In situ spectroscopic Study of the Electrochemical Reduction of CO2 on single facet Copper Nanoparticles
Summary
Converting CO2 into useful chemicals and fuels with renewably generated electricity is of
great technological and fundamental interest. Copper stands out as an electrocatalyst for
this electrochemical reduction, as it is the only metal that can induce C-C coupling and
therefore can reduce CO2 into a variety of valuable C2+ hydrocarbons. The product
distribution of these hydrocarbons depends on a lot of factors, of which the applied
potential and the exposed surface facets have the most profound influence. Generally
speaking it is known that the (100) facet produces more ethylene, while the (111) facet
produces more methane. The exact reaction mechanisms and their differences on the
different facets remain under debate. In this thesis research we use in situ Raman
spectroscopy and in silico DFT calculations to study the differences between the
electrochemical reduction of CO2 (eCO2RR) on copper nano cubes and octahedrons, which
have (100) and (111) facets exposed respectively. We found that, different to
polycrystalline Cu (pc-Cu), linear CO (COL) is not stabilized on the (100) or (111) facets
under working conditions. This lead to the conclusion that the C-C coupling mechanism
of the eCO2RR on both facets, probably involves at least one multiple bound CO species,
which are stabilized on the (100) and (111) surface. The 460, 500 and 535 cm–1 peaks were
observed on both facets and their origin was explored, but no intermediate could be
assigned to these peaks with certainty. A novel find for these peaks is their negative Stark
tuning rate, which has not yet been observed in literature. The direction of this tuning rate
suggests that the intermediate that is the origin of these peaks possess both a σ-orbital
as HOMO and a π*-orbital as LUMO, similar to CO. It was also shown that Stark tuning
rates can be calculated using DFT-calculations. This type of calculation may be used in the
future as a tool in determining the origin of the peaks in the 500 region, further elucidating
the eCO2RR mechanism.