Suppression of Hydrogen Evolution by Oxygen Reduction in Nanoporous Electrocatalysts.

Electroreduction of small molecules in aqueous solution often competes with the hydrogen evolution reaction (HER), especially if the reaction is driven even moderately hard using a large overpotential. Here, the oxygen reduction reaction (ORR) was studied under proton diffusion-limited conditions in slightly acidic electrolytes: a model system to study the relative transport kinetics of protons and reactants to an electrocatalyst and the relationship between transport and catalytic performance. Using dealloyed nanoporous nickel-platinum (np-NiPt) electrodes, we find the hydrogen evolution reaction can be completely suppressed even at high overpotentials (-400 mV vs RHE). In addition, the mechanism of oxygen reduction can be changed by using buffered versus unbuffered solutions, suggesting the reaction selectivity is associated with a transient rise (or lack thereof) in the interface pH at the np-NiPt surface. Independently controlling reactant transport to electrocatalyst surfaces at high overpotentials exhibited a surprisingly rich phenomenology that may offer a generalizable strategy to increase activity and selectivity during electroreduction reactions.

Atomic-scale surface roughness of rutile and implications for organic molecule adsorption.

Crystal surfaces provide physical interfaces between the geosphere and biosphere. It follows that the arrangement of atoms at the surfaces of crystals profoundly influences biological components at many levels, from cells through biopolymers to single organic molecules. Many studies have focused on the crystal-molecule interface in water using large, flat single crystals. However, little is known about atomic-scale surface structures of the nanometer- to micrometer-sized crystals of simple metal oxides typically used in batch adsorption experiments under conditions relevant to biogeochemistry and the origins of life. Here, we present atomic-resolution microscopy data with unprecedented detail of the circumferences of nanosized rutile (α-TiO2) crystals previously used in studies of the adsorption of protons, cations, and amino acids. The data suggest that one-third of the {110} faces, the largest faces on individual crystals, consist of steps at the atomic scale. The steps have the orientation to provide undercoordinated Ti atoms of the type and abundance for adsorption of amino acids as inferred from previous surface complexation modeling of batch adsorption data. A remarkably uniform pattern of step proportions emerges: the step proportions are independent of surface roughness and reflect their relative surface energies. Consequently, the external morphology of rutile nanometer- to micrometer-sized crystals imaged at the coarse scale of scanning electron microscope images is not an accurate indicator of the atomic smoothness or of the proportions of the steps present. Overall, our data strongly suggest that amino acids attach at these steps on the {110} surfaces of rutile.

Electrochemical measurement of the surface alloying kinetics of underpotentially deposited Ag on Au(111).

The cyclic voltammetry characterizing underpotential deposition (UPD) of Ag onto Au(111) varies in the literature with respect to the characteristic UPD peaks in both position and number. Rooryck et al. (1) confirmed that the discrepancy in terms of peak position, specifically the initial UPD to which a third of a monolayer of deposition is attributed, is due to a variation in the quality of the surface. Clean, smooth Au(111) surfaces yield a peak position of 0.53 V vs Ag0/Ag+, while rough disordered surfaces yield a peak position of 0.61 V vs Ag0/Ag+. Repetitive potential cycling in the UPD region resulted in a gradual shift in peak position, with time as the deposited Ag alloyed with, and was stripped from the surface leaving vacancies. We provide a methodology for tracking the rate at which UPD Ag alloys with the Au(111) surface without the use of continuous potential cycling. A simple kinetic model is developed for the surface alloying of Ag on Au(111), from which we extract an activation barrier and attempt frequency for this process. Notably, we introduce a novel technique for the inexpensive parallel fabrication of Au(111) single crystals that allowed us to build statistics and ensured reproducibility of our data.