In the past century,industrial and economic growth relied heavily on fossil fuels such as coal,oil,and natural gas.As the society energy demands continue to grow,these fossil fuel reserves are depleted,leading to sign...In the past century,industrial and economic growth relied heavily on fossil fuels such as coal,oil,and natural gas.As the society energy demands continue to grow,these fossil fuel reserves are depleted,leading to significant environmental issues[1].Currently,sustainable biomass resources have attracted much attention as potential substitutes to fossil fuels for producing biofuels and commodity chemicals[2].展开更多
A mild and simple process for the effective oxidation of 5-hydroxymethylfurfural（HMF） into 2,5-diformylfuran（DFF） has been developed using Na NO2 as the oxidant. Some important reaction parameters were investigate...A mild and simple process for the effective oxidation of 5-hydroxymethylfurfural（HMF） into 2,5-diformylfuran（DFF） has been developed using Na NO2 as the oxidant. Some important reaction parameters were investigated to optimize the oxidation of HMF into DFF. It was found that the reaction solvent was very crucial for this reaction. Trifluoroacetic acid was the best solvent for the oxidation of HMF into DFF by Na NO2.Under the optimal reaction condition, almost quantitative HMF conversion and high DFF yield of 90.4% were obtained after 1 h at room temperature.展开更多
A low-cost and easily prepared manganese carbonate(Mn CO_3) has been synthesized for catalytic conversion of 5-hydroxymethylfurfural(5-HMF) to 2,5-diformylfuran(DFF). The properties and morphology of the manganese car...A low-cost and easily prepared manganese carbonate(Mn CO_3) has been synthesized for catalytic conversion of 5-hydroxymethylfurfural(5-HMF) to 2,5-diformylfuran(DFF). The properties and morphology of the manganese carbonate were measured by SEM,XRD,TGA,BET and XPS. In this method,no harsh reaction conditions were required,and it was a simple and green process for the oxidation of 5-HMF into DFF. To achieve an optimum DFF yield,different reaction conditions,including reaction temperature,reaction time,catalyst amount,and solvents were investigated. Results from the experiments indicated that the highest DFF yield of 86.9% was obtained at 120 °C under atmospheric oxygen pressure after 6h. Finally,Mn CO_3 could be used at least five times with considerable stability.展开更多
The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catal...The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.展开更多
In this paper, we report a new catalytic system for realizing the rapid and efficient oxidation of 5-hydroxymethylfurfural(HMF). First, we used 9-azabicyclo [3.3.1]nonan-3-one-N-oxyl(keto-ABNO) as a catalyst for the a...In this paper, we report a new catalytic system for realizing the rapid and efficient oxidation of 5-hydroxymethylfurfural(HMF). First, we used 9-azabicyclo [3.3.1]nonan-3-one-N-oxyl(keto-ABNO) as a catalyst for the aerobic oxidation of 5-hydroxymethylfurfural(HMF) to 2,5-diformylfuran(DFF) in acetic acid. Then, we systematically studied the important reaction parameters, including the solvent, co-catalyst, and temperature. The results demonstrate that the acidic solvent used is crucial for the efficient oxidation of HMF to DFF. Under optimal conditions, we achieved a 93.4% yield of DFF within half an hour at room temperature. We also proposed the possible mechanism for this system.展开更多
One-pot direct conversion of cheap and abundant fructose to 2,5-diformylfuran (DFF) is highly desirable to achieve hundreds-fold value-increase and high atomic economy,yet it is still challenging due to the lack of su...One-pot direct conversion of cheap and abundant fructose to 2,5-diformylfuran (DFF) is highly desirable to achieve hundreds-fold value-increase and high atomic economy,yet it is still challenging due to the lack of suitable catalysts with cascade conversion ability.In this work,we developed a porous hybrid catalyst (i.e.PMo_(10)V_(2)@2Br-PIL) based on the assembly of polyoxometalates and porous polyionic liquids that can be applied in the one-pot conversion of fructose to DFF.The integration of PMo_(10)V_(2) with 2Br-PIL can impart both Brønsted acid and oxidation sites in the porous structure,thereby enabling the one-pot cascade conversion.As a result,PMo_(10)V_(2)@2Br-PIL demonstrated a remarkable DFF yield (95% yield),satisfying stability,recyclability and scale-up production ability (≈12.3 g in a batch experiment),demonstrating great potential for industrial production of DFF from fructose.Theoretical calculations revealed a synergistic effect of Brønsted acid sites and oxidation sites in PMo_(10)V_(2)@2Br-PIL,which promoted the one-pot conversion of fructose to DFF.This study enhances the understanding of biomass transformation over hybrid catalysts through synergetic acidic/oxidative catalysis,contributing to the development of highly active,selective,and multifunctional catalysts for one-pot biomass conversion.展开更多
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O_(2)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...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O_(2)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
基金funded by the Master,PhD Scholarship Programme of Vingroup Innovation Foundation(VINIF),code VINIF.2024.TS.035funded by Vietnam National University,Ho Chi Minh City(VNUHCM)under grant number NCM2024-18-01。
文摘In the past century,industrial and economic growth relied heavily on fossil fuels such as coal,oil,and natural gas.As the society energy demands continue to grow,these fossil fuel reserves are depleted,leading to significant environmental issues[1].Currently,sustainable biomass resources have attracted much attention as potential substitutes to fossil fuels for producing biofuels and commodity chemicals[2].
基金supported by the National Natural Science Foundation of China(21272065)Scientific Research Fund of Hunan Provincial Education Department(13C562+2 种基金15C0816)Outstanding Youth Project of Hunan Provincial Education Department(15B134)the funding offered by China Scholarship Council(201506720018)
文摘A mild and simple process for the effective oxidation of 5-hydroxymethylfurfural（HMF） into 2,5-diformylfuran（DFF） has been developed using Na NO2 as the oxidant. Some important reaction parameters were investigated to optimize the oxidation of HMF into DFF. It was found that the reaction solvent was very crucial for this reaction. Trifluoroacetic acid was the best solvent for the oxidation of HMF into DFF by Na NO2.Under the optimal reaction condition, almost quantitative HMF conversion and high DFF yield of 90.4% were obtained after 1 h at room temperature.
基金supported by the Natural Science Foundation of Tianjin (No. 16JCYBJC19600)the National Natural Science Foundation of China (No. 21621004)the Beiyang Young Scholar of Tianjin University (2012)
文摘A low-cost and easily prepared manganese carbonate(Mn CO_3) has been synthesized for catalytic conversion of 5-hydroxymethylfurfural(5-HMF) to 2,5-diformylfuran(DFF). The properties and morphology of the manganese carbonate were measured by SEM,XRD,TGA,BET and XPS. In this method,no harsh reaction conditions were required,and it was a simple and green process for the oxidation of 5-HMF into DFF. To achieve an optimum DFF yield,different reaction conditions,including reaction temperature,reaction time,catalyst amount,and solvents were investigated. Results from the experiments indicated that the highest DFF yield of 86.9% was obtained at 120 °C under atmospheric oxygen pressure after 6h. Finally,Mn CO_3 could be used at least five times with considerable stability.
文摘The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.
基金supported by the Natural Science Foundation of Tianjin,China(No.16JCYBJC19600)Natural Science Foundation of China(No.21621004)+1 种基金Beiyang Young Scholar of Tianjin University(2012)the State Key Laboratory of Chemical Engineering(No.SKL-ChE-08B01)
文摘In this paper, we report a new catalytic system for realizing the rapid and efficient oxidation of 5-hydroxymethylfurfural(HMF). First, we used 9-azabicyclo [3.3.1]nonan-3-one-N-oxyl(keto-ABNO) as a catalyst for the aerobic oxidation of 5-hydroxymethylfurfural(HMF) to 2,5-diformylfuran(DFF) in acetic acid. Then, we systematically studied the important reaction parameters, including the solvent, co-catalyst, and temperature. The results demonstrate that the acidic solvent used is crucial for the efficient oxidation of HMF to DFF. Under optimal conditions, we achieved a 93.4% yield of DFF within half an hour at room temperature. We also proposed the possible mechanism for this system.
基金financially supported by the National Natural Science Foundation of China(No.21871125,22475074,22171139 and 22201116)Natural Science Foundation of Guangdong Province(No.2023B1515020076)+2 种基金Natural Science Foundation of Shandong Province(No.ZR2022QB066 and ZR2023MB018)Dongying City School Cooperation Fund Key Project(SXHZ-2023-02-15)college Student Innovation and Entrepreneurship Training Plan of Liaocheng University(cxcy089).
文摘One-pot direct conversion of cheap and abundant fructose to 2,5-diformylfuran (DFF) is highly desirable to achieve hundreds-fold value-increase and high atomic economy,yet it is still challenging due to the lack of suitable catalysts with cascade conversion ability.In this work,we developed a porous hybrid catalyst (i.e.PMo_(10)V_(2)@2Br-PIL) based on the assembly of polyoxometalates and porous polyionic liquids that can be applied in the one-pot conversion of fructose to DFF.The integration of PMo_(10)V_(2) with 2Br-PIL can impart both Brønsted acid and oxidation sites in the porous structure,thereby enabling the one-pot cascade conversion.As a result,PMo_(10)V_(2)@2Br-PIL demonstrated a remarkable DFF yield (95% yield),satisfying stability,recyclability and scale-up production ability (≈12.3 g in a batch experiment),demonstrating great potential for industrial production of DFF from fructose.Theoretical calculations revealed a synergistic effect of Brønsted acid sites and oxidation sites in PMo_(10)V_(2)@2Br-PIL,which promoted the one-pot conversion of fructose to DFF.This study enhances the understanding of biomass transformation over hybrid catalysts through synergetic acidic/oxidative catalysis,contributing to the development of highly active,selective,and multifunctional catalysts for one-pot biomass conversion.
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O_(2)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%。
