Direct <i>In Situ</i> Measurement of Quantum Efficiencies of Charge Separation and Proton Reduction at TiO₂‑Protected GaP Photocathodes

Photoelectrochemical solar fuel generation at the semiconductor/liquid interface consists of multiple elementary steps, including charge separation, recombination, and catalytic reactions. While the overall incident light-to-current conversion efficiency (IPCE) can be readily measured, identifying the microscopic efficiency loss processes remains difficult. Here, we report simultaneous in situ transient photocurrent and transient reflectance spectroscopy (TRS) measurements of titanium dioxide-protected gallium phosphide photocathodes for water reduction in photoelectrochemical cells. Transient reflectance spectroscopy enables the direct probe of the separated charge carriers responsible for water reduction to follow their kinetics. Comparison with transient photocurrent measurement allows the direct probe of the initial charge separation quantum efficiency (ϕCS) and provides support for a transient photocurrent model that divides IPCE into the product of quantum efficiencies of light absorption (ϕabs), charge separation (ϕCS), and photoreduction (ϕred), i.e., IPCE = ϕabsϕCSϕred. Our study shows that there are two general key loss pathways: recombination within the bulk GaP that reduces ϕCS and interfacial recombination at the junction that decreases ϕred. Although both loss pathways can be reduced at a more negative applied bias, for GaP/TiO2, the initial charge separation loss is the key efficiency limiting factor. Our combined transient reflectance and photocurrent study provides a time-resolved view of microscopic steps involved in the overall light-to-current conversion process and provides detailed insights into the main loss pathways of the photoelectrochemical system

Solvent-Free Process to Produce Three Dimensional Graphene Network with High Electrochemical Stability

Three-dimensional (3D) graphene has attracted increasing attention in electrochemical devices. However, the existing preparation technologies usually involve a solvent process, which introduces defects and functional groups into the 3D network. Here, we find the defects and functional groups influence the electrochemical stability of graphene. After an electrochemical process, the current decreases by more than 1 order of magnitude, indicating remarkable etching of graphene. To improve the electrochemical stability, we develop a solvent-free preparation process to produce 3D graphene for the first time. After growth on a 3D microporous copper by chemical vapor deposition (CVD), the copper template is removed by a high temperature evaporation process, resulting in 3D graphene network without any solvent process involved. The samples exhibit remarkably improved stability with durable time 2 times, compared with normal CVD samples, and 55 times, compared with reduced graphite oxide, and no obvious etching is observed at 1.6 V versus saturated calomel electrode, showing great potential for application in future 3D graphene-based high stable electrochemical devices