3 research outputs found
A Density Functional Theory Study on Carbon Monoxide Adsorption on Platinum–Osmium and Platinum–Ruthenium–Osmium Alloys
Periodic density functional theory calculations on carbon
monoxide
(CO) adsorbed atop on platinum–osmium binary alloys (PtOs<sub>2</sub> and PtOs<sub>4</sub>) and the platinum–ruthenium–osmium
tertiary alloy (PtRu<sub>2</sub>Os<sub>2</sub>) are used to elucidate
the changes in the C–O and C–Pt bonds upon alloying
Pt with Ru/Os atoms. As Pt is alloyed with Ru/Os atoms, the adsorbate
internal bond (C–O bond) and the adsorbate–metal bond
(C–Pt bond) strengthen following the substrate trends of PtOs<sub>4</sub> > Pt > PtOs<sub>2</sub> > PtRu<sub>2</sub>Os<sub>2</sub> and
Pt > PtOs<sub>4</sub> > PtOs<sub>2</sub> > PtRu<sub>2</sub>Os<sub>2</sub>, respectively. These trends are manifested by the
corresponding
C–O and C–Pt stretching frequencies and the CO adsorption
energy variations. Here, we establish a theoretical framework based
on the π-attraction σ-repulsion mechanism to explain the
above results. This model correlates the charges, polarizations, and
electron densities of the adsorbate CO orbitals, and the sp/d populations
of the adsorbing Pt atom. For the systems studied here, the traditional
theoretical model of 5σ-donation/2π*-back-donation with
the metal substrate bands is not always sufficient to explain the
relative C–O and C–Pt bonds strengths
Ensemble Site Requirements for Oxidative Adsorption of Methanol and Ethanol on Pt Membrane Electrode Assemblies
The ensemble site requirements for the oxidative adsorption of
methanol and ethanol on platinum based membrane electrode assemblies
in operating liquid feed fuel cells were measured by CO stripping
voltammetry. At 30 °C and 0.2 V vs reference hydrogen electrode
(RHE), the CO<sub>ads</sub> coverage from directly dosed CO (CO<sub>CO</sub>), methanol (CO<sub>MeOH</sub>), and ethanol (CO<sub>EtOH</sub>) are 94%, 49%, and 39%, respectively. At 50 °C the CO<sub>MeOH</sub> and CO<sub>EtOH</sub> approach equality. The ratio of CO<sub>EtOH</sub>/CO<sub>MeOH</sub> was simulated with assumed ensemble site requirements
of 3 and 2 for ethanol and methanol respectively. Experimental and
simulated ratios of 0.79 and 0.78 suggest that high surface area fuel
cell Pt catalysts at 30 °C have adsorption properties similar
to that of a Pt (100) surface. Potential dependent infrared spectroscopy
of CO<sub>MeOH</sub> and CO<sub>EtOH</sub> from flash evaporated aqueous
alcohols delivered to a 50 °C fuel cell show lower CO<sub>EtOH</sub> relative to CO<sub>MeOH</sub> with Stark tuning rates below 10 cm<sup>–1</sup>/V
Ensemble Site Requirements for Oxidative Adsorption of Methanol and Ethanol on Pt Membrane Electrode Assemblies
The ensemble site requirements for the oxidative adsorption of
methanol and ethanol on platinum based membrane electrode assemblies
in operating liquid feed fuel cells were measured by CO stripping
voltammetry. At 30 °C and 0.2 V vs reference hydrogen electrode
(RHE), the CO<sub>ads</sub> coverage from directly dosed CO (CO<sub>CO</sub>), methanol (CO<sub>MeOH</sub>), and ethanol (CO<sub>EtOH</sub>) are 94%, 49%, and 39%, respectively. At 50 °C the CO<sub>MeOH</sub> and CO<sub>EtOH</sub> approach equality. The ratio of CO<sub>EtOH</sub>/CO<sub>MeOH</sub> was simulated with assumed ensemble site requirements
of 3 and 2 for ethanol and methanol respectively. Experimental and
simulated ratios of 0.79 and 0.78 suggest that high surface area fuel
cell Pt catalysts at 30 °C have adsorption properties similar
to that of a Pt (100) surface. Potential dependent infrared spectroscopy
of CO<sub>MeOH</sub> and CO<sub>EtOH</sub> from flash evaporated aqueous
alcohols delivered to a 50 °C fuel cell show lower CO<sub>EtOH</sub> relative to CO<sub>MeOH</sub> with Stark tuning rates below 10 cm<sup>–1</sup>/V