共查询到19条相似文献，搜索用时 171 毫秒
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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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Mn2+、Fe2+、Co2+、Ni2+、Cu2+、Zn2+、Cd2+对衣藻Chlamydomonas reinhardtii碳酸酐酶胞外酶(CAe)活性的影响研究表明,CAe活性对过渡金属的响应因金属种类的不同而不同;这些过渡金属影响CAe主要通过两个途径直接与CAe作用和间接影响藻细胞内CAe的新陈代谢. 相似文献
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内地核成分与结构的确定一直是地球深部研究的重要课题。目前地核的公认成分是铁和少量的镍。但由于地核密度低于纯粹的铁镍合金(固态内核2%～3%,液态外核6%～7%),其中必定掺杂有一定量的轻元素,其种类与浓度有待确定。除成分外,地核条件下铁的晶体结构也存在争议。根据地震学观测,声波沿地轴方向的传播速度比赤道平面方向快大约3%～4%。这意味着内地核是各向异性的;但在极端高压下,晶体结构中的原子应该按致密的密排六方结构(h.c.p)排列,而h.c.p结构对声波传输是高度各向同性的,这就需要确定地核条件下铁的晶体结构。根据第一性原理计算得到的高压下体系能量以及爱因斯坦谐振子模型,本项研究估算了给定结构的自由能以及掺杂轻元素后的影响。根据计算结果可以定性的分析得出,在高压OK下致密的h.c.p结构显然比疏松的体心立方(b.c.c)更稳定;而随着温度的升高,原子核的振动造成b.c.c结构的自由能比h.c.p结构下降得更快,因此在高温下b.c.c结构更稳定;掺杂轻元素后,这种优势变得更加明显,而3.6at.%的Si则恰好同时解释了2%～3%的密度缺失和b.c.c结构在内地核条件下的稳定性。因此我们建议内地核的基本结构与成分应为以体心立方结构存在的铁,掺杂约3.6at.%的硅元素,内地核温度至少在5500K以上。这一结论与其它更复杂的方法得到的结果一致。 相似文献
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通过高温固相反应制备了Er3+掺杂的nEr2O3:K2La2Ti3O10系列光催化剂,对样品进行了X射线衍射、扫描电镜、紫外可见吸收光谱和比表面积分析,并以染料降解考察了样品的光催化活性.研究表明.Er3+的适量掺杂抑制了K2La2Ti3O10粒径生长,增加了K2La2Ti3O10对太阳光的利用率.提高了K2La2Ti3O10的光催化活性.当n=0.003时,K2La2Ti3O10的光催化活性最大,在可见光和紫外光辎照下,可将多种染料水溶液降解.在可见光辐照下,其光催化活性优于市售的光催化剂TiO2(P25). 相似文献
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制备了不同阳离子掺杂改性的针铁矿,并采用XRD、红外、热重差热分析以及TEM等手段对其进行了表征,结果显示,掺入Mn~(2+)、Cr~(3+)、Al~(3+)后并未明显改变α-FeOOH的晶体结构类型,说明部分阳离子掺杂进入α-FeOOH晶格,从而分别形成因Fe~(3+)被Mn~(2+)、Cr~(3+)、Al~(3+)部分取代的固溶体;红外分析也得到类似结果;热重和差热分析以及TEM观察结果均表明几种金属阳离子没有形成氧化物相,可以确定这些离子已经进入针铁矿的晶格;紫外-可见漫反射光谱分析发现Mn~(2+)、Cr~(3+)掺杂者的能带隙较之纯相针铁矿的稍小,依次为2.18 e V和2.24 e V;而Al~(3+)掺杂者的能带隙与纯相针铁矿相比有所提高,增加至2.34 e V。此外还考查了不同阳离子掺杂及纯相针铁矿与Fe(Ⅱ)构成的复合系统对邻硝基苯酚(2-NP)的还原效果,研究表明,在溶液pH=6和25℃等的条件下,上述还原转化反应符合准一级动力学方程。其中,Fe(Ⅱ)/Al~(3+)掺杂针铁矿复合系统对2-NP的降解效果最好,在120 min时就达到了100%去除率,在一定浓度范围内,随着2-NP浓度的升高,2-NP的还原速率降低。而且,Fe(Ⅱ)/Al~(3+)-针铁矿复合系统速率常数(k)随着溶液的pH值增大而升高。 相似文献
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基于密度泛函理论(DFT)的平面波超软赝势方法,从第一性原理计算的角度,应用GGA对TiO2的高压相α-PbO2型TiO2的晶格参数和电子结构作了比较系统的计算,得到优化后的晶格参数与实验值十分符合.电子结构计算表明α-PbO2型TiO2属于间接带隙半导体,其禁带宽度为2.47 eV,大于锐钛矿型TiO2计算的带隙值Eg=2.12eV,主要原因在于α-PbO2型TiO2结构具有较低的晶体对称性,并且其Ti-O平均键长更长,Ti与O离子的正负电荷数较少,Ti3d轨道与O2p轨道杂化程度较弱.在理论上确认对称性较低的高压矿物-α-PbO2型TiO2高压相的光催化效果不及常态相锐钛矿型TiO2好. 相似文献
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利用对数正态分布图解析徐州城市土壤中重金属元素来源和确定地球化学背景值 总被引：9，自引：0，他引：9
城市土壤指示了城市环境中重金属污染的状况.为了更好地评价人为因素对城市土壤的影响强度,确定城市土壤重金属元素的地球化学背景值是十分必要的.以徐州城市表层土壤中Pb、Cu、Zn、V、Se和Ti等重金属为例,利用对数正态分布图区分了不同元素的来源,其中Ti和V主要来自土壤母质的分化,而Pb、Cu、Zn和Se等的来源则比较复杂,表现为受人为因素作用强烈.这些结果与利用多元统计方法(如聚类分析和主成分分析)获得的结果一致.利用对数正态分布图获得了Pb、Cu、Zn、V、Se和Ti等元素的地球化学背景值. 相似文献
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运用Tafel极化曲线和线性电势扫描法研究了常温弱酸性CuCl2-NaCl溶液中铜氯络合物体系的电化学放电机理。通过测量不同浓度配比的CuCl2-NaCl溶液的极化曲线得到各自的交换电流密度,然后根据电化学反应级数法计算直接在电极上放电的Cu(Ⅱ)-Cl络合物的配位数。并且运用线性电势扫描法进一步研究了此络合物在铂电极上的还原反应,在体系可逆的情况下计算得到其发生放电反应的离子浓度。结果表明:溶液中存在的主要络离子是[CuCl]+,在铂电极上发生电化学反应的铜络离子是[CuCl]+。铜氯络离子在铂电极上的还原反应分两步进行,其中第一步为可逆的单电子还原过程,体系中[CuCl]+和Cu的电化学反应级数均为一级;4.000 mol/L NaCl-0.100 mol/L CuCl2溶液体系中发生放电反应的[CuCl]+的浓度为0.086 mol/L。研究结果为目前学术界存在广泛分歧的Cu2+在高浓度氯离子溶液中的放电机理提供了重要的实验依据,同时对未来湿法冶金、地质和地球化学等领域中溶解态金属络合物的电化学分析具有一定的借鉴作用。 相似文献
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A local density approximation (LDA) band structure method, the Linear Muffin-Tin Orbital Atomic Sphere Approximation (LMTO-ASA) method has been used to calculate the electronic structures of the pyrite-type disulphides (MS2, where M = Mn, Fe, Co, Ni, Cu, Zn). The total density of states has been calculated for 10 eV above and below the Fermi Level, along with the separate contributions from metal and sulphur and shows that the metal d band occurs above the sulphur p bands in MnS2, FeS2, CoS2 and NiS2, whereas in CuS2, the d band passes through the sulphur p band and in ZnS2, it lies below the sulphur p band. Substantial hybridization of the metal d states with the sulphur states occurs. FeS2 is calculated to be a semiconductor with a direct band gap of 0.64 eV in good agreement with experiment. The calculated local densities of states have been used in turn to calculate X-ray photoelectron spectra and Bremsstrahlung Isochromat spectra for this series of compounds, and these also show reasonable agreement with experimental data. A particular strength of the LMTO-ASA method is the ability to calculate and predict certain bulk properties of solids of interest in mineral physics. This has enabled the first reasonably accurate calculations of the total energy of the valence electrons of the system for pyrite (FeS2), given as — 345.885 rydbergs per unit cell, and the equilibrium unit cell volume which is within 3.3% of that determined experimentally. A theoretical pressure vs. volume curve for pyrite was also calculated along with values for the bulk modulus. However, our calculations predict a bulk modulus of 6.75 Mbar which is too high by a factor of 4.6 due to the simplifying assumption of a uniform scaling of interatomic distances on compression. 相似文献
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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。 相似文献
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Synchrotron radiation S K-edge XANES spectra and unit-cell parameters are used to investigate the local electronic structure
of non-stoichiometric binary and ternary Fe-Co-Ni monosulfide solid solution (mss; M0.923S, M = Fe, Co, Ni) quenched from 800 °C and low pressure. The prominent absorption edge feature of the XANES spectra represents
transition of S 1s core level electrons to unoccupied S 3p σ* antibonding orbitals hybridized with empty metal 3d(eg) orbitals. There is a progressive increase in area of the edge peak from Fe0.923S to Ni0.923S and Co0.923S, which correlates with progressive decrease in c and a parameters for the NiAs-type subcell and increase in metallic character, and reflects increase in the number and availability
of empty eg
β orbitals and covalence of metal-S bonds. More generally, the area of the edge peak exhibits an inverse linear correlation
with a, c and unit-cell volume of binary and ternary mss. This inverse linear correlation is attributed to progressive increase in
covalence and M-S-M bonding interaction in the c-axis direction, through metal-S [M 3d(eg) - S 3p (or 3d)] π bonding. However, the area of the edge peak does not correlate very well with the average number of 3d
electrons per metal atom in these solid solutions, showing that the absorption of synchrotron radiation reflects the local
electronic structure of individual absorber atoms (i.e. the SM6 cluster), and is not a group (crystal energy band) effect.
Received: 21 March 2000 / Accepted: 14 July 2000 相似文献
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《Applied Geochemistry》1998,13(5):607-617
Distribution and forms of transition metals (Ti, Zn, Ni, Co, Mn, Fe, Cu, V and Cr) were investigated in oxidised, partly oxidised and reduced zones of sulphide-bearing fine-grained sediments located in the coastal areas of western Finland. Samples for the analysis and study of vertical distribution of elements were taken from each vertical 10 cm section in pits ranging in depth between 2 and 3 metres, while bulk samples for characterisation of species and forms of metals were taken from 3 zones in each pit: the acid sulphate soil (characterised by acid and oxidising conditions), transition zone (characterised by a steep pH gradient and partly oxidising conditions) and the reduced zone (pH >6). The former samples were digested in aqua regia (3:1:2 HCl:HNO3:H2O), while the latter were digested in aqua regia and hot concentrated acids (HClO4–HNO3–HCl–HF) and were subjected to extractions with acid ammonium acetate, H2O2 and acid ammonium oxalate. Each leachate was analysed for metals with ICP–AES.The vertical variation in the concentrations of Ti were small at all the studied sites indicating that the sediments are homogeneous and that the total losses of other elements from the soil profiles (acid sulphate soil+transition zone) are not extensive. Field observations, extractions with ammonium oxalate, and concentration–variation patterns indicated that Fe-oxide is largely precipitated and retained also in these acid soils. There are, however, indications of redistribution of Fe within the soil profiles. The results also demonstrated that Mn, Ni, Zn, Co and Cu have been lost in considerable amounts from the acid sulphate soils. However, whereas Mn in general has been lost throughout the soil profile, part of the Zn, Ni and Co released in the acid sulphate soils have migrated downward and been reimmobilised in the transition zone immediately above the reduced zone. Also Cu has been lost from the acid sulphate soil, but generally in smaller proportions than Mn, Zn, Ni and Co. Dissolved metal sulphides seem to be major sources of the mobilised metal fractions. A main part of the V and Cr in the sediments are associated with weathering-resistant minerals. These metals are therefore, like Ti, only to a limited extent mobilised by the oxidation of the sulphide-bearing sediments. 相似文献
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XPS measurements have been made of vacuum-fractured monoclinic pyrrhotite and troilite that highlight sulfur coordination (S 2p) and iron electronic state (Fe 2p) differences between these two minerals as a result of iron lattice site occupancy. Metal-like Fe states are observed in the Fe 2p spectrum of troilite due to increased occupancy of Fe lattice sites and increased Fe-Fe 3d orbital interaction within the constraints of the mineral structure. Additional electron population near the top of the troilite valence band is confirmed by XPS measurement. These results provide comprehensive experimental evidence for itinerent 3d electrons in the natural iron sulfides. 相似文献
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Effects of Heavy Metal Contamination on Microbial Biomass and Community Structure in Soils 总被引：5，自引：0，他引：5
Theeco environmentalpollutioncausedbyminingdevelopmentisaworldwideproblem ,whichhasarousedever increasingattentionofscientists.Inadditiontovegetationdestructionanderosionofcultivatedlanddirectlycausedbyminingdevelopment,scientistshaveplacedmorefocusontheenvironmentalproblemsinducedbythereleaseofharmfulsubstances ( particularlyheavymetals) .Especiallyundersurfaceconditions,thepiled upminewastes (minetailings)undergoweatheringundertheactionofaseriesofgeochemicalfactorssuchasthemineralogyofmineta… 相似文献
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LI Yan LU Anhuai WANG Changqiu School of Earth Space Sciences Peking University Beijing 《《地质学报》英文版》2006,80(2)
The photocatalytic reductive capability of a natural semiconducting mineral, sphalerite has been studied for the first time. The sphalerite from the Huangshaping deposit of Hunan Province performed great photoreductive capability that 91.95% of the Cr6+ was reduced under 9 h visible light irradiation, higher than the 70.58% under 9.5 h UV light irradiation. The highly reductive ability results from its super negative potential of electrons in the conduction band. Furthermore, Fe substitution for Zn introduces donor states, and the oxidation process of Fe2+ to Fe3+ makes it an effective hole-scavenger. Cd and Cu substitute for Zn also reduce the bandgap and help broaden the absorbing edge towards the visible light. These substituting metal ions in natural sphalerite make it a hyper-active photocatalyst and very attractive for solar energy utilization. 相似文献
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Photocatalytic Reduction of Cr^Ⅵ by Natural Sphalerite Suspensions under Visible Light Irradiation 总被引：4，自引：0，他引：4
LI Yan LU Anhuai WANG Changqiu 《《地质学报》英文版》2006,80(2):267-272
The photocatalytic reductive capability of a natural semiconducting mineral, sphalerite has been studied for the first time. The sphalerite from the Huangshaping deposit of Hunan Province performed great photoreductive capability that 91.95% of the Cr^6＋ was reduced under 9 h visible light irradiation, higher than the 70.58% under 9.5 h UV light irradiation. The highly reductive ability results from its super negative potential of electrons in the conduction band. Furthermore, Fe substitution for Zn introduces donor states, and the oxidation process of Fe^2＋ to Fe^3＋ makes it an effective hole-scavenger. Cd and Cu substitute for Zn also reduce the bandgap and help broaden the absorbing edge towards the visible light. These substituting metal ions in natural sphalerite make it a hyper-active photocatalyst and very attractive for solar energy utilization. 相似文献
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Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn47.7 Ca45.1 Mg7.2) CO3. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations. 相似文献