Molecular dynamics simulation of thermal transport properties of phonons at interface of Au-TiO₂ photoelectrode

Abstract

Thermoplasmonics originated from the relaxation process of plasmon resonances in nanostructures can be utilized as an efficient and highly localized heat source to merge in solar-hydrogen conversion, but there have been few studies on the interfacial heat transport properties of photoelectrode with the thermoplasmonics effect in the photoelectrochemical water splitting system. In this work, the effects of temperature, interfacial coupling strength and the addition of graphene layers on the interfacial thermal conductance of Au-TiO<sub>2</sub> electrodes are investigated by the non-equilibrium molecular dynamics method, and the variation of interfacial thermal conductance is analyzed by the phonon density of states. The results show that the interfacial thermal conductivity is increased by 78.55% when the temperature increases from 300 K to 800 K. This is related to the fact that more low-frequency phonons participate in the interface heat transport, allowing more heat to be transferred to TiO<sub>2</sub> to promote the interface reaction. As the coupling strength of the Au-TiO<sub>2</sub> interface increases, the interfacial thermal conductivity of the electrode increases and then tends to stabilize. The interfacial thermal conductivity can be optimized by increasing the degree of overlap of the phonon state densities of Au and TiO<sub>2</sub>. Adding a single layer of graphene can increase the interfacial thermal conductivity to 98.072 MW m<sup>-2</sup> K<sup>-1</sup>, but the addition of 2 and 3 layers of graphene can hinder interfacial heat transfer in Au and TiO<sub>2</sub> due to the interaction between the layers of graphene. When adding graphene layer, medium and high frequency phonons are stimulated to participate in the interfacial heat transfer, but with increase of the graphene layers, the number of low-frequency phonons in the range of 0~30 THz is reduced which dominates the interfacial thermal conductivity. The obtained results are useful in regulating the thermal transport properties of the photoelectrode interface, which can provide new insights and theoretical basis for the design and construction of composite photoelectrodes.