abstract
The chemical valorization/repurposing of biomass-derived chemicals contributes to a biobased economy. Furfural (Fur) is a recognized platform chemical produced from renewable lignocellulosic biomass, and furfuryl alcohol (FA) is its most important application. The aromatic aldehydes Fur and benzaldehyde (Bza) are commonly found in the slate of compounds produced via biomass pyrolysis. On the other hand, glycerol (Gly) is a by-product of the industrial production of biodiesel, derived from fatty acid components of biomass. This work focuses on acid catalyzed routes of Fur, Bza, Gly and FA, using a versatile crystalline lamellar coordination polymer catalyst, namely [Gd(H(4)nmp)(H2O)(2)]Cl center dot 2H(2)O (1) [H(6)nmp=nitrilotris(methylenephosphonic acid)] synthesized via an ecofriendly, relatively fast, mild microwave-assisted approach (in water, 70 degrees C/40 min). This is the first among crystalline coordination polymers or metal-organic framework type materials studied for the Fur/Gly and Bza/Gly reactions, giving heterobicyclic products of the type dioxolane and dioxane, and was also effective for the FA/ethanol reaction. 1 was stable and promoted the target catalytic reactions, selectively leading to heterobicyclic dioxane and dioxolane type products in the Fur/Gly and Bza/Gly reactions (up to 91% and 95% total yields respectively, at 90 degrees C/4 h), and, on the other hand, 2-(ethoxymethyl)furan and ethyl levulinate from heterocyclic FA.
keywords
ETHYL LEVULINATE BIOFUEL; BIO-ADDITIVE FUELS; ONE-STEP SYNTHESIS; FURFURYL ALCOHOL; SOLID ACID; EFFICIENT CONVERSION; GLYCEROL CARBONATE; CYCLIC ACETALS; CRUDE GLYCEROL; LIGNOCELLULOSIC BIOMASS
subject category
Chemistry, Physical
authors
Antunes, MM; Mendes, RF; Paz, FAA; Valente, AA
our authors
Anabela Tavares Aguiar Valente
Principal Researcher
Filipe Alexandre Almeida Paz
Principal Researcher
Maria Margarida Feitor Pintão Moreno Antunes
Junior Researcher
Ricardo Faria Mendes
Junior Researcheracknowledgements
This work was developed within the scope of the project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 and UIDP/50011/2020, financed by national funds through the Portuguese Foundation for Science and Technology (FCT)/MCTES. The position held by M.M.A. was funded by national funds (OE), through FCT, I.P., in the scope of the framework contract foreseen in the numbers 4, 5 and 6 of article 23 of the Decree-Law 57/2016 of 29 August, changed by Law 57/2017 of 19 July. R.F.M. gratefully acknowledges FCT for a Junior Research Position (CEECIND/00553/2017).