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Carbon riveted Pt/C catalyst was designed and prepared by in situ carbonized glucose in this paper. Characterization results show that carbon riveted Pt/C prevents Pt nanoparticles from coalescence. Its stability is markedly enhanced due to the anchoring effect of the carbon layers formed during the carbon riveting process.

In situ X-ray absorption spectroscopy, ex situ X-ray fluorescence, and X-ray powder diffraction enabled detailed core analysis of phase segregated nanostructured PtRu anode catalysts in an operating direct methanol fuel cell (DMFC). No change in the core structures of the phase segregated catalyst was observed as the potential traversed the current onset potential of the DMFC. The methodology was exemplified using a Johnson Matthey unsupported PtRu (1:1) anode catalyst incorporated into a DMFC membrane electrode assembly. During DMFC operation the catalyst is essentially metallic with half of the Ru incorporated into a face-centered cubic (FCC) Pt alloy lattice and the remaining half in an amorphous phase. The extended X-ray absorption fine structure (EXAFS) analysis suggests that the FCC lattice is not fully disordered. The EXAFS indicates that the Ru-O bond lengths were significantly shorter than those reported for Ru-O of ruthenium oxides, suggesting that the phases in which the Ru resides in the catalysts are not similar to oxides.

The electron density topology of carbon monoxide (CO) on dry and hydrated platinum is evaluated under the quantum theory of atoms in molecules (QTAIM) and by adsorbate orbital approaches. The impact of water co-adsorbate on the electronic, structural, and vibrational properties of CO on Pt are modelled by periodic density functional theory (DFT). At low CO coverage, increased hydration weakens C–O bonds and strengthens C–Pt bonds, as verified by changes in bond lengths and stretching frequencies. These results are consistent with QTAIM, the 5σ donation-2π* backdonation model, and our extended π-attraction σ-repulsion model (extended π-σ model). This work links changes in the non-zero eigenvalues of the electron density Hessian at QTAIM bond critical points to changes in the π and σ C–O bonds with systematic variation of CO/H2O co-adsorbate scenarios. QTAIM invariably shows bond strengths and lengths as being negatively correlated. For atop CO on hydrated Pt, QTAIM and phenomenological models are consistent with a direct correlation between C–O bond strength and CO coverage. However, DFT modelling in the absence of hydration shows that C–O bond lengths are not negatively correlated to their stretching frequencies, in contrast to the Badger rule: When QTAIM and phenomenological models do not agree, the use of the non-zero eigenvalues of the electron density Hessian as inputs to the phenomenological models, aligns them with QTAIM. The C–O and C–Pt bond strengths of bridge and three-fold bound CO on dry and hydrated platinum are also evaluated by QTAIM and adsorbate orbital analyses. [ABSTRACT FROM AUTHOR]

Abstract: The Nafion–Pt interfaces in membrane electrode assemblies of operating fuel cells were studied by operando infrared spectroscopy. The potential dependence of atop adsorbed CO peak frequencies were measured over the potential range of 0–600 mV (vs. NHE) at 60 °C. Complex Stark tuning of peak frequencies arise from a combination of potential dependent coverage effects, and changes in the extent of back-donation from the metal d-band to the renormalized 2π∗ MO of COads. The Nafion–Pt interface was studied at higher potentials (initiating at open circuit) by examining platinum reflectivity as a function of electrode potential. The oxygen reduction onset-current is coincident with the observance of a 2% step-increase in Pt reflectivity and emergence of Nafion–Pt interface spectra. [Copyright &y& Elsevier]

Abstract: Full multiple scattering models of X-ray absorption near edge spectra of Pt Janin clusters, with atop and bridge bound oxygen, were systematically improved by increasing the number of cluster atoms contributing X-ray photoelectrons from unity (limited-absorber model), to all six Janin cluster Pt atoms, and finally embedding the Janin cluster into a larger Pt reservoir with photoelectron contributions from all atoms. The simulated XANES of the adsorbate modified clusters were subtractively normalized to their respective clean clusters to yield Δ-XANES signatures. The sequential analysis of previously published limited-absorber model, and the isolated and embedded all atoms models provide insights concerning the relative contribution of surface vs. subsurface atoms to adsorbate induced ligand effects and charge compensation provided by the bulk lattice. Limitations to the application of Δ-XANES signatures to interpretation of Δ-XANES data obtained from an air-breathing fuel cell are discussed. [Copyright &y& Elsevier]

Abstract: A polymer electrolyte fuel cell enables operando X-ray absorption and infrared spectroscopy of the membrane electrode assembly catalytic layer with flowing fuel and air streams at controlled temperature. Time-dependent X-ray absorption near edge structure spectra of the Pt and Ni edge of Pt based catalysts of an air-breathing cathode show that catalyst restructuring, after a potential step, has time constants from minutes to hours. The infrared Stark tuning plots of CO adsorbed on Pt at 100, 200, 300 and 400mV vs. hydrogen reference electrode were obtained. The Stark tuning plots of CO adsorbed at 400mV exhibit a precipitous drop in frequency coincident with the adsorption potential. The turn-down potential decreases relative to the adsorption potential and is approximately constant after 300mV. These Stark tuning characteristics are attributed to potential dependent adsorption site selection by CO and competitive adsorption processes. [Copyright &y& Elsevier]