Abstract:The mechanism of selective oxidation of aqueous 5-hydroxymethylfurfural (HMF) at high pH was studied over supported Pt and Au catalysts. Results from labeling experiments conducted with 18 O 2 and H 2 18 O indicated that water was the source of oxygen atoms during the oxidation of HMF to 2-hydroxymethylfurancarboxylic acid (HFCA) and 2,5-furandicarboxylic acid (FDCA), presumably through direct participation of hydroxide in the catalytic cycle. Molecular oxygen was essential for the production of FDCA and playe… Show more
“…Davis et al improved the selectivity for FDCA up to 65 % by increasing the NaOH/HMF ratio from 2 to 20 over Au/TiO 2 . [11] The reason may be that the base can facilitate dehydrogenation of hydroxyl, and reduce the amount of carboxylic acid adsorbed on the Au surface, thus more active sites are unoccupied. These recent researches reveal that the oxidation of HMF to FDCA still exhibit problems such as instability, ion leaching, and the need of a high ratio of base, which need to be overcome.…”
Au nanoclusters with an average size of approximately 1 nm size supported on HY zeolite exhibit a superior catalytic performance for the selective oxidation of 5‐hydroxymethyl‐2‐furfural (HMF) into 2,5‐furandicarboxylic acid (FDCA). It achieved >99 % yield of 2,5‐furandicarboxylic acid in water under mild conditions (60 °C, 0.3 MPa oxygen), which is much higher than that of Au supported on metal oxides/hydroxide (TiO2, CeO2, and Mg(OH)2) and channel‐type zeolites (ZSM‐5 and H‐MOR). Detailed characterizations, such as X‐ray diffraction, transmission electron microscopy, N2‐physisorption, and H2‐temperature‐programmed reduction (TPR), revealed that the Au nanoclusters are well encapsulated in the HY zeolite supercage, which is considered to restrict and avoid further growing of the Au nanoclusters into large particles. The acidic hydroxyl groups of the supercage were proven to be responsible for the formation and stabilization of the gold nanoclusters. Moreover, the interaction between the hydroxyl groups in the supercage and the Au nanoclusters leads to electronic modification of the Au nanoparticles, which is supposed to contribute to the high efficiency in the catalytic oxidation of HMF to FDCA.
“…Davis et al improved the selectivity for FDCA up to 65 % by increasing the NaOH/HMF ratio from 2 to 20 over Au/TiO 2 . [11] The reason may be that the base can facilitate dehydrogenation of hydroxyl, and reduce the amount of carboxylic acid adsorbed on the Au surface, thus more active sites are unoccupied. These recent researches reveal that the oxidation of HMF to FDCA still exhibit problems such as instability, ion leaching, and the need of a high ratio of base, which need to be overcome.…”
Au nanoclusters with an average size of approximately 1 nm size supported on HY zeolite exhibit a superior catalytic performance for the selective oxidation of 5‐hydroxymethyl‐2‐furfural (HMF) into 2,5‐furandicarboxylic acid (FDCA). It achieved >99 % yield of 2,5‐furandicarboxylic acid in water under mild conditions (60 °C, 0.3 MPa oxygen), which is much higher than that of Au supported on metal oxides/hydroxide (TiO2, CeO2, and Mg(OH)2) and channel‐type zeolites (ZSM‐5 and H‐MOR). Detailed characterizations, such as X‐ray diffraction, transmission electron microscopy, N2‐physisorption, and H2‐temperature‐programmed reduction (TPR), revealed that the Au nanoclusters are well encapsulated in the HY zeolite supercage, which is considered to restrict and avoid further growing of the Au nanoclusters into large particles. The acidic hydroxyl groups of the supercage were proven to be responsible for the formation and stabilization of the gold nanoclusters. Moreover, the interaction between the hydroxyl groups in the supercage and the Au nanoclusters leads to electronic modification of the Au nanoparticles, which is supposed to contribute to the high efficiency in the catalytic oxidation of HMF to FDCA.
“…Also, direct oxidation of the aldehyde or alcohol in the presence of water, base and metal catalyst results in carboxylic acid formation (Scheme 5, reaction 6). 127,128 Subsequently, the formed carboxylic acids can also condensate into ketones with liberation of CO 2 (Scheme 5, reaction 7). 106,107,129,130 As…”
Section: Catalysis Science and Technology Minireviewmentioning
The Guerbet condensation reaction is an alcohol coupling reaction that has been known for more than a century. Because of the increasing availability of bio-based alcohol feedstock, this reaction is of growing importance and interest in terms of value chains of renewable chemical and biofuel production. Due to the specific branching pattern of the alcohol products, the Guerbet reaction has many interesting applications. In comparison to their linear isomers, branched-chain Guerbet alcohols have extremely low melting points and excellent fluidity. This review provides thermodynamic insights and unravels the various mechanistic steps involved. A comprehensive overview of the homogeneous, heterogeneous and combined homogeneous and heterogeneous catalytic systems described in published reports and patents is also given. Technological considerations, challenges and perspectives for the Guerbet chemistry are discussed.
“…[19][20][21][22] For instance, polyethylene furanoate (PEF), a copolymer from FDCA and ethyleneglycol, is an alternative for the non-renewable polyethylenetherephthalate (PET) in the manufacture of bottles and other packaging. PEF polymer has also improved properties for packing and bottles applications compared to PET, such as: lower permeability to water, oxygen, and carbon dioxide (which guarantees the quality and freshness of the product for longer time); and better thermal and mechanical properties, allowing a broader range of application.…”
Section: Lignocellulosic Biomass and Chemical Conversion Of Biomass Smentioning
Chemicals commodities and consumable, accounting for billions of ton of carbon per year, are produced in an industry based on non-renewable fossil feedstocks. Oil reserves are enough for feeding chemical industry for another century, and therefore, it is essential finding alternative sources of carbon for a progressive replacement of the industrial feedstock. In this context lignocellulosic, a renewable source of carbon composed mainly by polymers of sugars, appears as the most promising candidate. Herein, it will be discussed the status, challenges and prospective future of biomass as industrial feedstock in a raising biorefinery, aiming to clarify the real problems in the actual biomass processing. It will be shown that lignocellulosic biomass is able to replace oil in the production of several chemicals and also delivery new compounds with important applications. However, for a cost effective use of biomass, the development and improvement of solvent and catalytic systems play a leading role. The sustainability of biomass feedstock is also discussed from the economical, social and environmental points of view.
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