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1.
在简述半导体光催化理论及TiO2多相光催化作用近30年研究现状的基础上，重点对国内外一直处于空白状态的天然含钒金红石光催化性能进行研究。天然含钒金红石中部分Ti^4 被V^5 包括Fe^3 、Cu^2 和Zn^2 等杂质离子替代可引起其晶格畸变与缺陷。机械粉碎到70～80μm后可使其晶胞膨胀0.33％，原位加热700～1100℃其晶胞可膨胀0．93％～2．13％，淬火改性其晶胞收缩0．01％～0．07％。受热改性其体相中V^5 向表面偏析。对晶格畸变的修复可表现为晶面重构和再结晶作用及微应力释放作用。粉碎的金红石对卤代烃三氯乙烯和四氯乙烯具有一定的降解效果而表现出良好的光催化活性。加热1000℃，金红石对卤代烃的降解率明显提高。淬火1000℃和1100℃，金红石对卤代烃的降解速度大大加快。而电子辐射金红石对三氯乙烯的降解率则明显降低。通过52种金属氧化物和金属硫化物半导体矿物的初步研究，发现大多数金属氧化物矿物产生光电子的波长范围是249～777nm，吸收光主要是可见光。而大多数金属硫化物矿物产生光电子的最大波长大于921nm，吸收光主要是红外光，充分表明无机界具有光催化功能的半导体在可见光条件下就可以产生光电子与空穴。系统开展无机界矿物光催化作用研究，对揭示地球生命过程和环境演化有着不可替代的作用，对氧化降解地球表层系统中有机污染物尤其是不能自行降解的持久性有机污染物有着至关重要的作用。 相似文献
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采用基于密度泛函理论的第一性原理计算方法,对掺杂Fe和(或)V的金红石型TiO2的电子结构进行了计算。理论模拟的结果表明,纯金红石的禁带宽度为1.98 eV;Fe掺杂金红石型TiO2的禁带宽度为2.18 eV,由Fe3d和O2p轨道杂化在禁带中间形成了两条杂质能级;V掺杂金红石型TiO2的禁带宽度减小为1.80 eV,由V3d和O2p轨道杂化形成的杂质能级位于金红石的导带底,引入了一个浅施主能级;Fe和V共掺杂的金红石禁带中存在一个较宽的杂质能带,禁带宽度减小为1.73 eV。杂质能级的出现以及禁带宽度的减小使得Fe和V掺杂的金红石具有更好的可见光响应能力。同时,Fe和V的类质同像替代使得金红石中MO6八面体具有较大的畸变程度,有助于表面缺陷的增加,从而为光催化反应提供天然活性位。为进一步深入揭示含铁、钒等杂质的天然金红石的可见光催化机制提供了理论支持。 相似文献
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西藏班公湖带多不杂铜矿床是新近发现的具有超大型远景的典型富金斑岩铜矿床。金红石是富金斑岩铜矿中最特征的副矿物之一,对其结构和成分的研究可以反演成矿流体演化过程并确定斑岩铜矿的主矿体。在详细的野外地质考察基础上,对钾化带、强粘土化叠加钾化带样品中的金红石研究表明,金红石主要发育在黑云母斑晶中及其附近,呈不规则状、颗粒状(粒径约5~20μm)、长条状(一般长10~50μm,宽3~5μm)等。电子探针分析数据显示,多不杂富金斑岩铜矿中的金红石相对富集SiO2、V2O3、FeO,SiO2含量(质量分数,不同)在0·04%~4·40%范围之内;V2O3介于0.39%~1.13%,FeO为0·51%~3·01%;而其他成分相对较少,CaO0·02%~2·71%,MnO最高可达0·2%,SnO0·1%,Al2O3最高达1·97%,MgO0·96%,Cr2O30·63%,K2O一般0·11%~0·49%,Na2O一般0.1%~0·23%,CuO最高可达0.56%,不含NiO。Fe、Al、V、Sn、Cr、Si、Cu原子数与Ti表现出很好的负相关性,表明这些原子替代金红石的Ti而占据晶格;而金红石中K、Na、Ca较高则可能是由于补偿电荷平衡而进入金红石的晶格。金红石较高含量的CuO、K2O、Na2O,表明成矿热液富含Cu、K和Na,同时也暗示金红石在钾化带中形成。金红石与黑云母密切的关系表明,大多数金红石形成于黑云母蚀变或者重结晶的过程中。另外,多不杂富金斑岩型铜矿床矿体中的金红石w(V2O3)>0.4%,表明金红石中的V含量有助于确定斑岩铜矿中主矿体的范围,从而具有重要的找矿意义。 相似文献
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研究了山西代县天然金红石在紫外光和日光照射条件下对苯酚的光催化降解性能,考察了光照时间、pH值、苯酚初始浓度以及H2O2添加量对降解过程的影响。在紫外光照射下,酸性条件(pH=3.5)利于光催化降解,中性和碱性条件下降解效率较低;当初始浓度为60mg/L时,降解速率可达1.922mg/(L.h);H2O2作为电子捕获剂可提高苯酚降解速率,最佳投加量为2mL/L。在日光条件下,天然金红石对苯酚表现出良好的降解性能,照射7h后,降解率达87.68%,仅略低于P25型TiO2(99.72%),可在14h内完全降解。根据电子探针和X射线衍射分析结果,认为天然金红石晶格中的V、Fe等杂质可能是提高其可见光响应效果和光催化活性的主要原因。 相似文献
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孔道结构化合物(H3NCH2CH2NH3)3[(VO)4(PO4)2(HPO4)4]的钒氧化态与热稳定性关系研究 总被引：1，自引：0，他引：1
热处理脱除有机模板易导致VPO体系孔道结构化合物结构破坏,从而阻碍此类材料的实际应用。以孔道结构化合物(H3NCH2CH2NH3)3[(VO)4 (PO4 )2 (HPO4 )4 ](简称V2P3 en)为研究对象,利用热分析(DSC TG)、动态原位高温X 射线衍射(XRD)及多功能X 射线光电子能谱(XPS)等方法,研究了该化合物在不同气氛热处理过程中模板脱除及结构演化规律,重点探讨了钒氧化态的变化对结构稳定性的影响。结果表明,加热过程中随着有机模板的分解脱除,形成较强的还原环境,骨架中的部分钒被还原(V4+→V3+),使原有的配位环境([VⅣO5]三角双锥、[VⅣO6]畸变八面体)与钒的氧化态不符而导致结构重组。因此,钒氧化态的变化是影响热稳定性的重要因素之一。 相似文献
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天然含钒金红石样品经过1273K加热、淬火和高能电子辐照处理后性质发生不同程度的变化。XRD谱峰显示处理前后样品没有发生物相变化，显微IR图谱证明原样、加热、淬火样品的表面有少量吸附水存在，而辐射样品的显微IR图谱上没有检测到吸附水的吸收峰。用XPS分析比较了处理前后样品表面主要元素Ti、O和V的价态及含量，结果表明，原样经过处理后表面钒和氧的原子百分含量增加，其中淬火样品表面吸附水和钒的含量相对于原样增加最为明显，光催化活性相应较高；加热样品表面的吸附水和钒的含量比原样稍有增加，光催化活性与原样相当；电子辐射样品表面钒的原子百分含量相对原样增加不明显，而对水的吸附能力相对原样较低，光催化效率也略低。 相似文献
8.
天然半导体矿物金红石因结构中含有类质同象替代杂质元素V和Fe,具有一定的可见光吸收和光催化活性。为改善金红石的日光光催化性能,在H2还原气氛下,对天然金红石粉末进行500～900℃不同温度的热处理改性研究。紫外-可见漫反射吸收光谱（UV-Vis diffuse reflectance absorption spectra）表明H2还原处理显著改善了金红石在可见光区460～750 nm波段的光吸收,其中900℃处理样品的光吸收提升最为明显。电子顺磁共振（EPR）和X射线光电子能谱（XPS）测试表明,随着还原温度升高,杂质元素V和Fe从高价态（V5＋,Fe3＋）向较低的价态（V4＋,V3＋,Fe2＋）转化,同时金红石表面的化学吸附水含量也有所增加。本文认为H2还原热处理引起的过渡金属元素价态的改变,尤其是较低氧化态V离子（V4＋和V3＋）的形成,可能是导致金红石样品可见光吸收显著增加的主要原因。 相似文献
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广西资源车田红辉沸石特征的初步研究 总被引：19，自引：2，他引：19
红辉沸石属斜方晶系，a=1．36，b=1．81，c=1．78nm，V=4.394nm3。化学成分分析结果（％）：SiO258．76，Al2O314.13，CaO8．80，K2O0．11，Na2O0．18，Fe2O30．44，H2O 16．87，H2O1．25。计算的化学式为：（K0.017Na0.042Ca1.13）1.189［Al1.997，Si7.05，O18」·6．75H2O。Si／Al=3．53.N。=1．501，Nβ=1．495，Nγ=1．488。D=2.13g／cm3（实测）。钾离子（K ）交换量9．34～13·08mg／g，氨离子（NH4 ）交换量92.76～130．26mmol／100g。佛石晶体呈透明一半透明，为乳白色、瓷白色。单晶体呈板状、板柱状，集合体呈放射状、束状。单晶体长度可达30cm以上，但通常为5～15cm。红辉沸石呈脉状产出在断裂带中，矿体中沸石含量达95％以上，矿石的白度为91．7。它是一种质量较好、用途较广的极为罕见的沸石矿，也是国内外目前唯一具有工业意义的红辉沸石矿床。 相似文献
10.
南苏鲁超高压变质带东海地区富钛榴辉岩及金红石矿的成因 总被引：3，自引：1，他引：3
苏鲁超高压变质带南部的东海地区有富Fe—Ti的钛铁矿榴辉岩和富Ti的金红石榴辉岩。富Fe—Ti榴辉岩的次要矿物主要由钛铁矿和钛磁铁矿组成，可舍少量金红石，具有很低的Si02（38．0％-42．3％）、Na20＋K20（0．48％～2．13％）和Zr、Nb、Ta、Ba、1Kb、REE含量，很高的FeO（18．24％-25．33％）、V和Co含量，并具有不同程度的LREE亏损、明显的正Eu异常；富Ti金红石榴辉岩舍有丰富的金红石和磷灰石，SiO2含量范围（38．0％-54．8％）较宽，FeO含量较低，P2O5含量较高（可达4．1％），而X-TiO2与P205含量具正相关性。相对于原始地慢岩．富Ti金红石榴辉岩具有Rb、Th、K、Nb、Pr、Nd、Eu、Ti、Lu的负异常和Ba、Sr、Zr的正异常．并具相对较高的IKEE含量，LREE富集和HREE亏损的1KEE分配型式。岩石学和地球化学特征揭示，Fe—Ti榴辉岩的原岩是变质的Fe—Ti辉长岩，是基性岩浆强烈分离结晶作用形成的超基性-基性-中酸性层状侵入体的特征组成部分。 相似文献
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The effect of mineralogy and texture of Qara-aghaj ilmenite concentrate on titanium dioxide prepared via reduction-slagging acid leaching process as a raw material in chloride route was investigated. The concentrate contains 44.5 % TiO2 and its content in ilmenite lattice varies from 41.6–48 %. Hematite exsolved lamellae inside ilmenite which affect the reduction process positively are host of the most of the Cr and V as pigment colorizer metals. Apatite fine inclusions inside ilmenite as the source of Ca and P could have negative effects on synthetic rutile. Spinel ultrafine particles inside ilmenite containing Al and Si could also affect the synthetic rutile negatively. The other important elements which have been substituted in ilmenite lattice are Mg and Mn. The prepared titanium dioxide concentrate containing 91 % TiO2 and 0.6 % Fe2O3 is mainly formed by rutile and small amount of anatase and Ti2O3 phases. The solid solution of rutile inside Ti2O3 was also observed. The content of Cr, V, Mn, and Al are decreased to permissible amount during slagging and leaching process while the quantity of other impurities such as Mg, Si, and Ca are relatively high in the product, and they cause some difficulties in pigment production via chloride route. The Mg and Ca sourced from ilmenite lattice and apatite inclusions, respectively, can affect the precipitation process. So, it is predicted that Qara-aghaj ilmenite concentrate will be suitable for sulfate route, but it is necessary to investigate comprehensively. 相似文献
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《矿物学报》2013,(Z1)
Qara-aghaj and Skandian as hard rock titanium deposit and Kahnooj one as a placer deposit were investigated from applied mineralogical point of view. The mineralogical studies were carried out using XRD, XRF, optical microscopy, scanning electron microscopy and microprobe analysis. These studies indicated that ilmenite and magnetite are main valuable minerals in the studied ores. Pyroxene, olivine and plagioclase are the main gangue minerals in Qara-aghaj ore while chlorite and plagioclase are the major gangue minerals in Skandian ore. Plagioclase, clinopyroxene, amphibole, feldspate and some quartz are the important gangue minerals in kahnooj deposit. In all three ores ilmenite is mainly in the form of ilmenite grains but some lamellae of ilmenite with thickness between 0.1 to 20 μm have been occurred as exsolution textures inside magnetite grains, where the magnetite here can be referred to as ilmenomagnetite. In the hard rock ores some fine ilmenites have been disseminated in silicate minerals. The liberation degree of granular ilmenite was determined 150, 140 and 200 μm for Qara-aghaj, Skandian and Kahnooj, respectively. So, only the granular form of ilmenite is recoverable by physical methods. Some sphene and rutile as titanium containing minerals were observed mainly inside ilmenite phase in kahnooj ore. Some fine rutile was also found inside Skandian ilmenite while there were not any other titanium minerals inside Qara-aghaj ilmenite. Apatite is another valuable mineral which was found only in Qara-aghaj ore. Using SEM and microprobe analysis it was found that there are different amounts of exsolved fine lamellae of hematite inside ilmenite in Qara-aghaj and Kahnooj ores while it was not observed in Sckandian one. The average contents of TiO2 in the lattice of Qara-aghaj, Skandian and Kahnooj ilmenite were determined 51.13, 50.9% and 52.02%, respectively. FeO content of ilmenite lattice for all three samples is clearly lower than the theoretical content. This is due to the substitution of Mg and Mn for some Fe2+ ions in the ilmenite lattice. V2O3 content of magnetite lattice is up to 1%. So, magnetite can be a suitable source for production of vanadium as a by-product in all three deposits. 相似文献
13.
Vanadium and niobium behavior in rutile as a function of oxygen fugacity: evidence from natural samples 总被引：1，自引：0，他引：1
Vanadium occurs in multiple valence states in nature, whereas Nb is exclusively pentavalent. Both are compatible in rutile, but the relationship of V–Nb partitioning and dependence on oxygen fugacity (expressed as fO2) has not yet been systematically investigated. We acquired trace-element concentrations on rutile grains (n = 86) in nine eclogitic samples from the Dabie-Sulu orogenic belt by laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and combined them with published results in order to assess the direct and indirect effects of oxygen fugacity on the partitioning of V and Nb into rutile. A well-defined negative correlation between Nb (7–1,200 ppm) and V concentrations (50–3,200 ppm) was found, documenting a competitive relationship in the rutile crystal that does not appear to be controlled by bulk rock or mineral compositions. Based on the published relationship of RtDV and V valence with ?QFM, we suggest that the priority order of V incorporation into rutile is V4+ > V3+ > V5+. The inferred Nb–V competitive relationship in rutile from the Dabie-Sulu orogenic belt could be explained by decreasing fO2 due to dehydration reactions involving loss of oxidizing fluids during continental subduction: The increased proportion of V3+ (expressed as V3+/∑V) and attendant decrease in RtDV is suggested to lead to an increase in rutile lattice sites available for Nb5+. A similar effect may be observed under more oxidizing conditions. When V5+/∑V increases, RtDV shows a dramatic decline and Nb concentration increases considerably. This is possibly documented by rutile in highly metasomatized and oxidized MARID-type (MARID: mica–amphibole–rutile–ilmenite–diopside) mantle xenoliths from the Kaapvaal craton, which also show a negative V–Nb covariation. In addition, their Nb/Ta covaries with V concentrations: For V concentrations <1,250 ppm, Nb/Ta ranges between 35 and 45, whereas for V > 1,250 ppm, Nb/Ta is considerably lower (5–15). This relationship is mainly controlled by a change in Nb concentrations, suggesting that the indirect dependence of RtDNb on fO2, which is not mirrored in RtDTa, can exert considerable influence on rutile Nb–Ta fractionation. 相似文献
14.
Partition coefficients (D) for Nb and Ta between rutile and haplogranite melts in the K2O-Al2O3-SiO2 system have been measured as functions of the K2O/Al2O3 ratio, the concentrations of Nb2O5 and Ta2O5, the temperature, in air and at 1 atmosphere pressure. The Ds increase in value as the K* [K2O/(K2O + Al2O3)] molar ratio continuously decreases from highly peralkaline [K* ∼ 0.9] to highly peraluminous [K* ∼ 0.35] melts. The D values increase more dramatically with a unit decrease in K* in peraluminous melts than in peralkaline melts. This compositional dependence of Ds can be explained by the high activity
of NbAlO4 species in peraluminous melts and the high activity of KONb species (or low activity of NbAlO4 species) in peralkaline melts. A coupled substitution, Al+3 + Nb+5 (or Ta+5) = 2Ti+4, accounts for the Ds of Nb (Ta) being much greater in peraluminous melts than in peralkaline melts because this substitution
allows Nb (Ta) to enter into the rutile structure more easily. The Ds of Ta between rutile and melt are greater than those
of Nb at comparable concentrations because the molecular electronic polarizability of Ta is weaker than that of Nb. The Nb+5 with a large polarizing power forms a stronger covalent bond with oxygen than Ta+5 with a small polarizing power. The formation of the strong bond, Nb-O, distorts the rutile structure more severely than the
weak bond, Ta-O; therefore, it is easier for Ta to partition into rutile than for Nb. These results imply that the utilization
of the Nb/Ta ratio in liquid as a petrogenetic indicator in granitic melts must be done with caution if rutile (or other TiO2-rich phases) is a liquidus phase. The crystallization of rutile will increase the Nb/Ta ratio of the residual liquid because
the Ds of Ta between rutile and melts are greater than those of Nb.
Received: 28 December 1998 / Accepted 27 September 1999 相似文献
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L. Z. Reznitsky E. V. Sklyarov L. F. Suvorova I. G. Barash N. S. Karmanov 《Geology of Ore Deposits》2017,59(8):707-719
The paper presents data on accessory rutile in Cr–V-rich metamorphic rocks of the Slyudyanka crystalline (granulite) complex in the southern Baikal region. The geochemical features of the studied rutile are unique in combining isomorphic admixtures typical of the mineral from either mafic (Cr) or felsic igneous and associated metasomatic rocks (W), as well as the Nb and V contents, which are abnormally high for metamorphic rocks. The highest concentrations of these elements are as follows, wt %: 15.38 V2O3, 4.33 Cr2O3, 11.09 Nb2O5, 12.36 WO3. These high W and V contents have never been measured in natural rutile. The studied rutile is compared to that from other Cr–V-bearing rocks in the world and various genetic types. The optimal isomorphic substitutions and probable conditions of their realization are discussed. 相似文献
17.
含钒金红石可见光下催化降解亚甲基蓝实验研究 总被引：2，自引：0，他引：2
利用含有钒等杂质的金红石可部分吸收可见光的特性,以500 W卤素灯作为光源,实验研究了其对亚甲基蓝的可见光催化降解,结果表明,该金红石具有催化活性,7 h后亚甲基蓝可降解71 2%。经过加热、粉碎改性方法处理后的金红石光催化活性明显提高,加热1 100 ℃的金红石样品7 h后可使亚甲基蓝的降解率达到90 4%。增加光照强度、加入适当的H2O2 都可提高降解效果。实验为充分开发利用天然金红石提出了新的途径,为环境污染治理提出了新方法。 相似文献