Conversion of lignin into value-added chemicals is attracting growing attention due to the depletion of fossil fuels and the abundant resource of lignin. In this study, hydrothermal conversion of a model compound of lignin, catechol, into valueadded four-carbon dicarboxylic acids (C4-DCAs), such as tartaric (HOOC−CH(OH)−CH(OH)−COOH), malic (HOOC− CH 2 −CH(OH)−COOH), and fumaric (HOOCCHCHCOOH) acids was investigated. The yield of total C4-DCAs can reach as high as 41.0%, and alkali played a key role in not only promoting the production but also avoiding the decomposition of C4-DCAs. The reaction mechanism of hydrothermal conversion catechol into C4-DCAs showed that catechol is first oxidized to o-quinone, which is then attacked by the hydroxyl radical (OH • ) or the hydroperoxyl anion (HO 2 − ) via conjugate addition to decompose into C4-DCAs. This result is helpful to facilitate studies for developing a new, green, and sustainable process to produce value-added C4-DCAs from lignin.
The reduction of CuO with a lignin model compound, guaiacol, is investigated, to develop a new and green method for both Cu smelting and the utilization of lignin. The results showed that CuO can be completely reduced into Cu and guaiacol selectively converted to carboxylic acids such as fumaric, maleic, acetic, and formic acids at a mild temperature of 250 °C. The presence of NaOH has a significant effect on enhancing the reduction of CuO and the selective yield of carboxylic acids. Two possible reaction pathways were proposed for the reduction of CuO with guaiacol. One pathway involves the oxidative decomposition of guaiacol into carboxylic acids. The other reaction pathway proceeds with the polymerization of guaiacol into oligomers, which can be reused for CuO reduction due to their easy hydrolyzation to monomers under hydrothermal conditions.
To reveal the nature of CO2 reduction to formate with high efficiency by in situ hydrogen produced from hydrothermal reactions with iron, DFT calculations were used. A reaction pathway was proposed in which the formate was produced through the key intermediate species, namely iron hydride, produced in situ in the process of hydrogen gas production. In the in situ hydrogenation of CO2, the charge of H in the iron hydride was −0.135, and the Fe–H bond distance was approximately 1.537 Å. A C-H bond was formed as a transition state during the attack of Hδ− on Cδ+. Finally, a HCOO species was formed. The distance of the C-H bond was 1.107 Å. The calculated free energy barrier was 16.43 kcal/mol. This study may provide new insight into CO2 reduction to formate in hydrothermal reactions with metal.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.