Hyejin Jung

Effect of the Si/TiO2/BiVO4 Heterojunction on the Onset Potential of Photocurrents for Solar Water Oxidation

BiVO4 has been formed into heterojunctions with other metal oxide semiconductors to increase the efficiency for solar water oxidation. Here, we suggest that heterojunction photoanodes of Si and BiVO4 can also increase the efficiency of charge separation and reduce the onset potential of the photocurrent by utilizing the high conduction band edge potential of Si in a dual-absorber system. We found that a thin TiO2 interlayer is required in this structure to realize the suggested photocurrent density enhancement and shifts in onset potential. Si/TiO2/BiVO4 photoanodes showed 1.0 mA/cm(2) at 1.23 V versus the reversible hydrogen electrode (RHE) with 0.11 V (vs RHE) of onset potential, which were a 3.3-fold photocurrent density enhancement and a negative shift in onset potential of 300 mV compared to the performance of FTO/BiVO4 photoanodes.

Insight into Charge Separation in WO3/BiVO4 Heterojunction for Solar Water Splitting

Recently, the WO3/BiVO4 heterojunction has shown promising photoelectrochemical (PEC) water splitting activity based on its charge transfer and light absorption capability, and notable enhancement of the photocurrent has been achieved via morphological modification of WO3. We developed a graft copolymer-assisted protocol for the synthesis of WO3 mesoporous thin films on a transparent conducting electrode, wherein the particle size, particle shape, and thickness of the WO3 layer were controlled by tuning the interactions in the polymer/sol-gel hybrid. The PEC performance of the WO3 mesoporous photoanodes with various morphologies and the individual heterojunctions with BiVO4 (WO3/BiVO4) were characterized by measuring the photocurrents in the absence/presence of hole scavengers using light absorption spectroscopy and intensity-modulated photocurrent spectroscopy. The morphology of the WO3 photoanode directly influenced the charge separation efficiency within the WO3 layer and concomitant charge collection efficiency in the WO3/BiVO4 heterojunction, showing the smaller sized nanosphere WO3 layer showed higher values than did the plate-like or rod-like one. Notably, we observed that photocurrent density of WO3/BiVO4 was not dependent on the thickness of WO3 film or its charge collection time, implying slow charge flow from BiVO4 to WO3 can be a crucial issue in determining the photocurrent, rather than the charge separation within the nanosphere WO3 layer.

Synthesis of Bi2WO6 photoanode on transparent conducting oxide substrate with low onset potential for solar water splitting

To enable water splitting in photoelectrochemical cells, the conduction-band (CB) and valence-band edges must straddle the hydrogen-reduction and water-oxidation potentials; however, the CB edge potential of many photoanodic semiconductors is insufficient. Here, we demonstrate the nanostructured Bi2WO6 for photoanodic application, which has a high, flat-band potential of 0.15 V vs. RHE. Single-phase, orthorhombic Bi2WO6 nano-structures were successfully grown on an FTO substrate through a two-step hydrothermal synthesis with subsequent thermal treatment at 600 °C. The synthesized Bi2WO6 photoanode shows a lower onset potential and improved photocurrents which were enhanced further by a factor of three by coating the surface with Co-Pi. The low onset potential of the Bi2WO6/Co-Pi photoanode results in a higher operating photocurrent in a p/n photodiode cell combined with a p-Si/n-Si/Pt photocathode.

Mixed Copper States in Anodized Cu Electrocatalyst for Stable and Selective Ethylene Production from CO2 Reduction

Oxygen-Cu (O-Cu) combination catalysts have recently achieved highly improved selectivity for ethylene production from the electrochemical CO2 reduction reaction (CO2RR). In this study, we developed anodized copper (AN-Cu) Cu(OH)2 catalysts by a simple electrochemical synthesis method and achieved ∼40% Faradaic efficiency for ethylene production, and high stability over 40 h. Notably, the initial reduction conditions applied to AN-Cu were critical to achieving selective and stable ethylene production activity from the CO2RR, as the initial reduction condition affects the structures and chemical states, crucial for highly selective and stable ethylene production over methane. A highly negative reduction potential produced a catalyst maintaining long-term stability for the selective production of ethylene over methane, and a small amount of Cu(OH)2 was still observed on the catalyst surface. Meanwhile, when a mild reduction condition was applied to the AN-Cu, the Cu(OH)2 crystal structure and mixed states disappeared on the catalyst, becoming more favorable to methane production after few hours. These results show the selectivity of ethylene to methane in O-Cu combination catalysts is influenced by the electrochemical reduction environment related to the mixed valences. This will provide new strategies to improve durability of O-Cu combination catalysts for C-C coupling products from electrochemical CO2 conversion.