Photocatalytic Activities of Boron Doped Titanium Dioxide Nanoparticles and its Composite with Polyaniline

Abstract

Titanium dioxide (TiO₂) was doped with a nonmetalic element, boron (B), and the boron doped TiO₂ (B-TiO₂) was combined with polyaniline (Pani) through an in-situ polymerization technique. The photocatalytic activity of the prepared samples was monitored by the degradation of methylene blue under UV light irradiation. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy were used to reveal the effect of boron doping on the crystalline and chemical structure of the photocatalyst, respectively. The morphological and elemental compositional characteristics of the samples were evaluated using field emission scaning electron microscopy (FE-SEM) and energy dispersive x-ray analysis. The optical band gap energy of the prepared samples was obtained by UV-Visible (UV-Vis) spectroscopy. B-TiO₂ exhibited enhanced photocatalytic performance compared to the undoped photocatalyst. Furthermore, compared with TiO₂ and B-TiO₂, Pani/B-TiO₂ displayed superior photocatalytic activity. The composite achieved almost 26% methylene blue degradation within 150?minutes. Although the boron doping enhanced the crystallinity of TiO₂ slightly, it did not affect the morphology. FTIR confirmed the presence of tri-coordinated interstitial boron in the Ti–O–B bonds. The UV-Vis spectra displayed a red shift with the incorporation of the boron atoms. The incorporation of the boron atoms in the TiO₂ crystal structure are suggested to promote the separation of the photoinduced electron-hole pairs, a possible reason for the enhanced photocatalytic activity. B-TiO₂ and its composite with polyaniline could be considered as a promising photocatalyst to remove organic dyes from the wastewater.     

Design and fabrication of a TiO2/nano-silicon composite visible light photocatalyst

Nano-silicon (nc-Si) was utilized as the charges generator to promote the photocatalytic and super-hydrophilic reactivity of TiO₂ film under visible light irradiation. The photocatalytic ability of TiO₂/nc-Si composite photocatalyst was evaluated by a set of experiments to photodecompose 100 ppm methylene blue (MB) in aqueous solution. And the super-hydrophilic property was characterized by measuring the water droplet contacts angle, under visible light irradiation in atmospheric air and at room temperature. Under 100 mW/cm² visible light irradiation, the droplet contact angles were reduced to 0° within 4 h with nc-Si charge generator. Additionally, the rate constant of MB photo-degradation was promoted 6.6 times.     

Nanotitania-coated multi-walled carbon nanotube composite by facile colloidal processing route for photocatalytic applications

Multi-walled carbon nanotubes (MWCNTs) and titanium dioxide nanocomposites (MWCNTs/TiO₂) were fabricated by a simple novel colloidal processing route and tested as a photocatalyst for degradation of methylene blue under UV irradiation. The novel idea behind this work is to make MWCNTs and TiO₂ nanoparticle suspensions separately highly oppositely charged and utilize the electrostatic force of attraction between two entities to deposit nanotitania onto MWCNTs surface. Particle charge detector, scanning electron microscopy, transmission electron microscope, energy dispersive X-rays, X-rays diffraction (XRD), and Raman spectroscopy were used to characterize the composite. XRD and Raman spectroscopic analysis showed the crystalline structure of deposited TiO₂ over MWCNTs surface structure as anatase phase. It was found that MWCNTs/TiO₂ composite structure have much higher photocatalytic activity compared to TiO₂ nanoparticles. The composite material developed may find potential applications in the degradation of organic pollutants in aqueous medium under UV irradiation.     

Characterization and activity of visible-light-driven TiO2 photocatalyst codoped with lanthanum and iodine

The novel visible-light-activated La/I/TiO₂ nanocomposition photocatalyst was successfully synthesized using precipitation-dipping method, and characterized by X-ray powder diffraction (XRD), the Brunauer-Emmett-Teller (BET) method, transmission electron microscopy (TEM), thermogravimetry-differential scanning calorimetry (TG-DSC) and UV-vis diffuse reflectance spectroscopy (UV-vis DRS). The photocatalytic activity of La/I/TiO₂ was evaluated by studying photodegradation of reactive blue 19 as a probe reaction under simulated sunlight irradiation. Photocatalytic experiment results showed that the maximum specific photocatalytic activity of the La/I/TiO₂ photocatalyst appeared when the molar ratio of La/Ti was 2.0 at%, calcined at 350 °C for 2 h, due to the sample with good crystallization, high BET surface area and small crystal size. Under simulated sunlight irradiation, the degradation of reactive blue 19 aqueous solution reached 98.6% in 80 min, which showed La/I/TiO₂ photocatalyst to be much higher photocatalytic activity compared to standard Degussa P25 photocatalyst. The higher visible light activity is due to the codoping of lanthanum and iodine.     

Preparation, characterization and visible-light photocatalytic activity of AgI/AgCl/TiO2

In this paper, a novel composite photocatalyst AgI/AgCl/TiO₂ was prepared by ion exchange method and characterized by XRD, SEM and UV-Vis spectrometry. The as-prepared AgI/AgCl/TiO₂ composites show much higher photocatalytic activity than AgCl/TiO₂ and AgI/TiO₂ under visible-light irradiation (λ > 400 nm) in the process of methyl orange (MO) degradation. When the molar percentage of AgI to initial AgCl is 20% (sample SE-20%), the maximal degradation efficiency of MO has reached 85.8% after irradiation for 120 min. The enhancement of photocatalytic activity of the composite photocatalyst AgI/AgCl/TiO₂ will be attributed to its good absorption in the visible-light region, especially low recombination rate of the electron-hole pairs based on the photoluminescence (PL) spectra investigation of AgI/AgCl/TiO₂ and the matching band structures of AgI, AgCl and TiO₂. The detection of reactive species by radical scavengers displays that O₂⁻ and H₂O₂ are the main reactive species for the degradation of MO under visible-light irradiation. Moreover, PL analysis by using terephthalic acid (TA) as a probe molecule further reveals that OH can be negligible for the degradation of MO.     

Efficient visible-light-induced photocatalytic degradation of MO on the Cr-nanocrystalline titania-S

In order to improve visible light photocatalytic activities of the nanometer TiO₂, a novel and efficient Cr,S-codoped TiO₂ (Cr-TiO₂-S) photocatalyst was prepared by precipitation-doping method. The crystalline structure, morphology, particle size, and chemical structure of Cr-TiO₂-S were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and Fourier transform infrared (FT-IR) techniques, respectively. Results indicate that the doping of Cr and S, cause absorption edge shifts to the visible light region (λ > 420 nm) compare to the pure TiO₂, reduces average size of the TiO₂ crystallites, enhances desired lattice distortion of Ti, promotes separation of photo-induced electron and hole pair, and thus improves pollutant decomposition under visible light irradiation. The photocatalytic activities of Cr-TiO₂-S nanoparticles were evaluated using the photodegradation of methyl orange (MO) as probe reaction under the irradiation of UV and visible light and it was observed that the Cr-TiO₂-S photocatalyst shows higher visible photocatalytic activity than the pure TiO₂. The optimal Cr-TiO₂-S concentration to obtain the highest photocatalytic activity was 5 mol% for both of Cr and S.     

Preparation and characterization of visible light responsive Fe2O3-TiO2 composites

In this study we present the effects of iron oxide (Fe₂O₃) on titanium dioxide (TiO₂) in synthesising visible-light reactive photocatalysts. A Fe₂O₃-TiO₂ composite photocatalyst was synthesized from Fe₂(SO₄)₃ and Ti(SO₄)₂ by a ethanol-assisted hydrothermal method. The preparation conditions were optimized through the investigation of the effects of hydrothermal temperature and time as well as molar ratio of Ti to Fe on the photocatalytic activity. The visual, physical and chemical properties of the Fe₂O₃-TiO₂ composites were investigated. The results showed that α-Fe₂O₃ and anatase TiO₂ were present in the composites. The Fe₂O₃-TiO₂ synthesized under optimum condition consisted of mesoporous structure with an average pore size of 4 nm and a surface area of 43 m²/g. Under visible and solar light irradiation, the photocatalytic activity of optimized sample was significantly higher than that of pure TiO₂. This sample led to a photodegradation efficiency of 90% and 40% of auramine under visible light and solar light, respectively.     

First-principles study on anatase TiO2 codoped with nitrogen and praseodymium

The crystal structures, electronic structures and optical properties of nitrogen or/and praseodymium doped anatase TiO₂ were calculated by first principles with the plane-wave ultrasoft pseudopotential method based on density functional theory. Highly efficient visible-light-induced nitrogen or/and praseodymium doped anatase TiO₂ nanocrystal photocatalyst were synthesized by a microwave chemical method. The calculated results show that the photocatalytic activity of TiO₂ can be enhanced by N doping or Pr doping, and can be further enhanced by N+Pr codoping. The band gap change of the codoping TiO₂ is more obvious than that of the single ion doping, which results in the red shift of the optical absorption edges. The results are of great significance for the understanding and further development of visible-light response high activity modified TiO₂ photocatalyst. The photocatalytic activity of the samples for methyl blue degradation was investigated under the irradiation of fluorescent light. The experimental results show that the codoping TiO₂ photocatalytic activity is obviously higher than that of the single ion doping. The experimental results accord with the calculated results.     

Study on the photocatalytic activity of TiN/TiO2 nanoparticle formed by ball milling

TiN/TiO₂ nanoparticle photocatalyst was prepared by ball milling of TiO₂ in H₂O solution doped with TiN. The photocatalyst was characterized by UV–Vis diffuse reflection spectroscopy, X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Based on the results of the characterization, the mechanism of the increase in photocatalytic activity was investigated. The results show that when the amount of doped TiN is 0.15 wt%, the photocatalytic activity of the TiN/TiO₂ is at its peak. Compared with TiO₂, the photoabsorption wavelength range of the TiN/TiO₂ photocatalyst red-shifts about 30 nm, and the photoabsorption intensity increases as well. The photocatalytic activities of the photocatalyst are higher than that of TiO₂ under UV and visible light irradiation. The increase of surface Ti³⁺ reactive center and the extension of the photoabsorption wavelength are the main factors for the increase in the photocatalytic activity of the TiN/TiO₂. Doped TiN neither changes the TiO₂ crystal phase nor creates new crystal phase by ball milling.     

Sonodegradation and photodegradation of methyl orange by InVO4/TiO2 nanojunction composites under ultrasonic and visible light irradiation

The InVO₄/TiO₂ nanojunction composites with different weight ratio of 1:10, 1:25, 1:50 and 1:100 were successfully constructed using an ion impregnate method, followed by calcining temperature 400 °C for 2 h in Ar. The sono- and photo-catalytic activities of the InVO₄/TiO₂ nanojunction composites were evaluated through the degradation of methyl orange (MO) in aqueous solution under ultrasonic and visible light irradiation, respectively. The experimental results determined that the (1:50) InVO₄/TiO₂ nanojunction composite has exhibited the highest sonocatalytic activity. It can be ascribed to vectorial charge transfer at the co-excited InVO₄/TiO₂ interface under ultrasonic irradiation, results in the complete separation of electrons and holes. Interestingly, the (1:25) InVO₄/TiO₂ nanojunction composite displayed superior photocatalytic activity for MO degradation under visible light, indicating that InVO₄ as a narrow band gap sensitizer can expand photocatalytic activity of TiO₂ to visible region, and the charge transfer can be formed from high energy level of InVO₄ conduction band to the low energy level of TiO₂ conduction band in a present of excited InVO₄ alone under visible light irradiation. The sono- and photo-catalytic activities of the InVO₄/TiO₂ nanojunction composites were found to be dependent significantly on different InVO₄ contents, which can be explained by the influence of charge transfer on the basis of the work functions of different catalysis mechanism.     

10BaF2:NaF, Na3AlF6/TiO2 composite as a novel visible-light-driven photocatalyst based on upconversion emission

A rare-earth free upconversion luminescent material, 10BaF2：NaF, Na3AIF6, is synthesized by a hydrothermal method. The study of fluorescent spectrum indicates that it can convert visible light （550 nm-610 nm） into ultraviolet light （290 nm 350 nm）, and two emission peaks at 304 nm and 324 nm are observed under the excitation of 583 nm at room temperature. Subsequently, 10BaF2：NaF, Na3AIF6/TiO2 composite photocatalyst is prepared and its catalytic activity is evaluated by the photocatalytic reduction of CO2 under visible light irradiation （λ〉 515 nm）. The results show that 10BaF2：NaF, Na3AIF6/TiO2 is a more effective photocatalyst for CO2 reduction than pure TiO2, their corresponding methanol yields are 179 and 0 μmol/g-cat under the same conditions. Additionally, the mechanism of photocatalytic reduction of CO2 on 10BaF2：NaF, Na3AIF6/TiO2 is proposed.     

臭氧修饰(001)晶面TiO2纳米片及其光催化降解甲苯研究

本文系统研究了臭氧修饰对(001)主导晶面锐钛矿型TiO₂光催化剂降解甲苯性能的影响. 利用自行搭建的光催化VOCs降解装置对催化剂光降解甲苯的性能进行了测试. 通过多种表征手段,结合原位DRIFTS和DFT计算研究了臭氧表面修饰及甲苯吸附和降解机理. 结果表明,用臭氧进行表面修饰可以显著提高(001)主导晶面TiO₂光催化降解甲苯的性能. (001)晶面上丰富的5c-Ti不饱和配位是臭氧分子的吸附位点,其解离后形成的Ti-O键与H₂O分子结合,在表面生成大量孤立的Ti_5c-OH. Ti_5c-OH 是甲苯分子的吸附位,它的形成显著提高了对甲苯分子的吸附能力. 在光照下Ti_5c-OH与光生空穴结合能形成·OH自由基. 通过臭氧解离产生的O₂也可以与光生电子结合形成超氧自由基. 这些具有强氧化性活性自由基的形成促进了对气相甲苯的光催化降解速率.     

IR and XPS investigation of visible-light photocatalysis—Nitrogen-carbon-doped TiO2 film

To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Nitrogen and carbon doping TiO_2−x−yN_xC_y films were obtained by heating the TiO₂ gel in an ionized N₂ gas and then were calcined at 500 °C. The TiO_2−x−yN_xC_y films have revealed an improvement over the TiO₂ films under visible light (wavelength, 500 nm) in optical absorption and photocatalytic activity such as photodegradation of methyl orange. X-ray photoemission spectroscopy, infrared spectrum and UV-visible (UV-vis) spectroscopy were used to find the difference of two kinds of films. Nitrogen and carbon doped into substitutional sites of TiO₂ has been proven to be indispensable for band-gap narrowing and photocatalytic activity.     

Synthesis of a magnetically separable composite photocatalyst with high photocatalytic activity under sunlight

A novel magnetically separable composite photocatalyst (N-doped titania-coated γ-Fe₂O₃ magnetic activated carbon) was prepared. It consists of N-doped titania, activated carbon and γ-Fe₂O₃. The whole processes were carried out under low temperature. The prepared sample was characterized by XRD, DRS, SEM, BET and vibrating sample magnetometer (VSM). The photocatalytic activity was determined by degradation of Reactive Brilliant Red X-3B in an aqueous solution under solar irradiation. Results showed that this as-prepared composite photocatalyst exhibited much higher photocatalytic activity than Degussa P25. Furthermore, the photocatalyst can be separated easily by an external magnetic field. Thus, the photocatalyst can be recycled without mass losing, and the degradation percent of X-3B decreased less than 2% after six cycles.     

Assembly,characterization, and photocatalytic activities of TiO<Subscript>2</Subscript> nanotubes/CdS quantum dots nanocomposites

The semiconductor quantum dots (QDs) can be very efficient to tune the response of photocatalyst of TiO₂ to visible light. In this study, CdS QDs formed in situ with about 8 nm have been successfully deposited onto the surfaces of TiO₂ nanotubes (TNTs) to form TNTs/CdS QDs nanocomposites by use of a simple bifunctional organic linker, thiolactic acid. The diffuse reflectance spectroscopy (DRS) spectra of as prepared samples showed that the absorption edge of the TNTs/CdS composite is extended to visible range, with absorption edge at 530 nm. The photocatalytic activity and stability of TNTs/CdS were also evaluated for the photodegradation of rhodamine B. The results showed that when TNTs/CdS QDs was used, photocatalytic degradation of RhB under visible light irradiation reached 91.6%, higher than 45.4 and 30.5% for P25 and TNTs, respectively. This study indicated that the TNTs/CdS QDs nanocomposites were superior catalysts for photodegradation under visible light irradiation compared with TNTs and P25 samples, which may find wide application as a powerful photocatalyst in environmental field.     

Visible-light-driven titania photocatalyst co-doped with nitrogen and ferrum

Nitrogen and ferrum co-doped titania photocatalyst was prepared by the sol-gel route. The prepared photocatalyst was characterized by various techniques including X-ray diffraction (XRD), UV-vis diffusive reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), and N₂ adsorption-desorption isotherm. The photocatalytic activity of the co-doped titania photocatalyst was evaluated by the degradation of methyl orange (MO) from aqueous solution under visible light irradiation and was compared with that of the commercial TiO₂ photocatalyst (Degussa P25). The results revealed that the nitrogen doping could lead to the response to visible light and that the ferrum doping could improve the photocatalytic performance. The effects of the component and the annealing temperature of the co-doped titania photocatalyst on the photocatalytic activity were investigated.     

Investigation of photocatalytic reaction for thetitanium dioxide-phosphor composite

The present study examined the photocatalytic reaction of titanium dioxide (TiO₂)-coated, phosphor composite particles. Nanocrystalline TiO₂ layers were directly coated on the alkaline earth aluminate phosphor (CaAl₂O₄:Eu²⁺,Nd³⁺) particles by a sol-gel processing method and their photocatalytic reaction was analyzed according to the degradation of methylene blue aqueous solution under visible light irradiation. Compared with pure TiO₂, the TiO₂-coated phosphor powders showed a different photocatalytic mechanism and much faster photocatalytic reactivity under visible irradiation than that of pure TiO₂, which was almost negligible. The mechanism of the photocatalytic reactivity for the TiO₂-phosphor composite was discussed in terms of the energy band structure and phosphorescence. In addition, the TiO₂-coated phosphor powders were characterized by X-ray diffraction and transmission electron microscopy.     

CuAPTPP-TDI-TiO2光催化微球的合成及其光催化性能 (cited: 1)

采用Adler法合成了5-(4-氨基苯基)-10,15,20-三苯基卟啉铜配合物(CuAPTPP),通过甲苯二异氰酸酯(TDI)的桥联作用对TiO₂微球进行表面修饰,使TDI分子中的两个活性TDI基团分别与TiO₂表面的羟基和CuAPTPP的氨基反应,将CuAPTPP敏化剂分子以化学键合的方式固定在TiO₂表面,形成光催化微球CuAPTPP-TDI-TiO₂．通过FT-IR、XRD、SEM、EA、UV-Vis和DRS等测试手段对CuAPTPP-TDI-TiO₂进行结构表征．讨论了桥联分子TDI修饰量对光催化微球性能的影响,确定了TDI与TiO₂的最佳摩尔比．以亚甲基蓝(MB)为降解对象,考察了CuAPTPP-TDI-TiO₂微球的可见光催化性能．结果表明,桥联分子TDI在CuAPTPP与TiO₂微球表面形成了牢固的化学键,复合微球在150 W氙灯辐照下降解10 mg/LMB溶液,120 min降解率可达98.7%,其降解率过程服从一级动力学规律,测得降解速率常数为5.1×10^-2 min^-1,半衰期为11.3 min．催化微球在回收4次的条件下,对MB的降解率仍保持在90%以上．     

Enhanced photocatalytic activity of graphene–TiO2 composite under visible light irradiation

Novel graphene–TiO₂ (GR–TiO₂) composite photocatalysts were synthesized by hydrothermal method. During the hydrothermal process, both the reduction of graphene oxide and loading of TiO₂ nanoparticles on graphene were achieved. The structure, surface morphology, chemical composition and optical properties of composites were studied using XRD, TEM, XPS, DRS and PL spectroscopy. The absorption edge of TiO₂ shifted to visible-light region with increasing amount of graphene in the composite samples. The photocatalytic degradation of methyl orange (MO) was carried out using graphene–TiO₂ composite catalysts in order to study the photocatalytic efficiency. The results showed that GR–TiO₂ composites can efficiently photodegrade MO, showing an enhanced photocatalytic activity over pure TiO₂ under visible-light irradiation. The enhanced photocatalytic activity of the composite catalysts might be attributed to great adsorptivity of dyes, extended light absorption range and efficient charge separation due to giant π-conjugation system and two-dimensional planar structure of graphene.     

TiO2/carboxylate-rich porous carbon: A highly efficient visible-light-driven photocatalyst based on the ligand-to-metal charge transfer (LMCT) process

A novel visible-light-driven photocatalyst based on TiO₂/carboxylate-rich porous carbon composite (TiO₂/CRPC) was successfully synthesized by low temperature carbonization process in air. Sodium gluconate plays a crucial role in the formation of TiO₂/CRPC. Different functional groups of sodium gluconate play synergetic roles in the formation of TiO₂/CRPC. XRD and Raman spectra studies indicated that there are two different TiO₂ crystalline phases existing in TiO₂/CRPC, which are anatase and brookite, and the CRPC is amorphous. Via FT-IR and XPS spectra investigations, it was demonstrated that carboxylate group, the ligand-to-metal charge transfer (LMCT) forming functional group, was solidified into the CRPC and form the LMCT complex on TiO₂ surface through the fabrication of TiO₂/CRPC. Compared with the pure TiO₂, TiO₂/CRPC exhibit enhanced absorption in the UV and visible light region around 260–600 nm. The strong absorption in the visible light region gives TiO₂/CRPC advantages over pure TiO₂ for the degradation of organic pollutants. TiO₂/CRPC can activate O₂ in air under mild conditions and exhibit excellent visible-light-driven photocatalytic activities. However, TiO₂/C composite obtained by using glucose instead of sodium gluconate exhibits poor photocatalytic activity, which demonstrated that carboxylate–TiO₂ complexes are responsible for the prominent photocatalytic properties of TiO₂/CRPC under visible light irradiation.