Plasmon-resonance-enhanced visible-light photocatalytic activity of Ag quantum dots/TiO2 microspheres for methyl orange degradation

We successfully prepared Ag quantum dots modified TiO₂ microspheres by facile solvothermal and calcination method. The as-prepared Ag quantum dots/TiO₂ microspheres were characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The Ag quantum dots/TiO₂ photocatalyst showed excellent visible light absorption and efficient photocatalytic activity for methyl orange degradation. And the sample with the molar ratio of 0.05 (Ag to Ti) showed the best visible light photocatalytic activity for methyl orange degradation, mainly because of the surface plasmon resonance (SPR) effects of Ag quantum dots to generate electron and hole pairs for enhanced visible light photocatalysis. Finally, possible visible light photocatalytic mechanism of Ag quantum dots/TiO₂ microspheres for methyl orange degradation was proposed in detail.     

Solar photocatalytic activities of porous Nb-doped TiO2 microspheres prepared by ultrasonic spray pyrolysis

Ultrasonic spray pyrolysis method was used to prepare Nb-doped TiO₂ porous microspheres with an average diameter of 500 nm for solar photocatalytic applications. The effect of Nb-doping on morphology, structure, surface area, as well as spectral absorption properties of TiO₂ microspheres was investigated with SEM, TEM, XRD, Raman spectra, BET, and UV-Vis absorption spectra. The Nb-doping decreased the grain size of TiO₂ porous microsphere, and influenced its surface area and pore size distribution dependent on the doping concentration, but changed negligibly the morphology and size of TiO₂ microspheres. Moreover, the Nb-doping was observed to extend the spectral absorption of TiO₂ into visible spectrum, and the absorption onset was red-shifted for about 88 nm at a doping level of 5% compared to pristine TiO₂ microspheres. Under solar or visible irradiation, Nb-doped TiO₂ microspheres showed higher photocatalytic activity for methylene blue degradation compared with TiO₂ microspheres, which could be ascribed to the extended light absorption range and the suppression of electron-hole pair recombination.     

Synthesis of CuAPTPP-TDI-TiO2 Conjugated Microspheres and its Photocatalytic Activity (cited: 1)

The metal complex 5-(4-aminophenyl)-10,15,20-triphenylporphyrin copper (CuAPTPP) was covalently linked on the surface of TiO₂ microspheres by using toluene disocyanate (TDI) as a bridging bond unit. The hydroxyl group (-OH) of TiO₂ microspheres surface and the amino group (-NH₂) of CuAPTPP reacted respectively with the active -NCO groups of TDI to form a surface conjugated microsphere CuAPTPP-TDI-TiO₂ that was confirmed by FT-IR spectra. The CuAPTPP-TDI-TiO₂ microspheres were characterized with UV-visible, elemental analysis, XRD, SEM, and UV-Vis diffuse reflectance spectra. The effect of amounts of linked TDI on the performance of photocatalytic microspheres was discussed, and the optimal molar ratio of TDI:TiO₂ was established. The photocatalytic activity of CuAPTPP-TDI-TiO₂ was evaluated using the photocatalytic degradation of methylene blue (MB) under visible-light irradiation. The results showed that, TDI, as a bond unit, was used to form a steady chemical brigdging bond linking CuAPTPP and the surface of TiO₂ microspheres, and the prepared catalyst exhibited higher photocatalytic activity under visible-light irradiation for MB degradation. The degradation rate of 20 mg/L MB could reach 98.7% under Xe-lamp (150 W) irradiation in 120 min. The degradation of MB followed the first-order reaction model under visible light irradiation, and the rate constant of 5.1×10^-2 min^-1 and the half-life of 11.3 min were achieved. And the new photocatalyst can be recycled for 4 times, remaining 90.0% MB degradation rate.     

Fluorinated Mesoporous Anatase TiO<Subscript>2</Subscript> Microspheres with High Surface and Enhanced Photocatalytic Activity for the Degradation of Methyl Orange

Highly crystalline mesoporous TiO₂ microspheres with areas up to 122 m²/g and tunable pore size have been prepared through a combined sol–gel and solvothermal processes. The concentration of NaF exhibits a great effect on the morphology, crystallinity, crystal size and photocatalytic activity of the TiO₂ microspheres. A higher NaF concentration results in an increase in the average crystal size and pore size, whereas whereas it caused a decrease in the specific surface areas. All fluorinated TiO₂ microspheres showed a higher photocatalytic activity than P25 and pure TiO₂ microspheres obtained in the absence of NaF due to the effect of surface fluorination on the photoactivity of TiO₂. The approach described in this study provides a simple method to synthesize the micrometer-sized hierarchical structure of mesoporous TiO₂ microspheres that are ready for practical applications such as environmental pollutants removal and solar cell because these high active materials can be easily separated.     

Control of Spatially Homogeneous Distribution of Heteroatoms to Produce Red TiO2 Photocatalyst for Visible-Light Photocatalytic Water Splitting

The strong band-to-band absorption of photocatalysts spanning the whole visible-light region (400–700 nm) is critically important for solar-driven photocatalysis. Although it has been actively and widely used as a photocatalyst for various reactions in the past four decades, TiO₂ has a very poor ability to capture the whole spectrum of visible light. In this work, by controlling the spatially homogeneous distribution of boron and nitrogen heteroatoms in anatase TiO₂ microspheres with a predominance of high-energy {001} facets, a strong visible-light absorption spectrum with a sharp edge beyond 680 nm has been achieved. The red TiO₂ obtained with homogeneous doping of boron and nitrogen shows no increase in defects like Ti³⁺ that are commonly observed in doped TiO₂. More importantly, it has the ability to induce photocatalytic water oxidation to produce oxygen under the irradiation of visible light beyond 550 nm and also the photocatalytic reduction of water to produce hydrogen under visible light. These results demonstrate the great promise of using red TiO₂ for visible-light photocatalytic water splitting and also reveal an attractive strategy for realizing the wide-spectrum visible-light absorption of wide-band-gap oxide photocatalysts.     

Ultrasonic Preparation of Hierarchical Graphene‐Oxide/TiO2 Composite Microspheres for Efficient Photocatalytic Hydrogen Production

Hierarchical graphene oxide (GO)‐TiO₂ composite microspheres with different GO/TiO₂ mass ratios were successfully prepared by mixing GO and TiO₂ microspheres under ultrasonic conditions. Ultrasonication helped the GO and TiO₂ microsphere to uniformly mix on the microscale. The results showed that the GO‐TiO₂ composites that were prepared by ultrasonic mixing exhibited significantly higher hydrogen‐evolution rates than those that were synthesized by simple mechanical grinding, owing to synergetic effects, including enhanced light absorption and scattering, as well as improved interfacial charge transfer because of the excellent contact between the GO sheets and TiO₂ microspheres. In addition, GO‐TiO₂‐3 (3 wt. % GO) showed the highest hydrogen‐generation rate (305.6 μmol h^?), which was about 13 and 3.3‐times higher than those of TiO₂ microsphere and GO‐P25 (with 3 wt. % GO), respectively. Finally, a tentative mechanism for hydrogen production is proposed and supported by photoluminescence and transient photocurrent measurements. This work highlights the potential applications of GO‐TiO₂ composite microspheres in the field of clean‐energy production.     

Defect induced nickel,nitrogen-codoped mesoporous TiO2 microspheres with enhanced visible light photocatalytic activity

Nickel, nitrogen-codoped mesoporous TiO₂ microspheres (Ni–N–TiO₂) with high surface area, and an effective direct band gap energy of ∼2.58 eV. Nickel sulfate used as the Ni source and ammonia gas as the N source here. The efficiency of the as-prepared samples was investigated by monitoring the degradation of Rhodamine B under visible light irradiation. The experimental results indicate that Ni-doped mesoporous TiO₂ microspheres show higher photocatalytic activity than mesoporous TiO₂ microspheres under visible light irradiation. It mainly due to that the electron trap level (Ni²⁺/Ni⁺) promoting the separation of charge carriers and the oxygen vacancies inducing the visible light absorption. In addition, Ni–N–TiO₂ shows enhanced activity compared with Ni–TiO₂. Codopants and dopants are found to be uniformly distributed in TiO₂ matrix. Among the all samples the 0.5% molar quantity of Ni dopant and 500 °C 2 h nitriding condition gives the highest photocatalytic activity. The treatment of ammonia gas on Ni–TiO₂ sample induced oxygen vancancies, substitutional and interstitial N. A suitable treatment by ammonia gas also promote separation of charge carriers and the absorption of visible light. The active species generated in the photocatalytic system were also investigated. The strategy presented here gives a promising route towards the development of a metal and non-metal codoped semiconductor materials for applied photocatalysis and related applications.     

Correlation of the Catalytic Activity for Oxidation Taking Place on Various TiO2 Surfaces with Surface OH Groups and Surface Oxygen Vacancies

Three catalytic oxidation reactions have been studied: The ultraviolet (UV) light induced photocatalytic decomposition of the synthetic dye sulforhodamine B (SRB) in the presence of TiO₂ nanostructures in water, together with two reactions employing Au/TiO₂ nanostructure catalysts, namely, CO oxidation in air and the decomposition of formaldehyde under visible light irradiation. Four kinds of TiO₂ nanotubes and nanorods with different phases and compositions were prepared for this study, and gold nanoparticle (Au‐NP) catalysts were supported on some of these TiO₂ nanostructures (to form Au/TiO₂ catalysts). FTIR emission spectroscopy (IES) measurements provided evidence that the order of the surface OH regeneration ability of the four types of TiO₂ nanostructures studied gave the same trend as the catalytic activities of the TiO₂ nanostructures or their respective Au/TiO₂ catalysts for the three oxidation reactions. Both IES and X‐ray photoelectron spectroscopy (XPS) proved that anatase TiO₂ had the strongest OH regeneration ability among the four types of TiO₂ phases or compositions. Based on these results, a model for the surface OH group generation, absorption, and activation of molecular oxygen has been proposed: The oxygen vacancies at the bridging O^2? sites on TiO₂ surfaces dissociatively absorb water molecules to form OH groups that facilitate adsorption and activation of O₂ molecules in nearby oxygen vacancies by lowering the absorption energy of molecular O₂. A new mechanism for the photocatalytic formaldehyde decomposition with the Au/TiO₂ catalysts is also proposed, based on the photocatalytic activity of the Au‐NPs under visible light. The Au‐NPs absorb the light owing to the surface plasmon resonance effect and mediate the electron transfers that the reaction needs.     

Synthesis of anatase TiO2 in a vinyl-containing ionic liquid and its enhanced photocatalytic activity

TiO₂ microspheres were synthesized by the sol–gel method using the ionic liquid (IL) 1-vinyl-3-propylimidazolium iodide (VPIM⁺I^?) as a reaction medium, then calcined at 500 °C. The samples were characterized by X-ray diffraction, scanning electron microscopy, and ultraviolet–visible (UV–Vis) diffuse reflectance spectroscopy. The phase of TiO₂ microspheres is anatase, and VPIM⁺I^? is able to favor the growth of anatase phase and prevents the collapse of small pores. The photocatalytic activity of TiO₂-IL was tested by degradation of 2-nitrophenol under UV light illumination. The photocatalytic activity of TiO₂-IL was higher than that of samples prepared in the reaction medium without VPIM⁺I^?.     

可见光响应的铁掺杂TiO_2中空微球的制备及其光催化性能

以聚苯乙烯微球作为模板,水溶性过氧化钛配合物作为前驱体一步合成了掺铁TiO2中空微球,并利用XRD,SEM,TEM,XPS,UV-Vis等测试手段对样品进行了表征。结果表明,一步法制备的掺铁TiO2中空微球以锐钛矿相存在且具有良好的中空结构,掺杂少量铁到体系中,改变了其电子结构,使其吸收波长拓展到可见光区。光催化降解亚甲基蓝溶液的结果表明,掺杂0.75%铁的TiO2中空微球表现出更好的光催化性能。对Fe3+影响光催化活性的机理进行了讨论。     

Enhanced photocatalytic degradation of rhodamine B under visible light irradiation on mesoporous anatase TiO2 microspheres by codoping with W and N

Mesoporous anatase TiO₂ microspheres were prepared via solvothermal method. Ammonium tungstate was used as the W source, and ammonia gas flowing in an ammonothermal reactor as the N source for codoping. TiO₂:(W,N) mesoporous microspheres, which were prepared from solvothermal treatment at 160 °C for 16 h and thermal ammonolysis at 500 °C for 2 h after calcination, have high specific surface area of 106 m² g⁻¹. XPS results indicate the presence of N_O, N_i and W⁶⁺ in the codoped mesoporous TiO₂ microspheres. Monodoping with N shifts the absorption band edge of anatase TiO₂ from ultraviolet region to visible region. Although codoping with W makes the visible light absorbance decrease a little, the photocatalytic degradation of a cationic dye rhodamine B (RhB) on mesoporous TiO₂:(W,N) microspheres is increased to 1.7 times of that on mesoporous TiO₂:N microspheres. This may due to decreasing recombination centers by W-doping charge compensation.     

Study of the Efficiency of UV and Visible‐Light Photocatalytic Oxidation of Methanol on Mesoporous RuO2–TiO2 Nanocomposites

Mesoporous RuO₂–TiO₂ nanocomposites at different RuO₂ concentrations (0–10 wt %) are prepared through a simple one‐step sol–gel reaction of tetrabutyl orthotitanate with ruthenium(III) acetylacetonate in the presence of an F127 triblock copolymer as structure‐directing agent. The thus‐formed RuO₂–TiO₂ network gels are calcined at 450 °C for 4 h leading to mesoporous RuO₂–TiO₂ nanocomposites. The photocatalytic CH₃OH oxidation to HCHO is chosen as the test reaction to examine the photocatalytic activity of the mesoporous RuO₂–TiO₂ nanocomposites under UV and visible light. The photooxidation of CH₃OH is substantially affected by the loading amount and the degree of dispersion of RuO₂ particles onto the TiO₂, which indicates the exclusive effect of the RuO₂ nanoparticles on this photocatalytic reaction under visible light. The measured photonic efficiency ξ=0.53 % of 0.5 wt % RuO₂–TiO₂ nanocomposite for CH₃OH oxidation is maximal and the further increase of RuO₂ loading up to 10 wt % gradually decreases this value. The cause of the visible‐light photocatalytic behavior is the incorporation of small amounts of Ru⁴⁺ into the anatase lattice. On the other hand, under UV light, undoped TiO₂ shows a very good photonic efficiency, which is more than three times that for commercial photocatalyst, P‐25 (Evonik–Degussa); however, addition of RuO₂ suppresses the photonic efficiency of TiO₂. The proposed reaction mechanism based on the observed behavior of RuO₂–TiO₂ photocatalysts under UV and visible light is explored.     

Photocatalytic reduction of CO2 with H2O on TiO2 and Cu/TiO2 catalysts

Photoinduced reduction of CO₂ by H₂O to produce CH₄ and CH₃OH has been investigated on wellcharacterized standard TiO₂ catalysts and on a Cu²⁺ loaded TiO₂ catalyst. The efficiency of this photoreaction depends strongly on the kind of catalyst and the ratio of H₂O to CO₂. Anatase TiO₂, which has a large band gap and numerous surface OH groups, shows high efficiency for photocatalytic CH₄ formation. Photogenerated Ti³⁺ ions, H and CH₃ radicals are observed as reactive intermediates, by ESR at 77 K. Cu-loading of the small, powdered TiO₂ catalyst (Cu/TiO₂) brings about additional formation of CH₃OH. XPS studies suggest that Cu⁺ plays a significant role in CH₃OH formation.     

Synthesis and Enhanced Photocatalytic Activity of a Hierarchical Porous Flowerlike p–n Junction NiO/TiO2 Photocatalyst

Hierarchical flowerlike β‐Ni(OH)₂ superstructures composed of intermeshed nanoflakes are synthesized by hydrothermal treatment with a mixed solution of C₂H₄(NH₂)₂, NaOH, and Ni(NO₃)₂. The as‐prepared β‐Ni(OH)₂ superstructures could be easily changed into NiO superstructures without great morphology change by calcination at 400 °C for 5 h. Furthermore, the TiO₂ nanoparticles can be homogeneously deposited on the surface of NiO superstructures by dispersing β‐Ni(OH)₂ powders in Ti(OC₄H₉)₄–C₂H₅OH mixed solution and then vaporizing to remove the ethanol at 100 °C, and finally calcination at 400 °C for 5 h. The prepared NiO/TiO₂ p–n junction superstructures show much higher photocatalytic activity for photocatalytic degradation of p‐chlorophenol aqueous solution than conventional TiO₂ powders and NiO superstructures prepared under the same experimental conditions. An obvious enhancement in the photocatalytic activity can be related to several factors, including formation of hierarchical porous structures, dispersion of TiO₂ particles on the surface of NiO superstructures, and production of a p–n junction. Further results show that NiO/TiO₂ composite superstructures can be more readily separated from the slurry system by filtration or sedimentation after photocatalytic reaction and re‐used, compared with conventional powder photocatalysts. After many recycling experiments for the photodegradation of p‐chlorophenol, the NiO/TiO₂ composite sample does not exhibit any great activity loss, confirming that NiO/TiO₂ sample is stable and not photocorroded.     

火焰辅助热解方法制备Ag_2O/TiO_2及其光催化制氢性能

以钛酸丁酯和硝酸银为前驱体,采用一步火焰辅助热解法制备了Ag_2O/TiO_2光催化剂并研究了样品在紫外-可见光照射下的光催化制氢性能。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和紫外-可见漫反射吸收光谱(UV-Vis DRS)对样品进行了表征。XRD结果表明TiO_2均为锐钛矿晶型,Ag的引入对XRD结果无明显影响。SEM图显示未修饰的TiO_2是微球形貌,随着引入Ag含量的增加,微球减少直至消失。通过XPS分析和化学沉淀法表明样品中Ag的存在形式为Ag_2O。UV-Vis DRS测试发现引入Ag后提高了样品的光吸收。前驱体中Ag的量影响样品的光催化活性,最高的光催化制氢的活性可以达到相同条件下的P25的15倍。对光催化反应后的样品进行分析,认为在光催化过程中部分Ag_2O通过光生电子转化为Ag形成Ag/TiO_2,进一步提高光催化制氢活性。     

火焰辅助热解方法制备Ag2O/TiO2及其光催化制氢性能

以钛酸丁酯和硝酸银为前驱体,采用一步火焰辅助热解法制备了Ag₂O/TiO₂光催化剂并研究了样品在紫外-可见光照射下的光催化制氢性能。利用X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）和紫外-可见漫反射吸收光谱（UV-Vis DRS）对样品进行了表征。XRD结果表明TiO₂均为锐钛矿晶型,Ag的引入对XRD结果无明显影响。SEM图显示未修饰的TiO₂是微球形貌,随着引入Ag含量的增加,微球减少直至消失。通过XPS分析和化学沉淀法表明样品中Ag的存在形式为Ag₂O。UV-Vis DRS测试发现引入Ag后提高了样品的光吸收。前驱体中Ag的量影响样品的光催化活性,最高的光催化制氢的活性可以达到相同条件下的P25的15倍。对光催化反应后的样品进行分析,认为在光催化过程中部分Ag₂O通过光生电子转化为Ag形成Ag/TiO₂,进一步提高光催化制氢活性。     

Synthesis of Bi-doped TiO2 Nanotubes and Enhanced Photocatalytic Activity for Hydrogen Evolution from Glycerol Solution

Bi‐doped TiO₂ nanotubes with variable Bi/Ti ratios were synthesized by hydrothermal treatment in 10 mol·L^?1 NaOH (aq.) through using Bi‐doped TiO₂ particles derived from conventional sol‐gel method as starting materials. The effects of Bi content on the morphology, textural properties, photo absorption and photocatalytic activity of TiO₂ nanotubes were investigated. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS) observations of the obtained samples revealed the formation of titanate nanotube structure doped with Bi, which exists as a higher oxidation state than Bi³⁺. Bi‐doping TiO₂ nanotubes exhibited an extension of light absorption into the visible region and improved photocatalytic activities for hydrogen production from a glycerol/water mixed solution as compared with pure TiO₂ nanotubes. There was an optimal Bi‐doped content for the photocatalytic hydrogen production, and high content of Bi would retard the phase transition of titanate to anatase and result in morphology change from nanotube to nanobelt, which in turn decreases the photocatlytic activity for hydrogen evolution.     

Enhanced and suppressed effects of ionic liquid on the photocatalytic activity of TiO2

The effects of a room temperature ionic liquid, 1-butyl-3-methylimidazolium terafluoroborate ([Bmim]BF₄), on the photocatalytic performance of Degussa P25 TiO₂ were investigated. Also, the photocatalysis mechanism was systematically analyzed by conducting different reactive radical trapping experiments. The results showed that photogenerated electrons were the main reactive species involved in the photocatalytic degradation of methyl orange (MO), while ?OH radicals and photogenerated holes played an important role in the photocatalytic decomposition of rhodamine B (RhB). The addition of ionic liquid (IL) could slightly enhance the photocatalytic degradation rate of MO because adsorption of [Bmim]⁺ ions on the TiO₂ surface not only enhanced traping and transfer of photogenerated electrons, but also facilitated adsorption of negatively charged MO. On the contrary, IL suppressed the degradation rate of RhB because [Bmim]⁺ on the TiO₂ surface not only hindered the access of positively charged RhB to TiO₂, but also restricted the diffusion of positively charged holes to the TiO₂/solution interface.     

Porous TiO2 Nanotubes with Spatially Separated Platinum and CoOx Cocatalysts Produced by Atomic Layer Deposition for Photocatalytic Hydrogen Production

Efficient separation of photogenerated electrons and holes, and associated surface reactions, is a crucial aspect of efficient semiconductor photocatalytic systems employed for photocatalytic hydrogen production. A new CoO_x/TiO₂/Pt photocatalyst produced by template‐assisted atomic layer deposition is reported for photocatalytic hydrogen production on Pt and CoO_x dual cocatalysts. Pt nanoclusters acting as electron collectors and active sites for the reduction reaction are deposited on the inner surface of porous TiO₂ nanotubes, while CoO_x nanoclusters acting as hole collectors and active sites for oxidation reaction are deposited on the outer surface of porous TiO₂ nanotubes. A CoO_x/TiO₂/Pt photocatalyst, comprising ultra‐low concentrations of noble Pt (0.046 wt %) and CoO_x (0.019 wt %) deposited simultaneously with one atomic layer deposition cycle, achieves remarkably high photocatalytic efficiency (275.9 μmol h⁻¹), which is nearly five times as high as that of pristine TiO₂ nanotubes (56.5 μmol h⁻¹). The highly dispersed Pt and CoO_x nanoclusters, porous structure of TiO₂ nanotubes with large specific surface area, and the synergetic effect of the spatially separated Pt and CoO_x dual cocatalysts contribute to the excellent photocatalytic activity.     

Highly photocatalytic activity of metallic hydroxide/titanium dioxide nanoparticles prepared via a modified wet precipitation process

Surface modification is one important approach to increase the photocatalytic activity of TiO₂. By using a modified wet precipitation process, novel M(OH)_x/TiO₂ nanoparticles were synthesized, where M(OH)_x represents ferric or cupric hydroxide. The prepared M(OH)_x/TiO₂ powders were characterized with XRD, FT-IR, BET, UV–vis DRS, and TGA, and were observed to yield high photocatalytic ability by using methyl orange (MO) as a model compound of organic pollutants to be degraded. Due to the accelerating effects of the new photocatalyst, the half-time of MO during its photocatalytic degradation at pH 6.0 over M(OH)_x/TiO₂ was decreased from 332 min for unmodified neat TiO₂ to 63 min for Fe(OH)₃/TiO₂ and 65 min for Cu(OH)₂/TiO₂, respectively. The enhancing effects of M(OH)_x/TiO₂ was further observed in a wide composition range with various M/Ti atomic ratios in the photocatalysts and in a wide pH range of the MO solution from 3 to 7. This enhancing effect is mainly attributed to the increased trapping of the photogenerated electron by the higher valence sites (Fe(III) or Cu(II)) in the hydroxide layer near the M(OH)_x/TiO₂ interface and the enriched surface hydroxyl groups which accept photogenerated holes to yield more hydroxyl radicals.