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Tracking Electrochemistry on Single Nanoparticles with Surface-Enhanced Raman Scattering Spectroscopy and Microscopy

Studying electrochemical reactions on single nanoparticles is important to understand the heterogeneous performance of individual nanoparticles. This ...

University of Louisville

The understanding and rational design of heterogeneous catalysts for complex reactions, such as CO reduction, requires knowledge of elementary steps and chemical species prevalent on the catalyst surface under operating conditions. Using in situ nanoscale surface-enhanced Raman scattering, we probe the surface of a Ag nanoparticle during plasmon-excitation-driven CO reduction in water. Enabled by the high spatiotemporal resolution and surface sensitivity of our method, we detect a rich array of C-C species formed on the photocatalytically active surface. The abundance of multi-carbon compounds, such as butanol, suggests the favorability of kinetically challenging C-C coupling on the photoexcited Ag surface. Another advance of this work is the use of isotope labeling in nanoscale probing, which allows confirmation that detected species are the intermediates and products of the catalytic reaction rather than spurious contaminants. The surface chemical knowledge made accessible by our approach will inform the modeling and engineering of catalysts.

A rich catalog of C-C bonded species formed in CO reduction on a plasmonic photocatalyst.

Under the shielding effect of nanomicelles, a sustainable micellar technology for the design and convenient synthesis of ligand-free oxidizable ultrasmall Pd(0) nanoparticles (NPs) and their subsequent catalytic exploration for couplings of water-sensitive acid chlorides in water is reported. A proline-derived amphiphile, PS-750-M, plays a crucial role in stabilizing these NPs, preventing their aggregation and oxidation state changes. These NPs were characterized using C nuclear magnetic resonance (NMR), infrared (IR), and surface-enhanced Raman scattering (SERS) spectroscopy to evaluate the carbonyl interactions of PS-750-M with Pd. High-resolution transmission electron microscopy (HRTEM) and energy-dispersive X-ray spectroscopy (EDX) studies were performed to reveal the morphology, particle size distribution, and chemical composition, whereas X-ray photoelectron spectroscopy (XPS) measurements unveiled the oxidation state of the metal. In the cross-couplings of water-sensitive acid chlorides with boronic acids, the micelle's shielding effect and boronic acids plays a vital role in preventing unwanted side reactions, including the hydrolysis of acid chlorides under basic pH. This approach is scalable and the applications are showcased in multigram scale reactions.

Shielding Effect of Nanomicelles: Stable and Catalytically Active Oxidizable Pd(0) Nanoparticle Catalyst Compatible for Cross-Couplings of Water-Sensitive Acid Chlorides in Water.

Phosphine ligand-free bimetallic nanoparticles (NPs) composed of Ni(0)Pd(0) catalyze highly selective 1,4-reductions of enones, enamides, enenitriles, and ketoamides under aqueous micellar conditions. A minimal amount of Pd (Ni/Pd = 25:1) is needed to prepare these NPs, which results in reductions without impacting - and -benzyl, aldehyde, nitrile, and nitro functional groups. A broad range of substrates has been studied, including a gram-scale reaction. The metal-micelle binding is supported by surface-enhanced Raman spectroscopy data on both the NPs and their individual components. Optical imaging, high-resolution transmission electron microscopy, and energy-dispersive X-ray spectroscopy analyses reveal the formation of NP-containing micelles or vesicles, NP morphology, particle size distribution, and chemical composition. X-ray photoelectron spectroscopy measurements indicate the oxidation state of each metal within these bimetallic NPs.

Phosphine Ligand-Free Bimetallic Ni(0)Pd(0) Nanoparticles as a Catalyst for Facile, General, Sustainable, and Highly Selective 1,4-Reductions in Aqueous Micelles.

Plasmon excitation of metal electrodes is known to enhance important energy related electrochemical transformations in aqueous media. However, the low solubility of nonpolar gases and molecular reagents involved in many energy conversion reactions limits the number of products formed per unit time in aqueous media. In this Communication, we use linear sweep voltammetry to measure how electrochemical HO reduction in a nonaqueous solvent, acetonitrile, is enhanced by excitation of a plasmonic electrode. Plasmonically excited electrochemically roughened Au electrodes are found to produce photopotentials as large as 175 mV, which can be harnessed to lower the applied electrical bias required to drive the formation of H. As the solvent polarity increases, by an increase in the concentration of HO, the measured photopotential rapidly drops off to ∼50 mV. We propose a mechanism by which an increase in the HO concentration increasingly stabilizes the photocharged plasmonic electrode, lowering the photopotential available to assist in the electrochemical reaction. Our study demonstrates that solvent polarity is an essential experimental parameter to optimize plasmonic enhancement in electrochemistry.

Andrew J. Wilson

Department of Chemistry

University of Louisville

Tracking Electrochemistry on Single Nanoparticles with Surface-Enhanced Raman Scattering Spectroscopy and Microscopy

Andrew J. Wilson

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Department of Chemistry

University of Louisville

Tracking Electrochemistry on Single Nanoparticles with Surface-Enhanced Raman Scattering Spectroscopy and Microscopy

Department of Chemistry