黄钾铁矾固溶物的制备及拉曼光谱分析

利用水热法实验制备黄钾铁矾固溶系列样品AFe_3(SO_4)_2(OH)_6,其中A位置可以被K~+、Na~+和H_3O~+占据。此外,还制备近全钾占据的黄钾铁矾作为对比样品。对制备的黄钾铁矾群样品进行了拉曼光谱测试,黄钾铁矾的拉曼光谱分为羟基区(3000~4000cm~(-1))、硫酸根内部模式、点阵振动模三个主要部分,并对有异议的振动模的归属重新做了分析。利用拉曼光谱峰的数目以及频移,离子半径的大小、键长、键角的变化等信息,采用胡克定律分析了黄钾铁矾固溶系列A位置的离子替换作用。A位置离子的替换作用主要影响黄钾铁矾结构中OH基周围的环境,使得与羟基相关的振动模发生变化。     

基于光谱分析的砷黄铁矿生物浸出过程中铁/砷/硫形态转化研究

基于同步辐射装置的As/S的K边及Fe的L边X射线吸收近边结构光谱(XANES)和X射线衍射(SR-XRD),结合扫描电镜(SEM)、傅里叶红外光谱(FTIR)、电感耦合等离子体发射光谱(ICP-AES)及各项浸出参数的测定,系统研究了(中度嗜热菌、嗜热硫化杆菌)浸出砷黄铁矿过程中铁、砷、硫的形态转化。结果表明,在生物作用下,砷黄铁矿的溶解速率明显高于化学浸出体系,伴随矿物溶解释放到溶液中的砷和铁在生物浸出体系中主要为As(Ⅴ)和Fe3+,而在无菌化学浸出体系则主要为As(Ⅲ)和Fe2+;细菌胞外多聚物(EPS)在细菌与硫化矿物的相互作用过程中起着至关重要的作用, FTIR的结果表明,生物浸出体系中吸附在矿物表面的吸附菌的EPS中蛋白质和多糖的含量均高于游离菌EPS;SEM的结果表明,砷黄铁矿表面在生物浸出过程中逐渐被腐蚀,且有浸出产物覆盖,而化学浸出10 d后,矿物表面依旧比较光滑;SR-XRD的结果表明,元素硫(S0)、黄钾铁矾和砷酸铁在生物浸出第4 d生成,并随时间延长逐渐累积,最终成为浸出渣中的主要成分。Fe的L边XANES结果表明,在细菌作用下矿物表面逐渐被Fe(Ⅲ)浸出产物覆盖;As的K边XANES结果表明,浸出渣中砷的价态包括As(-Ⅰ), As(Ⅲ)和As(Ⅴ),拟合结果表明,经过10 d的生物浸出,砷黄铁矿、雌黄(As2S3)和砷酸铁在矿渣中所占的比例分别为18.6%, 23.5%和57.9%,化学浸出10 d后,矿渣中除未溶解的砷黄铁矿外,仅有少量砷酸铁(6.2%)形成;S的K边XANES拟合结果表明,经过10 d的生物浸出,砷黄铁矿、 S0、硫代硫酸盐、施氏矿物和黄钾铁矾在矿渣中所占的比例分别为15.3%, 23.7%, 3.5%, 11.3%和46.2%,而在化学浸出10 d后的矿渣中,仅拟合到少量S0(7.8%)。基于上述结果可以得出,铁、砷、硫在砷黄铁矿生物作用下的形态转化过程分别为:Fe(Ⅱ)-Fe(Ⅲ), As(-Ⅰ)-As(Ⅲ)-As(Ⅴ), S-→S0→S2O■→SO■。结合溶液中的浸出参数发现,随着S0、黄钾铁矾、砷酸铁和雌黄的大量累积,砷黄铁矿的生物浸出严重受阻。硫代硫酸盐的生成表明砷黄铁矿的溶解途径与黄铁矿相似。     

双金属层状配位聚合物{[ML][FeⅡFeⅡ(Ox)3]·H2O}∞的合成和波谱表征

合成和表征了两种新的Schiff碱配合物[ZnL(C104)·4H2O(A)和CdL(C104)·3H20(B)]，其中L=2-{2-(Aminomethyl-amino]-methyl}-phenol.A(或B）、FeSO4·7H2O和K3[Fe(ox)3]·3H2O进一步反应，生成了配位聚合物{[ML][Fe^ⅡFe^Ⅲ（ox)3]·H2O}∞，其中M=Zn^2+(C)或Cd^2+(D)．红外光谱和Mossbauer谱测定结果表明，C和D具有二维层状结构，其阴离子层由[Fe^ⅡFe^Ⅲ（ox)3]-单元构成．     

黄芩素稳定性研究

用紫外光谱研究了光、温度、pH、Na2SO3、FeSO4及抗坏血酸对黄芩素稳定性的影响.在室温条件下,黄芩素溶液的吸光度值在6h内强度有明显的下降;当温度升高或在避光条件下,偏酸性黄芩素溶液的吸光度值在6h内强度不变,而碱性条件下依然有下降趋势;但黄芩素溶液加入抗坏血酸或Na2SO3后,吸光度值可稳定不变.本文研究提示:黄芩素对光和pH稳定性差;抗坏血酸和Na2SO3具有提高黄芩素溶液稳定性的作用.     

Pt—SDB疏水催化剂的抗毒稳定性

用CECE流程处理含氚废水时，催化交换单元中的Pt-SDB疏水催化剂会遇到少量的H2SO4，NaOH，Fe^3＋，Ca^2＋，Na^＋，Cl^＋，SO3^2＋，H2S，SO2和CO，这些物质可能会引起Pt-SDB疏水催化剂的催化活性发生变化，即发生催化剂中毒。为探明Pt-SDB疏水催化剂在这些物质存在下催化活性的变化，将其装入催化活性测试床，在同样的实验条件下测试催化剂在中毒前后及再生后的催化活性，结果见图1～8。     

聚乙二醇800-PVP双水相体系萃取荧光测定阿司匹林肠溶片中水杨酸

研究了聚乙二醇 80 0 - PVP30 0 0 0 - (NH4) 2 SO4- H2 O双水相体系最佳分相条件以及溶液 p H、缓冲体系、分相盐 (NH4) 2 SO4用量等对水杨酸萃取率的影响。结果表明 ,分相盐量为 2 .0 g,在 p H6 .0 B.R.缓冲体系中水杨酸平均萃取率为 95 .0 %。该体系用于萃取荧光测定阿司匹林肠溶片中水杨酸含量 ,加标平均回收率为 94 .7%— 95 .0 %。     

一种新颖的稀土-2-羟基烟酸的配合物的结构和光谱性质研究

通过水热反应合成了一种新颖的稀土2-羟基烟酸的配合物{[LaL(HL)(H2O)3]1/3(SO4)2/3(H3O)2H2O}(H2L=2-hydroxynicotinic acid)。X-ray单晶衍射分析可知,2-羟基烟酸通过羧基O和羟基O原子桥连La离子,形成二维层状结构,层与层之间通过弱作用力拓展为三维结构。二维相关光谱分析表明N—H面外弯曲振动和C—H面外弯曲振动对磁微扰比较敏感,这可能是吡啶环上π电子云在磁微扰下变形引起C—H和N—H面外弯曲振动的响应,SO24-的ν4振动和羧基不对称伸缩振动对磁微扰也比较敏感;热微扰下N—H伸缩振动比较敏感。此外还对化合物进行了紫外和热重分析。     

碳结构锯齿形边缘对SO2的催化氧化机制研究

利用多孔碳实现SO2脱除和高值资源化具有耗水少、吸附剂可循环等优点,是当前重要技术方向,探究SO2在碳材料纳米空间中的吸附转化机制是该技术的理论基础。前期研究表明O2存在的条件下,碳材料中SO2会被催化氧化形成SO3,但具体的吸附催化位点和氧化路径有待进一步研究。本文采用密度泛函理论计算了SO2碳材料锯齿形不饱和碳原子处的吸附和催化氧化路径,发现:SO2和O2在不饱和碳原子处发生化学吸附。当O2在不饱和碳原子处优先吸附时,SO2会与活化的O2反应生成SO3和化学吸附态的O;当SO2在不饱和碳原子处优先吸附时,O2会在S原子附近活化,活化后的O2会与SO2反应生成气相SO3、化学吸附态SO3。本文计算结果为用于硫资源化的高性能碳材料合成提供了理论指导。     

无水五硼酸钾晶体高温性质振动光谱的研究

利用自行设计的反应器研究了高温条件下水蒸汽对无水五硼酸钾晶体结构的影响,借助于X射线衍射、红外光谱、Raman光谱等手段分析了无水五硼酸钾晶体高温性质的振动光谱。在水蒸汽的作用下,五硼酸钾的B₂O₃/K₂O(摩尔比)变小,X射线衍射分析表明750 ℃时晶体中有K₅B₁₉O_<sub>31存在,而红外光谱与Raman光谱分析表明由于水蒸汽的作用使得晶体中的三角形B₍₃₎—O结构单元向四面体B₍₄₎—O结构单元转变,四面体的B₍₄₎—O含量增加并且硼氧网络结构被进一步打断。     

包附SiO_2的r-Fe_2O_3磁粉在国内首次研制成功

中国科学技术大学磁学教研室有关同志为研制高密度记录用磁粉,从改进国内磁粉生产工艺着手,参考国外有关资料[1-4],并结合我国具体情况,于1979年下半年研制出包附SiO2的细微针状rFe2O3磁粉. 该磁粉研制的工艺特点是采用强碱法,在比常规反应温度和浓度均低的条件下制备铁黄(a-Fe     

施氏矿物Schwertmannite的微生物法合成、鉴定及其对重金属的吸附性能

在K+缺乏的FeSO4-H2O体系(pH 2.5)中,利用氧化亚铁硫杆菌对亚铁的生物氧化作用,合成了一种新型羟基硫酸高铁矿物Schwertmannite(施氏矿物)。借助扫描电镜(SEM)、X射线衍射(XRD)、傅里叶转换红外光谱(FTIR)、电感耦合等离子体原子发射光谱(ICP-AES)等方法对其组成和结构进行了分析与表征,同时还对其重金属吸附性能进行了研究。结果表明,A.ferrooxidans LX5休止细胞可在2 d内将在FeSO4-H2O体系中0.2 mol·L-1 Fe2+全部氧化成Fe3+,溶液pH由起始的2.5下降至2.10,约有15%的Fe2+被转化成红棕色沉淀,余下85%的Fe2+氧化后以Fe3+形式存在于溶液中。鉴定结果表明合成的红棕色羟基硫酸高铁沉淀为施氏矿物。吸附试验表明,施氏矿物对重金属阳离子Cu2+,Zn2+与 Cr3+的吸附受pH的控制,吸附率随pH的升高而增加,约在6.0～7.0时达到最大吸附率。当溶液中三种金属离子浓度为50 mg·L-1时,最大吸持率分别为99.3%,99.4%与87.6%。     

污泥生物淋滤过程中黄铁矾对重金属离子的吸附与共沉淀作用的模拟研究

生物淋滤处理可加速污泥中重金属(Zn,Cu和Cr)的溶出。但在淋滤后期,约有31%的已溶出的Cu2+被重新固持。并且,Cu2+浓度的再次下降与Fe3+沉淀形成黄铁矾的反应在时间上具有同步性。为阐明Cu2+固持机理,文章利用氧化亚铁硫杆菌的生物催化氧化作用,模拟生物淋滤环境在纯体系合成了黄铁矾。吸附试验表明,在pH 2.0～2.5的范围内(污泥生物淋滤过程中重金属溶出范围),黄铁矾对10 mg·L-1 Cu2+(该浓度与供试污泥生物淋滤中的Cu2+浓度相近)的吸附率低于9%,不能完全解释Cu2+的重新固持现象。共沉淀试验表明,Cu容易与黄铁矾形成共沉淀而掺入矿物的晶格。当Cu2+为10 mg·L-1时,约有44.6%的Cu2+与黄铁矾产生共沉淀而进入固相。可以认为,Cu与黄铁矾的共沉淀效应,是导致污泥生物淋滤后期Cu2+浓度再次下降的主要原因,黄铁矾对Cu2+的吸附只起极小的作用。     

Mössbauer effect evidence of a ferrous sulphate layer in the structure of green rust 2 and its atmospheric oxidation

Mössbauer spectra of green rust 2 run under vacuum from 78 K to 460 K, display a gradual change in the abundances of two out of three ferrous sites, with the ferric sites due to electronic exchange. Further oxidation in atmospheric conditions gives spectra displaying that the two first Fe²⁺ ions become oxidized to the ferric state, but that the last Fe²⁺ site remain unoxidized: thus, a ferrous sulphate layer in the structure of green rust 2 is left unchanged.     

The substitution of Fe2+ ions by Ni2+ ions in the green rust 2 compound studied by Mössbauer effect

Green rust 2 is usually obtained by oxidizing an initial mixture of FeSO₄ and NaOH solutions and a complete oxidation leads mainly towards γ oxyhydroxide known as lepidorocite. By adding some NiSO₄ one can stop at the first stage and Mössbauer spectra reveral only ferric doublets. This implies that the initial formula 4Fe(OH)₂, 2FeOOH, FeSO₄ of green rust 2 must be replaced byxNi(OH)₂, (6?x)FeOOH, NiSO₄, wherex scans from 2 to 4. It also means that all initial ferrous ions become oxidized into the ferric state leaving the Ni₂₊ ions unchanged. Therefore the end product of oxidation is the nickel containing green rust 2 at the place of the usual lepidocrocite.     

Mössbauer analysis of BIOX treatment of ores at Wiluna gold mine, Western Australia

Mössbauer phase analysis of samples taken from nine stages of the bacterial oxidation processing of gold ore at the Wiluna Gold Mine followed the transformation of the arsenopyrite/pyrite minerals. The principal end-stage phases were szomolnokite, ferric oxyhydroxides, ferric arsenates, jarosite and incompletely transformed pyrite, with higher hydrates of ferrous sulphate being created and then dehydrating to szomolnokite during the processing.     

Mössbauer study of synthetic oxidized vivianite at room temperature

Mössbauer spectroscopy has been used to study synthetic vivianites which are oxidized at room temperature in air. Six doublets, three ferrous and three ferric, have been used to fit the spectra recorded at 295 K. They have been attributed to the cations occupying the two different crystallographic sites. These sites were either isolated (I) or in pairs (II). In the case of the paired sites, two types of ferric cations and two types of ferrous cations can be distinguished, depending upon the degree of oxidation of the cation occupying the closest isolated site. Our experimental data showed that the ferrous cations occupying sites I were preferentially oxidized at the beginning of the oxidation process and that the rates of oxidation of the cations occupying two sites were comparable at a high oxidation level. We have also observed that the concentration of Fe³⁺ tends to a stabilized value of approximately 50% after 375 days, which also corresponds to the limit of stability of the vivianite structure.     

Revelation of Causes of Colour Change in Beryllium-Treated Sapphires

Blue sapphires are treated with Be in oxidizing atmosphere to change the blue colour into yellow. Untreated and Be-treated samples are examined using laser ablation inductively coupled-plasma-mass spectrometry （LA-ICP- MS）, electron spin resonance （ESR） and ultraviolet-visible （UV-vis） spectroscopy. The results show that the yellow colouration in Be-heated blue sapphires is not due to Be diffusion from the surface of sapphire. Be behaves as a sole catalyst in this process. We find that the charge transfer between the ferrous （Fe^2＋） and ferric （Fe^3＋） is the reason of the colour change. The above conclusions are confirmed by ESR measurements to determine the connections between the Fe3＋ ions before and after Be-treated heat treatments.     

不同因素影响下Fe(Ⅲ)水解中和法制备FeOOH矿相的光谱分析

羟基氧化铁(FeOOH)作为重金属等污染物的吸附材料倍受关注,但不同因素作用下形成的FeOOH产物矿相、结构性质的差异及其对环境功能的影响,却少有报道。采用X射线衍射仪,红外光谱仪,扫描电子显微镜和激光粒度分析仪,系统考察了Fe(Ⅲ)溶液水解中和形成FeOOH时,不同作用因素如铁盐种类、pH和温度等对产物矿相的影响。结果表明,pH 8条件下,Fe(Ⅲ)溶液水解产物均为二线水铁矿(Fe₅HO₈·4H₂O);随着pH升高,Fe₅HO₈·4H₂O会向α-FeOOH相转化。Cl-和NO-₃离子的存在分别有利于β-FeOOH和α-FeOOH的形成;SO2-₄会阻碍Fe₅HO₈·4H₂O向α-FeOOH相转化;Fe2+存在时,会促进Fe₅HO₈·4H₂O向α-FeOOH相转化。加热陈化,可促进Fe₅HO₈·4H₂O转化为α-FeOOH,且利于良好结晶α-FeOOH的形成。但pH≤5,富含Cl-的Fe(Ⅲ)溶液加热水解利于β-FeOOH的生成。不同因素影响下形成的FeOOH,在矿相、表面基团、颗粒形貌和粒径大小上存在一定的差异。     

Development of new chemical dosimeter for low dose range

Accurate measurement of low dose radiation in complex systems is of utmost importance in radiation biology and related areas. Ferrous Benzoic acid Xylenol orange (FBX) system is being widely used for measurement of low dose gamma radiation because of its reproducibility and precision. However, an additional step, i.e., dissolution of benzoic acid in water at higher temperature followed by cooling at room temperature is involved for the preparation of this dosimeter. This makes it inconvenient as a ready to use dosimeter. In the present work, the organic molecule, sorbitol has been used for measurement of low doses of radiation. The advantages of using sorbitol are its ready availability and instantaneous water solubility. Owing to its dissolution at room temperature, possible errors those are involved in calculation of dose due to thermal oxidation of ferrous ions during preparation of the FBX dosimetric solution could be made insignificant in the proposed dosimeter. In the present system, sorbitol acts as radiolytic sensitizer for the oxidation of ferrous ion, and xylenol orange forms a 1:1 complex specifically with ferric ions. Thus, the analytical detection limit of ferric ions is enhanced compared to other systems. Final composition of the dosimetric solution is; 0.5 mol/m³ xylenol orange, 10 mol/m³ sorbitol and 0.2 mol/m³ ferrous ion in 50 mol/m³ sulfuric acid. Radiolytic sensitization in combination with analytical enhancement of the ferrous based system, allows us to measure radiation dose in the range of 0.05 Gy–12 Gy with ease and high reproducibility.