Catalysing the reduction of oxygen in acidic media is a standing challenge. Although activity of platinum, the most active metal, can be substantially improved by alloying, alloy stability remains a concern. Here we report that platinum nanoparticles supported on graphite-rich boron carbide show a 50–100% increase in activity in acidic media and improved cycle stability compared to commercial carbon supported platinum nanoparticles. Transmission electron microscopy and x-ray absorption fine structure analysis confirm similar platinum nanoparticle shapes, sizes, lattice parameters, and cluster packing on both supports, while x-ray photoelectron and absorption spectroscopy demonstrate a change in electronic structure. This shows that purely electronic metal-support interactions can significantly improve oxygen reduction activity without inducing shape, alloying or strain effects and without compromising stability. Optimizing the electronic interaction between the catalyst and support is, therefore, a promising approach for advanced electrocatalysts where optimizing the catalytic nanoparticles themselves is constrained by other concerns.

In situ X-ray absorption and emission spectroscopies (XAS and XES) are used to provide details regarding the role of the accessibility and extent of redox activity of the Mn ions in determining the oxygen reduction activity of LaMnO3 and CaMnO3, with X-ray absorption near-edge structure (XANES) providing the average oxidation state, extended X-ray absorption fine structure (EXAFS) providing the local coordination environment, and XES providing the population ratios of the Mn2+, Mn3+, and Mn4+ sites as a function of the applied potential. For LaMnO3, XANES and XES show that Mn3+ is formed, but Mn4+ ions are retained, which leads to the 4e– reduction between 0.85 and 0.6 V. At more negative potentials, down to 0.2 V, EXAFS confirms an increase in oxygen vacancies as evidenced by changes in the Mn–O coordination distance and number, while XES shows that the Mn3+ to Mn4+ ratio increases. For CaMnO3, XANES and XES show the formation of both Mn3+ and Mn2+ as the potential is made more negative, with little retention of Mn4+ at 0.2 V. The EXAFS for CaMnO3 also indicates the formation of oxygen vacancies, but in contrast to LaMnO3, this is accompanied by loss of the perovskite structure leading to structural collapse. The results presented have implications in terms of understanding of both the pseudocapacitive response of Mn oxide electrocatalysts and the processes behind degradation of the activity of the materials.

The electrokinetic properties of Pt nanoparticles supported on Carbon (Pt/C) and Boron Carbide-Graphite composite (Pt/BC) are compared over a wide potential range. The influence of the support on the electronic state of Pt was investigated via in-situ X-ray Absorption Spectroscopy. Pt d-band filling, determined from XANES white line analysis, was lower and nearly constant between 0.4 and 0.95V vs. RHE for Pt/BC, indicating more positively charged particles in the double layer region and a delay in the onset of oxide formation by about 0.2V compared to the Pt/C catalyst, which showed a marked increase in d-band vacancies above 0.8V vs. RHE. Moreover, δμ analysis of the XANES data indicated a lack of sub-surface oxygen for the Pt/BC catalyst compared to the Pt/C catalyst above 0.9V vs. RHE. Additional anion adsorption on the Pt/BC in the double layer region, detected by CO displacement, was also confirmed by XANES analysis of the d-band occupancy. The H 2 oxidation activities of electrodes with low catalyst loadings were assessed under high mass transport conditions using the floating electrode methodology. The metal-support interaction between the Pt and BC support improved the maximum hydrogen oxidation current density by 1.4 times when compared to Pt/C

A simple, modified Metal–Organic Chemical Deposition (MOCD) method for Pt, PtRu and PtCo nanoparticle deposition onto a variety of support materials, including C, SiC, B4C, LaB6, TiB2, TiN and a ceramic/carbon nanofiber, is described.