Important Considerations in Plasmon-Enhanced Electrochemical Conversion at Voltage-Biased Electrodes.

In this perspective we compare plasmon-enhanced electrochemical conversion (PEEC) with photoelectrochemistry (PEC). PEEC is the oxidation or reduction of a reactant at the illuminated surface of a plasmonic metal (or other conductive material) while a potential bias is applied. PEC uses solar light to generate photoexcited electron-hole pairs to drive an electrochemical reaction at a biased or unbiased semiconductor photoelectrode. The mechanism of photoexcitation of charge carriers is different between PEEC and PEC. Here we explore how this difference affects the response of PEEC and PEC systems to changes in light, temperature, and surface morphology of the photoelectrode

A temperature-controlled photoelectrochemical cell for quantitative product analysis.

In this study, we describe the design and operation of a temperature-controlled photoelectrochemical cell for analysis of gaseous and liquid products formed at an illuminated working electrode. This cell is specifically designed to quantitatively analyze photoelectrochemical processes that yield multiple gas and liquid products at low current densities and exhibit limiting reactant concentrations that prevent these processes from being studied in traditional single chamber electrolytic cells. The geometry of the cell presented in this paper enables front-illumination of the photoelectrode and maximizes the electrode surface area to electrolyte volume ratio to increase liquid product concentration and hence enhances ex situ spectroscopic sensitivity toward them. Gas is bubbled through the electrolyte in the working electrode chamber during operation to maintain a saturated reactant concentration and to continuously mix the electrolyte. Gaseous products are detected by an in-line gas chromatograph, and liquid products are analyzed ex situ by nuclear magnetic resonance. Cell performance was validated by examining carbon dioxide reduction on a silver foil electrode, showing comparable results both to those reported in the literature and identical experiments performed in a standard parallel-electrode electrochemical cell. To demonstrate a photoelectrochemical application of the cell, CO2 reduction experiments were carried out on a plasmonic nanostructured silver photocathode and showed different product distributions under dark and illuminated conditions

Bottom-up meets top-down: Tailored raspberry-like Fe3O4-Pt nanocrystal superlattices

Supported catalysts are widely used in industry and can be optimized by tuning the composition, chemical structure, and interface of the nanoparticle catalyst and oxide support. Here we firstly combine a bottom up colloidal synthesis method with a top down atomic layer deposition (ALD) process to achieve a raspberry-like Pt-decorated Fe3O4 (Fe3O4-Pt) nanoparticle superlattices. This nanocomposite ensures the precision of the catalyst/support interface, improving the catalytic efficiency of the Fe3O4-Pt nanocomposite system. The morphology of the hybrid nanocomposites resulting from different cycles of ALD was monitored by scanning transmission electron microscopy, giving insight into the nucleation and growth mechanism of the ALD process. X-ray photoelectron spectroscopy studies confirm the anticipated electron transfer from Fe3O4 to Pt through the nanocomposite interface. Photocurrent measurement further suggests that Fe3O4 superlattices with controlled decoration of Pt have substantial promise for energy-efficient photoelectrocatalytic oxygen evolution reaction. This work opens a new avenue for designing supported catalyst architectures via precisely controlled decoration of single component superlattices with noble metals

Bottom-up meets top-down:Tailored raspberry-like Fe\u3csub\u3e3\u3c/sub\u3eO\u3csub\u3e4\u3c/sub\u3e-Pt nanocrystal superlattices

\u3cp\u3eSupported catalysts are widely used in industry and can be optimized by tuning the composition, chemical structure, and interface of the nanoparticle catalyst and oxide support. Here we firstly combine a bottom up colloidal synthesis method with a top down atomic layer deposition (ALD) process to achieve a raspberry-like Pt-decorated Fe\u3csub\u3e3\u3c/sub\u3eO\u3csub\u3e4\u3c/sub\u3e (Fe\u3csub\u3e3\u3c/sub\u3eO\u3csub\u3e4\u3c/sub\u3e-Pt) nanoparticle superlattices. This nanocomposite ensures the precision of the catalyst/support interface, improving the catalytic efficiency of the Fe\u3csub\u3e3\u3c/sub\u3eO\u3csub\u3e4\u3c/sub\u3e-Pt nanocomposite system. The morphology of the hybrid nanocomposites resulting from different cycles of ALD was monitored by scanning transmission electron microscopy, giving insight into the nucleation and growth mechanism of the ALD process. X-ray photoelectron spectroscopy studies confirm the anticipated electron transfer from Fe\u3csub\u3e3\u3c/sub\u3eO\u3csub\u3e4\u3c/sub\u3e to Pt through the nanocomposite interface. Photocurrent measurement further suggests that Fe\u3csub\u3e3\u3c/sub\u3eO\u3csub\u3e4\u3c/sub\u3e superlattices with controlled decoration of Pt have substantial promise for energy-efficient photoelectrocatalytic oxygen evolution reaction. This work opens a new avenue for designing supported catalyst architectures via precisely controlled decoration of single component superlattices with noble metals.\u3c/p\u3