3 research outputs found
Strain Effects on the Oxidation of CO and HCOOH at Au-Pd Core-Shell Nanoparticles
The mechanism of CO and HCOOH electrooxidation in an acidic solution on carbon-supported Au–Pd core–shell nanoparticles was investigated by differential electrochemical mass spectrometry and in situ Fourier transform infrared (FTIR) spectroscopy. Analysis performed in nanostructures with 1.3 ± 0.1 nm (CS1) and 9.9 ± 1.1 nm (CS10) Pd shells provides compelling evidence that the mechanism of adsorbed CO (COads) oxidation is affected by structural and electronic effects introduced by the Au cores. In the case of CS10, a band associated with adsorbed OH species (OHads) is observed in the potential range of CO oxidation. This feature is not detected in the case of CS1, suggesting that the reaction follows an alternative mechanism involving COOHads species. The faradaic charge associated with COads oxidation as well as the Stark slope measured from FTIR indicates that the overall affinity and orbital coupling of CO to Pd are weaker for CS1 shells. FTIR spectroscopy also revealed the presence of HCOOads intermediate species only in the case of CS1. This observation allowed us to conclude that the higher activity of CS10 toward this reaction is due to a fast HCOOads oxidation step, probably involving OHads, to generate CO2. Density functional theory calculations are used to estimate the contributions of the so-called ligand and strain effects on the local density of states of the Pd d-band. The calculations strongly suggest that the key parameter contributing to the change in mechanism is the effective lattice strain
Electrochemical Behavior of TiOxCy as Catalyst Support for Direct Ethanol Fuel Cells at Intermediate Temperature: From Planar Systems to Powders
To achieve complete oxidation of
ethanol (EOR) to CO<sub>2</sub>, higher operating temperatures (often
called intermediate-<i>T</i>, 150–200 °C) and
appropriate catalysts are
required. We examine here titanium oxycarbide (hereafter TiO<sub><i>x</i></sub>C<sub><i>y</i></sub>) as a possible alternative
to standard carbon-based supports to enhance the stability of the
catalyst/support assembly at intermediate-<i>T</i>. To test
this material as electrocatalyst support, a systematic study of its
behavior under electrochemical conditions was carried out. To have
a clear description of the chemical changes of TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> induced by electrochemical polarization
of the material, a special setup that allows the combination of X-ray
photoelectron spectroscopy and electrochemical measurements was used.
Subsequently, an electrochemical study was carried out on TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> powders, both
at room temperature and at 150 °C. The present study has revealed
that TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> is a sufficiently conductive material whose surface is passivated
by a TiO<sub>2</sub> film under working conditions, which prevents
the full oxidation of the TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> and can thus be considered a stable electrode material
for EOR working conditions. This result has also been confirmed through
density functional theory (DFT) calculations on a simplified model
system. Furthermore, it has been experimentally observed that ethanol
molecules adsorb on the TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> surface, inhibiting its oxidation. This result has
been confirmed by using in situ Fourier transform infrared spectroscopy
(FTIRS). The adsorption of ethanol is expected to favor the EOR in
the presence of suitable catalyst nanoparticles supported on TiO<sub><i>x</i></sub>C<sub><i>y</i></sub>
Electrochemical Behavior of TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> as Catalyst Support for Direct Ethanol Fuel Cells at Intermediate Temperature: From Planar Systems to Powders
To achieve complete oxidation of
ethanol (EOR) to CO<sub>2</sub>, higher operating temperatures (often
called intermediate-<i>T</i>, 150–200 °C) and
appropriate catalysts are
required. We examine here titanium oxycarbide (hereafter TiO<sub><i>x</i></sub>C<sub><i>y</i></sub>) as a possible alternative
to standard carbon-based supports to enhance the stability of the
catalyst/support assembly at intermediate-<i>T</i>. To test
this material as electrocatalyst support, a systematic study of its
behavior under electrochemical conditions was carried out. To have
a clear description of the chemical changes of TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> induced by electrochemical polarization
of the material, a special setup that allows the combination of X-ray
photoelectron spectroscopy and electrochemical measurements was used.
Subsequently, an electrochemical study was carried out on TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> powders, both
at room temperature and at 150 °C. The present study has revealed
that TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> is a sufficiently conductive material whose surface is passivated
by a TiO<sub>2</sub> film under working conditions, which prevents
the full oxidation of the TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> and can thus be considered a stable electrode material
for EOR working conditions. This result has also been confirmed through
density functional theory (DFT) calculations on a simplified model
system. Furthermore, it has been experimentally observed that ethanol
molecules adsorb on the TiO<sub><i>x</i></sub>C<sub><i>y</i></sub> surface, inhibiting its oxidation. This result has
been confirmed by using in situ Fourier transform infrared spectroscopy
(FTIRS). The adsorption of ethanol is expected to favor the EOR in
the presence of suitable catalyst nanoparticles supported on TiO<sub><i>x</i></sub>C<sub><i>y</i></sub>