Sm_(0.5)Sr_(0.5)CoO_3阴极氧还原动力学

利用极化、交流阻抗技术考察了担载于La0.9Sr0.1Ga0.8Mg0.2O3(LSGM)电解质上的Sm0.5Sr0.5CoO3-La0.8Sr0.2Ga0.8Mg0.15Co0.05O3(SSC-LSGMC5)复合阴极的氧还原反应动力学.在SSC-LSGMC5阴极氧还原反应的阻抗谱中可以观察到明显的两个半圆.高频环的电导与氧分压无关,低频环的电导正比于氧分压的0.5次方.并且低频环的氧分压级数随着反应温度的降低而减小,可能对应于吸附氧原子的扩散过程.SSC-LSGMC5极化曲线与经典的Butler-Volmer方程吻合.阴、阳极的电荷转移系数均为1左右,交换电流密度的氧分压级数为1/4,对应于电荷转移过程.实验结果显示SSC-LSGMC5上的氧还原反应机制随反应条件的不同而发生变化.     

High performance and stability of double perovskite-type oxide NdBa_(0.5)Ca_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ) as an oxygen electrode for reversible solid oxide electrochemical cell

In this study,we successfully synthesized double perovskite-type oxide NdBa_(0.5)Ca_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(NBCCF) using a conventional wet chemical method as the oxygen electrode for reversible solid oxide electrochemical cells (RSOCs).The polarization resistance (R_p) of the composite electrode NBCCFGd_(0.1)Ce_(0.9)O_2 (GDC) is only 0.079Ωcm~2 at 800℃under air.The single cell based on NBCCF-GDC electrode displays a peak power density of 0.941 W/cm~2 in fuel cell mode and a low R_p value of 0.134Ωcm~2.In electrolysis cell mode,the cell displays an outstanding oxygen evolution reaction (OER) activity and shows current density as high as 0.92 A/cm~2 with 50 vol%AH (Absolute Humidity) at 800℃and applied voltage of 1.3 V.Most importantly,the cell exhibits admirable durability of 60 h both in electrolysis mode and fuel cell mode with distinguished reversibility.All these results suggest that NBCCF is a promising candidate electrode for RSOC.     

K-Ce_(0.5)Zr_(0.5)O_2催化碳颗粒物燃烧性能

用等体积浸渍法制备了不同K负载量的xKNO3-Ce0.5Zr0.5O2系列催化剂,用程序升温氧化反应(TPO)考察催化剂对碳颗粒物(soot)燃烧的催化活性.并采用XRD、BET、FT-IR、XPS等技术对KNO3负载催化剂进行表征.结果表明KNO3负载量对催化剂的比表面、表面化学环境有显著的影响;KNO3能使催化剂对soot的催化燃烧活性有较大提高,且存在最佳负载量,当x=0.5时,催化剂的活性最好,碳颗粒物的起燃温度(T)i和峰顶温度(Tp)分别为290℃和360℃.在反应过程中,KNO3熔融状态的形成和K2CO3的生成,使催化活性明显提高.     

Mössbauer spectra of (Fe0.5Zn0.5)PS3 and its pyridine intercalate

Mössbauer spectra of (Fe_0.5Zn_0.5)PS₃, which is isomorphous with FePS₃, were measured at 300 and 80 K, and were compared with those of FePS₃. We succeeded in preparing (Fe_0.5Zn_0.5)PS₃ intercalated with pyridine. In the XRD pattern of the intercalate the diffraction peaks corresponding to (Fe_0.5Zn_0.5)PS₃ were completely missing, suggesting that the intercalation was completely performed with pyridine. The Mössbauer spectra were changed significantly by the intercalation suggesting the charge transfer from guest molecules to the host matrix. The replacement of iron by zinc has no influence on the electronic state of the iron atom, except for the magnetic interaction.     

Open-framework Borophosphate:(NH4)_(0.5)Fe~II_(0.5)Fe~III_(0.5)(H_2O)_2BP_2O_8·0.5H_2O

We are investigating the synthesis and properties of a new class of open framework borophosphate solids with the goal of being able to use in optical devices and magnetic materials. Only a few open-framework ferric borophosphate compounds with a chiral tetraheda-tetraheda helices, KFe(H2O)2BP2O8)H2O(1), Fe(H2O)2BP2O8H2O(2), (NH4)0.4-FeII0.55FeIII0.5(H2O)[BP2O8]0.6H2O(3) have been reported by Boy et al.1, Ylmaze et al.2 and Huang and Schfer et al.3. However, Huang and Schfer et…     

Bi_(0.5)Na_(0.5)TiO_3的制备及光催化性能研究

以Bi(NO3)3·5H2O、Na OH、Ti(OC4H9)4为原料,采用水热法制备Bi0.5Na0.5Ti O3纳米光催化剂。用XRD、TEM表征了Bi0.5Na0.5Ti O3光催化剂的结构和形貌。以亚甲基蓝为模型污染物,考察了不同浓度的Na OH对Bi0.5Na0.5Ti O3晶体在紫外光和可见光照射下光催化活性的影响。通过荧光技术研究了Bi0.5Na0.5Ti O3光催化剂表面羟基自由基的生成,探究了清除剂对光催化降解污染物活性的影响。结果表明:Na OH的浓度对Bi0.5Na0.5Ti O3光催化剂的紫外光和可见光活性有很大的影响,当Na OH浓度为8mol·L-1时制备的Bi0.5Na0.5Ti O3晶体光催化活性最高,光照1h,亚甲基蓝的紫外及可见光催化降解率分别达到69.8%、53.4%,在光催化降解过程中·O2ˉ和·OH起主要作用,尤其是·O2-起了重要作用。     

Novel Ba_(0.5)Sr_(0.5)Fe_(0.8)Zn_(0.2)O_(3-δ) membranes for POM

A novel cobalt-free perovskite based on Ba_(0.5)Sr_(0.5)Fe_(0.8)Zn_(0.2)O_(3-δ)(BSFZ)were prepared by EDTA-citric acid method.The lattice constants of the BSFZ perovskite were characterized by in situ high-temperature X-ray diffraction(HTXRD).The thermal expansion coefficient of BSFZ is 10.5×10~(-6)K~(-1),which is lower than that of cobalt-based perovskite materials.The BSFZ membrane was also used to construct reactors for the partial oxidation of methane(POM)to syngas.Results show that the BSFZ membrane...     

THE PREPARATION,STRUCTURE AND PROPERTES OF Sr_(0.5)Ca(0.5)CuO_2

Sr_(0.5)Ca_(0.5)CuO_2 has been synthesized by the solid state reaction.Thecompound crystallizes in an orthorhombic unit cell,space group D_(2h)~(17)-Cmcmwith a=3.444 ,b=16.11 ,c=3.868 .It decomposes shove 1038℃.Sr_(0.5)Ca_(0.5)CuO_2 is s black p-type semiconductor with resistivity 53Ω.cmat room tempersture.     

KTa_(0.5)Nb_(0.5)O_3电子结构的第一性原理研究

用全电势线性缀加平面波法 (FLAPW )计算了KTa0 .5Nb0 .5O3 铁电相和顺电相的态密度、能带结构 .通过对两相态密度的对比分析我们发现在铁电相 ,钽原子的d电子和氧原子的 2p电子以及铌原子d电子与氧原子的 2p电子之间存在强烈的轨道杂化 ,对能带的分析也得出同样的结论 .这种轨道杂化对KTa0 .5Nb0 .5O3 铁电性的稳定有着重要的意义 .钽原子在四方铁电体KTa1 xNbxO3 中的作用与在纯钽酸钾中的作用有明显的差别 .     

La_(0.5)Na_(0.5)TiO_3纳米晶的制备及光致发光研究

以硬脂酸、硝酸镧、氢氧化钠和钛酸四丁酯为原料制备了La0 .5Na0 .5TiO3 纳米晶 ,粒度最小可达 1 4nm ,烧成温度为 50 0℃ ,低于传统固相反应的合成温度。光致发光研究表明 :用 392nm光作激发光 ,在室温下观察到了一个强的蓝光发射带 ,并且它的强度和半宽度随粒度发生明显变化。     

KTa_(0.5)Nb_(0.5)O_3电子结构的第一性原理研究

用全电势线性缀加平面波法（FLAPW）计算了KTa_(0.5)Nb_(0.5)O_3铁电相和 顺电相的态密度、能带结构。通过对两相态密度的对比分析我们发现在铁电相，钽 原子的d电子和氧原子的2p电子以及铌原子d电子与氧原子的2p电子之间存在强烈的 轨道杂化，对能带的分析也得出同样的结论。这种轨道杂化对KTa_(0.5)Nb_(0.5) O_3铁电性的稳定有着重要的意义。钽原子在四方铁电体KTa_(1-x)Nb_xO_3中的作 用与在纯钽酸钾中的作用有明显的差别。     

Relationship between oxygen content and superconductivity of Tl0.5Pb0.5Sr2CuOy(y≈5)

The electronic energy band structures of the Tl_0.5Pb_0.5Sr₂Cu0_y (y5) superconductor were calculated and the effect of the oxygen content on its electronic structures was studied in the present paper. The results show that the oxygen content has a great influence on its electronic structures. The moderate oxygen content causes the number of bands near the Fermi surface to increase and results in a sudden change in the densities of states at the Fermi level E _f. The influence of the oxygen content on the electronic structures is mainly due to the peroxide pairs in the unit cell. The lower or higher oxygen content results in the decrease in the number of bands near E _f and the densities of states at E _f, which is of no advantage to superconductivity.     

钙钛矿锰氧化物(La_(1-x)Gd_x)_(0.5)Sr_(0.5)MnO_3的磁电阻效应

采用传统的高温固相法制备了多晶样品(La1-xGdx)0.5Sr0.5MnO3(x=0,0.1,0.2,0.3,0.4),利用X射线衍射仪(XRD)、超导量子磁强计(SQUID)、标准四端引线法分别对样品结构、磁性、电性以及磁电阻效应进行了研究。研究表明:Gd的少量替代并没有引起结构变化;随着Gd含量的增加,所有样品的居里温度TC和金属-绝缘体转变温度Tp都降低了;在TC附近发现了磁电阻效应,同时在低温下发现了更大的磁电阻;并且Gd的少量替代可使磁电阻MR增大。     

La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3在乙醇水蒸气重整中催化性能研究

用共沉淀法制备了La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3钙钛矿氧化物催化剂,用XRD、SEM、TPR、TG等对La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3钙钛矿氧化物的晶相结构、还原性能及反应50 h后的La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3钙钛矿氧化物表面积碳情况进行了分析,同时用微反色谱装置在不同的反应温度条件下的La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3钙钛矿氧化物的初活性、氢气平均选择性和积碳性能进行了探讨。结果表明,La_(0.5)Pr_(0.5)Ni_(0.7)Co_(0.3)O_3钙钛矿氧化物在乙醇水蒸气重整反应中具有较好的低温初活性和氢气的选择性,乙醇的平均转化率和氢气的选择性随着反应温度的升高而增大。当温度大于550℃时,转化率增幅不大,氢气的平均选择性在600℃时有所下降。反应温度升高催化剂的积碳量有所增多,积碳主要是不定型碳。     

Synthesis and Crystal Structure of Triacetyltribenzyl-Hexaazaisowurtzitane (TATBIW·0.5 H)_2O)

The hexanitro hexaaza isowurtzitane (HNIW) (2, 4, 6, 8, 10, 12-hexanitro-2, 4, 6, 8, 10,12-hexaazatetracyclo-[5.5.0.05,9.03,11]-dodecane), more commonly called CL-20, be-longs to the family of high energetic dense caged nitramines. It was first synthesized byA.T.Nielsen in 19871. HNIW is superior to HMX with respect to density, velocity,detonation pressure and enthalpy of formation. Based on cylinder expansion andtantalume plate acceleration experiments, the HNIW was found to be appr…     

Pd/CuO-Ce_(0.5)Mn_(0.5)O_2催化氧化合成葡萄糖醛酸及其内酯

用柠檬酸络合法制备了掺杂铈锰复合金属氧化物载体,采用沉淀法负载活性组分钯得到催化剂Pd/CuO-Ce0.5Mn0.5O2,用XRD、SEM和XPS对催化剂结构进行了表征分析,考察了不同CuO掺入量对葡甲苷的伯羟基选择氧化合成葡萄糖醛酸及其内酯的催化活性的影响。结果表明,CuO的掺入对载体的孔结构及活性组分在载体表面的分散都得到了不同程度的改善;Ce-Cu-Mn的协同作用有利于提高Pd的氧化还原性能。当CuO添加量为9%及Pd负载量为0.5%时,葡萄糖醛酸及其内酯的总收率可达70%。     

Dynamic isomer shift in charge-ordering manganite Y(0.5)Ca(0.5)MnO(3): Mössbauer spectroscopy study

We report the M?ssbauer spectroscopy study on Fe-doped charge-ordering manganite Y(0.5)Ca(0.5)MnO(3). The dynamic isomer shift is observed for charge-ordering manganite, and its origin may be due to strong Jahn-Teller distortions in Y(0.5)Ca(0.5)MnO(3), causing electron-phonon coupling. The evolution of M?ssbauer spectroscopy as a function of temperature shows two different phases with significantly different quadrupole splitting values below the charge-ordering transition temperature. This confirms that there exist two different Mn sites (i.e., Mn(3+) and Mn(4+) ions), which can be identified by the microscopic method of M?ssbauer spectroscopy.     

Role of Microstructure and Spectrum Features on the Catalysis Effect of Ce_(1-x)(Nd_(0.5)Eu_(0.5))_xO_(2-δ) Solid Solutions

Nanosized Ce_(1-x)(Nd_(0.5)Eu_(0.5))xO_(2-δ) solid solutions(x = 0.00~0.20) were synthesized by means of hydrothermal method.Then the solid solutions were ball milled with Mg_2Ni and Ni powders for 20 h to get the Mg_2Ni–Ni–5 mol% Ce_(1-x)(Nd_(0.5)Eu_(0.5))xO_(2-δ) composites.The structures and spectrum characteristics of the Ce_(1-x)(Nd_(0.5)Eu_(0.5))xO_(2-δ) solid solutions catalysts were analyzed systemically.XRD results showed that the doped samples exhibited single phase of CeO_2 fluorite structure.The cell parameters and cell volumes were increased with increasing the doped content.Raman spectrum revealed that the peak position of F_(2g) mode shift to higher wavenumbers and the peak corresponding to oxygen vacancies were observed distinctly for the doped samples.UV-Vis technique indicated that the absorption peaks of Eu~(3+) and Nd~(3+) ions appeared; the bandgap energy was decreased linearly.The electrochemical and kinetic properties of the Mg_2Ni–Ni–5 mol% Ce_(1-x)(Nd_(0.5)Eu_(0.5))xO_(2-δ) composites were measured.The maximum discharge capacity was increased from 722.3 mA h/g for x = 0.00 to 819.7 mA h/g for x = 0.16,and the cycle stability S_(20) increased from 25.0%(x = 0.00) to 42.2%(x = 0.20).The kinetic measurement proved that the catalytic activity of composite surfaces and the hydrogen diffusion rate were improved for the composites with doped catalysts,especially for the composites with x = 0.16 and x = 0.20.The catalysis mechanism was analyzed from the point of microstructure and spectrum features of the Ce_(1-x)(Nd_(0.5)Eu_(0.5))xO_(2-δ) solid solutions.     

Hydrothermal Synthesis of Pb_(1-1.5x)La_xZr_(0.5)Ti_(0.5)O_3 (x = 0.01-0.06) Nanocrystallites

Lanthanum doped lead zirconate titanate (PLZT) ceramics display excellent electrooptic and photostriction properties because of the existence of cavities in the perovskite structure1-3. The PLZT powders are conventionally prepared by solid state reaction4-5, and the wet chemical methods such as sol-gel techniques are then introduced6-7. However, the homogeneity, morphology and size of the particles, which greatly affect the sinterability and the property of the resulting ceramics, are dif…     

Synthesis and Crystal Structure of Tetraacetyldiazidoacetyl-hexaazaisowurtzitane (C_(18)H_(22)N_(12)O_6·0.5CH_3COCH_3)

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