Fabrication and photocatalytic performance of one-dimensional Ag3PO4 sensitized SrTiO3 nanowire

The 1D Ag₃PO₄ sensitized SrTiO₃ nanowires are prepared by simple route of electrospinning-in situ deposition technique. The results of the thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive Spectrometer (EDS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV–Visible diffuse reflectance spectroscopy (UV–Vis) indicate that the Ag₃PO₄ nanoparticles has been deposited on the surface of the SrTiO₃ nanowires successfully. Experimental results showed that compared with pure SrTiO₃, the as-prepared 1D Ag₃PO₄ sensitized SrTiO₃ nanowires exhibit obvious enhancement of photocatalytic performance and stability. Especially, the Ag₃PO₄/SrTiO₃ (3AS sample) had a satisfactory photocatalytic activity for degrading methylene blue (MB) more than 98% under visible light irradiation. As to pure SrTiO₃ and Ag₃PO₄, only 9.8% and 49% of MB was decomposed after 35?min irradiation respectively. Furthermore, the mechanism of the enhancing photocatalytic activity could be ascribed to the nano-heterojunction of the Ag₃PO₄/SrTiO₃, the visible light response of the Ag₃PO₄, and the 1D structure of the nanowires.     

Preparation and characterization of Cu2O/TiO2 nano–nano heterostructure photocatalysts

Cu₂O/TiO₂ nano–nano heterostructures with different concentrations of Cu₂O were prepared by an alcohol-aqueous based chemical precipitation method, and were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy and UV–vis diffuse reflection absorption spectra. The photocatalytic efficiency of the Cu₂O/TiO₂ heterostructures was evaluated by degradation of Acid Orange II in water under UV–vis light and visible light irradiation. The results show that the heterostructures have dramatically improved photocatalytic activity comparing with pure TiO₂ (P25). The prepared Cu₂O/TiO₂ heterostructures with the Cu₂O concentrations of 30% and 70% have the best photocatalytic efficiencies, which are 6 times and 27 times higher than that of pure TiO₂ (P25) under UV–vis light and visible light irradiation, respectively.     

One step synthesis of Ag/Ag3PO4/BiPO4 double-heterostructured nanocomposites with enhanced visible-light photocatalytic activity and stability

Heterogeneous Ag/Ag₃PO₄/BiPO₄ photocatalyst was synthesized by a one-step low temperature chemical bath method and exhibited better photocatalytic activity and better stability than those of individual Ag₃PO₄ or BiPO₄ nanoparticles for photodegradation of organic compounds (Rhodamine B) in the absence of electron accepters under visible light (λ>420 nm). The enhanced photocatalytic performance is mainly ascribed to the strong visible-light absorption originating from high efficient separations of photogenerated electron–hole pairs through Ag₃PO₄/BiPO₄ and Ag/Ag₃PO₄ heterostructures.     

Ag3PO4的制备及其复合材料研究进展

能源与环境已成为当前亟需解决的问题,半导体光催化技术因具有氧化降解有机污染物完全、不产生二次污染、易操作等优点,在环境治理和新能源开发领域成为热点研究课题之一。Ag3PO4因具有高量子效率、可见光响应及较高的光催化效率等特点而引起了广大研究者的关注,并具有广泛的应用前景。本文总结了Ag3PO4的制备方法、不同形貌Ag3PO4的可控合成及其复合材料的研究进展。     

Nitrogen-containing TiO2 photocatalysts: Part 1. Synthesis and solid characterization

A series of N-substituted Ti isopropoxide precursors were synthesized by using three different amine-type ligands. The resulting Ti-complexes were characterized by nuclear magnetic resonance (NMR) and used to obtain solid precipitates by a reverse microemulsion method. These N-rich solid precipitates were subjected to three calcination treatments differing in the gas atmosphere allowed to contact the solid, yielding nanosized materials. A thermogravimetric analysis of the solid precipitates, combined with a mass spectrometry/infrared study of the evolving gaseous products, were able to show the influence of preparation parameters, e.g. Ti-precursor nature and treatment conditions, in the decomposition process of the solid precursors and the formation of the final nanoparticulated solid catalysts. Both parameters affect the interaction between solid oxygen species (O²⁻; OH⁻) and N,C-containing fragments present in the solid precursors. The chemical (e.g. nitrogen content), structural (phase, cell parameters and volume, and defect structure) and morphological (BET area and primary particle size) properties of the catalytic final solids were studied as a function of the preparation conditions.     

Synthesis,characterization and demonstration of self-cleaning TiO2 coatings on glass and glazed ceramic tiles

An effort was made not only to demonstrate the performance of the self-cleaning coatings on building materials such as ceramic glazed tiles and glass windows, but also to understand the fundamental issues that are still alive in the field of self-cleaning surfaces based on photocatalysis. Nano TiO₂ transparent thin films were generated by dip, spray and flow coating method. The present results indicate that the inconsistent results in the self-cleaning studies may be due to the effect of aggregation of model pollutant (methylene blue) dye on TiO₂ surface. The effect of aliovalent metal ion (Ni²⁺, Fe³⁺, Nb⁵⁺) doping on phase formation, polymorphic transition, visible light absorbance and optical transparency of TiO₂ film were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV visible absorption spectroscopy. The improved visible light activity of doped TiO₂ thin film was correlated to the Ti(Ni/Fe)O₃ phase formation, UV and visible light absorbance, variation in the optical energy band gap and the probable light scattering associated with grain size.     

Electrochemical beaviour of the solid ionic conductor Ag7I4PO4

Electrochemical investigation of the solid superionic conductor Ag₇I₄PO₄ (0.8 AgI + 0.2 Ag₃PO₄) at room temperature and at 40°C were performed by means of cyclic voltammetry, cyclic chronoamperometry and cyclic chronocoulometry, normal pulse polarography and ac polarography. It was shown that the Ag⁺ ↔ Ag redox process on Pt and Ag working electrode occurs with a certain overvoltage, ie that for Ag⁺ → Ag⁺ oxidation and the return of Ag⁺ ions into the electrolyte a certain overvoltage is necessary. From the determined values of the exchange current one estimates the redox process as a rather fast one. The silver working electrode is electrochemically inactive, while only cathodically deposited silver is electrochemically active and can be oxidized to Ag⁺ ions. Chronoamperometry and chronocoulometry show that there is a certain difference in the behaviour of Pt and Ag working electrodes due to uneven passivating anodic processes. On the basis of measurements of faradaic and capacitance currents and their dependence on frequency, diagrams of complex impedance of the Pt/Ag₇I₄PO₄ interface at various anodic and cathodic polarizations of the Pt electrode were plotted. The dependence of the serial capacity of the interface on the dc potential and temperature are discussed.     

Nitrogen-containing TiO2 photocatalysts: Part 2. Photocatalytic behavior under sunlight excitation

A series of nanosized N-containing TiO₂-based materials with Anatase-type structure and synthesized by a microemulsion method were tested in the photocatalytic degradation of methylcyclohexene, a representative example of volatile organic compound (VOC) present in urban atmospheres. A combined diffuse reflectance infrared (DRIFTS) and X-ray absorption (XAS) spectroscopic study allows to analyze the nature and number of N-containing species and other defects (particularly oxygen vacancies) present in the solid catalysts. The structural characterization was used to interpret the UV–vis spectra of the solids and the resulting joint information allows to rationalize the photocatalytic activity differences observed through the samples under sunlight-type excitation. We founded that our samples contain substitutional and interstitial N-containing impurities and a significant number of oxygen vacancies. Photocatalytic activity is correlated with an optimum of oxygen vacancies, above and below which a decrease of the steady state reaction rate is observed. The physico-chemical bases of this behavior are discussed on the light of the above mentioned experimental results.     

Degradation of high temperature MEA with PBI-H3PO4 membrane in a life test

The article reports on the results of a 780 h life test of high temperature MEA with PBI-H₃PO₄ membrane. The MEA was loaded by current density 0.2 A cm⁻² for 763 h at 160 °C in hydrogen-air feed. The load was discontinued 14 times during the life test including three complete shut downs. In the course of the life test MEA characteristics were studied by electrochemical methods. Pt particle size growth was evaluated by ex situ measurements of electrochemical hydrogen adsorption/desorption with the cathode catalyst sampled after the life test and with pristine catalyst. Possible changes of electrochemically active surface area (ESA) of carbon support were monitored by electrochemical impedance studies (EIS) performed in the course of the MEA life test. Average Pt particle diameter was found 3.8 and 7.8 nm for pristine catalyst and for catalyst sampled after the life test, respectively. ESA of carbon support remained unchanged, membrane resistance decreased by ∼20%, hydrogen crossover increased by a factor of 14, although remained insignificant. Voltage loss rate in the life test was ∼25 μV h⁻¹. The major cause of the MEA degradation was identified as a loss of Pt ESA by particle size growth.     

Photocatalytic activation of TiO2 under visible light using Acid Red 44

The activation of TiO₂ photocatalyst for photocatalysis under the visible light using Acid Red 44 (C₁₀H₇N=NC₁₀H₃(SO₃Na)₂OH) is described. Adjustment of the pH enhanced the photocatalytic activation of TiO₂ in the presence of visible light. This confirms that the adsorption of a dye on TiO₂ surface is an important factor in dye-photosensitization. The differences in the photocatalytic activation mechanism under visible irradiated conditions with that of UV irradiated condition are proposed. The dye-sensitized photocatalysis under visible light was applied to the decomposition of phenol, is a toxic chemical used in industry and frequently discharged into water.     

Photooxidation reactions of polycyclic aromatic hydrocarbons over pure and Ag-loaded BiVO4 photocatalysts

Photooxidative degradations of nine polycyclic aromatic hydrocarbons (PAHs) using pure and Ag-loaded BiVO₄ photocatalysts have been examined in acetonitrile under visible light irradiation. Photoproducts have been identified by means of gas chromatography–mass spectrometry (GC–MS). Silver fine particles loaded on BiVO₄ surface improved the reaction rates of all PAHs degradations. In particular, anthracene and benz[a]anthracene (Bz[a]A) are efficiently oxidized to anthraquinone and benz[a]anthracene-7,12-dione, respectively. Photooxidation mechanism of anthracene and Bz[a]A has been clarified by the GC–MS analyses by the use of H₂¹⁸O as a reactant. It has been proved that OH radicals are generated through the oxidation of water by valence band holes on the Ag-BiVO₄ surface in acetonitrile, and greatly contribute to the degradations of these PAHs. The OH radical attack to PAHs probably determines the overall rates of oxidation of PAHs on Ag-BiVO₄ photocatalyst.     

Preparation of Ag@AgCl/g-C3N4/TiO2 porous ceramic films with enhanced photocatalysis performance and self-cleaning effect

We report a novel method to prepare translucent and stable Ag@AgCl/g-C₃N₄/TiO₂ ceramic films having strong photocatalytic activities and self-cleaning capabilities under light irradiation. Colloidal silica was used as an inorganic binder and P25 TiO₂ was added as a hydrophilicity enhancer without which a smooth coating was not achievable. Ag@AgCl of particle size around 30?nm, was synthesized by in-situ oxidation of nano-silver particles in porous g-C₃N₄/TiO₂ films. Optimal conditions for Ag@AgCl/g-C₃N₄/TiO₂ preparation in terms of strongest photocatalysis were established by tests on Rhodamine B degradation under visible and full spectral irradiations. A good adhesion strength of the porous films on glass substrate was achieved. Stability and reusability of the films were assessed by cycling tests. Possible photocatalytic mechanisms are proposed based on the basis of trapping experiments. Systematic characterization of the film suggests that the in-situ oxidation is an effective and practical method to produce nanoscale Ag@AgCl.     

Novel magnetically separable g-C3N4/AgBr/Fe3O4 nanocomposites as visible-light-driven photocatalysts with highly enhanced activities

In this study, we report novel magnetically separable g-C₃N₄/AgBr/Fe₃O₄ nanocomposites as visible-light-driven photocatalysts. The preparation method was simple, large-scale, and low-temperature and did not require any additives or post preparation treatments. The nanocomposites were characterized using X-ray diffraction, transmission electron microscopy, energy dispersive analysis of X-rays, UV–vis diffuse reflectance spectroscopy, Fourier transform-infrared spectroscopy, thermogravimetric analysis, and vibrating sample magnetometry techniques. Photocatalytic activity of the nanocomposites was investigated by degradation of rhodamine B under visible-light irradiation. The nanocomposite with 4:1 weight ratio of g-C₃N₄/AgBr to Fe₃O₄ exhibited superior activity in the degradation reaction. Activity of this nanocomposite was about 5.3 and 5-fold higher than those of g-C₃N₄, and g-C₃N₄/Fe₃O₄, respectively. Moreover, we investigated the influence of refluxing time, calcination temperature, and scavengers of reactive species on the degradation activity. Finally, the photocatalyst was magnetically separated, with high efficiency, from the treated solution after five successive cycles.     

Photocatalytic reduction of Ag2SO4 by the Dawson anion α-[P2W18O62] and tetracobalt sandwich complexes

The photocatalytic behaviours of the Dawson salt α-K₆[P₂W₁₈O₆₂] and two isomers of the tetracobalt Dawson-derived sandwich complexes, αββα-Na₁₇[Co₄(H₂O)(OH)(P₂W₁₅O₅₆)₂]·51H₂O·2NaCl and ααβα-Na₁₆[Co₄(H₂O)₂(P₂W₁₅O₅₆)₂]·51H₂O (abbreviated ββ-{Co₄P₄W₃₀} and αβ-{Co₄P₄W₃₀}, respectively), are described and compared.The direct photochemical excitation of the polyoxometalates (POM) in the presence of propan-2-ol as electron donor leads to their reduction. With polyoxometalates as photocatalyst and propan-2-ol as sacrificial electron donor, the reduction of Ag^I₂SO₄ from aqueous solutions is observed leading to metallic Ag_n⁰ clusters and colloidal metal nanoparticles stabilized by POM.In the case of both {Co₄P₄W₃₀}, TEM experiments reveal that most of the Ag_n particles obtained with a slight excess of Ag⁺ are spherical with a quite large distribution in size between 10 and 100 nm.     

Highly efficient photocatalytic activity and mechanism of novel Er3+ and Tb3+ co-doped BiOBr/ g-C3N5 towards sulfamethoxazole degradation

Bismuth oxyhalides (BiOX (X = Cl, Br, I) are considered to be an important p-type semiconductors in the photocatalysis applications. In particular, tetragonal BiOBr is considered as a stable photocatalyst due to its resilient absorption in the visible region with an band gap energy of 2.8 eV. In the meantime, lanthanide ions (with 3+ oxidation state) implies as conversion catalyst gained huge impact and remain a serious topic in materials chemistry. Here we synthesized upconversion photocatalyst mainly consists of BiOBr with the Er ³⁺ and Tb ³⁺ ions along with low band gap g-C₃N₅ for the improved photocatalytic performances. The synthesized Er³⁺/Tb³⁺@BiOBr-g-C₃N₅ heterojunction was systematically characterized by XRD, and FT-IR for the confirmation of the composite and their morphology were analysed with FESEM and HR-TEM analysis which revealed that the sheets of g-C₃N₅ were decorated by Er³⁺/Tb³⁺ loaded BiOBr microspheres. The XPS analysis confirmed the suitable oxidation state of all the individual elements existing in the composite. As the UV-DRS analysis showed that the band gap of the Er³⁺/Tb³⁺ BiOBr-gC₃N₅ heterojunction was narrowed to 2.64 eV. To evaluate the photocatalytic efficiency of the synthesized g-C₃N₅, Er³⁺/Tb³⁺@BiOBr and Er³⁺/Tb³⁺@BiOBr-gC₃N₅ heterojunction under the simulated visible light irradiation source towards the aqueous sulfamethoxazole degradation. The Er³⁺/Tb³⁺@BiOBr-gC₃N₅ heterojunction shows maximum degradation efficiency of 94.2% after 60 min of visible light irradiation whereas the pure g-C₃N₅ provided about 43.8% and Er³⁺/Tb³⁺@BiOBr implies 55.2% degradation efficiency. The plausible degradation mechanism of pollutant removal was proposed.     

Photocatalytic degradation of bisphenol A and dye by graphene-oxide/Ag3PO4 composite under visible light irradiation

A facile, one-step synthesis of graphene-oxide (GO)/Ag₃PO₄ was prepared. The as-prepared samples were characterized by scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS) and fourier transformed infrared (FT-IR) spectroscopy. The SEM image indicated that Ag₃PO₄ particles were mainly distributed on the surface of GO sheets uniformly. DRS analysis revealed that the samples had good visible light response. The photocatalytic activity of the composites was evaluated by the degradation of Rhodamine B (RhB) and Bisphenol A (BPA). The results indicated that the photocatalytic performance of GO/Ag₃PO₄ was greatly enhanced after introduction of GO. The photocatalytic degradation efficiency of colorless chemical pollutants (BPA) over GO/Ag₃PO₄ was higher than that of Ag₃PO₄, and the possible degradation path was proposed by liquid chromatography mass spectrometry (LC-MS) analysis. Moreover, the photocatalytic stability was discussed by XRD and FT-IR spectroscopy analysis. Based on the experimental results, a possible visible-light photocatalytic degradation mechanism was also discussed.     

Ultrasound-assisted synthesis of high-efficiency Ag3PO4/CeO2 heterojunction photocatalyst

The Ag₃PO₄/CeO₂ heterojunction photocatalyst prepared by an ultrasound-assisted method exhibits an enhanced photocatalytic activity compared to pure Ag₃PO₄, CeO₂, and Ag₃PO₄/CeO₂ obtained without ultrasound action. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and ultraviolet–visible absorption spectroscopy (UV–vis), and the effects of ultrasound on the physicochemical properties and photocatalytic activity of Ag₃PO₄/CeO₂ are discussed. Results show that the ultrasound-assisted synthesis method significantly improves the photocatalytic ability. The mechanism about the improvement was discussed in details.     

TiO2, TiO2/Ag and TiO2/Au photocatalysts prepared by spray pyrolysis

TiO₂, TiO₂/Ag and TiO₂/Au photocatalysts exhibiting a hollow spherical morphology were prepared by spray pyrolysis of aqueous solutions of titanium citrate complex and titanium oxalate precursors in one-step. Effects of precursor concentration and spray pyrolysis temperature were investigated. By subsequent heat treatment, photocatalysts with phase compositions from 10 to 100% rutile and crystallite sizes from 12 to 120 nm were obtained. A correlation between precursor concentration and size of the hollow spherical agglomerates obtained during spray pyrolysis was established. The anatase to rutile transformation was enhanced with metal incorporations and increased precursor concentration. The photocatalytic activity was evaluated by oxidation of methylene blue under UV-irradiation. As-prepared TiO₂ particles with large amounts of amorphous phase and organic residuals showed similar photocatalytic activity as the commercial Degussa P25. The metal incorporated samples showed comparable photocatalytic activity to the pure TiO₂ photocatalysts.     

Fabrication of heterogeneous photocatalysts for insight role of carbon nanofibre in hierarchical WO3/ MoSe2 composite for enhanced photocatalytic hydrogen generation

Mimicking the natural photosynthesis system, artificial photocatalysis facilitates effective utilization of solar energy for environmental sustainability and hydrogen energy production. In this work, the robust and efficient carbon fiber has been successfully incorporated into the interface between WO₃ nanodots and MoSe₂ needles using the facile hydrothermal and solvothermal method. The suitable interfacial contact of heterogeneous photocatalysts plays a significant role in the separation/transfer of interfacial photogenerated electron-hole pairs and hetero-junction. It seems an efficient approach for enhanced photocatalytic performance since the greater area of contact could improve the interfacial rate of charge transfer. The phase structure of prepared WO₃ nanodots changed from the monoclinic to hexagonal phase by the addition of co-catalyst. The experimental results exhibited that carbon fiber played a tri-functional role to boost up the photocatalytic activity over MoSe₂ nanostructures. It's not only act as operative co-catalyst but could also serve as the conductive electron bridges, rather than general cocatalyst, to accumulate electrons and encourage the hydrogen generation kinetics over the WO₃ photocatalysts. More interestingly, the WO₃?1% MoSe₂?1.5% carbon fiber and WO₃?1%MoSe₂ nanocomposites demonstrated the excellent rates of hydrogen evolution 438.7 and 356.2?mmol/g.h, which were 7.6 and 6.17 times higher when compared to that of pure MoSe₂, respectively. Under the visible light excitation, the atomically junction encourages fast electron transfer from nanofibers to MoSe₂ to suppress the rapid recombination kinetics within WO₃ nanodots and extend the lifetime of WO₃ charge carrier's, thereby releasing more photogenerated electrons with higher reducing power for hydrogen evolution. The current work can contribute with new perspectives and mechanistic insight for the design and development of heterogeneous photocatalysts WO₃ based nanostructures using the combination of MoSe₂ and trifunctional carbon nanofibers for environment and energy harvesting applications.     

Fabrication of magnetically recoverable Fe3O4/CdS/g-C3N4 photocatalysts for effective degradation of ciprofloxacin under visible light

Photocatalytic technology is an environmentally safe method of eliminating organic pollutants and antibiotics in wastewater. In this research, the performance of Fe₃O₄/CdS/g-C₃N₄ (FCN) photocatalyst for degradation of antibiotics was studied. The composite photocatalysts with different concentrations of g-C₃N₄ were prepared. FCN has better photocatalytic activity than degradation dyes in removal of antibiotics under visible light. This indicates that FCN could effectively hinder the recombination of carriers, and the addition of g-C₃N₄ increases the optical response range of CdS. At the same time, the introduction of Fe₃O₄ magnetic nanoparticles overcomes the problem of difficulty in recovery of the powder photocatalyst. The photocatalytic activity is not reduced to any significant after three cycles of use.