6338-41-6Relevant articles and documents
Aerobic oxidation of 5-hydroxymethylfurfural to 5-hydroxymethyl-2-furancarboxylic acid and its derivatives by heterogeneous NHC-catalysis
Brandolese, Arianna,Ragno, Daniele,Di Carmine, Graziano,Bernardi, Tatiana,Bortolini, Olga,Giovannini, Pier Paolo,Pandoli, Omar Ginoble,Altomare, Alessandra,Massi, Alessandro
, p. 8955 - 8964 (2018)
The application of the oxidative system composed of a heterogeneous triazolium pre-catalyst, iron(ii) phthalocyanine and air is described for the selective conversion of 5-hydroxymethylfurfural (HMF) into the added-value 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). The disclosed one-pot two-step procedure involved sequential oxidative esterifications of HMF to afford a polyester oligomer having hydroxyl and carboxyl terminal groups (Mw = 389-1258), which in turn was hydrolyzed by a supported base (Ambersep 900 OH) to yield HMFCA in 87% overall yield. The same strategy was adopted for the effective synthesis of ester and amide derivatives of HMFCA by nucleophilic depolymerization of the oligomeric intermediate with methanol and butylamine, respectively. The utilization of the disclosed oxidative system for the direct conversion of HMF and furfural into their corresponding ester, amide, and thioester derivatives is also reported.
Electrochemical biomass valorization on gold-metal oxide nanoscale heterojunctions enables investigation of both catalyst and reaction dynamics with: Operando surface-enhanced raman spectroscopy
Heidary, Nina,Kornienko, Nikolay
, p. 1798 - 1806 (2020)
The electrochemical oxidation of biomass platforms such as 5-hydroxymethylfurfural (HMF) to value-added chemicals is an emerging clean energy technology. However, mechanistic knowledge of this reaction in an electrochemical context is still lacking and operando studies are even more rare. In this work, we utilize core-shell gold-metal oxide nanostructures which enable operando surface-enhanced Raman spectroelectrochemical studies to simultaneously visualize catalyst material transformation and surface reaction intermediates under an applied voltage. As a case study, we show how the transformation of NiOOH from ～1-2 nm amorphous Ni layers facilitates the onset of HMF oxidation to 2,5-furandicarboxylic acid (FDCA), which is attained with 99% faradaic efficiency in 1 M KOH. In contrast to the case in 1 M KOH, NiOOH formation is suppressed, and consequently HMF oxidation is sluggish in 10 mM KOH, even at highly oxidizing potentials. Operando Raman experiments elucidate how surface adsorption and interaction dictates product selectivity and how the surface intermediates evolve with applied potential. We further extend our methodology to investigate NiFe, Co, Fe, and CoFe catalysts and demonstrate that high water oxidation activity is not necessarily correlated with excellent HMF oxidation performance and highlight catalytic factors important for this reaction such as reactant-surface interactions and the catalysts' physical and electronic structure. The insights extracted are expected to pave the way for a deepened understanding of a wide array of electrochemical systems such as for organic transformations and CO2 fixation.
Transforming Electrocatalytic Biomass Upgrading and Hydrogen Production from Electricity Input to Electricity Output
Chen, Ru,Du, Shiqian,Fu, Xian-Zhu,Gan, Lang,Gu, Kaizhi,Huang, Zhifeng,Li, Yafei,Liu, Tianyang,Tao, Li,Tian, Jing,Wang, Shuangyin,Wang, Tehua,Wei, Xiaoxiao,Zhou, Peng,Zou, Yuqin
supporting information, (2022/02/05)
Integrating biomass upgrading and hydrogen production in an electrocatalytic system is attractive both environmentally and in terms of sustainability. Conventional electrolyser systems coupling anodic biosubstrate electrooxidation with hydrogen evolution reaction usually require electricity input. Herein, we describe the development of an electrocatalytic system for simultaneous biomass upgrading, hydrogen production, and electricity generation. In contrast to conventional furfural electrooxidation, the employed low-potential furfural oxidation enabled the hydrogen atom of the aldehyde group to be released as gaseous hydrogen at the anode at a low potential of approximately 0 VRHE (vs. RHE). The integrated electrocatalytic system could generate electricity of about 2 kWh per cubic meter of hydrogen produced. This study may provide a transformative technology to convert electrocatalytic biomass upgrading and hydrogen production from a process requiring electricity input into a process to generate electricity.
Oxidation of 2,5-bis(hydroxymethyl)furan to 2,5-furandicarboxylic acid catalyzed by carbon nanotube-supported Pd catalysts
Chen, Chunlin,Hao, Panpan,Huai, Liyuan,Li, Zhenyu,Wang, Yongzhao,Zhang, Bingsen,Zhang, Jian,Zhao, Xi
, p. 793 - 801 (2022/02/05)
The selective oxidation of 2,5-bis(hydroxymethyl)furan (BHMF) in this work was proven as a promising route to produce 2,5-furandicarboxylic acid (FDCA), an emerging bio-based building-block with wide application. Under ambient pressure, the modified carbon nanotube-supported Pd-based catalysts demonstrate the maximum FDCA yield of 93.0% with a full conversion of BHMF after 60 min at 60 °C, much superior to that of the traditional route using 5-hydroxymethylfurfural (HMF) as substrates (only a yield of 35.7%). The participation of PdHx active species with metallic Pd can be responsible for the encouraging performance. Meanwhile, a possible reaction pathway proceeding through 2,5-diformylfuran (DFF) and 5-formyl-2-furancarboxylic acid (FFCA) as process intermediates is suggested for BHMF route. The present work may provide new opportunities to synthesize other high value-added oxygenates by using BHMF as an alternative feedstock.
Aerobic oxidation of 5-[(formyloxy)methyl]furfural to 2,5-furandicarboxylic acid over MoCuOx catalyst
Wang, Qian,Zhang, Jie,Jia, Wenlong,Yu, Xin,Chen, Jiahong,Sun, Yong,Wei, Zuojun,Yang, Shuliang,Tang, Xing,Zeng, Xianhai,Lin, Lu
, (2021/11/30)
Generally, 5-hydroxymethylfurfural (HMF) is used as feedstock to produce 2,5-furandicarboxylic acid (FDCA). Whereas, its poor stability in alkaline environment results in low yield of FDCA. By contrast, 5-[(formyloxy)methyl]furfural (FMF), a novel platform compound derived from HMF, with higher thermal and alkaline stability than HMF, is more promising to replace HMF as substrate for the production of FDCA. In this study, FMF was successfully converted into FDCA over MoCuOx by using NaClO as oxidant, undergoing 2,5-diformylfuran (DFF) and 5-hydroxymethylfuran-2-carboxylic acid (HMFCA) as intermediates. Under optimization condition (30 min, 40 °C), 100% yield of FDCA was obtained. Furthermore, it was also demonstrated that the yield of FDCA up to 90% was gained in 5 wt % FMF concentration. Higher oxygen species mobility and lattice oxygen ratio endowed MoCuOx excellent catalytic activity. The synergy of Mo and Cu species in MoCuOx ensured an efficient conversion of HMF to FDCA through synergistic redox couple of Mo6+/Mo5+ and Cu2+/Cu+.
Synthesis of 2,5-Diaryl Nonsymmetric Furans C6-Platform Chemicals via Catalytic Conversion of Biomass and the Formal Synthesis of Dantrolene
Chacón-Huete, Franklin,Lasso, Juan David,Szavay, Paul,Covone, Jason,Forgione, Pat
, p. 515 - 524 (2020/12/22)
Biomass-derived commodity chemical 5-hydroxymethyl furfural is an underutilized C6-platform chemical derived from cellulose that is ideal to prepare next-generation value-added products. We have developed an efficient synthetic strategy to access 2,5-diar
Base-free atmospheric O2-mediated oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic acid triggered by Mg-bearing MTW zeolite supported Au nanoparticles
Chen, Lei,Zhuang, Wenxia,Lan, Jingmin,Liu, Xiaoling,Jiang, Shi,Wang, Lei,Zhou, Yu,Wang, Jun
, (2021/03/29)
Mg-bearing MTW silicalite zeolite, MgSi-ZSM-12, was straightforwardly synthesized by involving an unusual acidic pre-gelation system and engaged as the task-specific support for loading the Au nanoparticles (NPs). The resulting Au/MgSi-ZSM-12 catalyst showed stably excellent activity for the oxidation of HMF into FDCA in the presence of atmospheric dioxygen (O2) without externally adding any liquid base, affording a yield of 87 % and turnover number (TON) of 331 based on the surface Au sites. Superior basicity was evidenced by embedding Mg species into the all-silica zeolitic skeleton, which enables strong, weak, and near-zero affinity towards aldehyde, alcohol, and carboxyl groups, respectively, thus, allows rapid and high-uptake adsorption of HMF, but negligible adsorption of FDCA. This unique feature of the Mg-bearing all-silica zeolite support together with its synergy with the active sites of Au NPs is revealed to accelerate the production of FDCA under the base-free mild condition.
Preparation method of 5-hydroxymethyl furoic acid
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Paragraph 0055-0089, (2021/05/12)
The invention provides a preparation method of 5-hydroxymethyl furoic acid, and the method comprises the following steps of: in the presence of air and/or oxygen, putting 5-hydroxymethyl furfural and a catalyst into a mixed solution of water and an organic solvent, and carrying out catalytic oxidation reaction to obtain the 5-hydroxymethyl furoic acid; the catalyst is prepared by the following steps of: mixing a carrier, an alkaline nitrogen-containing compound and an active component precursor, putting the mixture into a solvent, performing heating under a water bath condition, and carrying out reflux stirring treatment; and sequentially carrying out drying treatment and roasting reduction treatment on the mixture subjected to the reflux stirring treatment; wherein the active component precursor is selected from one or more of rhodium chloride, palladium chloride, chloroplatinic acid and ruthenium chloride, and the carrier is selected from one or more of activated carbon, graphite, fullerene and graphene oxide. The catalyst adopted by the method is high in activity, the product yield is high, the reaction does not need to be carried out in an alkaline environment, the reaction process is environment-friendly, the product is easy to separate, and the problem of complicated subsequent acid treatment in the traditional 5-hydroxymethyl furoic acid preparation process is solved.
(Hexamethylbenzene)Ru catalysts for the Aldehyde-Water Shift reaction
Phearman, Alexander S.,Moore, Jewelianna M.,Bhagwandin, Dayanni D.,Goldberg, Jonathan M.,Heinekey, D. Michael,Goldberg, Karen I.
supporting information, p. 1609 - 1615 (2021/03/09)
The Aldehyde-Water Shift (AWS) reaction uses H2O as a benign oxidant to convert aldehydes to carboxylic acids, producing H2, a valuable reagent and fuel, as its sole byproduct. (Hexamethylbenzene)RuIIcomplexes are demonstrated to have higher activity and selectivity (up to 95%) for AWS over disproportionation than previously reported catalysts.
CeO2@N/C@TiO2 Core-shell Nanosphere Catalyst for the Aerobic Oxidation of 5-Hydroxymethylfurfural to 5-Hydroxymethyl-2-Furancarboxylic Acid
Song, Yong,Waterhouse, Geoffrey I. N.,Han, Feng,Li, Yan,Ai, Shiyun
, p. 2931 - 2941 (2021/05/27)
Defective D-CeO2@N/C@TiO2 nanospheres, each comprising a spherical CeO2 core coated with shells of N-doped carbon and TiO2, were successfully synthesized then evaluated for the aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). Detailed catalyst characterization studies using XRD, SEM, TEM, TG-DTA, XPS, N2 physisorption confirmed the hierarchical core-shell structure of the D-CeO2@N/C@TiO2 nanospheres, with the defective surface structures created through a thermal hydrogenation process using NaBH4 promoting HMF conversion. The effect of various reaction parameters, including the reaction time, temperature, oxygen pressure, type of alkali co-reactant and the amount of catalyst, on HMF oxidation to HMFCA over the D-CeO2@N/C@TiO2 nanospheres were studied. Under the optimized reaction conditions (temperature 80 °C, reaction time 30 min, O2 pressure 1 MPa), a high HMF conversion of 87.8 % and a remarkable HMFCA selectivity of 100 % were obtained. In addition, the D-CeO2@N/C@TiO2 nanosphere catalyst showed great stability over four consecutive HMF oxidation tests, implying good catalyst stability. Experimental findings were used to develop a plausible reaction mechanism for the selective oxidation of HMF on the D-CeO2@N/C@TiO2 nanospheres.
