Semiconductor-based photocatalytic carbon dioxide ( CO2) reduction is of great scientific importance in the field of alleviating global warming and energy crisis. Surface amine modification and cocatalyst loading on the catalyst surface could improve CO2 adsorption capacity and photogenerated charge separation. Herein, amine-modified brookite–TiO2 ( NH2–B–TiO2) coupled metal species (Cu, Ag, Ni(OH)2) cocatalysts have been successfully synthesized by chemical reduction method. The photocatalytic CO2 reduction results show that the CH4 production rates of NH2– B–TiO2/Cu, NH2– B–TiO2/Ag, and NH2– B–TiO2/Ni(OH)2 are 3.2, 12.5, and 1.7 times that of NH2– B–TiO2 (0.74 μmmol g− 1 h− 1), respectively. Results show the introduction of metal species on the surface of the catalyst enhances the absorption range of sunlight and the photogenerated carrier separation efficiency, resulting in enhancing the performance of photocatalytic CO2 reduction. This work provides a strategy for designing metal species-loaded amine-modified brookite–TiO2 by surface/interface regulation to improve photocatalytic efficiency.

The conversion of CO2 into solar fuels by photocatalysis is a promising way to deal with the energy crisis and the greenhouse effect. The introduction of oxygen vacancy into semiconductor has been proved to be an effective strategy for enhancing CO2 photoreduction performance. Herein, TiO2- x nanostructures have been prepared by a simple solvothermal method and engineered by the reaction time. With the prolonging of reaction time, the oxygen vacancy signal gradually increases while the band gap becomes narrow for the as-synthesized TiO2- x nanostructures. The results show that the TiO2- x-6 h, TiO2- x-24 h, and TiO2- x-48 h samples have the main product of CH4 (more) and CO (less) for CO2 photoreduction. Among the three oxygen vacancy photocatalysts, the TiO2- x-24 h sample shows the highest CH4 generation rate of 41.8 μmol g− 1 h− 1. On the basis of photo/electrochemical measurements, the TiO2- x-24 h sample exhibits efficient electron–hole separation and charge transfer capabilities, thus allows much more electrons to participate in the reaction and finally promotes the photocatalytic CO2 reduction reaction. It further confirms that the optimization of oxygen vacancy concentration could facilitate the photoinduced charge separation and accordingly improve photocatalytic CO2 conversion.

Interest in the use of semiconductor-based photocatalyst materials for the degradation of organic pollutants in a liquid phase has grown, due to their excellent performance and response to the light source. Herein, we fabricated a NiO-SiCTiO2 ternary structured photocatalyst which had reduced bandgap energy, with strong activation under UV-light irradiation. The synthesized samples were examined using XRD, SEM, EDX, TEM, DRS, EIS techniques and photocurrent measurement. The results confirmed that the two types of metal oxides were well bonded to the SiC fiber surface. The junction of the new photocatalyst exhibited a large number of photoexcited electrons and holes. The holes tended to oxidize the water and form a hydroxyl radical, which promoted the decomposition of methylene blue. The close contact between the 2D SiC fiber and metal oxide semiconductors expanded the scope of absorption wavelength, and enhanced the usability of the ternary photocatalyst for the degradation of methylene blue. Among three synthesized samples, the NiO-SiC-TiO2 showed the best photocatalytic effect, and was considered to have excellent photoelectron transfer due to the synergy effect between the metal oxide and SiC.

To build a highly active photocatalytic system with high efficiency and low cast of TiO2, we report a facile hydrothermal technique to synthesize Ag2Se-nanoparticle-modified TiO2 composites. The physical characteristics of these samples are analyzed by X-ray diffraction, scanning electron microscopy with energy dispersive X-ray analysis, transmission electron microscopy and BET analysis. The XRD and TEM results show us that TiO2 is coupled with small sized Ag2Se nanoplate, which has an average grain size of about 30 nm in diameter. The agglomeration of Ag2Se nanoparticles is improved by the hydrothermal process, with dispersion improvement of the Ag2Se@TiO2 nanocomposite. Texbrite BA-L is selected as a simulated dye to study the photodegradation behavior of as-prepared samples under visible light radiation. A significant enhancement of about two times the photodegradation rate is observed for the Ag2Se@TiO2 nanocomposite compared with the control sample P25 and as-prepared TiO2. Long-term stability of Ag2Se@TiO2 is observed via ten iterations of recycling experiments under visible light irradiation.

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.

Transparent, photocatalytic, and self-cleaning TiO2 thin film is developed by TiO2 sol-gel coating on glass and polycarbonate (PC) substrates. Acetyl acetone (AcAc) suppresses the precipitation of TiO2 by forming a yellowish (complex) transparent sol-gel. XPS analysis confirms the presence of Ti2p and O1s in the thin films on glass and PC substrates. The TiO2- sol is prepared by stabilizing titanium (IV) isopropoxide (TTIP) with diethylamine and methyl alcohol. The addition of AcAcsilane coupling solution to the TiO2-sol instantaneously turns to yellowish color owing to the complexing of titanium with AcAc. The AcAc solution substantially improves the photocatalytic property of the TiO2 coating layer in MB solutions. The coated TiO2 film exhibits super hydrophilicity without and with light irradiation. The TiO2 thin film stabilized by adding 8.7 wt% AcAc shows the highest photo-degradation for methylene blue (MB) solution under UV light irradiation. Also, the optimum photocatalytic activity is obtained for the 8.7 wt% AcAc-stabilized TiO2 coating layer calcined at 450 oC. The thin-films on glass exhibit fast self-cleaning from oleic acid contamination within 45 min of UV-light irradiation. The appropriate curing time at 140 oC improves the anti-fogging and thermal stability of the TiO2 film coated on PC substrate. The watermark-free PC substrate is particularly beneficial to combat fogging problems of transparent substrates.

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.

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.

Self-cleaning and photocatalytic TiO2 thin films were prepared by a facile sol-gel method followed by spin coating using peroxo titanic acid as a precursor. The as-prepared thin films were heated at low temperature(110 °C) and high temperature (400 °C). Thin films were characterized by X-ray diffraction(XRD), Field-emission scanning electron microscopy(FESEM), UVVisible spectroscopy and water contact angle measurement. XRD analysis confirms the low crystallinity of thin films prepared at low temperature, while crystalline anatase phase was found the for high temperature thin film. The photocatalytic activity of thin films was studied by the photocatalytic degradation of methylene blue dye solution. Self-cleaning and photocatalytic performance of both low and high temperature thin films were compared.

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.

The formation mechanism and photocatalytic properties of a multiwalled carbon nanotube (MWCNT)/TiO2- based nanotube (TNTs) composite are investigated. The CNT/TNT composite is synthesized via a solution chemical route. It is confirmed that this 1-D nanotube composite has a core-shell nanotubular structure, where the TNT surrounds the CNT core. The photocatalytic activity investigated based on the methylene blue degradation test is superior to that of with pure TNT. The CNTs play two important roles in enhancing the photocatalytic activity. One is to act as a template to form the core-shell structure while titanate nanosheets are converted into nanotubes. The other is to act as an electron reservoir that facilitates charge separation and electron transfer from the TNT, thus decreasing the electronhole recombination efficiency.

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.

To improve photocatalytic efficiency, graphene/Ag/TiO2 nanotube catalyst was synthesized, and its surface characteristics and photocatalytic activity investigated. For deposition of Ag nanoparticles on the TiO2 nanotubes, a polymer compound containing CH3COOAg/poly(Llactide) was utilized, and the silver particles were precipitated by reducing the silver ions during the annealing process. Graphene deposition on the Ag/TiO2 nanotubes was achieved using an electrophoretic deposition process. Based on the dye degradation results, it was determined that the photocatalytic efficiency was significantly affected by deposition of silver particles and graphene on the TiO2 catalyst. Highly efficient destruction of the dye was obtained with the new graphene/Ag/TiO2 nanotube photocatalyst. This may be attributed to a synergistic effect of the graphene and Ag nanoparticles on the TiO2 nanotubes.

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.