光催化法处理含Cr（Ⅳ）废水的研究

采用P 25 TiO2作为光催化剂,研究了废水的pH值、Cr（Ⅳ）的初始浓度、气氛及有机物等因素对含铬废水中Cr（Ⅳ）去解率的影响。结果表明,在pH值为3.0时,光催化反应速率最大;反应气氛对该体系中Cr（Ⅳ）的光催化还原无明显影响;苯酚、葡萄糖等有机物的存在能有效地促进Cr（Ⅳ）的光催化还原,当加入与Cr（Ⅳ）等物质的量的苯酚或葡萄糖时,150 mL反应液[Cr（Ⅳ）浓度为0.96 mmol/L],0.15 g光催化剂,经12 W紫外灯照射反应120 m in,Cr（Ⅳ）完全被去除,相对于在反应体系中不加有机物时,Cr（Ⅳ）光催化还原效率提高了近100%;Cr（Ⅳ）的光催化还原符合L-H动力学规律。     

Cr(VI)-乙酸复合体系中硫酸盐掺杂的含钛高炉渣光催化还原Cr(VI)

采用煅烧的硫酸盐掺杂的含钛高炉渣作光催化剂,研究了Cr(VI)-乙酸(AA)复合体系中Cr(VI)的光催化还原效率,考察了初始pH值、Cr(VI)初始浓度、AA/Cr(VI)体积比、协同效率因子、光催化剂使用寿命等因素的影响. 结果表明,增大AA/Cr(VI)比到0.2%,Cr(VI)的还原效率先增大到27.55%随后逐渐降低. 酸性条件下,Cr(VI)单一体系和Cr(VI)-AA复合体系中Cr(VI)的还原率和吸附率都明显提高;相同反应时间下(110 min),初始pH 1.5时,2种体系中Cr(VI)的还原效率分别为76.32%(单一体系)和100%(复合体系). 复合体系中协同效率因子始终大于0. 循环使用5次后催化剂对Cr(VI)的光催化还原率为92.2%. Cr(VI)在Cr(VI)-AA体系中的光催化还原遵循Langmuir-Hinshelwood动力学规律.     

铂修饰TiO_2柱撑膨润土光催化还原含Cr(Ⅵ)废水的研究

采用光沉积法制备了铂修饰TiO2柱撑膨润土光催化剂,并将其应用于含Cr(Ⅵ)废水降解还原的光催化反应。研究了废水的pH值、Cr(Ⅵ)的初始浓度、有机物等因素对含铬废水中Cr(Ⅵ)的去除率的影响。结果表明,Pt-TiO2-bentonite用量为6 g/L,废水初始pH为3.0,初始浓度为0.48 mmol/L的Cr(Ⅵ)离子,经12 W紫外灯照射反应75 min,即能达到国家排放标准,Cr(Ⅵ)的光催化还原符合L-H动力学规律,并且该复合光催化剂具有良好的沉降性能和较好的重复使用性能。     

Cr（VI）-乙酸复合体系中硫酸盐掺杂的含钛高炉渣光催化还原Gr（VI）

采用煅烧的硫酸盐掺杂的含钛高炉渣作光催化剂,研究了Cr（VI）-乙酸（AA）复合体系中Cr（VI）的光催化还原效率,考察了初始pH值、Cr（VI）初始浓度、AA／Cr（VI）体积比、协同效率因子、光催化剂使用寿命等因素的影响。结果表明,增大AA／Cr（Vi）比到0.2％,Cr（VI）的还原效率先增大到27.55％随后逐渐降低。酸性条件下,Cr（VI）单一体系和Cr（VI）-AA复合体系中Cr（VI）的还原率和吸附率都明显提高;相同反应时间下（110m／n）,初始pH1.5时,2种体系中Cr（VI）的还原效率分别为76.32％（单一体系）和100％（复合体系）。复合体系中协同效率因子始终大于0。循环使用5次后催化剂对Cr（VI）的光催化还原率为92.2％。Cr（VI）在Cr（VI）-AA体系中的光催化还原遵循Langmuir-Hinshelwood动力学规律。     

ZnO/C复合光催化剂处理含Cr(VI)废水的试验研究

采用葡萄糖（glucose）还原水热法制备了ZnO/C复合光催化剂,并对其光催化还原含Cr(VI)废水的过程进行了研究。ZnO复合样品具有更窄的禁带宽度和更多的氧空位,从而进一步增加了可见光的利用效率和光吸收反应活性。ZnO/C光催化还原含铬废水的最佳条件为：ZnO/glucose摩尔比15/1,废水pH值4.0和催化剂用量0.2g/L。在上述工艺下,300W氙灯光照反应3h后,废水中的Cr(VI)还原率在80%以上。在此基础上,同样对还原过程中废水的电化学反应特性进行了研究。     

Mxene/g-C3N4二维光催化材料的制备及其处理水中Cr(VI)的性能研究

在合成单层Mxene和石墨相C₃N₄的基础上，采用一步静电自组装法制备了不同Mxene含量的Mxene/g-C₃N₄复合光催化剂，采用XRD、TEM、XPS等方法对样品的结构和形貌进行了表征。考察了可见光激发下Mxene/g-C₃N₄复合光催化剂光催化还原六价铬Cr(VI)的性能，分析了Mxene的负载量、溶液的pH值和不同的空穴牺牲剂对Mxene/g-C₃N₄光催化还原Cr(VI)性能的影响。结果表明，Mxene的负载不仅可以为光催化反应提供更多的表面活性位，还可以显著提高光生载流子的分离几率。当Mxene的负载量为10%、溶液pH值为2.0时，可见光还原Cr(VI)的效率比单一石墨相C3N4光催化剂提高了8.1倍。同时，酒石酸空穴牺牲剂的引入可以进一步提高光催化还原Cr(VI)效率。     

新型g-C3N4/CuS复合材料的制备及光催化研究

一步水热法合成CuS修饰的石墨相氮化碳(g-C3N4/CuS)复合光催化剂,通过FE-SEM、XRD、FTIR、UV-Vis-DRS等手段对其进行了表征,利用Cr(VI)溶液考察了g-C3N4/CuS在可见光下的光催化还原性能.实验结果表明,g-C3N4/CuS复合光催化剂的光催化活性明显优于单一的g-C3N4和CuS.可见光照射下,180 min内Cr(VI)的去除率可达70％以上.CuS的引入不仅扩宽了g-C3N4的可见光吸收范围,而且降低了g-C3N4光生电子和空穴的复合率,从而显著提高g-C3N4的光催化活性.该复合材料的催化活性受溶液的pH值影响较大,酸性条件下更有利于光催化反应的进行;共存低浓度腐殖酸对Cr(VI)的去除没有显著影响.g-C3N4/CuS具有良好的可见光催化活性,可用于废水中Cr(VI)的光催化还原去除.     

Cr(Ⅵ)-乙酸复合体系中硫酸盐掺杂的含钛高炉渣光催化还原Cr(Ⅵ)

采用煅烧的硫酸盐掺杂的含钛高炉渣作光催化剂,研究了Cr(Ⅵ)-乙酸(AA)复合体系中Cr(Ⅵ)的光催化还原效率,考察了初始pH值、cr(Ⅵ)初始浓度、AA/Cr(Ⅵ)体积比、协同效率因子、光催化剂使用寿命等因素的影响.结果表明,增大AA/Cr(Ⅵ)比到0.2%,Cr(Ⅵ)的还原效率先增大到27.55%随后逐渐降低.酸性条件下,Cr(Ⅵ)单一体系和Cr(Ⅵ)-AA复合体系中Cr(Ⅵ)的还原率和吸附率都明显提高;相同反应时间下(110 min),初始pH 1.5时,2种体系中Cr(Ⅵ)的还原效率分别为76.32%(单一体系)和100%(复合体系).复合体系中协同效率因子始终大于0.循环使用5次后催化剂对Cr(Ⅵ)的光催化还原率为92.2%.Cr(Ⅵ)在Cr(Ⅵ)-AA体系中的光催化还原遵循Langmuir-Hinsheiwood 动力学规律.     

TiO_2光催化还原有机废水中Cr(VI)的研究

二氧化钛具有较高的光稳定性和反应活性,可以用于光催化还原去除水中的重金属离子,本文以含有Cr(Ⅵ)的有机废水为研究体系,分别考察了环糊精、pH值、反应物初始浓度、催化剂用量等对光催化还原反应的影响。     

二氧化钛薄膜光电催化Cr(Ⅵ)的影响因素

以TiO2薄膜为工作电极,铂网作为辅助电极,甘汞电极为参比电极,进行紫外光光电催化还原Cr(VI),探讨了溶液初始pH值、Cr(VI)初始浓度以及柠檬酸浓度对反应性能的影响。结果表明,在酸性条件下,TiO2对Cr6+离子污染具有显著的光电催化还原消除效果;随着Cr(VI)初始浓度的增加,其光电催化还原反应速率降低;柠檬酸作为空穴捕获剂可有效地捕获光生空穴,在一定浓度范围内,Cr(VI)的光电还原反应速率随柠檬酸浓度的增加而增加。在pH为3、0.6 V偏压、0.006 g柠檬酸条件下,初始浓度为10 mg/L的Cr(VI)反应210 min时,其转化率达到82.19%。     

颗粒活性炭载纳米零价铁去除水中的Cr(Ⅵ)

以Fe2+溶液为原料、NaBH4为还原剂,采用传统液相还原技术合成了颗粒活性炭(GAC)载纳米零价铁(nZVI)复合材料GAC-nZVI,用扫描电镜对GAC-nZVI进行表征,通过间歇实验考察了其对去除Cr(VI)的影响。结果表明,GAC能阻止nZVI颗粒聚集,合成的GAC-nZVI能有效去除水中的Cr(VI)。在Cr(VI)初始浓度50 mg/L、温度40℃和pH=2.0、投加GAC-nZVI 3.0 g/L的条件下反应5 min,Cr(VI)去除率为99.4%。pH=2.0?4.0时,处理后水中总铬浓度均低于1 mg/L,表明残留少量Cr(III)。随pH值和Cr(VI)浓度增加,Cr(VI)去除率降低;随反应温度和GAC-nZVI投加量增加,Cr(VI)去除率增加。准一级动力学模型可用于描述Cr(VI)的去除过程。相同条件下,GAC-nZVI去除Cr(VI)的反应速率常数达0.19797 min?1,为原颗粒活性炭反应速率常数0.0023 min?1的86倍。随pH值降低或反应温度和GAC-nZVI投加量增加,反应速率常数增加。     

NiO_x修饰TiO_2纳米管光催化还原Cr(Ⅵ)离子研究

以TiO2纳米粒子(Degussa P25)为原料,经水热处理制得钛酸盐纳米管,通过离子交换将Ni2+插入钛酸盐纳米管,然后通过焙烧及氢气还原处理得到NiOx修饰TiO2纳米管,并考察了该纳米管在紫外光下还原Cr(Ⅵ)的性能。结果表明:经氢气还原处理后,NiOx的修饰能够显著提高TiO2纳米管的光催化还原Cr(Ⅵ)的活性,而未经还原处理的NiO对电子的转移起到了抑制作用。     

Zn~(2+)改性TiO_2对苯酚废水的光催化降解研究

采用溶胶-凝胶-浸渍法对二氧化钛进行Zn2+改性,并以苯酚废水为降解模型反应物,研究了Zn2+改性TiO2的光催化活性。结果表明,Zn2+改性能够提高二氧化钛的光催化活性,当Zn2+掺杂量为2.0%(质量百分比),煅烧温度为600℃,催化活性最好,当催化剂的投加量为3.0 g/L,通气量为600 mL/m in,pH值为3.3时,对苯酚废水溶液紫外灯光催化30 m in的降解率可达到98.2%。     

Photo‐reduction and adsorption in aqueous Cr(VI) solution by titanium dioxide,carbon nanotubes and their composite

BACKGROUND: This study compared the removal of aqueous Cr(VI) by multi‐walled carbon nanotubes (CNTs) modified by sulfuric acid, titanium dioxide (TiO₂) and composite of CNTs and TiO₂. RESULTS: More than 360 h contact time was needed to completely adsorb 3 mg L^?1 of Cr(VI) by CNTs, indicating that the rate of adsorption by CNTs alone was slow. The reaction time approaching equilibrium depended on the Cr(VI) concentration. XPS analysis of CNTs after adsorbing Cr(VI) showed that the Cr(VI) on the surface of CNTs was partially reduced to Cr(III). A 3 mg L^?1 solution of Cr(VI) was fully photocatalyzed by commercial TiO₂ (Degussa P25) in less than 0.5 h under UV irradiation. Unlike P25, reduction by another commercial TiO₂ (Hombikat UV100) took 4 h and more than 2 h were necessary for reduction by the composite. Thus the efficiency of Cr(VI) photo‐reduction by the composite was lower than by TiO₂, but higher than that by CNTs. XPS analysis of TiO₂ and composite showed the existence of both Cr(VI) and Cr(III) on their surfaces. CONCLUSION: In contrast to TiO₂, the reduction rate of aqueous Cr(VI) using CNTs as adsorbent was slow. P25 had a markedly higher photocatalytic efficiency than the composite or UV100 alone. Using P25 to reduce aqueous Cr(VI) has a higher potential for practical application. The diameters of TiO₂ and CNTs and the ratio of TiO₂/CNTs are key problems in the preparation of TiO₂/CNTs composite. Copyright © 2011 Society of Chemical Industry     

Reductive removal of hexavalent chromium from aqueous solution using sepiolite-stabilized zero-valent iron nanoparticles: Process optimization and kinetic studies

We studied the optimization of hexavalent chromium (Cr(VI)) removal from aqueous solution using the synthesized zero-valent iron nanoparticles stabilized with sepiolite clay (S-ZVIN), under various parameters such as reaction time (min), initial solution pH and concentration of S-ZVIN (g·L^?1) using response surface methodology (RSM). The kinetic study of Cr(VI) was conducted using three types of the most commonly used kinetic models including pseudo zero-order, pseudo first-order, and pseudo second-order models. The rate of reduction reaction showed the best fit with the pseudo first-order kinetic model. The process optimization results revealed a high agreement between the experimental and the predicted data (R²=0.945, Adj-R²=0.890). The results of statistical analyses showed that reaction time was the most impressive factor influencing the efficiency of removal process. The optimum conditions for maximum response (98.15%) were achieved at the initial pH of 4.7, S-ZVIN concentration of 1.3 g·L^?1 and the reaction time of 75 min.     

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.     

Chromium (VI) removal from water using starch coated nanoscale zerovalent iron particles supported on activated carbon

Starch coated nanoscale zerovalent iron (S-nZVI) was immobilized in activated carbon (AC) and its Cr (VI) removal characteristics were studied. Macroscopic evidence and mechanism analysis proved that S-nZVI and AC were closely linked and mutual complementary. Different factors including pH of the original solution, reaction time, and mass ratio (S-nZVI@AC/Cr =10:1, 20:1, 30:1, 50:1, 60:1, 70:1) were studied to analyze the removal rate. Results showed that the removal rate of Cr (Ⅵ) could reach 99.96% under the condition of pH of 5, and temperature =25?°C, when the mass ratio of S-nZVI@AC/Cr was 60:1. The removal of Cr(Ⅵ) by S-nZVI@AC followed pseudo-second-order kinetics. X-ray diffraction (XRD) resulted demonstrate that S-nZVI@AC existed in a Fe₃C state before reaction and in a Fe(III) state after reaction. XPS (X-ray photoelectrons spectroscopy) analysis suggested that the mechanism of Cr (VI) removal by S-nZVI@AC is adsorption and reduction. S-nZVI@AC might be a potential composite material for the purification and detoxification of Cr (VI) in water because of its efficiency and stability.     

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.     

Effect of pH on the removal of Cr(III) and Cr(VI) from aqueous solution by modified polyethyleneimine

A novel flocculant with the capacities of reduction and chelation was prepared in this paper. The flocculant, called polyethyleneimine–sodium xanthogenate (PEX), was synthesized by modifying polyethyleneimine with carbon disulfide and sodium hydroxide. The effect of pH on the removal of Cr(III) and Cr(VI) from aqueous solution with PEX was investigated by using flocculation experiments. The results showed that in the single-ion system (only including Cr(III) or Cr(VI) in the solution), the final Cr(III) decreased with the increase in pH from 2.0 to 10.0, while the final Cr(VI) increased at first and then decreased with the increase in this pH range studied. The removal of Cr(III) was not desirable at pH lower than 7.0, whereas the final Cr(VI) concentration reached the minimum value of 0.145 mg/L at pH 2.0. In the mixture system of Cr(III) and Cr(VI), the variation tendency for the removal of Cr(III) or Cr(VI) was very similar to that obtained in the single-ion system. The oxidation–reduction potential, zeta potential, and final pH in the supernatant were also measured to analyze the above results. Furthermore, FTIR spectra revealed that dithiocarboxylic acid groups on the macromolecular chains of PEX played a major role in the Cr(VI) reduction and Cr(III) chelation.