ATO/SiO2电极制备及对氯苯酚电催化降解研究

以SnCl2/SbCl3的乙二醇/乙腈混合溶液浸渍大孔SiO2为载体,经多次水解沉积、高温煅烧制备出大孔ATO/SiO2电极.SEM和XRD分析表明,ATO（Sb-SnO2）纳米微粒均匀负载在SiO2薄层上,4次水解沉积材料体积电阻率10Ω.cm,比表面积77 m^2.g^-1.电化学测试表明,大孔ATO/SiO2电极...     

电聚合苯胺过程的在线紫外-可见光谱

用在线紫外-可见光谱电化学的方法对0.5mol/L硫酸水溶液中苯胺在ITO导电玻璃电极上的电化学聚的过程进行了研究.结果表明在循环伏安条件下苯胺发生了电聚合,聚合速率与苯胺浓度成正关系;而且在线紫外-可见电化学光谱表明,在0.01mol/L苯胺溶液的电聚合过程的诱导期较长.恒电位条件下的在线紫外-可见电化学光谱显示苯胺浓度为0.05mol/L,电位为0.8V时,在ITO电极上苯胺低聚合物中间体可能产生于聚苯胺形成之前;而0.01mol/L苯胺在0.8V电位下不发生聚合,但在线紫外-可见光谱又显示此时在电极上可能存在小的苯胺低聚物的中间体;在线紫外-可见光谱表明这种中间体是可能产生并存在电极表面上的.     

铂纳米粒子和锰卟啉修饰的聚苯胺新材料的制备及表征

借助循环伏安电化学聚合制备了聚苯胺(PANi)/MnT1239卟啉复合材料,再利用还原恒电位沉积法负载铂纳米粒子(Pt NP),最终制备了聚苯胺/MnT1239卟啉/铂纳米粒子复合材料.电沉积铂之后聚苯胺/MnT1239卟啉材料发生明显样貌变化,棒状结构平均直径从90 nm增加到200 nm,材料具有较大的表面积,空间可负载性好.铂纳米粒子平均尺寸在20 nm,附着均匀,氧化峰电流在0.2 V处达到7.4 mA,电化学性能优良.     

MnO_2/聚苯胺复合材料的电化学电容

以P123为模板剂,软模板法制备出纳米MnO2.酸性条件下引入苯胺并聚合,得到了MnO2/聚苯胺复合材料.X射线衍射(XRD)、红外光谱(IR),扫描电子显微镜(SEM)表征观察样品的结构、形貌.循环伏安、交流阻抗、恒电流充放电等测试MnO2/聚苯胺电极的电化学性能.结果表明:引入苯胺改变了样品纳米MnO2的形貌.MnO2/聚苯胺电极比容量高达190.8F·g-1,500次循环电极比容量仅衰减4.7%,库仑效率均保持在97%以上.     

离子液体掺杂聚苯胺/纳米铜修饰电极制备及其在过氧化氢测定中的应用

在离子液体1-甲基咪唑-三氟乙酸中用循环伏安法(CV)电聚合苯胺制得离子液体掺杂聚苯胺膜修饰玻碳电极(IL-PANI/GCE),进一步在其表面原位电沉积纳米铜粒子,构制用于测定H2O2的新型离子液体掺杂聚苯胺/纳米铜(nano-Cu/IL-PANI/GCE)电化学传感器。用扫描电镜(SEM)、循环伏安法(CV)和电化学阻抗谱法(EIS)表征此修饰电极,并讨论了其对H2O2的电催化还原机制。在0.1 mol/L NaOH溶液和"0.35 V电位下,用电流法测定了H2O2的含量,在20～1.12 mmol/L浓度范围内线性关系良好;检出限为0.1μmol/L,响应时间约为3 s。     

在线紫外-可见光谱研究ITO导电玻璃电极上苯胺与对苯二胺的电化学共聚及其产物的表征

本文用在线紫外-可见光谱电化学的方法较详细地研究了在0.5M硫酸水溶液中苯胺、对苯二胺以及苯胺与对苯二胺混合体系在ITO导电玻璃电极上的电化学聚合和共聚合的过程。苯胺与对苯二胺在ITO导电玻璃上发生了电化学共聚合,在0.5M硫酸水溶液的纯苯胺和苯胺与对苯二胺共聚时的循环伏安曲线以及其对应的在线紫外-可见光谱表明对苯二胺的加入除了发生共聚外,也使聚合的速率明显加快;而且纯苯胺在循环伏安电化学聚合时在430nm处出现的吸收带因对苯二胺的加入而消失,说明对苯二胺的加入使聚合的机理与纯苯胺的聚合机理有明显不同,主要原因是苯胺产生的反应中间体可能很快与对苯二胺的阳离子自由基反应聚合。在导电玻璃ITO上的聚合物膜的反射傅立叶红外光谱表明,对苯二胺的加入可能产生了具有1,2取代模式结构,这说明了对苯二胺结合进入到聚合物中。这种共聚使得产物的表面形貌也发生了变化,聚合物扫描电镜图表明对笨二胺的加入有利于纤维状的表面形貌产生,纤维的直径可达到50nm粗细;同时用在线紫外-可见光谱研究了纯聚苯胺和共聚物随电位变化的电变色性质,结果表明在0v-0.6v之间共聚物与纯聚苯胺的在线紫外-可见光谱有明显的不同,且共聚物的电变色可逆性比纯聚苯胺好;同时SEM图也表明在0.8v电位下聚苯胺和共聚物表面形貌发生了团聚。     

铂-氧化铈/聚苯胺/聚砜复合膜电极的制备及对甲醇的电催化氧化

采用电化学聚合法制备了掺杂CeO2纳米粒子的聚苯胺(PAN)/聚砜(PSF)复合膜电极,在其上电沉积铂粒子,制得了铂-氧化铈/聚苯胺/聚砜的复合膜修饰电极。 复合膜的形貌和化学组分通过冷场发射扫描电子显微镜（Cold FE-SEM）和能量散射X射线谱（EDS）进行了表征,用循环伏安法和电化学交流阻抗法考察了复合膜电极对甲醇的电催化氧化性能。 结果表明,复合膜的双层多孔结构使铂粒子与CeO2粒子在复合膜内层的多孔聚苯胺上均匀沉积,粒子平均尺寸约为80 nm;CeO2为铂质量的7%时,铂-氧化铈/聚苯胺/聚砜复合膜修饰电极对甲醇有很好的电催化氧化性能和高的稳定性。     

三元复合材料PANI／Ag／MWNT的电化学行为和比电容

通过原位聚合的方式在银纳米粒子/多壁碳纳米管（Ag/MWCNT）复合材料的表面成功聚合苯胺单体制备了聚苯胺/银纳米粒子/多壁碳纳米管（PANI/Ag/MWCNT）三元复合材料苯．通过对三元复合材料的结构以及表面形貌进行分析,表明聚苯胺层完全包覆了Ag/MWCNT复合材料,形成了核壳式结构．同时银纳米粒子则以单质晶体的形态存在于多壁碳纳米管与聚苯胺层之间．三元复合材料电极在1 mol/L的KOH溶液中具有极低的阻抗,而与聚苯胺电极相比,这些复合材料电极则表现出更低的电阻、更高的电化学活性和更好的循环稳定性．尤其是当苯胺和Ag：MWCNTs质量比为5：5时,该复合材料电极在0.25 A/g的电流密度下表现出最大的比电容值为160 F/g．     

聚苯胺炭复合载体制备的钯催化剂对甲酸的电催化氧化

制备了导电高分子聚苯胺与活性炭的复合载体(PAnC),用PAnC作为载体制备的钯催化剂性能优于单独活性炭作为载体制备的催化剂。此外掺杂十二烷基磺酸钠制备的聚苯胺碳载体(PAnC-S)具有比PAnC更低的电荷传递电阻,10~25 nm的介孔数量明显增加,比表面积增大到94.9 m²/g。PAnC-S与PAnC粒径均匀,粒径均在30 nm左右。以PAnC-S和 PAnC为载体制备的钯催化剂比活性炭作载体制备的钯催化剂具有更大的电化学比表面积,分别为84.7和62.6 m²/g。对甲酸的氧化具有更高的电化学活性和稳定性。     

苯胺-邻硝基苯胺共聚物——高比容量锂二次电池新型正极材料

聚苯胺作为锂离子电池典型的有机正极材料,合成简单、资源丰富,但其电化学比容量与循环寿命始终难以满足实用要求.作者采用化学氧化聚合法合成了苯胺-邻硝基苯胺共聚物(Poly(Aniline/o-Nitroanil-ine,P(AN-oNA)),通过在聚苯胺主链引入强拉电子基团——硝基苯胺,增大共聚物的电子共轭体系,改善共聚物链段的稳定性,利用硝基苯胺基团的电化学可逆性提高共聚物的电化学活性.结果表明,P(AN-oNA)的初始充放电比容量高达186 mAh·g-1,比聚苯胺提高近37%,60周循环仍能维持168 mAh·g-1.此外,P(AN-oNA)电极的充放电电位平阶十分接近,电极的极化明显降低,电子转移反应速率加快.这种新型共聚物结构与性能对于发展有机正极材料具有重要的参考意义.     

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.     

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.     

La3Ru8B6 and Y3Os8B6, new members of a homologous series R(A)nM3n−1B2n

Two new compounds, La₃Ru₈B₆ and Y₃Os₈B₆, were synthesized by arc melting the elements. Their structural characterization was carried out at room temperature on as-cast samples by using X-ray diffractometry. According to X-ray single-crystal diffraction results these borides crystallize in Fmmm space group (no. 69), Z=4, a=5.5607(1) Å, b=9.8035(3) Å, c=17.5524(4) Å, ρ=8.956 Mg/m³, μ=25.23 mm⁻¹ for La₃Ru₈B₆ and a=5.4792(2) Å, b=9.5139(4) Å, c=17.6972(8) Å, ρ=13.343 Mg/m³, μ=128.23 mm⁻¹ for Y₃Os₈B₆. The crystal structure of La₃Ru₈B₆ was confirmed from Rietveld refinement of X-ray powder diffraction data. Both La₃Ru₈B₆ and Y₃Os₈B₆ compounds are isotypic with the Ca₃Rh₈B₆ compound and their structures are built up from CeCo₃B₂-type and CeAl₂Ga₂-type structural fragments taken in ratio 2:1. They are the members of structural series R(A)_nM_3n−1B_2n with n=3 (R is the rare earth metal, A the alkaline earth metal, and M the transition metal). Structural and atomic parameters were also obtained for La_0.94Ru₃B₂ compound from Rietveld refinement (CeCo₃B₂-type structure, P6/mmm space group (no. 191), a=5.5835(9) Å, c=3.0278(6) Å).     

Composition-induced phase transition in Ca14Zn6−xGa10+xO35+x/2 (x=0.0 and 0.5)

Novel complex oxides Ca₁₄Zn₆Ga₁₀O₃₅ and Ca₁₄Zn_5.5Ga_10.5O_35.25 were prepared in air at 1200 °C, 72 h. Refinements of their crystal structures using X-ray powder diffraction data showed that Ca₁₄Zn₆Ga₁₀O₃₅ is ordered (S.G. F23, =0.0458, R_p=0.0485, R_wp=0.0659, χ²=1.88) and Ca₁₄Zn_5.5Ga_10.5O_35.25 disordered (S.G. F432, =0.0346, R_p=0.0601, R_wp=0.0794, χ²=2.82) variants of the crystal structure of Ca₁₄Zn₆Al₁₀O₃₅. In the crystal structure of Ca₁₄Zn₆Ga₁₀O₃₅, there are large empty voids, which could be partially occupied by additional oxygen atoms upon substitution of Zn²⁺ by Ga³⁺ as in Ca₁₄Zn_5.5Ga_10.5O_35.25. These oxygen atoms are introduced into the crystal structure of Ca₁₄Zn_5.5Ga_10.5O_35.25 only as a part of four tetrahedra (Zn, Ga)O₄ groups sharing common vertex. This creates a situation where even a minor change in the chemical composition leads to considerable anion and cation disordering resulting in a change of space group from F23 (no. 196) to F432 (no. 209).     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…     

The crystal chemistry of Bi6TP2O15+x, T=Fe, Ni, Zn: Isomorphism and polymorphism, structural relationship to Bi6TiP2O16

The crystal structures of compounds with nominal compositions Bi₆FeP₂O_15+x (I), Bi₆NiP₂O_15+x (II) and Bi₆ZnP₂O_15+x (III) were determined from single-crystal X-ray diffraction data. They are monoclinic, space group I2, Z=2. The lattice parameters for (I) are a=11.2644(7), b=5.4380(3), c=11.1440(5) Å, β=96.154(4)°; for (II) a=11.259(7), b=5.461(4), c=11.109(7) Å, β=96.65(1)°; for (III) a=19.7271(5), b=5.4376(2), c=16.9730(6) Å, β=131.932(1)°. Least squares refinements on F² converged for (I) to R1=0.0554, wR₂=0.1408; for (II) R₁=0.0647, wR₂=0.1697; for (III) R₁=0.0385, wR₂=0.1023. The crystals are complexly twinned by 2-fold rotation about , by inversion and by mirror reflection. The structures consist of edge-sharing articulations of OBi₄ tetrahedra forming layers in the a-c plane that then continue by edge-sharing parallel to the b-axis. The three-dimensional networks are bridged by Fe and Ni octahedra in (I) and (II) and by Zn trigonal bipyramids in (III) as well as by oxygen atoms of the PO₄ moieties. Bi also randomly occupies the octahedral sites. Oxygen vacancies exist in the structures of the three compounds due to required charge balances and they occur in the octahedral coordination polyhedron of the transition metal. In compound (III), no positional disorder in atomic sites is present. The Bi-O coordination polyhedra are trigonal prisms with one, two or three faces capped. Magnetic susceptibility data for compound (I) were obtained between 4.2 and 350 K. Between 4.2 and 250 K it is paramagnetic, μ_eff=6.1 μ_B; a magnetic transition occurs above 250 K.     

A new 2212-type stair like structure: Bi14Sr21Fe12O61, m=5 member of the generic [Bi2Sr3Fe2O9]m[Bi4Sr6Fe2O16] family

A new oxide, Bi₁₄Sr₂₁Fe₁₂O_61, with a layered structure derived from the 2212 modulated type structure Bi₂Sr₃Fe₂O₉, was isolated. It crystallizes in the I2 space group, with the following parameters: a=16.58(3) Å, b=5.496(1) Å, c=35.27(2) Å and β=90.62°. The single crystal X-ray structure determination, coupled with electron microscopy, shows that this ferrite is the m=5 member of the [Bi₂Sr₃Fe₂O₉]_m[Bi₄Sr₆Fe₂O₁₆] collapsed family. This new collapsed structure can be described as slices of 2212 structure of five bismuth polyhedra thick along , shifted with respect to each other and interconnected by means of [Bi₄Sr₆Fe₂O₁₆] slices. The latter are the place of numerous defects like iron or strontium for bismuth substitution; they can be correlated to intergrowth defects with other members of the family.     

Synthesis and structural characterization of Al7C3N3-homeotypic aluminum silicon oxycarbonitride, (Al7−xSix)(OyCzN6−y−z) (x∼1.2, y∼1.0 and z∼3.5)

A new aluminum silicon oxycarbonitride, (Al_5.8Si_1.2)(O_1.0C_3.5N_1.5), has been synthesized and characterized by X-ray powder diffraction (XRPD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS). The title compound is hexagonal with space group P6₃/mmc and unit-cell dimensions a=0.322508(4) nm, c=3.17193(4) nm and V=0.285717(6) nm³. The atom ratios of Al:Si and those of O:C:N were, respectively, determined by EDX and EELS. The initial structural model was successfully derived from the XRPD data by the direct methods and further refined by the Rietveld method. The crystal is most probably composed of four types of domains with nearly the same fraction, each of which is isotypic to Al₇C₃N₃ with space group P6₃mc. The existence of another new oxycarbonitride (Al_6.6Si_1.4)(O_0.7C_4.3N_2.0), which must be homeotypic to Al₈C₃N₄, has been also demonstrated by XRPD and TEM.     

Non-centrosymmetric Ba3Ti3O6(BO3)2

The compound previously reported as Ba₂Ti₂B₂O₉ has been reformulated as Ba₃Ti₃B₂O₁₂, or Ba₃Ti₃O₆(BO₃)₂, a new barium titanium oxoborate. Small single crystals have been recovered from a melt with a composition of BaTiO₃:BaTiB₂O₆ (molar ratio) cooled between 1100°C and 850°C. The crystal structure has been determined by X-ray diffraction: hexagonal system, non-centrosymmetric space group, a=8.7377(11) Å, c=3.9147(8) Å, Z=1, wR(F²)=0.039 for 504 unique reflections. Ba₃Ti₃O₆(BO₃)₂ is isostructural with K₃Ta₃O₆(BO₃)₂. Preliminary measurements of nonlinear optical properties on microcrystalline samples show that the second harmonic generation efficiency of Ba₃Ti₃O₆(BO₃)₂ is equal to 95% of that of LiNbO₃.     

Synthesis and crystal structure of Bi6.4Pb0.6P2O15.2: A new polymorph in the series Bi6+xM1−xP2O15+y

Bi_6.4Pb_0.6P₂O_15.2 is a polymorph of structures with the general stoichiometry Bi_6+xM_1−xP₂O_15+y. However, unlike previously published structures that consist of layers formed by edge sharing OBi₄ tetrahedra bridged by PO₄ and TO₆ (T=transition metal) tetrahedra and octahedra the title compound's structure is more complex. It is monoclinic, C2, a=19.4698(4) Å, b=11.3692(3) Å, c=16.3809(5) Å, β=101.167(1)°, Z=10. Single-crystal X-ray diffraction data were refined by least squares on F² converging to R₁=0.0387, wR₂=0.0836 for 7023 intensities. The crystal twins by mirror reflection across (001) as the twin plane and twin component 1 equals 0.74(1). Oxygen ions are in tetrahedral coordination to four metal ions and the O(BiPb)₄ units share corners to form layers that are part of the three-dimensional framework. Eight oxygen ions form a cube around the two crystallographically independent Pb ions. Pb-O bond lengths vary from 2.265(14) to 2.869(14) Å. Pairs of such cubes share an edge to form a Pb₃O₂₀ unit. The two oxygen ions from the unshared edges are part of irregular Bi polyhedra. Other oxygen ions of Bi polyhedra are part only of O(BiPb)₄ units, and some oxygen ions of the polyhedra are also part of PO₄ tetrahedra. One, two, three and or four PO₄ moieties are connected to the Bi polyhedra. Bi-O bond lengths ?3.1 Å vary from 2.090(12) to 3.07(3) Å. The articulations of Pb cubes, Bi polyhedra and PO₄ tetrahedra link into the three-dimensional structure.