Ⅱ-Ⅵ族镉化物材料的MBE生长及器件应用进展

Ⅱ-Ⅵ族镉(Cd)化物,如CdTe、CdSe、CdSeTe等具有直接带隙、光学吸收系数高和电学特性优异等突出特点,在太阳电池、X及γ射线探测器、红外焦平面阵列(FPA)等方面均得到了广泛应用。文章简要综述了近年来用分子束外延(MBE)工艺生长镉化物微结构材料的研究进展和器件应用动态,并对镉化物在光电子领域中的发展前景进行了展望。

Bioaccumulation,subcellular distribution and chemical forms of cadmium in Aster subulatus Michx.

【Objective】Through analyzing the bioaccumulation capacity,subcellular distribution and chemical forms of cadmium(Cd)in Aster subulatus Michx.,this study was to provide reference for revealing the Cd tolerance mechanism of A.subulatus Michx.【Method】After cultured for 24 d under the action of Hoagland nutrient solution and gradient Cd concentrations(0,30,60 and 90 mg/L),A.subulatus Michx.were harvested,and its leaf,stem and root were treated by differential centrifugation,chemical reagent extraction,and digested with graphite digester,respectively,then the Cd content in the root,stem and leaf were determined by atomic absorption spectroscopy.【Result】The experimental results indicated that the bioaccumulation capacity of Cd in A.subulatus Michx.was root>stem>leaf,and the maximum Cd concentration in the root,stem and leaf of A.subulatus Michx.were 130.74,78.69 and 56.62 mg/kg(fresh matter),respectively.Most of Cd stored in the cell wall and the soluble fractions of the root and leaf of A.subulatus Michx.,with only a smaller portion Cd in organelle fraction.Analysis result of subcellular Cd content showed that 52.27%-58.61%of Cd for root was mainly stored in the soluble fraction,but 42.10%-63.28%of Cd for leaf was mainly stored in the cell wall fraction.The concentration of pectates and protein integrated-Cd was higher in the root and leaf compared to other chemical forms Cd.Pectates and protein integrated-Cd was the main chemical forms Cd in the root and leaf of A.subulatus Michx.,and their percentages were 68.91%-74.80%and 57.38%-83.80%,respectively.Cd treatment could significantly increase the proportion of water-soluble organic acid Cd from 13.64%to 22.72%in root and undissolved phosphate Cd from 10.02%to 32.78%in leaf with increasing Cd concentration in the culture medium.【Conclusion】The root,stem and leaf of A.subulatus Michx.has strong bioaccumulation capacity to Cd,Cd is primarily stored in the soluble fractions of the root and cell wall fractions of the leaf,and less toxic pectates and protein integrated-Cd is the main chemical forms Cd in the root and leaf of A.subulatus Michx.,this might be the main mechanism of Cd tolerance in A.subulatus Michx.

Mechanism of exogenous selenium alleviates cadmium induced toxicity in Bechmeria nivea(L.) Gaud(Ramie)

The protective role of exogenously supplied selenium （Se^6＋） on Bechmeria nivea （L.） Gaud （Ramie） subjected to cadmium （Cd） stress was studied in vitro, and the mechanism was discussed by investigating plant growth, malondialdehyde （MDA）, activity of antioxidative enzymes and DNA methylation pattern. Plants grown in hydroponic culture were supplied with spraying Se （selenate, 1.2μmol/L） and cadmium （Cd（NO3）2, 0, 3, 6 and 9 mg/L）, individually or simultaneously. At low Se spraying levels, SOD activity was increased by 35.34%, 43.18%, 3.63%under 3, 6 or 9 mg/L cadmium contents, POD was increased by 12.45%, 14.14%, 3.27%, and the level of DNA methylation was decreased by 10.70%, 18.18%and 15.59%, respectively. The results confirmed that spraying low Se on ramie leaves could enhance the activity of SOD and POD, and regulate DNA methylation in ramie leaves.

Effects of Sulfur Compounds on Cd Partitioning in a Simulated Municipal Solid Waste Incinerator

The effect of sulfur compounds （including sulfur, sulfide, sulfite and sulfate）, initial concentration of heavy metal and operating conditions on Cd emission in municipal solid waste （MSW） incineration were investi-gated using a simulated tubular furnace and simulated MSW spiked with Cd. The concentration of Cd was meas-ured by inductively coupled plasma-atomic emission spectrometry （ICP-AES） after digesting the samples including bottom ash, fly ash and flue gas according to related USEPA methods. The results show that S and Na2S tend to in- crease Cd partitioning in bottom ash, whereas Na2SO3 and Na2SO4 tend to reduce Cd partitioning in bottom ash. The effect of sulfur compounds on Cd partitioning in bottom ash was in the sequence of Na2S〉S〉Na2SO3〉 Na2SO4. chemical equilibrium analysis is also performed to determine the effect of sorbents on Cd adsorption. The calculations show that S presents strong affinity for Cd and restrains Cd adsorption by SiO2, whereas when temperature rises to between 830℃ and 1030℃, Cd adsorption efficiency of SiO2 is over 80% and the efficiency of Al2O3 is up to 85%.

Synergy of adsorption and visible light photocatalysis to decolor methyl orange by activated carbon/nanosized CdS/chitosan composite

Activated carbon/nanosized CdS/chitosan(AC/n-CdS/CS) composites as adsorbent and photoactive catalyst were prepared under low temperature(≤60 ℃) and ambient pressure.Methyl orange(MO) was chosen as a model pollutant to evaluate synergistic effect of adsorption and photocatalytic decolorization by this innovative photocatalyst under visible light irradiation.Effects of various parameters such as catalyst amount,initial MO concentration,solution pH and reuse of catalyst on the decolorization of MO were investigated to optimize operational conditions.The decolorization of MO catalyzed by AC/n-CdS/CS fits the Langmuir-Hinshelwood kinetics model,and a surface reaction,where the dyes are absorbed,is the controlling step of the process.Decolorization efficiency of MO is improved with the increase in catalyst amount within a certain range.The photodecolorization of MO is more efficient in acidic media than alkaline media.The decolorization efficiency of MO is still higher than 84% after five cycles and 60 min under visible light irradiation,which confirms the reusability of AC/n-CdS/CS composite catalyst.

ZnxCd1–xS quantum dot with enhanced photocatalytic H2-production performance

H2 is an important energy carrier for replacing fossil fuel in the future due to its high energy density and environmental friendliness.As a sustainable H2-generation method,photocatalytic H2 production by water splitting has attracted much interest.Here,oil-soluble ZnxCd1-xS quantum dot(ZCS QD)with a uniform particle size distribution were prepared by a hot-injection method.However,no photocatalytic H2-production activity was observed for the oil-soluble ZCS QD due to its hydrophobicity.Thus,the oil-soluble ZCS QD was converted into a water-soluble ZCS QD by a ligand-exchange method.The water-soluble ZCS QD exhibited excellent photocatalytic H2-production performance in the presence of glycerin and Ni^2+,with an apparent quantum efficiency of 15.9%under irradiation of 420 nm light.Further,the photocatalytic H2-generation activity of the ZCS QD was~10.7 times higher than that of the ZnxCd1-xS relative samples prepared by the conventional co-precipitation method.This work will inspire the design and fabrication of other semiconductor QD photocatalysts because QD exhibits excellent separation efficiency for photogenerated electron-hole pairs due to its small crystallite size.

Uptake, Subcellular Distribution, and Chemical Forms of Cadmium in Wild-Type and Mutant Rice

Wild-type （Zhonghua 11） and mutant rice （Oryza sativa L.） plants were used to investigate the effect of cadmium （Cd） application on biomass production, to characterize the influx of Cd from roots to shoots, and to determine the form, content, and subcellular distribution of Cd in the roots, leaf sheaths, and leaves of the rice plants. Seedlings were cultivated in a nutrient solution and were treated with 0.5 mmol L^-1 of Cd^2＋ for 14 d. The sensitivity of rice plants to Cd toxicity was tested by studying the changes in biomass production and by observing the onset of toxicity symptoms in the plants. Both the wild-type and mutant rice plants developed symptoms of Cd stress. In addition, Cd application significantly （P ≤ 0.01） decreased dry matter production of roots, leaf sheaths, and leaves of both types, especially the mutant. The Cd content in roots of the mutant was significantly （P ≤0.05） higher than that of the wild-type rice. However, there was no significant difference in the Cd content of roots, leaf sheaths, and leaves between the wild-type and mutant rice. Most of the Cd was bound to the cell wall of the roots, leaf sheaths, and leaves, and the mutant had greater Cd content in cell organelles than the wild type. The uneven subcellular distribution could be responsible for the Cd sensitivity of the mutant rice. Furthermore, different chemical forms of Cd were found to occur in the roots, leaf sheaths, and leaves of both types of rice plants. Ethanol-, water-, and NaCl-extractable Cd had greater toxicity than the other forms of Cd and induced stunted growth and chlorosis in the plants. The high Cd content of the toxic forms of Cd in the cell organelles could seriously damage the cells and the metabolic processes in mutant rice plants.

Chemical Behavior of Cadmium in Purple Soil as Affected by Surfactants and EDTA

A soil batch experiment was conducted to investigate both separate and compound effects of three types of surfactants: anionic dodecylbenzene sulfonic acid sodiumsalt (DBSS), cationic cetyltrimethylammonium bromide (CTAB), and non-ionic nonyl phenol polyethyleneoxy ether (TX-100), as well as ethylenediaminetetraacetic acid (EDTA) on cadmium solubility, sorption kinetics, and sorption-desorption behavior in purple soil. The results indicated that both individual application of the three types of surfactants and surfactants combined with EDTA could stimulate Cd extraction from the soil with a general effectiveness ranking of EDTA/TX-100 > EDTA/DBSS > EDTA/CTAB > EDTA > TX-100 > DBSS > CTAB. Further study showed that the compound application of surfactants and EDTA had stronger (P < 0.05) effects on Cd solubility than those added individually. The application of surfactants and EDTA to purple soil (P < 0.05) decreased the proportion of Cd sorbed, while their effectiveness ranking was similar to that of enhanced solubilization. The sorption kinetics of Cd in purple soil was best described by the double-constant equation, while the Freundlich equation gave an excellent fit to the sorption isotherm curves. Therefore, surfactant-enhanced remediation of Cd contaminated soil is feasible and further research should be conducted.

Removal of cadmium from aqueous solution by immobilized Microcystis aeruginosa:Isotherms,kinetics and thermodynamics

The Microcystis aeruginosa(MA) was immobilized on sodium alginate and used as biosorbent for removal of Cd(Ⅱ) ions from aqueous solution.The biosorption process is pH dependent,and the optimum biosorption was observed at pH 6.0 with the biosorption capacity of 98.38 mg/g.Among Langmuir,Freundlich and Temkin isotherm models,the Freundlich and the Temkin isotherm fit well with the experimental data.Cd(Ⅱ) ions biosorption follows the pseudo-second-order kinetic model.The rate controlling mechanism study reveals that film diffusion is the rate-limiting step and intraparticle diffusion is also involved in biosorption.Thermodynamic parameters,such as Gibbs free energy(ΔG°),the enthalpy(ΔH°) and entropy(ΔS°) were calculated,and revealed that the biosorption process is spontaneous,exothermic and random.Furthermore,the immobilized MA can be regenerated using 0.1 mol/L HCl solutions.

Comparative analysis on homogeneity of Pb and Cd in epoxy molding compounds

Reference materials for quantitative determination of regulated heavy metals, such as Pb and Cd in electronic components, were designed and investigated in terms of stability and homogeneity. Reference materials with two concentration levels of heavy metals were prepared by spiking Pb and Cd compounds to epoxy molding compounds made by mixing silica powders and epoxy resin. The concentration changes of the reference materials during stability test for 1 a were not observed. In the homogeneity assessment, the as-prepared reference materials were studied by using three different analytical tools, inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray fluoroescence spectrometry (XRF) and laser ablation ICP mass. The results show different homogeneities by the characteristics of analytical tools and the materials.

Electronic Structure of the Nanodiatomic Compounds CdS

The potential energy curves of the molecule CdS have been calculated for 245 internuclear distances in the range 2.15 A 〈 r ≤6.471 A for 17 states in the representation 2S＋lA（±）via CASSCF method. Multireference CI calculations （single and double excitations with Davidson corrections） were performed by using Gaussian basis sets for the two considered atoms. The potential energy curves, the harmonic frequency ωe, the internuclear distance re, the rotational constant Be, the electronic energy with respect to the ground state Te and the static dipole moment have been calculated. The comparison of these values to the available data in the literature shows a good agreement. To the best of our knowledge, eleven electronic states have been investigated here for the first time.

The influence of cadmium on the antioxidant enzyme activities in polychaete Perinereis aibuhitensis Grube(Annelida:Polychaeta)

The infaunal polychaete Perinereis aibuhitensis Grube,distributed widely along Asian coasts and estuaries,is considered a useful animal model in ecotoxicological tests and a promising candidate in biomonitoring programs.This paper deals with the activities of antioxidant enzymes including superoxide dismutase(SOD),catalase(CAT),and glutathione peroxidases(GSH-Px) in infaunal polychaete P.aibuhitensis exposed to a series of sublethal water-bound cadmium(Cd) concentrations(0,0.34,1.72,3.44,6.89,and 17.22 mg L-1) under a short-term exposure(1-8 d).The results indicate that the SOD and GSH-Px activities in P.aibuhitensis are stimulated first and then renewed to the original level.The CAT activity of worms decreases at an earlier exposure time but increases to the control values at a later exposure time.Our study suggests that Cd can interfere with the antioxidant defense system of P.aibuhitensis.However,the changes in antioxidant enzyme activities for this species do not show the best promise as biomarkers in Cd biomonitoring of estuarine and coastal zones because weak or non-dose-effect relationships between the antioxidant enzymes activities and Cd levels are found.

Effects of Cd on reductive transformation of lepidocrocite by Shewanella oneidensis MR-1

We investigated the reduction of lepidocrocite(γ-FeOOH) by Shewanella oneidensis MR-1 in the presence and absence of Cd. The results showed that Cd^(2+) retarded microbial reduction of γ-Fe OOH and avoided formation of magnetite. The inhibitory effect on γ-Fe OOH transformation may not result from Cd^(2+) toxicity to the bacterium; it rather was probably due to competitive adsorption between Cd^(2+) and Fe^(2+) on γ-Fe OOH as its surface reduction catalyzed by adsorbed Fe^(2+) was eliminated by adsorption of Cd^(2+).

Chemisorption and Physical Adsorption Roles in Cadmium Biosorption by Chlamydomonas Reinhardtii

The aim of this study was to investigate the mechanism of cadmium (Cd) adsorbed by microalgae Chlamydomonas reinhardtii (C.reinhardtii). The kinetic and adsorption isotherm of the process could be well described by mathematical models. Chemical modification experiments and Fourier transform infrared spectra indicated that carboxyl and amine groups were the important functional groups for adsorption of Cd. The maximum contribution of physical adsorption in the overall adsorption process was evaluated as 5.5%. These results indicated that chemisorption was the dominating mechanism of Cd biosorption by C.reinhardtii.

GST(phi) gene from Macrophyte Lemna minor is involved in cadmium exposure responses

Reactive oxygen species （ROS） scavengers, including ascorbate peroxidase, superoxide dismutase, catalase and peroxidase, are the most commonly used biomarkers in assessing an organisms＇ response to many biotic and abiotic stresses. In this study, we cloned an 866 bp GST（phi） gene in Lemna minor and investigated its characteristics, expression and enzymatic activities under 75 lamol/L cadmium concentrations in comparison with other ROS scavengers. GST（phi） gene expression patterns were similar to those of other scavengers of ROS. This suggests that GST（phi） might be involved in responding to heavy metal （cadmium） stress and that its expression level could be used as a bio-indicator in monitoring cadmium pollution.

Physiological Response of Hydrilla verticillata （I.f.） Royle Exposed to Cadmium Stress

Hydrilla verticillata （I.f.） Royle twigs were exposed to CdCI2 （50, 100, 200 and 500 BM） under continuous light for 48 hrs and the physiological parameters like photosynthetic pigment （chlorophylls a, b and carotenoids） contents, activities of antioxidative enzymes like superoxide dismutase （SOD）, catalase （CAT） and peroxidase （POX） along with lipid peroxidation level were determined. With respect to increase in Cd concentration in the medium and exposure duration, decrease in pigment contents, and decrease in the activities of SOD, CAT and POX were found. The increased levels of lipid peroxidation indicated the prevalence of oxidative stress situation in the tissues which might be one of the reasons behind Cd induced toxicity in Hydrilla verticillata. Since there was significant decrease in the activities of key antioxidative ezymes, the study suggests that Hydrilla verticillata may not be effective for phytoremediation of cadmium in these concentration ranges.

Immobilization of Lead and Cadmium in Contaminated Soil Using Amendments: A Review

Since the inception of industrial revolution, metal refining plants using pyrometallurgical processes have generated the prodigious emissions of lead(Pb) and cadmium(Cd). As the core target of such pollutants, a large number of soils are nowadays contaminated over widespread areas, posing a great threat to public health worldwide. Unlike organic pollutants, Pb and Cd do not undergo chemical or microbial breakdown and stay likely in site for longer duration after their release. Immobilization is an in-situ remediation technique that uses cost-effective soil amendments to reduce Pb and Cd availability in the contaminated soils. The Pb and Cd contamination in the soil environment is reviewed with focus on source enrichment, speciation and associated health risks, and immobilization options using various soil amendments. Commonly applied and emerging cost-effective soil amendments for Pb and Cd immobilization include phosphate compounds, liming, animal manure, biosolids, metal oxides, and biochar. These immobilizing agents could reduce the transfer of metal pollutants or residues to food web(plant uptake and leaching to subsurface water) and their long-term sustainability in heavy metal fixation needs further assessment.

Research on structural characteristics of large-scale CdS thin films deposited by CBD under low ammonia condition

Cadmium sulfide(Cd S) buffer layers with the scale of 10 cm×10 cm are deposited by chemical bath deposition(CBD) with different temperatures and thiourea concentrations under low ammonia condition.There are obvious hexagonal phases and cubic phases in Cd S thin films under the conditions of low temperature and high thiourea concentration.The main reason is that the heterogeneous reaction is dominant for homogeneous reaction.At low temperature,Cd S thin films with good uniformity and high transmittance are deposited by adjusting the thiourea concentration,and there is almost no precipitation in reaction solution.In addition,the low temperature is desired in assembly line.The transmittance and the band gap of Cd S thin films are above 80% and about 2.4 e V,respectively.These films are suitable for the buffer layers of large-scale Cu(In,Ga)Se2(CIGS) solar cells.