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The evolution of the analytical techniques allowed the detection of pollutants so called contaminants of emerging concern (CEC). Water scarcity is a reality lived by some populations. Thus, water reuse is mandatory to minimize this problematic. This implies that wastewater treatments must be improved. The Advanced Oxidation Processes (AOP) such as photocatalysis and ozonation can be suitable solutions for CECs abatement. Also, TiO2 powder catalyst is an important material in this field. However, its powder form presents a huge obstacle for industrial application, and the solution may be to support this material. This work studies the degradation of a mixture of 3 parabens by photocatalysis, catalytic and photocatalytic ozonation using TiO2 nanotube arrays (NTs). The studied catalysts were produced using electrolyte solutions with different ages, so the nanotubes growth ocurred at 5 (NTs_5) and 20 (NTs_20) anodization cycles. The toxicological assessment for the initial mixture, final samples and along the reaction time was performed using the cress seeds Lepidium sativum and the bacteria Aliivibrio fischeri. The photocatalysis with UVA radiation led to 50 % and 35 % parabens removal for NTs_5 and NTs_20 catalysts. This can be related to the different dimensional characteristics of the nanotubes. Ozone technologies led to total parabens degradation with an improvement when catalytic ozonation was applied. The use of NTs as catalysts in ozonation also reduced the transferred ozone dose (TOD) required for total parabens abatement when compared to single ozonation. The main parabens degradation mechanism seems to be via direct pathway by molecular ozone. Regarding the toxicity assessment, the toxicity did not change significatively, which can be explained by the intermediate’s formation.

A new and active material in the form of ZnIn2S4 microspheres decorated by CuInS2 quantum dots have been obtained by hydrothermal method for the first time. The optimum amount of CuInS2 quantum dots (1.13 wt.%) introduced into rection medium during ZnIn2S4 microspheres synthesis increased the photocatalytic H2 generation rate by 2.5 times than that of bare ZnIn2S4 photocatalysis under visible light irradiation. This sample exhibited strong photoactivity in the extended visible range up to 540 nm with 30.6% apparent quantum efficiency (λ = 420 nm).

Applied cutting-edge electronic structure and phonon simulations provide a reliable knowledge about the stability of perovskite structures and their electronic properties, which are crucial for des...

Ionic liquids (ILs) containing distinct nitrogen-bearing organic cations (pyridinium, pyrrolidinium, imidazolium, ammonium, morpholinium) were first used for the preparation of 23 IL-TiO2 types of composites by ionic liquid assisted solvothermal synthesis. These 23 optimal ILs structures (i.e. compounds exhibiting an optimal combination of specific properties, functionality, and safety) for synthesis and experimental validation were selected by computational high-throughput screening from a combinatorically created library containing 836 ILs theoretically designed and characterized candidates. Then, selected IL-TiO2 structures with potential photocatalytic activity were synthesized with the use of solvothermal reaction. Then, the decomposition level, the role of the individual IL cation structure on the morphology, thermal stability, surface and photocatalytic properties of the IL-TiO2 microparticles were determined experimentally. The chemoinformatic analysis of the relationship between the structure of the ionic liquid, its thermal stability under the conditions of synthesis and photocatalytic activity was applied for the first time. The results presented here are the first step in the development of methodology (combined experimental and theoretical) that may simplify the procedure of designing safer and more efficient TiO2-based photocatalyst. The developed computational methodology makes it possible to predict properties of newly synthesized IL-TiO2 materials before synthesis and identifies structural features of ILs that influence the efficiency of IL-TiO2 system. The presented approach reduces the number and cost of necessary experiments, as well as increases the success ratio of efficient TiO2-based photocatalyst design by a selection of optimal IL structures (i.e. ionic liquid characterized by a combination of most promising physicochemical features).

Photocatalytic water splitting has great potential in solar-hydrogen production as a low-cost and environmentally friendly method. Different unique techniques used to obtain photocatalysts with various modifications to improve H2 generation have been introduced. In the present work, SrTiO3 was successfully synthesized via the solvothermal method in the presence of ionic liquid (IL) - 1-butyl-3-methylimidazolium bromide ([BMIM][Br]) followed by surface decoration with Pt particles using the photodeposition method. The effect of the noble metal content and presence of IL on the morphology, optical and surface properties of SrTiO3, thereby the effectiveness of hydrogen generation, has been thoroughly examined and presented. Unexpectedly, the presence of [BMIM][Br] at the SrTiO3 surface affected the interaction between the semiconductor surface and platinum particles formed throughout photodeposition. Platinum particles at the surface of SrTiO3_IL were found to be in the form of 2D clusters with a size of 1 nm. In comparison, Pt deposited on SrTiO3 photocatalyst without application of IL created larger, three-dimensional structures with a diameter exceeding 5 nm. This is the reason why the total amount of platinum deposited on the SrTiO3_IL sample is smaller than that on SrTiO3 and justifies a higher efficiency of hydrogen generation of Pt modified SrTiO3 photocatalyst in comparison to SrTiO3 prepared in the presence of IL. The mechanism of H2 generation in the water-splitting reaction in the presence of SrTiO3_Pt photocatalyst was discussed.

The utilization of solar light to induce a photocatalytic reaction in the presence of wide band gap semiconductors requires the modification of their surface and optical properties. The Vis-to-UV up-conversion process (UCP) that occurs in lanthanide ions could be employed to induce TiO2. Thus, having in mind solar-forced photocatalysis, nanostructured TiO2 co-modified with Tm and Li was prepared via a hydrothermal method. In addition to the exhaustive surface characterization of the as-prepared samples, the partial density of states (PDOS) was computed to better understand the electronic structure and physicochemical properties of the prepared photocatalysts. It was demonstrated that Tm ions were beneficial for phenol degradation in the aqueous phase under visible irradiation, whereas the co-presence of Tm and Li ions was profitable for enhanced luminescence. Although action spectra revealed that excitation of Tm-TiO2 in the range from 400 to 490 nm led to the photodegradation of phenol and 2-propanol, the UCP was not responsible for the photocatalytic activity under Vis irradiation. Therefore, it is proposed that the formation of sub-band gap states from the lanthanide 4f level played a key role in the phenol degradation process.

Due to their photon up-converting capability, lanthanide ions are ideal candidates dopants for semiconductors for developing visible light-driven photocatalytic activity. Of particular relevance, the low luminescence efficiency of Ln-based nanoparticles is one of the main factors that limits their further applications. Carbon, which is present on the surface of all TiO2 photocatalysts, can be responsible for luminescence quenching processes and, thus, decreasing the photocatalytic activity of TiO2. This article presents a systematic experimental and theoretical study of the effects of carbon on the photocatalytic performance of Ho3+-modified TiO2. Ho3+-TiO2 photocatalysts modified with various carbon contents (from 0.5 to 20 mol.%) were successfully prepared using a simple hydrothermal method. As-obtained samples were characterized by UV–Vis diffuse reflectance spectroscopy (DRS/UV–Vis), X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), N2 adsorption measurements, photoluminescent spectroscopy (PL), field-emission scanning electron microscopy (FE-SEM) and scanning transmission microscopy (STEM). The photodegradation efficiency of phenol was estimated for visible light (λ > 420 nm and λ > 455 nm). The XPS and XRD analyses and theoretical calculations revealed that the substitutional doping of holmium and carbon in the TiO2 anatase structure resulted in the appearance of a new sub-band-gap. Changes in the material texture, BET surface area and pore volume can be easily controlled via carbon content in samples. Doping of the Ho3+-TiO2 photocatalysts with carbon resulted in quenching of the emission of Ho3+ and, thus, the photodegradation of phenol, was observed in samples containing smaller amounts of carbon. Sixty minutes of irradiation resulted in 89% of phenol degradation under visible light (λ > 420 nm).

The efficient and safe degradation of drugs present in wastewater requires the design of a new material possessing high activity for that process. In addition to other methods, photoelectrocatalysis (PEC) merges the strengths of both photocatalytic and electrochemical methods, and the efficiency could be enhanced by the type of photoelectrode material. To address this challenge, three Ti/TiO2 nanotube-based photoelectrodes, differing in their tube morphology, were prepared by anodic oxidation and employed for the degradation of the 5-fluorouracil (5-FU) drug by the PEC process. The highest efficiency for 5-fluorouracil (5-FU) degradation by PEC was observed for the photoelectrode with a 1.7 μm length, 65 nm diameter and 8 nm wall thickness of TiO2 nanotubes, which were prepared by Ti foil anodization at 30 V. The effects of applied potential, irradiation intensity, initial pH and 5-FU concentration on PEC were investigated. Furthermore, our findings showed that the mechanism of photoelectrocatalysis in the presence of TiO2 nanotubes is based on ∙OH and h+ activity. To determine the 5-FU degradation pathway, the organic byproducts were identified by LC-MS analysis. Furthermore, the ecotoxicity evaluated during PEC dropped with decreasing 5-FU concentration.

Application of Ti90RE10 alloys (RE = Ho, Er, Nd, Y, Ce, Tm) as a working electrode, instead of Ti pure foil in anodic oxidation in a fluoride-based electrolyte, resulted in formation of well-ordered nanotubes made of TiO2 and RE2O3 mixture, which could be efficiently used for pollutant removal from water and air phase upon UV and visible irradiation and easily separable from the reaction mixture to recycle. The as-prepared NTs were characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX), diffuse reflectance spectroscopy (DRS), luminescence spectroscopy, X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the synthesized samples was investigated used phenol and toluene as a model compounds to follow degradation kinetics. The influence of the RE metals on the photoelectrochemical performance of modified TiO2 NTs was investigated. Surface morphology analysis showed formation of uniform and vertically oriented NTs structures with an open tube top and smooth walls. The results of EDX, XRD and XPS analysis proved that RE ions exist as surface compounds (RE3+ oxides). Visible light induced photoactivity (both photocatalytic and photoelectrochemical) is mostly pronounced in the presence of nanotubes obtained by anodic oxidation of Ti90Ho10 alloy. These nanotubes are able to degrade toluene in the gas phase even by irradiation of low-powered light source, such as light emitting diodes (λmax = 465 nm). Photocatalytic test of phenol degradation in the presence of scavenger indicates that photogenerated electrons and superoxide radicals play a meaningful role in the photocatalytic degradation of pollutants under visible irradiation. In addition, the photoelectrochemical tests performed under the influence of visible light irradiation confirmed that the RE-modification of TiO2 NTs caused a significant increase of photocurrent (up to 10 times higher). The new and original results on the preparation of RE2O3/TiO2 nanotubes obtained in one step anodic oxidation and photocatalytic activity in aqueous and gas phases represent an important contribution then will benefit photocatalytic surfaces preparation technologies. Keywords: RE2O3-TiO2 nanotubes, Ti/RE alloys, Anodic oxidation, Photodegradation, visible-light-driven photocatalysis

The contemporary search for new catalysts for olefin oligomerization and polymerization is based on the study of coordinating compounds and/or organometallic compounds as post-metallocene catalysts. However known catalysts are suffered by many flaws, among others unsatisfactory activity, requirement of high pressure or instability at high temperatures. In this paper, we present a new catalyst i.e. the crystalline complex compound possesing high catalytic activity in the oligomerization of olefins, such as 2-chloro-2-propen-1-ol and ethylene under very mild conditions (room temperature, 0.12 bar for ethylene oligomerization, atmospheric pressure for 2-chloro-2-propen-1-ol oligomerization). New material - Cat-CrNP ( [nitrilotriacetato - 1,10–phenanthroline]chromium(III) tetrahydrate) has been obtained as crystalline form of the nitrilotriacetate complex compound of chromium(III) with 1,10-phenanthroline and characterized in terms of its crystal structure by the XRD method and by multi-analytical investigations towards its physicochemical propeties The yield of catalytic oligomerization over Cat-CrNP reached to 213.92 g ∙ mmol-1 ∙ h-1∙ bar-1 and 3232 g ∙ mmol-1 ∙ h-1 ∙ bar-1 for the 2-chloro-2-propen-1-ol and ethylene, respectively. Furthemore, the synthesis of Cat-CrNP is cheap, easy to perform and solvents used during preparation are environmentally friendly.

The design of an active, stable and efficient photocatalyst that is able to be used for hydrogen production is of great interest nowadays. Therefore, four methods of AgTaO3 perovskite synthesis, such as hydrothermal, solvothermal, sol-gel and solid state reactions, were proposed in this study to identify the one with the highest hydrogen generation efficiency by the water splitting reaction. The comprehensive results clearly show that the solid state reaction (SSR) led to the obtainment of a sample with an almost seven times higher photocatalytic activity than the other methods. Furthermore, four ionic liquids, all possessing nitrogen in the form of organic cations (two imidazoliums with different anions, ammonium and tetrazolium), were used for the first time to prepare composites consisting of AgTaO3 modified with IL and Pt, simultaneously. The effect of the ionic liquids (ILs) and Pt nanoparticles&rsquo, presence on the structure, morphology, optical properties, elemental composition and the effectiveness of the hydrogen generation was investigated and discussed. The morphology investigation revealed that the AgTaO3 photocatalysts with the application of [OMIM]-cation based ILs created smaller granules (&lt, 500 nm), whereas [TBA] [Cl] and [TPTZ] [Cl] ILs caused the formation of larger particles (up to 2 &mu, m). We found that various ILs used for the synthesis did not improve the photocatalytic activity of the obtained samples in comparison with pristine AgTaO3. It was detected that the compound with the highest ability for hydrogen generation under UV-Vis irradiation was the AgTaO3_0.2% Pt (248.5 &mu, mol∙g&minus, 1), having an almost 13 times higher efficiency in comparison with the non-modified pristine sample. It is evidenced that the enhanced photocatalytic activity of modified composites originated mainly from the presence of the platinum particles. The mechanism of photocatalytic H2 production under UV-Vis light irradiation in the presence of an AgTaO3_IL_Pt composite in the water splitting reaction was also proposed.

A series of novel ZnO quantum dots modified with rare earth metals was successfully prepared by a simple sol-gel approach. The effects of types (Eu, Er, Tb, Yb, Ho, La) and amounts (from 0.09 to 0.45 mmol) of lanthanides on the optical properties, structural characterization and photocatalytic activity of ZnO/RE QDs were systematically investigated. The X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) with energy dispersive X-ray analysis (EDX) and UV–Vis diffuse reflectance spectroscopy were used to characterize surface properties, while photoluminescence (PL) emission spectroscopy and UV–Vis-driven degradation of phenol in aqueous phase were applied to understand optical and photocatalytic properties. The experiments demonstrated that generally modification of ZnO QDs by lanthanides resulted in increase of photoactivity while photoluminesce decrease at the same moment. The highest photocatalytic activity among all obtained nanomaterials and the lowest photoluminescence quantum yield among ZnO/Er photocatalysts were observed for ZnO QDs modified with 0.09 mmol of erbium. Increased photocatalytic activity has been shown in successive samples: ZnO/0.09_Er > ZnO/0.18_Eu > ZnO/0.09_La > ZnO/0.27_Er > ZnO/0.18_Tb > pristine ZnO QDs. The experimental results were supported by calculations based on density functional theory (DFT) which revealed atomic and electronic structure of Er/La modified ZnO QDs.

Formation of a surface complex between organic molecules and TiO2 is one of the possible strategies for the development of visible light-induced TiO2 photoactivity. Herein, three ionic liquids (ILs) with the same cation and different anions (1-butylpirydynium chloride/bromide/iodide) have been applied for the surface modification of TiO2 and to understand the role of anions in visible light-induced activity of ILs-TiO2 systems. Photocatalytic screening tests (the measurements of phenol photodegradation reaction rate) revealed that anion type affected visible light activity (&lambda, &gt, 420 nm) of TiO2 obtained by the ILs-assisted solvothermal method. Density functional theory (DFT) calculations demonstrated that interactions between halogen anions and oxygen vacancies (OV) on the surface of the TiO2 particles could be responsible for the specific wavelength-induced excitation and finally for the observed photoactivity of titania under visible light. Finally, our theoretical calculations have been proven by experiments using monochromatic light (the apparent quantum efficiency was measured) and the properties of obtained samples were characterized using scanning electron microscopy (SEM), X-ray powder diffraction analysis (XRD), UV-Vis spectroscopy and X-ray photoelectron spectroscopy (XPS).

Conversion coatings are one of the primary types of galvanic coatings used to protect steel structures against corrosion. They are created through chemical reactions between the metal surface and the environment of the phosphating. This paper investigates the impact that the addition of new metal cations to the phosphating reaction environment has on the quality of the final coating. So far, standard phosphate coatings have contained only one primary element, such as zinc in the case of zinc coatings, or two elements, such as manganese and iron in the case of manganese coatings. The structural properties have been determined using a scanning electron microscope (SEM), X-ray diffraction (XRD), and electrochemical tests. New manganese coatings were produced through a reaction between the modified phosphating bath and the metal (Ba, Zn, Cd, Mo, Cu, Ce, Sr, and Ca). This change was noticeable in the structure of the produced manganese phosphate crystallites. A destructive effect of molybdenum and chromium was demonstrated. Microscopic analysis, XRD analysis and electrochemical tests suggest that the addition of new metal cations to the phosphating bath affects the corrosion resistance of the modified coating.

Silver phosphate (Ag3PO4) could be considered as visible light induced photocatalyst for pollutants degradation, due to its narrow band gap (∼2.4 eV). However, Ag3PO4 photoactivity depends on surface properties and synthesis route. In this study, differently shaped Ag3PO4 photocatalysts have been synthesized through the precipitation, ion exchange, soft-chemical or hydrothermal method. To correlate surface properties with photoactivity all samples were characterized towards morphology, crystal structure, specific surface area, optical properties, chemical composition and activity in phenol degradation upon visible light irradiation (λ > 420 and 455 nm). It is worthwhile noting that the most active Ag3PO4 samples possessed almost the same activity in phenol degradation upon irradiation from visible range (λ > 455 nm) that P25 TiO2 upon UV light. Phenol degradation rate equaled to 3.31 and 3.23 μmol/dm3/min in the presence of branched and rhombic dodecahedral Ag3PO4 particles, while it reached 3.36 μmol/dm3/min in the presence of P25 and UV light. Analysis of the degradation intermediates indicated that the benzoquinone was the primary byproducts of phenol degradation. Scavengers-assisted photocatalytic test confirmed that mainly O2− has been involved in phenol degradation under visible radiation. Surface composition analysis by XPS suggested that higher total silver content favors photoactivity, while higher ratio of Ag0 to Ag+ suppress photoactivity. Long term photocatalytic tests also implies that increase in Ag0 amount at the Ag3PO4 surface, due to photoreduction of Ag ions, rusulted in activity drop.

Novel triple-layered trimetallic Au/Pd/Pt nanoparticles (NPs) with a porous Pt shell, showing a hedgehog-like structure, were successfully bounded with TiO2 and NaTaO3 surfaces, and used for photoc...

This review provides an in-depth analysis of lanthanide-titania-modified semiconductor photocatalysts (Er-, Ho-, Nd- and Tm-TiO2) for the photocatalytic degradation of organic pollutants under UV and visible light irradiation. In the first section, the unique properties of the lanthanides are summarized. In the second section, the influence of the preparation methods and surface properties of the selected rare earth metals (RE) on the photocatalytic activity of TiO2 was surveyed. In the third section, the mechanism of the RE-TiO2 visible light photoactivity was described. Finally, first-principles computer simulations of the RE-TiO2 structure and energy along with the influence of the anti-Stokes up-conversion process on the photocatalytic activity of the RE-TiO2 were discussed in detail.

The oriented TiO2 nanotube arrays (NTs) are identified as a stable, active, and recyclable photocatalytic surface. However, their photoactivity is strictly dependent on morphology (especially length), which could be controlled by anodic oxidation parameters, including electrolyte properties. To control the morphology a series of NTs were successfully synthesized by a novel approach where ionic liquid (IL), ethylammonium nitrate [EAN][NO3], was used as an addition to an organic electrolyte. Using scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, diffuse reflectance UV–vis spectroscopy, and photoluminescence spectroscopy, we are able to show how electrolyte composition influences nanotubes’ surface properties and photocatalytic activity. It was found that the change in the amount of [EAN][NO3] in the electrolyte used for anodization in the range from 0.05 to 1.0 wt % affected dynamic viscosity, conductivity, and surface tension of the electrolyte and finally altered the morp...

New, monometallic nanoparticles (MNPs) decorated surface and rare earth (RE) ions doped lattice of perovskite-type (KTaO 3 )/pyrochlore-type (K 2 Ta 2 O 6 ) photocatalysts were successfully prepared by facile hydrothermal incorporation of RE ions into KTaO 3 /K 2 Ta 2 O 6 lattices followed by photodeposition of MNPs. The impact of noble metal type (MNPs = Au, Pt, Rh) and rare earth dopant type (RE = Er, Pr) on the physicochemical properties correlated with photoactivity of MNPs/RE-KTaO 3 and MNPs/RE-K 2 Ta 2 O 6 has been examined. All as-prepared photocatalysts were systematically characterized by UV–vis diffuse reflectance spectroscopy, photoluminescence emission spectroscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, fast Fourier transform, powder X-ray diffraction, and X-ray photoelectron spectroscopy. The crystal structure was presented using VESTA software. Photocatalytic activity of samples under visible light irradiation was determined by pollutant decomposition, while UV–vis induced activity was estimated by H 2 generation efficiency. The experimental results suggested a synergistic effect between MNPs and RE-ions-modified KTaO 3 /K 2 Ta 2 O 6 , which resulted in greatly improved photocatalytic performance compared with that of pristine KTaO 3 /K 2 Ta 2 O 6 . Inclusion of RE ions into KTaO 3 /K 2 Ta 2 O 6 lattices probably leads to formation of RE4 f states below the conduction band levels to electron transition by lower photon excitation energy, while photoreduction of MNPs on the RE-KTaO 3 /RE-K 2 Ta 2 O 6 surface causes localized surface plasmon resonance and activates surface by adsorption for both O 2 and H 2 O molecules. The highest visible-light-induced photoactivity was observed for the Au/Er-KTaO 3 sample (16.48%) in phenol solution degradation and for the Pt/Pr-K 2 Ta 2 O 6 photocatalyst (36.13%) in gaseous toluene removal, respectively. Active species-trapping tests indicate that O 2 − radicals are meaningfully involved in phenol oxidation under visible light irradiation. The largest amount of H 2 evaluation was observed for the Pt/Pr-K 2 Ta 2 O 6 sample (93.16 µmol/min) under UV–vis irradiation, which also showed a relatively good lifetime in recycling. The present study describes noble- and rare-earth-metal-modified KTaO 3 /K 2 Ta 2 O 6 as an advanced material in photocatalysis.

In the present work, two H2 evolution photocatalysts were prepared by employing two different oxides, TiO2 and zirconium titanate (ZrTiO4), as the support of various copper phases. For both the supports the same Cu loading (0.5% w/w) was adopted, but two different impregnation procedures have been followed, leading to different forms of Cu in the final composite material that are: (i) Cu(II) species dispersed on the oxide surface and (ii) Cu2O particles dispersed on the oxide surface. The present paper based on the parallel use of photocatalytic test and spectroscopic analysis performed in catalytic conditions illustrates the evolution of photocatalytic systems occurring during the H2 evolution reaction tests, pointing out that the as-prepared materials represent a pre-catalyst and they are modified during irradiation leading to the real working systems different from the starting ones. The herein presented spectroscopic analysis aims to contribute to the living debate on the oxidation state of copper in mixed Cu/oxide materials and on its role in hydrogen evolution under photocatalytic conditions.

Quantum dot (QD)-decorated semiconductor micro- and nanoparticles are a new class of functional nanomaterials that have attracted considerable interest for their unique structural, optical and electronic properties that result from the large surface-to-volume ratio and the quantum confinement effect. In addition, because of QDs' excellent light-harvesting capacity, unique photoinduced electron transfer, and up-conversion behaviour, semiconductor nanoparticles decorated with quantum dots have been used widely in photocatalytic applications for the degradation of organic pollutants in both the gas and aqueous phases. This review is a comprehensive overview of the recent progress in synthesis methods for quantum dots and quantum dot-decorated semiconductor composites with an emphasis on their composition, morphology and optical behaviour. Furthermore, various approaches used for the preparation of QD-based composites are discussed in detail with respect to visible and UV light-induced photoactivity. Finally, an outlook on future development is proposed with the goal of overcoming challenges and stimulating further research into this promising field.

A series of binary TiO2/SrTiO3 and ternary TiO2/SrTiO3_BiOI composites have been synthesized using multistep preparation method. Characterization of the obtained photocatalysts covered complex analysis including morphology + y (SEM), BET specific surface area, porosity, optical properties (DRS), chemical composition of surface (XPS), crystal structure and crystal size (XRD). UV–vis and Vis ligh induced photocatalytic activity was investigated in the model reaction of phenol degradation in the aqueous phase. The powder TiO2/SrTiO3_BiOI ternary composites exhibited a new photocatalytic properties and could be used in the heterogeneous photocatalysis processes. The photocatalytic activity observed in the phenol degradation reaction significantly increased under the visible light range irradiation. The best photocatalytic activity was observed for the TiO2/SrTiO3_BiOI_4 sample, about 30.2 % of phenol was decomposed after 1 h of visible light irradiation. The utilization of the nanolayered materials facilitates the separation of photocatalysts from the aqueous phase. Moreover, the composite was easily reused without the significant decrease of the photocatalytic activity in three subsequent cycles. After 5 h of Vis irradiation of the isotopically labeled (1-13C) phenol solution in the presence of the TiO2/SrTiO3_BiOI_4 composite, the salicylic, maleic, fumaric and malonic acids were detected using GC–MS equipment. The identification of degradation by-products led to clarification of phenol decomposition pathway. The role of active species during the decomposition process of organic compound was investigated using different types of active species scavengers.

Novel mono- and bimetallic nanoparticles (MNPs and BNPs) decorated surface of perovskite-type KTaO3 photocatalysts were successfully synthesized by hydrothermal reaction of KTaO3 followed by photodeposition of MNPs/BNPs. The effect of noble metal type (MNPs = Au, Ag, Pt, Pd, Rh, Ru or BNPs = Au/Pt, Ag/Pd, Rh/Ru), amount of metal precursor (0.5, 1.0, 1.5 or 2.0 wt%) as well as photoreduction method (simultaneous (both) or subsequent (seq) deposition of two metals) on the physicochemical and photocatalytic properties of MNPs- and BNPs-KTaO3 have been investigated. All as-prepared photocatalysts were subsequently characterized by UV–Vis diffuse reflectance spectroscopy (DRS), Brunauer-Emmett-Teller (BET) specific surface area and pore size distribution measurement, scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (PXRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) emission spectroscopy. The crystal structure was performed using visualization for electronic and structural analysis (VESTA). The photocatalytic activity under Vis light irradiation was estimated in phenol degradation in aqueous phase and toluene removal in gas phase, while under UV–Vis light irradiation was measured amount of H2 generation from formic acid solution. The absorption properties of O2 and H2O molecules on KTaO3(1 0 0) surface supported by Au or Au/Pt NPs was also investigated using density-functional theory (DFT). The experimental results show that, both MNPs-KTaO3 and BNPs-KTaO3 exhibit greatly enhanced pollutant decomposition efficiency under Vis light irradiation and highly improved H2 production under UV–Vis light irradiation compared with pristine KTaO3. MNPs deposition on KTaO3 surface effects by disperse metal particle size ranging from 11 nm (Ru NPs) to 112 nm (Au NPs). Simultaneous addition of Au/Pt precursors results in formation of agglomerated larger metal nanoparticles (50–100 nm) on KTaO3 surface than subsequent deposition of Au/Pt with composition of concentrated smaller metal nanoparticles (>50 nm) on KTaO3 surface. The 0.5 Au/1.5 Pt-KTaO3_both and 2.0 Rh-KTaO3 reveal the highest Vis-induced activity among prepared samples in aqueous phase (14.75% of phenol decomposition after 90 min of irradiation) and gas phase (41.98% of toluene removal after 60 min of irradiation), respectively. The theoretical calculations confirmed that adsorption energy of O2 and H2O molecules was increased after loading of Au or Au/Pt NPs on KTaO3(1 0 0) surface. Control tests with scavengers show that O2 − radical is significantly involved in phenol oxidation under Vis light irradiation, which proposed mechanism is based on direct electron transfer from MNPs/BNPs to conduction band of KTaO3. The highest amount of H2 evaluation is obtained also by 0.5 Au/1.5 Pt-KTaO3_both after 240 min of UV–Vis light irradiation (76.53 µmol/min), which is eleven times higher than for pristine KTaO3 (6.69 µmol/min). Moreover, the most photocatalytic samples for each model reaction present good repeatability and stability after subsequent three cycles. Summarized, MNPs- and BNPs-KTaO3 are promising material in advanced applications of photocatalysis.

Novel rare earth-doped K2Ta2O6 (RE-K2Ta2O6) photocatalysts were successfully synthesized by one-step hydrothermal method. The effect of dopant type (RE = Y, Yb, Ho, Pr, Er) and amount of rare earth precursor (2, 4, 8 and 10 mol%) on the physicochemical and photocatalytic properties of RE-K2Ta2O6 have been investigated. All as-prepared materials were subsequently characterized by UV–vis diffuse reflectance spectroscopy (DRS), Brunauer-Emmett-Teller (BET) specific surface area measurement, scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, mass magnetic susceptometry and photoluminescence (PL) emission spectroscopy. The photocatalytic activity under UV–vis light irradiation was estimated in phenol degradation in aqueous phase, toluene removal in gas phase and H2 generation from formic acid solution. The experimental results show that, novel RE-K2Ta2O6 exhibits greatly improved degradation efficiency under UV–vis light irradiation compared with pristine K2Ta2O6. The Er-K2Ta2O6 and Pr-K2Ta2O6, obtained by introducing of 2 mol% of RE ions during synthesis, reveal the highest photocatalytic activity among prepared samples in aqueous phase (33% of phenol decomposition after 90 min of irradiation) and gas phase (45% of toluene removal after 60 min of irradiation), respectively. Moreover, both photocatalysts present good stability after subsequent three cycles. The active species trapping test shows that OH and O2 − radicals are significantly involved in phenol oxidation under UV–vis light irradiation. The amount of H2 evolution increases with increasing addition of Er dopant into K2Ta2O6 lattice. The highest H2 production is obtained for 10 mol% Er-K2Ta2O6 after 240 min of UV–vis light irradiation (15.40 μmol/min). Enhanced photoactivity performance can be attributed to incorporation of RE ions at K+ lattice site in RE-K2Ta2O6, probably leading to formation of new RE 4f states below the conduction band of K2Ta2O6 structure. To investigate the localization of RE ions in K2Ta2O6 structure, the band structure and partial density of the states (PDOS) have been investigated. Computer simulations were performed using plane-wave based Vienna ab-initio simulation package (VASP) with the generalized gradient approximation (GGA) by Perdew-Burke-Ernzerhof (PBE). Moreover, inclusion of RE ions in K2Ta2O6 causes predominance pyrochlore phase formation over perovskite in regular cubic structure. Summarized, RE-doped K2Ta2O6 is promising material in photocatalytic degradation of organic pollutants and H2 generation processes. Our work may provide valuable information for rare earth doping semiconductor with improved photocatalytic performance.

Herein, the synthesis and application of functionalized quantum dot-based protease probes is described. Such probes are composed of nontoxic ZnO nanocrystals decorated by amino groups followed by linker and labeled peptide attachment. Spherical NH2-terminated ZnO quantum dots (QDs) with the average size ranging from 4 to 8 nm and strong emission centered at 530 nm were prepared using the sol–gel method. The fluorescence of ZnO QDs was quenched by the BHQ1 moiety present on the N-terminal amino group of the peptide. The enzymatic cleavage of the peptide mediated by the proteinase 3 (PR3) bond resulted in an increase in the QD probe fluorescence. This observation was verified using both model and biological systems; and the picomolar detection limit was found to be more than 30 times lower than that of the previously reported internally quenched peptide (a decrease in detection limit from 43 to 1.3 pmol was observed).

To investigate the effect of the ionic liquid (IL) chain length on the surface properties and photoactivity of TiO2, a series of TiO2 microspheres have been synthesized via a solvothermal method assisted by 1-methyl-3-octadecylimidazolium chloride ([ODMIM][Cl]) and 1-methyl-3-tetradecylimidazolium chloride ([TDMIM][Cl]). All as-prepared samples were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), scanning transmission microscopy (STEM) and the Brunauer–Emmett–Teller (BET) surface area method, whereas the photocatalytic activity was evaluated by the degradation of phenol in aqueous solution under visible light irradiation (λ > 420 nm). The highest photoefficiency (four times higher than pristine TiO2) was observed for the TiO2 sample obtained in the presence of [TDMIM][Cl] for a IL to TiO2 precursor molar ratio of 1:3. It was revealed that interactions between the ions of the ionic liquid and the surface of the growing titanium dioxide spheres results in a red-shift of absorption edge for the IL–TiO2 semiconductors. In this regard, the direct increase of the photoactivity of IL–TiO2 in comparison to pristine TiO2 was observed. The active species trapping experiments indicated that O2•− is the main active species, created at the surface of the IL–TiO2 material under visible-light illumination, and is responsible for the effective phenol degradation.

Nd-modified TiO2 photocatalysts have been obtained via hydrothermal (HT) and sol–hydrothermal (SHT) methods. The as-prepared samples were characterized by X-ray diffraction (XRD), BET surface area measurements, scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), luminescence spectroscopy and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity of the synthesized samples was evaluated by the degradation of phenol in aqueous solution under irradiation with UV–vis (λ > 350 nm) and vis (λ > 420 nm) light, as well as by the degradation of gaseous toluene under irradiation with vis (λmax = 415 nm) light. It was found that Nd-modified TiO2 is an efficient photocatalyst for the degradation of phenol and toluene under visible light. XPS analysis revealed that the photocatalyst prepared via HT method contains a three-times higher amount of hydroxy groups at the surface layer and a two-times higher amount of surface defects than that obtained by the SHT method. The photocatalytic efficiency of phenol and toluene degradation under vis irradiation in the presence of 0.25% Nd-TiO2(HT) reached 0.62 and 3.36 μmol·dm−1·min−1, respectively. Photocatalytic activity tests in the presence of Nd-TiO2 and scavenger confirm that superoxide radicals were responsible for the visible light-induced degradation of the model pollutant in aqueous solution.

Ordered titanium dioxide nanotube arrays fabricated via electrochemical route are considered as a promising material for photocatalytic applications. Due to their amorphous character, a subsequent crystallization step is usually required. In this work, well-aligned nanotube arrays were annealed under flowing gas streams of different compositions (air/steam, air, N2/steam, N2, and O2/steam) in a temperature range from 140 to 543 °C. Under continuous gas flow, the morphology of the crystallized titanium dioxide is strongly affected by the gas atmosphere. When using a dry gas for annealing, the tube structure was almost destroyed after 1 h treatment at 473 °C. In contrast, when annealing the titania nanotube array in a water vapor/gas stream, the tube morphology can be maintained up to 543 °C and 10 h annealing time. Moreover, nanotube arrays crystallized in a flowing gas atmosphere containing water vapor showed a significantly higher photocatalytic activity for phenol degradation under UV irradiation than nanotube arrays crystallized in a dry gas stream. Reasons for this behavior might be the preservation of the tubular structure as well as a lower concentration or density of structural defects in presence of water vapor which leads to an enhanced generation of reactive oxygen species when the arrays are exposed to UV-light.

The human health and environmental risk assessment of engineered nanomaterials (NPs) is nowadays of high interest. It is important to assess and predict the biological activity, toxicity, physicochemical properties, fate and transport of NPs. In this work, a combined experimental and computational study is performed in order to estimate the toxicity and develop a predictive model for heterogeneous NPs (i.e. modified NPs, created from more than one type of NPs). Quantitative structure–activity relationship (QSAR) methods have not been yet adopted for predicting the toxicity/physicochemical properties of modified heterogeneous nanoparticles (so-called heterogeneous NPs). Since the main problem for nano-QSAR/nano-QSPR modeling of heterogeneous NPs was a lack of appropriate descriptors that are able to express the specific characteristics of 2nd generation NPs, we developed here a novel approach. The novel approach to encode heterogeneous NPs is based on the idea of additive descriptors for mixture systems previously applied only to mixtures of organic/inorganic compounds. Thus, based on the proposed novel approach, we have performed experimental and theoretical studies to develop nano-QSAR models describing the cytotoxicity of 34 TiO2-based NPs modified by (poly)metallic clusters (Au, Ag, Pt) to the Chinese hamster ovary cell line. The models showed a good predictive ability and robustness. This approach can be used as an efficient tool for assessing the toxicity as well as physicochemical properties of unexplored heterogeneous NPs.

CdS quantum dot-decorated KNbO3 composite photocatalysts co-modified with Bi2S3 QDs were designed and synthesized by a combination of the hydrothermal method with a linker-assisted adsorption route, using starch and thioglycolic acid as capping agents, which facilitated the attachment of modifiers to the surface of potassium niobate. The quantum dots were successfully deposited onto the surface of the perovskite-type KNbO3 with a good dispersion and a stable heterostructure was formed. The as-prepared photocatalysts were subsequently characterized by UV-Vis diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), Fourier transform infrared spectroscopy (FT-IR), Brunauer–Emmett–Teller (BET) specific surface area, X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) emission spectroscopy. The obtained KNbO3-based composites showed greatly improved photocatalytic performance for the degradation of phenol in the aqueous phase under visible light irradiation (λ > 420 nm) over pristine KNbO3. The highest photocatalytic performance and enhanced stability were observed for the ternary 30% CdS–5%Bi2S3 quantum dot-decorated KNbO3 composite, which could be related to the enhanced visible-light absorption ability, efficient charge separation in the three-level electron transfer heterojunction, improved stability and appropriate amounts of composite components. The formation of a surface layer of CdO decreased the visible light photoactivity of the CdS QD-decorated KNbO3 photocatalysts. The main phenol oxidation intermediates were benzoquinone, catechol, hydroquinone, and 1,2,4-benzenetriol, which underwent further photooxidation to form non-cyclic organic acids. Action spectral analysis proved the better photocatalytic activity of the ternary CdS/B2S3 QDs co-decorated KNbO3 composite compared to the binary CdS QDs decorated KNbO3 sample and revealed that irradiation ranging from 420 to 520 nm was responsible for the visible light photoactivity.

Highly efficient and quite stable composite with core-shell-like architecture reported herein, responds to the challenge of sunlight-driven photocatalysts. The Ln(ndc)/TiO2 photocatalytic system comprises active lanthanide-carboxylate coordination networks (Nd, Er, Ho, and Tm as metal ions, and 2,6-naphthalene dicarboxylic acid as the organic linker) and inert titanium dioxide and allow to convert incompatible visible radiation into functional ultraviolet photons. The combination of the antenna-reactor photocatalyst complex with Ln(ndc) shell layers promotes light harvesting and efficient mass transfer, resulting in additional photoexcited electrons. The Nd(ndc) metal-organic frameworks successfully activate TiO2 via up-conversion energy transfer. The apparent quantum efficiency, determined at wavelengths corresponding to the transitions from the Nd3+ ground state, equals to 2.8% and 3.2% for 525 and 583 nm, respectively. Integration of the Nd(ndc) MOFs and TiO2 results in the highest efficiency of phenol degradation, affording a value of 87.5% after 60 min of visible light (λ > 420 nm) exposure.

In this study, we report a novel method of BaZrO3 and SrZrO3 surface modification by two different types of quantum dots (QDs, Cu2O and Bi2O3), which improved the photocatalytic performance of the obtained materials under UV-Vis light irradiation. Pristine BaZrO3 and SrZrO3 were prepared by the hydrothermal method. The deposition of Cu2O- and Bi2O3-QDs was carried out by chemical reduction. The morphology of the nanoparticles was estimated based on microscopic analysis (SEM, TEM). The perovskite structure and phase composition of polycrystals were confirmed by X-ray powder diffraction analysis (XRD). The elemental surface composition and the chemical character of detected elements were identified by X-ray photoelectron spectroscopy (XPS). The absorption ability and luminescence properties of nanocomposites were investigated by UV–Vis diffuse-reflectance spectroscopy (DRS UV-Vis) and luminescence spectroscopy. The influence of Cu2O/Bi2O3-QDs modification on the photocatalytic activity of BaZrO3 and SrZrO3 was evaluated by the phenol photodegradation process in the liquid phase under UV-Vis and toluene degradation in the gas phase under Vis irradiation. The highest photoactivity under UV-Vis light was observed for BaZrO3/1% Cu2O/33% Bi2O3 and SrZrO3/1% Cu2O/33% Bi2O3 samples. Research also demonstrated that single-type QD deposition (Cu2O or Bi2O3) on the zirconate surface decreases the photoactivity in comparison with pristine zirconates. The mechanism of photocatalytic activity of the obtained nanocomposites was investigated by the formation of hydroxyl radicals under UV-Vis irradiation in the presence of terephthalic acid.

The TiO2 modified by monometallic (Au-TiO2, Pt-TiO2) and bimetallic (Pt/Au-TiO2) NPs have been synthesized by a simple sol-gel method. The optimal dosage of individual components in Pt/Au composition on photocatalytic activity has been systematically investigated. The obtained photocatalysts were thoroughly characterized by BET surface area measurements, UV–vis diffuse-reflectance spectroscopy (DRS), X-ray diffraction analysis (XRD), scanning transmission microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activity under visible light (λ > 420 nm and λ > 455 nm) has been estimated in phenol degradation reaction in an aqueous phase. The best photocatalytic activity has been observed for −mono (0.5)Pt_TiO2 and bimetallic (0.5)Pt/(0.5)Au_TiO2 samples with an optimum platinum content. The Pt/Au_TiO2 radical formation mechanism was systematically investigated with the selected scavenger for the degradation process under vis light irradiation. The formation of O 2− with (0.5)Pt/(0.5)Au_TiO2 was established from the high inhibition of phenol degradation. Based on the XPS analysis it was observed that the greater photoactivity of bimetallic sample (0.5)Pt/(0.5)Au_TiO2 could result from a relatively higher content of platinum compared to gold on the surface layer. It must be noted that only platinum takes a significant part in Pt/Au composites on the photoactivity. Furthermore, in this work we present a linear relationship between the crystal size of TiO2 and the reaction rate of Au-TiO2, Pt-TiO2 and Pt/Au-TiO2.

The effect of the ionic liquid's (IL) anion type ([BIMIM][X], where X= [Br], [PF6] or [OctSO4]) and content on the morphology, surface properties and photoactivity of TiO2 obtained by solvothermal method has been systematically investigated. Our results revealed that the presence of [Br], [OctSO4] anions favor formation of anatase phase, while presence of [PF6] anion causes formation of mixture of anatase and Ti(OH)PO4 phases. The highest photocatalytic activity under visible radiation (approximately four times higher than pristine TiO2) was observed for the TiO2 sample grown in a presence of 1-butyl-3-methylimidazolium bromide for ionic liquid to TiO2 precursor molar ratio 1:2. Visible light induced phenol degradation was found to be realized mainly by oxygen radical anions, whereas the contributions of the other processes, involving reactions with trapped electrons, holes and hydroxyl radical, are limited in the overall reaction mechanism. Quantum chemical calculations concerning model of anatase vacancy suggest that charge transfer between the bromide anion and molecular oxygen interacting with the vacancy is a source of photoreactivity induced by visible photons.

The aim of this study was to verify the effect of Ag and Pt with different loadings (0.1 and 0.5wt.%) as dopants on TiO2for the degradation of a mixture of five parabens through photocatalytic ozonation. The effect of the treatment on the mixture toxicity over different species was also analyzed. The best catalyst in terms of parabens degradation was 0.5%Ag-TiO2.The decrease of metal loading on TiO2 decreased the parabens degradation efficiency as well as COD and TOC removal. Also this decrease has a slight effect over the treated solution toxicity over the different species tested.

Titania-supported palladium, gold and bimetallic nanoparticles (second-generation nanoparticles) demonstrate promising photocatalytic properties. However, due to unusual reactivity, second-generation nanoparticles can be hazardous for living organisms. Considering the ever-growing number of new types of nanoparticles that can potentially contaminate the environment, a determination of their toxicity is extremely important. The main aim of presented study was to investigate the cytotoxic effect of surface modified TiO2-based nanoparticles, to model their quantitative nanostructure–toxicity relationships and to reveal the toxicity mechanism. In this context, toxicity tests for surface-modified TiO2-based nanoparticles were performed in vitro, using Gram-negative bacteria Escherichia coli and Chinese hamster ovary (CHO-K1) cells. The obtained cytotoxicity data were analyzed by means of computational methods (quantitative structure–activity relationships, QSAR approach). Based on a combined experimental and computational approach, predictive models were developed, and relationships between cytotoxicity, size, and specific surface area (Brunauer–Emmett–Teller surface, BET) of nanoparticles were discussed.

Facile and environmentally benign one-step titanium anodization method for TiO 2 nanotubes (NTs) formation in a presence of ionic liquids (ILs) was proposed. Influence of the IL structure and its content in ethylene glycol electrolyte on morphology, surface properties and photoactivity of the TiO 2 NTs was investigated. Possible interactions between IL and TiO 2 NTs as well as the mechanism of NTs formation during anodic oxidation process were proposed. The outer diameter, wall thickness, and length of the IL-NTs were found to be proportionally related with increasing length of the hydrocarbon chain in the imidazolium cation of the IL (from 2 to 8), IL content, anodization potential and water content up to 10 vol.%. Moreover, for the first time, the effect of the IL’s structure on the UV–vis and Vis light-induced photoactivity of the IL-TiO 2 NTs was presented, and the active species ( OH and O 2 − radicals) involved in the photocatalytic reaction of phenol degradation were determined. The sample that exhibited the highest photoactivity under Vis irradiation (0.63 μmol dm −3 min −1 ) and greatest amounts of generated OH was TiO 2 NTs prepared at anodization potential 90 V in the electrolyte containing 0.1 mol of 1-octyl-3-methylimidazolium tetrafluoroborate [OMIM][BF 4 ] (represented by F − content) and 10 vol.% of water. Phenol degradation rate remained at level about 1.50 and 0.42 μmol dm −3 min −1 after 60 min of UV–vis and Vis irradiation after four cycles in the presence of [OMIM][BF 4 ] and thus obtained IL-NTs exhibited photostability. The reaction proceeds under mild reaction conditions, is step economical and provides one-dimensional nanostructures that meet the specifications for use in diverse photocatalytic applications.

Parabens are endocrine disrupting compounds (EDCs) used as antimicrobial and preservatives and are reaching natural water courses with dangerous consequences. The efficiency of several catalysts in catalytic ozonation compared to single ozonation was tested for a mixture of five parabens degradation. On catalytic ozonation noble metals (Pd, Pt, Ag, Au) supported on TiO 2 were used, and their activity was compared with TiO 2 . Single ozonation was able to totally oxidize the initial parabens mixture using a high transferred ozone dose (TOD) (around 170 mg/L). However, the COD reduction was very low (25%). The combination of ozonation with the catalysts tested improved the parabens degradation and COD removal using lower TOD values. For best catalysts, 0.5% Pt–TiO 2 and 0.5% Pd–TiO 2 , total degradation of parabens was achieved for a TOD of 70 mg/L, which represents an ozone dose decrease by a factor of almost 3 in comparison to single ozonation. Moreover, these catalytic systems led to a COD and TOC removal of 36% and 18% respectively. The toxicity of the parabens solutions before and after treatments was evaluated using four different biological preparations. The initial parabens mixture was very toxic, but after treatment with all the conditions proposed the Vibrio fischeri luminescence inhibition and Asian clam mortality decreased while the germination index of Lepidium sativum increased. The studies made in a mammalian neuronal preparation, Wistar rat brain slices, indicate that the parabens mixture treated using single or catalytic ozonation had no effect on the measured neuronal ROS signals, unlike the raw mixture. Although total COD and TOC removal was not achieved, indicating the presence of refractory compounds, the toxicity analysis indicates that the transformation products are less environmentally harmful than parabens. These results show that, even using low catalyst loads, noble metals (especially Pt and Pd) can truly enhance ozone action over pollutants.

A heterojunction with excellent visible light response and stability based on titanium dioxide nanotubes (TiO2 NTs), bismuth sulfide quantum dots (Bi2S3 QDs), and platinum nanoparticles (Pt NPs) is proposed. Both Pt NPs (3.0 ± 0.2 nm) and Bi2S3 QDs (3.50 ± 0.20 nm) are well distributed on the (i) top parts, (ii) inner walls, and (iii) outer walls of the TiO2 NTs. Visible-light-induced photoreaction was initialized by excitation of narrow band gap Bi2S3 QDs, followed by electron injection to the conduction band of TiO2, while Pt NPs acted as electron traps, enhacing O2–• generation. Phenol in the aqueous phase and toluene in the gas phase were efficiently degraded over Bi2S3–Pt NTs, even for wavelengths longer than 455 and 465 nm, respectively, while no degradation of model compounds was observed over pristine TiO2 NTs under the same irradiation conditions. Photocatalytic tests of phenol degradation in the presence of scavengers revealed that superoxide radicals were responsible for the visible-light degra...

The photocatalytic oxidation with UV-A irradiation was tested for the treatment of a mixture of five parabens (methylparaben, ethylparaben, propylparaben, butylparaben and benzylparaben) that may be present industrial wastewater. A wide variety of noble metals such as palladium (Pd), platinum (Pt), silver (Ag) and gold (Au), supported on titanium dioxide (TiO 2 ) were used, and their activity was compared with that of pure TiO 2 and photolysis. The degradation rate of single parabens followed a pseudo-first order kinetics. Besides, the photocatalytic reaction rate constant based on fluence was also determined. The kinetic constant increased with the number of carbons on the chain linked to the aromatic ring. Direct photolysis led to only 4% of parabens degradation whilst the presence of catalysts improved parabens depletion as well as TOC and COD removal. For the best catalysts, Ag and Pd on TiO 2 , a reduction higher than 50% of the initial parabens concentration was achieved after 180 min of reaction. The highest degradation rate was attained for BeP with Pd-TiO 2 (75%). These catalysts (Ag and Pd) led to a COD removal of 17 and 19%, whereas TOC removal reached 22 and 25%, respectively. The toxicity of the parabens solutions before and after all treatments was evaluated using three different species. For Vibrio fischeri the toxicity after treatment remains high. The germination index of Lepidium sativum increased in the presence of treated effluents while Corbicula fluminea mortality decreased for the solutions treated by photocatalysis using Pd-TiO 2 and Ag-TiO 2 . The fact that total COD removal and mineralization were not achieved, indicates the presence of some final refractory compounds. The toxicity analysis points out that, for the best catalysts, the treated solutions are less environmentally harmful than the initial mixture, since the parabens concentration could be substantially reduced. These results reveal that, even using low catalyst loads, Ag-TiO 2 and Pd-TiO 2 are interesting catalytic materials for photocatalytic degradation of industrial wastewater containing parabens.

A series of TiO2/SrTiO3 and SrTiO3 microspheres decorated by Rh, Ru or Pt NPs were prepared by facile hydrothermal method. The as-prepared samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) with energy-dispersive X-ray (EDX) spectroscopy, scanning electron microscopy (SEM), photoluminescence spectrometry (PL), Fourier transform infrared (FT-IR) and Raman spectra and diffuse reflectance spectroscopy (DRS). The formation mechanism of TiO2/SrTiO3 and SrTiO3 microspheres was proposed and the photocatalytic properties of the samples were characterized using phenol as the pollutant under the UV–vis and light irradiation. The gas chromatography-mass spectrometry was employed to detect organic intermediates to establish degradation pathway of isotopically labeled (1-13C) phenol. The role of the active species in the process of the degradation was evaluated using different types of active species scavengers as well as hydroxyl radical test with coumarin were also carried out. The PL spectra indicate that the formation of TiO2/SrTiO3 and SrTiO3 decreased the recombination rate of photogenerated carriers. The obtained results revealed that the samples showed an enhanced photocatalytic activity for the degradation of organic pollutant. The SrTiO3/Rh(0.05) photocatalyst showed a higher photodegradation rate under UV–vis and Vis light (3.6 and 1.2 μmol dm−3 min−1, respectively) compared to the unmodified SrTiO3 (0.6 and 0.2 μmol dm−3 min−1, respectively). The active species trapping experiments indicated that under UV–vis as well as Vis illumination O 2 - are the main active species in the degradation process. The main by-products detected in phenol oxidation were catechol, hydroquinone, malonic, fumaric and maleic acid. Moreover, GC–MS results indicated the formation of isotopically labeled and unlabeled maleic acid which could be generated by two different pathways: trough decomposition of catechol and hydroquinone at the same time.

Novel decahedral TiO 2 modified with Ru or Rh NPs were successfully synthesized by hydrothermal method. The effect of metal type as well as amount of noble metal precursor (0.05, 0.1, 0.2, 0.3 and 0.5 wt.%) on the photocatalytic activity were investigated. Decahedral TiO 2 decorated by Ru and Rh nanoparticles was prepared by photodeposition method, whereas Rh doped TiO 2 was obtained by one-step hydrothermal method with introduction of Rh precursor to the reagents mixture. All as-prepared photocatalysts were thoroughly characterized by UV–vis diffuse-reflectance spectroscopy (DRS), scanning electron microscopy (SEM), scanning transmission microscopy (TEM), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, Fourier transforms infrared spectra (FT-IR) and photoluminescence emission spectra (PL). The photocatalytic activity under UV–vis has been estimated in phenol degradation reaction in an aqueous phase. The gas chromatography–mass spectrometry was employed to detect organic intermediates to establish degradation pathway of isotopically labeled (1- 13 C) phenol. Experimental results showed that the novel material exhibited enhanced optical properties and a high degradation rate for phenol under UV–vis light. In particular, the photocatalyst which contains 0.2 wt.% Rh (0.2_Rh/TiO 2 _HT) exhibited the best photoefficiency among the prepared samples (79% of phenol was degraded after 90 min of irradiation). The role of the active species in the process of the degradation was evaluated by using different types of active species scavengers as well as hydroxyl radical test with coumarin were also carried out. The active species trapping experiments indicated that under UV–vis OH radicals and generated superoxide anion O 2 − were actively involved as the main active species in the oxidation of phenol.

A series of Er-, Yb-, Ho-, Tb-, Gd-, Pr-TiO 2 nanotubes (RE-NTs) was prepared via an electrochemical method. The as-prepared photocatalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV–vis absorption, scanning electron microscopy (SEM) and luminescent spectroscopy. The experiments demonstrated that toluene in the gas phase was successfully degraded under visible light (LEDs λ max = 465 nm) using RE-NTs. In the presence of the most active sample (Ho-NTs), the photodegradation of toluene reached 30% after 60 min of vis irradiation. To investigate the localization of RE in the TiO 2 structure, computer simulations were performed using the plane-wave-based Vienna ab-initio simulation package (VASP) implementing spin-polarized density-functional theory (DFT) and the generalized gradient approximation (GGA). It is proposed that during the electrochemical process, TiO 2 systems with new Ho-f states below the conduction band of TiO 2 is formed. The photocatalytic activity under Vis irradiation is attributable not to OH but to other forms of reactive oxygen species (O 2 − , HO 2 , H 2 O 2 ).

A series of microemulsion (ME) system, constituted by different water to surfactant molar ratios (Wo) and oil to surfactant mass ratios (S), have been applied for Pd-TiO2 preparation. The effect of ME properties on the morphology of Pd nanoparticles formed at TiO2 surface and an effect of Pd size and distribution on the surface and photocatalytic properties of Pd-TiO2 were investigated. Microemulsion systems were characterized by means of viscosity, density, dynamic light scattering as well as surface tension measurements to find a correlation between the conditions of Pd nanoparticles formation, their morphology and photocatalyst features. The photocatalysts were characterized by transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), UV–vis diffuse-reflectance spectroscopy (DRS), BET surface area and elemental analysis. The photocatalytic properties of Pd-modified TiO2 particles were studied in a model reaction of phenol photodegradation under Vis irradiation, as well as active species involved in the photocatalytic reaction were determined. Microemulsion composition was found to be a crucial parameter in determining the features of the TiO2-based photocatalysts covered by metallic nanoparticles. The highest photocatalytic activity under Vis radiation was observed for the Pd-TiO2 sample (average diameter 2.4 nm) obtained using 0.1 mol% Pd in the ME system containing 1.5 wt% of water and 82.8 wt% of cyclohexane with average droplet size of 2.83 ± 0.18 nm. In this regard, synthesis of such metal-semiconductor composites through the microemulsion route should always be preceded by investigation of ME properties in order to the eliminate the inhibitory effect of ME internal structure.

Well-organized TiO2 nanotube arrays were fabricated via one-step anodization process. The as-prepared TiO2 nanotubes were characterized by X-ray powder diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS) and scanning electron microscopy (SEM). Photocatalytic activity of obtained photocatalyst was studied in reaction of toluene degradation in the gas phase using low powered and low cost light-emitting diodes (UV LEDs) as an irradiation source. The effect of irradiation intensity and initial pollutant concentration on gas phase photoactivity of TiO2 nanotubes was analyzed. Obtained TiO2 nanotubes were smooth and vertically oriented with a length of about 1.7 ± 0.05 μm. The inner diameter and the wall thickness were 65 ± 2 nm and 6 ± 0.4 nm, respectively. The results showed that the initial toluene degradation rate increased (from 0.0062 up to 0.0567 μmol/min) with raising initial toluene concentration (50–400 ppm), while too high dose of irradiation (about 50 mW/cm2) reduced photocatalytic toluene degradation rate. The best stability of TiO2 nanotubes in three subsequent irradiation cycles was observed for irradiation intensity of 38 mW/cm2. Moreover, it was found that photocatalytic toluene degradation over TiO2 nanotubes showed first order kinetic behavior.

Novel CdTe-KTaO 3 composite photocatalysts were successfully synthesized by using thioglycolic acid (TGA) or 3-mercaptopropionic acid (MPA) as linker molecules which facilitated attachment of CdTe quantum dots to the surface of KTaO 3 nanocubes. The as-prepared photocatalysts were characterized by UV–vis diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) with energy dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FT-IR), Brunauer–Emmett–Teller (BET) specific surface area, X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) emission spectroscopy. The obtained CdTe-decorated KTaO 3 composites showed greatly improved photocatalytic performance for degradation of toluene in the gas phase under LEDs light irradiation (λ max = 415 nm) over pristine KTaO 3 . TGA-functionalized CdTe-KTaO 3 composites exhibited higher photocatalytic activity as compared with MPA-capped CdTe-KTaO 3 hybrids which can be ascribed to the shorter chain length of TGA molecule as compared with MPA linker and therefore faster electron transfer from TGA-CdTe nanodots to perovskite-type potassium tantalate. The significance of quantum size effect of CdTe QDs for enhancing photocatalytic performance of CdTeQDs-decorated KTaO 3 was also discussed.

The development of a photocatalyst with remarkable activity to degrade pollutants in aqueous and gas phase requires visible light-responsive stable materials, easily organized in the form of a thin layer (to exclude the highly expensive separation step). In this work, we present a one-step strategy for synthesizing material in the form of a self-organized TiO2/Ag2O nanotube (NT) array interlaced with silver nanoparticles (as in a cake with raisins) that exhibited photoactivity significantly enhanced compared to that of pristine TiO2 NTs under both ultraviolet (UV) and visible (vis) irradiation. An NT array composed of a mixture of TiO2 and Ag2O and spiked with Ag nanoparticles was formed via the anodization of a Ti–Ag alloy in a one-step reaction. Silver NPs have been formed during the in situ generation of Ag ions and were (i) embedded in the NT walls, (ii) stuck on the external NT walls, and (iii) placed inside the NTs. The enhancement of photocatalytic efficiency can be ascribed to the existence of an ...

Most efforts in heterogeneous photocatalysis are focused on development of new and stable photoactive materials efficient in degradation of various pollutants under visible-light irradiation. In this regard, the wide-bandgap perovskite semiconductors, i.e., SrTiO3 (titanate), SrSnO3 (stannate) and AgTaO3 (tantalate), were prepared by a solvothermal method, and then modified with carbon quantum dots (CQDs) or graphene quantum dots (GQDs) co-modified with erbium. The photocactivity was investigated for: (i) toluene degradation (gas phase), (ii) phenol decomposition (aqueous phase), and (iii) inactivation of Escherichia coli K12 bacteria. It has been found that the morphology of semiconductors depends on the synthesis conditions, resulting in the formation of spherical particles, rods and faceted particles for SrTiO3, SnSrO3 and AgTaO3, respectively. Additionally, deposition of CQDs and GQDs/erbium has resulted in an enhancement of light harvesting, thus improved photoactivity under visible-light irradiation. Samples modified with both erbium and GQDs revealed much higher photoactivity than corresponding pristine and CQDs-modified samples. Moreover, all photocatalyst modified with GQDs and Er exhibited a significant antibacterial properties under visible light irradiation (λ > 420 nm). Accordingly, it has been proposed that obtained semiconductors modified with QDs and Er are promising candidates as sustainable, clean and cheap materials for environmental purification under solar radiation.

The growing research interest on photoelectrocatalysis has encouraged the search for new materials with high activity and the development of methods for their synthesis. The successive ionic layer adsorption and reaction (SILAR) method is an effective way to synthesize materials with photoelectrocatalytic (PEC) properties that are active under visible radiation. Therefore, studies on the impact of the parameters of the SILAR method on the properties and PEC activity of TiO2 nanotubes sensitized with CdS quantum dots (QDs) were conducted. PEC activity was determined based on the efficiency of ifosfamide (IF) degradation, which is currently one of the most commonly detectable anticancer drugs in aquatic environment. The highest IF PEC degradation rate (0.0184 min−1) and the highest TOC removal (48%) was achieved with the CdS-Ti/TiO2_NO3−_0.1M_3c_60s photoelectrode. Among the SILAR parameters, the highest impact on the PEC IF degradation efficiency had the concentration of the Cd precursor, as well as the number and time of the cycles. Our studies showed that CdS-Ti/TiO2 nanocomposites exhibited more than twice higher photocatalytic and PEC IF degradation efficiency than pristine Ti/TiO2 under UV–Vis irradiation. In addition, the PEC mechanism of IF degradation using pristine Ti/TiO2 and CdS-Ti/TiO2 was compared, from which it was concluded that the higher PEC activity of the nanocomposites is due to the greater contribution of h+ and the generation of other oxidants caused by the presence of CdS QDs. Based on the identified degradation products, a pathway for PEC IF degradation was also proposed.

A novel synthesis process was used to prepare TiO 2 microspheres, TiO 2 P-25, SrTiO 3 and KTaO 3 decorated by CdTe QDs and/or Pt NPs. The effect of semiconductor matrix, presence of CdTe QDs and/or Pt NPs on the semiconductor surface as well as deposition technique of Pt NPs (photodeposition or radiolysis) on the photocatalytic activity were investigated. The as-prepared samples were characterized by X-ray powder diffractometry (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) with energy-dispersive X-ray (EDX) spectroscopy, scanning electron microscopy (SEM), photoluminescence spectrometry (PL), Fourier transform infrared (FT-IR) and Raman spectra, diffuse reflectance spectroscopy (DRS) and BET surface area analysis. The photocatalytic decomposition of toluene in gas phase, activated by light-emitting diodes (LEDs), with the CdTe/Pt nanoparticles-modified TiO 2 microspheres, P25, SrTiO 3 and KTaO 3 semiconductors was investigated under UV–vis and visible irradiation.The results showed that the photoactivity depends on semiconductor matrix. The highest photoactivity under Vis light was observed for KTaO 3 /CdTe-Pt (R) sample (56% of toluene was decompose after 30 min of irradiation). The efficiency of the most active sample was 3 times higher than result for P25 and two times higher than for unmodified KTaO 3 .