Taemin Ludvic Kim

Enhanced Photocatalytic Performance Depending on Morphology of Bismuth Vanadate Thin Film Synthesized by Pulsed Laser Deposition

We have fabricated high quality bismuth vanadate (BiVO4) polycrystalline thin films as photoanodes by pulsed laser deposition (PLD) without a postannealing process. The structure of the grown films is the photocatalytically active phase of scheelite-monoclinic BiVO4 which was obtained by X-ray diffraction (XRD) analysis. The change of surface morphology for the BIVO4 thin films depending on growth temperature during synthesis has been observed by scanning electron microscopy (SEM), and its influence on water splitting performance was investigated. The current density of the BiVO4 film grown on a glass substrate covered with fluorine-doped tin oxide (FTO) at 230 °C was as high as 3.0 mA/cm2 at 1.23 V versus the potential of the reversible hydrogen electrode (VRHE) under AM 1.5G illumination, which is the highest value so far in previously reported BiVO4 films grown by physical vapor deposition (PVD) methods. We expect that doping of transition metal or decoration of oxygen evolution catalyst (OEC) in our BiVO4 film might further enhance the performance.

Domain-engineered BiFeO3 thin-film photoanodes for highly enhanced ferroelectric solar water splitting

In photoelectrochemical (PEC) water splitting, charge separation and collection by the electric field in the photoactive material are the most important factors for improved conversion efficiency. Hence, ferroelectric oxides, in which electrons are the majority carriers, are considered promising photoanode materials because their high built-in potential, provided by their spontaneous polarization, can significantly enhance the separation and drift of photogenerated carriers. In this regard, the PEC properties of BiFeO3 thin-film photoanodes with different crystallographic orientations and consequent ferroelectric domain structures are investigated. As the crystallographic orientation changes from (001)pc via (110)pc to (111)pc, the ferroelastic domains in epitaxial BiFeO3 thin films become mono-variant and the spontaneous polarization levels increase to 110 μC/cm2. Consequently, the photocurrent density at 0 V vs. Ag/AgCl increases approximately 5.3-fold and the onset potential decreases by 0.180 V in the downward polarization state. It is further demonstrated that ferroelectric switching in the (111)pc BiFeO3 thin-film photoanode leads to an approximate change of 8,000% in the photocurrent density and a 0.330 V shift in the onset potential. This study strongly suggests that domain-engineered ferroelectric materials can be used as effective charge separation and collection layers for efficient solar water-splitting photoanodes.

Template-engineered epitaxial BiVO4 photoanodes for efficient solar water splitting

Bismuth vanadate (BiVO4) has attracted significant attention as a promising photoanode material for hydrogen production via photoelectrochemical (PEC) water splitting because of its narrow optical band gap and suitable band edge positions for water oxidation. However, the actual photoactivity of BiVO4 is considerably limited by its poor electron transport and slow water oxidation kinetics. Although several studies have been carried out to improve its photo-efficiency via the enhancement of electron transport and water oxidation kinetics, only a few studies have reported the growth of epitaxial BiVO4 to explore the fundamental properties of BiVO4 for PEC water splitting because extremely flat epitaxial films exhibit poor photo-efficiency because of their low surface-active area. However, studies of epitaxial BiVO4 still have the potential to provide new routes for improving its photo-efficiency. In this study, the growth of epitaxial BiVO4 is investigated using a thin γ-WO3 template layer deposited on a SrTiO3(001) substrate covered by a SrRuO3 (SRO) bottom electrode using pulsed laser deposition. Consequently, at 1.23 V vs. the RHE (reversible hydrogen electrode), the photocurrent density of epitaxial BiVO4 on the γ-WO3 template layer (2.20 mA cm−2) is approximately 10 times that of bare BiVO4, related to the effective charge transfer by the γ-WO3 intermediate layers and the subsequent increase in the surface-active area of epitaxial BiVO4. These results strongly suggest that epitaxial BiVO4 grown using a template layer can be a cornerstone for the in-depth understanding of the fundamental properties of BiVO4 for PEC water splitting.

Toward High-Performance Hematite Nanotube Photoanodes: Charge-Transfer Engineering at Heterointerfaces

Vertically ordered hematite nanotubes are considered to be promising photoactive materials for high-performance water-splitting photoanodes. However, the synthesis of hematite nanotubes directly on conducting substrates such as fluorine-doped tin oxide (FTO)/glass is difficult to be achieved because of the poor adhesion between hematite nanotubes and FTO/glass. Here, we report the synthesis of hematite nanotubes directly on FTO/glass substrate and high-performance photoelectrochemical properties of the nanotubes with NiFe cocatalysts. The hematite nanotubes are synthesized by a simple electrochemical anodization method. The adhesion of the hematite nanotubes to the FTO/glass substrate is drastically improved by dipping them in nonpolar cyclohexane prior to postannealing. Bare hematite nanotubes show a photocurrent density of 1.3 mA/cm(2) at 1.23 V vs a reversible hydrogen electrode, while hematite nanotubes with electrodeposited NiFe cocatalysts exhibit 2.1 mA/cm(2) at 1.23 V which is the highest photocurrent density reported for hematite nanotubes-based photoanodes for solar water splitting. Our work provides an efficient platform to obtain high-performance water-splitting photoanodes utilizing earth-abundant hematite and noble-metal-free cocatalysts.

Microscopic Evidence for Strong Interaction between Pd and Graphene Oxide that Results in Metal‐Decoration‐Induced Reduction of Graphene Oxide

Graphene oxide (GO) is reduced spontaneously when palladium nanoparticles are decorated on the surface. The oxygen functional groups at the GO surface near the nanoparticles are absorbed to the palladium to produce a palladium oxide interlayer. Palladium therefore grows on the GO with preferred orientations, resulting in unique microstructural and electrical properties.