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Development of robust and cost-effective smart materials requires rational chemical nanoengineering to provide viable technological solutions for a wide range of applications. Recently, a powerful approach based on the electrografting of diazonium salts has attracted a great deal of attention due to its numerous technological advantages. Several studies on graphene-based materials reveal that the covalent attachment of aryl groups via the above approach could lead to additional beneficial properties of this versatile material. Here, we developed the covalently linked metalorganic wires on two transparent, cheap, and conductive materials: fluorine-doped tin oxide (FTO) and FTO/single-layer graphene (FTO/SLG). The wires are terminated with nitrilotriacetic acid metal complexes, which are universal molecular anchors to immobilize His6-tagged proteins, such as biophotocatalysts and other types of redox-active proteins of great interest in biotechnology, optoelectronics, and artificial photosynthesis. We show for the first time that the covalent grafting of a diazonium salt precursor on two different electron-rich surfaces leads to the formation of the molecular wires that promote p-doping of SLG concomitantly with a significantly enhanced unidirectional cathodic photocurrent up to 1 ?A cm-2. Density functional theory modeling reveals that the exceptionally high photocurrent values are due to two distinct mechanisms of electron transfer originating from different orbitals/bands of the diazonium-derived wires depending on the nature of the chelating metal redox center. Importantly, the novel metalorganic interfaces reported here exhibit minimized back electron transfer, which is essential for the maximization of solar conversion efficiency. © 2022 American Chemical Society. All rights reserved.

A new indium precursor, namely, indium(II) chloride, was tested as a precursor in the synthesis of ternary Ag−In−S and quaternary Ag−In−Zn−S nanocrystals. This new precursor, being in fact a dimer of Cl2In−InCl2 chemical structure, is significantly more reactive than InCl3, typically used in the preparation of these types of nanocrystals. This was evidenced by carrying out comparative syntheses under the same reaction conditions using these two indium precursors in combination with the same silver (AgNO3) and zinc (zinc stearate) precursors. In particular, the use of indium(II) chloride in combination with low concentrations of the zinc precursor yielded spherical-shaped (D = 3.7−6.2 nm) Ag−In−Zn−S nanocrystals, whereas for higher concentrations of this precursor, rodlike nanoparticles (L = 9−10 nm) were obtained. In all cases, the resulting nanocrystals were enriched in indium (In/Ag = 1.5−10.3). Enhanced indium precursor conversion and formation of anisotropic, longitudinal nanoparticles were closely related to the presence of thiocarboxylic acid type of ligands in the reaction mixture. These ligands were generated in situ and subsequently bound to surfacial In(III) cations in the growing nanocrystals. The use of the new precursor of enhanced reactivity facilitated precise tuning of the photoluminescence color of the resulting nanocrystals in the spectral range from ca. 730 to 530 nm with photoluminescence quantum yield (PLQY) varying from 20 to 40%. The fabricated Ag−In−S and Ag−In−Zn−S nanocrystals exhibited the longest, reported to date, photoluminescence lifetimes of ∼9.4 and ∼1.4 μs, respectively. It was also demonstrated for the first time that ternary (Ag−In− S) and quaternary (Ag−In−Zn−S) nanocrystals could be applied as efficient photocatalysts, active under visible light (green) illumination, in the reaction of aldehydes reduction to alcohols.

This paper presents application of Finite Element Method in designing of a vibroisolated object. A model of power generator of 113 MW was chosen for the analysis. Such the generator is used in one of power plants in Silesia district. Several frequency domain dynamic analyses aimed at assessment of influence of vibroisolation on acceleration level of the generator foundation were performed. Three different models of the generator were considered. For the purposes of verification of the obtained results measured vibration accelerations were used.

Inspired by the easy intercalation of quinoxaline heterocyclic aromatic amines (HAAs) in double-stranded DNA (dsDNA), we synthesized a nucleobase-functionalized molecularly imprinted polymer (MIP) as the recognition unit of an impedimetric chemosensor for the selective determination of a 2-amino-3,7,8-trimethyl-3H-imidazo[4,5-f]quinoxaline (7,8-DiMeIQx) HAA. HAAs are generated in meat and fish processed at high temperatures. They are considered to be potent hazardous carcinogens. The MIP film was prepared by potentiodynamic electropolymerization of a pre-polymerization complex of two adenine- and one thymine-substituted bis(2,2′-bithien-5-yl)methane functional monomer molecules with one 7,8-DiMeIQx template molecule, in the presence of the 2,4,5,2′,4′,5′-hexa(thiophene-2-yl)-3,3′-bithiophene cross-linking monomer, in solution. The as-formed MIP chemosensor allowed for the selective impedimetric determination of 7,8-DiMeIQx in the 47 to 400 μM linear dynamic concentration range with a limit of detection of 15.5 μM. The chemosensor was successfully applied for 7,8-DiMeIQx determination in the pork meat extract as a proof of concept.

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).

The structural and chemical modification of TiO2 nanotubes (NTs) by the deposition of a well-controlled Au deposit was investigated using a combination of X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Scanning Transmission Electron Microscopy (STEM), Raman measurements, UV-Vis spectroscopy and photoelectrochemical investigations. The fabrication of the materials focused on two important factors: the deposition of Au nanoparticles (NPs) in UHV (ultra high vacuum) conditions (1–2 × 10−8 mbar) on TiO2 nanotubes (NTs) having a diameter of ∼110 nm, and modifying the electronic interaction between the TiO2 NTs and Au nanoparticles (NPs) with an average diameter of about 5 nm through the synergistic effects of SMSI (Strong Metal Support Interaction) and LSPR (Local Surface Plasmon Resonance). Due to the formation of unique places in the form of “hot spots”, the proposed nanostructures proved to be photoactive in the UV-Vis range, where a characteristic gold plasmonic peak was observed at a wavelength of 580 nm. The photocurrent density of Au deposited TiO2 NTs annealed at 650 °C was found to be much greater (14.7 μA cm−2) than the corresponding value (∼0.2 μA cm−2) for nanotubes in the as-received state. The IPCE (incident photon current efficiency) spectral evidence also indicates an enhancement of the photoconversion of TiO2 NTs due to Au NP deposition without any significant change in the band gap energy of the titanium dioxide (Eg ∼3.0 eV). This suggests that a plasmon-induced resonant energy transfer (PRET) was the dominant effect responsible for the photoactivity of the obtained materials.

Developing functional materials from biomass is a significant research subject due to its unique structure, abundant availability, biodegradability and low cost. A series of chitosan–lignin (CL) composites were prepared through a hydrothermal method by varying the weight ratio of chitosan and lignin. Subsequently, these CL composites were combined with titania (T) to form a nanocomposite (T/CL) using sol–gel and hydrothermal based methods. T/CL nanocomposites exhibited improved photocatalytic performance in comparison with sol–gel and hydrothermally prepared pristine titania (SGH-TiO2), towards the selective oxidation of benzyl alcohol (BnOH) to benzaldehyde (Bnald) under UV (375 nm) and visible light (515 nm). More specifically, the 75T/CL(25 : 75) nanocomposite (a representative photocatalyst from the 75T/CL nanocomposite series) showed very high selectivity (94%) towards Bnald at 55% BnOH conversion under UV light. Whereas, SGH-TiO2 titania exhibited much lower (68%) selectivity for Bnald at similar BnOH conversion. Moreover, the 75T/CL(25 : 75) nanocomposite also showed excellent Bnald selectivity (100%) at moderate BnOH conversion (19%) under visible light. Whereas, SGH-TiO2 did not show any activity for BnOH oxidation under visible light. XPS studies suggest that the visible light activity of the 75T/CL(25 : 75) nanocomposite is possibly related to the doping of nitrogen into titania from chitosan. However, according to UV-visible-DRS results, no direct evidence pertaining to the decrease in band-gap energy of titania was found upon coupling with the CL composite and the visible light activity was attributed to N-doping of titania. Overall, it was found that T/CL nanocomposites enhanced the photocatalytic performance of titania via improved light harvesting and higher selectivity through mediation of active radical species.

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...

The demands for high-purity hydrogen required in fuel-cell applications impose new goals and challenges for design of well performing water-gas shift (WGS) catalysts. Gold-based catalysts have exhibited high activity in the WGS reaction at low temperature. Preparation of appropriate and economically viable supports with complex composition by various synthesis procedures is an attractive approach to WGS performance improvement. The effect of two different preparation methods (wet impregnation or mechanical mixing) and ceria content (10, 20 or 30 wt%) on textural, structural, surface and reductive properties and WGS activity of gold catalysts was studied. Additionally, the role of Y2O3 as a promoter of ceria was examined. Long-term stability test was carried out at 260 °C over the most active catalyst. The composition of the best performing sample (composed of about 70 wt% alumina), prepared by mechanical mixing, was considered promising in case of practical applications because of its cost efficiency. The combination of gold nanoparticles and alumina supported Y-doped ceria proved an advantageous approach for developing new catalytic formulations with high effectiveness in clean hydrogen production.

Stable polymeric materials with embedded nano-objects, retaining their specific properties, are indispensable for the development of nanotechnology. Here, a method to obtain Pt, Pd, Au, and Ag nanoparticles (ca. 10 nm, independent of the metal) by the reduction of their ions in pectin, in the absence of additional reducing agents, is described. Specific interactions between the pectin functional groups and nanoparticles were detected, and they depend on the metal. Bundles and protruding nanoparticles are present on the surface of nanoparticles/pectin films. These films, deposited on the electrode surface, exhibit electrochemical response, characteristic for a given metal. Their electrocatalytic activity toward the oxidation of a few exemplary organic molecules was demonstrated. In particular, a synergetic effect of simultaneously prepared Au and Pt nanoparticles in pectin films on glucose electro-oxidation was found.

The structural and chemical modification of TiO

Understanding how Sb atoms are located in the ZnO crystal lattice and how they affect the layer parameters is essential to obtain p-type conductivity in ZnO:Sb. In this paper, the results of our extensive research (XPS, Raman, X-Ray, SIMS) of Sb doped ZnO films grown by Molecular Beam Epitaxy are presented. It is shown with use of high resolution X-ray Photoemission Spectroscopy (XPS) that three charge states of the Sb impurity: Sb3+, Sb5+, and Sb3− can exist in ZnO:Sb layers. The dominant charge state of Sb ions is 3 + while the contribution of 5 + is very low. The relative fraction of Sb atoms located at the Zn sites is about ∼90%, while ∼10% are incorporated in oxygen sites. It was found that increasing the Sb content in the layers increases the intensity of Raman modes at 511 cm−1, 533 cm−1, and 575 cm−1, which confirms their correlation with Sb doping. Additionally, a blue shift of the E2High Raman mode of ZnO was observed, related to the increase of strain in the oxygen sublattice. The relation between strain and stress for different Sb chemical states (Sb3+, Sb5+, Sb3−) in ZnO is calculated and compared with experimental results.

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.

Within the Waste2Fuel project, innovative, high-performance, and cost-effective fuel production methods are developed to target the “closed carbon cycle”. The catalysts supported on different metal oxides were characterized by XRD, XPS, Raman, UV-Vis, temperature-programmed techniques, then, they were tested in CO2 hydrogenation at 1 bar. Moreover, the V2O5 promotion was studied for Ni/Al2O3 catalyst. The precisely designed hydrotalcite-derived catalyst and vanadia-promoted Ni-catalysts deliver exceptional conversions for the studied processes, presenting high durability and selectivity, outperforming the best-known catalysts. The equilibrium conversion was reached at temperatures around 623 K, with the primary product of reaction CH4 (&gt, 97% CH4 yield). Although the Ni loading in hydrotalcite-derived NiWP is lower by more than 40%, compared to reference NiR catalyst and available commercial samples, the activity increases for this sample, reaching almost equilibrium values (GHSV = 1.2 × 104 h–1, 1 atm, and 293 K).

Solar energy‐driven processes for biomass valorization are priority for the growing industrialized society. To address this challenge, efficient visible light‐active photocatalyst for the selective oxidation of biomass‐derived platform chemical is highly desirable. Herein, selective oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF) was achieved by visible light‐driven photocatalysis over titania. Pristine titania is photocatalytically inactive under visible light, so an unconventional approach was employed for the visible light (λ=515 nm) sensitization of titania via a formation of a visible light‐absorbing complex of HMF (substrate) on the titania surface. Surface‐complexation of HMF on titania mediated ligand‐to‐metal charge transfer (LMCT) under visible light, which efficiently catalyzed the oxidation of HMF to DFF. A high DFF selectivity of 87 % was achieved with 59 % HMF conversion after 4 h of illumination. The apparent quantum yield obtained for DFF production was calculated to be 6.3 %. It was proposed that the dissociative interaction of hydroxyl groups of HMF and the titania surface is responsible for the surface‐complex formation. When the hydroxyl groups of titania were modified via surface‐fluorination or calcination the oxidation of HMF was inhibited under visible light, signifying that hydroxyl groups are decisive for photocatalytic activity., From ligand to metal: The selective oxidation of 5‐hydroxymethylfurfural (HMF) to 2,5‐diformylfuran (DFF) by visible light photocatalysis over titania is achieved with high DFF selectivity (87 %) at 59 % HMF conversion after 4 h of illumination. A complex of HMF on the titania surface acts as a sensitizer via a ligand‐to‐metal charge transfer (LMCT) under visible light.

CO₂ methanation is a very promising technology for the production of alternative fuels with the simultaneous use of greenhouse gases. Therefore, intensive research is carried out on the optimization of catalysts with excellent properties for operation in the area of low temperatures. Here, we present research on a catalyst composed of 19 wt % NiO supported on alumina/calcium aluminate. The catalyst was modified with V₂O₅ in order to be suited for extrusion and scale-up in the frame of power to gas technology. Samples with various vanadium contents (Ni–xV, where x represents the amount of vanadium) were prepared in the form of ground granules obtained from 0.5 mm diameter spherical grains. X-ray diffraction (XRD), transmission electron microscopy (TEM), skeletal infrared (IR), diffuse reflectance ultraviolet–visible-near-infrared (DR-UV–vis-NIR), and X-ray photoelectron (XPS) spectroscopies, as well as H₂ temperature-programmed reduction (H₂-TPR), were used to characterize the samples. Catalytic performances of the catalyst samples were tested in CO₂ hydrogenation at 1 atm. Among the many supported Ni catalysts tested in our laboratories, the catalysts of 0.5 and 1 wt % V showed very high activity, with the highest CH₄ yield of 97% at 623 K. These catalysts exhibited 100% CH₄ selectivity up to 673 K. The excellent performances of the studied catalysts are attributed to the possible formation of Ni–V solid solution alloy nanoparticles.

One of the challenges in research into photoelectrocatalytic (PEC) degradation of pollutants is finding the appropriate photoanode material, which has a significant impact on the process efficiency. Among all others, photoelectrodes based on an ordered TiO2 nanotube arrays are a promising material due to well-developed surface area and efficient charge separation. To increase the PEC activity of this material, the SILAR method was used to decorate Ti/TiO2 nanotubes by PbS quantum dots (QD). The ifosfamide (IF) degradation rate constants was twice as higher for PbS-Ti/TiO2 (0.0148 min 1) than for Ti/TiO2 (0.0072 min 1). Our research showed the highest efficiency of PEC degradation of drugs using IIIPbS-Ti/TiO2 made with 3 SILAR cycles (PbS QD size mainly 2–4 nm). The 4 and 6 of SILAR cycles resulted in the aggregation of PbS nanoparticles on the Ti/ TiO2 surface and decreased IF PEC degradation rate to 0.0043 and 0.0033 min 1, respectively. Research on PEC mechanism has shown that the drugs are degraded mainly by the activity of photogenerated holes and hydroxyl radicals. In addition, the identified drug intermediates made possible to propose a degradation pathways of anticancer drugs and the ecotoxicity test show no inhibition of Lemna minor growth of treated solutions.

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 chemosensor with a molecularly imprinted polymer (MIP) film as the recognition unit selective to a carnosine biomarker was molecularly engineered, devised and fabricated. The molecular structure of the pre-polymerization complex of the carnosine template with the carboxy and 18-crown-6 ether derivatives of bis(2,2′-bithien-5-yl)methane functional monomers was thermodynamically optimized by density functional theory (DFT) at the B3LYP/6-31g(d) level. The calculated high negative Gibbs free energy change, ΔG = −227.4 kJ mol−1, indicated the formation of a very stable complex. The solution of this complex was prepared and used for deposition of the MIP films on a Pt disk electrode or an Au electrode of the quartz crystal resonator by potentiodynamic electropolymerization. Subsequently, the carnosine template was extracted from the MIPs with 0.1 M NaOH, as confirmed by the differential pulse voltammetry (DPV), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy measurements. For carnosine sensing, impedimetric capacity (IC) measurements were performed under flow-injection analysis (FIA) conditions resulting in the limit of detection of 20 μM (at S/N = 3). This limit implied the readiness of the chemosensor for carnosine determination in clinical samples. Due to multiple modes of carnosine binding to MIP recognition sites, the IC chemosensor was found to be more selective to carnosine than to its common interferences including anserine, carcinine and histidine. Advantageously, the imprinting factor, determined by piezoelectric microgravimetry (PM), was high equaling 14.9.

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).

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.

We present a facile and green approach to produce crystalline TiO2 nanoparticles on a surface of different carbonaceous materials derived from lignocellulosic biomass such as STARBON-800® obtained by carbonization at 800°C and biochar-SWP700 (Soft Wood Pellets (SWP) obtained by pyrolysis at 700°C) via novel low-temperature ultrasound-promoted green methodology coupled with citric acid as a cross-linking agent. In comparison to other methods, the developed method has several significant benefits such as simplicity, great ability to get crystalline TiO2 particles (elimination of high-temperature treatment (material calcination at >300°C) needed in the conventional sol-gel method, which is extremely important in transforming amorphous TiO2 into a photoactive crystalline phase) elimination of risky chemicals and oxidizing agent, and also ability to change some parameters (e.g. ultrasound intensity). Prepared materials were characterized by XRD, DR UV-vis, N2 physisorption, HR-XPS, XRF, HR-TEM, FT-IR and subsequently tested for their photocatalytic activities both in photocatalytic phenol degradation (in water) and oxidation of methanol (in air) under UV and visible light irradiation.

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.

In this paper the current understanding of defects in acceptor doped ZnO is briefly reviewed. The results of investigations of ZnO:As/n-GaN heterojunctions which have been successfully fabricated by plasma assisted molecular beam epitaxy method are presented. The electrical properties of the junctions, as well as deep levels, have been studied by means of current-voltage (I-V), capacitance-voltage (C-V) characteristics and deep level transient spectroscopy (DLTS). Electrical measurements were supplemented by photoluminescence- (PL) along with secondary ion mass spectrometry (SIMS) and X-ray photoemission spectroscopy (XPS) investigations. The I-V measurements allowed for detailed analysis of current mechanisms, through which the presence of trap states in the investigated junction was confirmed. The C-V results proved that the depletion region of the diode is located within the ZnO:As layer. The DLTS measurements revealed the presence of three hole trap related signals. The activation energies and capture cross sections of these traps were determined and their possible origin has been ascribed. Obtained results allowed for better identification of defects found in the case of the analyzed heterostructure, as well as the studies of its electronic properties.

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.

A novel two-step ionic liquid assisted procedure was applied for a controllable synthesis of BiOBr/Bi2WO6 heterojunction thin films. The preparation route involved an anodic oxidation of tungsten foil and hydrothermal transformation of as-anodized oxide in the presence of bismuth precursor and ionic liquid, N-butylpyridinium bromide [BPy][Br]. The BiOBr plates with irregular shapes adhered to the surface of flower-like Bi2WO6 and formed a heterojunction between BiOBr and Bi2WO6, as confirmed by the analysis of their structure and composition. The highest efficiency of phenol degradation was achieved when the highest amount of IL was used (the apparent quantum efficiency was almost 8 and 71.5 times higher compared to BiOBr and Bi2WO6, respectively). In addition, superoxide radicals (•O2–) were found as the main factor responsible for the photodegradation. A possible reaction mechanism was further investigated as a function of monochromatic irradiation to determine the exact range of the composite photoactivity.