反应气氛对绿色合成纳米铁的组分及其活性的影响

成本低廉和无二次污染的"绿色"合成纳米材料是发展原位纳米环境修复技术的前沿研究课题之一.本文以绿茶提取液为还原剂和稳定剂进行"绿色"合成纳米铁,探讨在不同的气氛下"绿色"合成的纳米铁颗粒的主要成分,以期为调控合成纳米铁系材料提供基础研究.首先,利用扫描电子显微镜(SEM)、X射线能谱(EDS)、X射线光电子能谱分析(XPS)和傅里叶变换红外光谱(FTIR)等表征手段对不同反应气氛下合成的纳米铁颗粒的表面微观形貌、尺寸和价态结构进行分析.结果发现,在通入N2情况下,合成的纳米铁颗粒粒径为(84.7±11.5)nm,其主要成分以纳米零价铁为主;在通入空气情况下,合成的纳米铁粒径为(117.8±26.2)nm,其主要成分是纳米零价铁、氧化铁和四氧化三铁的混合物;通入O2时,合成的纳米铁粒径为(141.2±26.3)nm,其主要成分以四氧化三铁为主.其次,评价在不同气氛条件下合成纳米铁颗粒对去除亚甲基蓝(MB)的反应活性.结果表明,在反应温度313 K下降解初始浓度为50 mg·L-1的MB溶液,反应5 min时已达到平衡,通入N2合成的纳米铁降解MB,去除率高达98.7%,而通入O2合成的纳米铁反应效率低,对MB的去除率仅为65.3%.最后,从以上发现提出不同气氛下可以调控"绿色"合成的铁系纳米材料成分,从而导致不同的纳米修复环境中污染物的能力.     

The sorption of selenite from aqueous solutions by pyrite

Selenium (Se) is an essential trace nutrient for mammals; however, the range between deficit and toxic levels is narrow. In this study, the potential sorption of selenite onto pyrite particles from an aqueous solution was investigated. An intraparticle diffusion model was used to describe kinetic data of sorption, yielding diffusivity values of 5 × 10^?7 cm²/s. The Langmuir isotherm equation could be used to describe the experimental data. The fitting results indicated that b and {Se(IV)}_max have values of 0.37 L/mg and 3.49 mg/g, respectively. The sorption of selenite onto the surface of pyrite particles was dependent on a pH range of 2–12, and the quantity of sorption onto pyrite was negatively correlated with pH; that is, the amount of sorption onto pyrite increased with a decrease in pH. In addition, organic matter did not exert a significant effect on removal of selenite. With a reaction time greater than 1 week, sorption of selenite onto pyrite particles was found to partially reduce the amount of elemental Se.     

Application and mechanism of polysaccharide extracted from Enteromorpha to remove nano-ZnO and humic acid in coagulation process

Green source Ep was extracted from marine alga waste. The molecule model structure of Ep was studied and constructed. PAC-Ep coagulation system improves the efficiency of removal efficiency. Synergistic effects between NPs and HA make a big difference to enhance efficiency. Mechanism is charge neutralization, hydrogen bonding and adsorbing-complexing Enteromorpha polysaccharide (Ep) extracted from alga a novel green coagulant aid for nanoparticles (NPs) and heavy metal ions removal and the structure of EP was intensively studied in this study. The integration of Ep with polyaluminum chloride (PAC-Ep) coagulants exhibited higher coagulation performance than that of the polyaluminum chloride (PAC) because of the negatively charged NPs suspension and humic aid (HA) solution. Significant high removal efficiencies of dissolved organic matter (94.1%), turbidity (99.3%) and Zn ions (69.3%) were achieved by the PAC-Ep coagulants. The dual-coagulation properties of PAC-Ep for different pollutants was based on multiple mechanisms, including (i) Al³⁺ charge neutralization; (ii) hydroxy aluminum hydroxyl bridging formed polynuclearhydroxy complexes bridge and sweep colloidal particles; (iii) adsorption and bridging of Ep chain for the NPs and heavy metal ions. Results indicated that the destabilization of colloid was induced by the coexisting HA and higher removal was achieved as ions adsorption was enhance in the presence of HA complexation. On the basis of that, the extraction of polysaccharide is a promising candidate for its high coagulation performance in water treatment.     

X-ray absorption and photoelectron spectroscopy investigation of selenite reduction by Fe-bearing minerals

The long-lived radionuclide ⁷⁹Se is one of the elements of concern for the safe storage of high-level nuclear waste, since clay minerals in engineered barriers and natural aquifer sediments strongly adsorb cationic species, but to lesser extent anions like selenate (Se^VIO₄²⁻) and selenite (Se^IVO₃²⁻). Previous investigations have demonstrated, however, that Se^IV and Se^VI are reduced by surface-associated Fe^II, thereby forming insoluble Se⁰ and Fe selenides. Here we show that the mixed Fe^II/^III (hydr)oxides green rust and magnetite, and the Fe^II sulfide mackinawite reduce selenite rapidly (< 1 day) to FeSe, while the slightly slower reduction by the Fe^II carbonate siderite produces elemental Se. In the case of mackinawite, both S^−II and Fe^II surface atoms are oxidized at a ratio of one to four by producing a defective mackinawite surface. Comparison of these spectroscopic results with thermodynamic equilibrium modeling provides evidence that the nature of reduction end product in these Fe^II systems is controlled by the concentration of HSe⁻; Se⁰ forms only at lower HSe⁻ concentrations related to slower HSeO₃⁻ reduction kinetics. Even under thermodynamically unstable conditions, the initially formed Se solid phases may remain stable for longer periods since their low solubility prevents the dissolution required for a phase transformation into more stable solids. The reduction by Fe²⁺-montmorillonite is generally much slower and restricted to a pH range, where selenite is adsorbed (pH < 7), stressing the importance of a heterogeneous, surface-enhanced electron transfer reaction. Although the solids precipitated by the redox reaction are nanocrystalline, their solubility remains below 6.3 × 10^− 8 M. No evidence for aqueous metal selenide colloids nor for Se sorption to colloidal phases was found. Since Fe^II phases like the ones investigated here should be ubiquitous in the near field of nuclear waste disposals as well as in the surrounding aquifers, mobility of the fission product ⁷⁹Se may be much lower than previously assumed.     

相转移催化合成新型含硫氧螯合树脂

1　IntroductionAseveryoneknown ,chelatingresincontainingheteroatomsuchassulfur,nitrogen ,andoxygenpossessexcellentadsorptionandselectivitypropertiesformetalions,especiallyfornoblemetallicions.Therefore ,manyeffortshavebeendonetopreparetheabove mentionedre…     

铁催化聚丙烯腈脱氮的研究

应用热天平研究了载铁聚丙烯腈的脱氮碳化行为，负载铁对ＰＡＮ的稳定化和脱氮碳化均具有显著的催化作用，并在５８０－７６０℃范围内明显增加了Ｎ２形成速率。ＸＰＳ和ＸＲＤ对碳化过程中铁和氮化学形态变化的研究结果表明，铁催化反应机理可能是负载铁与吡啶氮作用形成中间体铁氮化物，后者进而分解释放出Ｎ２。     

二种高硫煤中硫氮化学形态的研究

利用ＸＰＳ技术研究了贵定煤和西班牙Ｍｅｑｕｉｅｎｚａ煤中硫和氮化学形态的分布，并结合硫Ｋ－边ＸＡＮＥＳ和Ｍｏｓｓｂａｕｅｒ谱着重考察贵定煤中硫化学形态。结果表明，贵定煤中含硫化合物主要以噻吩形态存在，其次为有机硫化物；而Ｍｅｑｕｉｅｎｚａ煤中以有机硫化物含量最大，噻吩硫次之，有关含氮化合物，Ｍｅｑｕｉｅｎｚａ煤以吡咯和吡啶氮为主，但在贵定煤中观察到较大浓度的氧化氮化合物。     

无机阳离子对TiO2光催化降解染料的影响

考察了6种无机阳离子对P-25 TiO2光催化降解染料的影响，结果发现，Cu^2 ，Mn^2 和Ni^2 对光催化反应有强烈的抑制作用，Ca^2 ，Mg^2 和Al^3 对光催化反应速率无明显的负影响．经X光电能谱(XPS)的分析，确定锰离子以氧化物的形式沉积在氧化钛表面，使催化剂不可逆的中毒．Cu^2 和Ni^2 通过俘获光致电子导致催化活性降低。     

Adsorption of picloram on clays nontronite,illite and kaolinite: equilibrium and herbicide-clays surface complexes

The picloram (PCM) adsorption on nontronite, illite and kaolinite was studied at pH 3, 5 and 7. The adsorption isotherms had well-fitted to Langmuir and Freundlich models equations. The interactions of PCM with the clay mineral surfaces exhibited an anionic profile adsorption, with a decrease in adsorption when the pH increases. The PCM adsorption capacity increases in the following order: kaolinite?<?illite?<?nontronite. The X-ray diffraction (XRD) analysis of PCM-clay samples revealed that the picloram molecule does not enter into the clays basal space. The interaction of PCM with clays surface sites through nitrogen of the pyridine ring was confirmed by X-ray photoelectron spectroscopy (XPS). Due to the anionic form of PCM, the adsorption onto the external and edges surface sites of the clay minerals was proposed.     

Phosphine functionalised multiwalled carbon nanotubes: A new adsorbent for the removal of nickel from aqueous solution

Synthesised triphenylphosphine-linked multiwalled carbon nanotubes (Tpp-MWCNTs) were used to study the adsorption of nickel in aqueous solutions and their adsorption capabilities were compared with purified MWCNTs. The adsorption capacity increased with an increase in pH for all adsorbents. The adsorption equilibrium was reached in 40 and 30 min for purified MWCNTs and Tpp-MWCNTs, respectively. Both Freundlich and Langmuir isotherms used to investigate the adsorption process fitted the experimental data well with the correlation coefficient R² close to 1 for all adsorbents. On the other hand, the experimental data fitted well with a pseudo second-order model. The speciation of nickel also influenced the adsorption on the purified and Tpp-MWCNTs. The adsorbents used in this study showed superior adsorption capacity when compared to other adsorbents reported in the literature.