• Journal of Electrochemical Science and Technology
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• v.14 no.4
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• pp.388-396
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• 2023

Photoelectrochemical (PEC) water splitting is a vital source of clean and sustainable hydrogen energy. Moreover, the large-scale H₂ production is currently necessary, while long-term stability and high PEC activity still remain important issues. In this study, a GaN-based photoelectrode was modified by an additional NH₃ treatment (900℃ for 10 min) and its PEC behavior was monitored. The bare GaN exhibited a highly crystalline wurtzite structure with the (002) plane and the optical bandgap was approximately 3.2 eV. In comparison, the NH₃-treated GaN film exhibited slightly reduced crystallinity and a small improvement in light absorption, resulting from the lattice stress or cracks induced by the excessive N supply. The minor surface nanotexturing created more surface area, providing electroactive reacting sites. From the surface XPS analysis, the formation of an N-Ga-O phase on the surface region of the GaN film was confirmed, which suppressed the charge recombination process and the positive shift of E_FB. Therefore, these effects boosted the PEC activity of the NH₃-treated GaN film, with J values of approximately 0.35 and 0.78 mA·cm^-2 at 0.0 and 1.23 V_RHE, respectively, and an onset potential (V_on) of -0.24 V_RHE. In addition, there was an approximate 50% improvement in the J value within the highly applied potential region with a positive shift of V_on. This result could be explained by the increased nanotexturing on the surface structure, the newly formed defect/trap states correlated to the positive V_on shift, and the formation of a GaO_xN_1-x phase, which partially blocked the charge recombination reaction.

• Korean Journal of Materials Research
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• v.27 no.11
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• pp.631-635
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• 2017

We report facile solution processing of mesoporous hematite (${\alpha}-Fe_2O_3$) thin films for high efficiency solar-driven water splitting. $Fe_2O_3$ thin films were prepared on fluorine doped tin oxide(FTO) conducting substrates by spin coating of a precursor solution followed by annealing at $550^{\circ}C$ for 30 min. in air ambient. Specifically, the precursor solution was prepared by dissolving non-toxic $FeCl_3$ as an Fe source in highly versatile dimethyl sulfoxide(DMSO) as a solvent. The as-deposited and annealed thin films were characterized for their morphological, structural and optical properties using field-emission scanning electron microscopy(FE-SEM), X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and UV-Vis absorption spectroscopy. The photoelectrochemical performance of the precursor (${\alpha}-FeOOH$) and annealed (${\alpha}-Fe_2O_3$) films were characterized and it was found that the ${\alpha}-Fe_2O_3$ film exhibited an increased photocurrent density of ${\sim}0.78mA/cm^2$ at 1.23 V vs. RHE, which is about 3.4 times higher than that of the ${\alpha}-FeOOH$ films ($0.23mA/cm^2$ at 1.23 V vs. RHE). The improved performance can be attributed to the improved crystallinity and porosity of ${\alpha}-Fe_2O_3$ thin films after annealing treatment at higher temperatures. Detailed electrical characterization was further carried out to elucidate the enhanced PEC performance of ${\alpha}-Fe_2O_3$ thin films.

• Transactions of the Korean hydrogen and new energy society
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• v.11 no.3
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• pp.119-125
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• 2000

To improve the photochemical energy conversion efficiency and the stability of CdS particulate film electrode which is used to produce hydrogen from the aqueous $H_2S$ solution photoelectrochemically, surface treatment of this film was carried out using $TiCl_4$ solution. CdS particles for preparation of the films were synthesized by precipitation reaction of $Cd({NO_3})_2{\cdot}9H_2O$ and $Na_2S{\cdot}4H_2O$. Then, the CdS sol was hydrothermally treated for 12hr in an autoclave with the variation of treatment temperature to control the crystalline phase of particles. CdS film electrode was thus prepared by annealing at $400^{\circ}C$ for 12hr of the wet-film cast at room temperature, and subsequently surface treated with $TiCl_4$ solution. The electrodes were characterized using XRD, SEM, and the photocurrent meter. The photocurrents of Cds film electrodes prepared with surface treatment were up to two times higher than the electrodes without surface treatment, indicating about $4.0mA/cm^2$. Hydrogen production rate in a continuous flow system using photoelectrochemical or photochemical cells prepared with surface treatment also increased in proportion to the increase of photocurrents.

• Elastomers and Composites
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• v.47 no.1
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• pp.2-8
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• 2012

In this study, in order to develop renewable bio-based nanocomposites, multi-functional nanocomposites from soybean resins (AESO, MAESO) and nanoclay were prepared. Photoelectrodes for environmental friendly dye-sensitized solar cell using soybean resin were also prepared. Organo-modified nanoclay was directly dispersed in functionalized soybean resins after mixing with styrene as a comonomer and radical initiator was used to copolymerize the nanocomposites. The observed morphology was a mixture of intercalated/exfoliated structure and the physical properties were improved by adding nanoclay. A nanocomposite using MAESO, which added COOH functional group to the soybean resin, showed better dispersibility than AESO composites. Ultrasonic treatment of the nanocomposites also improved the physical properties. Nanoporous $TiO_2$ photoelectrode was also prepared using soybean resins as a binder, after acid-treatment of $TiO_2$ surface using nitric acid. Dye-sensitized solar cells were prepared after adsorbing dye molecules on it. The $TiO_2$ photoelectrode prepared using soybean binder had high current density because of increased surface area by improved dispersibility. The photoelectrochemical properties and conversion efficiency of the solar cell were significantly improved using the soybean binder.

• Proceedings of the Materials Research Society of Korea Conference
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• 2010.05a
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• pp.3.1-3.1
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• 2010

Water splitting reaction using photocatalysts is of great interest in the utilization of solar energy [1]. In the present work, visible light-responsive $TiO_2$ thin films (Vis-$TiO_2$) were prepared by a radio frequency magnetron sputtering (RF-MS) deposition method and applied for the separate evolution of $H_2$ and $O_2$ from water as well as the photofuel cell. Special attentions will be focused on the effect of HF treatment of Vis-$TiO_2$ thin films on their photocatalytic activities. Vis-$TiO_2$ thin films were prepared by an RF-MS method using a calcined $TiO_2$ plate and Ar as the sputtering gas. The Vis-$TiO_2$ thin films were then deposited on the Ti foil substrate with the substrate temperature at 873 K (Vis-$TiO_2$/Ti). Vis-$TiO_2$/Ti thin films were immersed in a 0.045 vol% HF solution at room temperature. The effect of HF treatments on the activity of Vis-$TiO_2$/Ti thin films for the photocatalytic water splitting reaction have been investigated. Vis-$TiO_2$/Ti thin films treated with HF solution (HF-Vis-$TiO_2$/Ti) exhibited remarkable enhancement in the photocatalytic activity for $H_2$ evolution from a methanol aqueous solution as well as in the photoelectrochemical performance under visible light irradiation as compared with the untreated Vis-$TiO_2$/Ti thin films. Moreover, Pt-loaded HF-Vis-$TiO_2$/Ti thin films act as efficient and stable photocatalysts for the separate evolution of $H_2$ and $O_2$ from water under visible light irradiation in the presence of chemical bias. Thus, HF treatment was found to be an effective way to improve the photocatalytic activity of Vis-$TiO_2$/Ti thin films. Furthermore, unique separate type photofuel cell was fabricated using a Vis-$TiO_2$ thin film as an electrode, which can generate electrical power under solar light irradiation by using various kinds of biomass derivatives as fuel. It was found that the introduction of an iodine ($I^-/{I_3}^-$) redox solution at the cathode side enables the development of a highly efficient photofuel cell which can utilize a cost-efficient carbon electrode as an alternative to the Pt cathode.

• Proceedings of the Korean Vacuum Society Conference
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• 2012.02a
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• pp.213-213
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• 2012

It has been known that quantum confinement effect of CdSe nanocrystal was observed by increasing the number of deposition cycle using successive ionic layer adsorption and reaction (SILAR) method. Here, we report on thermally-induced quantum confinement effect of CdSe at the given cycle number using spin-coating technology. A cation precursor solution containing $0.3\;M\;Cd(NO_3)_2{\cdot}4H_2O$ is spun onto a $TiO_2$ nanoparticulate film, which is followed by spinning an anion precursor solution containing $0.3\;M\;Na_2\;SeSO_3$ to complete one cycle. The cycle is repeated up to 10 cycles, where the spin-coated $TiO_2$ film at each cycle is heated at temperature ranging from $100^{\circ}C$ to $250^{\circ}C$. The CdSe-sensitized $TiO_2$ nanostructured film is contacted with polysulfide redox electrolyte to construct photoelectrochemical solar cell. Photovoltaic performance is significantly dependent on the heat-treatment temperature. Incident photon-to-current conversion efficiency (IPCE) increases with increasing temperature, where the onset of the absorption increases from 600 nm for the $100^{\circ}C$- to 700 nm for the $150^{\circ}C$- and to 800 nm for the $200^{\circ}C$- and the $250^{\circ}C$-heat treatment. This is an indicative of quantum size effect. According to Tauc plot, the band gap energy decreases from 2.09 eV to 1.93 eV and to 1.76 eV as the temperature increases from $100^{\circ}C$ to $150^{\circ}C$ and to $200^{\circ}C$ (also $250^{\circ}C$), respectively. In addition, the size of CdSe increases gradually from 4.4 nm to 12.8 nm as the temperature increases from $100^{\circ}C$ to $250^{\circ}C$. From the differential thermogravimetric analysis, the increased size in CdSe by increasing the temperature at the same deposition condition is found to be attributed to the increase in energy for crystallization with $dH=240cal/^{\circ}C$. Due to the thermally induced quantum confinement effect, the conversion efficiency is substantially improved from 0.48% to 1.8% with increasing the heat-treatment temperature from $100^{\circ}C$ to $200^{\circ}C$.

• Clean Technology
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• v.18 no.3
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• pp.229-249
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• 2012

At present, global warming and depletion of fossil fuels have been one of the big issues which should be solved for sustainable development in the future. CCS (carbon capture and sequestration) technology as the post $CO_2$ reduction technology has been considered as a promising solution for global warming due to increased carbon emission. However, the environmental and ecological effects of CCS have drawn concerns. There are needs for noble post reduction technology. More recently, CCU (carbon capture and utilization) Technology, which emphasizes transforming carbon dioxide into value-added chemicals rather than storing it, has been attracted attentions in terms of preventing global warming and recycling the renewable carbon source. In this paper, various technologies developed for carbon dioxide conversion both in gas and liquid phase have been reviewed. For the thermochemical catalysis in gas phase, the development of the catalytic system which can be performed at mild condition and the separation and purification technology with low energy supply is required. For the photochemical conversion in liquid phase, efficient photosensitizers and photocatalysts should be developed, and the photoelectrochemical systems which can utilize solar and electric energy simultaneously are also in development for more efficient carbon dioxide conversion. The energy needed in CCU must be renewable or unutilized one. CCU will be a key connection technology between renewable energy and bio industry development.

• Transactions of the Korean hydrogen and new energy society
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• v.11 no.4
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• pp.161-169
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• 2000

In the case of photocatalytic hydrogen production from water, the performance-property relationships of CdS-TiO2 film type composite catalysts were investigated. To control the physical properties of the primary particles, the mixture of CdS and TiO2 nano-sols prepared by the sol-gel method at room temperature was hydrothermally treated at 240oC for 12hr. The film electrodes were prepared by the casting method. The photocurrents measured by a photoelectrochemical method and the hydrogen production rates measured by a photochemical method were closely dependent on the physical properties such as crystalline form, primary particle size and CdS/TiO2 mole ratio, and these varied in the range of 1.2~2.6 mA/cm2 and $1.0{\sim}1.6{\times}10-3mol/hr$, respectively.