Hostname: page-component-89b8bd64d-dvtzq Total loading time: 0 Render date: 2026-05-07T14:45:04.999Z Has data issue: false hasContentIssue false

Photocatalytic hot-carrier chemistry

Published online by Cambridge University Press:  10 January 2020

Yugang Sun
Affiliation:
Temple University, USA; ygsun@temple.edu
Zhiyong Tang
Affiliation:
National Center for Nanoscience and Technology, China; zytang@nanoctr.cn

Abstract

Light absorption in nanoparticles of semiconductors and metals excites electrons from ground states to high-energy levels, generating hot electrons with the addition of kinetic energy, and consequently, complimentary hot holes in the nanoparticles. These hot electrons are capable of injecting themselves into the empty antibonding orbitals of chemical bonds of reactant molecules adsorbed on the surface of the nanoparticles, thereby weakening the chemical bonds to trigger corresponding desirable chemical reactions. Hot-electron chemistry represents a fundamentally different mechanism of solar-to-chemical energy conversion compared to the traditional photochemistry that relies on the direct photo-excitation of electrons in reactant molecules and thermal catalysis. This issue of MRS Bulletin examines the generation and relaxation of hot electrons in typical nanoparticle systems, and the flow of hot electrons across the surfaces of the nanoparticles. The promise of hot-electron chemistry (and the complementary hot-hole chemistry) is supported by its application in many important reactions, including CO2 reduction, water splitting, hydrogenation, and coupling reactions, highlighting its great potential in achieving high energy-conversion efficiency and product selectivity.

Information

Type
Materials for Hot-Carrier Chemistry
Copyright
Copyright © Materials Research Society 2020
Figure 0

Figure 1. Schematic illustration of mechanisms responsible for weakening a chemical bond through photoexcitation of an electron that can fill the empty antibonding orbital of the chemical bond. The top process expresses the direct excitation of one electron from the bonding orbital to the empty antibonding orbital upon absorption of one photon. The bottom process describes an indirect strategy: electrons in a nanoparticle are first excited to the energy levels above its Fermi level (EF) upon light absorption, followed by the injection of one excited electron into the empty antibonding orbital of the chemical bond when the molecule is adsorbed on the surface of the nanoparticle. σ and σ* represent the bonding orbital filled with an electron pair and the empty antibonding orbital, respectively, of a sigma covalent chemical bond. In a complex molecule, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are usually used to describe the bonding orbital filled with electrons and the empty antibonding orbital, respectively.

Figure 1

Figure 2. Schematic illustration of hot-electron distribution in photoexcited nanoparticles of different material systems: (a) semiconductor, (b) metal, (c) semiconductor–metal composite with metal as the light absorber, and (d) metal–semiconductor composite with semiconductor as the light absorber. The arrows highlight the flow direction of hot electrons from the photocatalyst nanoparticles to the empty lowest unoccupied molecular orbital (LUMO) of molecules adsorbed on the surfaces of the nanoparticles. The blue color indicates cool electrons (i.e., electrons with energy below or near the Fermi level, EF, of the materials). The warming colors indicate hot electrons with energy above the Fermi level of the materials. Note: CB, conduction band; VB, valence band; HOMO, highest occupied molecular orbital.

Figure 2

Figure 3. Energy diagrams (black curves) of (a) an exergonic reaction and (b) an endergonic reaction, showing the requirement of activation energy in the reactant (R) to overcome the forward reaction energy barrier (Ea). Injection of hot electrons into the reactant molecules forms negatively charged transient intermediate (NCTI) species, which exhibit potential energy surface (PES) (red curves) significantly different from the reactant. Depending on the position of the PES valley of the NCTI, relaxing the NCTI to a ground state either (a) lowers the forward reaction energy barrier (Ea*) or (b) directly forms the product.