Stable water splitting using photoelectrodes with a cryogelated overlayer

Abstract Hydrogen production techniques based on solar-water splitting have emerged as carbon-free energy systems. Many researchers have developed highly efficient thin-film photoelectrochemical (PEC) devices made of low-cost and earth-abundant materials. However, solar water splitting systems suffer from short lifetimes due to catalyst instability that is attributed to both chemical dissolution and mechanical stress produced by hydrogen bubbles. A recent study found that the nanoporous hydrogel could prevent the structural degradation of the PEC devices. In this study, we investigate the protection mechanism of the hydrogel-based overlayer by engineering its porous structure using the cryogelation technique. Tests for cryogel overlayers with varied pore structures, such as disconnected micropores, interconnected micropores, and surface macropores, reveal that the hydrogen gas trapped in the cryogel protector reduce shear stress at the catalyst surface by providing bubble nucleation sites. The cryogelated overlayer effectively preserves the uniformly distributed platinum catalyst particles on the device surface for over 200 h. Our finding can help establish semi-permanent photoelectrochemical devices to realize a carbon-free society

Surface restoration of polycrystalline Sb2Se3 thin films by conjugated molecules enabling high-performance photocathodes for photoelectrochemical water splitting

Achieving both high onset potential and photocurrent in photoelectrodes is a key challenge while performing unassisted overall water splitting using tandem devices. We propose a simple interface modification strategy to maximize the performance of polycrystalline Sb2Se3 photocathodes for photoelectrochemical (PEC) water splitting. The para-aminobenzoic acid (PABA) modification at Sb2Se3/TiO2 interface enhanced both the onset potential and photocurrent of the Sb2Se3 photocathodes. The surface defects in the polycrystalline Sb2Se3 limited the photovoltage production, lowering the onset potential of the photocathode. Surface restoration using the conjugated PABA molecules efficiently passivated the surface defects on the Sb2Se3 and enabled the rapid photoelectron transport from the Sb2Se3 to the TiO2 layer. The PABA treated Sb2Se3 photocathode exhibited substantially improved PEC performance; the onset potential increased from 0.35 to 0.50 V compared to the reversible hydrogen electrode (VRHE), and the photocurrent density increased from 24 to 35 mA cm−2 at 0 VRHE

Interfacial Dipole Layer Enables High-Performance Heterojunctions for Photoelectrochemical Water Splitting

TiO2 has been widely used as an n-type overlayer, simultaneously serving as a protective layer for photocathodes. However, the photovoltage generated from a TiO2 junction with p-type absorbers, such as p-Si, Sb2Se3, SnS, and Cu2O, is insufficient. We report a dipole reorientation strategy to overcome this limitation by inserting a polyethylenimine ethoxylated (PEIE) layer between a p-type absorber and TiO2. Furthermore, we demonstrate that the PEIE dipole orientation can be rearranged by increasing the layer thickness, leading to an upward shift of the TiO2 band edge. The magnitude of band shift induced by the dipole effect depends on the TiO2 layer thickness. Using this approach, the onset potential was significantly improved to 0.5 V versus the reversible hydrogen electrode (VRHE) in a p-Si/PEIE/TiO2/Pt device. The versatility of the effective dipole reorientation strategy was demonstrated by application to a range of TiO2-protected heterojunction photocathodes based on Sb2Se3, Cu2O, and SnS

Efficient solar fuel production enabled by an iodide oxidation reaction on atomic layer deposited MoS2

Abstract Oxygen evolution reaction (OER) as a half‐anodic reaction of water splitting hinders the overall reaction efficiency owing to its thermodynamic and kinetic limitations. Iodide oxidation reaction (IOR) with low thermodynamic barrier and rapid reaction kinetics is a promising alternative to the OER. Herein, we present a molybdenum disulfide (MoS2) electrocatalyst for a high‐efficiency and remarkably durable anode enabling IOR. MoS2 nanosheets deposited on a porous carbon paper via atomic layer deposition show an IOR current density of 10 mA cm–2 at an anodic potential of 0.63 V with respect to the reversible hydrogen electrode owing to the porous substrate as well as the intrinsic iodide oxidation capability of MoS2 as confirmed by theoretical calculations. The lower positive potential applied to the MoS2‐based heterostructure during IOR electrocatalysis prevents deterioration of the active sites on MoS2, resulting in exceptional durability of 200 h. Subsequently, we fabricate a two‐electrode system comprising a MoS2 anode for IOR combined with a commercial Pt@C catalyst cathode for hydrogen evolution reaction. Moreover, the photovoltaic–electrochemical hydrogen production device comprising this electrolyzer and a single perovskite photovoltaic cell shows a record‐high current density of 21 mA cm–2 at 1 sun under unbiased conditions