Kinetic Isotope Effects Quantify pH-Sensitive Water Dynamics at the Pt Electrode Interface.

The pH-dependent kinetics of the hydrogen oxidation and evolution reactions (HERs and HORs) remain a fundamental conundrum in modern electrochemistry. Recent efforts have focused on the impact of the interfacial water network on the reaction kinetics. In this work, we quantify the importance of interfacial water dynamics on the overall hydrogen reaction kinetics with kinetic isotope effect (KIE) voltammetry experiments on single-crystal Pt(111) and Pt(110). Our results find a surface-sensitive KIE for both the HER and the HOR that is measurable in base but not in acid. Remarkably, the HOR in KOD on Pt(111) yields a KIE of up to 3.4 at moderate overpotentials, greater than any expected secondary KIE values, yet the HOR in DClO4 yields no measurable KIE. These results provide direct evidence that solvent dynamics play a crucial role in the alkaline but not in the acidic hydrogen reactions, thus reinforcing the importance of "beyond adsorption" phenomena in modern electrocatalysis.

Highly crystalline multimetallic nanoframes with three-dimensional electrocatalytic surfaces.

Control of structure at the atomic level can precisely and effectively tune catalytic properties of materials, enabling enhancement in both activity and durability. We synthesized a highly active and durable class of electrocatalysts by exploiting the structural evolution of platinum-nickel (Pt-Ni) bimetallic nanocrystals. The starting material, crystalline PtNi3 polyhedra, transforms in solution by interior erosion into Pt3Ni nanoframes with surfaces that offer three-dimensional molecular accessibility. The edges of the Pt-rich PtNi3 polyhedra are maintained in the final Pt3Ni nanoframes. Both the interior and exterior catalytic surfaces of this open-framework structure are composed of the nanosegregated Pt-skin structure, which exhibits enhanced oxygen reduction reaction (ORR) activity. The Pt3Ni nanoframe catalysts achieved a factor of 36 enhancement in mass activity and a factor of 22 enhancement in specific activity, respectively, for this reaction (relative to state-of-the-art platinum-carbon catalysts) during prolonged exposure to reaction conditions.

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.