Photoelectrochemical water splitting half reactions on semiconducting photoelectrodes have received much attention but efficient overall water splitting driven by a single photoelectrode has remained elusive due to stringent electronic and thermodynamic property requirements. Utilizing a tandem configuration wherein the total photovoltage is generated by complementary optical absorption across different semiconducting electrodes is a possible pathway to unassisted overall light-induced water splitting. Because of the low photovoltages generated by conventional photovoltaic materials (e.g., Si, CIGS), such systems typically consist of triple junction design that increases the complexity due to optoelectrical trade-offs and are also not cost-effective. Here, we show that a single solution processed organic-inorganic halide perovskite (CH3NH3PbI3) solar cell in tandem with a Fe2O3 photoanode can achieve overall unassisted water splitting with a solar-to-hydrogen conversion efficiency of 2.4%. Systematic electro-optical studies were performed to investigate the performance of tandem device. It was found that the overall efficiency was limited by the hematite's photocurrent and onset potential. To understand these limitations, we have estimated the intrinsic solar to chemical conversion efficiency of the doped and undoped Fe2O3 photoanodes. The total photopotential generated by our tandem system (1.87 V) exceeds both the thermodynamic and kinetic requirements (1.6 V), resulting in overall water splitting without the assistance of an electrical bias.

Here, we report a significant improvement of the photoelectrochemical (PEC) properties of hematite (α-Fe2O3) to oxidize water by doping with manganese. Hematite nanorods were grown on a fluorine-treated tin oxide (FTO) substrate by a hydrothermal method in the presence on Mn. Systematic physical analyses were performed to investigate the presence of Mn in the samples. Fe2O3 nanorods with 5 mol % Mn treatment showed a photocurrent density of 1.6 mA cm(-2) (75% higher than that of pristine Fe2O3) at 1.23 V versus RHE and a plateau photocurrent density of 3.2 mA cm(-2) at 1.8 V versus RHE in a 1 M NaOH electrolyte solution (pH 13.6). We attribute the increase in the photocurrent density, and thus in the oxygen evolving capacity, to the increased donor density resulting from Mn doping of the Fe2O3 nanorods, as confirmed by Mott-Schottky measurement, as well as the suppression of electron-hole recombination and enhancement in hole transport, as detected by chronoamperometry measurements.

Solar-driven photocathode converts carbon dioxide to C2and C3products.