钛磁铁矿的制备及其异相Fenton反应催化性能

在水相中合成了钛磁铁矿（Fe3-xTixO4）,并用XRD、MSssbauer、TG-DSC和SEM等手段对合成的Fe3-xTixO4进行了表征。结果表明,合成的Fe3-xTixO4为立方晶系尖晶石结构,样品中的钛离子都已经进入其晶格中;钛掺杂有抑制钛磁铁矿进一步向钛磁赤铁矿转化和稳定尖晶石结构的作用。此外,以亚甲基蓝降解为探针反应,考察了钛磁铁矿异相Fenton反应的催化性能。实验表明,钛含量较高的钛磁铁矿是一种性能优越的异相Fenton反应催化剂。     

坡缕石粘土对有机染料的吸附热力学研究

将甘肃靖远坡缕石粘土分离提纯,通过静态吸附实验,研究了坡缕石对水中有机染料亚甲基蓝、结晶紫和苯胺蓝的吸附等温线,探讨了吸附热力学特征.实验结果显示,在实验温度范围内3种染料在坡缕石上的吸附在30 min可达平衡,吸附等温线均能较好符合Langmuir模型,饱和吸附量大小顺序为:结晶紫＞亚甲基蓝＞苯胺蓝;吸附均为吸热过程,亚甲基蓝、结晶紫和苯胺蓝的吸附焓分别为15.52、9.26和2.59 kJ/mol;吸附Gibbs函数约为-35～-30 kJ/mol,吸附熵均大于零,吸附是自发过程.     

钙钛矿的燃烧合成与其光学功能研究

利用X射线衍射(XRD)、扫描电镜(SEM)和荧光光谱(PL)对凝胶燃烧法合成的钙钛矿和稀土Pr~(3+)掺杂钙钛矿两种功能矿物材料进行表征。结果表明:在反应温度900℃,保温时间1h条件下获得了结晶良好的单相的钙钛矿和Pr~(3+)掺杂的钙钛矿样品。Pr~(3+)掺杂样品CaTiO_3∶Pr~(3+)在340nm波长光的激发下,在618nm处监测到发射峰,对应着Pr~(3+)的~(1 )D_2→~3F_4的能级跃迁。光催化降解亚甲基蓝的实验表明,钙钛矿对其具有较好的光催化降解性能,Pr~(3+)的掺杂提高其光催化效率。     

微晶白云母负载纳米TiO2及其光催化性能研究

以微晶白云母为载体,钛酸丁酯为钛源,采用溶胶-凝胶法合成制备微晶白云母负载纳米TiO2光催化剂,然后用X射线衍射,扫描电镜等对微晶白云母负载TiO2光催化剂进行表征。再以微晶白云母负载纳米TiO2光催化剂对亚甲基蓝进行了光催化降解研究,特别针对有无紫外光照射条件下微晶白云母、纳米TiO2、微晶白云母/纳米TiO2等在亚甲基蓝溶液中的行为进行研究,结果表明:所制备的微晶白云母负载TiO2光催化剂对亚甲基蓝具有较好的光催化降解能力,1250目微晶白云母负载TiO2在紫外光照射下光催化反应4h,其降解率可达99%以上。     

硬脂酸钠改性蒙脱石对水中亚甲基蓝的吸附性能研究

以阴离子表面活性剂硬脂酸钠为改性剂制备了硬脂酸钠改性蒙脱石(NaSTA-MMT).FI-IR和XRD分析表明插层剂已进入蒙脱石层间,且随着硬脂酸钠量的增加蒙脱石层间距从1.274 nm增加到4.805 nm。亚甲基蓝吸附实验表明,硬脂酸钠改性蒙脱石吸附行为遵循伪二级动力学方程。平衡吸附量与平衡质量浓度之间的关系符合Langmuir等温吸附方程所描述的规律。硬脂酸钠改性膨润吸附亚甲基蓝表现为自发的表面物理吸附过程,吸附活化能、吸附焓变和熵变分别为2.36 kJ/mol-、21.47 kJ/mol和-44.45 J/mol.K。     

阴阳离子改性甘肃平凉钙基膨润土吸附行为研究

针对甘肃平凉钙基膨润土,以十六烷基氯化吡啶(CPC)和十二烷基磺酸钠(SDS)进行改性,研究了原土及其改性土对亚甲基蓝溶液的吸附特性,并从热力学和动力学角度探讨了吸附作用机理.结果表明,改性前后的膨润土对亚甲基蓝吸附能力大小为:SDS-Bt > Bt > SDS-CPC-Bt > CPC-Bt,其吸附动力学行为均符合伪二级动力学方程,吸附活化能较小.在298～353 K范围内,吸附反应为自发过程,表现为物理吸附,且亚甲基蓝在SDS-Bt、Bt和SDS-CPC-Bt上的吸附符合Langmuir等温方程,在CPC-Bt上的吸附则符合Tempkin等温方程.     

凹凸棒石对水中亚甲基蓝的吸附动力学研究

研究了凹凸棒石对水中亚甲基蓝的吸附动力学,在初始浓度为120~210mg/L、转速为100~200rpm、以及温度为298~328K的范围内,凹凸棒石对亚甲基蓝的吸附动力学数据均符合准二级速率方程。结果表明,凹凸棒石对亚甲基蓝的吸附仅发生在外表面,吸附表观活化能为13.92kJ/mol,说明此吸附并不是由单一的化学吸附为速率控制步骤,是由化学吸附和液膜扩散共同控制的吸附过程。凹凸棒石对水中亚甲基蓝的吸附动力学研究@彭书传$合肥工业大学资源与环境工程学院!230009 @王诗生$合肥工业大学资源与环境工程学院!230009 @陈天虎$合肥工业大学资源与环境…     

天然管状矿物埃洛石负载TiO_2的微结构及对亚甲基蓝的光催化降解研究

埃洛石是一种天然的管状粘土矿物,在环境治理方面有广泛的应用。室温条件下通过钛酸丁脂的水解反应在埃洛石上负载了TiO_2。分别在避光条件和紫外光照射下,通过亚甲基蓝溶液的降解研究了埃洛石和负载TiO_2埃洛石的吸附和光催化性能。通过亚甲基蓝被吸附和降解的量,评价了样品的吸附和光催化性能。由于复合了吸附和光催化性能,负载TiO_2埃洛石能迅速降解水中的有机污染物——亚甲基蓝,其降解速度要快于纯埃洛石,因为纯埃洛石只有吸附性能。这是埃洛石应用研究方面的一次新尝试。该研究对大气和水体中各种污染物的去除和降解必然有积极的指…     

铬磁铁矿催化异相Fenton法降解不同类型染料的对比研究

类质同象置换作用能显著增强磁铁矿的异相Fenton催化性能。目前,相关的研究大多采用亚甲基蓝作为模拟污染物。由于亚甲基蓝是阳离子型染料,而磁铁矿的零电荷点约为6.8,在中性条件下,亚甲基蓝很容易吸附在磁铁矿表面上。因     

纳米TiO2光催化降解亚甲基蓝

在以钛酸丁酯为钛源,采用溶胶-凝胶法合成制备纳米TiO2催化剂样品的基础上,将其用于在紫外光照射和无光照射条件下进行亚甲基蓝降解的实验研究,并与P-25纳米TiO2进行光催化降解对比研究。对在不同条件下合成制备样品的光催化降解率的差异,通过X射线粉晶衍射、扫描电镜等从物相组成、微观结构等因素上进行了分析和探讨。结果表明,采用溶胶-凝胶法在450℃焙烧2 h所得到的纳米TiO2具有很好的光催化降解亚甲基蓝的能力,当催化剂样品质量浓度为2.5 g/L,亚甲基蓝初始浓度为5.0 mg/L时,室温下光催化反应3 h,其降解率达98%以上,其光催化降解率比P-25纳米TiO2高;光催化降解率与催化剂样品的制备条件、物相组成、颗粒尺寸等因素有关。     

Ti K-edge XANES study on the coordination number and oxidation state of Titanium in pyroxene,olivine, armalcolite,ilmenite, and silicate glass during mare basalt petrogenesis

Lunar mare basalts are a product of partial melting of the lunar mantle under more reducing conditions when compared to those expected for the Earth’s upper mantle. Alongside Fe, Ti can be a major redox sensitive element in lunar magmas, and it can be enriched by up to a factor of ten in lunar basaltic glasses when compared to their terrestrial counterparts. Therefore, to better constrain the oxidation state of Ti and its coordination chemistry during lunar magmatic processes, we report new X-ray absorption near edge structure (XANES) spectroscopy measurements for a wide range of minerals (pyroxene, olivine, Fe–Ti oxides) and basaltic melt compositions involved in partial melting of the lunar mantle. Experiments were conducted in 1 bar gas-mixing furnaces at temperatures between 1100 and 1300 °C and oxygen fugacities (fO₂) that ranged from air to two orders of magnitude below the Fe–FeO redox equilibrium. Run products were analysed via electron microprobe and XANES Ti K-edge. Typical run products had large (>?100 µm) crystals in equilibrium with quenched silicate glass. Ti K-edge XANES spectra show a clear shift in energy of the absorption edge features from oxidizing to reducing conditions and yield an average valence for Fe–Ti oxides (armalcolite and ilmenite) of 3.6, i.e., a 40% of the overall Ti is Ti³⁺ under fO₂ conditions relevant to lunar magmatism (IW ??1.5 to ??1.8). Pyroxenes and olivine have average Ti valence of 3.75 (i.e., 25% of the overall Ti is trivalent), while in silicate glasses Ti is exclusively tetravalent. Pre-edge peak intensities also indicate that the coordination number of Ti varies from an average V-fold in silicate glass to VI-fold in the Fe–Ti oxides and a mixture between IV and VI-fold coordination in the pyroxenes and olivine, with up to 82% ^[IV]Ti⁴⁺ in the pyroxene. In addition, our results can help to better constrain the Ti³⁺/∑Ti of the lunar mantle phases during magmatic processes and are applied to provide first insights into the mechanisms that may control Ti mass-dependent equilibrium isotope fractionation in lunar mare basalts.     

山东蓝宝石铁离子的价态及其对色调的影响

山东蓝色蓝宝石的着色是由Ｔｉ４＋离子与Ｆｅ２＋离子合理配比而成，一般控制在Ｔｉ４＋／Ｆｅ２＋＝１的配比范围内。多余的Ｆｅ２＋和其它Ｆｅ３＋离子存在都不利于蓝色蓝宝石正常呈色。通过穆斯堡尔谱和电子顺磁共振谱分析，测定了山东蓝宝石中铁离子的不同价态和浓度。对Ｆｅ２＋和Ｆｅ３＋离子所引起的吸收光谱特征作了研究，查明只有Ｆｅ３＋浓度很高时才产生４７７ｎｍ吸收峰，是致使山东蓝宝石表观上呈深蓝带黑色调的的重要原因。     

金绿宝石和变石的呈色机理

对24块世界主要产地的金绿宝石和变石进行X荧光能谱分析,得到其所含的主要微量元素分别是Fe、Ga、Ti和Fe、Cr、Ti。金绿宝石和变石各1块样品的同步辐射X荧光能谱半定量分析表明金绿宝石中Fe含量平均为17 800×10^-6,Cr为855×10^-6;变石中Fe含量为16 060×10^-6,Cr含量达13 333×10^-6。对15个样品的可见吸收光谱进行测试及解释表明金绿宝石的可见吸收光谱是由Fe³⁺引起,变石的可见吸收光谱由Cr³⁺和Fe³⁺共同引起。色度学的分析和系列计算表明具有440～470 nm间最大吸收和540～630 nm宽吸收带的双峰形状的可见吸收光谱,可产生红-绿色的变石效应,通过向着该双峰形状的可见光谱的方向进行变石的优化处理可以获得宝石的变石效应。     

V oxidation state in Fe–Ti oxides by high-energy resolution fluorescence-detected X-ray absorption spectroscopy

The oxidation state of vanadium in natural and synthetic Fe–Ti oxides is determined using high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS). Eleven natural magnetite-bearing samples from a borehole of the Main Magnetite Layer of the Bushveld Complex (South Africa), five synthetic Fe oxide samples, and three natural hematite-bearing samples from Dharwar supergroup (India) are investigated. V K edge spectra were recorded on the ID26 beamline at the European Synchrotron Radiation Facility (Grenoble, France), and the pre-edge features were used to determine the local environment and oxidation state of vanadium. In the case of the magnetite samples (natural and synthetic), we show that vanadium is incorporated in the octahedral site of the spinel structure under two oxidation states: +III and +IV. The variations of the pre-edge area are interpreted as various proportions in V³⁺ and V⁴⁺ (between 9.5 and 16.3% of V⁴⁺), V³⁺ being the main oxidation state. In particular, the variations of the V⁴⁺/V³⁺ ratio along the profile of the Main Magnetite Layer seem to follow the crystallization sequence of the layer. In the case of the hematite samples from India, the pre-edge features indicate that vanadium is substituted to Fe and mainly incorporated as V⁴⁺ (between 40 and 72% of V⁴⁺). We also demonstrate the potentiality of HERFD-XAS for mineralogical studies, since it can filter out the unwanted fluorescence and give better resolved spectra than conventional XAS.     

彩色电气石致色离子的化学状态研究

为探究不同颜色电气石中致色元素的化学状态及其化学环境,利用X射线光电子能谱方法对绿色调（墨绿色、蓝绿色、淡绿色）和粉红色调电气石样品进行分析。结果表明,绿色调和粉红色调电气石样品中均含有少量的过渡金属离子,如Fe,Mn,Ti,Cr,且不含Li和Be。不同颜色的电气石晶体中过渡金属阳离子的化学状态相同,且分别为Fe3＋,Mn4＋,Ti4＋,Cr3＋,但其与阴离子配位的环境有所差别。绿色调电气石样品中虽然Fe的质量分数有较大的差别,但均有部分Fe元素与F结合,即占据晶体结构中的Y位;粉红色电气石样品中,Fe离子没有与F形成配位,仅占据结构中的Z位。相反,在粉红色电气石样品中,Mn主要与F结合配位的方式存在,占据结构中的Y位,而绿色调电气石样品中大部分的Mn与O配位成键,只有少部分的Mn与F结合配位。由于Fe3＋,Mn4＋离子对之间电荷转移的可能性不大,故电气石的颜色可能主要由于d—d电子跃迁和氧与金属离子（O2--M）间电荷转移吸收引起,尤其是由于化学环境的差异（包括配位阴离子种类、杂质缺陷、结构畸变等）所引起。     

The solid solution chemistry of vesuvianite

Solid solution in vesuvianite is elucidated by examining chemical trends and cation abundances in 22 microprobe analyses of samples from the Big Maria Mountains, southeastern California. Two recent structure refinements indicate 50 filled cation sites per formula, providing the basis for data normalization. Previous optical absorption and Mössbauer studies help clarify site occupancies. Stoichiometric abundances of Si and Ca + Na indicate 18 and 19 per formula, filling all 4- and 8-fold sites respectively. The four 6-fold A-sites are filled with Al. The solid solution occurs mainly within the eight 6-fold AlFe-sites (Al, Mg, Fe²⁺, Fe³⁺, Ti) and one 5-fold B-site (Mg, Fe²⁺, Fe³⁺). Chemical trends and crystal chemical constraints delineate eight independent substitutions.An extensive solid solution in the elements Mg, Fe, Al, and Ti suggests considerable potential as a petrogenetic indicator. In order to treat equilibria involving vesuvianite thermodynamically, a reference composition must be chosen and activity-composition relations modeled. For a reference composition, Mg-vesuvianite (Fe, Ti, Na-free) was chosen because of its chemical simplicity, but problems in ascertaining its stoichiometry have led previous workers to propose at least six different formulas. In this study, its formula is determined from the microprobe analyses by applying exchange vectors to substitute components of pure Mg-vesuvianite for Fe and Ti. This yields Ca₁₉Mg₂Al₁₁-Si₁₈ O₆₉(OH)₉, with AlFe-sites=MgAl₇, and B-sites=Mg. Subdivision of the AlFe-sites into at least two distinct sites is suggested by observed chemical trends which are explanable only when different substitutions are considered to operate within different AlFe-sites.A thermodynamic mole fraction is formulated for Mg-vesuvianite based on an ideal mixing-on-sites solution model. A method is provided for estimating the distribution of Fe between the AlFe- and B-sites. Thermodynamic mole fractions calculated using Fe site distributions estimated from microprobe data yield results similar to those calulated using Fe site distributions determined from Mössbauer analysis.     

新发现的沂蒙矿类质同象系列矿物──K(Ti_5Fe_3Cr_2Mg_2)_(12)O_(19)及Ba(Ti_5Fe_4Mg_2Cr)_(12)O_(19)

在山东蒙阴金伯利岩中，首次发现了沂蒙矿类质同象系列新的富Ti矿物（变）种。理想的晶体化学式可表达为：K（Ti5Fe3Cr2Mg2）12O19（简称K－Ti沂蒙矿）（Ba，K）（Ti5Fe4Mg2Cr）12O19（简称Ba－Ti沂蒙矿）从而与原来确定的沂蒙矿K（Cr5Ti3Fe2Mg2）12O19和钡钛铁铝矿（Ba，K）（Cr4Fe4Ti3Mg）12O19一起构成了金伯利岩中AM12O19磁铁铅矿型矿物的K-Cr、Ba－Cr、K-Ti、Ba-Ti四种端元类型的复杂类质同象系列。新发现的两个矿物（变）种均产出于具叶片状尖晶石出溶体的镁钛铁矿中。根据结构已知的沂蒙矿中原子的占位和配位多面体情况，分析了K－Ti，Ba－Ti沂蒙矿中各原子的占位和配位多面体，认为新发现的两个（变）种在成分上与沂蒙矿和钡钛铁铬矿有明显的区别。根据镁钛铁矿、尖晶石、沂蒙矿新（变）种、钙钛矿之间的相互关系，探讨了它们的形成环境，从而为这类矿物的地幔成因提供了直接证据。     

A Fe K-edge XAS study of amethyst

An X-ray absorption spectroscopy (XAS) study of the Fe local environment in natural amethyst (a variety of α-quartz, SiO₂) has been carried out. Room temperature measurements were performed at the Fe K-edge (7,112 eV), at both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions. Experimental results were then compared with DFT calculations. XANES experimental spectra suggest Fe to occur mainly in the trivalent state, although a fraction of Fe²⁺ is identified. EXAFS spectra, on the other hand, reveal an unusual short distance for the first coordination shell:  = 1.78(2) Å, the coordination number being 2.7(5). These results allow to establish that Fe replaces Si in its tetrahedral site, and that numerous local distortions are occurring as a consequence of the presence of Fe³⁺ variably compensated by protons and/or alkaline ions, or uncompensated. The formal valence of Fe, on the basis of both experimental and DFT structural features, can be either 4+ or 3+. Taking into account the XANES evidences, we suggest that Fe mainly occurs in the trivalent state, compensated by protons, and that a minor fraction of Fe⁴⁺ is stabilised by the favourable local structural arrangement.     

俄罗斯富铁型水热法合成祖母绿特征研究

针对近期市场上出现的俄罗斯富铁型水热法合成祖母绿,采用电子探针、傅里叶变换红外光谱仪和紫外-可见光谱仪等测试分析方法,从化学成分、宝石学特征及谱学进行初步研究。结果表明,俄罗斯富铁型水热法合成祖母绿内部有特征的红棕色假六方片状金属固体包裹体,化学成分以贫碱富铁含铜为特征,环状分子通道内I型水和Ⅱ型水同时存在,在760nm处有由Fe3＋的d-d电子跃迁导致的特征吸收峰。除此之外,笔者对比分析了俄罗斯富铁型、传统水热法合成祖母绿、桂林水热法合成祖母绿、助熔剂法合成祖母绿及天然祖母绿样品在谱学上的差异。