Artificial photosynthesis relies on the availability of synthetic photocatalysts that can drive CO2 reduction in presence water and light. From standpoint solar fuel production, it is desirable these perform under visible light produce energy-rich hydrocarbons from reduction. However, multistep nature CO2-to-hydrocarbon conversion poses a significant kinetic bottleneck when compared to CO production H2 evolution. Here, we show plasmonic Au nanoparticle harvest for multielectron, multiproton...

The ability of plasmonic nanoparticles to harness visible light can be being combined with their catalytic activity drive photocatalytic transformations. This Review introduces the promise this new class photocatalysts for fulfilling quest sunlight-driven recycling CO2 into transportable liquid fuels. We discuss prospects and challenges such an approach. Despite considerable advances, a selective, stable, efficient reduction reaction (CO2RR) catalyst has been elusive. These open may...

The chemisorption energy of simple gases on transition metals follows some remarkable systematic trends. We construct a theory which leads to an understanding the observed trends and relates essential parameters characterizing metals, viz., mean their density states, bandwidth, number $d$ electrons. is applied adsorption hydrogen oxygen $3d$ $4d$ metals. positions atomic levels (and nitrogen) with respect bands such that primary binding comes from transfer electrons surface metal atoms...

The chemical sensitivity of surface-enhanced Raman spectroscopy (SERS) methodologies allows for the investigation heterogeneous reactions with high sensitivity. Specifically, SERS are well-suited to study electron transfer (ET) reactions, which lie at heart numerous fundamental processes: electrocatalysis, solar energy conversion, storage in batteries, and biological events such as photosynthesis. Heterogeneous ET commonly monitored by electrochemical methods cyclic voltammetry, observing...

We report electrogenerated chemiluminescence (ECL) generated at single gold nanowire electrodes supported on tin-doped indium oxide. Unlike other nanoparticle electrochemical characterization techniques, ECL provides a massively parallel direct readout of activity individual without the need for extrinsic illumination or scanning probe. While is not observed from as-purchased nanowires due to surfactant layer, by removing layer and coating with polymer blend, readily measured. With an...

The understanding and rational design of heterogeneous catalysts for complex reactions, such as CO2 reduction, requires knowledge elementary steps chemical species prevalent on the catalyst surface under operating conditions. Using in situ nanoscale surface-enhanced Raman scattering, we probe a Ag nanoparticle during plasmon-excitation-driven reduction water. Enabled by high spatiotemporal resolution sensitivity our method, detect rich array C1-C4 formed photocatalytically active surface....

ConspectusPlasmonic nanostructures have garnered widescale scientific interest because of their strong light–matter interactions and the tunability absorption across solar spectrum. At heart superlative interaction with light is resonant excitation a collective oscillation electrons in nanostructure by incident electromagnetic field. These oscillations are known as localized surface plasmon resonances (LSPRs). In recent years, community has uncovered intriguing photochemical attributes noble...

In this Letter, we demonstrate site-specific redox potentials for Nile Blue adsorbed to Ag nanoparticle electrodes using surface-enhanced Raman scattering (SERS) superlocalization microscopy. is electrochemically modulated between its oxidized and reduced form, which can be optically read out through a corresponding gain or loss in SERS intensity. emission centroids are calculated by fitting the diffraction-limited two-dimensional Gaussian determine approximate location of emitter with 5–10...

Noble metals are prime candidates for electrocatalysts electrochemical energy conversions. In a separate realm, nanostructured noble found to exhibit photocatalytic activity under plasmonic excitation with no electrical bias. Here, we explore the convergence of electrocatalytic and in reactions performed excitation. We use as model hydrogen evolution reaction (HER) on Au nanoparticle (NP) electrocatalysts. observe that NP electrocatalyst enhances HER activity. trace mechanistic origin this...

This work provides a mechanistic understanding of hot-electron-based catalysis on Au nanoparticles (NPs) induced under plasmonic excitation. Plasmon excitation-induced hot-electron transfer from an NP (donor) to ferricyanide anion (acceptor) was studied as function the donor–acceptor distance set by thiolate-based self-assembled monolayer (SAM). Hot-electron-transfer rates and activation barrier heights were measured distance, up 20 Å. Hot-electron found be longer range than anticipated. The...

Abstract We study how visible light influences the activity of an electrocatalyst composed Au and Pt nanoparticles. The bimetallic composition imparts a dual functionality: component catalyzes electrochemical oxidation ammonia to liberate hydrogen absorbs by excitation localized surface plasmon resonances. Under visible‐light excitation, this catalyst exhibits enhanced kinetics, outperforming previously reported schemes. trace enhancement photochemical potential resulting from electron–hole...

Understanding and engineering electrochemical environments often come secondary to electrocatalyst design when optimizing the activity selectivity of electrocatalytic molecular transformations. In this study, we employ CO2 reduction in acetonitrile on nanoscale-roughened Ag catalysts as a model system operando surface-enhanced Raman scattering spectroscopy demonstrate that local environment H2O affects proton-coupled reactions. We show an electrolyte has absorbed ca. 4.3 wt % from air...

Abstract A growing number of reports have demonstrated plasmon-assisted electrochemical reactions, though debate exists around the mechanisms underlying enhanced activity. Here we address impact plasmonic photothermal heating with cyclic voltammetry measurements and finite-element simulations. We find that causes a reduction in hysteresis anodic cathodic waves voltammograms along an increase mass-transport limiting current density due to convection induced by temperature gradient. At slow...

Recent progress in molecular ferroelectrics (MOFEs) has been overshadowed by the lack of high-quality thin films for device integration. We report a water-based air-processable technique to prepare large-area MOFE films, controlled supersaturation growth at liquid-air interface under temperature gradient and external water partial pressure. used this fabricate ImClO4 found large, tunable room electroresistance: 20-fold resistance variation upon polarization switching. The as-grown are...

The combination of electrochemistry (EC) and single molecule surface-enhanced Raman spectroscopy (SMSERS) has recently proven to be a sensitive method investigate electron transfer (ET) reactions at the level. SMSERS can both detect redox-active molecules potentially monitor oxidized (O) reduced (R) forms one-electron ET reaction in experiment. Herein, we report progress toward complete monitoring with EC-SMSERS. We first obtained solution phase resonance (RR) spectrum Rhodamine 6G (R6G)...

In this review, we describe how external magnetic fields and the intrinsic magnetism of catalysts can affect electrocatalytic reactions using select literature reports.

Super-resolution surface-enhanced Raman scattering (SERS) is used to investigate local surface potentials on plasmonic gold and silver colloidal aggregates using the redox-active reporter molecule, Nile Blue A. This molecule electrochemically modulated between an oxidized emissive state a reduced dark state. The diffraction-limited SERS emission from of single nanoparticle aggregate fit two-dimensional Gaussian track position centroid as function applied potential. Potential-dependent...

Conventional electrochemistry and surface-enhanced Raman scattering (SERS) spectroelectrochemistry are used to probe the redox reaction of Nile Blue immobilized on gold electrodes. Covalent attachment (NB) through carbodiimide cross-linking shows appearance a second, new reaction, unobserved by solution phase or physisorbed NB. Each is characterized differential pulse voltammetry reveal two individual one-proton, one-electron electrochemical reactions. SERS along with characterization...

Under the shielding effect of nanomicelles, a sustainable micellar technology for design and convenient synthesis ligand-free oxidizable ultrasmall Pd(0) nanoparticles (NPs) their subsequent catalytic exploration couplings water-sensitive acid chlorides in water is reported. A proline-derived amphiphile, PS-750-M, plays crucial role stabilizing these NPs, preventing aggregation oxidation state changes. These NPs were characterized using 13C nuclear magnetic resonance (NMR), infrared (IR),...

Piezoelectric energy harvesters typically perform poorly in the low frequency, amplitude, and intermittent excitation environment of human movement. In this paper, a piezoelectric compliant mechanism (PCM) harvester is designed that consists polyvinylidene diflouoride (PVDF) unimorph clamped at base attached to tip. The has two flexures amplify tip displacement produce large motion proof mass frequency first mode with an efficient (nearly quadratic) shape. fabricated as separate, relatively...

The tether length of Nile Blue impacts molecular orientation leading to unique SERS spectroelectrochemistry.