Enhanced performance of glycerol electro-oxidation in alkaline media using bimetallic Au-Cu NPs supported by MWCNTs and reducible metal oxides

Abstract

Electrochemical technologies for valorizing glycerol, a byproduct of biodiesel production, into electric energy and value-added chemical products continue to be technologically and economically challenging. In this field, an ongoing challenge is developing more active, stable, and low-cost heterogeneous catalysts for the glycerol electro-oxidation reaction (GlyEOR). This paper reports the influence of the preparation procedure, which involves intermatrix synthesis (Cu and Au NPs), followed by galvanic displacement (Cu-Au NPs) in previously functionalized multi-walled carbon nanotubes (MWCNTs). It also discusses the role of the supports, CeO₂ NPs, and TiO₂ NPs, obtained by a hydrothermal microwave-assisted procedure, on the electroactivity of a hybrid bimetallic Cu-Au/MWCNT/MO₂ catalyst in the GlyEOR in alkaline media. The electrocatalytic behavior was studied and discussed in terms of structure, composition, and electroactivity of the synthesized materials, which were determined by Fourier-transform infrared spectroscopy (FTIR), flame atomic absorption spectroscopy (FAAS), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), X-ray photoelectronic spectroscopy (XPS), and cyclic voltammetry (CV). In addition, the role of the oxidation states of Cu and Au in the as-prepared catalysts (Cu/MWCNT, Au/MWCNT, Cu-Au/MWCNT, Cu-Au/MWCNT-CeO₂, and Cu-Au/MWCNT-TiO₂) was demonstrated. It was concluded that the preparation method of metal NPs for the controlled formation of the most catalytically active oxidation states of Cu and Au, together with the presence of a conductive and oxophilic microenvironment provided by carbon nanotubes and facile reducible oxides in optimized compositions, allows for an increase in the catalytic performance of synthesized catalysts in the GlyEOR.

Keywords: catalytic electroactivity; cerium oxide; cyclic voltammetry; glycerol electro-oxidation; hybrid catalysts; microwave assisted; oxidation state influence; titanium oxide.