• 한국재료학회지
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• 제31권6호
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• pp.353-366
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• 2021

In this study, photocatalytic degradation of ammonia in petrochemical wastewater is investigated by solar light photocatalysis. Two-dimensional ultra-thin atomic layer structured MoS₂ are synthesized via a simple hydrothermal method. We examine all prepared samples by means of physical techniques, such as SEM-EDX, HRTEM, FT-IR, BET, XRD, XPS, DRS and PL. And, we use fullerene modified MoS₂ nanosheets to enhance the activity of photochemically generated oxygen (PGO) species. Surface area and pore volumes of the MoS₂-fullerene samples significantly increase due to the existence of MoS₂. And, PGO oxidation of MB, TBA and TMST, causing its concentration in aqueous solution to decrease, is confirmed by the results of PL. The generation of reactive oxygen species is detected through the oxidation reaction from 1,5-diphenyl carbazide (DPCI) to 1,5-diphenyl carbazone (DPCO). It is found that the photocurrent density and the PGO effect increase in the case with modified fullerene. The experimental results show that this heterogeneous catalyst has a degradation of 88.43% achieved through visible light irradiation. The product for the degradation of NH₃ is identified as N₂, but not NO^2- or NO^3-.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2016년도 제50회 동계 정기학술대회 초록집
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• pp.246-246
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• 2016

Tungsten-nitrogen (W-N) co-doping has been known to enhance the photocatalytic activity of anatase titania nanoparticles by utilizing visible light. The doping effects are, however, largely dependent on calcination or annealing conditions, and thus, the massive production of quality-controlled photocatalysts still remains a challenge. Using density functional theory (DFT) thermodynamics and time-dependent DFT (TDDFT) computations, we investigate the atomic structures of N doping and W-N co-doping in anatase titania, as well as the effect of the thermal processing conditions. We find that W and N dopants predominantly constitute two complex structures: an N interstitial site near a Ti vacancy in the triple charge state and the simultaneous substitutions of Ti by W and the nearest O by N. The latter case induces highly localized shallow in-gap levels near the conduction band minimum (CBM) and the valence band maximum (VBM), whereas the defect complex yielded deep levels (1.9 eV above the VBM). Electronic structures suggest that substitutions of Ti by W and the nearest O by N improves the photocatalytic activity of anatase by band gap narrowing, while defective structure degrades the activity by an in-gap state-assisted electron-hole recombination, which explains the experimentally observed deep level-related photon absorption. Through the real-time propagation of TDDFT (rtp-TDDFT), we demonstrate that the presence of defective structure attracts excited electrons from the conduction band to a localized in-gap state within a much shorter time than the flat band lifetime of titania. Based on these results, we suggest that calcination under N-rich and O-poor conditions is desirable to eliminate the deep-level states to improve photocatalysis.

• Korean Chemical Engineering Research
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• 제54권1호
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• pp.127-134
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• 2016

A series of Ce-doped ZnO (Ce/ZnO) nanostructures were fabricated using the co-precipitation method, then a simply nontoxic hydrothermal approach was proposed for preparation of reduced graphene oxide (rGO)-Ce/ZnO composites. The synthesized composites were investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), photoluminescence spectroscopy (PL), electrochemical impedance spectroscopy (EIS), UV-vis diffuse reflectance spectroscopy (DRS) techniques and Raman pattern. The as-synthesized rGO-Ce/ZnO composites showed high photodecomposition efficiency in comparison with the rGO-ZnO, Ce/ZnO, pure ZnO under UV, visible-light and sunlight irradiation. The degradation of methylene blue (MB) (10 mg/L, 100ml) by 95.8% within 60 min by using rGO-2 (10 mg) under sunlight irradiation was observed. The repeated use of the rGO-2 was investigated, and the results showed almost no decay in the catalytic activity.

• Bulletin of the Korean Chemical Society
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• 제35권6호
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• pp.1794-1798
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• 2014

Graphitic g-$C_3N_4-WO_3$ composite was synthesized simply by decomposing melamine in the presence of $WO_3$ at $500^{\circ}C$. The obtained material was characterized by XRD, SEM, IR and XPS. The results showed that the as-prepared composite exhibits orthorhombic $WO_3$ phase coated by g-$C_3N_4$ and the g-$C_3N_4$ decomposed completely with N-doped $WO_3$ remaining at elevated calcination temperatures. The photocatalytic activity of the composite was evaluated by the photodegradation of methylene blue under visible light. An enhancement in photocatalytic activity for the graphitic g-$C_3N_4-WO_3$ composite compared to the conventional nitrogen-doped $WO_3$ was observed, which can be attributed to the presence of g-$C_3N_4$ in the material.

• 한국세라믹학회지
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• 제48권2호
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• pp.200-204
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• 2011

Increase of surface area and decrease of band gap in $TiO_2$ semiconductors are significant to improve the efficiency of water splitting by photoelectrolysis. In this study $TiO_2$ nanotube arrays with ~7 um length and ~100 nm diameter were fabricated by an anodizing technique of titanium foils using DMSO (dimethyl sulfoxide)-based electrolytes. Then to control the band gap of the $TiO_2$ arrays, they were annealed at $550^{\circ}C$ for up to 180 min in $NH_3$ gas ambient. The samples annealed in $NH_3$ gas for 30 min and 60 min showed superior photo-conversion efficiency for water splitting under white and visible light. A $TiO_2$ nanotube annealed in $NH_3$ gas ambient for a period longer than 120 min showed 1 order higher leakage current. It is believed that the decrease of band gap and increase of conductivity in $TiO_2$ nanotube arrays due to $NH_3$ gas treatments result in the superior water-splitting performance.

• Environmental Engineering Research
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• 제24권4호
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• pp.566-571
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• 2019

One-pot hydrothermal route was adopted to synthesize Al:BiVO₄, at 4 h and 8 h reaction durations, by adding 1% aluminiumoxide powder (w/v) to the precursors. The products were investigated using several characterization techniques that conform a significant morphological change and a decrease in bandgap energy of the materials upon Al modification of scheelite monoclinic bismuth vanadate matrix at both hydrothermal durations. Antibacterial experiments were performed against methicillin-resistant Staphylococcus aureus in visible light condition to harness the photoxidation property of Al-doped BiVO₄ and compare to that of unaltered BiVO₄. Minimum inhibitory concentration of the synthesized materials was identified. The results indicate that Al-doping on BiVO₄ has a significant effect on its photocatalytic antibacterial performance. Al:BiVO₄ synthesized at 8 h hydrothermal treatment parades excellent sunlight-driven photocatalysis compared to the one synthesized at 4 h.

• Journal of Industrial and Engineering Chemistry
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• 제67권
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• pp.28-51
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• 2018

Graphitic carbon nitride ($g-C_3N_4$) as a fascinating visible light active semiconductor photocatalyst has medium band gap, non-toxic nature, stable chemical structure and high thermal stability. Recently, intensive researches are focused on photocatalytic activity of $g-C_3N_4$ for wastewater treatment. This review demonstrates latest progress in fabrication of graphitic carbon nitride $C_3N_4$ incorporated nanocomposite to explore photocatalytic ability for water purification. The $g-C_3N_4$-based nanocomposites were categorized as $g-C_3N_4$ metal-free nanocomposite, noble metals/$g-C_3N_4$ heterojunction, non-metal doped $g-C_3N_4$, transition and post transition metal based $g-C_3N_4$ nanocomposite. Apart from fabrication methods, we emphasized on elaborating the mechanism of activity enhancement during photocatalytic process.

• 한국표면공학회지
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• 제37권6호
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• pp.307-312
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• 2004

Extensive efforts have been made in an attempt to utilize photocatalytic properties of $TiO_2$ in visible range. $TiO_2$ and TiO-N thin films were made by the DC reactive magnetron sputtering method at $300^{\circ}C$. Various gases (Ar, $O_2$ and $N_2$) were used and Ti target was impressed by 0.6 kW-5.8 kW power range. The hysteresis phenomenon of the $TiO_2$ thin film as a function of the discharge voltage characteristic was observed to be higher as applied power increases. That of TiO-N thin film was occurred at the 5.8 kW power. The cross section and surface roughness of thin films were observed by FE-SEM and AFM. Average surface roughness of TiO-N thin film was observed as $15.9\AA$ and that of $TiO_2$ as $13.2\AA$. The crystal phases of both $TiO_2$ and TiO-N thin films were found to be anatase structure. The atomic $\beta$-N (396 eV peak in N 1s XPS) was shown in the rutile crystal of TiO-N and was considered acting as the origin of wavelength shift to the visible light.

• Bulletin of the Korean Chemical Society
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• 제29권4호
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• pp.817-821
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• 2008

We have investigated the influence of the crystal structure on the chemical bonding nature and photocatalytic activity of cubic and hexagonal perovskite A[$Cr_{1/2}Ta_{1/2}$]O3 (A = Sr, Ba) compounds. According to neutron diffraction and field emission-scanning electron microscopy, the crystal structure and particle size of these compounds are strongly dependent on the nature of A-site cations. Also, it was found that the face-shared octahedra in the hexagonal phase are exclusively occupied by chromium ions, suggesting the presence of metallic (Cr-Cr) bonds. X-ray absorption and diffuse UV-vis spectroscopic analyses clearly demonstrated that, in comparison with cubic Sr[$Cr_{1/2}Ta_{1/2}$]$O_3$ phase, hexagonal Ba[$Cr_{1/2}Ta_{1/2}$]$O_3$ phase shows a decrease of Cr oxidation state as well as remarkable changes in interband Cr d-d transitions, which can be interpreted as a result of metallic (Cr-Cr) interactions. According to the test of photocatalytic activity, the present semiconducting materials have a distinct activity against the photodegradation of 4-chlorophenol. Also the Srbased compound was found to show a higher photocatalytic activity than the Ba-based one, which is attributable to its smaller particle size and its stronger absorption in visible light region.

• Bulletin of the Korean Chemical Society
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• 제33권11호
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• pp.3767-3771
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• 2012

In this study, we investigate the potential use of $TiO_2@SiO_2$ and $ZnO@SiO_2$ core/shell nanoparticles (NPs) as effective UV shielding agent. In the typical synthesis, $SiO_2$ was coated over different types of $TiO_2$ (anatase and rutile) and ZnO by sol-gel method. The synthesized $TiO_2@SiO_2$ and $ZnO@SiO_2$ NPs were characterized by UV-Vis, XRD, SEM and TEM. The UV-vis absorbance and transmittance spectra of core@shell NPs showed an efficient blocking effect in the UV region and more than 90% transmittance in the visible region. XRD and SAED studies confirmed the formation of amorphous $SiO_2$ coated over the $TiO_2$ and ZnO NPs. The FESEM and TEM images shows that coating of $SiO_2$ over the surface of anatase, rutile $TiO_2$ and ZnO NPs resulted in the increase in particle size by ~30 nm. In order to study the UV light shielding capability of the samples, photocatalytic degradation of methylene blue dye on $TiO_2@SiO_2$ and $ZnO@SiO_2$ NPs was performed. Photocatalytic activity for both types of $TiO_2$ NPs was partially suppressed. In comparison, the photocatalytic activity of ZnO almost vanished after the $SiO_2$ coating.