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
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
Two new Cu(II) coordination polymers, [Cu(FDA)(BPY)(H20)]n (1) and {[Cu(FDA)(BPY)(H2O)].2H2O}n (2) (H2FDA = 2,5-furandicarboxylic acid, BPY = 2,2'-bipyridine), have been synthesized and structural...Two new Cu(II) coordination polymers, [Cu(FDA)(BPY)(H20)]n (1) and {[Cu(FDA)(BPY)(H2O)].2H2O}n (2) (H2FDA = 2,5-furandicarboxylic acid, BPY = 2,2'-bipyridine), have been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a = 7.5915(15), b = 8.4050(17), c = 24.204(6) A, β = 99.05(3)°, V= 1525.1(6) A3, Dc = 1.706 g/crn3, C16HI2CuN206, Mr = 391.82, F(000) = 796, μ(MoKa) = 1.470 mm-l, Z = 4, R = 0.0633 and wR = 0.1059 for 2389 observed reflections (1 〉 2a(I)), R = 0.0738, and wR = 0.1098 for all data. Complex 2 belongs to triclinic space group PI with a = 8.8660(18), b = 8.9112(18), c = 12.525(3) A, a = 88.41(3), β = 69.38(3), γ = 66.95(3)°, V = 845.2(3) A3, Dc = 1.681 g/cm3, CI6HI6CuN2Os, Mr. = 427.85, F(000) = 438, μ(MoKα) = 1.342 mm-1, Z = 2, R = 0.0290 and wR = 0.0690 for 2767 observed reflections (I 〉 2σ(I)), R = 0.0329 and wR = 0.0706 for all data. Complexes 1 and 2 are both coordination polymers with one-dimensional chain structures bridged by the protonated FDA ligands, which are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions and π-π packing interactions between the chains.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
Selective oxidation of 5-hydroxymethylfurfual(HMF) to 2,5-furandicarboxylic acid(FDCA) as a bioplastics monomer is efficiently promoted by a simple system without noble-metal and base additives. In this work, graphene...Selective oxidation of 5-hydroxymethylfurfual(HMF) to 2,5-furandicarboxylic acid(FDCA) as a bioplastics monomer is efficiently promoted by a simple system without noble-metal and base additives. In this work, graphene oxide(GO) was first synthesised by an electrochemical method with flexible graphite paper(FGP) as start carbon material, then, nitrogen-doped graphene(NG) layers encapsulated Cu nanoparticles(NPs) was prepared by one-step thermal treatment of GO supported Cu2+ in flowing NH3 atmosphere. Compared with NG supported Cu NPs prepared by the traditional impregnation method, enhanced catalytic activity was achieved over Cu/NG and an FDCA yield of 95.2% was achieved under mild reaction conditions with tert-butylhydroperoxide(t-BuOOH) as the oxidant. Control experiments with different catalysts and different addition procedure of t-BuOOH showed the yield of HMF and various intermediates during reaction. From the changing of intermediates concentrations and reaction rates, a reaction pathway through HMF-DFF-FFCA-FDCA was proposed. This work gives a more convenient, more green,more economical and effective method in encapsulated metal NPs preparation and high selectivity in HMF oxidation to FDCA under mild conditions.展开更多
By using solvothermal method, two new main group metal coordination polymers based on 2,5-furandicarboxylic acid (H2FDA) ligand, [Sr2(FDA)E(H2O)5]n (1) and [Ba4(FDA)4(H2O)10]n (2), were produced and char...By using solvothermal method, two new main group metal coordination polymers based on 2,5-furandicarboxylic acid (H2FDA) ligand, [Sr2(FDA)E(H2O)5]n (1) and [Ba4(FDA)4(H2O)10]n (2), were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR, and powder X-ray diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 13.454(3), b = 13.426(3), c = 20.166(4) A, β = 107.06(3)°, V = 3482.4(13)A^3, Dc = 2.188 g/cm^3, CIEH14Sr2O15, Mr = 573.47, F(000) = 2256,μ(MoKα)= 6.21 mm^-1, Z = 8, R = 0.0522 and wR = 0.1229 for 2493 observed reflections (I〉 2σ(I)), and R = 0.0689 and wR = 0.1324 for all data. Compound 2 crystallizes in triclinic, space group el with α = 6.8382(14), b = 10.932(2), c = 25.571(5) A,α = 94.64(3), β= 95.41(3), γ = 107.83(3)°, V= 1799.4(6) A3, Dc = 2.484 g/cm^3, C24H28Ba4O30, Mr = 1345.82, F(000) = 1272,μ(MoKa) = 4.43 mm^-1, Z = 2, R = 0.0485 and wR = 0.0906 for 5020 observed reflections (I〉 2σ(I)), and R = 0.0706 and wR = 0.0991 for all data. In 1, the trinuclear clusters Sr3 are connected with adjacent four clusters by a carboxylate group to produce a two-dimensional (2D) sheet, which is extended by a FDA-based pillar into a 3D framework. In 2, neighbouring trinuclear clusters Ba3 are linked through two -O-C-O- of FDA^2- ligands to form one-dimensional (1D) chains, which are connected by a FDA-based pillar to construct a 2D framework. The thermal stabilities of 1 and 2 are also investigated.展开更多
Terephthalic acid,2,5-furandicarboxylic acid and 1,8-octanediol were adopted as monomers and antimony trioxide as catalyst,and poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) copolyesters identified ...Terephthalic acid,2,5-furandicarboxylic acid and 1,8-octanediol were adopted as monomers and antimony trioxide as catalyst,and poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) copolyesters identified as PEOT-x,where x is the mole fraction of furandicarboxylic acid in the samples,were synthesized by direct esterification.The molecular structure of the copolyesters was characterized by FTIR and 1H NMR spectroscopy.Gel permeation chromatography (GPC),differential scanning calorimetry (DSC),and thermogravimetric analysis (TGA) were used to characterize the molecular weight,molar mass dispersity,glass transition temperature,and thermal stability of the copolyesters,respectively.The mechanical properties of the samples were also investigated.The number-average molecular weight (M_(n)) of the samples varies from 9 700-18 800 g/mol,and molar mass dispersity (■=M_(w)/M_(n)) from 2.15-3.34.The initial decomposition temperature of the copolyesters is in the 332-356 ℃ range,with maximum decomposition rates at 390-410 ℃,while the glass transition temperature (Tg) varies from 0-33 ℃.Mechanical test shows that PEOT-10 has the highest tensile strength,while PEOT-90 has the largest tensile modulus and elongation at break.The experimental results show that these copolyesters can be synthesized with relatively high molecular weights,good thermal stability,and fair mechanical properties,which makes them excellent replacements for commercial polyesters,such as PET,and these properties can be tuned through the relative amounts of biomass monomer 2,5-furandicarboxylic acid used in the reactions.展开更多
Three new coordination polymers,namely [Zn(FDA)(phen)(H2O)·H2O]n(1),[Cd(HFDA)(phen)2(NO3)](2) and [Cd(FDA)(phen)]n(3)(H2FDA = 2,5-furandicarboxylic acid,phen = 1,10-phenanthroline) have be...Three new coordination polymers,namely [Zn(FDA)(phen)(H2O)·H2O]n(1),[Cd(HFDA)(phen)2(NO3)](2) and [Cd(FDA)(phen)]n(3)(H2FDA = 2,5-furandicarboxylic acid,phen = 1,10-phenanthroline) have been synthesized by the solvothermal method and characterized by elemental analysis,IR,powder X-ray diffraction,thermogravimetric analysis and X-ray single-crystal diffraction analysis.For 1,the neighboring Zn^2+ ions are bridged by FDA2-as linkers to form one-dimensional(1D) chains,and phen ligands are as the terminal ligands.Furthermore,the 1D chains are packed into a three-dimensional(3D) supramolecular structure through hydrogen bonds and π-π interactions.For 2,the H2FDA ligand is partial deprotonation,which is a rare phenomenon among other coordination polymers based on H2FDA.Under the synergetic effect of phen ligands and the partial deprotonation of H2FDA,the structure of 2 is discrete.For 3,the Cd^2+ ions are linked by two carboxylates of FDA^2-ligand to give rise to 1 D zig-zag chains,and phen ligands chelate the Cd^2+ ions like 1.In addition,solid-state luminescent spectra of three coordination polymers were also studied at room temperature.展开更多
By using solvothermal method, two new metal coordination polymers based on 2,5-furandicarboxylic acid(H2FDA) ligand and 4,4'-bipyridine(bipy), [Cu(FDA)(4,4'-bipy)(DMF)]n·solvent(1) and {[Zn(4,4'-b...By using solvothermal method, two new metal coordination polymers based on 2,5-furandicarboxylic acid(H2FDA) ligand and 4,4'-bipyridine(bipy), [Cu(FDA)(4,4'-bipy)(DMF)]n·solvent(1) and {[Zn(4,4'-bipy)(FDA)(DMF)]·DMF}n(2), were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR and powder X-ray diffraction. Compound 1 crystallizes in monoclinic space group P21/c with a = 11.104(2), b = 10.396(2), c = 18.772(4) , β = 96.20(3)o, V = 2154.2(7) 3, Dc = 1.378 g/cm^3, C19H17 Cu N3O6, Mr = 446.90, F(000) = 916, μ(Mo Kα) = 1.05 mm^-1, Z = 4, R = 0.0691 and wR = 0.1341 for 3537 observed reflections(I 2σ(I)), and R = 0.1062 and w R = 0.1482 for all data. Compound 2 crystallizes in monoclinic space group C2/c with a = 29.779(6), b = 9.6417(19), c = 17.292(3), β = 105.69(3)°, V = 4779.9(16) 3, Dc = 1.445 g/cm^3, C22H22N4O7 Zn, Mr = 519.81, F(000) = 2144, μ(Mo Kα)= 1.08 mm^-1, Z = 8, R = 0.0641 and w R = 0.1007 for 2985 observed reflections(I 2σ(I)), and R = 0.1028 and w R = 0.1112 for all data. Different coordination geometry of metal ions, square pyramid of Cu2+ and trigonal bipyramid of Zn2+, bring about different orientations of FDA2- ligands as well as 4,4'-bipyridine ligands, and furthermore distinct assembly structures for 1 and 2. The thermal stabilities of 1 and 2 are also investigated.展开更多
The organic compound 2,5-furandicarboxylic acid(FDCA) has been identified by the US Department of Energy(DOE) as a valuable platform chemical for a wide range of industrial applications. Currently, the most popula...The organic compound 2,5-furandicarboxylic acid(FDCA) has been identified by the US Department of Energy(DOE) as a valuable platform chemical for a wide range of industrial applications. Currently, the most popular route for FDCA synthesis is reported to be the oxidation of 5-hydroxymethylfurfural(HMF)by O_2 over the catalysis of noble metals(e.g., Au, Pt, Ru, and Pd). However, the high costs of noble metal catalysts remain a major barrier for producing FDCA at an industrial scale. Herein, we report a transition metal-free synthesis strategy for the oxidation of HMF to FDCA under O_2 or ambient air. A simple but unprecedented process for the aerobic oxidation of HMF was carried out in organic solvents using only bases as the promoters. According to the high performance liquid chromatography(HPLC) analysis, excellent product yield(91%) was obtained in the presence of NaOH in dimethylformamide(DMF) at room temperature(25 ℃). A plausible mechanism for the NaOH-promoted aerobic oxidation of HMF in DMF is also outlined in this paper. After the reaction, the sodium salt of FDCA particles were dispersed in the reaction mixture, making it possible for product separation and solvent reuse. The new HMF oxidation approach is expected to be a practical alternative to current ones, which depend on the use of noble metal catalysts.展开更多
Solvothermal reaction of 2,5-furandicarboxylic acid (H2FDA) ligand and Ca(NO3)24H2O affords a new coordination polymer, [Ca2(FDA)2(DMAC)(H2O)]n (1). The structure has been determined by single-crystal X-ra...Solvothermal reaction of 2,5-furandicarboxylic acid (H2FDA) ligand and Ca(NO3)24H2O affords a new coordination polymer, [Ca2(FDA)2(DMAC)(H2O)]n (1). The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR, powder X-ray diffraction and TGA. Compound I crystallizes in triclinic, space group Pi with a = 9.5387(19), b = 10.425(2), c = 11.590(2)A, a = 75.02(3), fl = 84.80(3), y = 80.99(3)~, V = 1098.1(4) A3, Dc = 1.492 g/cm^3, C16H15Ca2NO12, Mr = 493.45, F(O00) = 508, p(MoKa)= 0.580 mm-1, Z= 2, R = 0.0436 and wR = 0.0944 for 3865 observed reflections (I〉 2σ(/)), and R --- 0.0595 and wR = 0.1015 for all data. The structure of 1 exhibits a three-dimensional network with layer-pillar structure.展开更多
2,5-Furandicarboxylic acid(FDCA)is an important and renewable building block and can serve as an alternative to terephthalic acid in the production of biobased degradable plastic.In this study,Cu-doped MnO_(2) nanorod...2,5-Furandicarboxylic acid(FDCA)is an important and renewable building block and can serve as an alternative to terephthalic acid in the production of biobased degradable plastic.In this study,Cu-doped MnO_(2) nanorods were prepared by a facile hydrothermal redox method and employed as catalysts for the selective oxidation of 5-hydroxymethylfurfural(HMF)to FDCA using tert-butyl hydroperoxide(TBHP)as an oxidant.The catalysts were characterized using X-ray diffraction analysis,Fourier transform infrared spectroscopy,thermo-gravimetric analysis,and transmission electron microscopy.The effects of oxidants,solvents,and reaction conditions on the oxidation of HMF were investigated,and a reaction mechanism was proposed.Experimental results demonstrated that 99.4% conversion of HMF and 96.3% selectivity of FDCA were obtained under suitable conditions,and tert-butanol was the most suitable solvent when TBHP was used as an oxidant.More importantly,the Cu-doped MnO_(2) catalyst can maintain durable catalytic activity after being recycled for more than ten times.展开更多
An eco-friendly and economical route for the oxidation of 5-hydroxymethylfurfural(HMF) to 2,5-furandicarboxylic acid(FDCA) with atmospheric dioxygen as the sole oxidant under acid-,base-,metal-,and external initiator-...An eco-friendly and economical route for the oxidation of 5-hydroxymethylfurfural(HMF) to 2,5-furandicarboxylic acid(FDCA) with atmospheric dioxygen as the sole oxidant under acid-,base-,metal-,and external initiator-free conditions in minimal solvent was reported.In the present reaction,the 1,2-diethoxyethylane has a dual role:reaction medium and free-radical initiato r.The FDCA easily crystallizes during the reaction and was simple purified via recrystallization to provide the pure FDCA.展开更多
The depletion of petroleum resources and the intensification of environmental problems have necessitated the development of renewable products from bio-based chemicals instead of petroleum resources.Herein,a new kind ...The depletion of petroleum resources and the intensification of environmental problems have necessitated the development of renewable products from bio-based chemicals instead of petroleum resources.Herein,a new kind of ester lubricating oil,isooctyl furan dicarboxylate(isooctyl-FD),was prepared from bio-based 2,5-furandicarboxylic acid.The structure of isooctyl-FD was evaluated using nuclear magnetic resonance imaging and high-resolution mass spectroscopy.Its physicochemical and tribological properties including thermal and oxidation stabilities,flash point and pour point,viscosity and viscosity index,and friction-reducing and anti-wear properties were systematically evaluated.The results show that isooctyl-FD has comparable thermal and oxidation stability to the synthetic ester lubricating oil,isooctyl sebacate(isooctyl-S).Its friction-reducing and anti-wear properties are superior to isooctyl-S;however,its viscosity-temperature and low-temperature properties are inferior to isooctyl-S.展开更多
By using solvothermal method,a one-dimensional chain compound[KEu_(2)(FDCA)_(3)(H_(2)O)_(9)·0.5(FDCA)](1)was synthesized.Single-crystal X-ray diffraction data reveal that 1 crystallizes in monoclinic system,space...By using solvothermal method,a one-dimensional chain compound[KEu_(2)(FDCA)_(3)(H_(2)O)_(9)·0.5(FDCA)](1)was synthesized.Single-crystal X-ray diffraction data reveal that 1 crystallizes in monoclinic system,space group P21/n with a=12.1996(1),b=18.6454(2),c=17.7123(2)Å,β=98.8460(10)°,Dc=1.753 g/cm3,Z=2,V=3981.03(7)Å3,R=0.0544 and wR=0.1511 for 7886 observed reflections with I>2σ(I).In 1,three FDCA2–ligands construct a“23-crown-9-like”structure as the second building units(SBUs)to further form an infinite 1D chain.Meanwhile,the fluorescent result reveals that compound 1 can selectively and sensitively sense Fe^(3+)by the fluorescence quenching.展开更多
In order to explore new substitutes for 2,5 furandicarboxylic acid(FDCA)or poly(ethylene 2,5 furandicarboxylate)(PEF)and try to develop more ideal bio based polyesters,several thiophene aromatic polyesters(PETH,PPTH,P...In order to explore new substitutes for 2,5 furandicarboxylic acid(FDCA)or poly(ethylene 2,5 furandicarboxylate)(PEF)and try to develop more ideal bio based polyesters,several thiophene aromatic polyesters(PETH,PPTH,PBTH,and PHTH)were synthesized from dimethyl thiophene 2,5-dicarboxylate(DMTD)and different diols,including ethylene glycol,1,3-propanediol,1,4-butanediol,and 1,6-hexanediol.The chemical structures of obtained polyesters were confirmed by nuclear magnetic resonance spectroscopy(H-NMR and 1'C-NMR).Determined by GPC measurement,their average molecular weight(M.)varied from 5.22 x 10*g/mol to 7.94 x 10*g/mol with the molar-mass dispersity of 1.50-2.00.Based on the DSC and TGA results,the synthesized polyesters PETH,PPTH,and PBTH displayed comparable or even better thermal properties when compared with their FDCA-based analogues.From PETH to PHTH,their Tg varied from 64.6°Cto-1°C while Tsm ranged from 409 C to 380°C in nitrogen atmosphere,PETH showed elongation at break as high as 378%,tensile strength of 67 MPa,and tensile modulus of 1800 MPa.Meanwhile,the CO2 and O2 barrier of PETH was 12.0 and 6.6 folds higher than those of PET,respectively,and similar to those of PEF.Considering the overall properties,the synthesized thiophene aromatic polyesters,especially PETH,showed great potential to be used as an excellent bio based packaging material in the future.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
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(21031002 and 51073079)the Fundamental Research Funds for the Central Universitiesthe Application and Research in Cutting-edge Technologies in Tianjin Technology Projects in General(K11JCYBJC11100)
文摘Two new Cu(II) coordination polymers, [Cu(FDA)(BPY)(H20)]n (1) and {[Cu(FDA)(BPY)(H2O)].2H2O}n (2) (H2FDA = 2,5-furandicarboxylic acid, BPY = 2,2'-bipyridine), have been synthesized and structurally characterized by single-crystal X-ray diffraction as well as elemental analysis and IR. Compound 1 crystallizes in monoclinic, space group P21/c, with a = 7.5915(15), b = 8.4050(17), c = 24.204(6) A, β = 99.05(3)°, V= 1525.1(6) A3, Dc = 1.706 g/crn3, C16HI2CuN206, Mr = 391.82, F(000) = 796, μ(MoKa) = 1.470 mm-l, Z = 4, R = 0.0633 and wR = 0.1059 for 2389 observed reflections (1 〉 2a(I)), R = 0.0738, and wR = 0.1098 for all data. Complex 2 belongs to triclinic space group PI with a = 8.8660(18), b = 8.9112(18), c = 12.525(3) A, a = 88.41(3), β = 69.38(3), γ = 66.95(3)°, V = 845.2(3) A3, Dc = 1.681 g/cm3, CI6HI6CuN2Os, Mr. = 427.85, F(000) = 438, μ(MoKα) = 1.342 mm-1, Z = 2, R = 0.0290 and wR = 0.0690 for 2767 observed reflections (I 〉 2σ(I)), R = 0.0329 and wR = 0.0706 for all data. Complexes 1 and 2 are both coordination polymers with one-dimensional chain structures bridged by the protonated FDA ligands, which are assembled into three-dimensional supramolecular structures through hydrogen bonding interactions and π-π packing interactions between the chains.
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the National Natural Science Foundation of China(NNSFC)(21805145&U1610108)the Department of Science and Technology of Shandong Province(ZR2019BB068)+2 种基金the Department of Science and Technology of Shanxi Province(201705D211001)Scientific and Technological Innovation Programs of High Education Institutions in Shanxi(201802001-1)the Department of Human Resource and Social Security of Shanxi Province(Y6SW9613B1)。
文摘Selective oxidation of 5-hydroxymethylfurfual(HMF) to 2,5-furandicarboxylic acid(FDCA) as a bioplastics monomer is efficiently promoted by a simple system without noble-metal and base additives. In this work, graphene oxide(GO) was first synthesised by an electrochemical method with flexible graphite paper(FGP) as start carbon material, then, nitrogen-doped graphene(NG) layers encapsulated Cu nanoparticles(NPs) was prepared by one-step thermal treatment of GO supported Cu2+ in flowing NH3 atmosphere. Compared with NG supported Cu NPs prepared by the traditional impregnation method, enhanced catalytic activity was achieved over Cu/NG and an FDCA yield of 95.2% was achieved under mild reaction conditions with tert-butylhydroperoxide(t-BuOOH) as the oxidant. Control experiments with different catalysts and different addition procedure of t-BuOOH showed the yield of HMF and various intermediates during reaction. From the changing of intermediates concentrations and reaction rates, a reaction pathway through HMF-DFF-FFCA-FDCA was proposed. This work gives a more convenient, more green,more economical and effective method in encapsulated metal NPs preparation and high selectivity in HMF oxidation to FDCA under mild conditions.
基金supported by URT program of Beijing Institute of Petrochemical Technology(2015J00058 and 2015J00056)
文摘By using solvothermal method, two new main group metal coordination polymers based on 2,5-furandicarboxylic acid (H2FDA) ligand, [Sr2(FDA)E(H2O)5]n (1) and [Ba4(FDA)4(H2O)10]n (2), were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR, and powder X-ray diffraction. Compound 1 crystallizes in monoclinic, space group C2/c with a = 13.454(3), b = 13.426(3), c = 20.166(4) A, β = 107.06(3)°, V = 3482.4(13)A^3, Dc = 2.188 g/cm^3, CIEH14Sr2O15, Mr = 573.47, F(000) = 2256,μ(MoKα)= 6.21 mm^-1, Z = 8, R = 0.0522 and wR = 0.1229 for 2493 observed reflections (I〉 2σ(I)), and R = 0.0689 and wR = 0.1324 for all data. Compound 2 crystallizes in triclinic, space group el with α = 6.8382(14), b = 10.932(2), c = 25.571(5) A,α = 94.64(3), β= 95.41(3), γ = 107.83(3)°, V= 1799.4(6) A3, Dc = 2.484 g/cm^3, C24H28Ba4O30, Mr = 1345.82, F(000) = 1272,μ(MoKa) = 4.43 mm^-1, Z = 2, R = 0.0485 and wR = 0.0906 for 5020 observed reflections (I〉 2σ(I)), and R = 0.0706 and wR = 0.0991 for all data. In 1, the trinuclear clusters Sr3 are connected with adjacent four clusters by a carboxylate group to produce a two-dimensional (2D) sheet, which is extended by a FDA-based pillar into a 3D framework. In 2, neighbouring trinuclear clusters Ba3 are linked through two -O-C-O- of FDA^2- ligands to form one-dimensional (1D) chains, which are connected by a FDA-based pillar to construct a 2D framework. The thermal stabilities of 1 and 2 are also investigated.
基金Funded by the Program (BG20190227001) of High-end Foreign Experts of the State Administration of Foreign Experts Affairs (SAFEA)the 2021 Innovative Training Program for College Students in Hubei Province。
文摘Terephthalic acid,2,5-furandicarboxylic acid and 1,8-octanediol were adopted as monomers and antimony trioxide as catalyst,and poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) copolyesters identified as PEOT-x,where x is the mole fraction of furandicarboxylic acid in the samples,were synthesized by direct esterification.The molecular structure of the copolyesters was characterized by FTIR and 1H NMR spectroscopy.Gel permeation chromatography (GPC),differential scanning calorimetry (DSC),and thermogravimetric analysis (TGA) were used to characterize the molecular weight,molar mass dispersity,glass transition temperature,and thermal stability of the copolyesters,respectively.The mechanical properties of the samples were also investigated.The number-average molecular weight (M_(n)) of the samples varies from 9 700-18 800 g/mol,and molar mass dispersity (■=M_(w)/M_(n)) from 2.15-3.34.The initial decomposition temperature of the copolyesters is in the 332-356 ℃ range,with maximum decomposition rates at 390-410 ℃,while the glass transition temperature (Tg) varies from 0-33 ℃.Mechanical test shows that PEOT-10 has the highest tensile strength,while PEOT-90 has the largest tensile modulus and elongation at break.The experimental results show that these copolyesters can be synthesized with relatively high molecular weights,good thermal stability,and fair mechanical properties,which makes them excellent replacements for commercial polyesters,such as PET,and these properties can be tuned through the relative amounts of biomass monomer 2,5-furandicarboxylic acid used in the reactions.
基金supported by the National Natural Science Foundation of China(21501012)
文摘Three new coordination polymers,namely [Zn(FDA)(phen)(H2O)·H2O]n(1),[Cd(HFDA)(phen)2(NO3)](2) and [Cd(FDA)(phen)]n(3)(H2FDA = 2,5-furandicarboxylic acid,phen = 1,10-phenanthroline) have been synthesized by the solvothermal method and characterized by elemental analysis,IR,powder X-ray diffraction,thermogravimetric analysis and X-ray single-crystal diffraction analysis.For 1,the neighboring Zn^2+ ions are bridged by FDA2-as linkers to form one-dimensional(1D) chains,and phen ligands are as the terminal ligands.Furthermore,the 1D chains are packed into a three-dimensional(3D) supramolecular structure through hydrogen bonds and π-π interactions.For 2,the H2FDA ligand is partial deprotonation,which is a rare phenomenon among other coordination polymers based on H2FDA.Under the synergetic effect of phen ligands and the partial deprotonation of H2FDA,the structure of 2 is discrete.For 3,the Cd^2+ ions are linked by two carboxylates of FDA^2-ligand to give rise to 1 D zig-zag chains,and phen ligands chelate the Cd^2+ ions like 1.In addition,solid-state luminescent spectra of three coordination polymers were also studied at room temperature.
基金supported by URT program of Beijing Institute of Petrochemical Technology(Beijing municipal level 2015J00058)URT program of Beijing Institute of Petrochemical Technology(State level 2015J00056)
文摘By using solvothermal method, two new metal coordination polymers based on 2,5-furandicarboxylic acid(H2FDA) ligand and 4,4'-bipyridine(bipy), [Cu(FDA)(4,4'-bipy)(DMF)]n·solvent(1) and {[Zn(4,4'-bipy)(FDA)(DMF)]·DMF}n(2), were produced and characterized by single-crystal X-ray diffraction analyses, elemental analyses, IR and powder X-ray diffraction. Compound 1 crystallizes in monoclinic space group P21/c with a = 11.104(2), b = 10.396(2), c = 18.772(4) , β = 96.20(3)o, V = 2154.2(7) 3, Dc = 1.378 g/cm^3, C19H17 Cu N3O6, Mr = 446.90, F(000) = 916, μ(Mo Kα) = 1.05 mm^-1, Z = 4, R = 0.0691 and wR = 0.1341 for 3537 observed reflections(I 2σ(I)), and R = 0.1062 and w R = 0.1482 for all data. Compound 2 crystallizes in monoclinic space group C2/c with a = 29.779(6), b = 9.6417(19), c = 17.292(3), β = 105.69(3)°, V = 4779.9(16) 3, Dc = 1.445 g/cm^3, C22H22N4O7 Zn, Mr = 519.81, F(000) = 2144, μ(Mo Kα)= 1.08 mm^-1, Z = 8, R = 0.0641 and w R = 0.1007 for 2985 observed reflections(I 2σ(I)), and R = 0.1028 and w R = 0.1112 for all data. Different coordination geometry of metal ions, square pyramid of Cu2+ and trigonal bipyramid of Zn2+, bring about different orientations of FDA2- ligands as well as 4,4'-bipyridine ligands, and furthermore distinct assembly structures for 1 and 2. The thermal stabilities of 1 and 2 are also investigated.
基金This work was supported by the SEEDS grant from the Ohio Agricultural Research and Development Center(OARDC)of the Ohio State University,Ohio,USA[grant number 2016-105].
文摘The organic compound 2,5-furandicarboxylic acid(FDCA) has been identified by the US Department of Energy(DOE) as a valuable platform chemical for a wide range of industrial applications. Currently, the most popular route for FDCA synthesis is reported to be the oxidation of 5-hydroxymethylfurfural(HMF)by O_2 over the catalysis of noble metals(e.g., Au, Pt, Ru, and Pd). However, the high costs of noble metal catalysts remain a major barrier for producing FDCA at an industrial scale. Herein, we report a transition metal-free synthesis strategy for the oxidation of HMF to FDCA under O_2 or ambient air. A simple but unprecedented process for the aerobic oxidation of HMF was carried out in organic solvents using only bases as the promoters. According to the high performance liquid chromatography(HPLC) analysis, excellent product yield(91%) was obtained in the presence of NaOH in dimethylformamide(DMF) at room temperature(25 ℃). A plausible mechanism for the NaOH-promoted aerobic oxidation of HMF in DMF is also outlined in this paper. After the reaction, the sodium salt of FDCA particles were dispersed in the reaction mixture, making it possible for product separation and solvent reuse. The new HMF oxidation approach is expected to be a practical alternative to current ones, which depend on the use of noble metal catalysts.
基金supported by the science and technology research projects of Tianjin Health Bureau (W11KG127)
文摘Solvothermal reaction of 2,5-furandicarboxylic acid (H2FDA) ligand and Ca(NO3)24H2O affords a new coordination polymer, [Ca2(FDA)2(DMAC)(H2O)]n (1). The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR, powder X-ray diffraction and TGA. Compound I crystallizes in triclinic, space group Pi with a = 9.5387(19), b = 10.425(2), c = 11.590(2)A, a = 75.02(3), fl = 84.80(3), y = 80.99(3)~, V = 1098.1(4) A3, Dc = 1.492 g/cm^3, C16H15Ca2NO12, Mr = 493.45, F(O00) = 508, p(MoKa)= 0.580 mm-1, Z= 2, R = 0.0436 and wR = 0.0944 for 3865 observed reflections (I〉 2σ(/)), and R --- 0.0595 and wR = 0.1015 for all data. The structure of 1 exhibits a three-dimensional network with layer-pillar structure.
基金The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China(Grant No.21606082)Hunan Provincial Natural Science Foundation of China(No.2018JJ3334)+1 种基金China Postdoctoral Science Foundation(No.2019M662787)Hunan Provincial Innovation Foundation for Postgraduate(No.CX20200522).
文摘2,5-Furandicarboxylic acid(FDCA)is an important and renewable building block and can serve as an alternative to terephthalic acid in the production of biobased degradable plastic.In this study,Cu-doped MnO_(2) nanorods were prepared by a facile hydrothermal redox method and employed as catalysts for the selective oxidation of 5-hydroxymethylfurfural(HMF)to FDCA using tert-butyl hydroperoxide(TBHP)as an oxidant.The catalysts were characterized using X-ray diffraction analysis,Fourier transform infrared spectroscopy,thermo-gravimetric analysis,and transmission electron microscopy.The effects of oxidants,solvents,and reaction conditions on the oxidation of HMF were investigated,and a reaction mechanism was proposed.Experimental results demonstrated that 99.4% conversion of HMF and 96.3% selectivity of FDCA were obtained under suitable conditions,and tert-butanol was the most suitable solvent when TBHP was used as an oxidant.More importantly,the Cu-doped MnO_(2) catalyst can maintain durable catalytic activity after being recycled for more than ten times.
基金financial support from the Hunan Provincial Natural Science Foundation of China (Nos.2019JJ40090 and 2019JJ20008)
文摘An eco-friendly and economical route for the oxidation of 5-hydroxymethylfurfural(HMF) to 2,5-furandicarboxylic acid(FDCA) with atmospheric dioxygen as the sole oxidant under acid-,base-,metal-,and external initiator-free conditions in minimal solvent was reported.In the present reaction,the 1,2-diethoxyethylane has a dual role:reaction medium and free-radical initiato r.The FDCA easily crystallizes during the reaction and was simple purified via recrystallization to provide the pure FDCA.
基金National Natural Science Fund(51675006)the project of Science and Technology Department of Shaanxi Province(2016JZ017)the Local Servicing Research Project of the Education Department of Shanxi Province(15JF007).
文摘The depletion of petroleum resources and the intensification of environmental problems have necessitated the development of renewable products from bio-based chemicals instead of petroleum resources.Herein,a new kind of ester lubricating oil,isooctyl furan dicarboxylate(isooctyl-FD),was prepared from bio-based 2,5-furandicarboxylic acid.The structure of isooctyl-FD was evaluated using nuclear magnetic resonance imaging and high-resolution mass spectroscopy.Its physicochemical and tribological properties including thermal and oxidation stabilities,flash point and pour point,viscosity and viscosity index,and friction-reducing and anti-wear properties were systematically evaluated.The results show that isooctyl-FD has comparable thermal and oxidation stability to the synthetic ester lubricating oil,isooctyl sebacate(isooctyl-S).Its friction-reducing and anti-wear properties are superior to isooctyl-S;however,its viscosity-temperature and low-temperature properties are inferior to isooctyl-S.
基金supported by the High-level Teachers in Beijing Municipal Universities in the Period of 13th Five-year Plan (CIT&TCD201904044)URT program of Beijing Institute of Petrochemical Technology (2021J00003)
文摘By using solvothermal method,a one-dimensional chain compound[KEu_(2)(FDCA)_(3)(H_(2)O)_(9)·0.5(FDCA)](1)was synthesized.Single-crystal X-ray diffraction data reveal that 1 crystallizes in monoclinic system,space group P21/n with a=12.1996(1),b=18.6454(2),c=17.7123(2)Å,β=98.8460(10)°,Dc=1.753 g/cm3,Z=2,V=3981.03(7)Å3,R=0.0544 and wR=0.1511 for 7886 observed reflections with I>2σ(I).In 1,three FDCA2–ligands construct a“23-crown-9-like”structure as the second building units(SBUs)to further form an infinite 1D chain.Meanwhile,the fluorescent result reveals that compound 1 can selectively and sensitively sense Fe^(3+)by the fluorescence quenching.
基金This work was finanially supported by the National Natural Science Foundation of China(No.21975270)Zhejiang Provincial Natural Science Foundation of China(No.LR20E030001)+2 种基金Ningbo 2025 Key Scientific Research Programs(No.2018810015)National Key Research and Development Program of China(No.2018YFD0400700)Research Project of Ningbo Natural Science Foundation(No.2019A610141).
文摘In order to explore new substitutes for 2,5 furandicarboxylic acid(FDCA)or poly(ethylene 2,5 furandicarboxylate)(PEF)and try to develop more ideal bio based polyesters,several thiophene aromatic polyesters(PETH,PPTH,PBTH,and PHTH)were synthesized from dimethyl thiophene 2,5-dicarboxylate(DMTD)and different diols,including ethylene glycol,1,3-propanediol,1,4-butanediol,and 1,6-hexanediol.The chemical structures of obtained polyesters were confirmed by nuclear magnetic resonance spectroscopy(H-NMR and 1'C-NMR).Determined by GPC measurement,their average molecular weight(M.)varied from 5.22 x 10*g/mol to 7.94 x 10*g/mol with the molar-mass dispersity of 1.50-2.00.Based on the DSC and TGA results,the synthesized polyesters PETH,PPTH,and PBTH displayed comparable or even better thermal properties when compared with their FDCA-based analogues.From PETH to PHTH,their Tg varied from 64.6°Cto-1°C while Tsm ranged from 409 C to 380°C in nitrogen atmosphere,PETH showed elongation at break as high as 378%,tensile strength of 67 MPa,and tensile modulus of 1800 MPa.Meanwhile,the CO2 and O2 barrier of PETH was 12.0 and 6.6 folds higher than those of PET,respectively,and similar to those of PEF.Considering the overall properties,the synthesized thiophene aromatic polyesters,especially PETH,showed great potential to be used as an excellent bio based packaging material in the future.
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.