Quantitative Measurements of Electrocatalytic Reaction Rates with NanoSECM.

Scanning electrochemical microscopy (SECM) has been extensively used for mapping electrocatalytic surface reactivity; however, most of the studies were carried out using micrometer-sized tips, and no quantitative kinetic experiments on the nanoscale have yet been reported to date. As the diffusion-limited current density at a nanometer-sized electrode is very high, an inner-sphere electron-transfer process occurring at a nanotip typically produces a kinetic current at any attainable overpotential. Here, we develop a theory for substrate generation/tip collection (SG/TC) and feedback modes of SECM with a kinetic tip current and use it to evaluate the rates of hydrogen and oxygen evolution reactions in a neutral aqueous solution from the current-distance curves. The possibility of using chemically modified nanotips for kinetic measurements is also demonstrated. The effect of the substrate size on the shape of the current-distance curves in SG/TC mode SECM experiments is discussed.

Visualizing Overall Water Splitting on Single Microcrystals of Phosphorus-Doped BiVO4 by Photo-SECM.

Particulate bismuth vanadate (BiVO4) has attracted considerable interest as a promising photo(electro)catalyst for visible-light-driven water oxidation; however, overall water splitting (OWS) has been difficult to attain because its conduction band is too positive for efficient hydrogen evolution. Using photoscanning electrochemical microscopy (photo-SECM) with a chemically modified nanotip, we visualized for the first time the OWS at a single truncated bipyramidal microcrystal of phosphorus-doped BiVO4. The tip simultaneously served as a light guide to illuminate the photocatalyst and an electrochemical nanoprobe to observe and quantitatively measure local oxygen and hydrogen fluxes. The obtained current patterns for both O2 and H2 agree well with the accumulation of photogenerated electrons and holes on {010} basal and {110} lateral facets, respectively. The developed experimental approach is an important step toward nanoelectrochemical mapping of the activity of photocatalyst particles at the subfacet level.

Efficient Voltage-Driven Oxidation of Water and Alcohols by an Organic Molecular Catalyst Directly Attached to a Carbon Electrode.

The integration of heterogeneous electrocatalysis and molecular catalysis is a promising approach to designing new catalysts for the oxygen evolution reaction (OER) and other processes. We recently showed that the electrostatic potential drop across the double layer contributes to the driving force for electron transfer between a dissolved reactant and a molecular catalyst immobilized directly on the electrode surface. Here, we report high current densities and low onset potentials for water oxidation attained using a metal-free voltage-assisted molecular catalyst (TEMPO). Scanning electrochemical microscopy (SECM) was used to analyze the products and determine faradic efficiencies for the generation of H2O2 and O2. The same catalyst was employed for efficient oxidations of butanol, ethanol, glycerol, and H2O2. DFT calculations show that the applied voltage alters the electrostatic potential drop between TEMPO and the reactant as well as chemical bonding between them, thereby increasing the reaction rate. These results suggest a new route for designing next-generation hybrid molecular/electrocatalysts for OER and alcohol oxidations.

Photo-scanning Electrochemical Microscopy Observation of Overall Water Splitting at a Single Aluminum-Doped Strontium Titanium Oxide Microcrystal.

Particulate photocatalysts for the overall water splitting (OWS) reaction offer promise as devices for hydrogen fuel generation. Even though such photocatalysts have been studied for nearly 5 decades, much of the understanding of their function is derived from observations of catalyst ensembles and macroscopic photoelectrodes. This is because the sub-micrometer size of most OWS photocatalysts makes spatially resolved measurements of their local reactivity very difficult. Here, we employ photo-scanning electrochemical microscopy (photo-SECM) to quantitatively measure hydrogen and oxygen evolution at individual OWS photocatalyst particles for the first time. Micrometer-sized Al-doped SrTiO3/Rh2-yCryO3 photocatalyst particles were immobilized on a glass substrate and interrogated with a chemically modified SECM nanotip. The tip simultaneously served as a light guide to illuminate the photocatalyst and as an electrochemical nanoprobe to observe oxygen and hydrogen fluxes from the OWS. Local O2 and H2 fluxes obtained from chopped light experiments and photo-SECM approach curves using a COMSOL Multiphysics finite-element model confirmed stoichiometric H2/O2 evolution of 9.3/4.6 µmol cm-2 h-1 with no observable lag during chopped illumination cycles. Additionally, photoelectrochemical experiments on a single microcrystal attached to a nanoelectrode tip revealed a strong light intensity dependence of the OWS reaction. These results provide the first confirmation of OWS at single micrometer-sized photocatalyst particles. The developed experimental approach is an important step toward assessing the activity of photocatalyst particles at the nanometer scale.

Decoupling Through-Tip Illumination from Scanning in Nanoscale Photo-SECM.

The use of scanning electrochemical microscopy (SECM) for nanoscale imaging of photoelectrochemical processes at semiconductor surfaces has recently been demonstrated. To illuminate a microscopic portion of the substrate surface facing the SECM probe, a glass-sealed, polished tip simultaneously served as a nanoelectrode and a light guide. One issue affecting nanoscale photo-SECM experiments is mechanical interactions of the rigid optical fiber with the tip motion controlled by the piezo-positioner. Here we report an improved experimental setup in which the tip is mechanically decoupled from the fiber and light is delivered to the back of the tip capillary using a complex lens system. The advantages of this approach are evident from the improved quality of the approach curves and photo-SECM images. The light intensity delivered from the optical fiber to the tip is not changed significantly by their decoupling.

Voltage-Driven Molecular Catalysis of Electrochemical Reactions.

Heterogeneous electrocatalysis and molecular redox catalysis have developed over several decades as two distinct ways to facilitate charge-transfer processes essential for energy conversion and storage. Whereas electrocatalytic reactions are driven by the applied voltage, molecular catalytic processes are driven by the difference between standard potentials of the catalyst and the reactant. Here, we demonstrate that the rate of electron transfer between a dissolved reactant and a molecular catalyst immobilized directly on the surface of a carbon nanoelectrode is governed by combination of chemical driving force and electrostatic potential drop across the double layer. DFT calculations show that varying the applied voltage alters the potential drop between the surface-bound and dissolved redox species. These results suggest a new route for designing next-generation hybrid molecular/electrocatalysts.