Photocatalytic Bacterial Destruction and Mineralization by TiO2-Based Photocatalysts: A Mini Review.

This work presents an overview of the reports on the bacterial cell photocatalytic destruction and mineralization process in the presence of TiO2-based photocatalysts. The presented research included experiments conducted in air and water. Numerous works confirmed that a photocatalytic process with TiO2 led to bacteria and their organic residues' mineralization. Additionally, based on the obtained results, a possible two-stage mechanism of photocatalytic mineralization in the presence of TiO2-based materials was proposed. To help future studies, challenges of photocatalytic microorganism mineralization are also proposed. There are some aspects that need to be addressed, such as the lack of standardization of conducted research or relatively small amount of research on photocatalytic microorganism mineralization. According to our best knowledge, in the available literature, no work regarding a summary of previous research on photocatalytic bacterial mineralization process was found.

Thermal and/or Microwave Treatment: Insight into the Preparation of Titania-Based Materials for CO2 Photoreduction to Green Chemicals.

Titanium dioxide was synthesized via hydrolysis of titanium (IV) isopropoxide using a sol-gel method, under neutral or basic conditions, and heated in the microwave-assisted solvothermal reactor and/or high-temperature furnace. The phase composition of the prepared samples was determined using the X-ray diffraction method. The specific surface area and pore volumes were determined through low-temperature nitrogen adsorption/desorption studies. The photoactivity of the samples was tested through photocatalytic reduction of carbon dioxide. The composition of the gas phase was analyzed using gas chromatography, and hydrogen, carbon oxide, and methane were identified. The influence of pH and heat treatment on the physicochemical properties of titania-based materials during photoreduction of carbon dioxide have been studied. It was found that the photocatalysts prepared in neutral environment were shown to result in a higher content of hydrogen, carbon monoxide, and methane in the gas phase compared to photocatalysts obtained under basic conditions. The highest amounts of hydrogen were detected in the processes using photocatalysts heated in the microwave reactor, and double-heated photocatalysts.

Photocatalytic Inactivation of Co-Culture of E. coli and S. epidermidis Using APTES-Modified TiO2.

The presented work shows the antibacterial activity of TiO2 photocatalysts modified by 3-aminopropyltriethoxysilane (APTES). The APTES-functionalized TiO2 samples were obtained by the solvothermal process followed by calcination. The antibacterial activity of APTES/TiO2 samples was evaluated with two species of bacteria, Escherichia coli and Staphylococcus epidermidis, under artificial solar light (ASL) irradiation. The used bacteria are model organisms characterized by negative zeta potential (approx. -44.2 mV for E. coli and -42.3 mV for S. epidermidis). For the first time, the antibacterial properties of APTES-functionalized TiO2 were evaluated against mono- and co-cultured bacteria. The high antibacterial properties characterized the obtained APTES-modified nanomaterials. The best antibacterial properties were presented in the TiO2-4 h-120 °C-300 mM-Ar-300 °C sample (modified with 300 mM of APTES and calcined at 300 °C). The improvement of the antibacterial properties was attributed to a positive value of zeta potential, high surface area, and porous volume.

The Benefits of Using Saccharose for Photocatalytic Water Disinfection.

In this work, the characteristics of saccharose (sucrose)-modified TiO2 (C/TiO2) photocatalysts obtained using a hydrothermal method at low temperature (100 °C) are presented. The influence of C/TiO2 on survivability and enzyme activity (catalase and superoxide dismutase) of Gram-negative bacteria Escherichia coli (ATCC 29425) and Gram-positive bacteria Staphylococcus epidermidis (ATCC 49461) under UV-A and artificial solar light (ASL) were examined. The obtained TiO2-1%-S-100 photocatalysts were capable of total E. coli and S. epidermidis inactivation under ASL irradiation in less than 1 h. In addition, the impacts of sugars on the photocatalytic activity and disinfection performance are discussed.

Artificial Solar Light-Driven APTES/TiO2 Photocatalysts for Methylene Blue Removal from Water.

A visible-light photocatalytic performance of 3-aminopropyltriethoxysilane (APTES)-modified TiO2 nanomaterials obtained by solvothermal modification under elevated pressure, followed by calcination in an argon atmosphere at 800-1000 °C, is presented for the first time. The presence of silicon and carbon in the APTES/TiO2 photocatalysts contributed to the effective delay of the anatase-to-rutile phase transformation and the growth of the crystallites size of both polymorphous forms of TiO2 during heating. Thus, the calcined APTES-modified TiO2 exhibited higher pore volume and specific surface area compared with the reference materials. The change of TiO2 surface charge from positive to negative after the heat treatment increased the adsorption of the methylene blue compound. Consequently, due to the blocking of active sites on the TiO2 surface, the adsorption process negatively affected the photocatalytic properties. All calcined photocatalysts obtained after modification via APTES showed a higher dye decomposition degree than the reference samples. For all 3 modifier concentrations tested, the best photoactivity was noted for nanomaterials calcined at 900 °C due to a higher specific surface area than materials calcined at 1000 °C, and a larger number of active sites available on the TiO2 surface compared with samples annealed at 800 °C. It was found that the optimum concentration for TiO2 modification, at which the highest dye decomposition degree was noted, was 500 mM.

The Effect of the Modification of Carbon Spheres with ZnCl2 on the Adsorption Properties towards CO2.

Zinc chloride and potassium oxalate are often applied as activating agents for carbon materials. In this work, we present the preparation of ZnO/carbon spheres composites using resorcinol-formaldehyde resin as a carbon source in a solvothermal reactor heated with microwaves. Zinc chloride as a zinc oxide source and potassium oxalate as an activating agent were applied. The effect of their addition and preparation conditions on the adsorption properties towards carbon dioxide at 0 °C and 25 °C were investigated. Additionally, for all tested sorbents, the CO2 sorption tests at 40 °C, carried out utilizing a thermobalance, confirmed the trend of sorption capacity measured at 0 and 25 °C. Furthermore, the sample activated using potassium oxalate and modified using zinc chloride (a carbon-to-zinc ratio equal to 10:1) displayed not only a high CO2 adsorption capacity (2.69 mmol CO2/g at 40 °C) but also exhibited a stable performance during the consecutive multicycle adsorption-desorption process.

CO2 Sorbents Based on Spherical Carbon and Photoactive Metal Oxides: Insight into Adsorption Capacity, Selectivity and Regenerability.

This work aimed to obtain hybrid composites based on photoactive metal oxide and carbon having adsorption properties. The materials, composed of titanium dioxide or zinc oxide and spherical carbon, were obtained from resorcinol-formaldehyde resin, treated in a solvothermal reactor heated with microwaves and then subjected to carbonization, were received. The functional groups of pure carbon spheres (unsaturated stretching C=C, stretching C-OH and C-H bending vibrations), CS/ZnO and CS/TiO2 samples were determined by FT-IR analysis. The characteristic bands for ZnO and TiO2 were observed below 1000 cm-1. The thermal oxidative properties are similar for TiO2- and ZnO-modified carbon spheres. We have observed that the increased carbon sphere content in nanocomposites results in starting the decomposition process at a lower temperature, therefore, nanocomposites have a broader combustion temperature range. The effect of the oxides' addition to carbon spheres on their adsorption properties was evaluated in detail by examining CO2 adsorption from the gas phase. The selectivity of CO2 over N2 at a temperature of 25 °C and pressure of 1 bar (a novelty in testing CS-based sorbents) calculated for 3.00 CS/TiO2 and 4.00 CS/ZnO was 15.09 and 16.95, respectively. These nanocomposites exhibit excellent cyclic stability checked over 10 consecutive adsorption-desorption cycles.

Effect of APTES modified TiO2 on antioxidant enzymes activity secreted by Escherichia coli and Staphylococcus epidermidis.

In this work, the impact of APTES-modified TiO2 photocatalysts on antioxidant enzymes (catalase and superoxide dismutase) activity secreted by bacteria was presented. Microbial tests has been examined using Escherichia coli (ATCC 29425) and Staphylococcus epidermidis (ATCC 49461) as model organisms. It was found that APTES-TiO2 affected the activity of antioxidant enzymes. Additionally, obtained APTES-TiO2 photocatalysts were capable of total E. coli and S. epidermidis inactivation under artificial solar light irradiation. The sample modified with the concentration of APTES equals 300 mM (TiO2-4h-120°C-300mM) showed the strongest photocatalytic activity toward both bacteria species. The two-stage photocatalytic mechanism of bacteria response to photocatalysts was proposed.

Changes in Porous Parameters of the Ion Exchanged X Zeolite and Their Effect on CO2 Adsorption.

Zeolite 13X (NaX) was modified through ion-exchange with alkali and alkaline earth metal cations. The degree of ion exchange was thoroughly characterized with ICP, EDS and XRF methods. The new method of EDS data evaluation for zeolites was presented. It delivers the same reliable results as more complicated, expensive, time consuming and hazardous ICP approach. The highest adsorption capacities at 273 K and 0.95 bar were achieved for materials containing the alkali metals in the following order K < Na < Li, respectively, 4.54, 5.55 and 5.94 mmol/g. It was found that it is associated with the porous parameters of the ion-exchanged samples. The Li0.61Na0.39X form of zeolite exhibited the highest specific surface area of 624 m2/g and micropore volume of 0.35 cm3/g compared to sodium form 569 m2/g and 0.30 cm3/g, respectively. The increase of CO2 uptake is not related with deterioration of CO2 selectivity. At room temperature, the CO2 vs. N2 selectivity remains at a very high stable level prior and after ion exchange in co-adsorption process (XCO2 during adsorption 0.15; XCO2 during desorption 0.95) within measurement uncertainty. Additionally, the Li0.61Na0.39X sample was proven to be stable in the aging adsorption-desorption tests (200 sorption-desorption cycles; circa 11 days of continuous process) exhibiting the CO2 uptake decrease of about 6%. The exchange with alkaline earth metals (Mg, Ca) led to a significant decrease of SSA and micropore volume which correlated with lower CO2 adsorption capacities. Interestingly, the divalent cations cause formation of mesopores, due to the relaxation of lattice strains.

Photocatalytic oxidation of nitric oxide over AgNPs/TiO2-loaded carbon fiber cloths.

Series of AgNPs/TiO2-loaded carbon fiber cloth (CFC) composites were prepared by incorporation of pristine TiO2 and three AgNPs-modified TiO2 additives onto the surface of four commercial CFCs. AgNPs/TiO2 photocatalysts were synthesized by the wet impregnation method, including NaBH4 reduction of silver ions. The silver content in the modified photocatalyst was assessed by inductively coupled plasma optical emission spectrometry (ICP-OES) as well as XRD analysis. It can be indicated that silver was successfully reduced to Ag nanoparticles what was confirmed by UV-Vis/DRS as well as XRD methods. The photocatalytic activity of the AgNPs/TiO2-loaded CFCs was evaluated during the photocatalytic oxidation (PCO) tests of nitric oxide (NO) acting as a model air contaminant under UV light. It was found that the highest NO removal rate was observed for the AgNPs/TiO2-loaded CFC material containing 3.70 wt% of AgNPs. Modification of TiO2 with AgNPs stabilized the photocatalytic efficiency of the composites during 5 as well as 24 consecutive NO photooxidation cycles. It was also concluded that the presence of AgNPs was a key factor responsible for hindering NO2 formation.

Bacterial Inactivation on Concrete Plates Loaded with Modified TiO2 Photocatalysts under Visible Light Irradiation.

The antibacterial activity of concrete plates loaded with various titania photocatalysts was investigated. The target in bacteria testing was Escherichia coli K12. The presence of photocatalysts in the concrete matrix at a dose of 10 wt.% improved the antibacterial properties, which became significant depending on the type of the added photocatalyst. Total inactivation of E. coli irradiated under artificial solar light was observed on the concrete plates loaded with the following photocatalysts: TiO2/N,CMeOH-300, TiO2/N,CEtOH-100, TiO2/N,CisoPrOH-100 and TiO2/N-300. The modified Hom disinfection kinetic model was found as a best-fit model for the obtained results. The presence of nitrogen and carbon in the photocatalysts structure, as well as crystallite size, surface area and porosity, contributed to the increase of antibacterial properties of concrete plates.

Novel Photocatalytic Nanocomposite Made of Polymeric Carbon Nitride and Metal Oxide Nanoparticles.

Semiconducting polymers are promising materials for photocatalysis, batteries, fuel applications, etc. One of the most useful photocatalysts is polymeric carbon nitride (PCN), which is usually produced during melamine condensation. In this work, a novel method of obtaining a PCN nanocomposite, in which PCN forms an amorphous layer coating on oxide nanoparticles, is presented. Microwave hydrothermal synthesis (MHS) was used to synthesize a homogeneous mixture of nanoparticles consisting of 80 wt.% AlOOH and 20 wt.% of ZrO2. The nanopowders were mechanically milled with melamine, and the mixture was annealed in the temperature range of 400⁻600 °C with rapid heating and cooling. The above procedure lowers PCN formation to 400 °C. The following nanocomposite properties were investigated: band gap, specific surface area, particle size, morphology, phase composition, chemical composition, and photocatalytic activity. The specific surface of the PCN nanocomposite was as high as 70 m²/g, and the optical band gap was 3 eV. High photocatalytic activity in phenol degradation was observed. The proposed simple method, as well as the low-cost preparation procedure, permits the exploitation of PCN as a polymer semiconductor photocatalytic material.

Antibacterial properties of TiO2 modified with reduced graphene oxide.

In this paper, the antibacterial activity of titanium dioxide modified with reduced graphene oxide (rGO) was presented. TiO2/rGO photocatalysts were prepared by the hydrothermal method under elevated pressure at 180°C and heated at 100°C in Ar flow. The obtained photocatalysts were characterized by means of XRD, FTIR/DRS, UV-vis/DR, Raman spectroscopy and scanning electron microscopy (SEM). The carbon content was also examined. FTIR/DRS and Raman analysis confirmed the presence of rGO in the TiO2 structure, suggesting a successful modification. The antimicrobial photoactivity of photocatalysts was conducted against E. coli under an artificial solar light. The results show that all TiO2/rGO photocatalysts exhibited an antibacterial activity higher than unmodified TiO2. The best result was found for sample with 1.5wt% additive of reduced graphene oxide. In this case, total inactivation of E. coli was noticed after 75min of irradiation. It was found that the presence of rGO in sample improves the antimicrobial activity.

[Influence of titanium dioxide activated under visible light on survival of mold fungi]. / Wplyw ditlenku tytanu aktywowanego swiatlem widzialnym na przezywalnosc grzybów plesniowych.

BACKGROUND: In public and residential buildings, fungi are usually found in the dust or growing on building materials medium such. It has been known that a number of their spores may contaminate the indoor environment and deteriorate air quality in accommodation spaces. Previously designed air cleaning systems do not guarantee a complete removal of agents harmful to humans and animals. Therefore, there is a great need to develop a new solution to remove molds from indoor air. In recent years, photocatalysis based on titanium dioxide (TiO2) has been proposed as an effective method for air pollutants removal. The aim of the study was to determine the effect of TiO2 activated under artificial sun light (UV-VIS - ultraviolet - visible spectroscopy) on survival of fungi Penicillium chrysogenum and Aspergillus niger. MATERIAL AND METHODS: The commercial P 25 (Aeroxide P 25, Evonik, Germany) and nitrogen modified titanium dioxide (N-TiO2) were used. The microbiological study was performed using Penicillium chrysogenum and Aspergillus niger fungi. The survival of fungi was determined on the basis of changes in their concentration. RESULTS: It was found that N-TiO2 has a stronger antifungal activity against P. chrysogenum and A. niger than P 25. For N-TiO2, the complete elimination of molds was possible after 3 h under artificial solar light activation. The minimal concentration of photocatalyst was 0.01 g×dm-3 (P. chrysogenum) and 0.1 g×dm-3 (A. niger). CONCLUSIONS: The nitrogen modification of titanium dioxide produced expected results and N-TiO2 presented good antifungal activity. The findings of the presented investigation can lead to the development of air filter to be used for removal of harmful agents (including molds) from indoor environment. Med Pr 2018;69(1):59-65.

EFFECT OF WATER ACTIVITY AND TITANIA P25 PHOTOCATALYST ON INACTIVATION OF PATHOGENIC FUNGI--CONTRIBUTION TO THE PROTECTION OF PUBLIC HEALTH.

AIM: The aim of this study was to determine the antifungal activity of titanium dioxide activated by indoor light on Czapek Yeast Agar (CYA). METHODS: The agar plate method was used and titania P25 (Evonik) was added to the medium in the amount of 20 g.dm(-3). The control experiments without titania were also carried out. The water activity (a(w)) of the basal media was adjusted to 0.999, 0.997, 0.975, 0.950, 0.900 and 0.850 with sodium chloride. The photoactivity of titania was tested for six strains of potentially pathogenic fungi: Aspergillus versicolor (WB130, W11), Stachybotrys chartarum (STA1), Pseudallescheria boydii (AP25), Pseudallescheria ellipsoidea (ZUT1 2), Scedosporium apiospermum (ZUT1 1), Scedosporium aurantiacum (ZUT4BIS). After inoculation with fungal spore suspensions, one part of CYA plates was incubated in dark, while another part was daily exposed to indoor light for 12 hours per day.The plates were incubated at 25°C for 10 days. The daily growth rates (mm x day(-1)) were calculated from the linear regression equation. RESULTS: The CYA supplementation with titanium dioxide for different availability of water resulted in the decrease of fungal growth rates in dark and under irradiation. The lowest and the highest rates of daily growth were obtained in the presence and absence of titania for the low and high water activity (0.900 a(w) and 0.999 a(w)), respectively. CONCLUSIONS: Fungi did not grow on all examined media with the lowest water activity (a(w) ≤ 0.850) which confirmed necessity of water for their growth. The fungi Pseudallescheria-Scedosporium were the most sensitive to titania and water activity, while the strains of Aspergillus versicolor were the most resistant to the presence of titania and lack of water. It has been shown that the lack of accessible water resulted in the strongest action of titanium dioxide both in dark and under irradiation. For the lowest amount of accessible water irradiation of titania resulted in complete inhibition of fungal growth. While, under dark conditions, titania presence enhanced the growth of persistent fungi, i.e., Aspergillus versicolor. It is assumed that these fungi could obtain water from the water-rich titania surface.

Selenium as a marker of cancer risk and of selection for control examinations in surveillance.

Publication is summarization of existing data being results of literature review and our experience on usefulness of selenium as a diagnostic marker selection for control examinations in surveillance and as a marker of patients with high risk of cancers.

Formation of combustible hydrocarbons and H2 during photocatalytic decomposition of various organic compounds under aerated and deaerated conditions.

A possibility of photocatalytic production of useful aliphatic hydrocarbons and H2 from various organic compounds, including acetic acid, methanol, ethanol and glucose, over Fe-modified TiO2 is discussed. In particular, the influence of the reaction atmosphere (N2, air) was investigated. Different gases were identified in the headspace volume of the reactor depending on the substrate. In general, the evolution of the gases was more effective in air compared to a N2 atmosphere. In the presence of air, the gaseous phase contained CO2, CH4 and H2, regardless of the substrate used. Moreover, formation of C2H6 and C3H8 in the case of acetic acid and C2H6 in the case of ethanol was observed. In case of acetic acid and methanol an increase in H2 evolution under aerated conditions was observed. It was concluded that the photocatalytic decomposition of organic compounds with simultaneous generation of combustible hydrocarbons and hydrogen could be a promising method of "green energy" production.

On the Selectivity of Simultaneous CO2 and N2 Reduction Using TiO2/Carbon Sphere Photocatalysts Prepared by Microwave Treatment and Mounted on Silica Cloth.

This paper presents new photocatalysts obtained by treating carbon spheres (CS) and TiO2 in a microwave reactor at a pressure of 20 atm and a temperature of up to 300 °C for 15 min and then depositing TiO2/CS composites on glass fibre cloths. Such highly CO2-adsorbing photocatalysts showed photoactivity in the simultaneous water-splitting process, generating H2, reducing CO2 to CO and CH4, and reducing N2 to NH3. In addition, calculations of the hydrogen balance involved in all reactions were performed. Adding 1 g of carbon spheres per 1 g of TiO2 maintained the high selectivity of nitrogen fixation at 95.87-99.5%, which was continuously removed from the gas phase into the water as NH4+ ions.

Magnetic Resonance Studies of Hybrid Nanocomposites Containing Nanocrystalline TiO2 and Graphene-Related Materials.

Nanocomposites based on nanocrystalline titania modified with graphene-related materials (reduced and oxidized form of graphene) showed the existence of magnetic agglomerates. All parameters of magnetic resonance spectra strongly depended on the materials' modification processes. The reduction of graphene oxide significantly increased the number of magnetic moments, which caused crucial changes in the reorientation and relaxation processes. At room temperature, a wide resonance line dominated for all nanocomposites studied and in some cases, a narrow resonance line derived from the conduction electrons. Some nanocomposites (samples of titania modified with graphene oxide, prepared with the addition of water or butan-1-ol) showed a single domain magnetic (ferromagnetic) arrangement, and others (samples of titania modified with reduced graphene oxide) exhibited magnetic anisotropy. In addition, the spectra of EPR from free radicals were observed for all samples at the temperature of 4 K. The magnetic resonance imaging methods enable the capturing of even a small number of localized magnetic moments, which significantly affects the physicochemical properties of the materials.

New Insight on Carbon Dioxide-Mediated Hydrogen Production.

A new approach to hydrogen production from water is described. This simple method is based on carbon dioxide-mediated water decomposition under UV radiation. The water contained dissolved sodium hydroxide, and the solution was saturated with gaseous carbon dioxide. During saturation, the pH decreased from about 11.5 to 7-8. The formed bicarbonate and carbonate ions acted as scavengers for hydroxyl radicals, preventing the recombination of hydroxyl and hydrogen radicals and prioritizing hydrogen gas formation. In the presented method, not yet reported in the literature, hydrogen production is combined with carbon dioxide. For the best system with alkaline water (0.2 m NaOH) saturated with CO2 under UV-C, the hydrogen production amounted to 0.6 µmol h-1 during 24 h of radiation.