Electrochemistry offers novel processes to decarbonize the chemical industry by directly utilizing renewable electricity to convert renewable feedstocks into fuels and chemicals. Additionally, electrochemical systems are amenable for small-scale processing as they operate at near atmospheric pressure and temperature, making them an ideal technology for distributed and sustainable manufacturing. In this work, we evaluate the use of heterogeneous electrocatalysts and electrocatalytic reactors to produce fuels and chemicals from biomass-derived organic molecules. In particular, we evaluate the use of Ru-, IrO2-, and Pt-based heterogeneous catalysts for the electrocatalytic oxidation (ECO) of carboxylic acids into fuels and chemicals. Our results show that carboxylic acids can be electrochemically decarboxylated (ECDX) into paraffins, olefins, and alcohols via the Kolbe and non-Kolbe mechanisms. The obtained decarboxylation rate (TOFs) of the electrochemical route at room temperature and atmospheric pressure is one order of magnitude higher than the TOF of thermocatalytic decarboxylation at 300 °C and 37 bar. The ECDX activity, product selectivity, and current efficiency depend on operation potential and anode composition, Figure 1. Increasing the applied potential improves the rates of ECDX and oxygen evolution (OER), changing the current efficiency. Additionally, the product selectivity also changes with applied potential and electrode composition. We also found that the ECDX performance depends on the metal particle size and composition. Pt foil was active for ECDX, but Pt nanoparticles were only active for OER. However, RuO2 nanoparticles had higher ECDX activity than RuO2 thin film (TF) while preserving the product selectivity. We demonstrated that electrochemical reactions can be used to process real biomass-derived biocrude and wastewater generated during the hydrothermal liquefaction of biomass at room temperature and atmospheric pressure while simultaneously generating H2 as a valuable side product. We demonstrated this technology using real biomass-derived feedstocks and showed decarboxylation of carboxylic acids present in bio-oil as well as wastewater while simultaneously generating H2.

Electrochemical oxidation of biomass-derived molecules into fuels and chemicals

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