• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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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.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.12
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• pp.907-912
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• 2011

Development of visible light responsive photocatalysts is a promising research area to facilitate utilization of solar energy for hydrogen production via photocatalytic water splitting. In this study two groups of samples, nitrogen (N)-doped niobium pentoxide ($Nb_2O_5$) and titanium dioxide ($TiO_2$) ($Nb_2O_5-N$, $HNb_3O_8-N$, $TiO_2-N$) and N-undoped ones ($Nb_2O_5$ and $TiO_2$) were tested. In order to utilize visible light, nitrogen atoms were doped in selected photocatalysts by using urea. A shift of the absorption edges of the Ndoped samples in the visible light region was observed. Under visible light irradiation, N-doped samples were more prominent photocatalytic activities than the N-undoped samples. Specifically, 99.7% of rhodamine B (RhB) was degraded after 60 minutes of visible light irradiation with $TiO_2-N$. Since $TiO_2-N$ shows the highest activity of RhB degradation, it was supposed to generate the highest current response. However, $HNb_3O_8-N$ showed the highest current response ($63.7mA/cm^2$) than $TiO_2-N$. More interestingly, when we compare the hydrogen production, $Nb_2O_5-N$ produced $19.4{\mu}mol/h$ of hydrogen.

• Bulletin of the Korean Chemical Society
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• v.33 no.11
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• pp.3761-3766
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• 2012

$Ag_2Se$-Graphene/$TiO_2$ composite was synthesized by a facile sonochemical method. The as-prepared products were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM) and UV-vis diffuse reflectance spectrophotometer. During the reaction, both of the reduction of graphene oxide and loading of $Ag_2Se$ and $TiO_2$ particles were achieved. The as-prepared $Ag_2Se$-Graphene/$TiO_2$ composites possessed great adsorptivity of dyes, extended light absorption range, and efficient charge separation properties simultaneously. Hence, in the photodegradation of rhodamine B (Rh.B), a significant enhancement in the reaction rate was observed with $Ag_2Se$-Graphene/$TiO_2$ composites, compared to the pure $TiO_2$. The high activity can be attributed to the synergetic effects of high charge mobility, and red shift in absorption edge of $Ag_2Se$-Graphene/$TiO_2$ composites.

• Korean Journal of Metals and Materials
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• v.56 no.12
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• pp.900-909
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• 2018

A $ZnO/TiO_2$ photocatalyst decorated with PbS quantum dots (QDs) was synthesized to achieve high photocatalytic efficiency for the decomposition of dye in aqueous media. A $TiO_2$ porous layer, as a precursor photocatalyst, was fabricated using micro-arc oxidation, and exhibited irregular porous cells with anatase and rutile crystalline structures. Then, a ZnO-deposited $TiO_2$ catalyst was fabricated using a zinc acetate solution, and PbS QDs were uniformly deposited on the surface of the $ZnO/TiO_2$ photocatalyst using the successive ionic layer adsorption and reaction (SILAR) technique. For the PbS $QDs/ZnO/TiO_2$ photocatalyst, ZnO and PbS nanoparticles are uniformly precipitated on the $TiO_2$ surface. However, the diameters of the PbS particles were very fine, and their shape and distribution were relatively more homogeneous compared to the ZnO particles on the $TiO_2$ surface. The PbS QDs on the $TiO_2$ surface can induce changes in band gap energy due to the quantum confinement effect. The effective band gap of the PbS QDs was calculated to be 1.43 eV. To evaluate their photocatalytic properties, Aniline blue decomposition tests were performed. The presence of ZnO and PbS nanoparticles on the $TiO_2$ catalysts enhanced photoactivity by improving the absorption of visible light. The PbS $QDs/ZnO/TiO_2$ heterojunction photocatalyst showed a higher Aniline blue decomposition rate and photocatalytic activity, due to the quantum size effect of the PbS nanoparticles, and the more efficient transport of charge carriers.

• Journal of the Korean Ceramic Society
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• v.50 no.4
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• pp.251-256
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• 2013

Multiwalled carbon nanotubes (MWCNTs) modified with Pd and $TiO_2$ composite catalysts were synthesized by the sol-gel method followed by solvothermal treatment at low temperature. The chemical composition and surface structure were characterized by X-ray diffraction (XRD), energy-dispersive X-ray (EDX) spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Photocatalytic recycle degradation experiments were carried out under both UV and visible light irradiation in the presence of MWCNT/$TiO_2$ and Pd-MWCNT/$TiO_2$ composites. As expected, the nanosized Pd-MWCNT/$TiO_2$ photocatalysts had enhanced activity over the non Pd treated MWCNT/$TiO_2$ material in the degradation of a rhodamine B (Rh.B) solution. An increase in photocatalytic activity was observed and attributed to an increase in the photo-absorption effect by MWCNTs and the cooperative effect of Pd and $TiO_2$ nanoparticles. According to the recycled results, the as-prepared Pd-MWCNT/$TiO_2$ sample had a good effect on it.

• Korean Chemical Engineering Research
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• v.54 no.1
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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.

• 한국신재생에너지학회:학술대회논문집
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• 2010.06a
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• pp.227.1-227.1
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• 2010

본 연구는 자외선 영역의 흡수로 전자 정공의 전하쌍을 생성함으로써 광전압 및 전류를 일으키는 티타니아 물질을 금속지지체 표면에 양극산화로 튜브형 $TiO_2$(anodized tubular $TiO_2$; ATT)로 제조한 후 나노크기의 금속 혹은 $WO_3$입자를 담지하여 광감응 재료로 활용하였다. 이는 기존의 입자나 콜로이드 형태로 광촉매 물질을 고정화하여 사용한 재료의 탈리현상 및 효율저하를 극복하기 위함이다. ATT는 전해질 내에 전기화학적 에칭율과 화학적 용해율의 비율에 의해 나노튜브 길이 성장에 영향을 미치는데 이를 유기 전해질과 불산 전해질을 사용하여 정전압 혹은 정전류의 조건에서 다양한 길이의 $TiO_2$ 나노튜브를 제조하였다. 여기에 전기분해담지(electrolytic deposition; ELD)를 통하여 정전류 조건에서 다양한 금속(Pt, Pd, Ru)을 나노크기의 형태로 담지하여 광촉매 내 생성된 전자 정공의 재결합을 줄이고자 하였고 $WO_3$의 담지를 통하여 가시광 감응을 높이고자 하였다. 제조된 여러 조건의 시료는 SEM과 EDAX를 통하여 형태와 길이, 담지량을 확인 하고 XRD를 이용하여 열처리 온도에 따른 결정화상태를 확인하였으며 광전류 측정 및 Cr(VI)의 광환원과 MB의 광분해를 통하여 광효율을 관찰하였다. 금속이 도핑되었을 경우 순수 ATT보다 보통 3배의 흡착률과 UV광원 아래 2배의 광효율을 관찰할 수 있었는데 이 중 Pt의 담지가 가장 효율이 좋았으며 흡착률에서는 담지량의 증가에 따른 증가선을 관찰 할 수 있었으나 광원 사용시 3%담지율에서 최적을 확인 할 수 있었다. 또한 $TiO_2$외 가시광감응 활성을 높이기 위한 다양한 광촉매제조가 진행 중에 있다.

• Korean Journal of Optics and Photonics
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• v.16 no.2
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• pp.168-173
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• 2005

Ag-doped $TiO_2$ thin films were prepared by RF magnetron co-sputtering method, and their physical and chemical properties were examined as a function of calcination temperature. XRD results showed that the crystallite size of Ag-doped films was smaller than that of the $TiO_2$ thin films. SEM results showed that the particle size of $Ag/TiO_2$ film was smaller and more uniform than pure $TiO_2$ film. The films had high transparency in the visible range. The films calcined at $600^{\circ}C$ were the anatase phase, and the films calcined at $900^{\circ}C$ were a mixture of anatase and rutile phases. The absorption edge of films calcined at $900^{\circ}C$ was red-shifted. This is due to the augmented absorption resulting from the phase transformation from anatase to rutile phase. And the transmittance of films decreased by the light scattering and absorption in the films. Photocatalytic activity of $Ag/TiO_2$ thin films was higher than that of the pure $TiO_2$ thin films.

• Applied Chemistry for Engineering
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• v.19 no.3
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• pp.270-276
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• 2008

$N_2$ doped $TiO_2$ nano-sized powder was prepared using a DC arc plasma jet and investigated with XRD, BET, SEM, TEM, and photo-catalytic decomposition. Recently the research interest about the nano-sized $TiO_2$ powder has been increased to improve its photo-catalytic activity for the removal of environmental pollutants. Nitrogen gas, reacting gas, and titanium tetrachloride ($TiCl_4$) were used as the raw materials and injected into the plasma reactor to synthesize the $N_2$ doped $TiO_2$ power. The particle size and XRD peaks of the synthesized powder were analyzed as a function of the flow rate of the nitrogen gas. Also, the characteristics of the photo-catalytic decomposition using the prepared powder were studied. For comparing the photo-catalytic decomposition performance of $TiO_2$ powder with that of $TiO_2$ coating, $TiO_2$ thin films were prepared by the spin coating and the pulsed laser deposition. For the results of the acetaldehyde decomposition, the photo-catalytic activity of $TiO_{2-x}N_x$ powder was higher than that of the pure $TiO_2$ powder in the visible light region. For the methylene blue decomposition, the decomposition efficiency of $TiO_2$ powder was also higher than that of $TiO_2$ film.

• Applied Chemistry for Engineering
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• v.28 no.1
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• pp.1-7
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• 2017

Polydimethylsiloxane (PDMS) can be deposited on various substrates using chemical vapor deposition process, which results in the formation of PDMS thin films with thickness below 5 nm. PDMS layers can be evenly deposited on surfaces of nanoparticles composed of various chemical compositions such as $SiO_2$, $TiO_2$, ZnO, C, Ni, and NiO, and the PDMS-coated surface becomes completely hydrophobic. These hydrophobic layers are highly resistant towards degradation under acidic and basic environments and UV-exposures. Nanoparticles coated with PDMS can be used in various environmental applications: hydrophobic silica nanoparticles can selectively interact with oil from oil/water mixture, suppressing fast diffusion of spill-oil on water and allowing more facile physical separation of spill-oil from the water. Upon heat-treatments of PDMS-coated $TiO_2$ under vacuum conditions, $TiO_2$ surface becomes completely hydrophilic, accompanying formation oxygen vacancies responsible for visible-light absorption. The post-annealed $PDMS-TiO_2$ shows enhanced photocatalytic activity with respect to the bare $TiO_2$ for decomposition of organic dyes in water under visible light illumination. We show that the simple PDMS-coating process presented here can be useful in a variety of field of environmental science and technology.