To improve light absorption ability in the visible light region and the efficiency of the charge transfer reaction, Pd nanoparticles decorated with reduced TiO2 nanotube photocatalyst were synthesized. The reduced TiO2 nanotube photocatalyst was fabricated by anodic oxidation of Ti plate, followed by an electrochemical reduction process using applied cathodic potential. For TiO2 photocatalyst electrochemically reduced using an applied voltage of -1.3 V for 10 min, 38% of Ti4+ ions on TiO2 surface were converted to Ti3+ ion. The formation of Ti3+ species leads to the decrease in the band gap energy, resulting in an increase in the light absorption ability in the visible range. To obtain better photocatalytic efficiency, Pd nanoparticles were decorated through photoreduction process on the surface of reduced TiO2 nanotube photocatalyst (r10-TNT). The Pd nanoparticles decorated with reduced TiO2 nanotube photocatalyst exhibited enhanced photocurrent response, and high efficiency and rate constant for aniline blue degradation; these were ascribed to the synergistic effect of the new electronic state of the TiO2 band gap energy induced by formation of Ti3+ species on TiO2, and by improvement of the charge transfer reaction.

For the purpose of manufacturing a high efficiency TiO2 photocatalyst, B-doped TiO2 photocatalysts are synthesized using a plasma electrolytic oxidation method in 0.5 M H2SO4 electrolyte with different concentrations of H3BO3 as additive. For the B doped TiO2 layer fabricated from sulfuric electrolyte having a higher concentration of H3BO3 additive, the main XRD peaks of (101) and (200) anatase phase shift gradually toward the lower angle direction, indicating volume expansion of the TiO2 anatase lattice by incorporation of boron, when compared with TiO2 layers formed in sulfuric acid with lower concentration of additive. Moreover, XPS results indicate that the center of the binding energy peak of B1s increases from 191.45 eV to 191.98 eV, which suggests that most of boron atoms are doped interstitially in the TiO2 layer rather than substitutionally. The B doped TiO2 catalyst fabricated in sulfuric electrolyte with 1.0 M H3BO3 exhibits enhanced photocurrent response, and high efficiency and rate constant for dye degradation, which is ascribed to the synergistic effect of the new impurity energy band induced by introducing boron to the interstitial site and the improvement of charge transfer reaction.

In this work, TiO2 3D nanostructures (TF30) were prepared via a facile wet chemical process using ammonium hexafluorotitanate. The synthesized 3D TiO2 nanostructures exhibited well-defined crystalline and hierarchical structures assembled from TiO2 nanorods with different thicknesses and diameters, which comprised numerous small beads. Moreover, the maximum specific surface area of TiO2 3D nanostructures was observed to be 191 m2g-1, with concentration of F ions on the surface being 2 at%. The TiO2 3D nanostructures were tested as photocatalysts under UV irradiation using Rhodamine B solution in order to determine their photocatalytic performance. The TiO2 3D nanostructures showed a higher photocatalytic activity than that of the other TiO2 samples, which was likely associated with the combined effects of a high crystallinity, unique features of the hierarchical structure, a high specific surface area, and the advantage of adsorbing F ions.

A facile one-pot wet chemical process to prepare pure anatase TiO2 hollow structures using ammonium hexafluorotitanate as a precursor is developed. By defining the formic acid ratio, we fabricate TiO2 hollow structures containing fluorine on the surface. The TiO2 hollow sphere is composed of an anatase phase containing fluorine by various analytical techniques. A possible formation mechanism for the obtained hollow samples by self-transformation and Ostwald ripening is proposed. The TiO2 hollow structures containing fluorine exhibits 1.2 - 2.7 times higher performance than their counterparts in photocatalytic activity. The enhanced photocatalytic activity of the TiO2 hollow structures is attributed to the combined effects of high crystallinity, specific surface area (62 m2g-1), and the advantage of surface fluorine ions (at 8%) having strong electron-withdrawing ability of the surface ≡ Ti-F groups reduces the recombination of photogenerated electrons and holes.

To improve photocatalytic performance, CdS nanoparticle deposited TiO2 nanotubular photocatalysts are synthesized. The TiO2 nanotube is fabricated by electrochemical anodization at a constant voltage of 60 V, and annealed at 500 for crystallization. The CdS nanoparticles on TiO2 nanotubes are synthesized by successive ionic layer adsorption and reaction method. The surface characteristics and photocurrent responses of TNT/CdS photocatalysts are investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-Vis spectrometer and LED light source installed potentiostat. The bandgaps of the CdS deposited TiO2 photocatalysts are gradually narrowed with increasing of amounts of deposited CdS nanoparticles, which enhances visible light absorption ability of composite photocatalysts. Enhanced photoelectrochemical performance is observed in the nanocomposite TiO2 photocatalyst. However, the maximum photocurrent response and dye degradation efficiency are observed for TNT/CdS30 photocatalyst. The excellent photocatalytic performance of TNT/CdS30 catalyst can be ascribed to the synergistic effects of its better absorption ability of visible light region and efficient charge transport process.

Composites of P25 TiO2 and hexagonal WO3 nanorods are synthesized through ball-milling in order to study photocatalytic properties. Various composites of TiO2/WO3 are prepared by controlling the weight percentages (wt%) of WO3, in the range of 1–30 wt%, and milling time to investigate the effects of the composition ratio on the photocatalytic properties. Scanning electron microscopy, x-ray diffraction, and transmission electron microscopy are performed to characterize the structure, shape and size of the synthesized composites of TiO2/WO3. Methylene blue is used as a test dye to analyze the photocatalytic properties of the synthesized composite material. The photocatalytic activity shows that the decomposition efficiency of the dye due to the photocatalytic effect is the highest in the TiO2/ WO3 (3 wt%) composite, and the catalytic efficiency decreases sharply when the amount of WO3 is further increased. As the amount of WO3 added increases, dye-removal by adsorption occurs during centrifugation, instead of the decomposition of dyes by photocatalysts. Finally, TiO2/WO3 (3 wt%) composites are synthesized with various milling times. Experimental results show that the milling time has the best catalytic efficiency at 30 min, after which it gradually decreases. There is no significant change after 1 hour.

The coupling of two semiconducting materials is an efficient method to improve photocatalytic activity via the suppression of recombination of electron-hole pairs. In particular, the coupling between two different phases of TiO2, i.e., anatase and rutile, is particularly attractive for photocatalytic activity improvement of rutile TiO2 because these coupled TiO2 powders can retain the benefits of TiO2, one of the best photocatalysts. In this study, anatase TiO2 nanoparticles are synthesized and coupled on the surface of rutile TiO2 powders using a microemulsion method and heat treatment. Triton X-100, as a surfactant, is used to suppress the aggregation of anatase TiO2 nanoparticles and disperse anatase TiO2 nanoparticles uniformly on the surface of rutile TiO2 powders. Rutile TiO2 powders coupled with anatase TiO2 nanoparticles are successfully prepared. Additionally, we compare the photocatalytic activity of these rutile-anatase coupled TiO2 powders under ultraviolet (UV) light and demonstrate that the reason for the improvement of photocatalytic activity is microstructural.

F-containing TiO2 nanopowders are synthesized using simple wet processes (precipitation-based and hydrothermal) from ammonium hexafluorotitanate (AHFT, (NH4)2TiF6) as a precursor to apply as a photocatalyst for the degradation of rhodamine B (RhB). The surface properties of the prepared samples are evaluated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). The results confirm that the synthesized anatase TiO2 has sphere-like shapes, with numerous small nanoparticles containing fluorine on the surface. The photocatalytic activity of F-containing TiO2 compared with F-free TiO2 is characterized by measuring the degradation of RhB using a xenon lamp. The photocatalytic degradation of F-containing TiO2 exhibits improved photocatalytic activity, based on the positive effects of adsorbed F ions on the surface.

To improve photocatalytic performance, a PbS/ZnO/TiO2 nanotube catalyst was synthesized, and its surface characteristics and photocatalytic efficiency were investigated. The hybrid photocatalysts were produced by anodic oxidation and successive ionic layer adsorption and reaction(SILAR). The photocatalytic efficiency was evaluated using the dye degradation rate. The PbS/ZnO/TiO2 photocatalyst significantly enhanced the photocatalytic activity for dye degradation, which was ascribed to the synergistic effect of their better absorption of solar light and a decrease in the rate of excited electron-hole recombination.

메조포러스 공극구조를 갖는 광촉매 멤브레인은 다양한 환경기술에 적용될 수 있다. 본 연구에서는 TiO2 층을 형 성시킨 광촉매 반응기용 세라믹 멤브레인을 개발하고 이를 염색용액 처리에 적용하였다. 높은 공극률과 균질성을 지닌 TiO2 광촉매층을 그라프트 공중합체를 사용하여 제조하였다. 멤브레인은 광촉매 반응기와 멤브레인 여과를 결합시킨 하이브리드 광촉매 반응기에 성공적으로 적용하였다. 실험결과 정렬된 구조의 TiO2 층이 Al2O3 지지체에 형성되었다. TiO2 층 형성 후 제조된 세라믹 분리막의 순수 투과도는 형성된 광촉매 층 저항으로 감소하였다. 정렬된 구조의 TiO2 층은 UV 결합 시 5시간 안에 완벽한 염색용액 분해를 달성시킬 수 있었다. 광촉매 멤브레인의 염색용액 분해는 Langmuir-Hinshelwood 흡착 모델로 잘 설명할 수 있었다. 또한 TiO2 층이 고정화된 세라믹 멤브레인의 model Congo Red에 대한 1차 속도상수는 Al2O3 지지체 단독인 경우에 비해 약 6배 정도 큰 값을 나타내었다(0.0081 vs. 0.0013 min-1).

본 연구에서는 TiO2 nanotube 광촉매의 고도산화처리능을 비교하기 위해서 OH 라디칼 생성 력을 평가하고자 하였다. 자외선 조사에 따른 Probe compound인 4-Chlorobenzoic acid (pCBA)의 농 도 감소에 따라 OH radical 생성량을 산정하는 방법으로 광촉매 효율을 평가하였는데, TiO2 nanotube 표면에서의 전자의 흐름을 원활하게 하기 위하여 전기적 에너지를 주었을 시 광촉매 효율의 증가 가능 성 또한 확인하고자 자외선 조사 시 전류밀도를 인가하는 방법으로 실험을 진행하였다. 실험에 사용된 TiO2 nanotube는 전극효과를 부여하기 위해 양극산화법으로 티타늄판을 이용하여 제조하였으며, pCBA 용액에는 전도도를 부여하기 위하여 NaCl을 첨가하여 전해질로 사용하였다. 정전류 정전압 조건하에서 자외선조사 실험을 진행하였으며, 전류가 흐르는 광촉매에 자외선 조사 시 OH 라디칼 생성량은 광촉매 없이 자외선만 조사하였을 때에 비해 약 5.6배, TiO2 광촉매와 함께 자외선을 조사하였을 보다 약 2.2 배 증가하였다. 결과적으로 광촉매반응에 전기적 에너지를 부여하였을 시 시너지효과를 가져올 수 있는 가능성을 확인할 수 있었다.

A TiO2/CNT nanohybrid photocatalyst is synthesized via sol-gel route, with titanium (IV) isopropoxide and multi-walled carbon nanotubes (MWCNTs) as the starting materials. The microstructures and phase constitution of the nanohybrid TiO2/CNT (0.005wt%) samples after calcination at 450oC, 550oC and 650oC in air are compared with those of pure TiO2 using field-emission scanning electron microscopy and X-ray diffraction, respectively. In addition, the photocatalytic activity of the nanohybrid is compared with that of pure TiO2 with regard to the degradation of methyl orange under visible light irradiation. The TiO2/CNT composite exhibits a fast grain growth and phase transformation during calcination. The nanocomposite shows enhanced photocatalytic activity under visible light irradiation in comparison to pure TiO2 owing to not only better adsorption capability of CNT but also effective electron transfer between TiO2 and CNTs. However, the high calcination temperature of 650oC, regardless of addition of CNT, causes a decrease in photocatalytic activity because of grain growth and phase transformation to rutile. These results such as fast phase transformation to rutile and effective electron transfer are related to carbon doping into TiO2.

TiO2 nanoparticles were synthesized by a sol-gel process using titanium tetra isopropoxide as a precursor at room temperature. Ag-doped TiO2 nanoparticles were prepared by photoreduction of AgNO3 on TiO2 under UV light irradiation and calcinated at 400 oC. Ag-doped TiO2 nanoparticles were characterized for their structural and morphological properties by Xray diffractometry (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and transmission electron microscopy (TEM). The photocatalytic properties of the TiO2 and Ag-doped TiO2 nanoparticles were evaluated according to the degree of photocatalytic degradation of gaseous benzene under UV and visible light irradiation. To estimate the rate of photolysis under UV (λ = 365 nm) and visible (λ ≥ 410 nm) light, the residual concentration of benzene was monitored by gas chromatography (GC). Both undoped/doped nanoparticles showed about 80 % of photolysis of benzene under UV light. However, under visible light irradiation Ag-doped TiO2 nanoparticles exhibited a photocatalytic reaction toward the photodegradation of benzene more efficient than that of bare TiO2. The enhanced photocatalytic reaction of Ag-doped TiO2 nanoparticles is attributed to the decrease in the activation energy and to the existence of Ag in the TiO2 host lattice, which increases the absorption capacity in the visible region by acting as an electron trapper and promotes charge separation of the photoinduced electrons (e−) and holes (h+). The use of Ag-doped TiO2 nanoparticles preserved the option of an environmentally benign photocatalytic reaction using visible light; These particles can be applicable to environmental cleaning applications.

10 wt.% and 20 wt.%Li-TiO2 composite powders are synthesized by a sol-gel method using titanium isopropoxide and Li2CO3 as precursors. The as-received amorphous 10 wt.%Li-TiO2 composite powders crystallize into the anatase-type crystal structure upon calcination at 450oC, which then changes to the rutile phase at 750oC. The asreceived 20 wt%Li-TiO2 composite powders, on the other hand, crystallize into the anatase-type structure. As the calcination temperature increases, the anatase TiO2 phase gets transformed to the LiTiO2 phase. The peaks for the samples obtained after calcination at 900oC mainly exhibit the LiTiO2 and Li2TiO3 phases. For a comparison of the photocatalytic activity, 10 wt.% and 20 wt.% Li-TiO2 composite powders calcined at 450oC, 600oC, and 750oC are used. The 20 wt.%Li-TiO2 composite powders calcined at 600oC show excellent efficiency for the removal of methylorange

The potential use of UV-TiO2 photocatalytic oxidation absorbent reactor in the removal of gaseous formaldehyde was studied. This study was conducted inside a bench-type circulation reactor chamber at ambient air conditions. PCO (Photocatalytic Oxidaion) degradation test for formaldehyde was done repeatedly and the average was reported. It was evident that photocatalytic oxidation was proven to be an effective method to control indoor air pollutants, like formaldehyde in indoor air. However, by-products are produced in the case of formaldehyde degradation also CO2, CO, H2O and formic acid are produced. These by-products can inhibit the active site of the photocatalyst. Thus, addition of adsorbent succeeding the PCO-TiO2, acts as a secondary treatment wherein produced by-products from the degradation and unreacted HCHO will adhere to the surface of the adsorbent. In this study, synthetic zeolite and activated carbon pellets were used to control of by-products of formaldehyde. PCOTiO2 degradation alone achieves 86% for a period of 60 minutes. Addition of adsorbent improves the removal efficiency achieving 90% and 96% using activated carbon pellet and zeolite, respectively.

To synthesize a high-performance photocatalyst, N doped TiO2 nanotubes deposited with Ag nanoparticles were synthesized, and surface characteristics, electrochemical behaviors, and photocatalytic activity were investigated. The TiO2 nanotubular photocatalyst was fabricated by anodization; the Ag nanoparticles on the TiO2 nanotubes were synthesized by a reduction reaction in AgNO3 solution under UV irradiation. The XPS results of the N doped TiO2 nanotubes showed that the incorporated nitrogen ions were located in interstitial sites of the TiO2 crystal structure. The N doped titania nanotubes exhibited a high dye degradation rate, which is effectively attributable to the increase of visible light absorption due to interstitial nitrogen ions in the crystalline TiO2 structure. Moreover, the precipitated Ag particles on the titania nanotubes led to a decrease in the rate of electron-hole recombination; the photocurrent of this electrode was higher than that of the pure titania electrode. From electrochemical and dye degradation results, the photocurrent and photocatalytic efficiency were found to have been significantly affected by N doping and the deposition of Ag particles.

The most general photocatalyst, TiO2 and WO3, are acknowledged to be ineffective in range of visible light. Therefore, many efforts have been directed at improving their activity such as: band-gap narrowing with non-metal element doping and making composites with high specific surface area to effectively separate electrons and holes. In this paper, the method was introduced to prepare a photo-active catalyst to visible irradiation by making a mixture with TiO2 and WO3. In the TiO2-WO3 composite, WO3 absorbs visible light creating excited electrons and holes while some of the excited electrons move to TiO2 and the holes remain in WO3. This charge separation reduces electron-hole recombination resulting in an enhancement of photocatalytic activity. Added Ag plays the role of electron acceptor, retarding the recombination rate of excited electrons and holes. In making a mixture of TiO2-WO3 composite, the mixing route affects the photocatalytic activity. The planetary ball-mill method is more effective than magnetic stirring route, owing to a more effective dispersion of aggregated powders. The volume ratio of TiO2(4) and WO3(6) shows the most effective photocatalytic activity in the range of visible light in the view point of effective separation of electrons and holes.

가시광선에 감응하는 광촉매를 제조하기 위하여 TiO2에 질소(N)를 도핑하여 N-TiO2를 제조하였다. 제조한 광촉매의 결정성, 입자 형상 및 도핑 상태는 XRD, FE-SEM 및 XPS를 이용하여 조사하였다. 제조한 광촉매의 활성 평가는 메틸렌블루의 광분해로 조사하였다. 제조한 광촉매는 anatase type이었으며, pH가 높을수록 결정화도가 향상되었다. 제조한 광촉매의 입자 크기는 pH 2.0에서 5.42 nm, pH 4.7에서 5.99 nm, pH 9.0에서 7.58 nm로, 입자 크기는 pH가 증가 할수록 약간씩 증가하였다. 광촉매의 활성은 결정화도에 비례하였다. TiO2에 N를 도핑하여 제조한 N-TiO2가 가시광선 하에서도 활성을 나타냈다. TiO2에 도핑한 N는 격자 속에 존재하는 것이 아니라 표면에 존재하였다.