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In the pursuit of innovative solutions for modern technologies, particularly in the design and production of new micro/nanostructured materials, microorganisms acting as “natural microtechnologists” can serve as a valuable source of inspiration. This research focuses on harnessing the capabilities of unicellular algae (diatoms) to synthesize hybrid composites composed of AgNPs/TiO2NPs/pyrolyzed diatomaceous biomass (AgNPs/TiO2NPs/DBP). The composites were consistently fabricated through metabolic (biosynthesis) doping of diatom cells with titanium, pyrolysis of the doped diatomaceous biomass, and chemical doping of the pyrolyzed biomass with silver. To characterize the synthesized composites, their elemental and mineral composition, structure, morphology, and photoluminescent properties were analysed using techniques such as X-ray diffraction, scanning and transmission electron microscopy, and fluorescence spectroscopy. The study revealed the epitaxial growth of Ag/TiO2 nanoparticles on the surface of pyrolyzed diatom cells. The antimicrobial potential of the synthesized composites was evaluated using the minimum inhibitory concentration (MIC) method against prevalent drug-resistant microorganisms, including Staphylococcus aureus, Klebsiella pneumonia, and Escherichia coli, both from laboratory cultures and clinical isolates.

The development of modern technology is also towards the use of microorganisms as microfactories of the biomaterials with unique properties. Combining the original properties of biosilica extracted from diatoms (microalgae) together with immobilised silver and cerium in nanoparticle forms, allowed to obtain a modern composite material with antibacterial activity. The synthesised composites contained heteroepitaxially growing Ag/AgCl/CeO2 complex nanoparticles were studied using a different types of instrumental analysis. SEM-EDX and XRD analysis allowed the qualitative and quantitative determination of the elements present and their forms in the composites. TEM analysis allowed to information about the shape, size and structure specificity of the created nanoparticles. The possible mechanism of nanoparticles formation was suggested. Antibacterial properties of synthesised composites were characterised using a minimum inhibitory concentration test on six selected bacterial strains. Diatomaceous biosilica containing heteroepitaxially growing silver chloride, metallic silver, and cerium (IV) oxide nanoparticles have been prepared for the first time. The proposed method for synthesising composites did not use toxic reagents, making it environmentally friendly.

Hydroxyapatite (HA) layers are appropriate biomaterials for use in the modification of the surface of implants produced inter alia from a Ti6Al4V alloy. The issue that must be solved is to provide implants with appropriate biointegration properties, enabling the permanent link between them and bone tissues, which is not so easy with the HA layer. Our proposition is the use of the intermediate layer ((IL) = TiO

Reduced graphene oxide (rGO) was prepared by chemical reduction of graphene oxide (GO) (with a modified Hummers method) in aqueous solutions of hydrazine (N2H4), formaldehyde (CH2O), formic acid (HCO2H) accompanied by a microwave treatment at 250 °C (MWT) by a high pressure microwave reactor (HPMWR) at 55 bar. The substrates and received products were investigated by TEM, XRD, Raman and IR spectroscopies, XPS, XAES and REELS. MWT assisted reduction using different agents resulted in rGOs of a large number of vacancy defects, smaller than at GO surface C sp3 defects, oxygen groups and interstitial water, interlayer distance and diameter of stacking nanostructures (flakes). The average number of flake layers obtained from XRD and REELS was consistent, being the smallest for CH2O and then increasing for HCO2H and N2H4. The number of layers in rGOs increases with decreasing content of vacancy, C sp3 defects, oxygen groups, water and flake diameter. MWT conditions facilitate formation of vacancies and additional hydroxyl, carbonyl and carboxyl groups at these vacancies, provide no remarkable modification of flake diameter, what results in more competitive penetration of reducing agent between the interstitial sites than via vacancies. MWT reduction of GO using a weak reducing agent (CH2O) provided rGO of 8 layers thickness.

Functionalized carbon nanotubes are interesting, promising and unique delivery systems for anticancer drugs, which are now in the spotlight of nanomedicine. Connecting nanotubes with anticancer drugs or new compounds with anticancer properties aims at improving their stability, efficiency and reduces the toxic side effects of cancer treatment. In our research, we are interested in connecting functionalized MWCNTs-NH2 with [InH][trans-RuCl4(In)2], (KP1019) which is one of the most promising anticancer ruthenium(iii) drug candidates, known mainly as a cytotoxic agent for the treatment of platinum-resistant colorectal cancers. As a result of the amidation of MWCNTs (1), MWCNTs-NH2 (2) were obtained. Then, they were modified with [InH][RuCl4(In)2] (4) and the nanosystem [MWCNT-NH3+][RuCl4(In)2-] (3) was obtained. The characterization of the resulting products was performed using IR, Raman spectroscopy, thermal gravimetric, XRD, STEM-EDX, ESI-MS, ICP-MS, and XPS analyses. The cytotoxic activity has been tested on human lung carcinoma (A549), chronic myelogenous leukemia (K562) and human cervix carcinoma (HeLa) cells which showed the higher toxicity of the nanosystem than the ruthenium complex.

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 influence of the grinding process on the magnetic properties of as prepared and functionalized multiwall carbon nanotubes (MWCNTs) is presented. We have observed that 3 h mechanical grinding at 400 rpm in contrast to functionalization does not remove the iron contamination from MWCNTs. However, it changes the Fe chemical states. The magnetic properties of iron nanoparticles (Fe-NPs) embedded in the carbon matrix of MWCNTs have been analyzed in detail. We have proven that single-domain non-interacting Fe(C,O)-NPs enriched in the Fe3C phase (~10 nm) enclosed inside these nanotubes are responsible for their magnetic properties. Mechanical grinding revealed a unique impact of -COOH groups (compared to -COONH4 groups) on the magnetism of functionalized MWCNTs. In MWCNT-COOH ground in a steel mill, the contribution of the Fe2O3 and α-Fe phases increased while the content of the magnetically harder Fe3C phase decreased. This resulted in a 2-fold coercivity (Hc) decrease and saturation magnetization (MS) increase. A 2-fold remanence (Mr) decrease in MWCNT-COOH ground in an agate mill is related to the modified Fe(C,O)-NP magnetization dynamics. Comparison of the magnetostatic exchange and effective anisotropy length estimated for Fe(C,O)-NPs allows concluding that the anisotropy energy barrier is higher than the magnetostatic energy barrier. The enhanced contribution of surface anisotropy to the effective anisotropy constant and the unique effect of the -COOH groups on the magnetic properties of MWCNTs are discussed. The procedure for grinding carboxylated MWCNTs with embedded iron nanoparticles using a steel mill has a potential application for producing Fe-C nanocomposites with desired magnetic properties.

Functionalized carbon nanotubes are interesting, promising and unique delivery systems for anticancer drugs, which are now in the spotlight of nanomedicine. Connecting nanotubes with anticancer drugs or new compounds with anticancer properties aims at improving their stability, efficiency and reduces the toxic side effects of cancer treatment. In our research, we are interested in connecting functionalized MWCNTs-NH2 with [InH][trans-RuCl4(In)2], (KP1019) which is one of the most promising anticancer ruthenium(iii) drug candidates, known mainly as a cytotoxic agent for the treatment of platinum-resistant colorectal cancers. As a result of the amidation of MWCNTs (1), MWCNTs-NH2 (2) were obtained. Then, they were modified with [InH][RuCl4(In)2] (4) and the nanosystem [MWCNT-NH3+][RuCl4(In)2-] (3) was obtained. The characterization of the resulting products was performed using IR, Raman spectroscopy, thermal gravimetric, XRD, STEM-EDX, ESI-MS, ICP-MS, and XPS analyses. The cytotoxic activity has been tested on human lung carcinoma (A549), chronic myelogenous leukemia (K562) and human cervix carcinoma (HeLa) cells which showed the higher toxicity of the nanosystem than the ruthenium complex.

Novel visible light responsive materials for water splitting are essential for the efficient conversion of solar energy into hydrogen bond energy. Among other semiconductors, gadolinium orthovanadate has appropriate conduction and valence band edges positioned to split water molecules and a narrow band gap that allows the use of visible light for hydrogen generation. Thus, we present here that hydrogen evolution under visible light (λ > 420 nm) could be accomplished using hierarchical 3D GdVO4 particles, obtained by a simple, one pot hydrothermal synthesis. We found that applying various reaction components, such as EDTA-Na2 and EDTA, and adjusting the pH of the solution allow one to tune the shape of GdVO4 (such as short nanowires, long nanowires, short nanorods, long nanorods, nanoparticles and spheres – all having a tetragonal crystal structure) as well as optical and photocatalytic properties. The highest ability to photocatalytically split methanol solution into hydrogen under UV-Vis irradiation was detected for the long nanowire sample (42 μmol h−1), having almost 11 times higher efficiency in comparison with the weakest sample – short nanowires. In addition, GdVO4 spheres generated H2 more than 2 times (5.75 μmol h−1) in comparison with the short nanorod sample (2.5 μmol h−1) under visible light excitation. Photostable in three-hour work cycles, long nanowires and spheres were even able to generate hydrogen from pure water, reaching values of 17 and 3 μmol under UV-Vis and Vis light, respectively.

Herein, we show a composite formation method of tin/tin oxide nanoparticles with graphene oxide and CMC based on laser ablation technique as an electrode material for energy storage devices. The material exhibited a three-dimensional conducting graphene oxide network decorated with tin or tin oxide nanoparticles. The structure, homogeneous distribution of nanoparticles, and direct contact between inorganic and organic parts were confirmed by scanning electron microscopy and high-resolution transmission electron spectroscopy. Electrochemical performances of composite electrode material showed a reversible capacity of 644 mAh/g at a current density equal to 35 mA/g, and 424 mAh/g at 140 mA/g. The capacity retention of 90% after 250 cycles show that tested electrode material is suitable as a negative electrode for lithium-ion batteries.

Accidental freezing of aluminum-based vaccines occurs during their storage and transportation, in both developed and developing countries. Freezing damages the freeze-sensitive aluminum adjuvanted vaccines, through separation of lattice between aluminum adjuvant and antigen, leading to formation of aluminum aggregates, and loss of potency. In this study, we examined Alhydrogel™ ([AlO(OH)]xnH2O, aluminum hydroxide, hydrated for adsorption) stored under recommended conditions, and exposed to freezing temperature until solid-frozen. The main purpose of our research was to determine the destruction areas of the solid-frozen Alhydrogel™ using selected methods of scanning electron microscopy, energy dispersive X-ray spectroscopy, Raman spectroscopy, Fourier-transform infrared spectroscopy and transmission electron microscopy working in diffraction mode. The Zeta potential evaluation, measurements of albumin adsorption power, thermogravimetric analysis and estimation of the mass loss after drying indicated significant structural (physical) and chemical differences between the freeze-damaged and non-frozen vaccine adjuvant. The presented results are important to better understand the type and nature of damages occurring in freeze-damaged aluminum-based vaccines. These results can be used in future studies to improve the temperature stability of aluminum adjuvanted vaccines.

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.

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.

New composites consisting of decahedral anatase particles exposing {0 0 1} and {1 0 1} facets coupled with accordion-like layered Ti3C2 with boosted photocatalytic activity towards phenol and carbamazepine degradation were investigated. The photocatalysts were characterized with X-ray diffraction (XRD), diffuse reflectance spectroscopy (DR/UV–Vis), Brunauer-Emmett-Teller (BET) specific surface area, Raman spectroscopy, scanning electron microscopy (SEM), electron paramagnetic resonance (EPR) spectroscopy, emission spectroscopy, luminescence decay analysis, electrochemical impedance spectroscopy (EIS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and electrophoretic mobility measurements. The effect of hydrothermal reaction parameters on physicochemical, structural, and photocatalytic properties was studied. In all photodegradation processes, ortho-hydroxyphenol and para-hydroxyphenol were detected as the first intermediates of phenol decomposition. For the TiO2/Ti3C2(140,12) sample containing VTi, a higher concentration of para-hydroxyphenol than ortho-hydroxyphenol was observed, whereas for sample TiO2/Ti3C2(220,24) higher concentration of ortho-hydroxyphenol was noticed. The formation of surface heterojunction between {1 0 1} and {0 0 1} facets of decahedral anatase particles grown on Ti3C2 surface led to improved photoelectron transfer and enhanced photocatalytic activity towards degradation of carbamazepine - non-biodegradable and susceptible to bioaccumulation in living organisms commonly used pharmaceutical agent. Moreover, modification of TiO2/Ti3C2 surface with iron by magnetron sputtering deposition markedly improved photocatalytic activity in carbamazepine decomposition, with nearly 100% degradation in 60 min of irradiation under simulated solar light.

In order to investigate the effect of photointercalation on photoelectrochemical properties, two types of WO3-based photoanodes, bulk and exfoliated have been prepared and investigated. An aqueous exfoliation method is introduced for the simple fabrication of amorphous and hydrated WO3 nanomaterial using commercial bulk WO3 precursor. The comparison of obtained material with bulk WO3 was performed using Raman, UV–vis, and XPS as well as scanning and transmission electron microscopies. The photoelectrochemical and photocatalytic performances of bulk and exfoliated WO3 were compared. Generally, the proposed exfoliation procedure led to the preparation of photo(electro)catalyst characterized by better performance measured as a photocurrent of water oxidation and rate of methylene blue photodecomposition. The main aim of this research was to investigate the influence of alkali metal cations (Li+,Na+,K+,Cs+) presence in electrolyte on the photocatalytic and photo(electro)catalytic activity of the samples in a form of suspended powder and thin layer on transparent-conductive substrate (FTO), respectively.

In this work, we study the impact of the preceramic precursor vinyltriethoxysilane (VTES) on the electrochemical performance of silicon oxycarbide (SiOC) glass/graphite composites. We apply an innovative approach based on high-power ultrasounds in order to obtain highly homogenous composites with a uniform distribution of small graphitic flakes. This procedure enhances gelation and drying of VTES-based preceramic polymer/graphite blends. The SiOC/graphite composites reveal stable capacities (up to 520 mAh g−1 after 270 cycles), which are much higher than the sum derived from the ratio of the components. Additionally, the first cycle Coulombic efficiencies obtained for the composites are 15% higher than that of the pristine VTES-based SiOC ceramic. These properties are identified as the synergistic effect, originated from the addition of graphite to VTES-based SiOCs. Interestingly, such improvement in electrochemical performance is not noticed in the case of analogous SiOC/graphite composites based on phenyltriethoxysilane (PhTES) precursor. The microstructural investigation of the composites based on two different preceramic precursors using solid-state 29Si NMR and Raman Spectroscopy unveils the reason for such discrepancy in their electrochemical behaviour.

Within this work, monodisperse porous silicon nanospheres have been derived from monodisperse silica nanospheres via two different magnesiothermic reduction routes, namely (i) magnesiothermic reduction using a two-chamber set-up, and (ii) magnesiothermic reduction using NaCl as heat scavenger. Both methods allow a size- and shape-preserving preparation of mesoporous silicon. Crystalline silicon with a particle size of 56 nm and a specific surface area of 198 m2 g− 1 and amorphous silicon with a particle size of 35 nm and a specific surface area of 623 m2 g− 1 are synthesized using the two chamber and salt assisted routes, respectively. TEM micrographs confirm enhanced porous character of silicon from NaCl assisted route. An unstable electrochemical performance of the crystalline silicon is found, whereas the amorphous Si presents a stable electrochemical behavior.

In this work electrochemical performance of thin composite films consisted of poly(3,4-ethylenedioxythiophene) (PEDOT), graphene oxide (GOx) and oxidized multiwalled carbon nanotubes (oxMWCNTs) is investigated in various sulphates (Li2SO4, Na2SO4, K2SO4, MgSO4) and acidic (H2SO4) electrolytes. Capacitance values, rate capability and cycling stability achieved for the composite layers are correlated with the electrolytes’ properties such as the conductivity, viscosity, cation size and pH. The highest capacitance values are achieved in acidic solution (98.6 mF cm−2 at 1 mA cm−2), whereas cycling stability is better in neutral electrolytes (88.4% of initial capacitance value after 10′000 cycles recorded for symmetric supercapacitor in 0.5 M MgSO4 solution). Diffusion controlled and non-diffusion controlled capacitance contributions are calculated and the results are discussed considering various ranges of sweep rates taken into account in the linear fitting and extrapolation of parameters.

In search a hydrogen source, we synthesized TiO2-Cu-graphene composite photocatalyst for hydrogen evolution. The catalyst is a new and unique material as it consists of copper-decorated TiO2 particles covered tightly in graphene and obtained in a fluidized bed reactor. Both, reduction of copper from Cu(CH3COO) at the surface of TiO2 particles and covering of TiO2-Cu in graphene thin layer by Chemical Vapour Deposition (CVD) were performed subsequently in the flow reactor by manipulating the gas composition. Obtained photocatalysts were tested in regard to hydrogen generation from photo-induced water conversion with methanol as sacrificial agent. The hydrogen generation rate for the most active sample reached 2296.27 µmol H2 h−1 gcat−1. Combining experimental and computational approaches enabled to define the optimum combination of the synthesis parameters resulting in the highest photocatalytic activity for water splitting for green hydrogen production. The results indicate that the major factor affecting hydrogen production is temperature of the TiO2-Cu-graphene composite synthesis which in turn is inversely correlated to photoactivity.

Composite photocatalysts that consist of TiO 2 and noble metal nanostructures have been considered to be the promising and pivotal material for accessible enhancement of the efficiency in the photocatalytic process carried out in the aqueous and gas phases. In this work we fabricated porous TiO 2 microspheres through a hydrothermal process followed by photochemical reduction of noble metal nanoparticles at the TiO 2 surface. The morphology and structure of M-TiO 2 spheres (M = Ag, Au, Pt and Pd) were studied with the use of various techniques, including transmission electron microscopy (TEM), X-ray powder diffraction analysis (XRD), photoluminescence (PL) and UV–vis diffuse-reflectance spectroscopy (DRS). The effect of metal amount (from 0.1 to 1 wt.%.) on the photocatalytic activity during toluene degradation in gas phase and phenol degradation in aqueous phase was investigated. Additionally, the photocatalytic activity of the M-TiO 2 samples was evaluated by measuring the formation rate of photo-induced hydroxyl radicals ( OH) under UV–vis light irradiation using coumarin as a probe. The obtained results indicated that toluene could be mostly removed from the air over TiO 2 microspheres modified with Ag, Au, Pt, and Pd nanoparticles. UV-mediated photoreactivity was almost similar for all samples obtained by loading metals from solutions consisting of 0.1 and 1 wt.% of metal precursors. Under visible light, except for Au, in gas phase toluene oxidation, the optimized loading of the metals was 0.1 wt.-% (photoreactivity changed in order: Ag-TiO 2 ≈ Pd-TiO 2 > Pt-TiO 2 >> Au-TiO 2 ). In case of phenol degradation in the aqueous phase, in the presence of UV irradiation the highest amount of metal (1.5 wt.%) was profitable, while under the Vis light reaction the medium amount of metal (0.5 wt.%) was beneficial. Additionally, it was noticed that phenol was degraded not only via oxidation by OH radicals but probably also in direct reaction with the photogenerated carriers (e − /h + ), particulary in the presence of TiO 2 spheres loaded with Au and Ag nanoparticles.

Changes in the structure of various carbon materials generated by thermal treatment were analyzed by Fourier transform infrared (FTIR) spectroscopy. FTIR spectra of different commercially-available carbon materials (activated carbon, carbon black, carbon paper, powdered graphite, expanded graphite, multi-walled carbon nanotubes), as well as carbon film obtained by cellulose foil carbonization, were compared and discussed. The complicated nature of the absorption bands in the 1650–1500 cm–1 region suggests that aromatic ring bands and double bond (C=C) vibrations overlap C=O stretching vibration bands and OH binding vibration bands in different environmental surroundings and represent their mutual interactions. The band in the 1430–1440 cm–1 region observed for some carbon materials ("as received" – graphite, graphitized carbon black, carbon nanotubes), and as result of their thermal treatment (activated carbon) is probably due to antisymmetric stretching vibrations of polynuclear aromatic structures, which seems to be characteristic for more ordered aromatic carbon units (graphene-like) made from well-stacked graphite crystallites. The relative intensity of these bands depends on the degree of carbon material graphitization and can reflect the difference in their chemical reactivity and thermal durability. The changes in the relative intensity of the bands during thermal treatment can be interpreted as the result of the destruction of various surface functionalities, graphitization of the amorphous phase of carbon, and finally, by reactions between the freshly annealed carbon surface with oxygen and water molecules present in air (after contact at ambient temperature).

In this study, special attention is focused on the design of TiO2 morphology and microstructure in the two-step preparation procedure using TiOF2 as a precursor to study their photodegradation mineralization efficiency. Firstly, TiOF2 was synthesized by a simple solvothermal method using titanium(IV) tetrafluoride, which was further used as a precursor in preparation of anatase 2D nanosheets, octahedral, decahedral, and rectangular prisms shape structures. The as-obtained nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller surface area analysis (BET), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy and photoluminescence spectroscopy. It was assumed that TiOF2 could be applied as a useful precursor for the preparation of nanostructured TiO2 with defined morphology. Simple controlling of the reaction environment, together with the stabilizing effect of the introduced substrates, resulted in the formation of TiO2 particles with different morphologies and consequently exposed crystal facets. The presence of {0 0 1}, {1 0 1} and {1 0 0} facets influence on their photocatalytic activity but mostly on their mineralization efficiency and the pathway of phenol degradation. From the obtained series, the TiO2 octahedra exposing {1 0 1} facets exhibited the highest photoactivity and mineralization efficiency under UV–Vis light irradiation, which decreases as the other facets appear and become more exposed. The obtained results were compared with a computational study on the ∙OH and ∙O2– attack on the phenyl ring. Overall results showed that the surface effects of the photocatalyst could be an influencing factor in both mineralization efficiency and photodegradation products formation.

Bismuth tungstate (Bi2WO6) can work as a photocatalyst but suffers from rapid recombination of photogenerated charge carriers. Herein, density functional theory (DFT) simulations revealed that the formation of a thermodynamically stable AgInS2(112)/Bi2WO6(010) heterojunction could promote charge separation and enhance the photoactivity of Bi2WO6. To confirm these theoretical predictions, a new type of photocatalysts in the form of Bi2WO6 flower-like microspheres decorated with different amounts of AgInS2 quantum dots (QDs) was obtained using a three-step procedure. The optimized system, obtained by embedding 1 wt% AgInS2 QDs on a Bi2WO6 matrix, possessed an enhanced photocatalytic activity for both phenol degradation and water splitting under visible light irradiation (λ > 420 nm), as well as good reusability and stability during prolonged storage. Finally, DFT calculations of the adsorption energies of reagents (O2, H2O, and H2 molecules) on Bi2WO6 and AgInS2/Bi2WO6 surfaces showed that the surface of the AgInS2(112)/Bi2WO6(010) interface was more active, allowing this system to strongly interact with surrounding species such as H2, O2, and H2O and thereby inducing photocatalytic oxidation of OH– to •OH, reduction of O2 to O2•– or reduction of H+ to H2.

In this work, we report the synthesis of hydrated and non-crystalline WO3 flakes (WO3&minus, x) via an environmentally friendly and facile water-based strategy. This method is described, in the literature, as exfoliation, however, based on the results obtained, we cannot say unequivocally that we have obtained an exfoliated material. Nevertheless, the proposed modification procedure clearly affects the morphology of WO3 and leads to loss of crystallinity of the material. TEM techniques confirmed that the process leads to the formation of WO3 flakes of a few nanometers in thickness. X-ray diffractograms affirmed the poor crystallinity of the flakes, while spectroscopic methods showed that the materials after exfoliation were abundant with the surface groups. The thin film of hydrated and non-crystalline WO3 exhibits a seven times higher specific capacitance (Cs) in an aqueous electrolyte than bulk WO3 and shows an outstanding long-term cycling stability with a capacitance retention of 92% after 1000 chronopotentiometric cycles in the three-electrode system. In the two-electrode system, hydrated WO3&minus, x shows a Cs of 122 F g&minus, 1 at a current density of 0.5 A g&minus, 1. The developed supercapacitor shows an energy density of 60 Whkg&minus, 1 and power density of 803 Wkg&minus, 1 with a decrease of 16% in Csp after 10,000 cycles. On the other hand, WO3&minus, x is characterized by inferior properties as an anode material in lithium-ion batteries compared to bulk WO3. Lithium ions intercalate into a WO3 crystal framework and occupy trigonal cavity sites during the electrochemical polarization. If there is no regular layer structure, as in the case of the hydrated and non-crystalline WO3, the insertion of lithium ions between WO3 layers is not possible. Thus, in the case of a non-aqueous electrolyte, the specific capacity of the hydrated and non-crystalline WO3 electrode material is much lower in comparison with the specific capacity of the bulk WO3-based anode material.

The effect of type (AgInS2, SnS, CuS2, Bi2S3) and amount (5, 10, 15 wt%) of quantum dots (QDs) on the surface properties and photocatalytic activity of QDs-sensitized TiO2 composite, was investigated. AgInS2, SnS, CuS2, Bi2S3 QDs were obtained by hot-injection, sonochemical, microwave, and hot-injection method, respectively. To characterize of as-prepared samples high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-Vis spectroscopy and photoluminescence (PL) emission spectroscopy were applied. The size of AgInS2, SnS, CuS2, Bi2S3 QDs were 12, 2&ndash, 6, 3, and 1&ndash, 2 nm, respectively. The QDs and QDs-sensitized TiO2 composites obtained have been tested in toluene degradation under LEDs light irradiation (&lambda, max = 415 nm and &lambda, max = 375 nm). For pristine QDs the efficiency of toluene degradation increased in the order of AgInS2 &lt, Bi2S3 &lt, CuS &lt, SnS under 375 nm and AgInS2 &lt, SnS under 415 nm. In the presence of TiO2/SnS QDs_15% composite, 91% of toluene was degraded after 1 h of irradiation, and this efficiency was about 12 higher than that for pristine QDs under 375 nm. Generally, building the TiO2/AgInS2 and TiO2/SnS exhibited higher photoactivity under 375 nm than the pristine TiO2 and QDs which suggests a synergistic effect between QDs and TiO2 matrix.

Novel visible light responsive materials for water splitting are essential for the efficient conversion of solar energy into hydrogen bond energy. Among other semiconductors, gadolinium orthovanadate has appropriate conduction and valence band edges positioned to split water molecules and a narrow band gap that allows the use of visible light for hydrogen generation. Thus, we present here that hydrogen evolution under visible light (λ420 nm) could be accomplished using hierarchical 3D GdVO

TiO2/CuxOy nanotube (NT) arrays were synthesized using the anodization method in the presence of ethylene glycol and different parameters applied. The presence, morphology, and chemical character of the obtained structures was characterized using a variety of methods&mdash, SEM (scanning electron microscopy), XPS (X-ray photoelectron spectroscopy), XRD (X-ray crystallography), PL (photoluminescence), and EDX (energy-dispersive X-ray spectroscopy). A p-n mixed oxide heterojunction of Ti-Cu was created with a proved response to the visible light range and the stable form that were in contact with Ti. TiO2/CuxOy NTs presented the appearance of both Cu2O (mainly) and CuO components influencing the dimensions of the NTs (1.1&ndash, 1.3 &micro, m). Additionally, changes in voltage have been proven to affect the NTs&rsquo, length, which reached a value of 3.5 &micro, m for Ti90Cu10_50V. Degradation of phenol in the aqueous phase was observed in 16% of Ti85Cu15_30V after 1 h of visible light irradiation (&lambda, &gt, 420 nm). Scavenger tests for phenol degradation process in presence of NT samples exposed the responsibility of superoxide radicals for degradation of organic compounds in Vis light region. Inactivation of bacteria strains Escherichia coli (E. coli), Bacillus subtilis (B. subtilis), and Clostridium sp. in presence of obtained TiO2/CuxOy NT photocatalysts, and Vis light has been studied showing a great improvement in inactivation efficiency with a response rate of 97% inactivation for E. coli and 98% for Clostridium sp. in 60 min. Evidently, TEM (transmission electron microscopy) images confirmed the bacteria cells&rsquo, damage.

This paper compares the properties of two graphitized carbon blacks in the sorption and first stage of electrodegradation (dechlorination) of chlorophenoxyacetic acids and discusses the influence of surface area on the electrochemical behavior of these carbon materials. Two carbon blacks with ten-fold different surface areas (100 and 10 m2/g) were used as sorbents and electrode materials as received. Two chloroorganics with various numbers of Cl atoms in the molecule, 4-chlorophenoxyacetic acid and 2,4-dichlorophenoxyacetic acid, were adsorbed on the carbon samples from neutral aqueous electrolyte solutions containing low concentrations of adsorbate. Cyclovoltammetric studies of the graphitized carbon blacks were performed using powdered electrode techniques, and the drop in organics concentration during cyclization was measured using HPLC. For carbon black with a smaller surface area, the presence of faradaic reactions was not masked by capacitive currents, and well-shaped faradaic couple peaks characteristic of a quinine/hydroquinone-like adsorbed system were observed. This indicates that these materials are active in chloroorganics electrodegradation (by dechlorination). The extent of electrodegradation (a four-fold drop in organics concentration) observed for carbon black with a larger surface area indicates the dominant role of surface (porosity) development in these processes.

This report concerns carbonaceous electrodes doped with tin(II) oxide nanoparticles. Tin nanoparticles are obtained by pulsed laser ablation in water. Crystalline nanoparticles have been encapsulated in a carbonaceous matrix formed after pyrolysis of a mixture consisting of tin/tin(IV) oxide nanoparticles and gelatine. The obtained material is characterized by means of X-ray diffraction, selected area diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray analysis. Battery charging/discharging tests exhibit a capacity of 580 mA h g−1 for current densities of 100 mA g−1. The cycling performance of the material suggests that the tested nanocomposite can be used as an anode for lithium-ion batteries.