Application of polyaniline for the reduction of toxic Cr(VI) in water

Various oxidation states of polyaniline, as film and powder, were used for reduction of highly toxic Cr(VI) to less toxic Cr(III) ion. The effects of various parameters such as synthesis method, physical and oxidation state of polyaniline, film thickness, solution pH and initial Cr(VI) concentration on the kinetics and efficiency of reduction process were investigated. Results showed that a very broad concentration range of Cr(VI) solutions (10-10(5)ppb by emeraldine base and 10-10(6.5)ppb by leucoemeraldine) can be efficiently (>98%) reduced by polyaniline as film or powder. Cr(VI) solutions with concentrations higher than these ranges were caused to the overoxidation and degradation of polymer. Decreasing of solution pH, increased the kinetics and performance of reduction process, but lowered the Cr(VI) concentration ranges caused the overoxidation and degradation of the polymer. Higher reduction efficiencies were obtained for thicker electrochemically synthesized polyaniline films and for thinner chemically prepared polyaniline free standing films. The ability or capacity of various forms of polyaniline in Cr(VI) reduction was evaluated as the milligrams of Cr(VI) reduced by one gram of various forms of polyaniline.     

Lifetime and regeneration of immobilized titania for photocatalytic removal of aqueous hexavalent chromium

Immobilized titania (TiO2) batch reactors reduced hexavalent chromium (Cr(VI)) in the form of potassium dichromate (K2Cr2O7) to trivalent chromium (Cr(III)) in aqueous solution at pH 3 under 171 W/m2 light intensity. The light source was a 125-W ultraviolet (UV) lamp. The Cr(VI) reduction showed zero-order kinetics (k0), while the Cr(VI) adsorption fitted with first-order kinetics (k(1st)). Adsorption capacity increased with increasing initial Cr(VI) concentration, and the area of immobilized TiO2 limited the reduction efficiency. The lifetime of fresh immobilized TiO2 was approximately 14 h. In addition, the regeneration of TiO2 with 3M sodium hydroxide (NaOH) was necessary to improve adsorption reaction.     

Effects of tri-valent (Cr(III)) and hexa-valent (Cr(VI)) chromium on the growth of activated sludge

The effects of Cr(VI) and Cr(III) species on the activated sludge growth rate have been assessed for a batch growth system, for a range of chromium concentration between 0 and 320 mg l(-1). Cr(VI) was found to stimulate microbial growth for concentrations up to about 25 mg l(-1), exhibiting maximum growth stimulation at 10 mg l(-1), whilst the lethal dose was found to be between 80 and 160 mg l(-1). On the other hand, Cr(III) was also found to stimulate microbial growth for concentrations up to about 15 mg l(-1), (with a maximum stimulation concentration at 10 mg l(-1)), whilst the lethal dose was found to lie between 160 and 320 mg l(-1). The results indicate that Cr(VI) is more toxic to biomass at relatively high concentrations (higher than 70 mg l(-1)) whilst it has a more pronounced growth stimulation effect at relatively smaller concentrations (less than 25 mg l(-1)), compared with Cr(III).     

Aqueous Cr(VI) photo-reduction catalyzed by TiO2 and sulfated TiO2

TiO(2) and sulfated TiO(2) (SO(4)(2-)/TiO(2)) catalysts with different textural properties were prepared under different calcination temperatures and the photo-reduction of Cr(VI) to Cr(III) catalyzed by these catalysts was investigated. For the photocatalytic reduction of Cr(VI), the photocatalytic activities of the TiO(2) samples were found to be strongly dependent of the calcination temperature and TiO(2) calcined at 400 degrees C showed a higher catalytic activity compared to other TiO(2) catalysts. In contrast, sulfation of TiO(2) stabilized the catalytic activities of SO(4)(2-)/TiO(2) catalysts. At low calcination temperature, SO(4)(2-)/TiO(2) catalysts exhibited catalytic activities almost comparable with that of TiO(2) and the catalytic activities of SO(4)(2-)/TiO(2) catalysts were markedly higher than TiO(2) under high calcination temperature. In addition, the removal of surface SO(4)(2-) of SO(4)(2-)/TiO(2) catalyst led to a marked decrease of the catalytic activity for Cr(VI) photo-reduction, suggesting that the presence of surface SO(4)(2-) provided an acid environment over the catalyst surface and favored the photo-reduction of Cr(VI).     

Photocatalytic reduction of Cr(VI) on the new hetero-system CuAl2O4/TiO2

A magnetic adsorbent, amine-functionalized silica magnetite (NH(2)/SiO(2)/Fe(3)O(4)), has been synthesized to behave as an anionic or cationic adsorbent by adjusting the pH value of the aqueous solution to make amino groups protonic or neutral. NH(2)/SiO(2)/Fe(3)O(4) were used to adsorb copper ions (metal cation) and Reactive Black 5 (RB5, anionic dye) in an aqueous solution in a batch system, and the maximum adsorption were found to occur at pH 5.5 and 3.0, respectively. The adsorption equilibrium data were all fitted the Langmuir isotherm equation reasonably well, with a maximum adsorption capacity of 10.41 mg g(-1) for copper ions and of 217 m g g(-1) for RB5. A pseudo-second-order model also could best describe the adsorption kinetics, and the derived activation energy for copper ions and RB5 were 26.92 kJ mol(-1) and 12.06 kJ mol(-1), respectively. The optimum conditions to desorb cationic and anionic adsorbates from NH(2)/SiO(2)/Fe(3)O(4) were provided by a solution with 0.1M HNO(3) for copper ions and with 0.05 M NaOH for RB5.     

Kinetic and regeneration studies of photocatalytic magnetic separable beads for chromium (VI) reduction under sunlight

Physical adsorption and photocatalytic reduction of Cr(VI) in magnetic separable beads were investigated. In order to elucidate the kinetics of photocatalytic process, operating parameters such as catalyst dosage and the initial concentration were examined in detail. It was observed that the reduction rate of Cr(VI) increased with an increase in the catalyst loading, as this translated into an increase in the number of available active sites. Critical scrutiny of the percentage of the initial reduction rate versus time at various initial concentration of Cr(VI) revealed that the rate of substrate conversion decreased as the initial concentration increased. The kinetic analysis of the photoreduction showed that the removal of Cr(VI) satisfactory obeyed the pseudo first-order kinetic according to the Langmuir-Hinshelwood (L-H) model and the absorption of Cr(VI) on the magnetic beads surfaces was the controlling step in the entire reduction process. Furthermore, desorption experiments by elution of the loaded gels with sodium hydroxide indicated that the magnetic photocatalyst beads could be reused without significant losses of their initial properties even after 3 adsorption-desorption cycles.     

Simultaneous photocatalytic reduction of Cr(VI) and oxidation of bisphenol A induced by Fe(III)-OH complexes in water

Simultaneously photocatalytic reduction of Cr(VI) and oxidation of bisphenol A (BPA) in aqueous solution in the presence of Fe(III)-OH complexes were investigated under a 250 W metal halide lamp (lambda>or=365 nm). Synergy effect of the simultaneous photocatalytic oxidation and reduction of both pollutants was achieved. The effects of initial pH value, initial concentration of BPA, Cr(VI) and Fe(III) were preliminarily investigated. The results showed that both photocatalytic reduction of Cr(VI) and degradation of BPA could occur simultaneously in the Fe(III)/Cr(VI)/BPA ternary system, and the rates of photocatalytic reduction of Cr(VI) and the oxidation of BPA were more rapid at a low pH range of 2.0-3.0. The increase of the initial concentration of Fe(III) was favorable to both photocatalytic reduction of Cr(VI) and oxidation of BPA. The reduction efficiency of Cr(VI) decreased with increasing initial concentrations of Cr(VI) and BPA, but the degradation efficiency of BPA was not changed obviously at different Cr(VI) concentrations.     

Controlled loading of MnS2 on porous TiO2 nanosheets for enhanced photocatalytic hydrogen evolution

Journal of Materials Science: Materials in Electronics - In this report, spherical nanoparticles/2D nanosheets based MnS2/TiO2 nanocomposites were prepared in different weight compositions which...     

石墨烯-CuO/TiO_2复合催化剂的合成及光催化制氢活性

采用溶剂热法合成了石墨烯-CuO/TiO_2复合催化剂,通过扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、紫外-可见漫反射(DRS)表征复合催化剂的微观形貌、结构和光学特性。以H_2PtCl_6为无机前驱体对其进行Pt负载,研究了不同石墨烯负载量对制氢活性的影响及太阳光下的制氢活性。结果表明,石墨烯负载量为0.5%(质量分数)时,复合催化剂制氢活性最高,石墨烯和CuO协同作用提高了TiO_2对可见光的利用及光催化分解C_2H_5OH/H_2O制氢活性。在可见光下照射5h后,样品的产氢量达到1 083.54μmol,太阳光光照5h后产氢量(4 374.51μmol)为P25(1598.25μmol)的2.74倍。     

High-temperature reduction of chromium (VI) in solid alkali

Chromium (VI) that exists in many industrial wastes is considered highly toxic. One of the most common ways to dispose of these wastes is to reduce chromium (VI) to chromium (III), which is less toxic and can be relatively easily removed or fixed. However, the reduction of chromium (VI) is often conducted in acidic solutions and the chromium (VI) in alkaline solid wastes is hardly to be fully removed. The present study describes a new method for reducing chromium (VI) in alkaline solid. By mixing alkaline solids containing chromium (VI) with an aqueous sucrose solution and then calcinating the resulting mixture at 400-600 degrees C in inertial gas, chromium (VI) can be easily reduced to an insoluble chromium oxide. The reduced fraction can reach up to 99% in 10-20 min under the conditions of temperature above 600 degrees C and sucrose/chromium > or = 1 g/1 g.     

Removal of chromium Cr(VI) by low-cost chemically activated carbon materials from water

Low-cost, chemically activated carbon materials, Pellet-600 and PVA-300, were prepared at relatively low temperatures and show more effective removal efficiency of Cr(VI) from water than commercially available activated carbons tested. The Pellet-600 is a pelletized carbon material with high mesoporous volumes and surface area, and the PVA-300 is composed of a high surface area carbon coating on a fiberglass mat substrate. A much faster adsorption kinetics and a much higher adsorption capacity for Cr(VI) are achieved by the Pellet-600. At very low concentrations of Cr(VI), the PVA-300 displays a strong adsorption ability for Cr(VI). XPS data show an increase in the atomic ratio of Cr/C and oxidation of carbon materials after adsorption of Cr(VI). These results suggest that a high content of mesopores with a high surface area and surface functional groups greatly improve the Cr(VI) removal efficiency from water.     

Photocatalytic reduction of Cr(VI) over different TiO2 photocatalysts and the effects of dissolved organic species

The toxic Cr(VI) in industrial wastewaters can be removed by a reduction from Cr(VI) to Cr(III) and a followed precipitation treatment. The reduction of Cr(VI) to Cr(III) is able to be achieved by a photocatalytic process. Thus, photocatalytic reduction of Cr(VI) over TiO2 catalysts was investigated in both the absence and presence of organic compounds. The TiO(2) catalyst was pre-calcined at different temperatures to tune the photocatalytic activity and surface area of the photocatalyst. Under the tested conditions, the photocatalytic reduction of Cr(VI) behaved as a pseudo-first-order reaction in kinetics. In the absence of any organic species, the rate constant (kCr) for the photocatalytic reduction of Cr(VI) was found to be increased initially, passing a maximum, and then decreased, as calcination temperature was increased. In the presence of organic compounds, however, kCr was decreased with the increase of calcination temperature. A marked synergistic effect between the photocatalytic reduction of Cr(VI) and organic compounds was observed over the photocatalyst with the largest specific surface area. These results demonstrated that the photocatalytic reduction of Cr(VI) alone was dependent on both of specific surface area and crystalline structure of the photocatalyst in the absence of any organic compounds, but was dominated by the specific surface area of the photocatalyst in the presence of organic compounds because of the synergistic effect between the photocatalytic reduction of Cr(IV) and the photocatalytic oxidation of organic compounds.     

Chromium adsorption and Cr(VI) reduction to trivalent chromium in aqueous solutions by soya cake

Chromium as Cr(VI) is a industrially produced pollutant. Hexavalent chromium can be reduced to the trivalent state using various reductive agents or it can be removed from solution by surface-active adsorbents. In this study, both of these methods were evaluated using soya cake. A high efficiency for reduction of Cr(VI) to trivalent chromium was observed at pH < 1. Increasing the temperature, also increased the yield. Experimentally, the optimum time and soya cake mass were 5h and 0.7 g, respectively. In the second treatment method, a high efficiency for adsorption of chromium was also observed at pH < 1. The favorable temperature for adsorption was found to be 20 degrees C. Experimentally, the best time was 1h and with increasing soya cake mass up to 30 g, the adsorption efficiency was increased. Dissolution of LiCl in the experimental solutions, increased the efficiency of adsorption, however, this effect was not observed in the case of KCl. Langmuir isotherm constants, Q and b, for ground soybeans, were found to be 2.8 x 10(-4)mg/mg and 0.623, respectively. Freundlich isotherm constants, K(f) and n, were found to be 1.4 x 10(-4) and 4.99, respectively.     

硫脲/海藻酸钠对Cr(VI)的吸附和光催化还原协同去除机制

光催化是一种高效去除溶液中的Cr(VI)的方法。相较于吸附法,其可以在短时间内将Cr(VI)还原Cr(III)。对海藻酸钠(SA)进行化学改性,以戊二醛为交联剂,将硫脲接枝到SA上制备硫脲/海藻酸钠凝胶球(GTSA),探究在光照条件下其对溶液中的Cr(VI)的吸附和还原机制。相较于SA,GTSA对不同波长光的吸收能力大幅增加,吸附和还原Cr(VI)的能力增加,在紫外汞灯的照射下,pH=1时,Cr(VI)的去除率达99%,还原率达79%。通过FTIR、SEM、UV-DRS和XPS对GTSA吸附还原Cr(VI)的过程进行机制分析,结果表明Cr(VI)的去除过程是静电吸附与光催化还原的协同作用。     

Cr(VI) reduction in aqueous solutions by siderite

Hexavalent chromium is a common and toxic pollutant in soils and wastewaters. Reduction of the mobile Cr(VI) to less mobile and less toxic Cr(III) is a solution for decontamination of industrial effluents. In this study, the reduction of hexavalent chromium in aqueous solutions by siderite was investigated. The influences of amount of acid, contact time, siderite dosage, initial Cr(VI) concentration, temperature and particle size of siderite have been tested in batch runs. The process was found to be acid, temperature and concentration dependent. The amount of acid is the most effective parameter affecting the Cr(VI) reduction since carbonaceous gangue minerals consume acid by side reactions. The highest Cr(VI) reduction efficiency (100%) occurred in the 50 mg/l Cr(VI) solution containing two times acid with respect to stoichiometric amount of Cr(VI) and at the conditions of siderite dosage 20 g/l, contact time 120 min and temperature 25 degrees C. Reduction efficiency increased with increase in temperature and decrease in particle size. The reduction capacity of siderite was found to be 17 mg-Cr(VI)/g.     

Removal of hexavalent chromium [Cr(VI)] from aqueous solutions by the diatomite-supported/unsupported magnetite nanoparticles

Diatomite-supported/unsupported magnetite nanoparticles were prepared by co-precipitation and hydrosol methods, and characterized by X-ray diffraction, nitrogen adsorption, elemental analysis, differential scanning calorimetry, transmission electron microscopy and X-ray photoelectron spectroscopy. The average sizes of the unsupported and supported magnetite nanoparticles are around 25 and 15 nm, respectively. The supported magnetite nanoparticles exist on the surface or inside the pores of diatom shells, with better dispersing and less coaggregation than the unsupported ones. The uptake of hexavalent chromium [Cr(VI)] on the synthesized magnetite nanoparticles was mainly governed by a physico-chemical process, which included an electrostatic attraction followed by a redox process in which Cr(VI) was reduced into trivalent chromium [Cr(III)]. The adsorption of Cr(VI) was highly pH-dependent and the kinetics of the adsorption followed a pseudo-second-order model. The adsorption data of diatomite-supported/unsupported magnetite fit well with the Langmuir isotherm equation. The supported magnetite showed a better adsorption capacity per unit mass of magnetite than unsupported magnetite, and was more thermally stable than their unsupported counterparts. These results indicate that the diatomite-supported/unsupported magnetite nanoparticles are readily prepared, enabling promising applications for the removal of Cr(VI) from aqueous solution.     

Biological detoxification of Cr(VI) using wood-husk immobilized Acinetobacter haemolyticus

Acinetobacter haemolyticus, a Gram-negative aerobic locally isolated bacterium, immobilized on wood-husk showed the ability to detoxify Cr(VI) to Cr(III). Wood-husk, a natural cellulose-based support material, packed in an upward-flow column was used as support material for bacterial attachment. Around 97% of the Cr(VI) in wastewater containing 15 mg L(-1) of Cr(VI) was reduced at a flow rate of 8.0 mL min(-1). The wastewater containing Cr(VI) was added with liquid pineapple wastewater as nutrient source for the bacteria. Electron microscopic examinations of the wood-husk after 42 days of column operation showed gradual colonization of the wood-husk by bacterial biofilm. The use of 0.1% (v/v) formaldehyde as a disinfecting agent inhibited growth of bacteria present in the final wastewater discharge. This finding is important in view of the ethical code regarding possible introduction of exogenous bacterial species into the environment.     

Facile synthesis of Ti3C2 MXene-modified Bi2.15WO6 nanosheets with enhanced reactivity for photocatalytic reduction of Cr(VI)

Through a facile hydrothermal method, we have successfully prepared Ti₃C₂/Bi_2.15WO₆ (TC/BWO) composite, and systematically investigated their reactivity for the photocatalytic reduction of Cr(VI) under visible light. X-ray diffraction and Raman analysis confirm the formation of heterostructure between Bi_2.15WO₆ and Ti₃C₂. The resultant 7TC/BWO composite exhibits enhanced photoactivity toward Cr(VI) reduction. After 120 min irradiation, the conversion of Cr(VI) reaches 92.5% with the quasi-first-order kinetic constant of k = 0.0145 min^?1, which is higher than that of pure BWO (30% and k = 0.0005 min^?1). The electrochemical and photoluminescent characterization confirm that the introduction of Ti₃C₂ is conducive to the separation of carriers, thus significantly improves the photocatalytic performance of TC/BWO. Furthermore, the radical capture experiments verify that the electrons are important for enhancing reduction of Cr(VI) to Cr(III). As a result, this research provides a comprehensive understanding of the reduction of Cr(VI) by TC/BWO composite under visible light.     

Synthesis of carbon nanotube-TiO(2) nanotubular material for reversible hydrogen storage

A material consisting of multi-walled carbon nanotubes (MWCNTs) and larger titania (TiO(2)) nanotube arrays has been produced and found to be efficient for reversible hydrogen (H(2)) storage. The TiO(2) nanotube arrays (diameter ～60?nm and length ～2-3?μm) are grown on a Ti substrate, and?MWCNTs a few μm in length and ～30-60?nm in diameter are grown inside these TiO(2) nanotubes using chemical vapor deposition with cobalt as a catalyst. The resulting material has been used in H(2) storage experiments based on a volumetric method using the pressure, composition, and temperature relationship of the storage media. This material can store up to 2.5?wt% of H(2) at 77?K under 25?bar with more than 90% reversibility.