Unraveling Photothermal-Enhanced bulk charge transport and surface oxygen reactions in TiO2 photoanodes for highly efficient photoelectrochemical water oxidation

Titanium dioxide (TiO2) has been extensively used as an important photoanode material for photoelectrochemical (PEC) water splitting, but its activity is greatly hindered by the low charge transport and sluggish oxygen evolution reaction (OER) kinetics. Herein, we demonstrate spinel oxide NiCo2O4 (NCO) acted as both photothermal material and oxygen evolution cocatalyst could significantly promote the PEC performance of TiO2 photoanodes, and a high photocurrent of 2.34 mA cm-2 at 1.23 V vs. reversible hydrogen electrode has been achieved by NCO/TiO2 photoanodes assisted by the photothermal effect. Importantly, a mechanism is proposed to explain the enhanced bulk charge transport and surface OER activity by an integrated various operando characterizations and density functional theory (DFT) study. Intensity-modulated photocurrent spectroscopy (IMPS) analysis and DFT calculations imply the relatively high temperature induced by the photothermal effect could accelerate small polaron hopping in the bulk of TiO2, which is verified by the electron diffusion coefficient variation of TiO2 with oxygen vacancies at different temperatures. Operando cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) reveal that photothermal conversion facilitates the oxidation of Ni2+ at lower potential and promotes the adsorption of *OH and deprotonation of *OOH intermediates. This work provides deep insight into the photothermal-enhanced PEC performance by observing the bulk small polaron hopping and surface dynamic evolution during the PEC process, which may underpin future advances in promoting PEC and photocatalytic performances of small-polaron-type semiconductors.