Combined effects of adsorption and photocatalysis by hybrid TiO2/ZnO-calcium alginate beads for the removal of copper

The use of nanosized titanium dioxide(TiO_2) and zinc oxide(ZnO) in the suspension form during treatment makes the recovering and recycling of photocatalysts difficult.Hence,supported photocatalysts are preferred for practical water treatment applications.This study was conducted to investigate the efficiency of calcium alginate(CaAlg) beads that were immobilized with hybrid photocatalysts,TiO_2/ZnO to form TiO_2/ZnO-CaAlg.These immobilized beads,with three different mass ratios of TiO_2:ZnO(1:1,1:2,and 2:1) were used to remove Cu(Ⅱ) in aqueous solutions in the presence of ultraviolet light.These beads were subjected to three cycles of photocatalytic treatment with different initial Cu(Ⅱ) concentrations(10-80 ppm).EDX spectra have confirmed the inclusion of Ti and Zn on the surface of the CaAlg beads.Meanwhile,the surface morphology of the beads as determined using SEM,has indicated differences of before and after the photocatalytic treatment of Cu(Ⅱ).Among all three,the equivalent mass ratio TiO_2/ZnO-CaAlg beads have shown the best performance in removing Cu(Ⅱ) during all three recycling experiments.Those TiO_2/ZnO-CaAlg beads have also shown consistent removal of Cu,ranging from 7.14-52.0 ppm(first cycle) for initial concentrations of10-80 ppm.In comparison,bare CaAlg was only able to remove 6.9-48 ppm of similar initial Cu concentrations.Thus,the potential use of TiO_2/ZnO-CaAlg beads as environmentally friendly composite material can be further extended for heavy metal removal from contaminated water.     

Ag–AgBr/TiO2/RGO nanocomposite: Synthesis, characterization, photocatalytic activity and aggregation evaluation

Ag–AgBr/TiO_2 supported on reduced graphene oxide(Ag–AgBr/TiO_2/RGO) with different mass ratios of grapheme oxide(GO) to TiO_2 were synthesized via a facile solvothermal-photo reduction method. Compared to the single-, two-and three-component nanocomposites,the four-component nanocomposite, Ag–AgBr/TiO_2/RGO-1 with mass ratio of GO to TiO_2at 1%, exhibited a much higher photocatalytic activity for the degradation of penicillin G(PG)under white light-emitting diode(LED-W) irradiation. The PG degradation efficiency increased with the increase of mass ratio of GO to TiO_2 from 0.2% to 1%, then it decreased with the increase of mass ratio of GO to TiO_2 from 1% to 5%. The zeta potentials of RGO-nanocomposites became more negative with the presence of humic acid(HA) due to the negatively charged HA adsorption, resulting in the shift of points of zero charge to lower values of pH. The aggregations of nanocomposites were more significant due to the bridging effect of HA. Furthermore, the aggregated particle sizes were larger for RGO-nanocomposites compared to other nanoparticles, due to the bindings of the carboxylic and phenolic functional groups in HA with the oxygen-containing functional groups in the RGO-nanocomposites.The microfiltration(MF) membrane was effective for the nanocomposites separation. In the continuous flow through submerged membrane photoreactor(sMPR) system, backwashing operation could efficiently reduce membrane fouling and recover TiO_2, and thus indirectly facilitate the PG removal.     

不同镉浓度及pH条件下纳米沸石对土壤镉形态及大白菜镉吸收的影响

采用室内培养试验研究了不同镉浓度(1、5、10和15 mg·kg-1)及pH条件下(4、5、6、7和8)纳米沸石和普通沸石施用量(0、5、10和20 g·kg-1)对土壤镉形态分布和CEC的影响,并通过盆栽试验研究了纳米沸石和普通沸石施用量对大白菜生长、镉含量及积累量的影响.结果表明,施用纳米沸石和普通沸石均显著降低了土壤可交换态镉(EX-F)含量和FDC(即土壤中镉的某种形态占总镉的质量分数),增加了碳酸盐结合态(CAB-F)、铁锰氧化态(FMO-F)、有机态(OM-F)和残渣态(RES-F)镉含量和FDC.培养结束时,沸石处理使可交换态镉FDC从0 d时的72.0%~88.0%降至2.4%~10.7%,各处理土壤镉主要以可交换态存在.土壤pH与土壤EX-F镉含量存在极显著的负相关关系(P0.01),与FMO-F和OM-F镉含量存在极显著的正相关(P0.01).土壤CEC与土壤EX-F镉含量均存在极显著负相关关系(P0.01).施用沸石使大白菜植株各部位干重较对照增加了14.3%~131.4%,地上部和根镉含量分别降低了1.0%~75.0%和3.8%~53.2%.新晋菜三号各部位镉含量和镉积累量明显高于山东四号品种.与普通沸石相比,纳米沸石显著提高大白菜生物量的同时,也显著降低了大白菜镉含量及镉积累量.     

基于神经网络模型绿色合成纳米氧化锰及其性能研究

近年来,基于对纳米材料生物毒性和合成成本的考虑,纳米材料的绿色合成和应用在环境领域受到了广泛关注,但迄今仍面临纳米材料的绿色合成机制尚未明确及去除效率不理想两个问题.本研究选择As（III）和As（V）作为目标污染物,通过神经网络模型对纳米氧化锰（MONPs）的合成条件进行优化,发现当污染物浓度和材料投加量分别为0.1 mg?L^-1和5 mg?L^-1时,优化后的MONPs对As（III）和As（V）的去除 效率分别从43.9%、80.0%提高到90.2%、92.2%.从SEM的结果中发现优化后的材料粒径更小,根据EDS和FTIR结果,可以证明优化后材料中的Mn元素比例显著增加.另外,XRD和XPS结果则证明优化后材料从原来的Mn（II）变为Mn（IV）,提高了材料的氧化能力.Zeta电位结果表明优化后材料表面的负电荷减少,进而循环伏安法结果证实了材料电子转移能力的提高,均有利于As的去除.最后,优化后MONPs在经过5次重复利用后仍具高的性能,同时对多种重金属具有一定的吸附能力.显然,基于神经网络模型绿色合成氧化锰纳米材料对砷污染修复具有 较强的针对性和实用性.     

铜锰基整体式催化剂对烧结烟气CO净化特性

基于改性铜锰氧化物作为CO催化活性组分,分别制备了催化剂原粉、以泡沫金属、堇青石为载体的两种整体式催化剂,在实验室配气条件下对比了3种样品的CO催化效率及稳定性,优选了堇青石整体式催化剂,并在某钢厂实际烧结烟气条件下测试了其在不同催化剂负载量、空速、温度下的CO催化效率、稳定性以及衰减后样品催化特性;最后批量制备了2m³优选整体式催化剂并开展了6000m³/h烧结烟气CO净化中试实验.结果表明,烟气高浓水蒸气显著抑制CO催化反应,经240h催化后T₉₀最大提升38℃;催化剂负载量越高,T₉₀越低,催化效率衰减时间越短,稳定后的效率越高,但随着空速增加,该优势减小;1440h(2个月)中试实验中,进气温度185~195℃下,CO催化效率大于85%(平均90%),出口CO浓度低于1000×10^-6,出口平均烟温达220℃,具有节能减排双重效益.     

The combined toxicity and mechanism of multi-walled carbon nanotubes and nano copper oxide toward freshwater algae: Tetradesmus obliquus

Nanoparticles(NPs) are widely used for their special physical properties and released into the natural environment. When two types of NPs exist in the same environment, the presence of one type of NP may affect the properties of the other type of NP. This study investigated the toxic effects of multi-walled carbon nanotubes(MWCNTs) and copper oxide nanoparticles(Cu O NPs) on Tetradesmus obliquus. Both NPs had toxic effects on algae, and the toxic effects of MWCNTs were significantly stronger tha...     

Effects of cobalt doping on the reactivity of hausmannite for As(III) oxidation and As(V) adsorption

Hausmannite is a common low valence Mn oxide mineral, with a distorted spinel structure, in surficial sediments. Although natural Mn oxides often contain various impurities of transitional metals (TMs), few studies have addressed the effect and related mechanism of TM doping on the reactivity of hausmannite with metal pollutants. Here, the reactivity of cobalt (Co) doped hausmannite with aqueous As(III) and As(V) was studied. Co doping decreased the point of zero charge of hausmannite and its adsorption capacity for As(V). Despite a reduction of the initial As(III) oxidation rate, Co-doped hausmannite could effectively oxidize As(III) to As(V), followed by the adsorption and fixation of a large amount of As(V) on the mineral surface. Arsenic K-edge EXAFS analysis of the samples after As(V) adsorption and As(III) oxidation revealed that only As(V) was adsorbed on the mineral surface, with an average As-Mn distance of 3.25–3.30 Å, indicating the formation of bidentate binuclear complexes. These results provide new insights into the interaction mechanism between TMs and low valence Mn oxides and their effect on the geochemical behaviors of metal pollutants.     

蛇纹石综合利用的方法及其发展

简述了蛇纹石综合利用的方法，比较了它们的优缺点，提出了进一步发展的设想。     

Cu-Mg-Al催化剂上NOx储存及分解性能研究

采用共沉淀方法制备了Cu-Mg-Al水滑石混合氧化物催化剂,并对该催化剂及其前驱物进行了XRD表征.使用等温吸附、程序升温脱附以及C₃H₆程序升温表面反应分别考察了催化剂上NO_x储存及分解反应性能.结果表明,由于Cu-Mg-Al催化剂中CuO组分发挥了NO氧化作用,促进了进气中NO_x以硝酸盐方式吸附在催化剂上,因此该催化剂具有很好的NO_x储存性能;在富燃条件下,C₃H₆能够显著降低催化剂上硝酸盐的热稳定性,在160～360 ℃温度范围内,这些硝酸盐会迅速分解成气态NO_x,同时随着C₃H₆加入量的提高,C₃H₆也可以将少量气态NO_x进行还原.     

Preparation, characterization, and photocatalytic activities of boron- and cerium-codoped TiO2

Boron- and cerium-codoped TiO2 photocatalysts were synthesized using modified sol-gel reaction process and characterized by X- ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, particle size distribution （PSD）, diffuse reflectance spectra （DRS）, and Brunauer-Emmett-Teller （BET）. The photocatalytic activities were evaluated by monitoring the degradation of dye Acid Red B （ARB）. The results showed that the prepared photocatalysts were mixed oxides mainly consisting of titania, ceria, and boron oxide. The structure of TiO2 could be transformed from amorphous to anatase and then to rutile by increasing calcination temperature; the transformation being accompanied by the growth of particle size without any obvious change in phase structure of CeO2. The XPS of B1.6Ce1.0-TiO2 prepared at 500℃ showed that a few boron atoms were incorporated into titania and ceria lattice, whereas others existed as B2O3. Cerium ions existed in two states, Ce^3＋ and Ce^4＋, and the atomic ratio of Ce^3＋/Ce^4＋ was 1.86. When boron and cerium were doped, the UV-Vis adsorption band wavelength showed an obvious shift toward the visible range （〈526 nm）. As the atomic ratio of Ce/Ti increased to 1.0, the absorbance edge wavelength increased to 481 nm. The absorbance edge wavelength decreased for higher cerium doping levels （Ce/Ti=2.0）. The particles size ranged from 122 to 255 nm with a domain at 168 nm （39.4%）. The degradation of ARB dye indicated that the photocatalytic activities of boron- and cerium-codoped TiO2 were much higher than those of P25 （a standard TiO2 powder）. The activities increased as the boron doping increased, whereas decreased when the Ce/Ti atomic ratio was greater than 0.5. The optimum atomic ratio of B/Ti and Ce/Ti was 1.6 and 0.5, respectively.