Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis

Abstract : The oxygen reduction reaction (ORR) is a key reaction for energy conversion and storage systems such as polymer electrolyte membrane fuel cells (PEMFCs). Studies on Pt and Pt-transition metal alloy single crystals have established that the ORR is best electrocatalyzed on bimetallic alloys and at (111) facets. Combining alloying and ensemble effects recently led to 20-30-fold enhancement of the specific activity (normalized per real cm 2 of catalyst) for the ORR on PtNi/C nanooctahedra relative to Pt/C nanoparticles. However, due to the highly oxidizing conditions of the PEMFC cathode, the stability of PtNi/C octahedra is poor in PEMFC cathode operating conditions, thus compromising their utilization in real devices. Strikingly, it also turned out recently that structurally-disordered PtNi nano-catalysts, such as hollow PtNi/C nanoparticles, dealloyed PtNi/C nanoparticles, PtNi aerogels or PtNi nanowires feature highly desirable and sustainable ORR activity (x 10-12 in specific activity relative to pure Pt/C). However, to date, the mechanisms of this unexpected ORR activity enhancement remain unclear, and prevent further development of this vital technology for a carbon-free energy future. To shed fundamental light onto these issues, state-of-the art PtNi/C nanocatalysts with distinct atomic composition, size, shape and density of disorder were synthesized. Their disorder was quantified experimentally, using the values of microstrain (a parameter accessible by the Rietveld refinement of wide-angle X-ray scattering patterns) that is representative of the local distortion of a crystal lattice. Thanks to ab initio calculations, the contributions of bulk and surface structural disorder were disentangled, and a new parameter, the surface distortion (SD), was established. The SD descriptor was used to rationalize the ORR activity enhancement of the two classes of materials (structurally-ordered and structurally-disordered), and to probe their stability in simulated PEMFC cathode operating conditions.
Document type :
Conference papers
Complete list of metadatas
Contributor : Frédéric Maillard <>
Submitted on : Wednesday, November 6, 2019 - 3:55:04 PM
Last modification on : Wednesday, November 13, 2019 - 9:14:16 AM


  • HAL Id : hal-02351938, version 1



Frédéric Maillard, Raphaël Chattot, Pierre Bordet, Jakub Drnec, Tristan Asset, et al.. Surface distortion as a unifying concept and descriptor in oxygen reduction reaction electrocatalysis. Third International Symposium on Nanoporous Materials by Alloy Corrosion, Feb 2019, Philadelphie, United States. ⟨hal-02351938⟩



Record views