Hot Electron Phenomena at Solid–Liquid Interfaces

Abstract

Understanding the role of energy dissipation and charge transfer under exothermic chemical reactions on metal catalyst surfaces is important for elucidating the fundamental phenomena at solid–gas and solid–liquid interfaces. Recently, many surface chemistry studies have been conducted on the solid–liquid interface, so correlating electronic excitation in the liquid-phase with the reaction mechanism plays a crucial role in heterogeneous catalysis. In this review, we introduce the detection principle of electron transfer at the solid–liquid interface by developing cutting-edge technologies with metal–semiconductor Schottky nanodiodes. The kinetics of hot electron excitation are well correlated with the reaction rates, demonstrating that the operando method for understanding nonadiabatic interactions is helpful in studying the reaction mechanism of surface molecular processes. In addition to the detection of hot electrons excited by a catalytic reaction, we highlight recent results on how the transfer of the hot electrons influences surface chemical and photoelectrochemical reactions.

Plasmon-Enhanced C–C Bond Cleavage toward Efficient Ethanol Electrooxidation

“…Under appropriate light illumination, plasmonic nanostructure can generate energetic carriers and/or local heating effect at and near the nanostructured metal surface, which has become a promising approach to driven a catalytic process effectively in mild conditions. − For example, oxygen can be activated on illuminated plasmonic nanostructures under low temperature . Localized surface plasmon resonance (LSPR) provides the possibility of coupling photon energy with surface electrochemical active sites to improve the EOR process.…”

Engineering Ultrathin Alloy Shell in Au@AuPd Core‐Shell Nanoparticles for Efficient Plasmon‐Driven Photocatalysis

“…Thus, the ultrathin AuPd shells (i.e., sub-monolayer) of Au@AuPd NPs are beneficial to maximize the field strength and prolong the lifetime of hot carriers at the surface layer. [17,36,60,74,[76][77][78] Based on these facts, it is demonstrated that the notable light-enhanced catalytic performance of Au@AuPd NPs with 10 at% of Pd arises from the synergistic effect of two key factors: first, the maximization of the surface charge heterogeneity achieved through an increasing number of single-atom Pd sites (i.e., Au-Pd interfaces); and second, the efficient funneling of hot electrons from Au to Pd amplified by the surface plasmon effect. Notably, the performance of the Au@AuPd catalyst was highly comparable to other AuPd photocatalysts, even under air atmosphere and at relatively lower temperatures and metal loading.…”

Ultrafast and Nanoscale Energy Transduction Mechanisms and Coupled Thermal Transport across Interfaces

“…However, this is not to suggest that electronic and photonic energy transport does not arise across such interfaces; this should come as no surprise due to the fact that application spaces such as electrochemical and photochemical catalysis both rely on interfacial charge transport and sustain large optical-mode activity for radiative transport. Indeed, a recent review by Lee et al 252 on the role of interfacial hot-electron processes across solid−liquid interfaces provides an in-depth survey of many recent works. Nonetheless, the heat flux of such processes remains quite small relative to vibrational energy transport based on our current understanding; further interfacial engineering and excitation may be likely to increase the contribution of electron-mediated heat fluxes across solid−liquid interfaces and thus deserves continued exploration.…”