Proceedings of Materials for Sustainable Development Conference (MAT-SUS) (NFM22)
Publication date: 11th July 2022
Fossil fuels constitute a source of energy and feedstock for chemicals; however, their use is being limited due to their availability and the large amount of greenhouse gases released when they are burnt. For these reasons, the scientific community have looked into novel ways to obtain energy based on renewable sources. In this scenario, the development of new technologies, such as (photo)electrochemistry, that guarantees the obtention of high amounts of energy with lower greenhouse emissions, are an urgent necessity.
The reactions most studied in (photo)electrochemistry are water splitting and CO2 reduction.[1] However, these reactions still lack economic viability due to the high energy consumption and relatively low energy conversion efficiency. In this context, different reactions are being explored to avoid the inconvenient that H2O oxidation and CO2 reduction still possess, such as the oxidation/reduction of furanoic derivatives to obtain added-value compounds.[2]
Among these furanoic compounds, 5-hydroximethylfurfural (HMF) is a very interesting chemical derived from lignocellulose-derived biomass, which is a very promising building block for the variety of high-added value chemical ranging from fuels to plastics, through oxidation, dehydration and hydrogenation processes of functionalities (−OH and −C=O) attached to the furan ring.[3] For example, the main product in the reduction of HMF is 2,5-bis(hydroxymethyl)furan (BHMF), that can be used as a precursor for the synthesis of many bio-based polymers, including polyurethanes, polyethers and polyamides. Other reduction products can be observed depending on the reaction conditions (electrocatalysts, pH and/or reductions potentials), such as 5-methylfurfuryl alcohol (MFA), which is used as flavoring and in making sealants and cements, showing the versatility of the HMF.
Most of the current research on HMF electroreduction is based on Ag and/or Cu as electrocatalyst in basic media, where BHMF is the main product, due to the large overpotential for the hydrogen evolution reaction (HER).[3] In this work, we have studied the electroreduction of HMF in acid conditions (0.5 M NaH2PO4, pH = 4.0) with Cu, Au and Cu/Au electrodes, because Au lower overpotential in acid pH for HER. When the reduction is held at a -1.0 V vs. Ag/AgCl potential only BHMF is observed, but when a more negative potential is used (-1.1 and -1.2 V vs. Ag/AgCl) BHMF and MFA are produced showing a competition between HER and the electroreduction of the furan compounds. At larger potential (-1.3 V vs. Ag/AgCl) lower quantities of BHMF and MFA are obtained, given the predominance of HER.
These results show the great versatility of HMF at acid pH, allowing to obtain different compounds according to the applied potential.
We thank project PID2020-116093RB-C41, funded by MCIN/AEI/10.13039/501100011033, projects IDIFEDER/2020/013 and PROMETEO/2020/02 funded by Generalitat Valenciana and project UJI-B2019-20 funded by University Jaume I.
The authors thank Servicio Central de Instrumentación Científica (SCIC) from Universitat Jaume I.
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