Search Results (4)

This study focuses on enhancing the photoelectrocatalytic (PEC) performance of LaFeO₃ photocathodes by incorporating Ag nanocrystals. LaFeO₃, a perovskite-type metal oxide semiconductor, has potential in PEC water splitting but suffers from fast charge carrier recombination. Ag nanoparticles are introduced due to their surface plasmon resonance (SPR) property and ability to form Schottky junctions with LaFeO₃. A series of Ag/LaFeO₃ materials are prepared using the molten salt method for LaFeO₃ synthesis and the direct reduction method for Ag loading. The results show that Ag nanoparticles are uniformly dispersed on LaFeO₃. The 3 mol% Ag/LaFeO₃ photocathode demonstrates a remarkable ninefold increase in photocurrent density (15 mA·cm⁻² at −0.2 V vs. RHE) compared to pure LaFeO₃ (1.7 mA·cm⁻²). The band gap of LaFeO₃ is reduced from 2.07 eV to 1.92 eV with 3 mol% Ag loading, and the charge transfer impedance is reduced by 77%, while the carrier concentration increases by 2.3 times. The novelty of this work lies in the comprehensive investigation of the interaction mechanisms between Ag nanoparticles and LaFeO₃, which lead to enhanced light absorption, improved charge separation, and increased electrochemical activity. The optimized Ag loading not only improves the photocatalytic efficiency but also enhances the stability of the photocathode. This work provides valuable insights into the interaction between Ag and LaFeO₃, and offers experimental and theoretical support for developing efficient photocatalytic materials for PEC water splitting. Full article

Perovskite-type lanthanum iron oxide, LaFeO₃, is a promising photocathode material that can achieve water splitting under visible light. However, the performance of this photoelectrode material is limited by significant electron-hole recombination. In this work, we explore different strategies to optimize the activity of a nanostructured porous LaFeO₃ film, which demonstrates enhanced photoelectrocatalytic activity due to the reduced diffusion length of the charge carriers. We found that surface passivation is not an efficient approach for enhancing the photoelectrochemical performance of LaFeO₃, as it is sufficiently stable under photoelectrocatalytic conditions. Instead, the deposition of a Pt co-catalyst was shown to be essential for maximizing the photoelectrochemical activity both in hydrogen evolution and oxygen reduction reactions. Illumination-induced band edge unpinning was found to be a major challenge for the further development of LaFeO₃ photocathodes for water-splitting applications. Full article

The development of visible-light-responsive semiconductor-based photoelectrodes is a prerequisite for the construction of efficient photoelectrochemical (PEC) cells for solar water splitting. Surface modification with an electrocatalyst on the photoelectrode is effective for maximizing the water splitting efficiency of the PEC cell. Herein, we investigate the effects of surface modification of Ta₃N₅ photoanodes with electrocatalysts consisting of Ni, Fe, and Co oxides, and their mixture, on the PEC oxygen evolution reaction (OER) performance. Among the investigated samples, NiFeO_x-modified Ta₃N₅ (NiFeO_x/Ta₃N₅) photoanodes showed the lowest onset potential for OER. A PEC cell with a parallel configuration consisting of a NiFeO_x/Ta₃N₅ photoanode and an Al-doped La₅Ti₂Cu_0.9Ag_0.1S₅O₇ (LTCA:Al) photocathode exhibited stoichiometric hydrogen and oxygen generation from water splitting, without any external bias voltage. The solar-to-hydrogen energy conversion efficiency (STH) of this cell for water splitting was found to be 0.2% at 1 min after the start of the reaction. In addition, water splitting by a PEC cell with a tandem configuration incorporating a NiFeO_x/Ta₃N₅ transparent photoanode prepared on a quartz insulating substrate as a front-side electrode and a LTCA:Al photocathode as a back side electrode was demonstrated, and the STH was found to be 0.04% at the initial stage of the reaction. Full article

Tandem photoelectrochemical cells (PECs), made up of a solid electrolyte membrane between two low-cost photoelectrodes, were investigated to produce “green” hydrogen by exploiting renewable solar energy. The assembly of the PEC consisted of an anionic solid polymer electrolyte membrane (gas separator) clamped between an n-type Fe₂O₃ photoanode and a p-type CuO photocathode. The semiconductors were deposited on fluorine-doped tin oxide (FTO) transparent substrates and the cell was investigated with the hematite surface directly exposed to a solar simulator. Ionomer dispersions obtained from the dissolution of commercial polymers in the appropriate solvents were employed as an ionic interface with the photoelectrodes. Thus, the overall photoelectrochemical water splitting occurred in two membrane-separated compartments, i.e., the oxygen evolution reaction (OER) at the anode and the hydrogen evolution reaction (HER) at the cathode. A cost-effective NiFeOx co-catalyst was deposited on the hematite photoanode surface and investigated as a surface catalytic enhancer in order to improve the OER kinetics, this reaction being the rate-determining step of the entire process. The co-catalyst was compared with other well-known OER electrocatalysts such as La_0.6Sr_0.4Fe_0.8CoO₃ (LSFCO) perovskite and IrRuOx. The Ni-Fe oxide was the most promising co-catalyst for the oxygen evolution in the anionic environment in terms of an enhanced PEC photocurrent and efficiency. The materials were physico-chemically characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Full article