Thermal-Driven Dynamic Shape Change of Bimetallic Nanoparticles Extends Hot Electron Lifetime of Pt/MoS₂ Catalysts

Abstract

Using a combination of time-domain density functional theory and nonadiabatic (NA) molecular dynamics, we demonstrate that the replacement of noble Pt with cheap Sn in the Pt nanoparticles sensitized MoS 2 greatly retards the photoexcited "hot" electron relaxation. The simulations show that Sn substitution causes significant geometry distortion associated with the Sn dopant detaching from the Pt nanoparticle base, which decreases the NA coupling and creates an isolated trap state distant from the electron donor state. Generally, smaller NA coupling delays "hot" electron relaxation. At the same time, the photoexcited electron on MoS 2 first populates the nanoparticles state and then slowly goes to the trap state, following relaxation to the nanoparticle acceptor state over 1 ps. As a result, the "hot" electron lives over 3.5 times longer than that in pristine Pt/MoS 2 system. The longlived "hot" electron associated with the reduced cost establishes a novel concept for developing high-efficient and cost-effective photocatalysts and photovoltaics.

Near-infrared-featured broadband CO2 reduction with water to hydrocarbons by surface plasmon

“…3a . Compared to the continuous states near E f of PdCu metal, these quasi isolated trap states can effectively extend the lifetime of hot electrons and increase the probability of electron re-excitation by another low-energy photon 40 , 41 , which makes the utilization of low-energy photons possible. Such a multiphoton absorption behavior can be corroborated by the superlinear law dependence between CH 4 production rate and light intensity (see Figs.…”

Enhanced Electron Transfer and Spin Flip through Spin–Orbital Couplings in Organic/Inorganic Heterojunctions: A Nonadiabatic Surface Hopping Simulation

“…NA-MD methods implementing the surface hopping (SH) scheme in the framework of time-dependent Kohn–Sham (TDKS) equation (in brief, TDKS-based NA-MD) − provide a detailed description of spin-free electronic state transitions resulting from electron–phonon couplings (EPCs), such as the charge transfer, hot carriers relaxation, and nonradiative recombination in condensed matter systems. ,,,− More recently, NA-MD has started to report SOC effects on these nonadiabatic processes, ,− yet SOC-induced spin dynamics is unreported to the best of our knowledge. Consequently, the fundamental knowledge of the fate of electron spin during the interlayer charge transfer and relaxation in solids, which is important for light harvesting, efficiency promotion of organic solar cells, and applicable high-IQE luminescent devices, , continues to be a missing piece of information because of the absence of suitable theoretical tools. ,, Therefore, there is an urgent need to investigate SOC-induced spin-related electron dynamics at organic/inorganic interfaces.…”

“…In contrast, the LUMO exhibits a mixture of the donor and acceptor, revealing the large coupling between the donor and acceptor states, consistent with the DOS analysis. Previous theoretical studies linked the donors’ delocalization on acceptors with improved NACs and ultrafast charge transfer across the interface. ,,,,,− …”

Charge-Compensated Doping Extends Carrier Lifetimes in SrTiO3 by Passivating Oxygen Vacancy Defects

“…The pure-dephasing time can be estimated using the second-order cumulant approximation . This method has been successfully applied to investigate photoexcitation dynamics in a variety of materials, including metal oxide, − black phosphorus, , transition metal dichalcogenides, − and perovskites. , A detailed description of the NA-MD approach has been reported elsewhere. , …”