from the experiments indicated that the highest DFF yield of 86.9% was obtained at 120 °C under atmospheric oxygen pressure after 6h. Finally,Mn CO_3 could be used at least five times with considerable stability.
基金financially supported by the Joint Science and Technology Funds of Guizhou Science and Technology Department of Anshun Municipal Government and the Anshun University (No. LH[2015]7694)the 2016 National Innovative Entrepreneurship Training Program for Undergraduates (No. 201510667020)
文摘Mesoporous Ti-Mo mixed oxides were prepared via a facile approach using stearic acid as the template, and were characterized using XRD FT-IR, nitrogen adsorption-desorption isotherm and TEM techniques. The catalytic activity of the prepared mesoporous Ti-Mo mixed oxides was first evaluated for the dehydration of fructose to 5-hydroxymethylfurfural(HMF), and a 50.3% yield of HMF was obtained within 60min at 120℃. Moreover, moderate yields of HMF could also be achieved from glucose and sucrose. The mesoporous catalyst could be simply separated from the reaction mixture after termination of the reaction and reused five times with no significant loss of catalytic activity.
基金supported by the Natural Science Foundation of Jiangsu Province (BK20151380)NSF of China (21103087 and 21872067)supported by the Fundamental Research Funds for the Central Universities (020514380116)。
文摘To study the effect of adjacent hydroxyl to the active sites, several acid catalysts, i.e. substituted benzoic acids with adjacent carboxyl are employed in the fructose dehydration to 5-hydroxymethylfurfural(HMF).Experimental results reveal that Br?nsted acid sites with adjacent carboxyl present higher catalytic ability than isolated ones. Computational results suggest that the adjacent sites lead to co-interaction on fructose, corresponding more stable transition state and faster HMF formation rate. Based on the enhancement from the adjacent sites, a novel ordered mesoporous carbon(OMC) full of carboxyls in surface is prepared and turns out to be an effective solid catalyst for HMF production from fructose derived from biomass.
基金supported by the National Natural Science Foundation of China(21272065)Scientific Research Fund of Hunan Provincial Education Department(13C562+2 种基金15C0816)Outstanding Youth Project of Hunan Provincial Education Department(15B134)the funding offered by China Scholarship Council(201506720018)
文摘A mild and simple process for the effective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) has been developed using Na NO2 as the oxidant. Some important reaction parameters were investigated to optimize the oxidation of HMF into DFF. It was found that the reaction solvent was very crucial for this reaction. Trifluoroacetic acid was the best solvent for the oxidation of HMF into DFF by Na NO2.Under the optimal reaction condition, almost quantitative HMF conversion and high DFF yield of 90.4% were obtained after 1 h at room temperature.
基金funding supported by the National Natural Science Foundation of China(22078275)the Key-Area Research and Development Program of Guangdong Province(2020B0101070001)+1 种基金the Natural Science Foundation of Fujian Province of China(2021H0009)the Petro China Innovation Foundation(2019D-5007-0413)。
文摘Developing an efficient and easily available catalyst for the selective conversion of biomass-derived 5-hydroxymethylfurfural(HMF)into furan-2,5-dimethylcarboxylate(FDMC),a valuable biomass-based monomer,remains a high demand but formidable challenge.Herein,a facile strategy for the synthesis of N-doped carbon-supported Co/Fe bimetallic catalyst(CoFe-NC)was developed,which provided an outstanding FDMC yield of 93%in a batch reactor(base-free,80℃,2 bar O_(2),4 h).Interestingly,CoFe-NC also gave a high FDMC yield of 91%under continuous-flow conditions for 80 h(5 bar O_(2),80℃,GHSV 1320 h^(-1),LHSV 0.6 h^(-1),base-free).Notably,it is the first time that a non-noble catalyst gave such a high FDMC yield under continuous-flow conditions.The introduction of Fe could greatly improve both the electron intensity of Co-N_(x)species and basicity of the catalyst,which endowed CoFe-NC with improved O_(2)activation capacity and enhanced dehydrogenation activity for the oxidation-esterification of HMF.This work delineates the efficient strategy on the construction of N-doped carbon-supported non-noble catalyst,which might open a new avenue for developing highly efficient catalyst for FDMC production.
基金We gratefully acknowledge the financial supports from the National Natural Science Foundation of China(Nos.22072126,22002133,21676230 and 21373177)the Natural Science Foundation of Shandong Province(ZR2020QB055)the Young Scholars Research Fund of Yantai University(No.HY19B26).
文摘The selective aerobic oxidation of biomass-derived 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid (FDCA, a potential renewable substitution of fossil-based terephthalic acid to produce polyethylene 2,5-furandicarboxylate plastic) is an appealing transformation for constructing eco-friendly and sustainable chemical processes. Au supported catalysts have showed encouraging performances for this well-received conversion, whose catalytic behavior was greatly affected by the adopted support derived from the existence of metal-support interactions. Herein, a series of Mg-Beta zeolites were hydrothermally synthesized via developed structural reconstruction, which were employed as basic supports for Au catalysts to construct bifunctional catalysts. The relationship between structure (Au particle size, basicity within zeolites and Auδ+ contents) and FDCA yield was concretely established. The conclusion was made that the utilization of Mg-Beta zeolites with strong basicity as the support could not only improve the FDCA yield but also decrease the amount of additional base. Furthermore, the possible reaction mechanism was also proposed via tracking time-dependent variations of corresponding organics and controlled experiment. This work provides some guidance for rationally designing multifunctional catalysts in the view of integrating metal catalysts with metallosilicate zeolites, which was beneficial to the catalytic upgrading of organic compounds with multiple functional groups.
基金the National Natural Science Foundation of China(No.21503187)the“Light of West China”Program of the Chinese Academy of Sciences for the financial support.
文摘Anisotropic MnO2 nanostructures,includingα-phase nanowire,α-phase nanorod,δ-phase nanosheet,α+δ-phase nanowire,and amorphous fl occule,were synthesized by a simple hydrothermal method through adjusting the pH of the precursor solution and using diff erent counterions.The catalytic properties of the as-synthesized MnO2 nanomaterials in the selective oxidation of benzyl alcohol(BA)and 5-hydroxymethylfurfural(HMF)were evaluated.The eff ects of micromorphology,phase structure,and redox state on the catalytic activity of MnO2 nanomaterials were investigated.The results showed that the intrinsic catalytic oxidation activity was mainly infl uenced by the unique anisotropic structure and surface chemical property of MnO2.With one-dimensional and 2D structures exposing highly active surfaces,unique crystal forms,and high oxidation state of Mn,the intrinsic activities for MnO2 catalysts synthesized in pH 1,5,and 10 solutions(denoted as MnO2-pH1,MnO2-pH5,and MnO2-pH10,respectively)were twice higher than those of other MnO2 catalysts in oxidation of BA and HMF.With a moderate aspect ratio,theα+δnanowire of MnO2-pH10 exhibited the highest average oxidation state,most abundant active sites,and the best catalytic oxidation activity.