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Oxygen-vacancy-rich MnO_(x)supported RuO_(x)for efficient base-free oxidation of 5-hydroxymethylfurfural and 5-methoxymethylfurfural to 2,5-furandicarboxylic acid
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作者 Jiali Wu Weizhen Xie +7 位作者 Yining Zhang Xixian Ke Tianyuan Li Huayu Fang Yong Sun Xianhai Zeng Lu Lin Xing Tang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第8期670-683,I0015,共15页
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
关键词 Base-free oxidation Oxygen-vacancy-rich 5-HYDROXYMETHYLFURFURAL 5-Methoxymethylfurfural 2 5-furandicarboxylic acid
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Transforming liquid flow fuel cells to controllable reactors for highlyefficient oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid at low temperature
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作者 Ye Qiang Xi Liu +2 位作者 Denghao Ouyang Zhao Jiang Xuebing Zhao 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2024年第3期621-631,I0014,共12页
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
关键词 5-HYDROXYMETHYLFURFURAL 2 5-furandicarboxylic acid ELECTRODEPOSITION Electron transport chain Liquid flow fuel cell
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Two New Cu(Ⅱ) Coordination Polymers Based on 2,5-Furandicarboxylic Acid and 2,2'-bipyridine:Synthesis and Crystal Structure 被引量:4
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作者 王浩 温荣梅 +3 位作者 常泽 王倩 李楠 孔令钰 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2014年第1期97-103,共7页
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
关键词 2 5-furandicarboxylic acid copper complex crystal structure 2 2'-bipyridine
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2,5-Furandicarboxylic acid production via catalytic oxidation of 5-hydroxymethylfurfural:Catalysts,processes and reaction mechanism 被引量:10
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作者 Chunlin Chen Lingchen Wang +4 位作者 Bin Zhu Zhenqiang Zhou Soliman I.El-Hout Jie Yang Jian Zhang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2021年第3期528-554,共27页
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
关键词 5-HYDROXYMETHYLFURFURAL 2 5-furandicarboxylic acid Catalytic oxidation Mechanism
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High efficient catalytic oxidation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid under benign conditions with nitrogen-doped graphene encapsulated Cu nanoparticles 被引量:3
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作者 Chaoxin Yang Xiao Li +7 位作者 Zhenzhou Zhang Bohan Lv Jiachun Li Zhenjian Liu Wanzhen Zhu Furong Tao Guangqiang Lv Yongxing Yang 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2020年第11期96-105,共10页
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
关键词 Graphene oxide Encapsulated nanoparticles 5-hydroxymethylfurfual 2 5-furandicarboxylic acid Oxidation Noble-metal free
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Two New Main Group Metal Coordination Polymers Based on 2,5-Furandicarboxylic Acid: Syntheses and Crystal Structures 被引量:2
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作者 王浩 刘洋 +2 位作者 陈飞 郭雨萌 章应辉 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2015年第4期585-593,共9页
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
关键词 2 5-furandicarboxylic acid main group crystal structure
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Synthesis and Characterization of Poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) Copolyester 被引量:1
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作者 CHENG Zhengzai CHENG Junpeng +5 位作者 CHEN Jun XIONG Jing SUN Xin JIA Ruyan YUAN Beibei Gauthier Mario 《Journal of Wuhan University of Technology(Materials Science)》 SCIE EI CAS 2021年第4期557-561,共5页
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
关键词 2 5-furandicarboxylic acid terephthalic acid melt polymerization COPOLYESTERS
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Crystal Structures and Luminescent Properties of Three Coordination Polymers Based on 2,5-Furandicarboxylic Acid Ligand and 1,10-Phenanthroline 被引量:3
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作者 赵帅 郝学敏 +2 位作者 王浩 伍一波 郭文莉 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2018年第1期131-139,共9页
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
关键词 2 5-furandicarboxylic acid 1 10-phenanthroline crystal structure
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Metal-directed Assembly of Two Distinct Coordination Polymers with 2,5-Furandicarboxylic Acid and 4,4'-Bipyridine 被引量:3
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作者 王浩 邢光建 +2 位作者 陈飞 孙杰 章应辉 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2015年第7期1113-1120,共8页
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
关键词 2 5-furandicarboxylic acid 4 4'-bipyridine metal-directed coordination polymer
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A new approach for the aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid without using transition metal catalysts 被引量:5
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作者 Lu Zhang Xiaolan Luo Yebo Li 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2018年第1期243-249,共7页
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
关键词 Aerobic oxidation 5-Hydroxymethylfur fural2 5-furandicarboxylic acid Sodium hydroxide Transition metal catalyst-free
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A Novel Calcium(Ⅱ) Coordination Polymer Based on 2,5-Furandicarboxylic Acid:Synthesis and Crystal Structure 被引量:3
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作者 王浩 孔令钰 +1 位作者 李楠 王倩 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2013年第7期999-1004,共6页
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
关键词 2 5-furandiearboxylic acid ealcium(II) crystal structure
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FDCA,FDME,2,5-呋喃二甲酸聚酯的工业开发及应用研究进展
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作者 陈锡荣 《合成树脂及塑料》 CAS 北大核心 2024年第5期68-72,共5页
具有芳杂环结构的2,5-呋喃二甲酸(FDCA)与精对苯二甲酸(PTA)结构类似,可广泛用于聚酯、聚酰胺、金属有机骨架材料、医药化学品合成、增塑剂等方面,在多个领域成为PTA理想的生物基替代品。目前,市场尚无FDCA,2,5-呋喃二甲酸二甲酯(FDME),... 具有芳杂环结构的2,5-呋喃二甲酸(FDCA)与精对苯二甲酸(PTA)结构类似,可广泛用于聚酯、聚酰胺、金属有机骨架材料、医药化学品合成、增塑剂等方面,在多个领域成为PTA理想的生物基替代品。目前,市场尚无FDCA,2,5-呋喃二甲酸二甲酯(FDME),聚2,5-呋喃二甲酸乙二酯(PEF)的工业化产品,FDCA,PEF由于生产成本高、技术难度大,仍处于研究阶段。欧洲、北美等国家在持续推动FDCA,FDME及PEF商业化工作中保持领先,其中,PEF对CO_(2),O_(2),H_(2)O的阻隔性能极好,将在生鲜食品包装领域有着广阔的应用前景。 展开更多
关键词 2 5-呋喃二甲酸 2 5-呋喃二甲酸二甲酯 2 5-呋喃二甲酸乙二酯 聚酯 发展趋势
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基于2,5-二溴对苯二羧酸配体的镧系金属有机骨架的合成、结构及性质
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作者 罗小玲 邹品田 +4 位作者 王小燕 刘峥 孔翔飞 唐群 王胜 《无机化学学报》 SCIE CAS CSCD 北大核心 2024年第6期1143-1150,共8页
采用溶剂热法,以2,5-二溴对苯二甲酸(H_(2)L)为配体,分别与六水合硝酸钕、六水合硝酸钆反应合成了_(2)种镧系金属有机骨架(MOFs):{[Nd_(2)(L)_(3)(DMF)_(2)(H_(2)O)_(2)]·_(2)DMF}n(1)和{[Gd_(2)(L)_(3)(DMF)_(2)(H_(2)O)_(2)]... 采用溶剂热法,以2,5-二溴对苯二甲酸(H_(2)L)为配体,分别与六水合硝酸钕、六水合硝酸钆反应合成了_(2)种镧系金属有机骨架(MOFs):{[Nd_(2)(L)_(3)(DMF)_(2)(H_(2)O)_(2)]·_(2)DMF}n(1)和{[Gd_(2)(L)_(3)(DMF)_(2)(H_(2)O)_(2)]·2DMF}n(_(2))。通过单晶X射线衍射、粉末X射线衍射、红外光谱、元素分析、荧光光谱、热重分析等测试方法对其进行了结构表征与性质研究。结果表明,2个配合物均是以稀土离子为金属节点,与配体相互连接,形成无限延伸的三维网状结构。 展开更多
关键词 镧系 2 5-二溴对苯二甲酸 金属有机骨架 晶体结构
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电催化5-羟甲基糠醛氧化为2,5-呋喃二甲酸的研究进展 被引量:2
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作者 潘远江 郭珍燕 +1 位作者 黄金术 李虎 《能源环境保护》 2024年第2期81-93,共13页
在可持续发展导向下,替代能源需求不断增加,生物质资源的有效利用成为研究焦点。5-羟甲基糠醛(HMF)作为一种生物质基平台化合物,具有广阔的应用前景。通过选择性氧化反应,HMF可以转化为高附加值化合物,如2,5-呋喃二甲酸(FDCA)。近年来,... 在可持续发展导向下,替代能源需求不断增加,生物质资源的有效利用成为研究焦点。5-羟甲基糠醛(HMF)作为一种生物质基平台化合物,具有广阔的应用前景。通过选择性氧化反应,HMF可以转化为高附加值化合物,如2,5-呋喃二甲酸(FDCA)。近年来,电催化氧化作为一种绿色环保的新型手段,在HMF转化为FDCA的研究中取得了显著进展。然而,这一过程涉及竞争反应,如水氧化,对FDCA的产率和法拉第效率产生影响。催化剂对降低反应能垒、提高产物选择性至关重要,但面临稳定性不足、过电位偏高和酸性环境下活性不足等挑战。聚焦于高效催化剂的研究进展,从贵金属催化剂到非贵金属催化剂和非金属催化剂进行深入探讨,旨在为生物质的高效转化提供有益参考。 展开更多
关键词 电化学氧化 生物质 5-羟甲基糠醛 2 5-呋喃二甲酸 电催化剂
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电化学合成2,5-二甲氧基-2,5-二氢呋喃甲醇工艺研究
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作者 孙任伟 马养民 《应用化工》 CAS CSCD 北大核心 2024年第1期118-121,共4页
以糠醇为原料,NaBr为电解质,甲醇为溶剂,利用电化学法合成焦袂康酸中间体2,5-二甲氧基-2,5-二氢呋喃甲醇,考察反应时间、NaBr添加量、反应温度对产率的影响。结果表明,反应时间与反应温度对产率有显著影响,NaBr添加量对产率影响不显著... 以糠醇为原料,NaBr为电解质,甲醇为溶剂,利用电化学法合成焦袂康酸中间体2,5-二甲氧基-2,5-二氢呋喃甲醇,考察反应时间、NaBr添加量、反应温度对产率的影响。结果表明,反应时间与反应温度对产率有显著影响,NaBr添加量对产率影响不显著。当加入糠醇3 g(24 mmol),恒压15 V,最优条件为反应时间2.4 h,NaBr添加量为1.76 g,反应温度-10℃时,平均电流0.93 A,2,5-二甲氧基-2,5-二氢呋喃甲醇产率为67.9%。 展开更多
关键词 糠醇 2 5-二甲氧基-2 5-二氢呋喃甲醇 焦袂康酸 Box-Behnken
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芳构化法合成2,5-二羟基对苯二甲酸反应机理的密度泛函理论研究
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作者 王先飞 钱刚 《分子催化(中英文)》 CAS CSCD 北大核心 2024年第3期234-244,I0002,共12页
采用密度泛函理论(DFT)计算,研究了由1,4-环己二酮-2,5-二甲酸二甲酯(DMSS)制备2,5-二羟基对苯二甲酸(DHTA)的反应机理.其中,采用IEFPCM溶剂模型着重计算了DMSS由酮式互变异构为烯醇式的溶剂效应,并探究了碘在催化DMSS烯醇式氧化芳构化... 采用密度泛函理论(DFT)计算,研究了由1,4-环己二酮-2,5-二甲酸二甲酯(DMSS)制备2,5-二羟基对苯二甲酸(DHTA)的反应机理.其中,采用IEFPCM溶剂模型着重计算了DMSS由酮式互变异构为烯醇式的溶剂效应,并探究了碘在催化DMSS烯醇式氧化芳构化过程中的作用机制.计算结果表明,在溶剂分子的辅助下,DMSS酮-烯醇式互变异构反应的能垒显著降低;芳构化过程中,碘首先与过氧化氢反应生成活性物质次碘酸,其催化DMSS烯醇式发生碘代反应,并经过后续的消去和互变异构生成2,5-二羟基对苯二甲酸二甲酯(DMDHT),DMDHT进一步水解生成DHTA.同时,通过核磁共振氢谱测试验证了DMSS酮-烯醇式互变异构的溶剂效应;反应性能考评实验结果表明,相较于无催化剂,在碘的催化作用下,DMDHT产品的纯度和收率更高. 展开更多
关键词 2 5-二羟基对苯二甲酸 DFT 互变异构 芳构化 反应机理
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5-羟甲基糠醛路线合成2,5-呋喃二甲酸的研究进展
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作者 许智扬 祝钧 《中国塑料》 CAS CSCD 北大核心 2024年第2期61-69,共9页
2,5-呋喃二甲酸(FDCA)是一种能够合成生物基聚酯的重要单体,目前在新型可降解塑料等领域具有广阔的应用前景,如何高效且低廉地制备FDCA已经逐步成为了热点问题。本文系统地综述了近年来通过5-羟甲基糠醛(HMF)路线合成FDCA的主要研究进展... 2,5-呋喃二甲酸(FDCA)是一种能够合成生物基聚酯的重要单体,目前在新型可降解塑料等领域具有广阔的应用前景,如何高效且低廉地制备FDCA已经逐步成为了热点问题。本文系统地综述了近年来通过5-羟甲基糠醛(HMF)路线合成FDCA的主要研究进展,首先介绍了HMF路线和其他路线的联系和区别,解释了HMF路线的优点。其次,详细介绍和分析了由HMF合成FDCA的方法,包括直接氧化法、贵金属催化法、过渡金属催化法、光电催化氧化法、酶催化法和全细胞生物催化法。此外,在介绍上述方法的基础上,说明了这些方法的优缺点,总结了HMF路线制备FDCA目前仍面临的挑战,包括催化剂的选择、改善与开发,反应条件优化和对中间产物的处理,还对未来由HMF路线来制备FDCA的前景进行展望。 展开更多
关键词 2 5-呋喃二甲酸 5-羟甲基糠醛 多相热催化氧化法 光电催化法 生物催化法
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5-羟甲基糠醛电氧化合成2,5-呋喃二甲酸的研究进展
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作者 范子毅 温慧明 +1 位作者 张文君 陈祖鹏 《林产化学与工业》 CAS CSCD 北大核心 2024年第5期147-158,共12页
5-羟甲基糠醛(HMF)作为顶级生物质衍生平台分子,可用于生产各种高附加值的化学品。其中,2,5-呋喃二甲酸(FDCA)作为HMF的氧化产物,被认为是石油基单体对苯二甲酸的有效替代品,在合成可再生聚乙烯呋喃二甲酸酯材料方面发挥了重要作用。近... 5-羟甲基糠醛(HMF)作为顶级生物质衍生平台分子,可用于生产各种高附加值的化学品。其中,2,5-呋喃二甲酸(FDCA)作为HMF的氧化产物,被认为是石油基单体对苯二甲酸的有效替代品,在合成可再生聚乙烯呋喃二甲酸酯材料方面发挥了重要作用。近年来,电催化HMF氧化(HMFOR)合成FDCA取得了显著进展。本文在简单介绍电催化HMFOR合成FDCA反应途径的基础上,详细综述了用于电催化HMFOR合成FDCA的各类高效催化剂,包括贵金属催化剂、非贵金属催化剂和非金属催化剂,其中非贵金属催化剂主要有镍基、钴基、铜基、锰基、钒基催化剂。此外,还介绍了电催化HMFOR耦合电解水析氢反应(HER)、二氧化碳还原反应(CO_(2)RR)、氮还原反应(N_(2)RR)等阴极还原反应。最后对未来的研究方向和发展前景作了展望,以期为后续电催化HMFOR的基础研究和技术升级提供借鉴。 展开更多
关键词 电氧化 生物质 电催化剂 5-羟甲基糠醛 2 5-呋喃二甲酸
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KNaPHI光催化氧化5-羟甲基糠醛选择性生成2,5-呋喃二甲酸
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作者 裴习瑞 张佳元 +1 位作者 钮腾飞 倪邦庆 《林产化学与工业》 CAS CSCD 北大核心 2024年第5期249-257,共9页
以KOH、NaOH和三聚氰胺为原料,使用一种自下而上的方法制备得到光催化剂聚七嗪酰亚胺钾钠混合物(KNaPHI),采用SEM、TEM、FT-IR、XRD、XPS、ICP-OES等方法分析了该催化剂的形貌、结构及元素组成,测试了其氧化还原电势、能带结构及光电性... 以KOH、NaOH和三聚氰胺为原料,使用一种自下而上的方法制备得到光催化剂聚七嗪酰亚胺钾钠混合物(KNaPHI),采用SEM、TEM、FT-IR、XRD、XPS、ICP-OES等方法分析了该催化剂的形貌、结构及元素组成,测试了其氧化还原电势、能带结构及光电性能,并考察了KNaPHI光催化氧化5-羟甲基糠醛(HMF)制备2,5-呋喃二甲酸(FDCA)的性能。研究结果表明:KNaPHI催化剂为片层块状结构,表面光滑平整,主要由C、N、O、K、Na这5种元素组成;具有光吸收性能,这使得催化剂光生载流子能够定向移动,进而提高了其光电效应。与传统的固体氮化碳相比,KNaPHI纳米颗粒可以在水中形成拟均相的溶液,从而实现对底物的高效光催化。在1 mmol(126 mg)HMF、3 mL水溶剂、40 mg KNaPHI催化剂、101.325 kPa O_(2)、50 W紫外灯光照射、室温反应24 h的最佳反应条件下,HMF的转化率达到82%,产物FDCA的选择性为91%;在循环使用5次后,催化剂水溶液仍然保持较好的催化效果,原料转化率和产物选择性仅略微下降。活性物质捕获实验结果发现超氧阴离子自由基(O_(2)^(-)·)和空穴(h^(+))是HMF光催化氧化生成FDCA的主要活性物质。 展开更多
关键词 生物质选择性氧化 光催化 5-羟甲基糠醛 2 5-呋喃二甲酸
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电催化5-羟甲基糠醛制备2,5-呋喃二甲酸的研究进展
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作者 姜均政 徐宝钗 彭祥 《天津科技大学学报》 CAS 2024年第5期1-13,共13页
5–羟甲基糠醛(HMF)作为一种重要的生物质资源备受关注,其氧化产物2,5–呋喃二甲酸具有替代对苯二甲酸合成高聚物的商业潜力。生物质资源的充分利用可减少对传统化石能源的依赖,而将生物质高效催化转化为高价值化学品是生物质循环利用... 5–羟甲基糠醛(HMF)作为一种重要的生物质资源备受关注,其氧化产物2,5–呋喃二甲酸具有替代对苯二甲酸合成高聚物的商业潜力。生物质资源的充分利用可减少对传统化石能源的依赖,而将生物质高效催化转化为高价值化学品是生物质循环利用的重要途径之一。本文系统综述了依赖pH的HMF电催化氧化反应路径,并深入分析其反应机制;重点讨论用于HMF催化氧化反应的电催化剂的设计策略,并总结了催化剂研究的最新进展及其电催化性能的优化策略;对未来的研究方向进行展望。对这些研究进展的系统分析,将为实现生物质资源的可持续利用和高效转化提供理论和实践指导。 展开更多
关键词 5–羟甲基糠醛 2 5–呋喃二甲酸 生物质利用 电催化氧化 电催化剂
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