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Hot electrons are crucial for unraveling the intrinsic relationship between chemical reactions and charge transfer in heterogeneous catalysis. Significant research focused on real-time detection of reaction-driven hot electron flow (chemicurrent) to elucidate the energy conversion mechanisms, but it remains elusive because carrier generation contributes to only part of the entire process. Here, a theoretical model for quantifying the chemicurrent yield is presented by clarifying the contributions of hot carrier losses from the internal emission and multiple reflections. The experimental chemicurrent yield verifies our model with a reliable mean free path of hot electrons, emphasizing the importance of comprehensive consideration of the transport process besides hot electron generation. Moreover, Pt nanoparticles (NPs)-decorated Au/TiO 2 is examined, showing the role of NPs-induced carrier losses in the performance of catalytic nanodiodes. These findings are expected to contribute to understanding the hot electron detection efficiency and designing nanodiodes with enhanced hot carrier flow and catalytic activity.

The synergistic catalytic performances of bimetallic catalysts are often attributed to the reaction mechanism associated with the alloying process of the catalytic metals. Chemically induced hot electron flux is strongly correlated with catalytic activity, and the interference between two metals at the atomic level can have a huge impact on the hot electron generation on the bimetallic catalysts. In this study, we investigate the correlation between catalytic synergy and hot electron chemistry driven by the electron coupling effect using a model system of Au-Pd bimetallic nanoparticles. We show that the bimetallic nanocatalysts exhibit enhanced catalytic activity under the hydrogen oxidation reaction compared with that of monometallic Pd nanocatalysts. Analysis of the hot electron flux generated in each system revealed the formation of Au/PdO x interfaces, resulting in high reactivity on the bimetallic catalyst. In further experiments with engineering the Au@Pd core-shell structures, we reveal that the hot electron flux, when the topmost surface Pd atoms were less affected by inner Au, due to the concrete shell, was smaller than the alloyed one. The alloyed bimetallic catalyst forming the metal-oxide interfaces has a more direct effect on the hot electron chemistry, as well as on the catalytic reactivity. The great significance of this study is in the confirmation that the change in the hot electron formation rate with the metal-oxide interfaces can be observed by shell engineering of nanocatalysts.

Significant research has focused on enhancing catalytic performance through solar energy conversion, and the design of photocatalysis incorporating surface plasmons is drawing considerable attention as a highly competitive catalyst system. Although the hot electron process is the primary mechanism in plasmonic photocatalysis, the precise function of hot electron transport in catalytic reactions remains unclear due to the absence of direct measurement. Here, we demonstrate the intrinsic relationship between surface-plasmon-driven hot electrons and catalytic activity during hydrogen oxidation, utilizing catalytic Schottky nanodiodes (Pt/Ag/TiO 2 ) for antenna-reactor plasmonic photocatalysis. The simultaneous and independent measurements of hot electron flow and catalytic turnover rate show that the plasmonic effect amplifies the flow of reaction-induced hot electrons (chemicurrent), leading to enhanced catalytic activity. Plasmonic photocatalytic performance can be controlled with light wavelengths, intensity, surface temperature, and structures. These results elucidate the hot electron flow on photocatalysis and offer improved strategies for efficient catalytic devices.

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.

Hot electron flux, generated by both incident light energy and the heat of the catalytic reaction, is a major element for energy conversion at the surface. Controlling hot electron flux in a reversible manner is extremely important for achieving high energy conversion efficiency. Here we demonstrate that hot electron flux can be controlled by tuning the Schottky barrier height. This phenomenon was monitored by using a Schottky nanodiode composed of a metal-semiconductor. The formation of a Schottky barrier at a nanometer scale inevitably accompanies an intrinsic image potential between the metal-semiconductor junction, which lowers the effective Schottky barrier height. When a reverse bias is applied to the nanodiode, an additional image potential participates in a secondary barrier lowering, leading to the increased hot electron flow. Besides, a decrease of tunneling width results in facile electron transport through the barrier. The increased hot electron flux by the chemical reaction (chemicurrent) and by the photon absorption (photocurrent) indicates hot electrons are captured more effectively by modifying the Schottky barrier. This study can shed light on a quantitative understanding and application of charge behavior at metal-semiconductor interfaces, in solar energy conversion, or in a catalytic reaction.

Identifying the electronic behavior of metal-oxide interfaces is essential for understanding the origin of catalytic properties and for engineering catalyst structures with the desired reactivity. For a mechanistic understanding of hot electron dynamics at inverse oxide/metal interfaces, we employed a new catalytic nanodiode by combining Co3O4 nanocubes (NCs) with a Pt/TiO2 nanodiode that exhibits nanoscale metal-oxide interfaces. We show that the chemicurrent, which is well correlated with the catalytic activity, is enhanced at the inverse oxide/metal (CoO/Pt) interfaces during H2 oxidation. Based on quantitative visualization of the electronic transfer efficiency with chemicurrent yield, we show that electronic perturbation of oxide/metal interfacial sites not only promotes the generation of hot electrons, but improves catalytic activity.

We present the design of a three-dimensional Pt/mesoporous TiO 2 Schottky nanodiode that can capture hot electrons more effectively, compared with a typical two-dimensional Schottky diode. Both chemically induced and photon-induced hot electrons were measured on the three-dimensional Pt/mesoporous TiO 2 Schottky nanodiode. An increase in the number of interfacial sites between the platinum and support oxide affects the collection of hot electrons generated by both the catalytic reaction and light injection. We show that hot electrons flowing 2.5 times higher are detected as the current in the mesoporous system, compared with typical two-dimensional nanodiode systems that have a planar Schottky junction. Identical trends for the chemicurrent and photocurrent in the mesoporous system demonstrate that the enhanced hot electrons are attributed to the larger interface area between the metal and the mesoporous TiO 2 support fabricated by the anodization process. This three-dimensional Schottky nanodiode can provide insights into hot electron generation on a practical catalytic device.

A novel three-dimensional catalytic nanodiode composed of a Pt thin film on TiO 2 nanotubes was designed for the efficient detection of the flux of hot electrons, or chemicurrent, under hydrogen oxidation. We verify a significant increase in the chemicurrent from the fast transport of electrons across the ordered supporting oxide layer. This study demonstrates the direct detection of hot electrons on well-ordered TiO 2 nanotubes during the catalytic reaction.