The growing use of nano titanium dioxide (TiO2) in consumer and agricultural products has accelerated its introduction into terrestrial environments, where its impact has not been documented extensively. TiO2 toxicity arises primarily from its ability to photochemically generate reactive oxygen species (ROS), including hydrogen peroxide (H2O2). While common ligands in soil porewaters can either hinder or enhance the degradation of organic contaminants by TiO2, their effects on ROS production by TiO2 have not been understood clearly. The objective of this study was to assess the effect of phosphate (P) and nitrate on UV-irradiated anatase, nano-TiO2. Accordingly, H2O2-generation kinetics experiments were conducted in UV-irradiated TiO2 under environmentally relevant concentrations of the ligands (0, 50, 100, and 250 μM) and pH values (4.00 ± 0.02 and 8.00 ± 0.02) from 0–100 min. Under all conditions, H2O2 grew logarithmically and reached between 5.38 and 22.98 μM after 100 min. At pH 4.00 ± 0.02, H2O2 production was suppressed by P but not by nitrate. Conversely, at pH 8.00 ± 0.02, nitrate did not affect H2O2 concentration while P increased it. Non-specific, minimal adsorption of nitrate prevented interference with the photoreactivity of TiO2. Due to the pH-dependent behavior of suspended TiO2 and H2O2 degradation rates, specific adsorption of P on TiO2 impeded its ability to produce H2O2 photochemically at pH 4.00 ± 0.02 but amplified it at pH 8.00 ± 0.02.

Anthropogenic activity releases hazardous contaminants and pollutants that are not removed fully by water treatments. Among such pollutants, bisphenol-A (BPA) and bisphenol-S (BPS) are included in a series of Endocrine Disruptive Compounds, which may cause disruption due to hormone blockage or mimicking. Thus, even though those pollutants are not considered lethal, they are hazardous to health due to their similarity to 17β-estradiol, and they have been shown to cause developmental malformation in Zebrafish and breast and prostate tumors in rodents. Both BPA and BPS have been found in water sources at concentrations >30 μg L–1 and since water treatment plants are ineffective at removing them, their concentration is constantly increasing. The purpose of the present study, using a collection of experiments performed by B.Sc. and M.Sc. students, was to apply clay-based materials to the removal of such health hazards from water. Specifically adapted modified clays as neutral organoclays can optimize the interaction between pollutants and the matrix to achieve efficient adsorption. Such an approach is very effective for relatively insoluble pollutants such as BPA, but less so for the more soluble BPS. On the other hand, BPS can be photodegraded catalytically using raw clay or TiO2-impregnated clay. At low catalyst concentration, the modified clay was as effective as a commercial TiO2 catalyst, whereas combining it with H2O2 yielded considerably better results. In summary, clay minerals offer solutions for the removal of health-hazardous pollutants from water, based on different procedures and mechanisms. The versality of clay minerals allows 'tailoring' specifically adapted materials that might improve their efficiency based on such very specific pollutant-matrix interactions.

The aim of the present study was to synthesize a photocatalyst on the basis of TiO2 with kaolin as the support material. Properties such as layered structure and a suitable particle size of kaolin could be beneficial in the production of a high-quality and relatively cheap photocatalyst on an industrial scale. Homogeneous hydrolysis with urea as a precipitation agent and kaolin as support material was used to obtain a kaolin surface covered with TiO2. Samples were characterized by means of X-ray powder diffraction, infrared and Raman spectroscopy, high-resolution transmission electron microscopy, Brunauer-Emmett-Teller surface area, and Barrett-Joyner-Halenda porosity determination. Photocatalytic activity was assessed by a Reactive Black 5 azo dye discoloration in a water suspension and by acetone decomposition on a thin layer of sample in a gas phase. The characterization confirmed that the well crystallized TiO2 was distributed effectively over the whole surface of a kaolin substrate, and photocatalytic tests revealed that the active surface layer of titania particles on kaolin performed well, suggesting that kaolin acts as a suitable support.

Powder-type semiconductor photocatalysts are widely applicable but their defects (e.g. easy agglomeration during preparation and recyclability in the suspension system) limit their practical application. In the current study, perovskite oxide photocatalytic material was loaded onto a muscovite substrate to overcome the problems of low stability, easy agglomeration, and difficult recovery. A photocatalytically active LaNi0.95Fe0.05O3/muscovite composite material was synthesized by a sol-gel impregnation method. Phase composition, morphology, and interfacial interaction of the composites, denoted as LNFBY-x (x: mass ratio of LNF to muscovite), were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and other analytical methods. According to the results, the particle size of LNF nanoparticles was regulated effectively by compounding with muscovite, and the agglomeration of LNF decreased. LNF nanoparticles were distributed evenly and attached in dense fashion to the surface of muscovite, thereby increasing the contact area with the reaction medium. The nanoparticles were connected to the silicon-oxygen tetrahedral sheet of the muscovite via Si–O–La, Si–O–Ni, and Si–O–Fe bonds, which increased the bonding strength between the composite components and expedited the transfer of photogenerated charge. More highly active oxygen species were produced, and a growing number of chemically active moieties (٠O2- and ٠OH) was generated in the photocatalytic reaction. LNFBY-1.00 demonstrated the best photocatalytic activity. A degradation rate of methyl orange of 99.03% was achieved after visible-light irradiation for 120 min, which decreased to 75.75% after five repeated uses, thereby indicating high stability and recycling ability. The photocatalytic LaNi0.95Fe0.05O3/muscovite composite material exhibited potential for application in environmental remediation practices.

Reduced graphene oxide supported titanium dioxide (GO/TiO2) heterojunction composites as highly active photocatalysts were synthesized via simple ultrasonic mixing and hydrothermal reaction using TiCl3 and GO as precursors. Their structure and morphology were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, Raman spectra, UV-vis spectroscopy, and thermogravimetic analysis. The GO/TiO2 heterojunction composites were used to degrade methyl orange (MO). The adsorption and photocatalytic degradation rate of the prepared GO/TiO2 composites increased by nearly three times compared with that of pristine TiO2 or GO, which reached up 90%, to degrade MO after 4 h, which provides a simple method to obtain photocatalytic materials.

A bimetallic metal–organic frameworks (MOFs)-templated strategy was developed to fabricate mesoporous CdxZn1−xS polyhedrons with improved photocatalytic hydrogen evolution activity, and the formation mechanism of these mesoporous polyhedrons was discussed in detail. Incorporating Cd atoms, the Brunauer–Emmett–Teller surface areas of mesoporous CdxZn1−xS polyhedrons were significantly increased (271 m2/g), providing more exposed active sites compared with ZnS. In addition, suitable conduction band potential (< −0.55 eV) of the mesoporous CdxZn1−xS polyhedrons was also beneficial for the photocatalysis. Impressively, by the co-effects of mesoporous structure and modified conduction band, the mesoporous CdxZn1−xS polyhedrons exhibited better photocatalytic activity for hydrogen evolution than most reported photocatalysts without noble metals. The maximum hydrogen evolution rate of the CSZ3 reached 4.10 mmol/(h g) under visible-light irradiation and without any cocatalyst condition. This facile strategy for the construction of mesoporous CdxZn1−xS polyhedrons provided a deep insight to fabricate other metal sulfides for a variety of photochemical applications.

Flower-like AgI/Bi5O7I hybrid photocatalysts were fabricated via a hydrothermal method and the subsequent heating process with AgI/Bi4O5I2 as the intermediate. X-ray powder diffraction, Raman, X-ray photoelectron spectroscopy, diffuse reflectance spectra, scanning electron microscopy, transmission electron microscopy, photoluminescence, and electrochemical methods were used to reveal the structure, elemental content, morphology, and charge separation capabilities of the as-prepared samples. The photocatalytic test showed that the AgI/Bi5O7I composites own much higher photoactivity than pure AgI and Bi5O7I. Based on the result of XPS analysis, the composite is believed to be the Ag/AgI/Bi5O7I system. Due to the suitable band potentials of AgI and Bi5O7I, the ternary system can form a heterojunction structure which works in a Z-scheme mechanism with Ag nanoparticles as the transfer media. The guided charge transfer in the composite prolongs the life time of charge carriers and eventually leads to the high photocatalytic activity of AgI/Bi5O7I. Additionally, the flower-like structure of the composite also contributes to the photocatalytic reaction.

TiO2/stevensite nanocomposite photocatalysts were synthesized by a solvothermal method using TiCl3/HCl as reactants and the stevensite clay mineral extract as support. The prepared photocatalyst samples were then characterized using various techniques such as X-ray diffraction (XRD), Infrared spectroscopy (IR) and Transmission Electron Microscopy (TEM). The Points of Zero Charge (PZC) of the various samples were evaluated by titration of the non-modified and the Ti-modified clay aqueous dispersions, with cationic surfactant solutions. The photocatalytic activity of the resulting nanocomposites samples were evaluated for the removal of Orange G (OG) from aqueous solution as a model dye pollutant. The data indicate that the formation of Na+-stevensite by the TiO2 particles leads to TiO2/stevensite nanocomposites having higher specific surface areas and mesopore volumes, and lower PZC values. Further, the photocatalytic activity was greater for the TiO2/stevensite nanocomposites having the greatest Ti amount, as compared to a pure TiO2 sample, and increased with the increase of the TiO2 content in the TiO2/stevensite nanocomposites.

The present study investigated the removal of methylene blue (MB) and orange II (OII) dyes from synthetic wastewater by means of adsorption and photocatalysis using natural kaolins. ForMB adsorption, the raw kaolinite-rich samples showed the greatest adsorption capacity, with rapid uptake (90% after 20 min). The experimental results were fitted better using the Langmuir isotherm model parameters compared to the Freundlich model, suggesting that the adsorption corresponds to monolayer coverage of MB molecules over the kaolinite surface. For OII, neither the Langmuir nor the Freundlich model gave reliable results, because the adsorption of anionic dye molecules by the clayey particles is not favoured.

Mixtures of kaolinite/Degussa TiO2 were also prepared, and their photocatalytic properties under UVlight exposure were investigated. Decolourization of MB solutions was observed, even in a mixture with low TiO2 content. This is related to the combined effect of adsorption and photocatalysis and, unlike the pure clay samples, the efficiency of such mixtures against OII was only slightly weaker (80–94%).

For TiO2-impregnated clays, with the kaolinite layers separated by sol-gel TiO2 particles, the MB removal was slow and effective only after >24 h due to the complexity of the bonding of MB molecules. On the other hand, the removal performance against OII solutions was very efficient (nearly 100%) within only 2 h. This excellent performance was attributed to morphological changes in clay particles.

Zn-Al layered double hydroxides (LDH), before and after calcination, were tested for the removal of indigo carmine (IC) dye from solution. These LDH photocatalysts were characterized by powder x-ray diffraction (PXRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetry/differential thermogravimetry (TG/DTG), nitrogen physisorption at −196°C, scanning electron microscopy (SEM) and diffuse reflectance spectrophotometry (DRS). The different photocatalysts were supported on polyacrylonitrile (PAN) nanofibres, so that filtration was unnecessary.

The PXRD and FTIR analyses showed that the IC adsorption on c-Zn-Al-3-500 (LDH calcined at 500°C) was enhanced by construction of the hydrotalcite matrix intercalated with the dye. The intercalation was clearly evidenced by the appearance of a peak at low °2θ values. All of the materials prepared exhibited photocatalytic activity, which for the c-Zn-Al-3-500 was comparable to that of commercial PAN-supported ZnO nanoparticles (100% degradation after 180 min). Kinetic studies showed that the degradation of the IC followed a pseudo-first order rate. The high activity and the ease of both synthesis and separation processes rendered this photocatalyst a promising candidate for environmental remediation.

The novel visible-light-responsive direct solid-state Z-scheme g-C3N4/BiOI heterojunction has been synthesized successfully by means of a solid phase calcination method and used for the degradation of microcystin-LR (MC-LR). The layered g-C3N4 disperses on the surface of BiOI microspheres. The samples are characterized by FESEM, HRTEM, XRD, FT-IR, UV-vis spectroscopy, XPS, BET, PL, and Mott–Sckottky. The photocatalytic activity and photodegradation mechanism of the as-prepared g-C3N4/BiOI microsphere photocatalysts are conducted under visible light irradiation using MC-LR as the target pollutant. The g-C3N4/BiOI material exhibits superior photocatalytic performance when compared with pure BiOI, the possible reason is the efficient separation of photogenerated carriers at the interface between g-C3N4 and BiOI. The heterostructure is responsible for the improved separation efficiency of photogenerated electron–hole pairs and thus the higher photocatalytic activity. The possible photocatalytic mechanism is proposed based on relative band positions of these two semiconductors.

A new plasmonic photocatalyst Ag/Bi7Ta3O18 was fabricated by photodeposition-hydrothermal method. The phase composition, microstructure, surface areas, average pore size, UV-vis diffuse reflection spectra, and photocatalytic activities of composite photocatalysts were investigated in detail. The results of the measurements indicated that the Ag0 nanoparticle successfully loads on the surface of Bi7Ta3O18, and the 0.06 Ag/Bi7Ta3O18 photocatalysts exhibited the best photocatalytic activity for the degradation of Rhodamine B (RhB). The improved photocatalytic activity could be contributed to the localized surface plasmon resonance caused by the collective oscillation of the surface electrons of Ag nanoparticles. Additionally, the photocatalytic reaction mechanism was studied by photoluminescence photocurrent, and electron spin resonance analysis. As a result, the Ag nanoparticles onto the Bi7Ta3O18 surface enlarged the electron–hole separation, and the (˙OH) was the dominated active species of degradation RhB in the photocatalytic process.

Many researchers are investigating the extreme resilience of bacterial endospores against chemical and physical inactivating agents. The presence of vegetative cells in spore suspensions can result in overly optimistic assessment of inactivating agents; therefore, various spore purification methods have been applied to separate spores from vegetative cells prior to testing. The present study was undertaken to evaluate the effect of two widely used spore purification methodologies on spore integrity and susceptibility to ultraviolet-A (UVA) radiation and free radicals generated from photocatalysts. Bacillus subtilis and Bacillus cereus spores were purified by procedures that involved heat shock alone or chemical washes, lysozyme treatment and heat shock (CLH). The purified spores were exposed to UVA radiation or free radicals generated by photocatalyst and susceptibility were evaluated in terms of survival ratio. The effect of purification procedure on the spore morphology was investigated with electron microscopy. The CLH purification process significantly damages spore coats and increases the susceptibility of Bacillus spores to UVA radiation and photocatalytic inactivation. It is therefore likely that the survival of CLH treated spores in extra-terrestrial environments would be less than that of the same spores purified by a less aggressive procedure.

Recently, solution combustion synthetic approach has emerged as a potential route to synthesize a wide range of catalytic oxides. Nano TiO2 was synthesized by solution combustion methods using glycine, urea, and oxalyldihydrazide as fuels. X-ray diffraction and field emission scanning electron microscopy analyses revealed the structural and morphological differences of TiO2 synthesized with different fuels. The oxidizer to fuel ratio from lean to rich conditions also played a crucial role in determining the polymorphic percentage concentration in the synthesized TiO2 powders. However, diffuse reflectance spectroscopy and photoluminescence spectroscopy studies did not show any significant differences in the electronic properties of the synthesized TiO2. As the polymorphic composite phases synergistically influence the catalytic performances, photodegradation of methylene blue (MB) and photo hydrogen production were studied with the synthesized catalysts. The synergistic role crucially depended on the specific reaction. The presence of different TiO2 polymorphs due to difference in fuels during combustion controlled the photocatalytic efficiency of the catalysts toward MB degradation and hydrogen production.

Due to the increasingly severe environmental pollution problems, the development of semiconductor photocatalysts is being extensively carried out because they have exhibited high activities for the degradation of many organic and inorganic pollutants. In this study, waxberry-like Ni11(HPO3)8(OH)6 microball photocatalysts with a diameter of 10–20 μm have been successfully synthesized via a solvothermal route by using NiSO4 as a Ni-source and NaH2PO2 as a P-source in a mixture of ethylene glycol and water under the optimized conditions with a Ni:P molar ratio of 1:2 at 200 °C for 16 h. The as-prepared photocatalysts were characterized by powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis, Brunauer–Emmett–Teller N2 adsorption, zeta potential, ultraviolet-visible (UV–vis) absorption, and photocatalysis tests. The decolourization of organic dyes, methylene blue and rhodamine B, under ultraviolet light over the as-prepared products reveals an excellent photocatalytic performance due to the good absorption for ultraviolet light.

A novel and efficient photocatalyst of three dimensional (3D) Ba5Ta4O15 flower-like microsphere was synthesized via an alkaline etch under hydrothermal condition. The influence of reaction temperature, reaction time, and alkaline concentration on the morphology were investigated for the 3D Ba5Ta4O15 flower-like microsphere photocatalyst. The morphology and structure of the 3D Ba5Ta4O15 were characterized using x-ray diffraction, scanning electron microscope, transmission electron microscope, and high-resolution transmission electron microscopy. The results show that the elegant flower-like structure was composed of Ba5Ta4O15 nanosheets. The 3D Ba5Ta4O15 flower-like microspheres show a higher photocatalytic activity in the degradation of methylene blue under ultraviolet light than the bulk Ba5Ta4O15 microcrystal by the solid-state-reacted synthesized. The UV–vis diffuse reflectance spectra, photoluminescence spectra, volumetric adsorption method, and photocurrent response of the Ba5Ta4O15 photocatalyst were characterized indicated that the higher photocatalytic activity of flower-like Ba5Ta4O15 microspheres was due to the high crystallinity, large surface area and the effective charge separation.

Morphologically controllable copper sulfide (CuS) nanoneedle, nanowall, and nanosheet networks on copper substrates have been fabricated by a simple, facile, and fast method based on low-temperature chemical vapor deposition through simply adjusting the reaction conditions such as the temperature and flow rate of argon gas. The compositional and structural analyses indicated that all the obtained nano-networks were single-crystalline. And their growths were possibly controlled by a solid–liquid–solid mechanism. The photocatalytic activities of the different shaped CuS nanostructures have been evaluated by their photodegradation on rhodamine B and methylene blue in aqueous phase, which revealed that in both cases the CuS nanoneedles nano-network exhibited better performance than the other two nanostructures.

Ag–TiO2 hybrids are useful in various applications, such as photocatalysis, solar energy conversion, and biosensoring. In this study, oil-decorated TiO2 films were used to induce the formation of Ag nanoplates in AgNO3 solution via a photocatalytic method. Ag nanoplates in the products can be controlled by changing the oil-decoration time of films or changing the AgNO3 concentration of the solution. Oil decoration was found to be necessary in the formation of Ag nanoplates, and a critical concentration of AgNO3 solution was needed. The oil layer on the TiO2 films was demonstrated to play a role in the prevention of the reoxidation of the Ag atoms, and a growth model was proposed to interpret the formation of Ag nanoplates on the oil-decorated TiO2 films.

In this study, CeO2 nanowires–reduced graphene oxide hybrids (CeO2 NWs–RGO) were synthesized by a green hydrothermal method using CeO2 NWs and graphene oxide (GO) as raw materials. During the process of reduction of GO, hydrothermal condition with supercritical water provides thermal and chemical factors to synthesize RGO. The photocatalytic experimental results show that the CeO2 NWs–RGO hybrids exhibit enhanced photocatalytic activity for degradation of Rhodamine B (RhB) under UV-light irradiation. It is found that the degree of photocatalytic activity enhancement strongly depends on the mass ratio of RGO in the hybrids, and the remarkable photocatalytic activity is 20 times that of pristine CeO2 NWs when the loading amount of RGO is 8.0 wt%. The enhancement of photocatalytic activity can be attributed to the excellently elevated absorption ability for the dye through π–π conjugation as well as the effective inhibition of the recombination of photogenerated electrons because of the electronic interaction between CeO2 NWs and RGO sheets.

Doping of a heteroatom such as nitrogen in carbon nanomaterials provides a means to tailor their electronic properties and chemical reactivities. In this article, we present simple methods to synthesize carbon quantum dots (CQDs) with high nitrogen doping content (18–22%), involving the reaction of glucose in the presence of urea under hydrothermal conditions or by microwave irradiation. The N-doped carbon quantum dots (N-CQDs) show high aqueous solubility and tunable photoluminescence (PL). Interaction of N-CQDs with exfoliated graphene or dimethylaniline quenches PL. Interaction of N-doped as well as undoped C-dots with electron-donating tetrathiafulvalene and electron-withdrawing tetracyanoethylene has been examined. The intense blue PL of CQDs has been exploited to produce white light by mixing the CQDs with yellow light emitting ZnO nanoparticles or graphene oxide. The N-doped CQDs exhibit superior photocatalytic activity compared to pristine CQDs.