Study on photocatalytic degradation of gaseous dichloromethane using pure and iron ion-doped TiO2 prepared by the sol-gel method

The synthesis of TiO₂ and Fe–TiO₂ by sol–gel method is demonstrated and characterized. The characterization of TiO₂ and Fe–TiO₂ is performed with instruments, including TGA/DTA, FTIR, UV–Vis, N₂ adsorption and SEM. Dichloromethane is used for the photocatalytic activity test. From the results of dichloromethane photocatalyitc degradation, the calcined temperature of TiO₂ and the presence of water vapor influence the photocatalytic activity. The optimum doping amount of iron ions is 0.005 mol%, and this can enhance the photocatalytic activity, while too great an amount will make the iron ions become recombination centers for the electron–hole pairs and reduce the photocatalytic activity. UV–Vis diffuse reflectance spectra of Fe–TiO₂ show an increase in absorbency in the visible light region with the increase in iron ions doping concentration The intermediate of dichloromethane photodegradation includes CHCl₃, CCl₄, CH₂Cl₂ and COCl₂. The presence of iron ions may reduce the adsorption of Cl element on the surface of the photocatalyst.     

Effect of void structure of photocatalyst paper on VOC decomposition

TiO₂ powder-containing paper composites, called TiO₂ paper, were prepared by a papermaking technique, and their photocatalytic efficiency was investigated. The TiO₂ paper has a porous structure originating from the layered pulp fiber network, with TiO₂ powders scattered on the fiber matrix. Under UV irradiation, the TiO₂ paper decomposed gaseous acetaldehyde more effectively than powdery TiO₂ and a pulp/TiO₂ mixture not in paper form. Scanning electron microscopy and mercury intrusion analysis revealed that the TiO₂ paper had characteristic unique voids ca. 10 μm in diameter, which might have contributed to the improved photocatalytic performance. TiO₂ paper composites having different void structures were prepared by using beaten pulp fibers with different degrees of freeness and/or ceramic fibers. The photodecomposition efficiency was affected by the void structure of the photocatalyst paper, and the initial degradation rate of acetaldehyde increased with an increase in the total pore volume of TiO₂ paper. The paper voids presumably provided suitable conditions for TiO₂ catalysis, resulting in higher photocatalytic performance by TiO₂ paper than by TiO₂ powder and a pulp/TiO₂ mixture not in paper form.     

Removal of humic acid using TiO2 photocatalytic process--fractionation and molecular weight characterisation studies

The photocatalytic removal of humic acid (HA) using TiO₂ under UVA irradiation was examined by monitoring changes in the UV₂₅₄ absorbance, dissolved organic carbon (DOC) concentration, apparent molecular weight distribution, and trihalomethane formation potentials (THMFPs) over treatment time. A resin fractionation technique in which the samples were fractionated into four components: very hydrophobic acids (VHA), slightly hydrophobic acids, hydrophilic charged (CHA) and hydrophilic neutral (NEU) was also employed to elucidate the changes in the chemical nature of the HA components during treatment. The UVA/TiO₂ process was found to be effective in removing more than 80% DOC and 90% UV₂₅₄ absorbance. The THMFPs of samples were decreased to below 20 μg l⁻¹ after treatments, which demonstrate the potential to meet increasingly stringent regulatory level of trihalomethanes in water. Resin fractionation analysis showed that the VHA fraction was decreased considerably as a result of photocatalytic treatments, forming CHA intermediates which were further degraded with increased irradiation time. The NEU fraction, which comprised of non-UV-absorbing low molecular weight compounds, was found to be the most persistent component.     

Defect-enhanced photocatalytic removal of dimethylarsinic acid over mixed-phase mesoporous TiO2

Much attention has been paid to the pollutant dimethylarsenic acid(DMA),because of its high toxicity even at very low doses.Although TiO_2 photocatalytic oxidation(PCO) is one of the few effective methods for treating DMA-containing water,the efficient decomposition of DMA and simultaneous removal of toxic arsenic species remains a significant but challenging task.Here,defective mesoporous TiO_2 with mixed-phase structure was synthesized and used as both photocatalyst and adsorbent for DMA removal.Due to the reduced band-gap and enhanced separation of photogenerated charge carriers, the oxygen-deficient TiO_2 nanostructures exhibited 4.2 times higher PCO efficiency than commercial TiO_2(P25).More importantly,the high surface area of the mesoporous TiO_2 provided sufficient active sites for in-situ adsorption and reaction,resulting in the efficient removal of as-formed As(V).Combining the experimental and characterization results,the different roles of reactive species during PCO reactions were clarified.In the presence of hole(h~+) as the dominant oxidation species,DMA was demethylated and transformed into MMA.Thereafter,MMA was subsequently reduced to As(Ⅲ) by photo-generated electrons.Superoxide radicals(O_2~(·-)) played a significant role in oxidizing As(Ⅲ) into As(Ⅴ),which was finally adsorptively removed by the mesoporous TiO_2.     

Immobilization of self-assembled pre-dispersed nano-TiO2 onto montmorillonite and its photocatalytic activity

The immobilization of pre-dispersed Ti O_2 colloids onto the external surface of the clay mineral montmorillonite(Mt) was accomplished and regulated via a self-assembly method employing the cationic surfactant cetyltrimethylammonium bromide(CTAB). The role of CTAB in the synthesis process was investigated by preparing a series of Ti O_2-CTAB-Mt composites(TCM) with various CTAB doses. The results indicated that a uniform and continuous Ti O_2 film was deposited on the external surface of montmorillonite in the composite synthesized with 0.1 wt.% of CTAB, and the TCM nano-composites showed much higher values for specific surface area, average pore size and pore volume than the raw montmorillonite clay. Then, the formed TCM materials were applied in photocatalytic degradation of 2,4-dichlorophenol(2,4-DCP) in aqueous solution. The degradation efficiency reached as high as 94.7%. Based on the degradation intermediates benezoquinone, fumaric acid and oxalic acid identified by LC–MS analysis, a mechanism for the photocatalytic oxidation of 2,4-DCP on Ti O_2/Mt nano-composites is proposed.     

Synergetic degradation of Methylene Blue through photocatalysis and Fenton reaction on two-dimensional molybdenite-Fe

The greatest problem in conventional Fenton reaction is the slow production of ROS（reactive oxygen species） because of the inefficient Fe³⁺/Fe²⁺ conversion. Based on the extraordinary photo-response property of two-dimensional molybdenite（2DM）, photogenerated electrons can be easy separated to accelerate the regeneration of Fe²⁺ . In this work, Fe²⁺ -anchored2DM（2DM-Fe） was prepared and used as a heterogeneous Fenton catalyst to investigate the degrada...     

Enhanced solar-light-driven photocatalytic properties of novel Z-scheme binary BiPO4 nanorods anchored onto NiFe2O4 nanoplates: Efficient removal of toxic organic pollutants

Global environmental problems have been increasing with the growth of the world economy and have become a crucial issue. To replace fossil fuels, sustainable and eco-friendly catalysts are required for the removal of organic pollutants. In this study, nickel ferrite (NiFe₂O₄) was prepared using a simple wet-chemical synthesis, followed by calcination; bismuth phosphate (BiPO₄) was also prepared using a hydrothermal method. Further, NiFe₂O₄/BiPO₄ nanocomposites were prepared using a hydrothermal technique. Numerous characterization studies, such as structural, morphology, surface area, optical, photoluminescence, and photoelectrochemical investigations, were used to analyze NiFe₂O₄/BiPO₄ nanocomposites. The morphology analysis indicated a successful decoration of BiPO₄ nanorods on the surface of NiFe₂O₄ nanoplate. Further, the bandgap of the NiFe₂O₄/BiPO₄ nanocomposites was modified owing to the formation of a heterostructure. The as-prepared NiFe₂O₄/BiPO₄ nanocomposite exhibited promising properties to be used as a novel heterostructure for tetracycline (TC) and Rhodamine B (RhB) removal. The NiFe₂O₄/BiPO₄ nanocomposite degrades TC (98%) and RhB (99%) pollutants upon solar-light irradiation within 100 and 60 min, respectively. Moreover, the trapping experiments confirmed the Z-scheme approach of the prepared nanocomposites. The efficient separation and transfer of photogenerated electron-hole pairs rendered by the heterostructure were confirmed by utilizing electrochemical impedance spectroscopy, photocurrent experiments, and photoluminescence. Mott–Schottky measurements were used determine the positions of the conduction and valence bands of the samples, and the detailed mechanism of photocatalytic degradation of toxic pollutants was projected and discussed.     

Visible–light driven photocatalytic degradation of bisphenol-A using ultrasonically synthesized polypyrrole/K-birnessite nanohybrids: Experimental and DFT studies

Although manganese oxides are known for their semiconductor characteristics, the photocatalytic performance of conducting polymer intercalated K-Birnessite(K-Bi) has not been explored till date. With the view to design a visible light driven organic–inorganic hybrid photocatalyst for rapid degradation of Bisphenol A(BPA), the present work reports the ultrasound-assisted green synthesis of K-Bi/polypyrrole(Ppy) nanohybrids. The loading of Ppy in K-Bi was confirmed by thermogravimetric analysis while the formation of organic–inorganic hybrid was confirmed by infrared spectroscopy. K-Bi revealed a band gap of 2.8 e V while for the nanohybrids it was found to be ranging between 2.4 and 1.6 e V. X-ray diffraction studies confirmed partial intercalation of Ppy chains in the inter-layer space of K-Bi. High resolution transmission electron microscopy and scanning electron microscopy studies showed mixed morphology of K-Birnessite/Ppy nanohybrids. Rapid degradation of BPA was observed under visible irradiation in presence of K-Bi/Ppy nanohybrids and almost90% degradation of 20 mg/L BPA solution was achieved within 120 min. The degradation was found to follow pseudo-first order kinetics and the degraded fragments were identified using liquid chromatography-mass spectrometry. Degradation pathway was proposed based on density-functional theory calculations of fukui index predicting the radical easyattacking(f0) and(f-) sites in BPA.     

Photo-oxidation of NO using an exterior paint--screening of various commercial titania in powder pressed and paint films

The present work aims to evaluate the photocatalytic activity of photo-TiO(2) from various producers (Evonik, Kemira, Kronos, Millennium, Sachtleben and Tayca), in the form of powder pressed films and upon incorporation in a water-based paint, for outdoor NO abatement. The photocatalytic activity of the different samples was evaluated in terms of NO conversion and selectivity towards nitrite and nitrate ions following approximately the ISO 22197-1:2007(E) standard. The highest yields obtained for powder pressed films were achieved with VLP7000 (0.70), followed by VLP7101 (0.55) and UVLP7500 (0.55), all from Kronos. On the other hand, when incorporated in paint films, the highest yields were obtained with PC500 and PC105 from Millennium and UV100 from Sachtleben (ca. 0.15). The paint matrix plays an important role on the photocatalytic activity. In particular, the time for steady state is one or two orders of magnitude higher when the photocatalysts are incorporated in paint films in relation to the powder pressed films. The paint films were activated following the procedure recommended by the above-mentioned standard. However, the photocatalytic activity of films incorporating P25 (Evonik) was displayed only when higher power radiation and higher humidity conditions were used. This allowed for similar levels of photocatalytic activity as the other paint films.     

Photocatalytic activity of tungsten-doped TiO2 with hydrothermal treatment under blue light irradiation

Tungsten doping and hydrothermal treatment were found to significantly improve the visible-light photoactivity of TiO(2) synthesized by the sol-gel method. It was observed that TiO(2) doped with a 0.5% W:Ti mole ratio and treated with 4 h of hydrothermal curing showed photoactivity under blue light irradiation equal to 74% of the commercial Degussa P-25 under UV irradiation, i.e., 0.01 mM 2-chlorophenol was completely removed in 120 and 90 min, respectively. Light absorptivity and photocatalytic activity under blue light irradiation were not dependent on the crystallite structure of the TiO(2). The oxidation kinetics under blue light irradiation can be effectively explained by the Langmuir-Hinshelwood model with an apparent reaction rate constant and a Langmuir constant of 3.60 × 10(-4) mM min(-1) and 206.53 mM(-1), respectively.