2,5-furandicarboxylic acid (FDCA) is one of the most important bio-sourced building blocks and several routes have been reported for its synthesis. FDCA is presumed to be an ideal green alternative to terephthalate, which is one of the predominant monomers in polymer industry. This Minireview concerns the synthesis of FDCA by using various carboxylation reactions and discusses the synthesis of FDCA starting from furoic acid and CO 2 and using different catalytic and stoichiometric processes. This process is of high interest, as it avoids the glucose isomerization step and selectivity issues observed during the 5-hydroxymethylfurfural oxidation step of the current alternative route to FDCA. Discussion focuses on the main parameters that govern selectivity and activity in the carboxylation processes. Moreover, various previously described processes, such as the Henkel reaction and enzymatic, homogeneous catalytic, and photoelectrocatalytic processes, are also discussed.
Chemisorption of hydrogen on metallic particles is often used to estimate the metal dispersion (D), the metal particle size (d), and the metallic specific surface area (SM), currently assuming a stoichiometry of one hydrogen atom H adsorbed per surface metal atom M. This assumption leads to a large error when estimating D, d, and SM, and a rigorous method is needed to tackle this problem. A model describing the statistics of the metal surface atom and site distribution on perfect cuboctahedron clusters, already developed for Pt, is applied to Pd, Ir, and Rh, using the density functional theory (DFT) calculation of the literature to determine the most favorable adsorption sites for each metal. The model predicts the H/M values for each metal, in the range 0–1.08 for Pd, 0–2.77 for Ir, and 0–2.31 for Rh, depending on the particle size, clearly showing that the hypothesis of H/M = 1 is not always confirmed. A set of equations is then given for precisely calculating D, d, and SM for each metal directly from the H chemisorption results determined experimentally, without any assumption about the H/M stoichiometry. This methodology provides a powerful tool for accurate determination of metal dispersion, metal particle size, and metallic specific surface area from chemisorption experiments.
2,5-furandicarboxylic acid (2,5-FDCA) is a biomass derivate of high importance that is used as a building block in the synthesis of green polymers such as poly(ethylene furandicarboxylate) (PEF). PEF is presumed to be an ideal substitute for the predominant polymer in industry, the poly(ethylene terephthalate) (PET). Current routes for 2,5-FDCA synthesis require 5-hydroxymethylfurfural (HMF) as a reactant, which generates undesirable co-products due to the complicated oxidation step. Therefore, direct CO2 carboxylation of furoic acid salts (FA, produced from furfural, derivate of inedible lignocellulosic biomass) to 2,5-FDCA is potentially a good alternative. Herein, we present the primary results obtained on the carboxylation reaction of potassium 2-furoate (K2F) to synthesize 2,5-FDCA, using heterogeneous catalysts. An experimental setup was firstly validated, and then several operation conditions were optimized, using heterogeneous catalysts instead of the semi-heterogeneous counterparts (molten salts). Ag/SiO2 catalyst showed interesting results regarding the K2F conversion and space–time yield of 2,5-FDCA.
One of the most trending topics in catalysis recently is the use of renewable sources and/or non-waste technologies to generate products with high added value. That is why, the present review resumes the advances in catalyst design for biomass chemical valorization. The variety of involved reactions and functionality of obtained molecules requires the use of multifunctional catalyst able to increase the efficiency and selectivity of the selected process. The use of glucose as platform molecule is proposed here and its use as starting point for biobased plastics production is revised with special attention paid to the proposed tandem Bronsted/Lewis acid catalysts.
The high life expectancy of the world population provokes increase in demand for food and energy. As a result, the intense industrialization and the application of fossil sources is responsible for high levels of CO2 emission and waste generation. To mitigate the CO2 emission a practical solution at the very short term is urgently needed. The capture of CO2 and its application in chemical processes for the valorization of residual biomass are of great importance nowadays. The application of CO2 in the selective carboxylation of furoic acid for the production of 2,5-furandicarboxylic acid (FDCA), a bio-based monomer, has been an important step towards obtaining biopolymers to replace petroleum-based plastics such as polyethylene terephthalate (PET). In this project report, we discuss on the current challenges for obtaining the 2,5-FDCA precursor from the furfural in two main routes involving oxidation and carboxylation via heterogeneous catalysis. We present the main objectives and discuss the importance of this research for the development of more sustainable processes.
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