Jum Suk Jang

Heterojunction BiVO4/WO3 electrodes for enhanced photoactivity of water oxidation

Heterojunction electrodes were fabricated by layer-by-layer deposition of WO3 and BiVO4 on a conducting glass, and investigated for photoelectrochemical water oxidation under simulated solar light. The electrode with the optimal composition of four layers of WO3 covered by a single layer of BiVO4 showed enhanced photoactivity by 74% relative to bare WO3 and 730% relative to bare BiVO4. According to the flat band potential and optical band gap measurements, both semiconductors can absorb visible light and have band edge positions that allow the transfer of photoelectrons from BiVO4 to WO3. The electrochemical impedance spectroscopy revealed poor charge transfer characteristics of BiVO4, which accounts for the low photoactivity of bare BiVO4. The measurements of the incident photon-to-current conversion efficiency spectra showed that the heterojunction electrode utilized effectively light up to 540 nm covering absorption by both WO3 and BiVO4 layers. Thus, in heterojunction electrodes, the photogenerated electrons in BiVO4 are transferred to WO3 layers with good charge transport characteristics and contribute to the high photoactivity. They combine merits of the two semiconductors, i.e. excellent charge transport characteristics of WO3 and good light absorption capability of BiVO4 for enhanced photoactivity.

Microwave synthesis of single-crystalline perovskite BiFeO3 nanocubes for photoelectrode and photocatalytic applications

A simple microwave synthesis procedure has been developed for the single-crystalline perovskite nanocubes composed of bismuth ferrite (BiFeO3). Typical nanocubes had sizes ranging from 50to200nm. The single-crystalline nature of nanocubes was confirmed by high resolution transmission electron microscopy and selected area electron diffraction pattern. X-ray diffraction pattern showed the rhombohedral phase with R3c space group. The material showed photoinduced water oxidation activity in both photoelectrochemical and photocatalytic modes. It could become a useful material for photoelectrode and photocatalytic applications.

Photocatalytic and Photoelectrochemical Water Oxidation over Metal‐Doped Monoclinic BiVO4 Photoanodes

The visible-light-induced water oxidation ability of metal-ion-doped BiVO(4) was investigated and of 12 metal ion dopants tested, only W and Mo dramatically enhanced the water photo-oxidation activity of bare BiVO(4); Mo had the highest improvement by a factor of about six. Thus, BiVO(4) and W- or Mo-doped (2 atom %) BiVO(4) photoanodes about 1 μm thick were fabricated onto transparent conducting substrate by a metal-organic decomposition/spin-coating method. Under simulated one sun (air mass 1.5G, 100 mW cm(-2)) and at 1.23 V versus a reversible hydrogen electrode, the highest photocurrent density (J(PH)) of about 2.38 mA cm(-2) was achieved for Mo doping followed by W doping (J(PH) ≈ 1.98 mA cm(-2)), whereas undoped BiVO(4) gave a J(PH) value of about 0.42 mA cm(-2). The photoelectrochemical water oxidation activity of W- and Mo-doped BiVO(4) photoanodes corresponded to the incident photon to current conversion efficiency of about 35 and 40 % respectively. Electrochemical impedance spectroscopy and Mott-Schottky analysis indicated a positive flat band shift of about 30 mV, a carrier concentration 1.6-2 times higher, and a charge-transfer resistance reduced by 3-4-fold for W- or Mo-doped BiVO(4) relative to undoped BiVO(4). Electronic structure calculations revealed that both W and Mo were shallow donors and Mo doping generated superior conductivity to W doping. The photo-oxidation activity of water on BiVO(4) photoanodes (undoped<W doped<Mo doped) was in accordance with the results from electrochemical impedance spectroscopy, Mott-Schottky analysis, and theoretical electronic structural calculations. Thus, Mo or W doping enhanced the photocatalytic and photoelectrochemical water oxidation activity of monoclinic BiVO(4) by drastically reducing its charge-transfer resistance and thereby minimizing photoexcited electron-hole pair recombination.

Photocatalytic hydrogen production from water-methanol mixtures using N-doped Sr2Nb2O7 under visible light irradiation: effects of catalyst structure.

Nitrogen-doped perovskite type materials, Sr2Nb2O7-xNx (0, 1.5 < x < 2.8), have been studied as visible light-active photocatalysts for hydrogen production from methanol-water mixtures. Nitrogen doping in Sr2Nb2O7 red-shifted the light absorption edge into the visible light range and induced visible light photocatalytic activity. There existed an optimum amount of nitrogen doping that showed the maximum rate of hydrogen production. Among the potential variables that might cause this activity variation, the crystal structure appeared to be the most important. Thus, as the extent of N-doping increased, the original orthorhombic structure of the layered perovskite was transformed into an unlayered cubic oxynitride structure. The most active catalytic phase was an intermediate phase still maintaining the original layered perovskite structure, but with a part of its oxygen replaced by nitrogen and oxygen vacancy to adjust the charge difference between oxygen and doped nitrogen. These experimental observations were explained by density functional theory calculations. Thus, in Sr2Nb2O7-xNx, N2p orbital was the main contributor to the top of the valence band, causing band gap narrowing while the bottom of conduction band due to Nb 4d orbital remained almost unchanged.

Band gap tuning of lead-substituted BaSnO3 for visible light photocatalysis

The Pb substitution effect was investigated experimentally and theoretically on the crystal structure of BaSnO3 and on the photo-oxidation activity of H2O. The chemically doped Pb in BaSnO3 induced a concentration-dependent redshift of the experimental band gap (BG). The BaPb0.8Sn0.2O3 system produced 32μmol∕h of O2 under λ⩾420nm photons, but no O2 for BaSnO3. The DFT calculations of BaPbxSn1−xO3 (x=0,0.5,1) by using generalized approximation, implying the BG alteration and the photocatalytic activity of BaPbxSn1−xO3, are due to the induced Pb 6s orbital in the BG of BaSnO3. Thus Pb modified the insulating nature of BaSnO3 to semiconducting and semimetallic.

Engineered Nanorod Perovskite Film Photocatalysts to Harvest Visible Light

The recent fl ourishing of nanostructured materials has widened its potential applications in the much-desired effi cient energy materials. Specifi cally, materials for solar hydrogen production by water splitting should possess superior optoelectric properties in addition to suitable band energetics and durability in aqueous solutions. The tunability of the physicochemical properties of nanostructred materials by virtue of their size and shape renders a wider applicability. Since the critical limitation of popular TiO 2 photocatalyst that absorbs only UV light, [ 1 , 2 ] the fi eld of visible light water splitting photocatalyst is currently being nurtured by various kinds of conventional and new single component materials (CdS, WO 3 , Fe 2 O 3 , TaON, etc.), as well as composite materials. [ 3–20 ] However, there is still much potential for nanostructured materials in this area. There have been several reports on the binary [ 3–6 ] and ternary metal oxides, [ 7–13 ]

Geometric Effect of Single or Double Metal-Tipped CdSe Nanorods on Photocatalytic H2 Generation

In the present work, we focused on geometrical (single- or double-tipped) and compositional (Pt or Au) variations of active metal components in a well-defined CdSe nanorod system. These colloidal nanostructures were employed for photocatalytic hydrogen generation from water under the identical reaction conditions with visible light irradiation. The catalysts exhibited significant dependency of the catalytic activity, specifically on the catalyst geometry and the choice of the metal tips, determined by the energetic consideration of electron transfer to the metal tips and hole transfer to the sacrificial reagents on the CdSe nanorods.

Bifunctional TiO2 underlayer for α-Fe2O3 nanorod based photoelectrochemical cells: enhanced interface and Ti4+ doping

A thin, compact TiO2 underlayer for hematite-based photoelectrochemical cells was prepared by simple spin coating and showed a dramatic increase in device performance and photocurrent density. The introduction of TiO2 underlayers induced a noticeable change in the nanostructure. In contrast to the conventional strategies based on underlayers, the compact TiO2 underlayers can act as both a charge recombination barrier and also as a source for titanium dopants. One could simply take advantage of fortuitous doping of Sn from FTO into hematite lattice during the activation step, and is converted into intentional doping of Ti4+ from the TiO2 underlayer into the hematite lattice. Ti4+ doping in hematite lattice is highly probable during the sintering of FTO/TiO2/α-Fe2O3 photoanodes at 800 °C, which has been confirmed by XPS measurements. Based on electrochemical studies, it is evident that the TiO2 underlayer effectively suppresses charge recombination at the FTO/α-Fe2O3 interface and provides possible Ti4+ doping apart from Sn diffusion from FTO substrates when sintered at high temperature (800 °C). In contrast, only charge recombination was suppressed at lower sintering temperature (550 °C). This is the first report on the elemental doping of Ti4+ from the TiO2 underlayer when sintered at high temperature.

Fabrication of graphene-based electrode in less than a minute through hybrid microwave annealing.

Highly efficient and stable MoS2 nanocrystals on graphene sheets (MoS2/GR) are synthesized via a hybrid microwave annealing process. Through only 45 second-irradiation using a household microwave oven equipped with a graphite susceptor, crystallization of MoS2 and thermal reduction of graphene oxide into graphene are achieved, indicating that our synthetic method is ultrafast and energy-economic. Graphene plays a crucial role as an excellent microwave absorber as well as an ideal support material that mediates the growth of MoS2 nanocrystals. The formed MoS2/GR electrocatalyst exhibits high activity of hydrogen evolution reaction with small onset overpotential of 0.1 V and Tafel slope of 50 mV per decade together with an excellent stability in acid media. Thus our hybrid microwave annealing could be an efficient generic method to fabricate various graphene-based hybrid electric materials for broad applications.

Indium induced band gap tailoring in AgGa1−xInxS2 chalcopyrite structure for visible light photocatalysis

Indium was substituted at gallium site in chalcopyrite AgGaS(2) structure by using a simple solid solution method. The spectroscopic analysis using extended x-ray absorption fine structure and x-ray photoelectron spectroscopy confirmed the indium substitution in AgGaS(2) lattice. The band gap energy of AgGa(1-x)In(x)S(2) (x=0-1) estimated from the onset of absorption edge was found to be reduced from 2.67 eV (x=0) to 1.9 eV (x=1) by indium substitution. The theoretical and experimental studies showed that the indium s orbitals in AgGa(1-x)In(x)S(2) tailored the band gap energy, thereby modified the photocatalytic activity of the AgGa(1-x)In(x)S(2).