Correlations between structure and thermodynamic properties of spinels and their applications in technology

Measurements a/the Gibbs' energy enthalpy and entrupy vffarmation oj chromites, vanadites and alumlnat.:s 0/ F", Ni. Co'. Mn, Zn Mg and Cd, using solid oxide galvanic cells over a ternperature range extending approximately lOOO°C, have shown that the '~'Ilir"!,,, J'JrIl/iJ~ tion 0/ cubic 2-3 oxide spinel phases (MX!O,), from component oxide (MO) with rock-salt and X.Os whir c(1f'l/!ldwn st!'llt'lw,·. call b,' represented by a semi-empirical correlalion, ~S~ = --LiS + L'i,SM +~S~:"d(±O.3) cal.deg-1 mol-1 where /',.SM Is the entropy 0/calian mixing oillhe tetrahedral alld octahedral sites o/the spinel and Sr:~ is tlie enfropy associaf,'d Wifh Ih,' randomization a/the lahn-Telier distortions. A review a/the methods/or evaluating the cation distriblltion lfl spille!s suggeJ{j' l/r,l! Ihe most promising scheme is based Oil octahedral site preference energies from the crystal field theory for the Iral1silioll IIIl'f"! IlIIL';. For I/""-Irallsifioll melal cal ions site preference energies are derived relative /0 thol'lt fLI, [ransilion metal ions from measured high tClllP('ftJi ure Cal iUlI disll iiJuriol1 in spine! phases thar contail! one IransilioJl metal and another non-transition metal carion. For 2-3 srinds compulatiorrs b,IS"J Oil i.!c[J;' Temkin mixing on each catioll subialtice predici JistributionJ that are In fair agreement with X-ray and 1I1'IIIrOll ditTraction, /IIdg""!ic dll.! electrical propcrries, and spectroscopic measurements. In 2-4 spineis mixing vI ions do not foliow strictly ideal slllIistli:al Jaws, Th,' OIl/up) associated with the randomizalion 0/the Jllhn-Teller dislOriioll" appear to be significant, only ill spinels witll 3d'. 3d', 3d' (ifld~UI' iOtls in tetrahedral and 3d' and 3d9 ions in octahedral positions. Application 0/this structural model for predicting the thermodynamic proputies ofspinel solid .,olutiofl5 or,' illustrated. F,lr complex systems additional contributions arising from strain fields, redox equilibria and off-center ions have to be qllalllififti. The entropy correlation for spinels provides a method for evaluating structure tran:.jormafiofl entropies in silllple o.\id.-s, ["founlllion on the relative stabilities ofoxides in different crystallCtructures is USe/III for computer ea/culaliof! a/phase dfugrullls ofIlIrer,',,1 III (N.lll1ie5 by method, similar to thost: used by Kaufman and Bernstein for refractory alloy systems. Examples oftechnoiogical appliCation tnclude the predictioll ofdeoxidation equilibria in Fe-Mn-AI-O s),slelll at 1600°C duj ,'Ulllpltfalion 0/phase relutions in Fe-Ni-Cr-S system,

Metal doped nanosized titania used for the photocatalytic degradation of rhodamine B dye under visible-light

Metal-doped anatase nanosized titania photocatalysts were successfully synthesized using a sal gel process. Different amounts of the dopants (0.2, 0.4, 0.6, 0.8 and 1.0%) of the metals (Ag, Ni, Co and Pd) were utilized. The UV-Vis spectra (solid state diffuse reflectance spectra) of the doped nanoparticles exhibited a red shift in the absorption edge as a result of metal doping. The metal-doped nanoparticles were investigated for their photocatalytic activity under visible-light irradiation using Rhodamine B (Rh B) as a control pollutant. The results obtained indicate that the metal-doped titania had the highest activity at 0.4% metal loading. The kinetic models revealed that the photodegradation of Rh B followed a pseudo first order reaction. From ion chromatography (IC) analysis the degradation by-products Rhodamine B fragments were found to be acetate, chloride, nitrite, carbonate and nitrate ions.

Geochemical behaviour of dissolved trace elements in a monsoon-dominated tropical river basin, Southwestern India

The study presents a 3-year time series data on dissolved trace elements and rare earth elements (REEs) in a monsoon-dominated river basin, the Nethravati River in tropical Southwestern India. The river basin lies on the metamorphic transition boundary which separates the Peninsular Gneiss and Southern Granulitic province belonging to Archean and Tertiary-Quaternary period (Western Dharwar Craton). The basin lithology is mainly composed of granite gneiss, charnockite and metasediment. This study highlights the importance of time series data for better estimation of metal fluxes and to understand the geochemical behaviour of metals in a river basin. The dissolved trace elements show seasonality in the river water metal concentrations forming two distinct groups of metals. First group is composed of heavy metals and minor elements that show higher concentrations during dry season and lesser concentrations during the monsoon season. Second group is composed of metals belonging to lanthanides and actinides with higher concentration in the monsoon and lower concentrations during the dry season. Although the metal concentration of both the groups appears to be controlled by the discharge, there are important biogeochemical processes affecting their concentration. This includes redox reactions (for Fe, Mn, As, Mo, Ba and Ce) and pH-mediated adsorption/desorption reactions (for Ni, Co, Cr, Cu and REEs). The abundance of Fe and Mn oxyhydroxides as a result of redox processes could be driving the geochemical redistribution of metals in the river water. There is a Ce anomaly (Ce/Ce*) at different time periods, both negative and positive, in case of dissolved phase, whereas there is positive anomaly in the particulate and bed sediments. The Ce anomaly correlates with the variations in the dissolved oxygen indicating the redistribution of Ce between particulate and dissolved phase under acidic to neutral pH and lower concentrations of dissolved organic carbon. Unlike other tropical and major world rivers, the effect of organic complexation on metal variability is negligible in the Nethravati River water.

Wave propagation of phonon and phason displacement modes in quasicrystals: Determination of wave parameters

The paper presents the study of wave propagation in quasicrystals. Our interest is in the computation of the wavenumber (k(n)) and group speed (c(g)) of the phonon and phason displacement modes of one, two, and three dimensional quasicrystals. These wave parameter expressions are derived and computed using the elasto-hydrodynamic equations for quasicrystals. For the computation of the wavenumber and group speeds, we use Fourier transform approximation of the phonon and the phason displacement modes. The characteristic equations obtained are a polynomial equation of the wavenumber (k(n)), with frequency as a parameter. The corresponding group speeds (c(g)) for different frequencies are then computed from the wavenumber k(n). The variation of wavenumber and group speeds with frequency is plotted for the 1-D quasicrystal, 2-D decagonal Al-Ni-Co quasicrystals, and 3-D icosahedral Al-Pd-Mn and Zn-Mg-Sc quasicrystals. From the wavenumber and group speeds plots, we obtain the cut-off frequencies for different spatial wavenumber eta(m). The results show that for 1-D, 2-D, and 3-D quasicrystals, the phonon displacement modes are non-dispersive for low values of eta(m) and becomes dispersive for increasing values of eta(m). The cut-off frequencies are not observed for very low values of eta(m), whereas the cut-off frequency starts to appear with increasing eta(m). The group speeds of the phason displacement modes are orders of magnitude lower than that of the phonon displacement modes, showing that the phason modes do not propagate, and they are essentially the diffusive modes. The group speeds of the phason modes are also not influenced by eta(m). The group speeds for the 2-D quasicrystal at 35 kHz is also simulated numerically using Galerkin spectral finite element methods in frequency domain and is compared with the results obtained using wave propagation analysis. The effect of the phonon and phason elastic constants on the group speeds is studied using 3-D icosahedral Al-Pd-Mn and Zn-Mg-Sc quasicrystals. It is also shown that the phason elastic constants and the coupling coefficient do not affect the group speeds of the phonon displacement modes. (C) 2015 AIP Publishing LLC.

Electron transfer in cytochrome c oxidase : the rate of electron equillibration between cytochrome a and copper A

Intramolecular electron transfer in partially reduced cytochrome c oxidase has been studied by means of perturbed equilibrium techniques. We have prepared a three electron reduced, CO inhibited form of the enzyme in which cytochrome a and copper A are partially reduced an in intramolecular redox equilibrium. When these samples were photolyzed using a nitrogen laser (0.6 µs, 1.0 mJ pulses) changes in absorbance at 598 nm and 830 nm were observed which are consistent with a fast electron from cytochrome a to copper A. The absorbance changes at 598 nm have an apparent rate of 17,200 ± 1,700 s^(-1) (1σ), at pH 7.0 and 25.5 °C. These changes were not observed in either the CO mixed valence or CO inhibited fully reduced forms of the enzyme. The rate is fastest at about pH 8.0, and falls off in either direction, and there is a small, but clear temperature dependence. The process was also observed in the cytochrome c -- cytochrome c oxidase high affinity complex.

This rate is far faster than any rate measured or inferred previously for the cytochrome a -- copper A electron equilibration, but the interpretation of these results is hampered by the fact that the relaxation could only be followed during the time before CO became rebound to the oxygen binding site. The meaning of our our measured rate is discussed, along with other reported rates for this process. In addition, a temperature-jump experiment on the same system is discussed.

We have also prepared a partially reduced, cyanide inhibited form of the enzyme in which cytochrome a, copper A and copper B are partially reduced and in redox equilibrium. Warming these samples produced absorbance changes at 605 nm which indicate that cytochrome a was becoming more oxidized, but there were no parallel changes in absorbance at 830 nm as would be expected if copper A was becoming reduced. We concluded that electrons were being redistributed from cytochrome a to copper B. The kinetics of the absorbance changes at 605 nm were investigated by temperature-jump methods. Although a rate could not be resolved, we concluded that the process must occur with an (apparent) rate larger than 10,000 s^(-1).

During the course of the temperature-jump experiments, we also found that non-redox related, temperature dependent absorbance changes in fully reduced CO inhibited cytochrome c oxidase, and in the cyanide mixed valence enzyme, took place with an (apparent) rate faster that 30,000 s^(-1).

Produção de biodiesel pela rota heterogênea empregando catalisadores a base de Zn e Al

Nos últimos anos, a busca por fontes de energia renováveis e o desenvolvimento de novas tecnologias para a produção de biocombustíveis têm sido objeto de intensa investigação. O biodiesel é um combustível biodegradável, derivado de fontes renováveis e é obtido em escala industrial principalmente através da reação de transesterificação de óleos vegetais e/ou gorduras animais com metanol na presença de catalisadores homogêneos, como NaOH. Entretanto, a utilização de catalisadores heterogêneos tem sido sugerida por diversos autores, por apresentar vantagens como a eliminação dos problemas de separação e purificação dos produtos obtidos. No presente trabalho foi investigada a produção de biodiesel a partir da transesterificação do óleo de soja com metanol utilizando óxidos mistos de Zn e Al como catalisadores sólidos básicos. A influência das variáveis: temperatura, concentração de catalisador e relação molar metanol/óleo de soja na produção de biodiesel foi avaliada. Os catalisadores preparados apresentaram predominantemente sítios básicos e foram ativos frente à reação estudada, sendo os resultados mais promissores apresentados pelo óxido misto com relação molar Al/(Al+Zn)=0,50, obtido por tratamento térmico à 450C, que apresentou rendimentos em ésteres metílicos de até 98,5% sob condições específicas. A metodologia da superfície de resposta foi utilizada visando estabelecer as condições ótimas para maximizar o rendimento em ésteres metílicos, tendo sido encontradas a temperatura de 165oC e a concentração de catalisador de 5,8% m/m em relação massa de óleo, no caso da relação molar metanol/óleo de soja limitada em 15. Essa limitação teve como objetivo garantir um processo viável em escala comercial

Avaliação de aditivos para remoção catalítica de SOx em unidades de fcc

Os óxidos de enxofre (SOx) são um dos maiores poluentes atmosféricos e um dos precursores da chuva ácida. Um levantamento feito na Petrobrás mostrou que cerca de 17% dos SOx emitidos numa refinaria são oriundos do processo de FCC. Com o avanço dos controles ambientais, traduzido numa legislação mais restritiva, a técnica de incorporação de aditivos para remoção de SOx em UFCCs apresenta-se como a alternativa de menor custo frente outras tecnologias de abate das emissões de SOx. No presente trabalho, foram estudados aditivos constituídos por compostos derivados de hidrotalcitas com a substituição parcial do magnésio e do alumínio por cobre e/ou manganês, sendo estes impregnados ou não por dióxido de cério. Estes aditivos foram submetidos a testes de desempenho em uma unidade multi-propósito acoplada a um micro-GC/TCD. Em todos os testes, a corrente gasosa para a etapa de adsorção oxidativa foi de 1700 ppm de SO2 e 1,5% O2 em He e, para a etapa de regeneração, 30% H2/He. No primeiro conjunto de testes, realizou-se uma adsorção a 720C de 10 min e regeneração com um patamar a 530C, seguido de um TPR até 800C. Observou-se que as amostras impregnadas com cério apresentaram o melhor desempenho na remoção de SO2, indicando que o cério pode ter um papel de promotor da oxidação de SO2 a SO3. Os resultados do TPR mostram que as amostras com cério e com manganês parecem apresentar menores temperaturas de redução dos sulfatos, apesar das maiores liberações de H2S serem identificadas nas amostras com cobre. No segundo conjunto de testes, a adsorção foi a 720C durante 35 min e a regeneração a 650C por 5 minutos em um patamar de 5 minutos, seguida de um TPR até 800C. Para os tempos de sulfatação curtos (5 e 10 min), os resultados confirmaram o efeito positivo que a incorporação de CeO2 apresenta sobre a adsorção oxidativa do SO2. Todavia, para tempos de reação maiores (35 min), não se observou uma correlação clara entre a composição química do catalisador e a quantidade total de SOx removida. Os aditivos foram ainda testados em ciclos de reação-regeneração em condições equivalentes ao segundo conjunto de testes descrito. De um modo geral, os aditivos que contêm cobre têm uma vida útil superior aos demais, possivelmente, pelo fato do cobre ter importante papel na regeneração do aditivo

Plasma stabilisation of metallic nanoparticles on silicon for the growth of carbon nanotubes

Ammonia (NH 3) plasma pretreatment is used to form and temporarily reduce the mobility of Ni, Co, or Fe nanoparticles on boron-doped mono- and poly-crystalline silicon. X-ray photoemission spectroscopy proves that NH 3 plasma nitrides the Si supports during nanoparticle formation which prevents excessive nanoparticle sintering/diffusion into the bulk of Si during carbon nanotube growth by chemical vapour deposition. The nitridation of Si thus leads to nanotube vertical alignment and the growth of nanotube forests by root growth mechanism. © 2012 American Institute of Physics.

武汉东湖沉积物中重金属生物有效性研究

沉积物中的酸挥发性硫化物(AVS)是预测厌氧沉积物中重金属生物有效性的重要参数,SEM/AVS大于1时沉积物中重金属具有潜在生物毒性,小于1时则无生物有效性. 本文研究了东湖三个不同污染负荷的站点的同步提取金属SEM(Cu, Zn, Pb, Cd, Ni, Co, Ag, Cr)和SEM/AVS的深度分布,研究表明东湖沉积物中主要重金属是Zn, Cr和Cu,约占SEM总量的90%. I站、II站沉积物中AVS是重金属生物有效性的主控因子之一,对重金属的深度分布影响较大,重金属不具有生物有效性;III站沉积

Evaluation of bimetallic catalysts for the growth of carbon nanotube forests

We systematically study the growth of carbon nanotube forests by chemical vapor deposition using evaporated monometallic or bimetallic Ni, Co, or Fe films supported on alumina. Our results show two regimes of catalytic activity. When the total thickness of catalyst is larger than nominally 1nm, bimetallic catalysts tend to outperform the equivalent layers of a single metal, yielding taller forests of multi-walled carbon nanotubes (CNTs). In contrast, for layers thinner than ~1nm, bimetallic catalysts are notably less active than individually. However, the amount of small diameter and single-walled CNTs is significantly increased. This possible transition at ~1nm might be related to different catalyst composition after annealing, depending whether or not the films overlap during evaporation and alloy during catalyst formation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In vitro recording of neural activity using carbon nanosheet microelectrodes

The advent of nanotechnology has revolutionised our ability to engineer electrode interfaces. These are particularly attractive to measure biopotentials, and to study the nervous system. In this work, we demonstrate enhanced in vitro recording of neuronal activity using electrodes decorated with carbon nanosheets (CNSs). This material comprises of vertically aligned, free standing conductive sheets of only a few graphene layers with a high surfacearea- to-volume ratio, which makes them an interesting material for biomedical electrodes. Further, compared to carbon nanotubes, CNSs can be synthesised without the need for metallic catalysts like Ni, Co or Fe, thereby reducing potential cytotoxicity risks. Electrochemical measurements show a five times higher charge storage capacity, and an almost ten times higher double layer capacitance as compared to TiN. In vitro experiments were performed by culturing primary hippocampal neurons from mice on micropatterned electrodes. Neurophysiological recordings exhibited high signal-to-noise ratios of 6.4, which is a twofold improvement over standard TiN electrodes under the same conditions. © 2013 Elsevier Ltd. All rights reserved.

The role of CeO2-ZrO2 as support in the ZnO-ZnCr2O4 catalysts for autothermal reforming of methanol

Autothermal reforming of methanol for hydrogen production was investigated over ZnO-ZnCr2O4 supported on a series of metal oxides (Al2O3, CeO2, ZrO2 and CeO2-ZrO2)CeO2-ZrO2 mixed oxides with Ce /Zr molar ratio of 4/1 was found to be the optimal support which showed significant effect on the catalytic activity and selectivity. The ZnO-ZnCr2O4/CeO2-ZrO2 and ZnO-ZnCr2O4 catalysts were characterized by XRD, TEM, H-2-TPR and XPS. The results show that CeO2-ZrO2 mixed oxides have significant effect on the catalytic performance and the supported catalyst shows more uniform temperature distribution in the catalyst bed which was mainly due to its reasonable redox properties.

稀土锰氧化物和双钙钛矿氧化物的合成及电磁性能研究

本文对钙钛矿锰氧化物La0.67Sr0.33MnO3、La0.67Sr0.33Mn1-xFexO3和双钙钛矿氧化物Sr2－xLaxMnMoO6、Sr2－xLaxMnWO6和Sr2(Ni，Co)WO6的结构、磁性和磁电阻效应进行了系统地研究。 利用溶胶-凝胶方法制得La0.67Sr0.33MnO3粉体，通过不同的烧结温度，可以对样品的微观结构进行调控。其中，晶界的状态对自旋电子的输运产生了明显的影响。900℃和1300℃烧结的样品，都出现了远低于居里温度的金属－半导体导电行为转变，表明自旋电子的传输不仅与晶粒的大小有关，而且与晶界状态密切联系。合适的烧结条件，可以得到大的，使用温区较宽的磁电阻效应。 在La0.67Sr0.33Mn1-xFexO3(0≤x≤0.2)体系中，Fe3＋的掺入没有明显改变La0.67Sr0.33MnO3的结构和晶胞参数，但却极大地降低了样品的居里温度。在x≥0.08时同样出现了低于居里温度的金属－半导体导电行为转变，这是由体系的铁磁态磁不均匀性导致的。电子顺磁共振研究表明，La0.67Sr0.33Mn1-xFexO3(0≤x≤0.20)的EPR谱中峰对峰宽（ΔHpp）在Tmin前后两种温区的线宽展宽机制不同。随着掺杂量的增加，在Tmin处的线宽逐渐变宽并且出现低场顺磁信号。x=0.20的样品，低场顺磁信号在380K左右开始衰减，与La0.67Sr0.33MnO3的顺磁信号具有类似的行为。我们利用相分离模型对系列样品的电子顺磁共振信号的变化规律进行了解释。 在Sr2－xLaxMnMoO6 (0≤x≤1)系列样品中，所有的样品都具有双钙钛矿有序结构。磁化强度、居里温度随掺杂量的增加而增大，但都存在磁受挫行为。在5T的外场下磁化强度依然没有饱和，实际测得的磁矩远远小于理论预测的结果。在低掺杂状态下出现分步磁化。La3+的掺入，不仅改变了体系电子能带的状况，而且极大的改变了体系的结构因素，两者竞争的结果，使体系的电磁性能产生了复杂的变化。

非茂过渡金属烯烃聚合催化剂的研究

本论文合成、表征了一系列以镍、钦为中心离子的非茂过渡金属配合物，研究了这些配合物催化烯烃聚合的反应行为。主要工作和结论如下：1．合成、表征了一系列水杨醛亚胺中性镍配合物。在改性甲基铝氧烷（MMAO）的活化下，这些中性镍配合物可高效催化降冰片烯伽BE）的加成聚合，在优化条件下，催化活性高达7.1×107 gPNBE／molNi.h，聚降冰片烯的分子量高达1.5×106g／mol。2．合成、表征了三种新型p一二酮单亚胺中性镍配合物。X-射线分析表明，这些中性镍配合物的空间构型为扭曲的平面四边形。在Ni（CO）2的活化下，这些中性镍配合物可催化乙烯聚合生成以甲基支化为主的支化聚乙烯。在MMAO的活化下，这些中性镍配合物是降冰片烯加成聚合的高效催化剂，在优化条件下，催化活性高达4.5×107gPNBE／molNi.h，聚降冰片烯的分子量高达1.1×106g／mol。另外，这些中性镍配合物在MMAO的活化下，可催化甲基丙烯酸甲酷（MMA）聚合，生成富间规的聚甲基丙烯酸甲酷（rr一70％）。令人惊讶的是，这些中性镍配合物／MMAO体系还能催化乙烯和MMA的共聚合反应，生成乙烯与MMA的无规共聚物，极性单体的插入率可达16.7 mol％。3．合成、表征了一系列新型β-二酮单亚胺钦配合物。X-射线分析表明，这些钦配合物的立体构型为含有一个CZ轴的变形八面体。常温下，这些钦配合物在MMAO的活化下，可以高效催化乙烯活性聚合，催化活性可达1.3×l06g PE/molTi-h，生成无支链的线性聚乙烯。常温下，这些钦配合物瓜IMAO体系还能高效催化乙烯和降冰片烯的活性共聚合反应，催化活性高达3.2×106gpolymer／molTi'h，所得聚合物为乙烯与降冰片烯的交替共聚物（COC）。利用该催化体系的活性聚合性质，制备了包含半晶和无定形两种结构片段的新型A-B二嵌段共聚物（PE-b1ock-COC）。4．合成、表征了一系列新型β-二亚胺钦配合物。在MMAO的活化下，这些钦配合物可以常温催化乙烯聚合，在优化条件下，催化活性可达4.6×105 gPe／molTi-h，生成双峰分布的聚乙烯，重均分子量高达6.6×105g／mol。

镍-金属氢化物电池新型负极材料研究

贮氢合金是镍一金属氢化物电池的核心材料，其综合性能的改善是提高镍一金属氢化物电池性能的关键。本研究以探索镍一金属氢化物电池新型负极材料为目的，以非ABS型贮氢合金为研究对象，采用X射线衍射、Rietveld分析、恒电流充／放电、P-C-T曲线及线性微极化等方法，从基础和潜在应用等方面详细研究了非ABS型合金的结构与电化学性能。对La-Ni体系中非ABS型二元合金的结构和电化学性能的研究表明，LaNi_(228)具有最优异的高倍率充电性能；La_2Ni_7合金电极的高倍率放电性能最佳；La_7Ni_3在低温条件下表现出较好的放电性能。然而，所有得到的La-Ni合金电极容量远低于其理论容量。因此，必须通过进一步研究，如元素取代、热处理、表面处理等来提高其电化学容量。对RENi_3（RE＝La，Ce，Pr，Nd，Sm，Gd，Th，Dy，Ho，Er，Y）研究表明：YNi_3合金因其具有最大的晶胞体积，最小的密度，而表现出最好的高倍率充／放电性能及低温放电性能，但其高温放电性能需要进一步提高，以满足实际应用的要求。用Al、Mn、Ti、Fe、Sn、Si、Cr、M。、Cu和Co十种元素取代Ni进行了大量的配方筛选工作。得到了大量的实验数据，并发现LaNi_(3.7)Al_(0.3)合金电极电化学放电容量最高，达290.8mAh／g；LaNi_(3.7)Mo_(0.3)合金电极的高倍率放电性能最好，在以4200mA/g的电流密度下进行放电时，其放电容量仍达到145.8mA/g；而I镍一金属氢化物电池新型负极材料研究镍一金属氢化物电池新型负极材料的研究Al的取代会使合金电极性能对温度不敏感。以我们的实验为基础，进一步进行合金配方的微调，具有可能开发出具有实用价值的贮氢合金的潜力。在Ar保护下用真空电弧炉熔炼合成了四种Lal一xMg：（NICoAI）3．6体系贮氢合金，制成姐卜Ni电池负极，通过恒电流充／放电方法研究了其电化学性能。结果表明：Lal一xMg：（NiCoAI）3．6体系金属氢化物电极较容易活化，室温下具有优异的高倍率放电性能，在以4200mA／g电流放电时，La卜汉gx（NICoAI）36合金电极的放电容量是ABS型合金电极的3倍，达152hah／g，显示出良好的动力学特性。R，入1兮Ni（R：raree田劝，Ca，Y）型合金因能吸引／释放1．8一1．87％质量的HZ而被认为是种很有希望的贮氢合金。但其吸／放氢平台过高，循环寿命短。如何提高Rh厦g剑19循环稳定性是这类合金能否成功商业化的关键。研究发现，Co能够显著提高ABS型合金电极的循环寿命，但其价格太贵。人们发现Al在提高电极寿命方面与C。有类似的作用，但Al元素的添加因其在碱性电解质的作用下在电极表面易生成致密的氧化膜而不利于氢的扩散，进而对高倍率放电性能不利。入物在提高电极表面活性，改善其高倍率放电性方面作用明显。本工作在前面的基础上用Al和MO联合取代Ni，以期待同时改善La一Mg一Ni一Co合金的循环稳定性和高倍率放电性能。详细研究了La07Mg03Ni切一（A105Mo05）x（x：o，0．2，0．4，0．6，0．8）系列贮氢合金的晶体结构和电化学性能。X射线衍射及Rietveld分析发现：所有La07Mg03Ni4D一x（A105Mo05）x合金均为包含PuNi3结构的六方LaZMgNig相、CaCus结构的LaNis主相及L匆Ni7，LaN儿和LaNi杂相的多相结构。合金中La（La，Mg）剑19相及LaNis相的晶格参数及晶胞体积均随合金中Al和Mo含量的增加而增大。用电化学方法测得的RC一T曲线显示：Al和'fo部分取代Ni降低了氢的平台压力。随合金中Al和Mo含量的增加，电极的电化学容量从329．7（x＝0）、徽橇毓孺鑫盆一11瀚加至365．物A吨（＝0．6）后又降低到351．3毗吨（x＝0．8）。当以1200m刀g的电流密度进行放电时，其I｛RD从62．0％沁0）增加到82．1％沁0．8）。线性微极化结果显示：Al和Mo的添加增大了合金表面的交换电流密度，因而也改善了合金电极的高倍率放电性能。另外，Al和M。取代合金中的Ni增大了氢在电极合金中的扩散系数（D），改善了La07Mgo3Ni4。一x（Alo5M。。5）x（X＝o，0．2，0．4，0．6，0．8）合金电极的低温放电性能（LTD）。