为实现蓝藻水华(CBB)的资源化利用,开发2,5-二甲酰呋喃(DFF)的绿色催化合成技术,将CBB高温炭化制成蓝藻基氮杂化活性炭(N-AC-CB),用于催化O2氧化5-羟甲糠醛(HMF)合成DFF反应。采用XRD、Raman、BET、FTIR、XPS对N-AC-CB进行了表征,考察了...为实现蓝藻水华(CBB)的资源化利用,开发2,5-二甲酰呋喃(DFF)的绿色催化合成技术,将CBB高温炭化制成蓝藻基氮杂化活性炭(N-AC-CB),用于催化O2氧化5-羟甲糠醛(HMF)合成DFF反应。采用XRD、Raman、BET、FTIR、XPS对N-AC-CB进行了表征,考察了CBB炭化温度和反应条件(反应温度、时间、氧压、溶剂)对反应的影响。结果表明,炭化温度700℃制备的N-AC-CB-700具有较好的催化性能,其所含石墨型氮杂化结构对形成催化活性中心起重要作用,总氮含量(5.90%)和石墨型氮含量(1.83%)均最高;在以6.37 g(0.05 mol)HMF为原料、1.20 g N-AC-CB-700为催化剂、150 mL N,N-二甲基乙酰胺为溶剂、反应温度100℃、氧压1.25 MPa、反应时间10 h的最优反应条件下,HMF转化率为100.0%,DFF收率为92.8%。N-AC-CB-700循环使用7次后,催化活性与首次使用相比仅下降5.4%,循环使用9次后,催化活性下降13.3%。展开更多
Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardan...Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardant strategies often compromise their mechanical properties,hindering their practical applications.Herein,a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)-based comonomer(DDP)was used to synthesize flame-retardant poly(ethylene furandicarboxylate-co-phosphaphenanthrene)(PEFDn).The covalent integration of DDP confers intrinsic flame retardancy,avoiding the plasticization and migration issues associated with additive-type systems.Upon thermal decomposition,the DOPO-derived moieties release phosphoric acid and radical scavengers,promoting char formation and suppressing flame propagation.Furthermore,density functional theory(DFT)calculations combined with non-covalent interaction(NCI)analysis revealed that DOPO dimer molecules adopt a stable parallel-displaced π-π stacking configu ration,potentially facilitating microphase separation and enhancing the energy dissipation capability.PEFD_(10)achieves a UL-94 V-0 rating while simultaneously increasing impact toughness from 1.5 kJ/m^(2) to 14.7 kJ/m^(2).Im portantly,PEFDn maintained acceptable oxygen-barrier properties.PEFD10 also exhibited high transparency and UV-shielding performance.The combination of intrinsic flame safety,im pact-toughness resistance,UV shielding,and an oxygen barrier ensures reliable protection of electrical components and long-term operational stability.The integration of multiple critical properties within a single bio-based material represents a novel approach fo r enabling sustainable polymer solutions for high-pe rformance electrical applications.展开更多
The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products,making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire ...The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products,making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire process.To achieve the efficient selective oxidation of HMF to FDCA,a series of NiCo_(2)O_(4)catalysts with different morphologies,such as flaky,echinoids,pompon and corolla,were prepared and characterized by XRD,SEM,TEM,BET,XPS,and FTIR.Among the four catalysts,flaky NiCo_(2)O_(4)exhibited the most excellent catalytic activity and stability,with a FDCA yield of 60.1%within 12 h at 80℃without alkali participation.The excellent performance of flaky NiCo_(2)O_(4)catalyst is attributed to the oxygen vacancies and acid sites generated by the exposed(400)facets.The oxygen vacancies and acid sites on the catalyst surface can precisely adsorb-CHO and-CH_(2)-OH of HMF,respectively,and this synergistic effect promotes the efficient production of FDCA.This work is of great significance for fundamentally study the effect of micro-topography or crystal-plane reaction properties on surfaces.展开更多
文摘为实现蓝藻水华(CBB)的资源化利用,开发2,5-二甲酰呋喃(DFF)的绿色催化合成技术,将CBB高温炭化制成蓝藻基氮杂化活性炭(N-AC-CB),用于催化O2氧化5-羟甲糠醛(HMF)合成DFF反应。采用XRD、Raman、BET、FTIR、XPS对N-AC-CB进行了表征,考察了CBB炭化温度和反应条件(反应温度、时间、氧压、溶剂)对反应的影响。结果表明,炭化温度700℃制备的N-AC-CB-700具有较好的催化性能,其所含石墨型氮杂化结构对形成催化活性中心起重要作用,总氮含量(5.90%)和石墨型氮含量(1.83%)均最高;在以6.37 g(0.05 mol)HMF为原料、1.20 g N-AC-CB-700为催化剂、150 mL N,N-二甲基乙酰胺为溶剂、反应温度100℃、氧压1.25 MPa、反应时间10 h的最优反应条件下,HMF转化率为100.0%,DFF收率为92.8%。N-AC-CB-700循环使用7次后,催化活性与首次使用相比仅下降5.4%,循环使用9次后,催化活性下降13.3%。
基金financially supported by the National Key Research and Development Program of China(No.2021YFB3700300)the National Natural Science Foundation of China(Nos.52573017 and U21B2093)+1 种基金Key Research and Development Program of Ningbo(No.2022Z200)the Zhejiang Provincial Natural Science Foundation(No.LY23E030005)。
文摘Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardant strategies often compromise their mechanical properties,hindering their practical applications.Herein,a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)-based comonomer(DDP)was used to synthesize flame-retardant poly(ethylene furandicarboxylate-co-phosphaphenanthrene)(PEFDn).The covalent integration of DDP confers intrinsic flame retardancy,avoiding the plasticization and migration issues associated with additive-type systems.Upon thermal decomposition,the DOPO-derived moieties release phosphoric acid and radical scavengers,promoting char formation and suppressing flame propagation.Furthermore,density functional theory(DFT)calculations combined with non-covalent interaction(NCI)analysis revealed that DOPO dimer molecules adopt a stable parallel-displaced π-π stacking configu ration,potentially facilitating microphase separation and enhancing the energy dissipation capability.PEFD_(10)achieves a UL-94 V-0 rating while simultaneously increasing impact toughness from 1.5 kJ/m^(2) to 14.7 kJ/m^(2).Im portantly,PEFDn maintained acceptable oxygen-barrier properties.PEFD10 also exhibited high transparency and UV-shielding performance.The combination of intrinsic flame safety,im pact-toughness resistance,UV shielding,and an oxygen barrier ensures reliable protection of electrical components and long-term operational stability.The integration of multiple critical properties within a single bio-based material represents a novel approach fo r enabling sustainable polymer solutions for high-pe rformance electrical applications.
基金supported by the Swedish Energy Agency(P47500-1)the National Key R&D Program of China(2020YFA0710200)+2 种基金the National Natural Science Foundation of China(22378401 and U22A20416)the financial support from STINT(CH2019-8287)financial support from the European Union and Swedish Energy Agency(P2020-90066).
文摘The catalytic oxidation of HMF involves a cascading reaction with multiple intermediate products,making it crucial to enhance the oriented adsorption capacity of specific functional groups for accelerating the entire process.To achieve the efficient selective oxidation of HMF to FDCA,a series of NiCo_(2)O_(4)catalysts with different morphologies,such as flaky,echinoids,pompon and corolla,were prepared and characterized by XRD,SEM,TEM,BET,XPS,and FTIR.Among the four catalysts,flaky NiCo_(2)O_(4)exhibited the most excellent catalytic activity and stability,with a FDCA yield of 60.1%within 12 h at 80℃without alkali participation.The excellent performance of flaky NiCo_(2)O_(4)catalyst is attributed to the oxygen vacancies and acid sites generated by the exposed(400)facets.The oxygen vacancies and acid sites on the catalyst surface can precisely adsorb-CHO and-CH_(2)-OH of HMF,respectively,and this synergistic effect promotes the efficient production of FDCA.This work is of great significance for fundamentally study the effect of micro-topography or crystal-plane reaction properties on surfaces.
