Recent Publications Feed (ADMIN)

A scanning electrochemical droplet cell technique has been employed to screen the intrinsic electrocatalytic hydrogen evolution reaction (HER) activity of hexagonal boron nitride (h-BN) nanosheets supported on different metal substrates (Cu and Au). Local (spatially-resolved) voltammetry and Tafel analysis reveal that electronic interaction with the underlying metal substrate plays a significant role in modulating the electrocatalytic activity of h-BN, with Au-supported h-BN exhibiting significantly enhanced HER charge-transfer kinetics (exchange current is ca. two orders of magnitude larger) compared to Cu-supported h-BN, making the former material the superior support in a catalytic sense.

While quinone proton coupled electron transfer (PCET) under buffered conditions is well understood, the situation is more complicated in unbuffered aqueous solutions. With a view to producing a quinone-based voltammetric pH electrode that can function universally in both buffered and unbuffered solutions by following a two-electron (2e–)/two-proton (2H+) Nernstian pathway over a wide pH range, the voltammetric response of strongly electronically coupled surface-bound quinones, directly integrated into a boron-doped diamond (BDD) electrode, is investigated. A laser ablation process enables integration of quinones into the BDD electrode surface with a high pKa1 (first protonation state) and with controllable, very low surface coverages (as low as 2 orders of magnitude below monolayer coverage). Under buffered conditions, one wave results for all pH values, and the 2e–/2H+ pathway is followed across the entire pH range. The measured ET rate constant values, from Laviron analysis, are also high, indicative of fast ET pathways. Under unbuffered conditions, one wave is again observed for all pH values; however, deviations from the buffered 2e–/2H+ behavior are seen in the neutral region (pH 6–8). While 2e–/2H+ transfer is maintained at all times, we attribute the observed deviation to local pH changes caused by the consumption and generation of protons at the electrode surface during the redox electrochemistry of the quinone. The associated proton fluxes generated at such sparse surface coverages are thought to be sufficiently high enough to prevent ET from occurring exclusively via a proton-independent route. By reducing surface coverage (down to ∼4 × 10–12mol cm–2; the limit of our laser ablation process) local pH changes can be reduced but are not eradicated completely. By moving to a pulsed voltammetric technique, where for each potential step protons consumed at the electrode are immediately replaced, it is possible, provided the surface coverage is low enough, to obtain a Nernstian 2e–/2H+ response across a wide pH range in unbuffered solution.

Review Article as part of the Fundamental and Applied Reviews in Analytical Chemistry 2019 special issue.