Effects of the preparation method of the ternary CdS/TiO_2/Pt hybrid photocatalysts on visible light-induced hydrogen production

A variety of combinations of CdS, TiO2, and Pt in preparing the hybrid catalysts were studied for hydrogen production under visible light ( > 420 nm) irradiation. The preparation method sensitively influenced the activity of the ternary hybrid catalysts. The formation of the potential gradient at the interface between CdS and TiO2 is necessary in achieving the efficient charge separation and transfer and how the platinum as a cocatalyst is loaded onto the CdS/TiO2 hybrid catalysts determines the overall hydrogen production efficiency. The common method of photoplatinization of CdS/TiO2 hybrid [Pt-(CdS/TiO2)] was much less efficient than the present method in which Pt was photodeposited on bare TiO2, which was followed by the deposition of CdS [CdS/(Pt-TiO2)]. The CdS/(Pt-TiO2) has the hydrogen production rate ranging (6–9) × 10-3 mol h-1 g-1, which is higher by a factor of 3–30 than that of Pt-(CdS/TiO2). The photocatalytic activity of the ternary hybrid catalysts was extremely sensitive to where the platinum is loaded. The photoactivity of the hybrid catalyst was also assessed in terms of the photocurrent collected by the methyl viologen electron shuttle in the catalyst suspension. CdS/(Pt-TiO2) generated higher photocurrents than Pt-(CdS/TiO2) by a factor of 2–7. The extreme sensitivity of the preparation method to the hydrogen production activity should be taken into account when hybrid photocatalysts are designed and prepared

Combinatorial doping of TiO_2 with platinum (Pt), chromium (Cr), vanadium (V), and nickel (Ni) to achieve enhanced photocatalytic activity with visible light irradiation

Titanium dioxide (TiO_2) was doped with the combination of several metal ions including platinum (Pt), chromium (Cr), vanadium (V), and nickel (Ni). The doped TiO_2 materials were synthesized by standard sol-gel methods with doping levels of 0.1 to 0.5 at.%. The resulting materials were characterized by x-ray diffraction (XRD), BET surface-area measurement, scanning electron microscopy (SEM), and UV-vis diffuse reflectance spectroscopy (DRS). The visible light photocatalytic activity of the codoped samples was quantified by measuring the rate of the oxidation of iodide, the rate of degradation of methylene blue (MB), and the rate of oxidation of phenol in aqueous solutions at λ > 400 nm. 0.3 at.% Pt-Cr-TiO_2 and 0.3 at.% Cr-V-TiO_2 showed the highest visible light photocatalytic activity with respect to MB degradation and iodide oxidation, respectively. However, none of the codoped TiO_2 samples were found to have enhanced photocatalytic activity for phenol degradation when compared to their single-doped TiO_2 counterparts

Effects of Single Metal-Ion Doping on the Visible-Light Photoreactivity of TiO_2

Titanium dioxide (M-TiO_2), which was doped with 13 different metal ions (i.e., silver (Ag^+), rubidium (Rb^+), nickel (Ni^(2+)), cobalt (Co^(2+)), copper (Cu^(2+)), vanadium (V^(3+)), ruthenium (Ru^(3+)), iron (Fe^(3+)), osmium (Os^(3+)), yttrium (Y^(3+)), lanthanum (La^(3+)), platinum (Pt^(4+), Pt^(2+)), and chromium (Cr3+, Cr6+)) at doping levels ranging from 0.1 to 1.0 at. %, was synthesized by standard sol−gel methods and characterized by X-ray diffraction, BET surface area measurement, SEM, and UV−vis diffuse reflectance spectroscopy. Doping with Pt(IV/II), Cr(III), V(III), and Fe(III) resulted in a lower anatase to rutile phase transformation (A−R phase transformation) temperature for the resultant TiO_2 particles, while doping with Ru(III) inhibited the A−R phase transformation. Metal-ion doping also resulted in a red shift of the photophysical response of TiO_2 that was reflected in an extended absorption in the visible region between 400 and 700 nm. In contrast, doping with Ag(I), Rb(I), Y(III), and La(III) did not result in a red shift of the absorption spectrum of TiO_2. As confirmed by elemental composition analysis by energy dispersive X-ray spectroscopy, the latter group of ions was unable to be substituted for Ti(IV) in the crystalline matrix due to their incompatible ionic radii. The photocatalytic activities of doped TiO_2 samples were quantified in terms of the photobleaching of methylene blue, the oxidation of iodide (I^(−)), and the oxidative degradation of phenol in aqueous solution both under visible-light irradiation (λ > 400 nm) and under broader-band UV−vis irradiation (λ > 320 nm). Pt- and Cr-doped TiO_2, which had relatively high percentages of rutile in the particle phase, showed significantly enhanced visible-light photocatalytic activity for all three reaction classes

Sonochemical Degradation of Perfluorooctane Sulfonate (PFOS) and Perfluorooctanoate (PFOA) in Landfill Groundwater: Environmental Matrix Effects

Perfluorinated chemicals such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are environmentally persistent and recalcitrant to most conventional chemical and microbial treatment technologies. In this paper, we show that sonolysis is able to decompose PFOS and PFOA present in groundwater beneath a landfill. However, the pseudo first-order rate constant for the sonochemical degradation in the landfill groundwater is reduced by 61 and 56% relative to MilliQ water for PFOS and PFOA, respectively, primarily due to the presence of other organic constituents. In this study, we evaluate the effect of various organic compounds on the sonochemical decomposition rates of PFOS and PFOA. Organic components in environmental matrices may reduce the sonochemical degradation rates of PFOS and PFOA by competitive adsorption onto the bubble−water interface or by lowering the average interfacial temperatures during transient bubble collapse events. The effect of individual organic compounds depends on the Langmuir adsorption constant, the Henry’s law constant, the specific heat capacity, and the overall endothermic heat of dissociation. Volatile organic compounds (VOCs) are identified as the primary cause of the sonochemical rate reduction for PFOS and PFOA in landfill groundwater, whereas the effect of dissolved natural organic matter (DOM) is not significant. Finally, a combined process of ozonation and sonolysis is shown to substantially recover the rate loss for PFOS and PFOA in landfill groundwater

Reductive defluorination of aqueous perfluorinated alkyl surfactants : effects of ionic headgroup and chain length

Perfluorinated chemicals (PFCs) are distributed throughout the environment. In the case of perfluorinated alkyl carboxylates and sulfonates, they can be classified as persistent organic pollutants since they are resistant to environmentally relevant reduction, oxidation, and hydrolytic processes. With this in mind, we report on the reductive defluorination of perfluorobutanoate, PFBA (C_3F_7CO_2−), perfluorohexanoate, PFHA (C_5F_(11)CO_2−), perfluorooctanoate, PFOA (C_7F_(15)CO_2−), perfluorobutane sulfonate, PFBS (C_4F_9SO_3−), perfluorohexane sulfonate, PFHS (C_6F_(13)SO_3−), and perfluorooctane sulfonate, PFOS (C_8F_(17)SO_3−) by aquated electrons, eaq−, that are generated from the UV photolysis (λ = 254 nm) of iodide. The ionic headgroup (-SO_3− vs -CO_2−) has a significant effect on the reduction kinetics and extent of defluorination (F index = −[F−]_(produced)/[PFC]_(degraded)). Perfluoroalkylsulfonate reduction kinetics and the F index increase linearly with increasing chain length. In contrast, perfluoroalkylcarboxylate chain length appears to have a negligible effect on the observed kinetics and the F index. H/F ratios in the gaseous fluoro-organic products are consistent with measured F indexes. Incomplete defluorination of the gaseous products suggests a reductive cleavage of the ionic headgroup occurs before complete defluorination. Detailed mechanisms involving initiation by aquated electrons are proposed

In Situ-Generated Reactive Oxygen Species in Precharged Titania and Tungsten Trioxide Composite Catalyst Membrane Filters: Application to As(III) Oxidation in the Absence of Irradiation

This study demonstrates that in situ-generated reactive oxygen species (ROSs) in prephotocharged TiO₂ and WO₃ (TW) composite particle-embedded inorganic membrane filters oxidize arsenite (As(III)) into arsenate (As(V)) without any auxiliary chemical oxidants under ambient conditions in the dark. TW membrane filters have been charged with UV or simulated sunlight and subsequently transferred to a once-through flow-type system. The charged TW filters can transfer the stored electrons to dissolved O₂, producing ROSs that mediate As(III) oxidation in the dark. Dramatic inhibition of As(V) production with O₂ removal or addition of ROS quenchers indicates an ROS-mediated As(III) oxidation mechanism. Electron paramagnetic spectroscopic analysis has confirmed the formation of the HO₂•/O₂•– pair in the dark. The WO₃ fraction in the TW filter significantly influences the performance of the As(III) oxidation, while As(V) production is enhanced with increasing charging time and solution pH. The As(III) oxidation is terminated when the singly charged TW filter is fully discharged; however, recharging of TW recovers the catalytic activity for As(III) oxidation. The proposed oxidation process using charged TW membrane filters is practical and environmentally benign for the continuous treatment of As(III)-contaminated water during periods of unavailability of sunlight

In Situ-Generated Reactive Oxygen Species in Precharged Titania and Tungsten Trioxide Composite Catalyst Membrane Filters: Application to As(III) Oxidation in the Absence of Irradiation

This study demonstrates that in situ-generated reactive oxygen species (ROSs) in prephotocharged TiO₂ and WO₃ (TW) composite particle-embedded inorganic membrane filters oxidize arsenite (As(III)) into arsenate (As(V)) without any auxiliary chemical oxidants under ambient conditions in the dark. TW membrane filters have been charged with UV or simulated sunlight and subsequently transferred to a once-through flow-type system. The charged TW filters can transfer the stored electrons to dissolved O₂, producing ROSs that mediate As(III) oxidation in the dark. Dramatic inhibition of As(V) production with O₂ removal or addition of ROS quenchers indicates an ROS-mediated As(III) oxidation mechanism. Electron paramagnetic spectroscopic analysis has confirmed the formation of the HO₂•/O₂•– pair in the dark. The WO₃ fraction in the TW filter significantly influences the performance of the As(III) oxidation, while As(V) production is enhanced with increasing charging time and solution pH. The As(III) oxidation is terminated when the singly charged TW filter is fully discharged; however, recharging of TW recovers the catalytic activity for As(III) oxidation. The proposed oxidation process using charged TW membrane filters is practical and environmentally benign for the continuous treatment of As(III)-contaminated water during periods of unavailability of sunlight

Sonochemical Degradation of Perfluorooctane Sulfonate (PFOS) and Perfluorooctanoate (PFOA) in Groundwater: Kinetic Effects of Matrix Inorganics

Ultrasonic irradiation has been shown to effectively degrade perfluorinated chemicals (PFCs) such as perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) in aqueous solution. Reduced PFC sonochemical degradation rates in organic-rich groundwater taken from beneath a landfill, however, testify to the negative kinetic effects of the organic groundwater constituents. In this study, the PFOX (X = S or A) sonochemical degradation rates in a groundwater sample with organic concentrations about 10 times lower than those in the groundwater taken from beneath a landfill are found to be 29.7% and 20.5% lower, respectively, than the rates in Milli-Q water, suggesting that inorganic groundwater constituents also negatively affect PFC sonochemical kinetics. To determine the source of the groundwater matrix effects, we evaluate the effects of various inorganic species on PFOX sonochemical kinetics. Anions over the range of 1−10 mM show Hofmeister effects on the sonochemical degradation rates of PFOX, k_(ClO_4)^(−PFOX) > k_(NO_3)^(−PFOX) ~ k_(Cl^−)^(−PFOX) ≥ k_(MQ)^(−PFOX) > k_(HCO_3)^(−PFOX) ~ k_(SO_(4)^(2−)^(−PFOX). In contrast, common cations at 5 mM have negligible effects. Initial solution pH enhances the degradation rates of PFOX at 3, but has negligible effects over the range of 4 to 11. The observed inorganic effects on sonochemical kinetics are hypothesized to be due to ions’ partitioning to and interaction with the bubble−water interface. Finally, it is shown that the rate reduction in the groundwater in this study is primarily due to the presence of bicarbonate and thus can be fully rectified by pH adjustment prior to sonolysis