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

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 MoS₂ 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 MoS₂ 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/MoS₂ system. The long-lived "hot" electron associated with the reduced cost establishes a novel concept for developing high-efficient and cost-effective photocatalysts and photovoltaics.