共查询到20条相似文献,搜索用时 31 毫秒
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应用热力学特性函数、齐次函数定理和勒让德变换等概念和方法从理论上探讨了热力学公式RTlnKco=ΔrGmo(T,co)在推导和应用方面的问题。严格的数学论证表明该式是背离热力学原理的,它近似地适用于液相,但应用于气相则可能产生较大偏差。 相似文献
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A series of single-phase LixNi0.8-yCo0.2ZnyOp(0.96 ≤x≤ 1.10, 0 ≤y≤ 0.05, 2 ≤p≤ 2(1+y) ) (different in the y values) were synthesized by a two-step solid state reaction method, in which LiOH·H2O, Zn-doped spherical Ni(OH)2 and Co2O3 were used as the precursors. The ICP-AES analyses proved that the Zn-doped compounds synthesized had the nonstoichiometric form. The results of the XRD, SEM identified that the uniform particles of the as-prepared materials having a good layered structure were fine, narrowly distributed and well crystallized. The electrochemical performance test was carried out and the results showed that the as-prepared Zn-doped materials had not only a high capacity, but also a better cycling stability characterization than the un-doped one. The Li1.06Ni0.75Co0.22Zn0.03O2.03 material has an initial reversible capacity as high as 160.5mAh·g-1; and a first discharge efficiency 89.2%, and exhibits satisfactory cyclic stability with 90% retainable capacity after 50 cycles. 相似文献
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合成了Zr1-xMxWMoO8-x/2(M=Er,Tm,Yb,Sc,In,Ga,Al)和Zr1-xMxW2O8-x/2(M=Eu,Er,Yb,Sc,In,Ga,Al)2个系列的固溶体,前者具有β-ZrW2O8结构类型(简称β相);后者具有α-ZrW2O8结构类型(简称α相)。建立了相和相的晶胞参数与M3+离子浓度的Vegard方程,测定了上述固溶体的固溶度。讨论了M3+离子的化学性质与Vegard斜率SV的关系。分析了α相的SαA与β相的SβA的关系;揭示了α-Zr1-xMxW2O8-x/2晶格中2[WO4]四面体对的取向有序程度对晶格畸变的贡献。提出上述固溶体的晶胞参数随溶质浓度增加而减小,主要是由于氧空位缺陷相互作用的结果。 相似文献
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利用溶胶-凝胶分配理论对氢键溶液的模型体系进行研究, 给出了凝胶点后氢键网络中各结构参数的计算方案, 并进行相应的数值计算. 结果表明, 因受体基团本身的性质及两类质子受体基团的数量比不同, 受体基团的竞争作用对网络结构有明显影响, 这提供了控制氢键网络结构特征的可能方法. 相似文献
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采用高温固相法制备了4种高纯度晶相组成的LixZryOz三元化合物,研究了焙烧温度、时间、反应物的种类和初始反应物物质的量比对产物组成的影响,进一步用XRD、SEM及BET分析方法对产物的晶相结构、表面形貌及比表面积进行了表征.实验结果表明,Li2CO3与ZrO2在适当条件下可以合成得到单斜相Li3ZrO3;以LiOH替代Li2CO3,在适当条件下可以分别合成得到四方相Li2ZrO3和三斜/单斜相Li6Zr2O7;进一步以Zr(NO3)4·5H2O代替Zr02,可将单斜相Li6Zr2O7的制备时间由96 h缩短至24 h.SEM照片显示产物硬团聚明显,粒径分布在1~10μm间,BET分析表明样品比表面积处于1.0~9.0 m2·g-1间分布,反应过程中锂的过量以及长时间高温焙烧是引起产物粒径长大和产生硬团聚的主要原因. 相似文献
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钙钛矿型LaxSr1-xNi1-yCoyO3光电催化活性研究 总被引:8,自引:0,他引:8
用甘氨酸-硝酸盐燃烧合成法, 制备LaxSr1-xNi1-yCoyO3复合氧化物的陶瓷粉末, 对钙钛矿氧化物进行了XRD结构分析. 在通氧或不通氧下测试氧还原和氧析出的循环伏安曲线. 结果表明: 该氧电极具有双功能催化特性, 但不完全可逆. 利用汞灯作为激发光源, 进行几种水溶性染料和五种混合染料光解实验, 利用紫外-可见、红外以及人工神经网络光度法研究LaxSr1-xNi1-yCoyO3的催化性能. 结果表明: LaxSr1-xNi1-yCoyO3 (x=0.7, 0.9, 1; y=0.3, 0.75)复合氧化物都具有较强光催化特性; LaxSr1-xNi1-yCoyO3的光催化活性高于LaxSr1-xNiO3, 这与B位离子(Ni2—, Co2-)的电子构型有关; Co2+的加入可使LaxSr1-xNiO3的光催化活性有所提高. 相似文献
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Nataliya Melnychenko-Koblyuk Peter Rogl Harald Schmid 《Journal of solid state chemistry》2009,182(7):1754-1760
Phase relations at 700 °C, 800 °C and solidus temperatures have been derived for the clathrate system Ba8CuxGe46−x−y□y via X-ray single crystal and powder diffractometry combined with electron probe micro analysis and differential thermal analysis. The ternary clathrate phase derives from binary Ba8Ge43□3 and extends up to x=6. Structure investigations define cubic primitive symmetry with the space group type consistent with a clathrate type I structure throughout the entire homogeneity region 0<x?6 but defect-free Ba8CuxGe46−x exists for x?5.5. 相似文献
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采用改进的水热法成功合成了单分散的纯相锶铁氧体纳米片。借助DLS、XRD、FTIR、SEM、EDS和VSM等分析测试手段对SrFe12O19铁氧体粉体的粒度、结构、形貌和磁性能进行表征。研究结果表明,在240℃保温5 h,物质的量之比nFe3+/nSr2+(RF/S)和nOH-/nNO3-(RO/N)分别为5和2时,所得产物为单分散的纯相六角SrFe12O19铁氧体纳米片。随着RF/S和RO/N的变化,合成样品中有少量SrCO3和Fe2O3杂相存在,这主要与反应条件和离子比例有关。磁性能测试结果显示,所得纯相的六角SrF12O19铁氧体纳米片具有优异的磁性能,其饱和磁化强度和矫顽力分别达到60.91 emu·g-1和94.83 kA·m-1,使其在医疗、催化和生物等高技术领域具有潜在的应用。 相似文献
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将不同比例的铈锆前驱体负载到ZIF-67,氮气气氛焙烧制备CexZr1-xO2/Co/C-N催化剂,对催化剂进行了XRD,H2-TPR、XPS表征,并在固定床反应器评价其CO2加氢制甲醇性能。XRD结果表明,在铈中加入适量锆形成铈锆固溶体,铈锆固溶体与钴物种较强的相互作用力可以阻止表明金属Co的氧化。但过量加入的锆又会削弱这一作用力,部分金属Co被氧化为Co3O4。H2-TPR结果表明适量的锆的加入改善催化剂的还原性能,催化剂还原温度降低。XPS证实了25%Ce0.67Zr0.33O2/Co/C-N催化剂中含有更多的氧空穴及氮含量,氧空穴和碱性氮都有利于CO2的解离吸附。优化后的25%Ce0.67Zr0.33O2/Co/C-N 催化剂在225 oC,2 MPa,GHSV = 6 L/gcat/h反应条件下取得最高甲醇时空收率,为3.0 mmol/gcat/h。 相似文献
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采用改进的水热法成功合成了单分散的纯相锶铁氧体纳米片。借助DLS、XRD、FTIR、SEM、EDS和VSM等分析测试手段对SrFe12O19铁氧体粉体的粒度、结构、形貌和磁性能进行表征。研究结果表明,在240℃保温5 h,物质的量之比nFe3+/nSr2+(RF/S)和nOH-/nNO-(RO/N)分别为5和2时,所得产物为单分散的纯相六角SrFe12O19铁氧体纳米片。随着RF/S和RO/N的变化,合成样品中有少量SrCO3和Fe2O3杂相存在,这主要与反应条件和离子比例有关。磁性能测试结果显示,所得纯相的六角SrF12O19铁氧体纳米片具有优异的磁性能,其饱和磁化强度和矫顽力分别达到60.91 emu·g-1和94.83 kA·m-1,使其在医疗、催化和生物等高技术领域具有潜在的应用。 相似文献
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采用微波溶剂热法成功制备直接Z型Zn_2SnO_(4-x)N_x/ZnO_(1-y)N_y核壳结构异质结光催化剂。2种物质不同的功函数改变了其表面电荷密度,并在界面处形成内建电场,导致其从传统的Ⅰ型镶嵌异质结转变为Ⅱ型异质结,再转变为Z型异质结构。N杂质原子替代O原子进入Zn_2SnO_4和ZnO的晶格,在两者的价带(VB)顶部形成双杂质能级。核壳结构的Z型异质结光催化剂对罗丹明B的降解速率为纯相Zn_2SnO_(4-x)N_x的1.40~1.43倍,同时具有良好的循环稳定性,且可以降解亚甲基蓝、甲基橙、水杨酸等污染物。Z型异质结的形成使其光生电子-空穴对具有较强的氧化还原能力,而双杂质能级的存在可以拓宽其光响应范围并提高载流子的分离效率。因此,Zn_2SnO_(4-x)N_x/ZnO_(1-y)N_y异质结光催化剂高的光催化活性归因于Z型异质结和双杂质能级的协同作用。 相似文献
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The structures of compounds in the perovskite series Ba2LnSnxNb1−xO6−δ (Ln=Pr and Tb and x=0, 0.1, 0.2, …, 1.0) have been examined using synchrotron X-ray and neutron diffraction. It was found that niobate members of both series feature full B-site cation ordering but that this order is lost with increasing x. X-ray absorption near-edge structure (XANES) and near-infrared spectroscopies indicate that the oxidation state of the lanthanide cations gradually changes from Ln3+ to Ln4+ with increased Sn4+ doping. This is believed to be the cause of the loss of B-site ordering. Least squares analysis of the XANES spectra suggests that the rate of the transformation of Ln3+ cations to the tetravalent state is such that the Pr series contains no oxygen vacancies while the Tb series may contain a very small amount of vacancies, with δ≈0.02. 相似文献
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纳米钙钛矿LaxSr1-xFe1-yCoyO3复合氧化物的制备和表征 总被引:1,自引:0,他引:1
用甘氨酸-硝酸盐燃烧合成法,制备LaxSr1-xFe1-yCoyO3复合氧化物的陶瓷粉末,对该钙钛矿型氧化物进行了XRD、IR、紫外漫反射光谱及循环伏安曲线分析。结果表明:该复合氧化物粉体平均晶粒为15.3~29.8 nm,为立方和正交晶系。该氧电极具有双功能催化特性,但不完全可逆。对水溶液染料进行光解实验,利用紫外-可见、人工神经网络光度法研究LaxSr1-xFe1-yCoyO3的催化性能。结果表明:CO2+的加入可使LaxSr1-xFeO3的光催化活性有所提高,B位离子(Fe3+,CO2+)改变与加入,使LaxSr1-xFe1-yCoyO3(x=0.7,0.3;y=0.3,0.9,1)光催化活性高于LaxSr1-xFeO3。同时,对5种染料进行紫外光解,在0.75 h,脱色率大于91%,并为动力学一级反应。 相似文献
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多元掺杂尖晶石型Li1.02MxMn2-xQyO4-y正极材料的电化学特性 总被引:2,自引:0,他引:2
The effect of doping on the electrochemical performance was studied for spinel type Li1.02MxMn2-xQyO4-y used as cathode material in lithium-ion battery. TG/DTA curves of the precursor(the raw materials) doped with different elements were studied. The spinel materials Li1.02Mn2O4, Li1.02Co0.02Cr0.01La0.01Mn1.96F0.02O3.98, Li1.02Co0.02Cr0.01 La0.01Mn1.96Cl0.02O3.98, Li1.02Co0.02La1.02Mn1.97Cl0.02O3.98, Li1.02Co0.02Cr0.01Mn1.97O4, were prepared by solid-state reaction method after the pretreatment of conversion under low temperature and uniform mixing. X-ray diffraction patterns showed that all the samples had perfect spinel structure. SEM indicated that the particles of the samples had uniform size and were distributed evenly. The results of the charge/discharge curves showed that Li1.02Co0.02Cr0.01La0.01Mn1.96F0.02O3.98 had better performance than other materials according to the inhibition of decline of reversible capacity of spinel Li1.02MxMn2-xQyO4-y. Therefore, cycle performance had been improved so obviously that 93.9% of the initial capacity were preserved after 100 cycles. Furthermore, electrochemical impedance tests were carried out with the spinel Li1.02Co0.02Cr0.01La0.01Mn1.96F0.02O3.98 as working electrode, Lithium as counter electrode and reference electrode. Results showed that this material possessed good charge/discharge reversible capability and had the lowest impedance in 3.95~4.25 V range (on the stage of charge / discharge). 相似文献
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以Sm3+作为激活剂,Bi3+作为辅助激活剂,采用水热法合成Ca1-x-ySmxBiySiO3前驱体,然后在1 100 ℃焙烧得到系列橙红色荧光粉.用X-射线衍射仪、扫描电镜和荧光分光光度计和傅里叶变换红外光谱等手段对样品的组成、结构和形貌及其发光性质进行分析和表征.分析结果表明:产物都为三斜晶系结构的Ca1-x-ySmxBiySiO3和四方结构的方石英SiO2共熔体.在405 nm近紫外光激发下,产物的发射光谱由3个峰组成,发射峰值位于566、606和650 nm处,分别归属于Sm3+的4G5/2→6HJ/2(J=5,7,9)跃迁.产物的激发光谱在405 nm有很强的发射带,与近紫外LED芯片匹配.随着Sm3+掺量的增加,样品发光强度先增强后减弱,当Sm3+的物质的量分数为3%时发光强度达到最大,浓度猝灭机理为电偶极-电偶极相互作用.当Bi3+的物质的量分数在0.3%~1.5%时,对产物Ca0.97Sm0.03SiO3的荧光强度起敏化作用.Sm3+和Bi3+的最佳物质的量分数分别为3%和0.5%. 相似文献
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以堇青石蜂窝陶瓷为载体,CuxCe1-xO2-x/SBA-15为催化活性组分,制备了一系列10%~60%Cu0.5Ce0.5O1.5/SBA-15/堇青石和50%CuxCe1-xO2-x/SBA-15/堇青石(x=0~1)整体式催化剂,采用低温氮吸附-脱附、XRD、XPS和H2-TPR对催化剂进行了表征,在微型固定床反应器中评价了催化剂的CO催化氧化活性。结果表明:整体式催化剂仍然保持SBA-15的介孔结构,催化剂中除了堇青石的物相外,还有CuO和CeO2物相,催化剂表面的Cu以Cu2+和Cu+两种状态存在,Ce以Ce4+状态存在,催化剂表面的氧化还原性能与Cu0.5Ce0.5O1.5的含量和Cu、Ce的比例有一定的关系,50%Cu0.5Ce0.5O1.5/SBA-15/堇青石催化剂具有最好催化活性,CO可以在140℃完全转化。 相似文献
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E. Kandyel 《Journal of solid state chemistry》2008,181(11):3137-3144
A new series of Sr-based Hg-1212 superconducting cuprate (Hg1−ySey)Sr2(Y1−xCax)Cu2O6+δ (y=0.25; 0.0?x?0.7) have been successfully synthesized using a highly homogenous and reactive precursor Sr2(Y1−xCax)Cu2Oz prepared by the citrate sol-gel process. This chemical method is fast, cheap, reproducible and more efficient than the traditional solid-state reaction method. X-ray diffraction (XRD) and Energy dispersive X-ray analyses (EDX) studies have shown that Se is required for stabilization of the Sr-based Hg-1212 phase (Hg1−ySey)Sr2YCu2O6+δ; y≈0.25. On the other hand, electrical resistivity and magnetic susceptibility measurements indicated that substitution of Y by Ca is necessary to induce superconductivity in the 1212 (Hg0.75Se0.25)Sr2(Y1−xCax)Cu2O6+δ samples. Superconductivity is observed only for samples with x?0.3 and Tc increases with increasing Ca content as well as O2-annealing. A maximum Tc(onset) of 85 K is found in the (Hg0.75Se0.25)Sr2(Y0.3Ca0.7)Cu2O6.84 sample annealed in an oxygen atmosphere. The structure of O2-annealed samples was investigated by the Rietveld refinement. For all samples, it was found that Se substitutes at the Hg site. Each Se atom is surrounded by four oxygen atoms O(3), but these are not at the ideal site. Rather, these oxygen atoms are shifted along the [110] direction ((0.3989, 0.3989, 0) in the case of x=0.5), implying a four-fold split site with an occupancy of 0.22(2) for each of them. 相似文献