Electrocatalytic oxidation of more stable 2,5-furanedimethanol(FDM)for 2,5-furanediformic acid(FDCA)generation with concurrent hydrogen production is attractive but still nascent compared to 5-Hydroxymethyl-2-furaldeh...Electrocatalytic oxidation of more stable 2,5-furanedimethanol(FDM)for 2,5-furanediformic acid(FDCA)generation with concurrent hydrogen production is attractive but still nascent compared to 5-Hydroxymethyl-2-furaldehyde(HMF).The need for effective and stable bifunctional electrocatalysts that are efficient for the FDM cell is thus quite significant.Wood serves as an ideal matrix for boosting the performance of catalysts,since its hierarchical porous structures facilitate mass transport and provide abundant active sites.Unfortunately,it has never been demonstrated for electrochemically organic synthesis.Herein,the effectiveness of Fe-CoP in catalyzing FDM oxidation was demonstrated by density functional theory(DFT)calculations and experiments,and a renewable carbonized porous wood decorated with Fe-doped CoP nanoleaves(Fe-CoP/CW)was constructed for electrocatalytic FDCA and hydrogen generation.The obtained Fe-CoP/CW as an anode in FDM solution afforded a current density of 100 mA cm^(−2)with a yield of 90%FDCA at a potential no more than 1.50 V vs RHE,which was 90 mV and 350 mV lower than Fe-CoP/carbon cloth(CC)and IrO_(2).In addition,Fe-CoP/CW showed excellent long-term stability for 108-h FDM oxidation in strong alkaline solution.Remarkably,in stark contrast to Fe-CoP/CC and Pt,the hydrogen evolution performance of Fe-CoP/CW was not impacted by FDM at the cathode,and it required exceptionally low overpotentials of 0.19 V to achieve 100 mA cm^(−2).As a result,in terms of the overall cell,the hydrogen production rate was 0.756 mmol cm^(−2)h^(−1),which was 3.57 times higher than those of commonly used commercial Pt|IrO_(2)cell,presenting a Faraday efficiency of near 100%.This work will pave the way towards the implementation of highly suited bifunctional electrodes and the possibility of affordable,effective,and environmentally-friendly wood-derived electrocatalysts for electrochemically organic synthesis.展开更多
It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for elec...It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for electrocatalytic HMF oxidative reaction(e-HMFOR)have been facing low Faradaic efficiency(FE)and high water splitting voltage.Herein,we propose a strategy of the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction by constructing a Co-Ni paired site,where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site,thus giving the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction superior electrocata lytic performances for e-HMFOR and water splitting.By optimizing conditions,the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction has high conversion of 99.7%,high selectivity of 99.9%,and high FE of 98.4%at 1.3 V,as well as low cell voltage of 1.31 V at 10 mA cm^(-2)in 1 M KOH+0.1 M HMF.This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H_(2)in an economical manner.展开更多
2,5-Furandicarboxylic acid（2,5-FDCA） has been regarded as the ideal bio-based alternative to terephthalic acid（TPA）. In recent years, great efforts have been made to synthesize 2,5-FDCA through the following meth...2,5-Furandicarboxylic acid（2,5-FDCA） has been regarded as the ideal bio-based alternative to terephthalic acid（TPA）. In recent years, great efforts have been made to synthesize 2,5-FDCA through the following methods：（1） oxidation of 5-hydroxymethylfurfural（HMF） in the presence of complex biocatalyst or metallic catalyst;（2） conversion of 2-furoic acid via the well-known Henkel Reaction. Herein, a new strategy for the synthesis of 2,5-FDCA from furan and acetic anhydride under mild condition is reported. The purity of the resulted 2,5-FDCA was above 99.9%. Acetic acid and iodoform generated in the reaction were recyclable and no other harmful by-products were detected. The thus-obtained 2,5-FDCA was applied for the preparation of poly（ethylene furandicarboxylate）（PEF） of high quality in terms of high molecular weight and good appearance.展开更多
Developing highly efficient and cost-effective catalysts for electrochemically oxidizing biomass-derived 5-hydroxymethylfurfural(HMF)into value-added 2,5-furandicarboxylic acid(FDCA)is of great importance.Herein,we re...Developing highly efficient and cost-effective catalysts for electrochemically oxidizing biomass-derived 5-hydroxymethylfurfural(HMF)into value-added 2,5-furandicarboxylic acid(FDCA)is of great importance.Herein,we report a controllable nitrogen doping strategy to significantly improve the catalytic activity of Co_(3)O_(4)nanowires for highly selective electro-oxidation of HMF into FDCA.The nitrogen doping leads to the generation of defects including nitrogen dopants and oxygen vacancies in Co_(3)O_(4)nanowires,which is conducive to the formation of catalytically active sites.As a result,the electro-oxidation potential for HMF is only 1.38 V(vs.RHE)when the current density reaches 50 mA/cm^(2).More importantly,the conversion rate of HMF is as high as 99.5%,and the yield of FDCA is up to 96.4%.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
Co-based catalysts are promising alternatives to precious metals for the selective and effective oxidation of 5-hydroxymethylfurfural(HMF)to the higher value-added 2,5-furandicarboxylic acid(FDCA).However,these cataly...Co-based catalysts are promising alternatives to precious metals for the selective and effective oxidation of 5-hydroxymethylfurfural(HMF)to the higher value-added 2,5-furandicarboxylic acid(FDCA).However,these catalysts still suffer from unsatisfactory activity and poor selectivity.A series of N-doped carbon-supported Co-based dual-metal nanoparticles(NPs)have been designed,among which the Co-Cu_(1.4)-CN_(x) exhibits enhanced HMF oxidative activity,achieving FDCA formation rates 4 times higher than that of pristine Co-CN_(x),with 100%FDCA selectivity.Density functional theory(DFT)calculations evidenced that the increased electron density on Co sites induced by Cu can mediate the positive electronegativity offset to downshift the dband center of Co-Cu_(1.4)-CN_(x),thus reducing the energy barriers for the conversion of HMF to FDCA.Such findings will support the development of superior non-precious metal catalysts for HMF oxidation.展开更多
基金supported by the National Natural Science Foundation of China(22008199,22172119)China Postdoctoral Science Foundation(No.2021M692643)+3 种基金the Natural Science Foundation of Anhui Education Department(2022AH051045)the Natural Science Basic Research Plan in Shaanxi Province of China(2021JM-047)the National Science Fund for Distinguished Young Scholars(21825204)Open Project of the State Key Laboratory of Transducer Technology(SKT2307).
文摘Electrocatalytic oxidation of more stable 2,5-furanedimethanol(FDM)for 2,5-furanediformic acid(FDCA)generation with concurrent hydrogen production is attractive but still nascent compared to 5-Hydroxymethyl-2-furaldehyde(HMF).The need for effective and stable bifunctional electrocatalysts that are efficient for the FDM cell is thus quite significant.Wood serves as an ideal matrix for boosting the performance of catalysts,since its hierarchical porous structures facilitate mass transport and provide abundant active sites.Unfortunately,it has never been demonstrated for electrochemically organic synthesis.Herein,the effectiveness of Fe-CoP in catalyzing FDM oxidation was demonstrated by density functional theory(DFT)calculations and experiments,and a renewable carbonized porous wood decorated with Fe-doped CoP nanoleaves(Fe-CoP/CW)was constructed for electrocatalytic FDCA and hydrogen generation.The obtained Fe-CoP/CW as an anode in FDM solution afforded a current density of 100 mA cm^(−2)with a yield of 90%FDCA at a potential no more than 1.50 V vs RHE,which was 90 mV and 350 mV lower than Fe-CoP/carbon cloth(CC)and IrO_(2).In addition,Fe-CoP/CW showed excellent long-term stability for 108-h FDM oxidation in strong alkaline solution.Remarkably,in stark contrast to Fe-CoP/CC and Pt,the hydrogen evolution performance of Fe-CoP/CW was not impacted by FDM at the cathode,and it required exceptionally low overpotentials of 0.19 V to achieve 100 mA cm^(−2).As a result,in terms of the overall cell,the hydrogen production rate was 0.756 mmol cm^(−2)h^(−1),which was 3.57 times higher than those of commonly used commercial Pt|IrO_(2)cell,presenting a Faraday efficiency of near 100%.This work will pave the way towards the implementation of highly suited bifunctional electrodes and the possibility of affordable,effective,and environmentally-friendly wood-derived electrocatalysts for electrochemically organic synthesis.
基金supported by the National Natural Science Foundation of China(22302019)the Changzhou Sci&Tech Program(CJ20220214).
文摘It is very appealing that 5-hydroxymethylfurfural(HMF)is electrocatalytical oxidized as 2,5-furandicarboxylic acid(FDCA)linking to non-classical cathodic hydrogen(H_(2))production.However,the electrocatalysts for electrocatalytic HMF oxidative reaction(e-HMFOR)have been facing low Faradaic efficiency(FE)and high water splitting voltage.Herein,we propose a strategy of the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction by constructing a Co-Ni paired site,where the Co site is in charge of adsorbing for HMF while the electrons are transferred to the Ni site,thus giving the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction superior electrocata lytic performances for e-HMFOR and water splitting.By optimizing conditions,the NiSeO_(3)@(CoSeO_(3))_(4)heterojunction has high conversion of 99.7%,high selectivity of 99.9%,and high FE of 98.4%at 1.3 V,as well as low cell voltage of 1.31 V at 10 mA cm^(-2)in 1 M KOH+0.1 M HMF.This study offers a potential insight for e-HMFOR to high value-added FDCA coupling water splitting to produce H_(2)in an economical manner.
基金financially supported by the National Natural Science Foundation of China(Nos.51373194 and 51503217)National Key Technology Support Program(No.2015BAD15B08)
文摘2,5-Furandicarboxylic acid（2,5-FDCA） has been regarded as the ideal bio-based alternative to terephthalic acid（TPA）. In recent years, great efforts have been made to synthesize 2,5-FDCA through the following methods：（1） oxidation of 5-hydroxymethylfurfural（HMF） in the presence of complex biocatalyst or metallic catalyst;（2） conversion of 2-furoic acid via the well-known Henkel Reaction. Herein, a new strategy for the synthesis of 2,5-FDCA from furan and acetic anhydride under mild condition is reported. The purity of the resulted 2,5-FDCA was above 99.9%. Acetic acid and iodoform generated in the reaction were recyclable and no other harmful by-products were detected. The thus-obtained 2,5-FDCA was applied for the preparation of poly（ethylene furandicarboxylate）（PEF） of high quality in terms of high molecular weight and good appearance.
基金supported by the National Natural Science Foundation of China(Nos.22075159 and 21775078)Youth Innovation Team Project of Shandong Provincial Education Department(No.2019KJC023)。
文摘Developing highly efficient and cost-effective catalysts for electrochemically oxidizing biomass-derived 5-hydroxymethylfurfural(HMF)into value-added 2,5-furandicarboxylic acid(FDCA)is of great importance.Herein,we report a controllable nitrogen doping strategy to significantly improve the catalytic activity of Co_(3)O_(4)nanowires for highly selective electro-oxidation of HMF into FDCA.The nitrogen doping leads to the generation of defects including nitrogen dopants and oxygen vacancies in Co_(3)O_(4)nanowires,which is conducive to the formation of catalytically active sites.As a result,the electro-oxidation potential for HMF is only 1.38 V(vs.RHE)when the current density reaches 50 mA/cm^(2).More importantly,the conversion rate of HMF is as high as 99.5%,and the yield of FDCA is up to 96.4%.
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.
基金the National Natural Science Foundation of China(Nos.51902281,51801075,and 82160421)the Natural Science Foundation of Jiangsu Province(No.BK20211322)the Scientific and Technological Projects of Henan Province(No.212102210293).
文摘Co-based catalysts are promising alternatives to precious metals for the selective and effective oxidation of 5-hydroxymethylfurfural(HMF)to the higher value-added 2,5-furandicarboxylic acid(FDCA).However,these catalysts still suffer from unsatisfactory activity and poor selectivity.A series of N-doped carbon-supported Co-based dual-metal nanoparticles(NPs)have been designed,among which the Co-Cu_(1.4)-CN_(x) exhibits enhanced HMF oxidative activity,achieving FDCA formation rates 4 times higher than that of pristine Co-CN_(x),with 100%FDCA selectivity.Density functional theory(DFT)calculations evidenced that the increased electron density on Co sites induced by Cu can mediate the positive electronegativity offset to downshift the dband center of Co-Cu_(1.4)-CN_(x),thus reducing the energy barriers for the conversion of HMF to FDCA.Such findings will support the development of superior non-precious metal catalysts for HMF oxidation.
