A Photoelectrochemical and Spectroscopic Studies of Photoelectrodes with Hematite∣Catalyst∣Electrolyte Interface Toward Oxygen Evolution Reaction
Authors: Lee Hyun Joo , Lim Sung Yul 
Published: September 2023

One of the recent issues in the world is climate change caused by global warming. Many countries have set an ultimate goal for carbon neutrality to prevent from further increase of the global temperatures. In this regard, research on development of renewable energy sources without any carbon emissions has been intensively conducted. Among many promising chemical fuels with sustainability, Hydrogen (H2) can be produced by water (H2O) splitting.
Especially, water splitting driven by photoelectrochemical reactions has great advantages in H2 generation: photovoltage generated by light absorption in semiconductors may significantly reduce the applied overpotential which should be provided by external circuits. This photoelectrochemical system, called photoelectrochemical cell (PEC) for water splitting is basically composed of photoelectrodes, catalysts, and membranes for generation of photogenerated charge carriers, reducing overpotential by improving charge transfer kinetics, and prevention of H2 and Oxygen (O2) crossover, respectively. When photons from solar light with energies greater than band gap are incident on the photoelectrodes, an electron-hole pair (EHP) is formed in the semiconductor. These EHPs are separated and transported to the surface, driven by band bending formed at the semiconductors. In photoanodes, the most of the charge carriers arrived at the electrode surface are holes (h+s), which oxidizes H2O at the photoelectrode-electrolyte interface. The transfer of holes accompanies the proton transfers, thereby producing O2. The separated electrons (e−s) should travel to the (photo)cathode along the external circuit and generate H2. However, the overall efficiency of water splitting using PEC still confronts many challenges for wide commercialization, including the low solar-to-hydrogen (STH) efficiencies. In order to improve the performance, the semiconductor efficiently utilizes the photons in the visible light region, which takes 45% of solar irradiation. In this perspective, hematite (α-Fe2O3) is one of the most promising candidates for the semiconductor as photoanodes owing to is narrow band gap of 1.9 ~ 2.2 eV, which is in the range between 550 ~ 650 nm. Meticulous cares should be also taken in catalysts localization to prevent from the parasitic photon loss, as well as the selection of catalytic materials. Because catalysts attribute to the improved charge transfer kinetics but also simultaneously become the sites that obstruct the light penetration to the semiconductor, resulting in the lower light absorption. Furthermore, physical and chemical composition of catalysts on the semiconductor surface significantly influence the charge transfer rates for the photoelectrochemical reactions by varying the electrical field gradient formed at the semiconductor∣catalyst∣electrolyte interface. As several procedures are additionally involved in the PEC, the electrochemical reaction pathways become more complicated rather than the one in electrolyzers utilizing conductive electrodes. Therefore, underlying understanding in semiconductor∣catalyst∣electrolyte interface is crucial to achieve the high performance in PECs.
Herein, we demonstrate the hematite∣catalyst∣electrolyte interface as the photoanodes to investigate the photoelectrochemical reaction pathways in water oxidation. Hematite is the perfect material as the semiconductor model, not only due to the narrow band gap in the region of visible light but also the excellent stability even when exposed to the electrolytes and electrochemical environments. The hematite is fabricated by simple hydrothermal reactions, followed by step-wise heat treatment. The structure of hematite is optimized by varying hydrothermal temperatures, affecting the crystallinity and exposed area of the conductive substrate, fluorine-doped tin oxide (FTO). The recombination by back reduction is occurred at the exposed FTO surface by pinholes in hematite, which directly contact the electrolyte. Moreover, the localization of Co-based catalysts is also easily controlled by light-guided electrodeposition. In this hematite∣catalyst∣electrolyte interface, the overall water oxidation pathways are investigated by photoelectrochemical and Raman spectroscopic studies. It is expected that our study in here contributes to the in-depth understanding on the complicated photoelectrochemical reaction mechanism, might leading to the improved performance for wide commercialization of PEC.