Sangbaek Park

Hydrated Manganese(II) Phosphate (Mn3(PO4)2·3H2O) as a Water Oxidation Catalyst

The development of a water oxidation catalyst has been a demanding challenge in realizing water splitting systems. The asymmetric geometry and flexible ligation of the biological Mn4CaO5 cluster are important properties for the function of photosystem II, and these properties can be applied to the design of new inorganic water oxidation catalysts. We identified a new crystal structure, Mn3(PO4)2·3H2O, that precipitates spontaneously in aqueous solution at room temperature and demonstrated its high catalytic performance under neutral conditions. The bulky phosphate polyhedron induces a less-ordered Mn geometry in Mn3(PO4)2·3H2O. Computational analysis indicated that the structural flexibility in Mn3(PO4)2·3H2O could stabilize the Jahn-Teller-distorted Mn(III) and thus facilitate Mn(II) oxidation. This study provides valuable insights into the interplay between atomic structure and catalytic activity.

General Strategy for Fabricating Transparent TiO2 Nanotube Arrays for Dye-Sensitized Photoelectrodes: Illumination Geometry and Transport Properties

We report on the preparation of transparent oriented titania nanotube (NT) photoelectrodes and the effect of illumination direction on light harvesting, electron transport, and recombination in dye-sensitized solar cells (DSSCs) incorporating these electrodes. High solar conversion efficiency requires that the incident light enters the cell from the photoelectrode side. However, it has been synthetically challenging to prepare transparent TiO(2) NT electrodes by directly anodizing Ti metal films on transparent conducting oxide (TCO) substrates because of the difficulties of controlling the synthetic conditions. We describe a general synthetic strategy for fabricating transparent TiO(2) NT films on TCO substrates. With the aid of a conducting Nb-doped TiO(2) (NTO) layer between the Ti film and TCO substrate, the Ti film was anodized completely without degrading the TCO. The NTO layer was found to protect the TCO from degradation through a self-terminating mechanism by arresting the electric field-assisted dissolution process at the NT-NTO interface. The illumination direction and wavelength of the light incident on the DSSCs were shown to strongly influence the incident photon-to-current conversion efficiency, light-harvesting, and charge-collection properties, which, in turn, affect the photocurrent density, photovoltage, and solar energy conversion efficiency. Effects of NT film thickness on the properties and performance of DSSCs were also examined. Illuminating the cell from the photoelectrode substantially increased the conversion efficiency compared with illuminating it from the counter-electrode side.

Heteroepitaxial growth of ZnO nanosheet bands on ZnCo2O4 submicron rods toward high-performance Li ion battery electrodes

AbstractWe report the direct synthesis of ZnCo2O4 and ZnO/ZnCo2O4 submicron rod arrays grown on Ni foil current collectors via an ammonia-evaporation-induced method by controlling the ratio of Zn to Co. These three-dimensional (3D) hierarchical self-supported nanostructures are composed of one-dimensional (1D) ZnCo2O4 rods and two-dimensional (2D) ZnO nanosheet bands perpendicular to the axis of the each ZnCo2O4 rod. We carefully deal with the heteroepitaxial growth mechanisms of hexagonal ZnO nanosheets from a crystallographic point of view. Furthermore, we demonstrate the ability of these high-surface-area ZnO/ZnCo2O4 heterostructured rods to enable improved electrolyte permeability and Li ion transfer, thereby enhancing their Li storage capability (∼900 mA·h·g−1 at a rate of 45 mA·h·g−1) for Li ion battery electrodes.

An iron oxide photoanode with hierarchical nanostructure for efficient water oxidation

Hematite (α-Fe2O3) has been attracting attention for photoelectrochemical water oxidation due to its visible light photon absorption capacity and high chemical stability, but the short-diffusion length of holes and the large overpotential are still challenging to overcome. Here, in an effort to address these challenges, we develop a hierarchically nanostructured photoanode composed of iron-oxides; Ti-doped hematite nanorods are decorated with an undoped hematite underlayer and β-FeOOH nano-branches. The Ti-doped hematite nanorod array is prepared by hydrothermal synthesis, and this nanostructure offers enhanced separation of photogenerated charges. The underlayer not only increases the photocurrent density but also improves the onset potential. The photocurrent further increases by the epitaxially grown β-FeOOH nano-branches on the hematite, but the onset potential is positively shifted by the β-FeOOH due to increasing flat-band potential. The analyses of the photocurrent transients and electrochemical impedance spectra reveal that β-FeOOH improves the photocurrent by decreasing the resistance to charge transfer through the anode/electrolyte. This study demonstrates a new possibility for improving the efficiency of a hematite photoanode with the interface of other iron-oxides.

A ferroelectric photocatalyst for enhancing hydrogen evolution: polarized particulate suspension

A particle-based photocatalyst with a permanent internal field prepared by a corona poling method is presented as a novel approach to enhance the hydrogen evolution reaction in a particulate-suspension system. Photocatalytic activity of K0.5Na0.5NbO3 was significantly improved by 7.4 times after the polarization.

Tailoring uniform γ-MnO2 nanosheets on highly conductive three-dimensional current collectors for high-performance supercapacitor electrodes

Recent efforts have focused on the fabrication and application of three-dimensional (3-D) nanoarchitecture electrodes, which can exhibit excellent electrochemical performance. Herein, a novel strategy towards the design and synthesis of size- and thickness-tunable two-dimensional (2-D) MnO2 nanosheets on highly conductive one-dimensional (1-D) backbone arrays has been developed via a facile, one-step enhanced chemical bath deposition (ECBD) method at a low temperature (∼50 °C). Inclusion of an oxidizing agent, BrO3−, in the solution was crucial in controlling the heterogeneous nucleation and growth of the nanosheets, and in inducing the formation of the tailored and uniformly arranged nanosheet arrays. We fabricated supercapacitor devices based on 3-D MnO2 nanosheets with conductive Sb-doped SnO2 nanobelts as the backbone. They achieved a specific capacitance of 162 F·g−1 at an extremely high current density of 20 A·g−1, and good cycling stability that shows a capacitance retention of ≈92% of its initial value, along with a coulombic efficiency of almost 100% after 5,000 cycles in an aqueous solution of 1 M Na2SO4. The results were attributed to the unique hierarchical structures, which provided a short diffusion path of electrolyte ions by means of the 2-D sheets and direct electrical connections to the current collector by 1-D arrays as well as the prevention of aggregation by virtue of the well-aligned 3-D structure.

Enhanced Photocatalytic Activity of Ultrathin Ba5Nb4O15 Two-Dimensional Nanosheets.

Anisotropic two-dimensional (2D) nanosheets of the layered perovskite, Ba5Nb4O15, with thicknesses of 5-10 nm and lateral sizes of 300-1200 nm, were synthesized by a hydrothermal route. The influences of the 2D morphology of the material on the crystal and electronic structures, light absorption properties, and photocatalytic activity were investigated. The ultrathin nanosheets showed much-enhanced photocatalytic activity compared to both thick nanosheets (∼30 nm) and micrometer-sized particles for the evolution of H2 from water splitting under UV light illumination. This enhanced activity is predominantly attributed to the larger surface area, higher optical absorption, and charge separation ability of the 2D nanosheet, which results from the variation of the local crystal structure arising from the ultrathin morphology of the Ba5Nb4O15.

Enhanced performance of NaTaO3 using molecular co-catalyst [Mo3S4]4+ for water splitting into H2 and O2

Photocatalytic activity of NaTaO(3) was significantly improved by using a molecular co-catalyst [Mo(3)S(4)](4+). Its hydrogen production rate is 28 times higher than pure NaTaO(3). This study presents the potential of bioinspired molecular metal clusters as efficient co-catalysts.

Surface-area-tuned, quantum-dot-sensitized heterostructured nanoarchitectures for highly efficient photoelectrodes

Harvesting solar energy to produce clean hydrogen from photoelectrolysis of water presents a valuable opportunity to find alternatives for fossil fuels. Three-dimensional nanoarchitecturing techniques can afford enhanced photoelectrochemical properties by improving geometrical and structural effects. Here, we report quantum-dot sensitized TiO2-Sb:SnO2 heterostructures as a model electrode to enable the optimization of the structural effects through the creation of a highly conductive pathway using a transparent conducting oxide (TCO), coupled with a high surface area, by introducing branching and low interfacial resistance via an epitaxial relationship. An examination of various morphologies (dot, rod, and lamella shape) of TiO2 reveals that the rod-shaped TiO2-Sb:SnO2 is a more effective structure than the others. A photoelectrode fabricated using optimized CdS-TiO2-Sb:SnO2 produces a photocurrent density of 7.75 mA/cm2 at 0.4 V versus a reversible hydrogen electrode. These results demonstrate that constructing a branched heterostructure based on TCO can realize highperformance photoelectrochemical devices.

Hierarchical assembly of TiO2-SrTiO3 heterostructures on conductive SnO2 backbone nanobelts for enhanced photoelectrochemical and photocatalytic performance.

Heterostructures can play a role in enhanced photoinduced electrochemical and catalytic reactions due to the advantageous combination of two compounds. Herein, we demonstrate the fabrication of Sb:SnO2@TiO2-SrTiO3 3D heterostructures via a simple hydrothermal method using a conductive Sb:SnO2@TiO2 nanobelt electrode as a template. XRD, FESEM, and TEM analyses confirm that a well-dispersed and crystalized SrTiO3 layer is formed on the surface of TiO2 nanorods. The photoelectrochemical (PEC) performance of the heterostructure is optimized by controlling the reaction time. Details about the effect of the hydrothermal reaction time on the PEC performance are discussed. The optimized Sb:SnO2@TiO2-SrTiO3 heterostructure exhibited a higher onset potential and a saturated photocurrent in comparison to the Sb:SnO2@TiO2 nanostructure. The result is attributed to a Fermi level shift and a blocking layer effect caused by the SrTiO3. Furthermore, the photocatalytic degradation of methylene blue was significantly enhanced on the optimized Sb:SnO2@TiO2-SrTiO3. This work demonstrates that a synergetic effect between three-dimensional nanoarchitecturing and a heterojunction structure is responsible for enhanced PEC as well as improved photocatalytic performance levels, both of which can be extended to other metal-oxide and/or ternary compounds.