5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated...5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.展开更多
The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catal...The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.展开更多
Design of non-noble metal electrocatalysts for biomass conversion to high-value chemicals and understanding the related catalytic mechanisms are of profound significance but have remained a major challenge.Here,we dev...Design of non-noble metal electrocatalysts for biomass conversion to high-value chemicals and understanding the related catalytic mechanisms are of profound significance but have remained a major challenge.Here,we developed a novel biomass-derived electrocatalyst(denoted as Cu/NC),featuring with electron-deficient copper nanoparticles anchored on N-doped carbon nanosheets,for the electrochemical reduction of 5-hydroxymethylfurfural(HMF)to 2,5-bis(hydroxymethyl)furan(BHMF,a vital precursor of functional polymers).The optimized Cu/NC electrocatalyst exhibited an excellent performance with high Faradaic efficiency(89.5%)and selectivity(90.8%)of BHMF at a low concentration of HMF(18.1 mM).Even at a very high HMF concentration(108.6 mM),the Faraday efficiency and selectivity of BHMF could still reach 74.8%and 81.1%,respectively.This performance approached those of the reported noble metal-based electrocatalysts.Mechanism study revealed that the N doping in the Cu/NC catalyst could regulate the electronic structure of Cu,strengthening the adsorption of the HMF carbonyl group,and thus boosting the selectivity of BHMF.Additionally,strong electronic metal-support interactions of Cu and the N-doped carbon support optimized the charge transfer rate,thus promoting the dissociation of water to the active hydrogen(H^(*))species and boosting the reaction kinetic rate of H^(*)and HMF.展开更多
The selective oxidation of 2,5‐bis(hydroxymethyl)furan(BHMF)in this work was proven as a promising route to produce 2,5‐furandicarboxylic acid(FDCA),an emerging bio‐based building‐block with wide application.Under...The selective oxidation of 2,5‐bis(hydroxymethyl)furan(BHMF)in this work was proven as a promising route to produce 2,5‐furandicarboxylic acid(FDCA),an emerging bio‐based building‐block with wide application.Under ambient pressure,the modified carbon nanotube‐supported Pd‐based catalysts demonstrate the maximum FDCA yield of 93.0%with a full conversion of BHMF after 60 min at 60°C,much superior to that of the traditional route using 5‐hydroxymethylfurfural(HMF)as substrates(only a yield of 35.7%).The participation of PdH_(x) active species with metallic Pd can be responsible for the encouraging performance.Meanwhile,a possible reaction pathway proceeding through 2,5‐diformylfuran(DFF)and 5‐formyl‐2‐furancarboxylic acid(FFCA)as process intermediates is suggested for BHMF route.The present work may provide new opportunities to synthesize other high value‐added oxygenates by using BHMF as an alternative feedstock.展开更多
Biomass-derived 2,5-bis(hydroxymethyl)furan(BHMF)has received great attention and interest due to its broad application prospects in polyesters and medicine.Over the past decades,the catalytic systems including thermo...Biomass-derived 2,5-bis(hydroxymethyl)furan(BHMF)has received great attention and interest due to its broad application prospects in polyesters and medicine.Over the past decades,the catalytic systems including thermocatalytic,biocatalytic,electrocatalytic,and photocatalytic hydrogenation of 5-hydroxymethylfurfural(HMF)into BHMF have been developed to a great extent.To understand the present status and challenges of BHMF production,this review systematically evaluates recent findings and developments of HMF hydrogenation through various reaction systems,with an emphasis on catalyst screening,synthesis processes,and reaction mechanism.Furthermore,a few potential research trends are also proposed,in order to provide innovative ideas for further exploration of BHMF synthesis in a simpler,efficient,and economical way.展开更多
2,5-bis(hydroxymethyl)furan(BHMF)is an important monomer of polyester.Its oxygen-containing rigid ring structure and symmetrical diol functional group establish it as an alternative to petroleum-based monomer with uni...2,5-bis(hydroxymethyl)furan(BHMF)is an important monomer of polyester.Its oxygen-containing rigid ring structure and symmetrical diol functional group establish it as an alternative to petroleum-based monomer with unique advantages for the prodution of the degradable bio-based polyester materials.Herein,we prepared a boehmite-supported copper-oxide catalyst for the selective hydrogenation of 5-hydroxymethylfurfural into BHMF via catalytic transfer hydrogenation(CTH).Further,ethanol successfully replaced conventional high-pressure hydrogen as the hydrogen donor,with up to 96.9% BHMF selectivity achieved under suitable conditions.Through characterization and factor investigations,it was noted that CuO is crucial for high BHMF selectivity.Furthermore,kinetic studies revealed a higher by-product activation energy compared to that of BHMF,which explained the influence of reaction temperature on product distribution.To establish the catalyst structure-activity correlation,a possible mechanism was proposed.The copper-oxide catalyst deactivated following CTH because ethanol reduced the CuO,which consequently decreased the active sites.Finally,calcination of the catalyst in air recovered its activity.These results will have a positive impact on hydrogenation processes in the biomass industry.展开更多
2,5-Bis(hydroxymethyl)furan(BHMF)is a high-value,bio-based,rigid diol that resembles aromatic monomers for the production of different polyesters.In this work,a carbon nanotubes(CNTs)-supported nickel catalyst(Ni/CNTs...2,5-Bis(hydroxymethyl)furan(BHMF)is a high-value,bio-based,rigid diol that resembles aromatic monomers for the production of different polyesters.In this work,a carbon nanotubes(CNTs)-supported nickel catalyst(Ni/CNTs)was prepared and used for the selective hydrogenation of 5-hydroxymethylfurfural(HMF)to BHMF at low hydrogen pressure.The prepared catalyst was analyzed by nitrogen adsorption-desorption isotherms,X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS).According to kinetic studies,the rate constant for BHMF formation is significantly larger than that for the formation of the byproduct,5-methyl furfural(MF).At optimal reaction conditions,conversion and selectivity rates of HMF and BHMF were 99.8%and 95.0%,respectively.The mechanistic study indicated the coexistence of Ni0 and Ni2+species on the catalyst surface affects the catalytic performance.A possible mechanism was proposed to describe the synergetic effects of Ni0 and Ni2+.Furthermore,the catalyst can be easily separated from the reaction mixture for recycling.展开更多
Streptomyces zerumbet W14, a novel species of the endophyte genus Streptomyces was isolated from the rhizome tissue of Zingiber zerumbet (L.) Smith. Identification of strain W14 was based on its morphology, chemotaxon...Streptomyces zerumbet W14, a novel species of the endophyte genus Streptomyces was isolated from the rhizome tissue of Zingiber zerumbet (L.) Smith. Identification of strain W14 was based on its morphology, chemotaxonomy and phylogenetic analysis using 16S rDNA sequence. It was classified as the secondary meabolites of the culture extract were studied. The major active ingredients from the crude extract were purified by silica gel column chromatography and identified by spectroscopic data. The crude extract and purified compounds were tested for their biological activities on antibacterial and anti-inflammatory properties. The crude extract showed inhibition on the growth of Gram-positive bacteria with the MIC and MBC values of 8 - 32 μg/ml and 32 - 128 μg/ml, respectively. The isolated compounds were identified to be methyl 5-(hydroxymethyl)furan-2-carboxylate (1) and geldanamycin (2). Bioassay studies showed that compound 1 had antibacterial activity against Staphylococus aureus ATCC 25923 and Methicillin Resistant S. aureus strain Sp6 (clinical isolate) with the MIC and MBC values of 1 μg/ml and 16 - 64 μg/ml, respectively, and also showed activity against Bacillus Calmette-Guérin (vaccine strain) with MIC and MBC values of 128.00 μg/ml and 128.00 μg/ml, respectively. The compound 2 at the concentration of 1 - 5 μg/ml had in vitro anti-inflammatory activity on LPS-induced RAW 264.7 cells by inhibition of mRNA expression and production of inducible NO synthase (iNOS), tumor necrosis factor-alpha (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6). These results suggest that compounds 1 and 2 produced by S. zerumbet W14 (an endophyte of Z. Zerumbet) have antibacterial and anti-inflammatory activities, respectively. Therefore, the future studies on these compounds could be useful for the management of bacterial infections and inflammatory diseases.展开更多
基金financially supported by the National Key R&D Program of China 2021YFC2101604)the National Natural Science Foundation of China(22278339,21978248)+1 种基金the Guangdong Provincial Key Research and Development Program(2020B0101070001)the Natural Science Foundation of Fujian Province of China(2019J06005)。
文摘5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.
文摘The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.
基金supported by the National Natural Science Foundation of China(Nos.22225501 and 52073173)the Key Research Projects of Universities in Henan Province(No.23A530005)+1 种基金the National Key Laboratory of Biobased Transport Fuel Technology of China(No.KFKT2022002)the Project of Nanyang Collaborative Innovation(No.22XTCX12004,Nanyang Research Institute of Zhengzhou University).
文摘Design of non-noble metal electrocatalysts for biomass conversion to high-value chemicals and understanding the related catalytic mechanisms are of profound significance but have remained a major challenge.Here,we developed a novel biomass-derived electrocatalyst(denoted as Cu/NC),featuring with electron-deficient copper nanoparticles anchored on N-doped carbon nanosheets,for the electrochemical reduction of 5-hydroxymethylfurfural(HMF)to 2,5-bis(hydroxymethyl)furan(BHMF,a vital precursor of functional polymers).The optimized Cu/NC electrocatalyst exhibited an excellent performance with high Faradaic efficiency(89.5%)and selectivity(90.8%)of BHMF at a low concentration of HMF(18.1 mM).Even at a very high HMF concentration(108.6 mM),the Faraday efficiency and selectivity of BHMF could still reach 74.8%and 81.1%,respectively.This performance approached those of the reported noble metal-based electrocatalysts.Mechanism study revealed that the N doping in the Cu/NC catalyst could regulate the electronic structure of Cu,strengthening the adsorption of the HMF carbonyl group,and thus boosting the selectivity of BHMF.Additionally,strong electronic metal-support interactions of Cu and the N-doped carbon support optimized the charge transfer rate,thus promoting the dissociation of water to the active hydrogen(H^(*))species and boosting the reaction kinetic rate of H^(*)and HMF.
文摘The selective oxidation of 2,5‐bis(hydroxymethyl)furan(BHMF)in this work was proven as a promising route to produce 2,5‐furandicarboxylic acid(FDCA),an emerging bio‐based building‐block with wide application.Under ambient pressure,the modified carbon nanotube‐supported Pd‐based catalysts demonstrate the maximum FDCA yield of 93.0%with a full conversion of BHMF after 60 min at 60°C,much superior to that of the traditional route using 5‐hydroxymethylfurfural(HMF)as substrates(only a yield of 35.7%).The participation of PdH_(x) active species with metallic Pd can be responsible for the encouraging performance.Meanwhile,a possible reaction pathway proceeding through 2,5‐diformylfuran(DFF)and 5‐formyl‐2‐furancarboxylic acid(FFCA)as process intermediates is suggested for BHMF route.The present work may provide new opportunities to synthesize other high value‐added oxygenates by using BHMF as an alternative feedstock.
基金the financial support of the National Natural Science Foundation of China(22278121,21975070)Hunan Provincial Innovation Foundation for Postgraduate(QL20210132)the funding offered by China Scholarship Council(202106720021).
文摘Biomass-derived 2,5-bis(hydroxymethyl)furan(BHMF)has received great attention and interest due to its broad application prospects in polyesters and medicine.Over the past decades,the catalytic systems including thermocatalytic,biocatalytic,electrocatalytic,and photocatalytic hydrogenation of 5-hydroxymethylfurfural(HMF)into BHMF have been developed to a great extent.To understand the present status and challenges of BHMF production,this review systematically evaluates recent findings and developments of HMF hydrogenation through various reaction systems,with an emphasis on catalyst screening,synthesis processes,and reaction mechanism.Furthermore,a few potential research trends are also proposed,in order to provide innovative ideas for further exploration of BHMF synthesis in a simpler,efficient,and economical way.
基金support of the National Natural Science Foundation of China (Grant No.22278121)Scientific Research Fund of Hunan Provincial Education Department (Grant No.20B364)+1 种基金Hunan Provincial Innovation Foundation for Postgraduate (Grant No.QL20210132)Science and Technology Planning Project of Hunan Province (Grant Nos.2021GK5083,2021GK4049,2018TP1017).
文摘2,5-bis(hydroxymethyl)furan(BHMF)is an important monomer of polyester.Its oxygen-containing rigid ring structure and symmetrical diol functional group establish it as an alternative to petroleum-based monomer with unique advantages for the prodution of the degradable bio-based polyester materials.Herein,we prepared a boehmite-supported copper-oxide catalyst for the selective hydrogenation of 5-hydroxymethylfurfural into BHMF via catalytic transfer hydrogenation(CTH).Further,ethanol successfully replaced conventional high-pressure hydrogen as the hydrogen donor,with up to 96.9% BHMF selectivity achieved under suitable conditions.Through characterization and factor investigations,it was noted that CuO is crucial for high BHMF selectivity.Furthermore,kinetic studies revealed a higher by-product activation energy compared to that of BHMF,which explained the influence of reaction temperature on product distribution.To establish the catalyst structure-activity correlation,a possible mechanism was proposed.The copper-oxide catalyst deactivated following CTH because ethanol reduced the CuO,which consequently decreased the active sites.Finally,calcination of the catalyst in air recovered its activity.These results will have a positive impact on hydrogenation processes in the biomass industry.
基金the financial support of the National Natural Science Foundation of China(Nos.22278121 and 21975070)the China Postdoctoral Science Foundation(2019 M662787)the Science and Technology Planning Project of Hunan Province(2021GK5083).
文摘2,5-Bis(hydroxymethyl)furan(BHMF)is a high-value,bio-based,rigid diol that resembles aromatic monomers for the production of different polyesters.In this work,a carbon nanotubes(CNTs)-supported nickel catalyst(Ni/CNTs)was prepared and used for the selective hydrogenation of 5-hydroxymethylfurfural(HMF)to BHMF at low hydrogen pressure.The prepared catalyst was analyzed by nitrogen adsorption-desorption isotherms,X-ray diffraction(XRD),and X-ray photoelectron spectroscopy(XPS).According to kinetic studies,the rate constant for BHMF formation is significantly larger than that for the formation of the byproduct,5-methyl furfural(MF).At optimal reaction conditions,conversion and selectivity rates of HMF and BHMF were 99.8%and 95.0%,respectively.The mechanistic study indicated the coexistence of Ni0 and Ni2+species on the catalyst surface affects the catalytic performance.A possible mechanism was proposed to describe the synergetic effects of Ni0 and Ni2+.Furthermore,the catalyst can be easily separated from the reaction mixture for recycling.
文摘Streptomyces zerumbet W14, a novel species of the endophyte genus Streptomyces was isolated from the rhizome tissue of Zingiber zerumbet (L.) Smith. Identification of strain W14 was based on its morphology, chemotaxonomy and phylogenetic analysis using 16S rDNA sequence. It was classified as the secondary meabolites of the culture extract were studied. The major active ingredients from the crude extract were purified by silica gel column chromatography and identified by spectroscopic data. The crude extract and purified compounds were tested for their biological activities on antibacterial and anti-inflammatory properties. The crude extract showed inhibition on the growth of Gram-positive bacteria with the MIC and MBC values of 8 - 32 μg/ml and 32 - 128 μg/ml, respectively. The isolated compounds were identified to be methyl 5-(hydroxymethyl)furan-2-carboxylate (1) and geldanamycin (2). Bioassay studies showed that compound 1 had antibacterial activity against Staphylococus aureus ATCC 25923 and Methicillin Resistant S. aureus strain Sp6 (clinical isolate) with the MIC and MBC values of 1 μg/ml and 16 - 64 μg/ml, respectively, and also showed activity against Bacillus Calmette-Guérin (vaccine strain) with MIC and MBC values of 128.00 μg/ml and 128.00 μg/ml, respectively. The compound 2 at the concentration of 1 - 5 μg/ml had in vitro anti-inflammatory activity on LPS-induced RAW 264.7 cells by inhibition of mRNA expression and production of inducible NO synthase (iNOS), tumor necrosis factor-alpha (TNF-α), interleukin-1β (IL-1β), and interleukin-6 (IL-6). These results suggest that compounds 1 and 2 produced by S. zerumbet W14 (an endophyte of Z. Zerumbet) have antibacterial and anti-inflammatory activities, respectively. Therefore, the future studies on these compounds could be useful for the management of bacterial infections and inflammatory diseases.
