Ji-Wook Jang

Single-crystalline, wormlike hematite photoanodes for efficient solar water splitting

A hematite photoanode showing a stable, record-breaking performance of 4.32 mA/cm2 photoelectrochemical water oxidation current at 1.23 V vs. RHE under simulated 1-sun (100 mW/cm2) irradiation is reported. This photocurrent corresponds to ca. 34% of the maximum theoretical limit expected for hematite with a band gap of 2.1 V. The photoanode produced stoichiometric hydrogen and oxygen gases in amounts close to the expected values from the photocurrent. The hematitle has a unique single-crystalline “wormlike” morphology produced by in-situ two-step annealing at 550°C and 800°C of β-FeOOH nanorods grown directly on a transparent conducting oxide glass via an all-solution method. In addition, it is modified by platinum doping to improve the charge transfer characteristics of hematite and an oxygen-evolving co-catalyst on the surface.

Phosphate doping into monoclinic BiVO4 for enhanced photoelectrochemical water oxidation activity.

Phos-phorus is a typical dopant for silicon or germanium to make itan n-type semiconductor. However, it has been rarely used asdopant for semiconductor photocatalysts. This is rathersurprising because other non-metallic elements, such as N,C, and S, have been widely used as anionic dopants forphotocatalysts to reduce their band-gap energies.

Fabrication of CaFe2O4/TaON Heterojunction Photoanode for Photoelectrochemical Water Oxidation

Tantalum oxynitride photoanode is fabricated and modified with calcium ferrite to form a heterojunction anode for a photoelectrochemical water splitting cell. The synthesized powders are loaded sequentially to the transparent conducting glass by electrophoretic deposition, which is advantageous to form a uniform layer and a junction structure. X-ray diffraction, UV-vis diffuse reflectance spectroscopy, scanning electron microscopy, and impedance spectroscopy analysis are conducted to investigate the structural, morphological, and electrochemical characteristics of the anode. The introduction of CaFe2O4 overlayer onto TaON electrode increases the photocurrent density about five times at 1.23 V vs reversible hydrogen electrode without any co-catalyst. Impedance spectroscopy analysis indicates that the junction formation increased photocurrent density by reducing the resistance to the transport of charge carriers and thereby enhancing the electron-hole separation. This photocurrent generation is a result of the overall water splitting as confirmed by evolution of hydrogen and oxygen in a stoichiometric ratio. From the study of different junction configurations, it is established that the intimate contact between TaON and CaFe2O4 is critical for enhanced performance of the heterojunction anode for photoelectrochemical water oxidation under simulated sun light.

Enabling unassisted solar water splitting by iron oxide and silicon

Photoelectrochemical (PEC) water splitting promises a solution to the problem of large-scale solar energy storage. However, its development has been impeded by the poor performance of photoanodes, particularly in their capability for photovoltage generation. Many examples employing photovoltaic modules to correct the deficiency for unassisted solar water splitting have been reported to-date. Here we show that, by using the prototypical photoanode material of haematite as a study tool, structural disorders on or near the surfaces are important causes of the low photovoltages. We develop a facile re-growth strategy to reduce surface disorders and as a consequence, a turn-on voltage of 0.45 V (versus reversible hydrogen electrode) is achieved. This result permits us to construct a photoelectrochemical device with a haematite photoanode and Si photocathode to split water at an overall efficiency of 0.91%, with NiFeOx and TiO2/Pt overlayers, respectively.

Three-dimensional type II ZnO/ZnSe heterostructures and their visible light photocatalytic activities.

We report a method for synthesizing three distinct type II 3D ZnO/ZnSe heterostructures through simple solution-based surface modification reactions in which polycrystalline ZnSe nanoparticles formed on the surfaces of single-crystalline ZnO building blocks of 3D superstructures. The experimental results suggested a possible formation mechanism for these heterostructures. The formation of the ZnO/ZnSe heterostructures was assumed to result from a dissolution-recrystallization mechanism. The optical properties of the 3D ZnO/ZnSe heterostructures were probed by UV-vis diffuse reflectance spectroscopy. The 3D ZnO/ZnSe heterostructures exhibited absorption in the visible spectral region. The visible photocatalytic activities of 3D ZnO/ZnSe heterostructures were much higher than those of the 3D pure ZnO structures. The activities of the 3D ZnO/ZnSe heterostructures varied according to the structures under visible light. The morphologies and exposed crystal faces of pure ZnO building blocks prior to surface modification had a significant effect on the visible light photocatalytic processes of ZnO/ZnSe heterostructures after surface modification.

Precursor Effects of Citric Acid and Citrates on ZnO Crystal Formation

We have studied the precursor effects of citric acid and various citrates-including triethyl citrate, tripotassium citrate, trisodium citrate and triammonium citrate-on the formation of ZnO crystals in alkaline solution. These citrate-related chemicals could be divided into three groups (group A, triethyl citrate; group B, tripotassium citrate and trisodium citrate; and group C, citric acid and triammonium citrate) based on their activity for modifying the ZnO growth direction and solution pH dependency on their concentration. We could obtain ZnO structures with various distinct morphologies by simply changing the concentration of citric acid or citrate additive dissolved in the alkaline reaction solution. On the basis of the results, we propose the growth mechanisms underlying the formation of the various ZnO structures in the absence and presence of citric acid or citrate additives.

Carbon-doped ZnO nanostructures synthesized using vitamin C for visible light photocatalysis

We report the synthesis of carbon-doped zinc oxide nanostructures using vitamin C, and their visible light photocatalytic activity. Amorphous/crystalline vitamin C–ZnO (VitC–ZnO) structures were obtained from a solution of zinc nitrate hexahydrate, HMT, and vitamin C through heating at 95 °C for 1 h. VitC–ZnO structures were calcined in air at 500 °C for 2 h to create C-doped ZnO nanostructures. Calcined structures were polycrystalline, with an average crystal domain size of 7 nm. EDS, XPS, and XRD analysis revealed the substitution of oxygen with carbon and the formation of Zn–C bonds in the C-doped ZnO nanostructures. The carbon concentrations, in the form of carbide, were controlled by varying the concentrations of vitamin C (more than 1 mM) added to reaction solutions. On the basis of these experimental results, we propose a possible formation mechanism for C-doped ZnO nanostructures. The C-doped ZnO nanostructures exhibited visible light absorption bands that were red-shifted relative to the UV exciton absorption of pure ZnO nanostructures. The visible light (λ ≥ 420 nm) photocatalytic activities of C-doped ZnO nanostructures were much better than the activities of pure ZnO nanostructures.

Graphene–carbon nanotube composite as an effective conducting scaffold to enhance the photoelectrochemical water oxidation activity of a hematite film

The iron oxide photoanode was modified with a graphene–carbon nanotube (CNT) composite conducting scaffold for efficient charge transfer from Fe2O3 particles to transparent conducting oxide substrate in photoelectrochemical water splitting cells. The Fe2O3–composite photoanode showed a photocurrent increase of 530% compared with to the bare Fe2O3 photoanode at 1.23 V vs. RHE, while the increase was only 200 and 240% for Fe2O3–CNT and Fe2O3–graphene photoanodes, respectively. This remarkable performance enhancement by the composite scaffold was attributed to synergistic effects induced by the formation of a 3D-like architecture from 1D CNT and 2D graphene. They become a spacer for each other forming a more open and highly exposed structure, in which both 2D graphene and 1D CNT can exist in the forms with much less self-agglomeration, thus not only enlarging the contact area between the conducting scaffold and Fe2O3 particles but also recovering in part the intrinsic conducting ability of graphene and CNT.

Porous ZnO–ZnSe nanocomposites for visible light photocatalysis

We report the synthesis of porous ZnO-ZnSe nanocomposites for use in visible light photocatalysis. Porous ZnO nanostructures were synthesized by a microwave-assisted hydrothermal reaction then converted into porous ZnO-ZnSe nanocomposites by a microwave-assisted dissolution-recrystallization process using an aqueous solution containing selenium ions. ZnO and ZnSe nanocrystallites of the nanocomposites were well-mixed (rather than forming simple core-shell (ZnO-ZnSe) structures), particularly, in the outer regions. Both ZnO and ZnSe were present at the surface and exposed to the environment. The porous ZnO-ZnSe nanocomposites showed absorption bands in the visible region as well as in the UV region. The porous ZnO-ZnSe nanocomposites had much higher activities than the porous ZnO nanostructures. Control experiments using cutoff filters revealed that the main photocatalytic activity of the synthesized nanostructures arose from photo-excitation of the semiconductor (ZnO or ZnSe) via absorption of light of an energy equal to or exceeding the band gap energy.

Photoelectrochemical water splitting over ordered honeycomb hematite electrodes stabilized by alumina shielding

Highly ordered, honeycomb-like iron oxide (hematite) films were fabricated by double-step anodic oxidation of iron foil. The honeycomb structure obtained by double step anodization was found to be more effective in producing a large area film with homogeneous pore distribution compared to nanotubes fabricated by the conventional single-step anodic oxidation process. To prevent agglomeration of the hematite film during the annealing process, a thin alumina layer was deposited on the hematite film surface by atomic layer deposition. With this alumina shielding and subsequent removal by alkaline treatment, one-dimensional (1-D) hematite nanostructure was preserved perfectly after annealing at 550 °C. This highly ordered 1-D nanostructure film showed much enhanced photoelectrochemical cell performances relative to hematite films with low degrees of ordering.