The selective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) is an important reaction for renewable biomass building blocks. Compared with thermal catalytic processes, photocatalytic production ...The selective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) is an important reaction for renewable biomass building blocks. Compared with thermal catalytic processes, photocatalytic production of DFF from HMF has attracted tremendous attention. Herein, the MoS_(2)/CdIn_(2)S_(4)(MC)flower-like heterojunctions were prepared and considered as photocatalysts for selective oxidation of HMF into DFF under visible-light irradiation in aqueous solution. Results demonstrated MoS_(2) in MC heterojunction could promote the separation of photoexcited electron-hole pairs, while the amount of MoS_(2) dropping was proved influenced on the photocatalytic performance. 80.93% of DFF selectivity was realized when using 12.5% MC as photocatalyst. In addition, the MC catalyst also showed great potential in transformation of other biomass derived benzyl-and furyl-alcohols. The catalytic mechanism suggested that ·O_(2)^(-) was the decisive active radical for HMF oxidation. Therefore, the MC heterojunction could be applied in photocatalytic conversion of biomass to valuable chemicals under ambient condition.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
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
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
The biobased renewable monomer 2,5-diformylfuran is polymerised using various N-heterocyclic carbene(NHC)catalysts in dimethyl sulfoxide(DMSO)affording a low molar mass polymer.It is shown that catalyst structure as w...The biobased renewable monomer 2,5-diformylfuran is polymerised using various N-heterocyclic carbene(NHC)catalysts in dimethyl sulfoxide(DMSO)affording a low molar mass polymer.It is shown that catalyst structure as well as the temperature and time the polymerization is running have a noticeable effect on its molar mass.The obtained material is characterized by nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),differential scanning calorimetry(DSC)and X-ray diffraction(XRD).An attempt at chain extension with diamine leads to precipitation of the polymer.This new biobased polymer material might be useful as a sustainable resin.展开更多
The synthesis of fine chemicals and fuel candidates from renewable biomass-based feedstocks has attracted much attention due to declining fossil resource.Many value-added furan derivatives,such as 5-hydroxymethylfurfu...The synthesis of fine chemicals and fuel candidates from renewable biomass-based feedstocks has attracted much attention due to declining fossil resource.Many value-added furan derivatives,such as 5-hydroxymethylfurfural(HMF),2,5-diformyfuran(DFF)and 2,5-furandicarboxylic acid,have been successfully produced from carbohydrates.Among these,DFF,the aerobic oxidation product of HMF,is a key chemical and can be used in organic synthesis and functional polymer manufacture.In this review,different catalytic systems for the synthesis of DFF from monosaccharide,disaccharide and polysaccharide were summarized,while reaction pathways and catalyst stability were also commented.Besides,the applications of DFF were introduced in brief.Then,prospects of more effective methods to DFF production and application were discussed.展开更多
目的建立气相色谱-质谱法(gas chromatography mass spectrometry,GC-MS)测定食品中合成香料3-乙酰基-2,5-二甲基呋喃的方法。方法样品用正己烷涡旋提取后过滤,含油脂样品采用冷冻过滤技术去除油脂和其他杂质,选用TG-5MS毛细管色谱柱(30...目的建立气相色谱-质谱法(gas chromatography mass spectrometry,GC-MS)测定食品中合成香料3-乙酰基-2,5-二甲基呋喃的方法。方法样品用正己烷涡旋提取后过滤,含油脂样品采用冷冻过滤技术去除油脂和其他杂质,选用TG-5MS毛细管色谱柱(30 m×0.25 mm,0.25μm),载气流速1 mL/min进行分离后进质谱分析。结果3-乙酰基-2,5-二甲基呋喃在0.005~10.000μg/L质量浓度范围内曲线线性良好,相关系数为0.9997;在不同基质及不同加标浓度下,加标回收率为80.16%~103.76%,相对标准偏差为1.83%~7.87%(n=6);3-乙酰基-2,5-二甲基呋喃在不同基质中的检出限均可达到1μg/kg,定量限均可达到3μg/kg。结论该方法简单、准确度高、灵敏度好,可以用于食品中3-乙酰基-2,5-二甲基呋喃含量的快速检测,为合成香料的安全使用和监管提供技术手段。展开更多
基金funded by the National Key Research and Development Program of China ( 2018YFB1501704)the National Natural Science Foundation of China (22078018)the Beijing Natural Science Foundation (2222016)。
文摘The selective oxidation of 5-hydroxymethylfurfural(HMF) into 2,5-diformylfuran(DFF) is an important reaction for renewable biomass building blocks. Compared with thermal catalytic processes, photocatalytic production of DFF from HMF has attracted tremendous attention. Herein, the MoS_(2)/CdIn_(2)S_(4)(MC)flower-like heterojunctions were prepared and considered as photocatalysts for selective oxidation of HMF into DFF under visible-light irradiation in aqueous solution. Results demonstrated MoS_(2) in MC heterojunction could promote the separation of photoexcited electron-hole pairs, while the amount of MoS_(2) dropping was proved influenced on the photocatalytic performance. 80.93% of DFF selectivity was realized when using 12.5% MC as photocatalyst. In addition, the MC catalyst also showed great potential in transformation of other biomass derived benzyl-and furyl-alcohols. The catalytic mechanism suggested that ·O_(2)^(-) was the decisive active radical for HMF oxidation. Therefore, the MC heterojunction could be applied in photocatalytic conversion of biomass to valuable chemicals under ambient condition.
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.
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.
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This research was funded by Research Foundation-Flanders,grant number G0D5416N。
文摘The biobased renewable monomer 2,5-diformylfuran is polymerised using various N-heterocyclic carbene(NHC)catalysts in dimethyl sulfoxide(DMSO)affording a low molar mass polymer.It is shown that catalyst structure as well as the temperature and time the polymerization is running have a noticeable effect on its molar mass.The obtained material is characterized by nuclear magnetic resonance(NMR),thermogravimetric analysis(TGA),differential scanning calorimetry(DSC)and X-ray diffraction(XRD).An attempt at chain extension with diamine leads to precipitation of the polymer.This new biobased polymer material might be useful as a sustainable resin.
基金Start-up Foundation of Highlevel Talents(1956037)in Chongqing Technology and Business University and Municipal Key Disciplines Construction Project of Chemical Engineering in Chongqing(950619013).
文摘The synthesis of fine chemicals and fuel candidates from renewable biomass-based feedstocks has attracted much attention due to declining fossil resource.Many value-added furan derivatives,such as 5-hydroxymethylfurfural(HMF),2,5-diformyfuran(DFF)and 2,5-furandicarboxylic acid,have been successfully produced from carbohydrates.Among these,DFF,the aerobic oxidation product of HMF,is a key chemical and can be used in organic synthesis and functional polymer manufacture.In this review,different catalytic systems for the synthesis of DFF from monosaccharide,disaccharide and polysaccharide were summarized,while reaction pathways and catalyst stability were also commented.Besides,the applications of DFF were introduced in brief.Then,prospects of more effective methods to DFF production and application were discussed.
