钴(Ⅲ)-胺配合物模板导向合成新型草酸盐化合物[Co(dien)2][NaCO2(C2O4)4]·H20

以Co(dien)2·Cl3为模板剂,在水热条件下导向合成出新型草酸盐化合物[Co(dien)2]·[NaC02(C2O4).].H2O,并通过X射线单晶结构分析、元素分析、ICP以及X射线粉末衍射分析对该化合物的结构进行了表征.结果表明,该化合物结构属于单斜晶系,C2/c空间群,晶胞参数a=1.3805(3)nm,b...     

Crystal Structure of Borophosphate with 6_1 Screw Axis Helices

1 INTRODUCTION Most materials with nonlinear optical pro- perties and electro-optical applications are either borates or phosphates. LBO(LiB3O5), KTP(KtiO- PO4), BBO(b-BaB2O4) and KDP(KH2PO4) are well- known commercially and extensively used for different optical elements. In recent years, the compounds combined both borate and phosphate groups have been synthesized and structurally characterized with quite different anionic partial structures. In particular, the use of hydrot…     

Di- and tricobalt Dawson sandwich complexes: synthesis,spectroscopic characterization,and electrochemical behavior of Na(18)[(NaOH(2))(2)Co(2)(P(2)W(15)O(56))(2)] and Na(17)[(NaOH(2))Co(3)(H(2)O)(P(2)W(15)O(56))(2)

The reaction of the trivacant Dawson anion alpha-[P(2)W(15)O(56)](12-) and the divalent cations Co(2+) is known to form the tetracobalt sandwich complex [Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-) (Co(4)P(4)W(30)). Two new complexes, with different Co/P(2)W(15) stoichiometry, [(NaOH(2))(2)Co(2)(P(2)W(15)O(56))(2)](18-) (Na(2)Co(2)P(4)W(30)) and [(NaOH(2))Co(3)(H(2)O)(P(2)W(15)O(56))(2)](17-) (NaCo(3)P(4)W(30)), have been synthesized as aqueous-soluble sodium salts, by a slight modification of the reaction conditions. Both compounds were characterized by IR, elemental analysis, and (31)P solution NMR spectroscopy. These species are "lacunary" sandwich complexes, which add Co(2+) cations according to Na(2)Co(2)P(4)W(30) + Co(2+) --> NaCo(3)P(4)W(30) + Na(+) followed by NaCo(3)P(4)W(30) + Co(2+) --> Co(4)P(4)W(30) + Na(+). A Li(+)/Na(+) exchange in the cavity was evidenced by (31)P dynamic NMR spectroscopy. The electrochemical behaviors of the sandwich complexes [(NaOH(2))Co(3)(H(2)O)(P(2)W(15)O(56))(2)](17-) and [(NaOH(2))(2)Co(2)(P(2)W(15)O(56))(2)](18-) were investigated in aqueous solutions and compared with that of [Co(4)(H(2)O)(2)(P(2)W(15)O(56))(2)](16-). These complexes showed an electrocatalytic effect on nitrite reduction.     

Li_3PO_4包覆LiMn_2O_4正极材料的结构表征和电化学性能

采用共沉淀法在尖晶石LiMn2O4颗粒表面包覆Li3PO4.XRD、SEM研究结果表明,包覆后的材料仍为尖晶石结构,粒径均匀.电化学性能测试表明,Li3PO4包覆层的存在,减少了正极材料与电解液的直接接触,抑制了高温下电解液对LiMn2O4材料的侵蚀,从而有效改善了高温下材料的循环性能.在40℃时,包覆样品的比容量衰减率都低于未包覆样品,其中包覆1%Li3PO4的样品的初始比容量为110.4mAh/g,50次循环后比容量为84.1mAh/g.     

Pt/Co3O4/3DOM Al2O3：甲苯燃烧的高效催化剂

与硫氧化物、氮氧化物、一氧化碳以及悬浮颗粒一样,大部分挥发性有机物(VOCs)污染大气环境.控制 VOCs排放有多种方法,其中催化氧化法是一种有效技术,关键在于获得高效催化剂.
　　近年来,负载过渡金属和贵金属催化剂因具有比单纯负载贵金属和单纯负载过渡金属氧化物更好的催化性能而备受关注.在负载贵金属催化剂中,高比表面积载体负载 Pt, Pd或 Rh催化剂得到广泛而深入的研究,尽管这些催化剂成本较高,但是其对 VOCs氧化反应显示了很高的低温催化活性.众所周知,催化活性取决于贵金属和 VOCs的种类,不同负载贵金属催化剂对特定反应会表现出不同的催化活性.负载 Pt催化剂对长链碳氢化合物和芳香族化合物氧化反应表现出更高的活性.相对于负载贵金属催化剂,负载过渡金属氧化物催化剂不仅具有良好的氧化活性,而且价格低廉.迄今已发现许多过渡金属氧化物(如 Co3O4, Cr2O3和 MnO2等)对典型 VOCs氧化反应具有催化活性,其中 Co3O4的催化活性尤为突出.研究表明, Co3O4的性质和分散度是决定其性能的关键因素,制备方法、载体性质和过渡金属氧化物负载量对 Co3O4的物化性质具有重要影响,而且在负载 Pt催化剂中添加金属氧化物能改善其催化性能.尽管多孔氧化铝是一种常用的载体材料,但目前尚无文献报道三维有序大孔-介孔氧化铝负载 Co3O4和 Pt纳米粒子催化剂的制备及其对甲苯氧化反应的催化性能.
　　本文采用聚甲基丙烯酸甲酯微球胶晶模板法、等体积浸渍法和聚乙烯醇保护的硼氢化钠还原法制备了三维有序大孔-介孔(3DOM Al2O3)负载 Co3O4和 Pt (xPt/yCo3O4/3DOM Al2O3, Pt的质量分数(x%)为0-1.4%, Co3O4的质量分数(y%)为0-9.2%)纳米催化剂.通过电感耦合等离子体原子发射光谱、X射线衍射、氮气吸附-脱附、扫描电子显微镜、透射电子显微镜、选区电子衍射、X射线光电子能谱及氢气程序升温还原等技术表征了催化剂的物化性质,利用固定床微型石英反应器评价了催化剂对甲苯氧化反应的催化活性.结果表明,xPt/yCo3O4/3DOMAl2O3催化剂具有多级孔结构(大孔孔径为180–200 nm,介孔孔径为4–6 nm),比表面积为94?102 m2/g.粒径为18.3 nm的 Co3O4纳米粒子和粒径为2.3?2.5 nm的 Pt纳米粒子均匀分散在3DOM Al2O3表面.在xPt/yCo3O4/3DOM Al2O3催化剂中,1.3Pt/8.9Co3O4/3DOM Al2O3拥有最高的 Oads浓度、最好的低温还原性和最高的甲苯氧化反应催化活性(当空速为20000mL g–1 h–1时,甲苯转化率达90%的反应温度为160oC).基于催化剂的活性数据和结构表征,我们认为,1.3Pt/8.9Co3O4/3DOM Al2O3优异的催化性能与其高分散的 Pt纳米粒子、高的 Oads浓度、好的低温还原性、Pt和 Co3O4纳米粒子间的强相互作用以及多级孔结构相关.     

长寿命、高倍率(Li4Ti5O12-AC)/( LiMn2O4-AC)电池电容的制备及性能研究

以商业微米级锰酸锂(LiMn2O4)为正极,钛酸锂(Li4Ti5O12)为负极,分别与商业活性炭(AC)复合,组装成软包装电池电容样品并进行电化学测试。测试结果表明：当样品正负极均复合AC时,其电化学性能要优于只有正极复合AC和未复合AC的样品。其中,正负极活性炭复合比例为5 wt.%,负极与正极的理论容量比(N/P)为1.01时,电池电容样品拥有良好的倍率性能,且其在0.5 C时的放电比容量为56.4 mAh/g,5 C时的容量保持率为0.5 C的72.2%。此外,与未复合AC的样品相比,单体在5 C倍率下经2000次循环后的容量保持率仍有77.5%,远高于前者的30.4%。     

Co3O4/CeO2的氧化还原性能及反应条件对其CO氧化活性的影响

采用沉淀氧化法制备了Co₃O₄/CeO₂催化剂。运用XRD、BET和TPR表征手段,考察了不同钴铈比及焙烧温度对钴铈复合氧化物物理及化学性能的影响,并分别在干、湿条件下进行了一氧化碳氧化反应研究。结果表明,与纯的Co₃O₄相比,在不同比例的Co₃O₄/CeO₂均经723 K焙烧的各种催化剂中,钴铈原子比为9∶1的复合氧化物粒径较小,比表面积较大,说明适当比例铈的添加能使Co₃O₄具有较小的粒径。此氧化物经538 K温度焙烧制得的钴铈比为9∶1的复合氧化物中Co₃O₄平均粒径为7.2 nm, BET比表面积为167.6 m²/g。经TPR考察发现其具有最优的氧化还原性能。     

Mixed-metal sandwich complexes [M(II)2(H2O)2Fe(III)2(P2W15O56)2]14- (M(II) = Co, Mn): synthesis and stability. The molecular structure of [M(II)2(H2O)2Fe(III)2(P2W15O56)2]14-

Two new mixed-metal sandwich complexes [M(II)2(H2O)2Fe(III)2(P2W15O56)2]14- (abbreviated [M2Fe2P4W30], M(II) = Co(II), Mn(II)) were obtained at pH 3 by addition of M2+ to [Na2(H2O)2Fe(III)2(P2W15O56)2]16- (abbreviated [Na2Fe2P4W30]) without substitution in the alpha-[P2W15O56]12- (abbreviated [P2W15]) units. Their X-ray structures are reported. At lower pH, back conversion to [Na2Fe2P4W30] was followed by 31P NMR, electrochemistry and UV-visible spectroscopy. The preparation and the characterization in solution of the lacunary intermediate [NaCo(II)(H2O)2Fe(III)2(P2W15O56)2]15- (abbreviated [NaCoFe2P4W30]) is also described.     

有序介孔碳负载NiCo2O4电极的制备及其超电容性能

以有序介孔碳(OMC)为载体,采用共沉淀法制备了OMC/NiCo2O4复合物.用X射线衍射(XRD)、傅里叶变换红外(FT-IR)光谱和透射电镜(TEM)研究其结构与形貌,发现NiCo2O4纳米颗粒均匀地负载在有序介孔碳上.循环伏安和恒流充放电测试表明,NiCo2O4质量分数为40%时,在1A·g-1的电流密度下,复合物电极的比电容可以达到577.0F·g-1,电流密度为8A·g-1时,比电容可以达到470.8F·g-1,并具有良好的循环稳定性.在2A·g-1的电流密度下,经过2000次循环后,比电容还可达到508.4F·g-1,电容保持率为92.7%.     

负极材料Li_4Ti_5O_(12)的蔗糖改性研究

以蔗糖为碳源,采用固相法合成了C改性的Li4Ti5O12材料.XRD衍射分析表明,C的引入没有改变Li4Ti5O12的尖晶石结构,且缓解了颗粒间的团聚,并以初始蔗糖含量为10%(by mass)样品的电化学性能最佳.0.2C放电倍率下首次放电比容量达179.1 mAh/g,在2C和3C倍率下首次放电比容量仍达143.8 mAh/g和129.4 mAh/g.循环伏安和电化学阻抗测试显示改性后的Li4Ti5O12材料电极极化程度较小,并且具有较小的电极反应阻抗.     

层状钒青铜纳米片的制备及其锂离子电池阳极材料性能

室温下, 在水溶液中将铵根离子和水分子插入到商用V₂O₅纳米颗粒的层间, 制得了层状的钒青 铜[(NH₄)₂V₆O₁₆·H₂O]纳米片. 该纳米片的尺寸为2~10 μm, 厚度为50~250 nm. 与商用V₂O₅纳米颗粒相比, (NH₄)₂V₆O₁₆·H₂O纳米片用作锂离子电池(LIBs)的阳极材料时, 其性能得到较大提升, 包括大的可逆放电容量 (0.1 A/g时为1148 mA·h/g)、 出色的循环性能(循环70圈后在0.1 A/g时具有1002 mA·h/g的高容量)和高倍率性能(在0.1 A/g时具有1070 mA·h/g的可逆性能). 研究结果表明, (NH₄)₂V₆O₁₆·H₂O纳米片可以作为锂离子电池优良的阳极材料, 也有望应用于其它(如钠离子电池和锌离子电池等)可再充电电池.     

Sodium cobalt aminomethylidenediphosphonate with a novel open framework structure

This paper reports the synthesis and crystal structure of a cobalt aminomethylenediphosphonate compound NaCo(2)[NH(3)CH(PO(3))(PO(3)H(0.5))](2)(H(2)O)(2).xH(2)O (1). It shows a novel open framework structure in which layers of Co(2)[NH(3)CH(PO(3))(PO(3)H(0.5))](2)(H(2)O)(2) are connected by NaO(6) linkages. The magnetic studies show a dominant antiferromagnetic exchange between the Co(II) ions.     

Synthesis,structural, and electrochemical properties of NaCo(PO<Subscript>3</Subscript>)<Subscript>3</Subscript> cathode for sodium-ion batteries

A new Co-base sodium metaphosphate compound, NaCo(PO₃)₃, has been synthesized here by solid-state method. The crystal structure is refined by the Rietveld method, and the results reveal that NaCo(PO₃)₃ has an orthorhombic structure with the space group of P2 ₁ 2 ₁ 2 ₁ and lattice parameters of a = 14.2453(2) Å, b = 14.2306(1) Å, and c = 14.2603(2) Å. Its typical morphology and chemical composition are confirmed by scanning electron microscopy (SEM) and energy-dispersive spectrometry (EDS). The valence states of all elements and the internal/external vibrational modes of NaCoP₃O₉ compound are measured by X-ray photoelectron and vibrational spectrum, where a typical feature of the (PO₃)^? polyanion group is observed. Meanwhile, the electrochemical properties of NaCo(PO₃)₃ cathode for sodium-ion batteries are also elevated and an initial discharge capacity of 33.8 mAh/g can be obtained at 0.05 C within 1.5–4.2 V. After 20 cycles, a discharge capacity of 26.7 mAh/g can be obtained and a well-kept oxidation–reduction plateau is still observed for NaCo(PO₃)₃ cathode, indicating the good reversibility of this metaphosphate electrode.     

Electrochemical insertion of magnesium ions into V2O5 from aprotic electrolytes with varied water content

The electrochemical performance of V2O5 has been studied in propylene carbonate (PC)-containing magnesium perchlorate [Mg(ClO4)2] electrolytes in view of their application as positive electrode in the rechargeable magnesium batteries. V2O5 exhibited good properties in hosting magnesium ions and its electrochemical performance depended on the amount of H2O in the electrolytes. The highest first discharge specific capacities of V2O5 electrode was up to 158.6 mAh/g in 1 mol dm(-3) Mg(ClO4)2 + 1.79 mol dm(-3) H2O/PC electrolytes. Electrochemical impedance spectroscopy (EIS) and charging-discharging tests showed that a reasonable amount of H2O in the electrolyte solution facilitated the electrochemical performance of V2O5 electrodes.     

分子印迹磁性固相萃取/液相色谱法检测奶制品中的双酚A

以双酚A(BPA)为模板分子,磁性二氧化硅(Fe_3O_4@SiO_2)为载体,4-乙烯基吡啶(4-VP)为功能单体,采用表面分子印迹技术制备了双酚A磁性分子印迹聚合物微球(Fe_3O_4@SiO_2-MIPs)。通过红外光谱、透射电镜等对Fe_3O_4@SiO_2-MIPs进行了结构和形貌的表征。将制得的Fe_3O_4@SiO_2-MIPs作为磁性吸附剂,分离富集奶制品中的BPA,建立了分子印迹磁性固相萃取/液相色谱法测定奶制品中BPA的新方法。结果表明,在优化条件下,Fe_3O_4@SiO_2-MIPs对BPA具有良好的选择性,最大吸附容量达13.50 mg/g,在0.05~5.0 mmol/L浓度范围内有良好的线性关系(r2=0.993 4),方法检出限为0.037μg/L,样品加标回收率为86.2%~93.1%,相对标准偏差为2.9%~3.8%。该方法高效快速,选择性好,可用于牛奶样品中痕量BPA的检测。     

锂离子电池新型快充负极材料Li4Ti5O12的改性研究

采用传统固相法制备尖晶石型Li4Ti5O12, 在前驱物中掺杂聚合物裂解碳材料聚并苯(PAS). 经四探针测试仪测量, 电导率提高9个数量级. 复合物的电化学性能测试结果表明, 其循环性和高倍率性能得到了明显改善.     

Magnetization-induced double-layer capacitance enhancement in active carbon/Fe3O4 nanocomposites

The effects of magnetic fields on electrochemical processes have made a great impact on both theoretical and practical significances in im-proving capacitor performance. In this study, active carbon/Fe...     

NF/rGO/Co_3O_4/NiO电极的制备及在超级电容器中的应用

以泡沫镍(NF)为集流体,在优化好的电位、时间和浓度下,将还原氧化石墨烯(rGO)、金属氧化物(Co_3O_4和NiO)直接生长在泡沫镍上,制备了NF/rGO/Co_3O_4和NF/rGO/Co_3O_4/NiO电极.运用三电极体系对电极材料进行了恒流充放电(GCD)和交流阻抗(EIS)等测试.结果表明,复合材料NF/rGO/Co_3O_4/NiO具有较高的比容量(电流密度为2 A/g时,比容量达到1188.6 F/g)和较好的循环稳定性(2000周充放电后,稳定性达到80.5%).该材料还具有较高的倍率性能,当电流密度由2 A/g增至12 A/g时,倍率性能仍能达到75.7%.     

Magnetization-induced double-layer capacitance enhancement in active carbon/Fe_3O_4 nanocomposites

The effects of magnetic fields on electrochemical processes have made a great impact on both theoretical and practical significances in improving capacitor performance. In this study, active carbon/Fe3O4-NPs nanocomposites(AC/Fe3O4-NPs) were synthesized using a facile hydrothermal method and ultrasonic technique. Transmission electron micrographs(TEM) showed that Fe3O4nanoparticles(Fe3O4-NPs) grew along the edge of AC. AC/Fe3O4-NPs nanocomposites were further used as an electrochemical electrode, and its electrochemical performance was tested under magnetization and non-magnetization conditions, respectively, in a three-electrode electrochemical device. Micro-magnetic field could improve the electric double-layer capacitance, reduce the charge transfer resistance, and enhance the discharge performance. The capacitance enhancement of magnetized electrode was increased by 33.1% at the current density of 1 A/g, and the energy density was improved to 15.97 Wh/kg, due to the addition of magnetic particles.     

Synthesis of a polyester macromonomer via the cobalt-catalyzed alternating copolymerization of propylene oxide and carbon monoxide

The alternating copolymerization of propylene oxide and carbon monoxide was investigated with cobalt complexes. The NaCo(CO)₄/amine catalyst system selectively yielded oligo(3-hydroxybutyrate)s bearing a polymerizable crotonate end group, whereas the use of Co₂(CO)₈ as a cobalt source resulted in a smaller concentration of the crotonate end group and a high degree of polymerization. The high selectivity for the oligoesters with the crotonate end group with the NaCo(CO)₄/amine system was attributed to its more basic reaction condition. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4666–4670, 2004