SnS2/TiO2 nanocomposites with enhanced visible light-driven photoreduction of aqueous Cr(VI)

SnS₂/TiO₂ nanocomposites have been synthesized via microwave assisted hydrothermal treatment of tetrabutyl titanate in the presence of SnS₂ nanoplates in the solvent of ethanol at 160 °C for 1 h. The physical and chemical properties of SnS₂/TiO₂ were studied by XRD, FESEM, EDS, TEM, XPS and UV–vis diffuse reflectance spectra (DRS). The photocatalytic activity of SnS₂/TiO₂ nanocomposites were evaluated by photoreduction of aqueous Cr(VI) under visible light (λ>420 nm) irradiation. The experimental results showed that the SnS₂/TiO₂ nanocomposites exhibited excellent reduction efficiency of Cr(VI) (~87%) than that of pure TiO₂ and SnS₂. The SnS₂/TiO₂ nanocomposites were expected to be a promising candidate as effective photocatalysts in the treatment of Cr(VI) wastewater.     

Photocatalytic reduction of hexavalent chromium (Cr(VI)) using rotating TiO<Subscript>2</Subscript> mesh

An immobilized TiO₂ electrode for photocatalytic hydrogen production is applied to reduce toxic Cr(VI) to non toxic Cr(III) in aqueous solution under UV irradiation. To overcome the limitation of powder TiO₂, a novel technique of immobilization based on anodization was applied and investigated under various experimental conditions. The anodization was performed with three different electrolytes (single or mixed), and then the anodized samples were annealed under an oxygen stream. Among the three kinds of anodized/annealed TiO₂ on Ti foil, Sample II (anodized at 20 V in 0.5% HF for 45 min at 5 °C, and annealed at 450 °C for 5 hr in ambient oxygen at a flow rate of 400 mL/min) was more effective for both Cr(VI) reduction than the other samples. Based on the electrolyte compositions, nanotubular TiO₂ grown on Ti meshes was fabricated for the purpose of its light-harvesting ability and efficiency, where the anodized/annealed TiO₂ on meshes were rotated in the center of the reactor and Cr(VI) could be effectively reduced at rotation speeds ranging from 0 to 64 rpm. In case of Sample II, it was found that up to 98 % of the Cr(VI) was reduced in 30 min at 64 rpm.     

TiO2 catalysed reduction of Cr(VI) in aqueous solutions under ultraviolet illumination

The photoassisted reduction of Cr(VI) to Cr(III) in aqueous suspensions of TiO₂ under ultraviolet (UV) illumination has been studied by determining the amount of Cr(VI) photoreduced at different irradiation times, the mass of catalyst in suspension, the Cr(VI) initial concentration and the pH. Samples of wastes from metal-surface treatment industries have been used to test this photocatalytic procedure for Cr(VI) elimination in a real ease. It has been observed that the presence in these samples of certain species such as Fe(III) and Cr(III) at low concentrations can increase significantly the yield of Cr(VI) photoreduction. It is assumed that these cations act by maintaining the pH during the photoreduction process, preventing the alkalization by hydrolysis of the solution.     

TiO2 nanoparticles assembled on graphene oxide nanosheets with high photocatalytic activity for removal of pollutants

A novel method was developed to synthesize graphite oxide/TiO₂ composites as a highly efficient photocatalyst by in situ depositing TiO₂ nanoparticles on graphene oxide nano-sheets by a liquid phase deposition, followed by a calcination treatment at 200 °C. The two-dimensional porous graphene oxide/TiO₂ composites had specific surface area of 80 m² g⁻¹ being considerably larger than that of P25 and the similarly prepared neat TiO₂ particles without using graphene oxide. The composites exhibited excellent photocatalytic activity, being influenced by post-calcination temperature, graphene oxide content and solution pH. Under optimal conditions, the photo-oxidative degradation rate of methyl orange and the photo-reductive conversion rate of Cr(VI) over the composites were as high as 7.4 and 5.4 times that over P25, respectively. The excellent enhancing effect of graphene oxide nano-sheets on the photocatalytic properties of TiO₂ was attributed to a thin two-dimensional sheet support, a large surface area and much increased adsorption capacity, and the strong electron transfer ability of the thermally reduced graphene oxide in the composite.     

Enhanced catalytic oxidation via nano Cu0.5Mg0.5Fe2O4 embedded in CNTs for adsorption–reduction of hexavalent chromium

A catalyst consisting of Cu_0.5Mg_0.5Fe₂O₄ (CMF) supported on carbon nanotubes (CNTs) which exhibits great potential as an adsorbent for treating Cr(VI)-contaminated wastewater has been successfully prepared. The ferrite possesses excellent magnetic properties, while CNTs have the advantage of a large surface area. This composite material not only prevents the aggregation of magnetic materials and enhances the exposure of active sites but also effectively solves the recycling problem of CNTs. Our results show that the adsorption capacity of Cu_0.5Mg_0.5Fe₂O₄–carbon nanotubes (CMF-CNTs) for Cr(VI) wastewater (45.60 mg/g) is 1.49 times higher than that of Cu_0.5Mg_0.5Fe₂O₄ (30.48 mg/g). Compared to a single catalyst, CMF-CNTs not only improve the dispersibility of magnetic materials but also exhibit synergistic effects between the composite materials, enhancing the chemical adsorption capacity. After five consecutive adsorption and desorption experiments, the adsorption capacity of CMF-CNTs remains at 88% of its initial value. Furthermore, the study of the catalyst before and after adsorption by XPS reveals that the valence state transition of Fe³⁺/Fe²⁺ and Cu²⁺/Cu⁺ plays a crucial role in the adsorption process. The results of this study demonstrate the potential of using waste materials for effective wastewater treatment and provide insights into the development of new adsorbents for pollutant removal.     

Enhanced adsorptive removal of Cr(VI) in aqueous solution by polyethyleneimine modified palygorskite

Polyethyleneimine (PEI) modified palygorskite (Pal) was used for the adsorption of Cr(VI) in aqueous solution. The absorbent was characterized by Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). Characterized results confirmed that the Pal has been successfully modified by PEI. The modification of PEI increased the Cr(VI) adsorption performance of the Pal by the adsorption combined reduction mechanism, and amino groups of the adsorbent play the main role in the enhanced Cr(VI) adsorption. The maximum adsorption capacity was 51.10 mg·g⁻¹ at pH 4.0 and 25 °C. The adsorption kinetics of Cr(VI) on the adsorbent conforms to the Langmuir isotherm model. The maximum adsorption occurs at pH 3, and then the adsorption capacity of PEI-Pal was decreased with the increase of pH values. The adsorption kinetics of Cr(VI) on PEI-Pal was modeled with pseudo-second-order model. The addition of Cl⁻, SO₄²⁻ and PO₄³⁻ reduced the Cr(VI) adsorption by competition with Cr(VI) for the active sites of PEI-Pal. The Cr(VI) saturated PEI-Pal can be regenerated in alkaline solution, and the adsorption capacity can still be maintained at 30.44 mg·g⁻¹ after 4 cycles. The results demonstrate that PEI-Pal can be used as a potential adsorbent of Cr(VI) in aqueous solutions.     

Preparation and photoelectrocatalytic properties of titania/carbon nanotube composite films

Composite films of TiO₂ and carbon nanotubes (CNTs) were prepared on titanium sheets by liquid phase deposition and the photoelectrocatalytic (PEC) properties of the films were investigated through the degradation of methyl orange (MO) in 0.1 M solutions. It was demonstrated that CNTs in the TiO₂ film significantly decreased the charge transfer resistance and increased the anodic photocurrent response of the film under UV light irradiation when the bias was above −0.1 V. The PEC performance of the CNT-based composite film could be tuned by controlling the preparation parameters including the deposition time and calcination temperature. The deposition time and calcination temperature were optimized at 1 h and 450 °C, respectively. On the TiO₂/CNT film prepared under the optimized conditions, 95% of the added MO (10 mg L⁻¹) was degraded within 90 min, which was much higher than the 60% removal seen on the pure TiO₂ films.     

Nanoflower-like CdS and SnS2 loaded TiO2 nanotube arrays for photocatalytic wastewater treatment and hydrogen production

In this work, nanoflower-like CdS/SnS₂/TiO₂ NTs ternary heterojunction photocatalysts were synthesized by a hydrothermal method, the relationship between the morphology, microscopic morphology, crystallinity, elemental presence state and hydrogen production performance of the ternary photocatalysts were investigated by SEM, TEM, XRD and XPS, respectively. The photocatalytic performance, electrochemical property and hydrogen production capacity of CdS/SnS₂/TiO₂ NTs were compared with pure TiO₂ NTs, CdS/TiO₂ NTs and SnS₂/TiO₂ NTs. After 2 h of photocatalytic reaction, the removal efficiency of MB wastewater reached 100%, and the photocatalytic efficiencies toward RhB and Cr(VI) removal reached 86.08% and 80.93% after 3 h, respectively. The electron spin resonance (ESR) technique certified the active radical groups that played a role in the catalytic process and further investigated the possible photocatalytic mechanism. Hydrogen production per unit time achieved 97.14 μmol h^?1 cm^?2, this work provides the new technique to achieve solar energy conversion for hydrogen generation.     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite oxide and its photocatalytic degradation of rhodamine B

The composite semiconductor photocatalyst TiO₂/SiO₂ was prepared by template-hydrothermal method using carbon spheres as the template. The structural and optical properties of TiO₂/SiO₂ were characterized by XRD, SEM, BET, UV–Vis DRS, TG-DTA, PL techniques. The formation of hydroxyl radical on the surface of TiO₂/SiO₂ was studied with terephthalic acid as the probe molecule, combined with fluorescence technique. The results showed that the specific surface area of TiO₂/SiO₂ composite was 327.9 m²/g, and the specific surface area of TiO₂/SiO₂ was larger than that of pure TiO₂. Photocatalytic degradation of rhodamine B showed that TiO₂/SiO₂ composite oxide under visible light illumination 40 min, the degradation rate was 98.6 % and the degradation rate of pure TiO₂ was only 11.9 %. The apparent first-order rate constant of TiO₂/SiO₂ was 33 times that of pure TiO₂ and more than 6 times that of P25 when the molar ratio of Ti to Si was 1:1 under visible light irradiation. Moreover, it’s also as much as 5 times that of pure TiO₂ and is more than 1 times that of P25 under UV light irradiation 25 min. Based on the experimental results, ^·O₂ ^? and h⁺ were suggested to be the major active species which was responsible for the degradation reaction. The increased photocatalytic activity of TiO₂/SiO₂ may be mainly attributed to effectively suppressing the recombination of hole/electron pairs. After the photocatalyst TiO₂/SiO₂ was reused 5 times, the degradation rate of rhodamine B could reach 89.2 % under visible light irradiation. Moreover, The composite semiconductor photocatalyst TiO₂/SiO₂ was selective towards the degradation of rhodamine B.     

Spectroscopic characterization of the reduction and removal of chromium (VI) by tropical peat and humin

The reduction of Cr(VI) to Cr(III) in aqueous solution, and the subsequent removal of Cr(III) using in natura peat or its humin fraction, was characterized by electron paramagnetic resonance (EPR), ultraviolet–visible (UV–Vis) spectroscopy and X-ray photoelectron (XPS) spectroscopy. EPR spectroscopy g-factors ranging from 2.0029 to 2.0030 indicated the presence of organic free radicals (OFR) associated with carbon atoms. The spin densities of the samples increased with pH in the range pH 2.0–pH 6.0. An XPS spectroscopy peak at 579.0 eV was attributed to Cr(VI), and peaks at 576.8 eV and 677.3 eV to two different chemical forms of Cr(III). Removal of chromium increased with the reduction of Cr(VI) to Cr(III), and removal rates after 50 h were 13% (peat) and 15% (humin) at pH 6.0, and 70% (peat) and 80% (humin) at pH 2.0. The greater efficiency of the humin fraction in the reduction/removal process is discussed in terms of the chemical structures of these materials.     

Synthesis and characterization of polypyrrole using TiO2 nanotube@poly(sodium styrene sulfonate) as dopant and template

A polypyrrole (PPy) using TiO₂ nanotube@poly(sodium styrene sulfonate) (TiO₂@PSS) as dopant and template was synthesized by chemical oxidation polymerization. The template TiO₂@PSS consisting of a TiO₂ nanotube core and PSS on the surface was prepared by a “grafting from” approach. PPy on the layer of TiO₂@PSS (TiO₂@PSS/PPy) was characterized by transmission electron microscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy (XPS), Fourier‐transform infrared spectrometry (FTIR), Raman spectroscopic analysis, UV‐visible (UV‐vis) spectroscopy, thermo gravimetric analysis, and electrical conductivity analysis. Results showed that TiO₂@PSS/PPy was successfully fabricated. The electrical conductivity of the TiO₂@PSS/PPy nanocomposites at room temperature was 11.6 S cm⁻¹, which was higher than that of the PPy (4.2 S cm⁻¹). This result was consistent with those based on FTIR, UV‐vis spectroscopy, and XPS analyses. The nanocomposites have nanoparticle size and controllable morphology and thus potential applications in photoelectrochemical devices, photocatalytic devices, conductive inks, electronic printing sensors, and electrodes. POLYM. COMPOS., 37:462–467, 2016. © 2014 Society of Plastics Engineers     

Photodegradation behavior of the polycarbonate/TiO2 composite films under the UV irradiation in ambient air condition

Photocatalytic degradation mechanism of the polycarbonate(PC)/TiO₂ composite films was studied under the ambient air condition in order to investigate the feasibility of the PC/TiO₂ composite as a photodegradable polymer. TiO₂ composition in the PC/TiO₂ composite was changed from 0 wt% to 4 wt%. Photodegradation behaviors of the composite films were compared with that of the pure PC films by performing the weight loss monitoring under UV irradiation, FTIR spectroscopy, color measurement analysis, SEM, and XPS analysis. The weight loss rate of the PC/TiO₂ composite film (33% weight loss after 300 h) with 4 wt% TiO₂ was twice as high as the pure PC films (14% weight loss after 300 h). The increase in the FTIR hydroxyl peak, and carbonyl peak intensity and the yellowing observation during the photodegradation were due to the formation of the photoproducts (aliphatic, aromatic chain‐ketones, aromatic, and OH radical) and the structural modification of polycarbonate. XPS analysis of composite film showed the photodegradation of the polymer surface and TiO₂ particles exposure on the surface of the composite films matrix. POLYM. COMPOS., 36:1462–1468, 2015. © 2014 Society of Plastics Engineers     

Effect of nano‐TiO2 on MP‐25 resin

MP‐25 resin is a chlorine‐containing polymer widely used in coatings. The effects of two types of nano‐TiO₂ (P‐25 and RM301 LP) on MP‐25 were studied with saline immersion, UV irradiation, and electrochemical impedance spectroscopy. UV irradiation was evaluated in terms of gloss change and X‐ray photoelectron spectroscopy (XPS). The results indicate that, compared to pigment R‐930 TiO₂, P‐25 reduced the immersion resistance and accelerated UV aging of the MP‐25 coating, whereas RM301 LP showed the opposite effects. XPS analysis showed that MP‐25 resin degraded under UV irradiation via dechlorination and C? C bond breakage, similarly to poly(vinyl chloride), but RM301 LP could inhibit the aging of MP‐25 to a certain extent. A skin effect of oxygen and chlorine was identified in MP‐25 resin by XPS. RM301 LP could improve the impedance of the MP‐25 coating because of its excellent fill capacity. Hence, rutile nano‐TiO₂ RM301 LP represents an excellent additive for MP‐25 resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Direct hydrolysis synthesis of BiOI flowerlike hierarchical structures and it's photocatalytic activity under simulated sunlight irradiation

BiOI flowerlike hierarchical structure was synthesized via direct hydrolysis from BiI₃ and characterized by powder X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS) spectra, and transmission electron microscopy (TEM). As-synthesized BiOI showed higher photocatalytic activity in aqueous RhB photodegradation system than P25 TiO₂ under simulated sunlight irradiation. The trapping experiments of active species and electron spin resonance (ESR) experiment during the photocatalytic reaction showed that the photocatalytic degradation of organic pollutants in BiOI system proceeds through direct hole transfer and O₂⁻ rather than OH.     

Hydrophilic TiO2 decorated carbon nanotubes/sulfonated poly(ether ether ketone) composite proton exchange membranes for fuel cells

Sulfonated poly(ether ether ketone) (SPEEK) is currently considered to be one of the most potential candidates of commercial perfluorinated sulfonic acid proton exchange membranes. To balance the proton conductivity and mechanical properties of SPEEK, nano TiO₂ coated carbon nanotubes (TiO₂@CNTs) were prepared using a benzyl alcohol-assisted sol-gel method and then used as a new nanofiller to modify SPEEK to prepare SPEEK/TiO₂@CNTs composite membranes. The thick insulated TiO₂ coating layer can effectively avoid the risk of electronic short-circuiting formed by CNTs, while the hydrophilicity of TiO₂ can also reduce the polar difference between CNTs and SPEEK matrix, thus promoting the homogeneous dispersion of CNTs in the composites. As a result, the composite membranes demonstrated simultaneously improved strength and proton conductivity. Incorporating 5 wt% of TiO₂@CNTs exhibited 31% growth in mechanical strength when compared with pure SPEEK. Moreover, the maximum conductivity was 0.104 S cm⁻¹ (80°C) for the composite membrane with 5 wt% of TiO₂@CNTs, which was nearly twice as high as that of SPEEK membrane (0.052 S cm⁻¹).     

Preparation and electrochemical properties of composites of carbon nanotubes loaded with Ag and TiO2 nanoparticle for use as anode material in lithium-ion batteries

Carbon nanotubes (CNTs) loaded with Ag and TiO₂ nanoparticles (Ag-TiO₂/CNTs) are a composite showing promise as an anode material in lithium-ion batteries. Here we prepare Ag-TiO₂/CNTs via hydrolysis and reduction processes. The morphology, structure, and electrochemical performance of the composite were investigated by transmission electron microscopy, X-ray diffraction, and a variety of electrochemical techniques. The results show that the TiO₂ and Ag nanoparticles were uniformly deposited on the surface of CNTs with crystallite sizes of ∼12 and 30 nm, respectively. The Ag-TiO₂/CNTs anode materials showed superior cycling stability and a high reversible capacity of 172 mAh/g after 30 cycles. Ag addition not only increases the electronic conductivity of the composites, but also allows convenient transfer of Li-ion in the composite structure.     

Cr(VI) reduction by bio and bioinorganic catalysis via use of bio‐H2: a sustainable approach for remediation of wastes

Use of biologically‐produced hydrogen (bio‐H₂) as an electron donor for Cr(VI) reduction by native and palladized cells of Desulfovibrio vulgaris NCIMB 8303 was demonstrated. The bio‐H₂ was produced fermentatively by Escherichia coli HD701 (a strain upregulated with respect to formate hydrogenlyase expression) using glucose solution or two industrial confectionery wastes as fermentable substrates. Maximum Cr(VI) reduction occurred at the expense of bio‐H₂ using palladized biomass (bio‐Pd(0)), with negligible residual Cr(VI) remaining from a 0.5 mmol dm^?3 solution after 2.5 h. Use of bio‐H₂ as the electron donor for Cr(VI) reduction by agar‐immobilized bio‐Pd(0) in a continuous‐flow system gave 90% reduction efficiency at a flow residence time of 0.7 h, which was maintained for the duration of bio‐H₂ evolution by E. coli HD701. This study shows the potential to remediate toxic metal waste at the expense of food processing waste, as a sustainable alternative to landfilling. Copyright © 2007 Society of Chemical Industry     

Photochemical elimination of Cr(VI) from neutral–alkaline solutions

The elimination of Cr(VI) from aqueous solutions at neutral and low alkaline pH by photocatalytic reduction to Cr(III), using ZnO powder as catalyst, is investigated. The study has been performed by determination of the percentage of Cr(VI) eliminated in the presence of some species (i.e. Zn(II), Cd(II), Ni(II), Ca(II), CH₃COO^?, PO^3-₄, CO^2-₃, S^2- and NH₃) which usually are found in wastes together with Cr(VI). The results obtained show that the presence of some species prevents the alkalinization of the solution during irradiation, which increases the yield of Cr(VI) photoreduction. Other species, such as S^2- and NH 3 , are oxidized during illumination: thus they prevent electron–hole recombination and, consequently, increase the yield of the Cr(VI) elimination.     

Removal of Chromium(VI) and Chromium(III) from Aqueous Solution by Grainless Stalk of Corn

Abstract

Grainless stalk of corn (GLSC) was tested for removal of Cr(VI) and Cr(III) from aqueous solution at different pH, contact time, temperature, and chromium/adsorbent ratio. The results show that the optimum pH for removal of Cr(VI) is 0.84, while the optimum pH for removal of Cr(III) is 4.6. The adsorption processes of both Cr(VI) and Cr(III) onto GLSC were found to follow first-order kinetics. Values of k _ads of 0.037 and 0.018 min^?1 were obtained for Cr(VI) and Cr(III), respectively. The adsorption capacity of GLSC was calculated from the Langmuir isotherm as 7.1 mg g^?1 at pH 0.84 for Cr(VI), and as 7.3 mg g^?1 at pH 4.6 for Cr(III), at 20°C. At the optimum pH for Cr(VI) removal, Cr(VI) reduces to Cr(III). EPR spectroscopy shows the presence of Cr(V) + Cr(III)-bound-GLSC at short contact times and adsorbed Cr(III) as the final oxidation state of Cr(VI)-treated GLSC. The results indicate that, at pH ≈ 1, GLSC can completely remove Cr(VI) from aqueous solution through an adsorption-coupled reduction mechanism to yield adsorbed Cr(III) and the less toxic aqueous Cr(III), which can be further removed at pH 4.6.     

Synthesis of TiO2 microspheres by ultrasonic spray pyrolysis and photocatalytic activity evaluation

This work presents and discusses TiO₂ microspheres synthesized by ultrasonic spray pyrolysis. A simple setup allowed for the continuous production of TiO₂ nanocrystals. During the process, the particles experienced a short residence time (ca. 40 s) at the set temperature (700 °C), promoting phase stability and limited particle coarsening. As a result, porous anatase TiO₂ microspheres with crystallite size ～8 nm and specific surface area ～27 m² g^-1 were produced as soft spherical agglomerates of ～0.6 μm. Samples were analyzed using X-ray diffraction, BET specific surface area, SEM, TEM, XPS, and UV/Vis diffuse reflectance spectra, as well as in their photocatalytic activities. Photoactivity was evaluated through the degradation of the model contaminant acetaminophen under UV irradiation, and the results confirmed the superior performance of the synthesized TiO₂ microspheres, exceeding the commercial standard TiO₂ P25 by ca. 60% in terms of reactivity.