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
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.