新型超大容量电容器电极材料—纳米水合MnO_2的研究

本文用KMnO4氧化MnSO4制得纳米水合MnO2粉末。以该粉末作为活性物质制成电极分别在物质的量浓度为0.1mol·L-1的Na2SO4、0.5mol·L-1的Na2SO4、2.0mol·L-1的NH42SO4水溶液中在0.0～0.85VSCE电位范围内用循环伏安考察电极的电容性能循环伏安结果表明该材料在0.5mol·L-1Na2SO4水溶液中表现出良好的电容性能用恒流充放电测得其比容量可达177.5F·g-1。经5000次循环电极容量保持90%以上。     

MnO2电沉积直立碳纳米管制备超级电容器

以直立碳纳米管为基底,以pH=6.0的0.1 mol/L Na2SO4为底液,采用电化学沉积法在0.2 mol/L Mn(CH3COO)2溶液中制备了直立碳纳米管与MnO2复合材料. SEM测试结果表明,复合材料表面呈现多孔状结构. 通过循环伏安、恒流充放电、交流阻抗等电化学方法对复合材料修饰电极进行电容性质测试. 结果表明,在1 mol/L KCl溶液中,0～0.6 V(vs.Ag/AgCl参比)电位窗口内此复合材料表现出优良的超电容性能. 直立碳纳米管电极的比电容为16 F/g,在碳纳米管表面沉积上MnO2修饰层后,复合材料电极的比电容增大至330 F/g,比电容量大幅提升近20倍. 同时扫描200圈后,直立碳纳米管与MnO2复合材料的循环伏安曲线变化很小,具有相当好的循环寿命和电容稳定性能.     

IrO2电极在含有机小分子水溶液中的电化学活性

通过循环伏安（CV）与电化学阻抗谱（EIS）测试研究了Ti基IrO2系活性涂层电极在含甲醇、甲酸及甲醛三种有机小分子的Na2SO4溶液中的电化学活性,其中以电极/溶液界面的双电层电容来表征电极的活性.结果表明,与同浓度H2SO4溶液相比,该电极在Na2SO4溶液中的电化学活性发生明显下降.有机小分子的加入降低了电极的活性表面积.发现有机物能在较宽的电位范围内发生氧化反应,但在该种电极上的电氧化速率较慢.然而,伴随着析氧反应的发生,有机物的氧化也随之加快.     

MnO2电沉积直立碳纳米管制备超级电容器的研究

以直立碳纳米管为基底,以pH=6.0的0.1mol/L Na2SO4 为底液,采用电化学沉积法在0.2 mol/L Mn(CH3COO)2溶液中制备了直立碳纳米管与二氧化锰复合材料。SEM测试结果表明复合材料表面呈现多孔状结构。通过循环伏安,恒流充放电,交流阻抗等电化学方法对复合材料修饰电极进行电容性质测试。实验结果表明,在1mol/L KCl 溶液中,0-0.6V(vs. 银/氯化银参比)电位窗口内此复合材料表现出优良的超电容性能。直立碳纳米管电极的比电容为16 F/g,在碳纳米管表面沉积上二氧化锰修饰层后,此复合材料电极的比电容增大至330 F/g,比电容量大幅提升近20倍。同时扫描200圈后,直立碳纳米管与二氧化锰复合材料的循环伏安曲线变化很小,说明其具有相当好的循环寿命和电容稳定性能。     

α-MnO2微球的制备及其电化学电容性质

以Ag片作催化剂在室温下制备了具有较高比表面积(177m2/g)的电化学电容器材料MnO2。XRD测试和SEM分析表明,所制备的MnO2为纳米纤维组成的仙人球状微球结构的α-MnO2。交流阻抗、循环伏安、恒流充放电和循环寿命等电化学测试均表明,所合成的α-MnO2微球在1mol/LNa2SO4水溶液中具有良好的电化学电容性能,单电极比电容可达187.1F/g,经1000次循环后电极容量仍保持在90%以上。     

喷墨打印法制备MnO2薄膜电极的超电容性能

在碱性条件下用KMnO4氧化MnSO4制备得到粒径约小于200 nm 的MnO2微粒. 将MnO2粉末、乙炔黑、分散剂Lomar-D、粘度控制剂乙醇胺、粘结剂羧甲基纤维素钠(CMCS)及去离子水按质量比200:40:4:1:1:4000混合, 超声分散得到稳定的“墨水”体系. 用计算机喷墨打印得到MnO2超薄电极. SEM测试结果表明电极表面均匀, 厚度约为2.5 μm. 循环伏安法和恒电流充放电实验结果表明, 在1 mol·L-1 Li2SO4溶液中, 电位区间为0-0.85 V(vs SCE)内MnO2超薄电极表现出优良的超电容性能. 在以9.4 A·g-1充放电时, MnO2超薄电极的放电比电容为154 F·g-1, 循环2000周后, 电容量几乎不变.     

对甲苯磺酸掺杂聚(苯胺/中性红)复合物的乳液聚合法制备及电化学电容行为

以对甲基苯磺酸(TSA)为掺杂剂和乳化剂,过硫酸铵(APS)为引发剂,采用现场乳液聚合方法合成了对甲基苯磺酸掺杂聚(苯胺/中性红)复合材料(TSA-PANI/PNR).利用X射线衍射(XRD)和电子扫描显微镜(SEM)对共聚物复合材料的结构和形貌进行了分析和表征.以此复合材料为活性物质制备电极,以l mol/LH2SO4水溶液为电解液组装超级电容器,通过恒电流充放电、循环伏安和交流阻抗等技术研究了其电化学性能.研究结果表明,TSA-PANI/PNR电极具有比TSA/PANI更优良的电化学性能.扫描速度为1 mV/s的循环伏安曲线计算结果表明,其单电极比电容可达到1350 F/g,而TSA/PANI在相同的扫速下其单电极比电容仅为1038 F/g;在5 mA放电电流下,TSA-PANI/PNR组装的电容器首次充放电比电容可达到348 F/g,1000次循环后容量保持87%.     

单扫描示波极谱法测定巯基乙酸的研究

在H2SO4－NH4OAc(pH3．5）溶液中，巯基乙酸有一灵敏的还原波。当使用单扫描极谱法时，其二阶导数峰电位位于－0．320V（vs.SCE)。用直流极谱法，单极描极谱法和循环伏安法研究了该体系的极谱行为和电极反应机理。结果表明，当使用单扫描极谱法时，该体系属于有吸附性的准可逆过程，测得电极反应电子转移数n=1,H^ ，反应数n′＝1。用单扫描极谱法可测定巯基乙酸，测定的线性范围为0.04-2.0mg.L^-1，该方法用于冷烫液中巯基乙酸的测定，结果满意。     

超级电容器纳米氧化锰电极材料的合成与表征

以聚乙二醇为分散剂 ,利用高锰酸钾和醋酸锰溶液之间的化学共沉淀法制备纳米水合氧化锰 .借助SEM ,TEM ,FT IR ,XRD和BET分析手段对样品结构及性能进行表征 .研究结果表明 ,SEM和TEM显示所得粉体为纳米粉体 ,粒径大约为10～ 3 0nm左右 ,XRD分析表明该粉体为无定型α MnO2 ·nH2 O ,FT IR分析表明获得的粉体为水合物 ,BET测试比表面积达160 7m2 /g .以氧化锰为研究电极 ,饱和甘汞电极 (SCE)为参比电极 ,铂片为辅助电极的三电极体系中 ,以 1mol/L的Na2 SO4溶液为电解液 ,通过循环伏安法研究其电化学行为 .实验结果表明 ,纳米氧化锰是理想的超级电容器电极材料 ,在电位窗口为 -0 2～ 0 9V (vs .SCE)范围内 ,扫描速度为 4mV/s ,其比电容达到 2 0 3 4F/g .     

聚5-磺基水杨酸修饰电极上对苯二酚的电化学行为

用循环伏安法将 5 磺基水杨酸修饰于玻碳电极表面 ,制备出对对苯二酚具有电催化作用的聚合物膜修饰电极。研究了对苯二酚 (HQ)在该聚合物薄膜修饰电极上的电化学行为。在 0 5mmol/LH2 SO4底液中 ,HQ在该电极上的线性范围为 2 0× 1 0 - 6～ 1 0× 1 0 - 4 mol/L。该修饰电极可将对苯二酚和邻苯二酚(CC)的氧化峰分开约 1 0 5mV     

Li_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3,Na_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3的离子交换研究

研究了在不同温度下的NaNO3和AgNO3水溶液中Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3离子交换行为.实验表明Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3均显示出了高选择性与Na+和Ag+进行离子交换的特征,且对Ag+的选择性高于Na+.升高温度可显著提高Ag/Li和Ag/Na的交换反应速度.     

Near infrared study of aqueous rare-earth ethylsulfates

The near infrared spectra of aqueous solutions of the ethylsulfates of La, Nd, Gd, Tb, Er, Yb, Lu, Y, and Na have been determined from about 0.2 mol-dm^–3 to nearly saturation. The extinction coefficients of water have been calculated taking into account the absorption of ethylslfate anions determined in separate experiments. Their values appeared to be nearly the same as that of pure water. The relative contents of free OH groups in 0.5 and 0.7M solutions have been estimated from the absorbances at 1160 nm. They were lower in solutions of the heavy rare-earth ethylsulfates (Tb, Er, Yb, Lu) than in equimolar solutions of the lighter ones (La, Nd), confirming our previous view that secondary hydration of the heavy trivalent rare-earth cations is distinctly stronger than that of the lighter ones. A comparison of the spectra of these aqueous ethylsulfates with those of perchlorates shows that the structure-breaking ability of the C₂H₅SO ₄ ^– ion is much smaller than that of perchlorate anion.     

Crystal growth, structure determination, and optical properties of new potassium-rare-earth silicates K3RESi2O7 (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

Single crystals of K₃RESi₂O₇ (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were grown from a potassium fluoride flux. Two different structure types were found for this series. Silicates containing the larger rare earths, RE=Gd, Tb, Dy, Ho, Er, Tm, Yb crystallize in a structure K₃RESi₂O₇ that contains the rare-earth cation in both a slightly distorted octahedral and an ideal trigonal prismatic coordination environment, while in K₃LuSi₂O₇, containing the smallest of the rare earths, lutetium is found solely in an octahedral coordination environment. The structure of K₃LuSi₂O₇ crystallizes in space group P6₃/mmc with a=5.71160(10) Å and c=13.8883(6) Å. The structures containing the remaining rare earths crystallize in the space group P6₃/mcm with the lattice parameters of a=9.9359(2) Å, c=14.4295(4) Å, (K₃GdSi₂O₇); a=9.88730(10) Å, c=14.3856(3) Å, (K₃TbSi₂O₇); a=9.8673(2) Å, c=14.3572(4) Å, (K₃DySi₂O₇); a=9.8408(3) Å, c=14.3206(6) Å, (K₃HoSi₂O₇); a=9.82120(10) Å, c=14.2986(2) Å, (K₃ErSi₂O₇); a=9.80200(10) Å, c=14.2863(4) Å, (K₃TmSi₂O₇); a=9.78190(10) Å, c=14.2401(3) Å, (K₃YbSi₂O₇). The optical properties of the silicates were investigated and K₃TbSi₂O₇ was found to fluoresce in the visible.     

Structural studies of five layer Aurivillius oxides: A2Bi4Ti5O18 (A=Ca, Sr, Ba and Pb)

The room temperature structures of the five layer Aurivillius phases A₂Bi₄Ti₅O₁₈ (A=Ca, Sr, Ba and Pb) have been refined from powder neutron diffraction data using the Rietveld method. The structures consist of [Bi₂O₂]²⁺ layers interleaved with perovskite-like [A₂Bi₂Ti₅O₁₆]²⁻ blocks. The structures were refined in the orthorhombic space group B2eb (SG. No. 41), Z=4, and the unit cell parameters of the oxides are a=5.4251(2), b=5.4034(1), c=48.486(1); a=5.4650(2), b=5.4625(3), c=48.852(1); a=5.4988(3), b=5.4980(4), c=50.352(1); a=5.4701(2), b=5.4577(2), c=49.643(1) for A=Ca, Sr, Ba and Pb, respectively. The structural features of the compounds were found similar to n=2-4 layers bismuth oxides. The strain caused by mismatch of cell parameter requirements for the [Bi₂O₂]²⁺ layers and perovskite-like [A₂Bi₂Ti₅O₁₆]²⁻ blocks were relieved by tilting of the TiO₆ octahedra. Variable temperature synchrotron X-ray studies for Ca and Pb compounds showed that the orthorhombic structure persisted up to 675 and 475 K, respectively. Raman spectra of the compounds are also presented.     

电感耦合等离子体光谱法(ICP-AES)测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量

针对银精矿样品复杂,难消解的特点,研究了不同酸溶法和碱熔法对样品的消解情况,建立了硝酸,盐酸,氢氟酸,高氯酸消解银精矿的方法。根据元素灵敏度和抗干扰性,选定各元素的测定波长。通过酸溶样和碱熔样测定结果比对,验证了方法准确性。建立了四酸消解-电感耦合等离子体光谱法测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的方法,元素的线性相关系数均在0.9999以上。通过共存元素干扰实验,确定了银精矿中高含量元素(铜、铅、锌、铁、锑、铋等)对测定元素结果没有影响。方法检出限：Cu 0.0063 mg/L, Pb 0.0159 mg/L ,Zn 0.0090 mg/L,As 0.0192 mg/L, Cd 0.0093 mg/L ,Ca 0.0084 mg/L, Mg 0.0075 mg/L, Mn 0.0081 mg/L。测定下限：Cu 0.0105mg/L,Pb 0.0265 mg/L, Zn 0.0150 mg/L, As 0.0320 mg/L, Cd 0.0155 mg/L, Ca 0.0140 mg/L, Mg 0.0125 mg/L,Mn 0.0135 mg/L。3个样品的相对标准偏差在0.87%~3.56%之间,加标回收率在95.00%~103.56%之间。方法流程短,操作简单,快速,灵敏度和再现性高,结果准确可靠,可以满足银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的测定。     

Preparation of ZrO2-TiO2-CeO2 and Its Application in the Selective Catalytic Reduction of NO with NH3

TiO₂,ZrO₂-TiO₂,andZrO₂-TiO₂-CeO₂ were prepared by co-precipitation method and characterized by X-ray diffraction (XRD), specific surface area measurements (BET), temperature programmed desorption (NH₃-TPD), oxygen storage capacity (OSC), and temperature programmed reduction (H₂-TPR). The results showed that ZrO₂-TiO₂-CeO₂ exhibited large number of surface strong acid, possessed some oxygen storage capacity, and strong redox property. The three materials were used as supports and the monolith catalysts were prepared with 1% (w) V₂O₅ and 9% (w)WO₃ for selective catalytic reduction (SCR) of NO with ammonia in the presence of excessive O₂, and the results of catalytic activity showed that the catalyst used ZrO₂-TiO₂-CeO₂ as support yielded nearly 100% NO conversion at 275 °C at a gas hourly space velocity (GHSV) of 10000 h⁻¹, and it had the best catalytic activity and showed great potential for practical application.     

Structure Study of Bi2.5Na0.5Ta2O9 and Bi2.5Nam−1.5NbmO3m+3 (m=2-4) by Neutron Powder Diffraction and Electron Microscopy

The crystal structures of Bi_2.5Na_0.5Ta₂O₉ and Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=3,4) have been investigated by the Rietveld analysis of their neutron powder diffraction patterns (λ=1.470 Å). These compounds belong to the Aurivillius phase family and are built up by (Bi₂O₂)²⁺ fluorite layers and (A_m-1B_mO_3m+1)^2- (m=2-4) pseudo-perovskite slabs. Bi_2.5Na_0.5Ta₂O₉ (m=2) and Bi_2.5Na_2.5Nb₄O₁₅ (m=4) crystallize in the orthorhombic space group A2₁am, Z=4, with lattice constants of a=5.4763(4), b=5.4478(4), c=24.9710 (15) and a=5.5095(5), b=5.4783(5), c=40.553(3) Å, respectively. Bi_2.5Na_1.5Nb₃O₁₂ (m=3) has been refined in the orthorhombic space group B2cb, Z=4, with the unit-cell parameters a=5.5024(7), b=5.4622(7), and c=32.735(4) Å. In comparison with its isostructural Nb analogue, the structure of Bi_2.5Na_0.5Ta₂O₉ is less distorted and bond valence sum calculations indicate that the Ta-O bonds are somewhat stronger than the Nb-O bonds. The cell parameters a and b increase with increasing m for the compounds Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=2-4), causing a greater strain in the structure. Electron microscopy studies verify that the intergrowth of mixed perovskite layers, caused by stacking faults, also increases with increasing m.     

Sol-gel synthesis of K3InF6 and structural characterization of K2InC10O10H6F9, K3InC12O14H4F18 and K3InC12O12F18

K₃InF₆ is synthesized by a sol-gel route starting from indium and potassium acetates dissolved in isopropanol in the stoichiometry 1:3, with trifluoroacetic acid as fluorinating agent. The crystal structures of the organic precursors were solved by X-ray diffraction methods on single crystals. Three organic compounds were isolated and identified: K₂InC₁₀O₁₀H₆F₉, K₃InC₁₂O₁₄H₄F₁₈ and K₃InC₁₂O₁₂F₁₈. The first one, deficient in potassium in comparison with the initial stoichiometry, is unstable. In its crystal structure, acetate as well as trifluoroacetate anions are coordinated to the indium atom. The two other precursors are obtained, respectively, by quick and slow evaporation of the solution. They correspond to the final organic compounds, which give K₃InF₆ by decomposition at high temperature. The crystal structure of K₃InC₁₂O₁₄H₄F₁₈ is characterized by complex anions [In(CF₃COO)₄(OH_x)₂]^(5−2x)− and isolated [CF₃COOH_2−x]^(x−1)− molecules with x=2 or 1, surrounded by K⁺ cations. The crystal structure of K₃InC₁₂O₁₂F₁₈ is only constituted by complex anions [In(CF₃COO)₆]³⁻ and K⁺ cations. For all these compounds, potassium cations ensure only the electroneutrality of the structure. IR spectra of K₂InC₁₀O₁₀H₆F₉ and K₃InC₁₂O₁₂F₁₈ were also performed at room temperature on pulverized crystals.     

The Phase Relations in the System In2O3–TiO2–MgO at 1100 and 1350°C

The phase relations in the system In₂O₃–TiO₂–MgO at 1100 and 1350°C are determined by a classical quenching method. In this system, there are four pseudobinary compounds, In₂TiO₅, MgTi₂O₅ (pseudobrookite type), MgTiO₃ (ilmenite type), and Mg₂TiO₄ (spinel type) at 1100°C. At 1350°C, in addition to these compounds there exist a spinel-type solid solution Mg_2−xIn_2xTi_1−xO₄ (0≤x≤1) and a compound In₆Ti₆MgO₂₂ with lattice constants a=5.9236(7) Å, b=3.3862(4) Å, c=6.3609(7) Å, β=108.15(1)°, and q=0.369, which is isostructural with the monoclinic In₃Ti₂FeO₁₀ in the system In₂O₃–TiO₂–MgO. The relation between the lattice constants of the spinel phase and the composition nearly satisfies Vegard's law. In₆Ti₆MgO₂₂ extends a solid solution range to In₂₀Ti₁₇Mg₃O₆₇ with lattice constants of a=5.9230(5) Å, b=3.3823(3) Å, c=6.3698(6) Å, β=108.10(5)°, and q=0.360. The distributions of constituent cations in the solid solutions are discussed in terms of their ionic radius and site preference effect.     

B2O3-Bi2O3-ZnO-Al2O3玻璃助烧剂对BaTiO3陶瓷烧结条件、晶体结构和介电性能的影响

通过调节B₂O₃‐Bi₂O₃‐ZnO‐Al₂O₃(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO₃)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明：添加适量的BBZA玻璃能够有效地将BaTiO₃陶瓷烧结温度由1350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO₃的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO₃陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO₃晶粒表面。优化的BaTiO₃陶瓷制备条件如下：BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO₃陶瓷介电常数达到1364,介电损耗低至1.2%。