Abstract:The implementation of cost-effective and sustainable biorefineries to substitute the petroleum-based economy is dependent on coupling the production of bioenergy with high-value chemicals. For this purpose, the US Department of Energy identified a group of key target compounds to be produced from renewable biomass. Among them, 5-hydroxymethylfurfural (HMF) can be obtained by dehydration of the hexoses present in biomass and is an extremely versatile molecule that can be further converted into a wide range of h… Show more
“…Aldehydes, such as HMF, are toxic molecules for living organisms; some microorganisms, like bacteria and fungi, developed detoxification mechanisms to convert toxic HMF to “non‐toxic” molecules, and this mechanism can be exploited for FDCA production. This biotransformation process has important advantages and is receiving increasing attention in recent years [101–110] . In fact, the whole‐cell catalysts are often robust, benefitting from a protective barrier, reactive substrates, endogenous cofactors, and enzymes that perpetuate catalytic pathways and inhibit by‐products [111,112] .…”
Section: Biocatalytic Methodsmentioning
confidence: 99%
“…This biotransformation process has important advantages and is receiving increasing attention in recent years. [101][102][103][104][105][106][107][108][109][110] In fact, the whole-cell catalysts are often robust, benefitting from a protective barrier, reactive substrates, endogenous cofactors, and enzymes that perpetuate catalytic pathways and inhibit byproducts. [111,112] In the last years, several microorganisms involved in HMF conversion to FDCA have been studied.…”
2,5-Furandicarboxylic acid (FDCA) is currently considered one of the most relevant bio-sourced building blocks, representing a fully sustainable competitor for terephthalic acid as well as the main component in green polymers such as poly(ethylene 2,5furandicarboxylate) (PEF). The oxidation of biobased 5hydroxymethylfurfural (HMF) represents the most straightforward approach to obtain FDCA, thus attracting the attention of both academia and industries, as testified by Avantium with the creation of a new plant expected to produce 5000 tons per year. Several approaches allow the oxidation of HMF to FDCA. Metal-mediated homogeneous and heterogeneous catalysis, metal-free catalysis, electrochemical approaches, light-mediated procedures, as well as biocatalytic processes share the target to achieve FDCA in high yield and mild conditions. This Review aims to give an up-to-date overview of the current developments in the main synthetic pathways to obtain FDCA from HMF, with a specific focus on process sustainability.
“…Aldehydes, such as HMF, are toxic molecules for living organisms; some microorganisms, like bacteria and fungi, developed detoxification mechanisms to convert toxic HMF to “non‐toxic” molecules, and this mechanism can be exploited for FDCA production. This biotransformation process has important advantages and is receiving increasing attention in recent years [101–110] . In fact, the whole‐cell catalysts are often robust, benefitting from a protective barrier, reactive substrates, endogenous cofactors, and enzymes that perpetuate catalytic pathways and inhibit by‐products [111,112] .…”
Section: Biocatalytic Methodsmentioning
confidence: 99%
“…This biotransformation process has important advantages and is receiving increasing attention in recent years. [101][102][103][104][105][106][107][108][109][110] In fact, the whole-cell catalysts are often robust, benefitting from a protective barrier, reactive substrates, endogenous cofactors, and enzymes that perpetuate catalytic pathways and inhibit byproducts. [111,112] In the last years, several microorganisms involved in HMF conversion to FDCA have been studied.…”
2,5-Furandicarboxylic acid (FDCA) is currently considered one of the most relevant bio-sourced building blocks, representing a fully sustainable competitor for terephthalic acid as well as the main component in green polymers such as poly(ethylene 2,5furandicarboxylate) (PEF). The oxidation of biobased 5hydroxymethylfurfural (HMF) represents the most straightforward approach to obtain FDCA, thus attracting the attention of both academia and industries, as testified by Avantium with the creation of a new plant expected to produce 5000 tons per year. Several approaches allow the oxidation of HMF to FDCA. Metal-mediated homogeneous and heterogeneous catalysis, metal-free catalysis, electrochemical approaches, light-mediated procedures, as well as biocatalytic processes share the target to achieve FDCA in high yield and mild conditions. This Review aims to give an up-to-date overview of the current developments in the main synthetic pathways to obtain FDCA from HMF, with a specific focus on process sustainability.
“…The most possible method for large-scale production is to prepare FDCA by the catalytic reaction of HMF, which can be converted from biomass resources. For different oxidation methods, the catalytic methods for preparing FDCA from HMF can be divided into thermal catalysis [ 92 ], photocatalysis [ 93 ], electrocatalysis [ 94 ], and biocatalysis [ 95 ]. According to the current production level, thermal catalysis is the most compatible method in industry.…”
Section: Catalytic Conversion Of Hmf On Popsmentioning
In the face of the current energy and environmental problems, the full use of biomass resources instead of fossil energy to produce a series of high-value chemicals has great application prospects. 5-hydroxymethylfurfural (HMF), which can be synthesized from lignocellulose as a raw material, is an important biological platform molecule. Its preparation and the catalytic oxidation of subsequent products have important research significance and practical value. In the actual production process, porous organic polymer (POP) catalysts are highly suitable for biomass catalytic conversion due to their high efficiency, low cost, good designability, and environmentally friendly features. Here, we briefly describe the application of various types of POPs (including COFs, PAFs, HCPs, and CMPs) in the preparation and catalytic conversion of HMF from lignocellulosic biomass and analyze the influence of the structural properties of catalysts on the catalytic performance. Finally, we summarize some challenges that POPs catalysts face in biomass catalytic conversion and prospect the important research directions in the future. This review provides valuable references for the efficient conversion of biomass resources into high-value chemicals in practical applications.
“… − HMF can be reduced to generate 2,5-diformylfuran (BHMF) or selectively oxidized into 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), 5-formyl-2-furancarboxylic acid (FFCA), 2,5-diformylfuran (DFF), and 2,5-furandicarboxylic acid (FDCA) . Among these derivatives, HMFCA is generated by selectively oxidizing the aldehyde group of HMF and is a promising starting material for synthetic polyester. , Besides, HMFCA has been reported to have antitumor activity and can be used as an interleukin inhibitor. − …”
Red seaweed is a kind of important renewable biomass owing to its great advantages over terrestrial biomass, but present research mainly focused on the biorefinery of fermentable sugars from red seaweeds only. In this study, we proposed an effective comprehensive utilization strategy for upgrading red seaweed (Gelidium amansii) to D-galactose and 5-hydroxymethyl-2furancarboxylic acid (HMFCA) via chemocatalysis and biocatalysis in tandem. With G. amansii as raw feedstock, high yields of Dgalactose (85.5%) and 5-hydroxymethylfurfural (HMF) (50.9%) were first achieved by oxalic acid catalysis. HMF was separated and further selectively oxidized to HMFCA by whole cells of Pseudomonas rhodesiae NL2019 with a yield of 83.9%. Particularly, G. amansii hydrolysate was also used as the carbon source (Dgalactose) for cell growth and as an inducer (HMF) to promote the catalytic capacity of P. rhodesiae cells. In this way, we established a cost-competitive, highly efficient, and environmentally friendly chemoenzymatic approach for the simultaneous valorization of all components of red seaweed.
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