Alcohol oxidation using α-Fe2O3 and BiVO4: mechanistic and kinetic insides
Laia Francàs Forcada a
a Department of Chemistry, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, Barcelona 08193, Spain
Proceedings of International Conference on Frontiers in Electrocatalytic Transformations (INTERECT)
València, Spain, 2021 November 22nd - 23rd
Organizers: Elena Mas Marzá and Ward van der Stam
Invited Speaker, Laia Francàs Forcada, presentation 005
Publication date: 10th November 2021

Nowadays, the mitigation and reverse of the climate change is one of the main global challenges we, as a society, are facing. For this purpose, we must use and store renewable energy to be used as fuels, electricity or to produce fine chemicals. One of the most attractive alternatives is the use of sunlight to drive these processes given that the energy coming from the sun to Earth in one hour, if fully harnessed, is enough to energetically sustain the whole planet for a full year. In this context, using sunlight to drive redox transformations is a promising technology to decarbonize transportation, heating and fine chemicals sectors.

Sunlight driven processes are complex since they involve several steps that need to take place simultaneously in a harmoniously and synchronized manner. Firstly, the light, with the right energy, is absorbed by promoting electrons from the highest occupied energetic level (valence band in semiconductors) to the lowest unoccupied one (conduction band in semiconductors), generating oxidative equivalents (holes). These charges are accumulated to the surface/electrolyte interface, and holes are used to oxidise a substrate and the electrons will either be used to reduce protons, CO2 to generate carbon-based products or N2 to generate NH3. When the oxidative reaction is water oxidation, this is the bottleneck of the whole solar- driven process.[1] Some approaches consider the possibility of substituting this demanding process for an organic molecule oxidation, which can be energetically less demanding and potentially also producing added value compounds.[2–4]

In this talk I will focus on the use of methanol and glycerol as substrates in the oxidative reaction using conventional metal oxide photoanodes: α-Fe2O3 and BiVO4. [4] In addition, I will discuss the use of the combined electrochemical and optical technique to probe the catalytic function of these photoanodes under operational conditions. [5-7] This technique opens a new possibility of studying multielectron reaction mechanisms on non-ideal metal oxides. From these experiments I will discuss some kinetic mechanistic parameters important to design more efficient systems.

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