Electrocatalysis of the HER in acid and alkaline media

Trends in the HER are studied on selected metals (M= Cu, Ag, Au, Pt, Ru, Ir, Ti) in acid and alkaline environments. We found that with the exception of Pt, Ir and Au, due to high coverage by spectator species on non-noble metal catalysts, experimentally established positions of Cu , Ag, Ru and Ti in the observed volcano relations are still uncertain. We also found that while in acidic solutions the M-Hupd binding energy most likely is controlling the activity trends, the trends in activity in alkaline solutions are controlled by a delicate balance between two descriptors: the M-Had interaction as well as the energetics required to dissociate water molecules. The importance of the second descriptor is confirmed by introducing bifunctional catalysts such as M modified by Ni(OH); e.g. while the latter serves to enhance catalytic decomposition of water, the metal sites are required for collecting and recombining the produced hydrogen intermediates

Origin of Anomalous Activities for Electrocatalysts in Alkaline Electrolytes

Pt extended surfaces and nanoparticle electrodes are used to understand the origin of anomalous activities for electrocatalytic reactions in alkaline electrolytes as a function of cycling/time. Scanning tunneling microscopy (STM) of the surfaces before and after cycling in alkaline electrolytes was used to understand the morphology of the impurities and their impact on the catalytic sites. The nature of the contaminant species is identified as 3d-transition metal cations, and the formation of hydr(oxy)oxides of these elements is established as the main reason for the observed behavior. We find that, while for the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR) the blocking of the sites by the undesired 3d-transition metal hydr(oxy)oxide species leads to deactivation of the reaction activities, the CO oxidation reaction and the hydrogen evolution reaction (HER) can have beneficial effects from the same impurities, the latter being dependent on the exact nature of the adsorbing species. These results show the significance of impurities present in real electrolytes and their impact on electrocatalysis.Office of Science, Office of Basic Energy Sciences, Division of Materials Science, U.S. Department of Energy [DE-AC02-06CH11357]Office of Science, Office of Basic Energy Sciences, Division of Materials Science, U.S. Department of EnergyChemical Sciences and Engineering Division at Argonne National LaboratoryChemical Sciences and Engineering Division at Argonne National LaboratoryCAPESCAPESFAPESPFAPES

Origin of Anomalous Activities for Electrocatalysts in Alkaline Electrolytes

Pt extended surfaces and nanoparticle electrodes are used to understand the origin of anomalous activities for electrocatalytic reactions in alkaline electrolytes as a function of cycling/time. Scanning tunneling microscopy (STM) of the surfaces before and after cycling in alkaline electrolytes was used to understand the morphology of the impurities and their impact on the catalytic sites. The nature of the contaminant species is identified as <i>3d</i>-transition metal cations, and the formation of hydr­(oxy)­oxides of these elements is established as the main reason for the observed behavior. We find that, while for the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR) the blocking of the sites by the undesired <i>3d</i>-transition metal hydr­(oxy)­oxide species leads to deactivation of the reaction activities, the CO oxidation reaction and the hydrogen evolution reaction (HER) can have beneficial effects from the same impurities, the latter being dependent on the exact nature of the adsorbing species. These results show the significance of impurities present in real electrolytes and their impact on electrocatalysis

In Situ Anomalous Small-Angle X‑ray Scattering Studies of Platinum Nanoparticle Fuel Cell Electrocatalyst Degradation

Polymer electrolyte fuel cells (PEFCs) are a promising high-efficiency energy conversion technology, but their cost-effective implementation, especially for automotive power, has been hindered by degradation of the electrochemically active surface area (ECA) of the Pt nanoparticle electrocatalysts. While numerous studies using ex situ post-mortem techniques have provided insight into the effect of operating conditions on ECA loss, the governing mechanisms and underlying processes are not fully understood. Toward the goal of elucidating the electrocatalyst degradation mechanisms, we have followed Pt nanoparticle growth during potential cycling of the electrocatalyst in an aqueous acidic environment using in situ anomalous small-angle X-ray scattering (ASAXS). ASAXS patterns were analyzed to obtain particle size distributions (PSDs) of the Pt nanoparticle electrocatalysts at periodic intervals during the potential cycling. Oxide coverages reached under the applied potential cycling protocols were both calculated and determined experimentally. Changes in the PSD, mean diameter, and geometric surface area identify the mechanism behind Pt nanoparticle coarsening in an aqueous environment. Over the first 80 potential cycles, the dominant Pt surface area loss mechanism when cycling to 1.0–1.1 V was found to be preferential dissolution or loss of the smallest particles with varying extents of reprecipitation of the dissolved species onto existing particles, resulting in particle growth, depending on potential profile. Correlation of ASAXS-determined particle growth with both calculated and voltammetrically determined oxide coverages demonstrates that the oxide coverage is playing a key role in the dissolution process and in the corresponding growth of the mean Pt nanoparticle size and loss of ECA. This understanding potentially reduces the complex changes in PSD and ECA resulting from various voltage profiles to a response dependent on oxide coverage