• Korean Journal of Materials Research
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• v.30 no.9
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• pp.441-446
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• 2020

Synthesizing nanostructured thin films of oxide semiconductors is a promising approach to fabricate highly efficient photoelectrodes for hydrogen production via photoelectrochemical (PEC) water splitting. In this work, we investigate the feasibility as an efficient photoanode for PEC water oxidation of zinc oxide (ZnO) nanostructured thin films synthesized via a simple method combined with sputtering Zn metallic films on a fluorine-doped tin oxide (FTO) coated glass substrate and subsequent thermal oxidation of the sputtered Zn metallic films in dry air. Characterization of the structural, optical, and PEC properties of the ZnO nanostructured thin film synthesized at varying Zn sputtering powers reveals that we can obtain an optimum ZnO nanostructured thin film as PEC photoanode at a sputtering power of 40 W. The photocurrent density and optimal photocurrent conversion efficiency for the optimum ZnO nanostructured thin film photoanode are found to be 0.1 mA/㎠ and 0.51 %, respectively, at a potential of 0.72 V vs. RHE. Our results illustrate that the ZnO nanostructured thin film has promising potential as an efficient photoanode for PEC water splitting.

• Korean Journal of Materials Research
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• v.32 no.1
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• pp.30-35
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• 2022

The development of advanced materials to improve the efficiency of photoelectrochemical (PEC) water splitting paves the way for widespread renewable energy technologies. Efficient photoanodes with strong absorbance in visible light increases the effectiveness of solar energy conversion systems. MoS₂ in a two-dimensional semiconductor that has excellent absorption performance in visible light and high catalytic activity, showing considerable potential as an agent of PEC water splitting. In this study, we successfully modulated the MoS₂ morphology on indium tin oxide substrate by using the metalorganic chemical vapor deposition method, and applied the PEC application. The PEC photocurrent of the vertically grown MoS₂ nanosheet structure significantly increased relative to that of MoS₂ nanoparticles because of the efficient transfer of charge carriers and high-density active sites. The enhanced photocurrent was attributed to the efficient charge separation and improved light absorption of the MoS₂ nanosheet structure. Meanwhile, the photocurrent property of thick nanosheets decreased because of the limit imposed by the diffusion lengths of carriers. This study proposes a valuable photoelectrode design with suitable nanosheet morphology for efficient PEC water splitting.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.87-87
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• 2010

Photoelectrochemical (PEC) systems are promising methods of producing H2 gas using solar energy in an aqueous solution. The photoelectrochemical properties of numerous metal oxides have been studied. Among them, the PEC systems based on TiO2 have been extensively studied. However, the drawback of a PEC system with TiO2 is that only ultraviolet (UV) light can be absorbed because of its large band gap (3.2 - 3.4 eV). Two approaches have been introduced in order to use PEC cells in the visible light region. The first method includes doping impurities, such as nitrogen, into TiO2, and this technique has been extensively studied in an attempt to narrow the band gap. In comparison, research on the second method, which includes visible light water splitting in molecular photosystems, has been slow. Mallouk et al. recently developed electrochemical water-splitting cells using the Ru(II) complex as the visible light photosensitizer. the dye-sensitized PEC cell consisted of a dye-sensitized TiO2 layer, a Pt counter electrode, and an aqueous solution between them. Under a visible light (< 3 eV) illumination, only the dye molecule absorbed the light and became excited because TiO2 had the wide band gap. The light absorption of the dye was followed by the transfer of an electron from the excited state (S*) of the dye to the conduction band (CB) of TiO2 and its subsequent transfer to the transparent conducting oxide (TCO). The electrons moved through the wire to the Pt, where the water reduction (or H2 evolution) occurred. The oxidized dye molecules caused the water oxidation because their HOMO level was below the H2O/O2 level. Organic dyes have been developed as metal-free alternatives to the Ru(II) complexes because of their tunable optical and electronic properties and low-cost manufacturing. Recently, organic dye molecules containing multi-branched, multi-anchoring groups have received a great deal of interest. In this work, tri-branched tri-anchoring organic dyes (Dye 2) were designed and applied to visible light water-splitting cells based on dye-sensitized TiO2 electrodes. Dye 2 had a molecular structure containing one donor (D) and three acceptor (A) groups, and each ended with an anchoring functionality. In comparison, mono-anchoring dyes (Dye 1) were also synthesized. The PEC response of the Dye 2-sensitized TiO2 film was much better than the Dye 1-sensitized or unsensitized TiO2 films.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.70-70
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• 2013

As the costs of carbon-footprinetd fuels grow continuously and simultaneously atmospheric carbon dioxide concentration increases, solar fuels are receiving growing attention as alternative clean energy carriers. These fuels include molecular hydrogen and hydrogen peroxide produced from water, and hydrocarbons converted from carbon dioxide. For high efficiency solar fuel production, not only light absorbers (oxide semiconductors, Si, inorganic complexes, etc) should absorb most sunlight, but also charge separation and interfacial charge transfers need to occur efficiently. With this in mind, this talk will introduce the fundamentals of solar fuel production and artificial photosynthesis, and then discuss in detail on photoelectrochemical (PEC) water splitting and CO2 conversion. This talk largely divides into two section: PEC water oxidation and PEC CO2 reduction. The former is very important for proton-coupled electron transfer to CO2. For this oxidation, a variety of oxide semiconductors have been tested including TiO2, ZnO, WO3, BiVO4, and Fe2O3. Although they are essentially capable of oxidizing water into molecular oxygen, the efficiency is very low primarily because of high overpotentials and slow kinetics. This challenge has been overcome by coupling with oxygen evolving catalysts (OECs) and/or doping donor elements. In the latter, surface-modified p-Si electrodes are fabricated to absorb visible light and catalyze the CO2 reduction. For modification, metal nanoparticles are electrodeposited on the p-Si and their PEC performance is compared.

• Journal of Energy Engineering
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• v.15 no.2 s.46
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• pp.96-106
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• 2006

Among several different hydrogen production technologies, solar hydrogen system for water splitting is the only clean and sustainable energy supplier. Hydrogen production by water-splitting utilizing solar energy has attracted considerable interest since the pioneering work of Honda and Fujishima in 1979, who discovered that water can be photo-electrochemically decomposed into hydrogen and oxygen using a semiconductor ($TiO_2$) electrode under UV irradiation. Most efforts to utilize solar ray lead to explore visible responding photocatalysts, PEC cells and other fusion technology like bio-photocatalytic conversion. In this paper, photon utilization technologies for water splitting have been briefly reviewed except solar thermal utilization technology.

• Korean Journal of Materials Research
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• v.28 no.4
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• pp.214-220
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• 2018

We report on the fabrication and photoelectrochemical(PEC) properties of a $Cu_2O$ thin film/ZnO nanorod array oxide p-n heterojunction structure with ZnO nanorods embedded in $Cu_2O$ thin film as an efficient photoelectrode for solar-driven water splitting. A vertically oriented n-type ZnO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type $Cu_2O$ thin film was directly electrodeposited onto the vertically oriented ZnO nanorods array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were characterized using X-ray diffraction and scanning electron microscopy as well as Raman scattering. The PEC properties of the fabricated $Cu_2O/ZnO$ p-n heterojunction photoelectrode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the $Cu_2O/ZnO$ photoelectrode was found to exhibit a negligible dark current and high photocurrent density, e.g., $0.77mA/cm^2$ at 0.5 V vs $Hg/HgCl_2$ in a $1mM\;Na_2SO_4$ electrolyte, revealing an effective operation of the oxide heterostructure. In particular, a significant PEC performance was observed even at an applied bias of 0 V vs $Hg/HgCl_2$, which made the device self-powered. The observed PEC performance was attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential, including the light absorption and separation processes of photoinduced charge carriers.

• Korean Journal of Materials Research
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• v.29 no.3
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• pp.196-203
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• 2019

We report on the fabrication and characterization of an oxide photoanode with a zinc oxide (ZnO) nanorod array embedded in cuprous oxide ($Cu_2O$) thin film, namely a $ZnO/Cu_2O$ oxide p-n heterostructure photoanode, for enhanced efficiency of visible light driven photoelectrochemical (PEC) water splitting. A vertically oriented n-type ZnO nanorod array is first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type $Cu_2O$ thin film is directly electrodeposited onto the vertically oriented ZnO nanorod array to form an oxide p-n heterostructure. The introduction of $Cu_2O$ layer produces a noticeable enhancement in the visible light absorption. From the observed PEC current density versus voltage (J-V) behavior under visible light illumination, the photoconversion efficiency of this $ZnO/Cu_2O$ p-n heterostructure photoanode is found to reach 0.39 %, which is seven times that of a pristine ZnO nanorod photoanode. In particular, a significant PEC performance is observed even at an applied bias of 0 V vs $Hg/Hg_2Cl_2$, which makes the device self-powered. The observed improvement in the PEC performance is attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential including the light absorption and separation processes of photoinduced charge carriers, which provides a new avenue for preparing efficient photoanodes for PEC water splitting.

• Journal of Electrochemical Science and Technology
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• v.13 no.3
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• pp.377-389
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• 2022

The current global energy supply depends heavily on fossil fuels. This makes technology such as direct water splitting from harvesting solar energy in photoelectrochemical (PEC) systems potentially attractive due to its a promising route for environmentally benign hydrogen production. In this study, undoped and nickel-doped molybdenum oxide photoanodes (called photoanodes S₁ and S₂ respectively) were synthesized through electrodeposition by applying -1.377 V vs Ag/AgCl (3 M KCl) for 3 hours on an FTO-coated glass substrate immersed in molibdatecitrate aqueous solutions at pH 9. Scanning electron microscopy (SEM), atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS) were used for microstructural and compositional characterizations of the photoanodes. In addition, the optical and photoelectrochemical characterizations of these photoanodes were performed by UV-Visible spectroscopy, and linear scanning voltammetry (LSV) respectively. The results showed that all the photoanodes produced exhibit conductivity and catalytic properties that make them attractive for water splitting application in a photoelectrochemical cell. In this context, the photoanode S₂ exhibited better photocatalytic activity than the photoanode S₁. In addition, photoanode S₂ had the lowest optical band-gap energy value (2.58 eV), which would allow better utilization of the solar spectrum.

• Journal of Surface Science and Engineering
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• v.51 no.4
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• pp.237-242
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• 2018

We report on the fabrication and photoelectrochemical (PEC) properties of a ZnO nanorod array structure as an efficient photoelectrode for hydrogen production from sunlight-driven water splitting. Vertically aligned ZnO nanorods were grown on an indium-tin-oxide-coated glass substrate via seed-mediated hydrothermal synthesis method with the use of a ZnO nanoparticle seed layer, which was formed by thermally oxidizing a sputtered Zn metal thin film. The structural and morphological properties of the synthesized ZnO nanorods were examined using X-ray diffraction and scanning electron microscopy, as well as Raman scattering. The PEC properties of the fabricated ZnO nanorod photoelectrode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the vertically aligned ZnO nanorod photoelectrode was found to exhibit a negligible dark current and high photocurrent density, e.g., $0.65mA/cm^2$ at 0.8 V vs Ag/AgCl in a 1 mM $Na_2SO_4$ electrolyte. In particular, a significant PEC performance was observed even at an applied bias of 0 V vs Ag/AgCl, which made the device self-powered.

• Rapid Communication in Photoscience
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• v.3 no.2
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• pp.35-37
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• 2014

PEC (photoelectrochemical) water splitting for $O_2/H_2$ production is one of the promising but difficult way to utilize solar energy. Among photocatalytic materials for PEC water oxidation, $BiVO_4$ (Eg = 2.4 eV) has been recently intensively studied since it has various advantageous properties. But its maximum efficiency has not been realized owing to kinetic factors - slow water oxidation at surface & insufficient stability. These problems can be simultaneously solved by application of oxygen evolution catalyst (OEC) such as $CoO_x$, Co-Pi, $IrO_x$ etc. Herein we report the first successful application of $NiFeO_x$ OEC on $BiVO_4$, showing good performance compared to other effective OEC applied on $BiVO_4$ under basic conditions. The enhanced activity of OEC loaded $BiVO_4$ has been supported by the surface charge separation efficiency and electrochemical impedance studies.