The
cost-effective production of green hydrogen is one of the most
important challenges for a sustainable energy transition. To decrease
the cost of the production of hydrogen through electrolysis, there
are several obstacles that must be overcome. For instance, more active
and stable anodes made of abundant and cheap materials will contribute
to lowering capital and operational expenditure. It is well known
that the oxidation of water requires high overpotentials, which is
the main limitation of the performance of the device. In this context,
substituting the oxidation of water [oxygen evolution reaction (OER)]
at the anode of electrolyzers by the oxidation of biomass-derived
substances contributes to the overall process by decreasing the power
input of the devices and, in some cases, by producing value-added
chemicals. Herein, we revisited some of the most important fundamental
aspects of the electrooxidation of alcohols and polyols on metal-based
catalysts, focusing on reaction descriptors. Then, we moved to the
electrooxidation of these molecules on metal oxides, revisiting some
of the literature about their application in heterogeneous catalysis
and for OER, to get insights about the relation of the structure of
the materials and their activity. Due to the lack of fundamental knowledge
about the electrooxidation of alcohols and polyols on metallic oxides
and to the vast literature about the use of perovskite oxides for
OER, we propose to start systematic studies using perovskite oxides
for the electrooxidation of alcohols and polyols. Consequently, we
presented results for LaCoO3, LaFeO3, LaMnO3, and LaNiO3 and proposed a mechanism for the electrooxidation
of glycerol based on the formation and reactivity of MOH(O) species.
We believe that fundamental and systematic studies on this topic would
permit the establishment of reaction descriptors, speeding up the
search for suitable materials for this reaction and paving the way
for more cost-effective production of green hydrogen.