SDM—1型耐硫催化剂甲烷化反应动力学：II.宏观动力学模型

本文以工业应用为目的，采用内循环无梯度反应器，在５７３－６７３Ｋ，０．３０－１．２０ＭＰａ的条件下，原料气组成为Ｈ２ ５０－５４％，ＣＯ１１．７－２０．７％，ＣＨ４ ２．１－１４．３％，ＣＯ２ ６．４－１１．５％，Ｎ２ １２．２－１８．１％范围内，研究了φ×３ｍｍＳＤＭ－１型城市煤气耐硫甲烷化催化剂的宏观动力学方程选择 ＣＯ＋３Ｈ２＝ＣＨ４＋Ｈ２Ｏ （１） ＣＯ＋Ｈ２Ｏ＝ＣＯ２＋Ｈ２ （２）     

NO在Sm2—xSrxNiO4上的催化还原

在具有Ｋ２ＮｉＦ４型结构的Ｓｍ２－ｘＳｒｘＮｉＯ４（ｘ＝０．４，０．５，０．６，０．８，１．０，１．２，１．４，１．５）化合物上进行了ＣＯ催化还原ＮＯ的研究。结果表明，低温、低Ｓｒ＾２＋取借代量与高温、高Ｓｒ＾２＋取代量的反应途径不同，这可从化合物的结构、化合物中金属－氧键的标准生成焓的总和、ＮＯ还原的表现活化能及化合物上Ｏ２的脱附行为等得到解释。     

（Sr，Ba）_（1－x）Eu_xTiO_3的高温高压合成及XPS研究

用高温高压法合成了Ｓｒ１－ｘＥｕｘＴｉＯ３（ｘ＝０．０，０．１，０．２，０．３，０．４，０．５）及Ｂａ０．３Ｅｕ０．７ＴｉＯ３化合物．结果表明，所有样品均为立方结构，样品中存在Ｅｕ（Ⅱ）和Ｅｕ（Ⅲ）的混合价．Ｅｕ３＋的掺入直接影响了Ｓｒ离子与氧离子的结合，使Ｓｒ３ｐ３／２的结合能随ｘ的增加而增加．     

SDM－1型耐硫催化剂甲烷化反应动力学Ⅱ．宏观动力学模型

本文以工业应用为目的，采用内循环无梯度反应器，在５７３～６７３Ｋ，０．３０～１．２０ＭＰａ的条件下，原料气组成为Ｈ＿２５０～５４％，ＣＯ１１．７～２０．７％，ＣＨ＿４２．１～１４．３％，ＣＯ＿２６．４～１１．５％，Ｎ＿２１２．２～１８．１％范围内，研究了φ５×３ｍｍＳＤＭ－１型城市煤气耐硫甲烷化催化剂的宏观动力学方程。选择ＣＯ＋３Ｈ＿２＝ＣＨ＿４＋Ｈ＿２Ｏ（１）ＣＯ＋Ｈ＿２Ｏ＝ＣＯ＿２＋Ｈ＿２（２）为系统的独立反应，获得了可靠的动力学模型，井讨论了反应条件对甲烷化反应效率因子的影响。     

磷酸锡盐的水热合成及其表征

用水热合成出系列化合物ＭＳｎ２（ＰＯ４）３（Ｍ＝Ｎａ，Ｋ，ＮＨ４），该化合物具有ＮＡＳＩＣＯＮ型三维骨架结构，测得其晶胞参数为：（１）ＮａＳｎ２（ＰＯ４）３，ａ＝０．８５２６９２）ｎｍ，ｃ＝２．２４７（４）ｎｍ；（２）ＫＳｎ２（ＰＯ４）３，ａ＝０．８３６６（１）ｎｍ，ｃ＝２．３５６（４）ｎｍ；（３）ＮＨ４Ｓｎ２（ＰＯ４）３，ａ＝０＼８３３０（１）ｎｍ，ｃ＝２＼３９０（５）ｎｍ．热分析结果表明，在较     

NdSr_（1－x）M_xNiO_4（M＝Ca，Ba）的合成，结构和电学磁学性

用固相法首次合成了ＮｄＳｒ＿（１－ｘ）Ｍ＿ｘＮｉＯ＿４（Ｍ＝Ｃａ：０．０≤１．０；Ｍ＝Ｂａ：０．０≤ｘ≤０．６）系列复合氧化物，并研究了其结构，红外光谱，电学性质和磁学性质。除ＮｄＣａＮｉＯ以正交晶系结晶外，其它试样的结构均属于四方晶系。ＩＲ谱显示随Ｃａ￣（２＋）离子含量的增加，ＮｄＳｒ＿（１－ｘ）Ｍ＿ｘＮｉＯ＿４的Ｎｉ－Ｏ键缩短，Ｃａ￣（２＋）和Ｂａ￣（２＋）引入ＮｄＳｒＮｉＯ＿４以取代Ｓｒ￣（２＋），使试样由金属性导电转变为半导体性导电；随Ｃａ￣（２＋）含量增加，试样的室温电阻率增大。７７～３００Ｋ磁化率与温度关系曲线显示，所有试样的Ｎｉ￣（３＋）都以低自旋状态存在。     

两个环己烷螺含氮杂环化合物的合成和晶体结构

环己酮与硫代碳酰肼在不同介质中的反应，合成出两个不同的环己烷螺含氮杂环化合物。经Ｘ－射线结构分析确定它们分别为１，２，４，５－四氮螺［５，５］十一烷－３－硫酮，Ｃ＿７Ｈ＿（１４）Ｎ＿４Ｓ（Ⅰ）和１，２，４，－三氮螺［４，５］癸－１－烯－４－氨基－３－硫酮。Ｃ＿７Ｈ＿（１２）Ｎ＿４Ｓ＿ｘ（Ｓ＿ｘ＝０．８Ｓ＋０．２Ｏ）（Ⅱ）。晶体学参数分别为（Ⅰ）：Ｐ２＿１／ｃ，ａ＝１２．０２６（４），ｂ＝２６．８１７（６），ｃ＝１２．０４２（３），β＝１１５．９４（２）°，Ｚ＝４，Ｖ＝９３３．４（１０），Ｍ＿ｒ＝１８６．２８；（Ⅱ）：Ｐ２＿１／ｍ，ａ＝６．５９５（７），ｂ＝６．８１７（６），ｃ＝１０．５７２（６），β＝１０６．３（１）°，Ｖ＝４５６（１），Ｚ＝２，Ｍ＿ｒ＝１８１．０５。最终一致因子分别为Ｒ＝０．０５４，Ｒ＿ｗ＝０．０６５和Ｒ＝０．０８９，Ｒ＿ｗ＝０．０９６。两个化合物中，环己烷都为椅式构型，它与其螺联的６员氮杂环，５员氮杂环的最小二乘平面间的夹角分别为６８．９４和９０°。并对合成反应途径作了初步讨论。     

三卤代锡钨（钼）双核化合物的制备和晶体结构

ＣｐＭ（ＣＯ）３ＳｎＰｈ３和ＣｐＭ（ｃｏ）３ｓＮｐＨ２ｘ（Ｃｐ＝Ｃ５Ｈ４ＣＨ３，Ｃ５Ｈ４ＣＯＣＨ３；Ｍ＝Ｍｏ，Ｗ；Ｘ＝Ｃｌ，Ｂｒ）与ＨＣｌ或ＨＢｒ发生取代反应，得到三氯、三溴以及混合三卤代锡钨（钼）双核化合物，并经元素分析、＾１Ｈ ＮＭＲ、ＩＲ表征。化合物Ｃｌ３ＳｎＷ（ＣＯ）３Ｃ５Ｈ４ＣＯＣＨ３的晶体属单斜晶系，空间群为Ｐ２１／ｃ，ａ＝０．７６８６（３）ｎｍ，ｂ＝１．２６２２（２）ｎｍ，ｃ＝１．６     

（Sr,Ba）1—xEuxTiO3的高温高压合成及XPS研究

用高温高压法合成了Ｓｒ１－ｘＥｕｘＴｉＯ３（ｘ＝０．０，０．１，０．２，０．３，０．４，０．５）及Ｂａ０３。Ｅ０。７ＴＯ３化合物。结果表明，所有样品均为立方结构，样品中存在Ｅｕ（Ⅱ）和Ｅｕ（Ⅲ）混合价。Ｅｕ＾３＋的掺入直接影响了Ｓｒ离子与氧离子的结合。使Ｓｒ３ｐ３／２的结合能随Ｘ的增加而增加。     

改性SrTiO3陶瓷电容器材料的化学制备及电性研究

本文采用（Ｃ４Ｈ９Ｏ）４Ｔｉ，Ｓｒ（ＮＯ３）２和Ｎｉ（ＮＯ３）３为原料制成柠檬酸多元配合物溶液，经过形成溶胶凝胶过程，在一定条件下进行热分解，获得组成为：０．９１ＳｒＴｉＯ３＋０．０９（Ｂｉ２Ｏ３．３ＴｉＯ２）的陶瓷粉料，上述粉料掺入３ｍｏｌ％ＰｂＯ，３Ｍｏｌ％Ｌｉ２Ｏ和０．４ｍｏｌ％Ｒｂ２Ｏ后经混全，压片、干燥和烧结等步骤制成改性ＳｒＴｉＯ３电容器材料，电性研究表明，用这种材料制成的电容器其介电     

过渡金属二取代三元杂多酸盐的制备和表征

在水中由Na2 WO4 ·2H2 O ,Na2 MoO4 ·2H2 O和KH2 PO4 ·2H2 O反应生成具有半Dawson结构的钨钼混配杂多阴离子Na9PW6Mo3O34 ·1 0H2 O。以阴离子和过渡金属硝酸盐为原料在水溶液中合成了一系列过渡金属二取代的具有Keggin结构的杂多酸四丁基铵盐 [TBA]4 Hn[PW7Mo3M2 O38(H2 O) 2 ]·C3H6O(n =1 ,M =Fe3+;n =3,M =Mn2 +,Co2 +,Ni2 +,Cu2 +) ,用元素分析和波谱进行了表征。     

Vibrational analysis of Ag3(PO2NH)3, Na3(PO2NH)3 x H2O, Na3(PO2NH)3 x 4H2O,

FT IR and FT Raman spectra of Ag3(PO2NH), (Compound 1), Na3(PO2NH)3 x H2O (Compound II), Na3(PO2NH)3 x 4H2O (Compound III), [C(NH2)3]3(PO2NH)3 x H2O (Compound IV) and (NH4)4(PO2NH)4 x 4H2O (Compound V) are recorded and analyzed on the basis of the anions, cations and water molecules present in each of them. The PO2NH- anion ring in compound I is distorted due to the influence of Ag+ cation. Wide variation in the hydrogen bond lengths in compound III is indicated by the splitting of the v2 and v3 modes of vibration of water molecules. The NH4 ion in compound V occupies lower site symmetry and exhibits hindered rotation in the lattice. The correlations between the symmetric and asymmetric stretching vibrations of P-N-P bridge and the P-N-P bond angle have also been discussed.     

Structural Changes and Phase Transitions in Whitlockite-Like Phosphates

New compounds with a g -Ca 3 (PO 4 ) 2 structure type were found in three systems: Sr 9+ x M 1.5 m x (PO 4 ) 7 ( M = Mn, Fe, Co, Ni, Cu, and Cd; space group R 3 m ; Z = 3), Sr 9 R (PO 4 ) 7 ( R = Al, Sc, Cr, Fe, Ga, In, and Gd-Lu; space group P 2/ c , Z = 4), and Sr 9+2 x M 1+ x A 1 m 6 x (PO 4 ) 7 ( M = Mn, Ni, Cd; space group R 3 c and Z = 6 for A = Na, K; space group P 2/ m and Z = 4 for A = Li). Crystal structures of these compounds were determined by time-of-flight neutron, synchrotron X-ray, and laboratory X-ray powder diffraction. Reversible polar-to-centrosymmetric phase transitions ( R 3 c {\begin{array}{c}\\[-14pt]\hspace*{.5pt}\to\\[-7pt]\hspace*{-.5pt}\gets \end{array}} R 3 m ) were observed at high temperatures in Ca 3 m x Sr x (PO 4 ) 2 (0 h x h 12/7), Ca 10.5 m 1.5 x Fe x (PO 4 ) 7 (0 h x h 1), and Ca 9 R (PO 4 ) 7 . Solid solutions Ca 3 m x Sr x (PO 4 ) 2 (13/7 h x h 16/7) are centosymmetric with space group R 3 m at room temperature. These phase transitions were studied by high-temperature X-ray diffraction, second-harmonic generation, DSC, electric-conductivity and dielectric measurements.     

298.16 K时Na+, Mg2+//Cl-, SO42-, NO3-, H2O体系中NaCl饱和区域相平衡

采用等温溶解平衡法研究了五元体系Na+, Mg2+//Cl-, SO42-, NO3-, H2O在298.16 K下氯化钠饱和平衡体系的溶解度, 获得了相应的投影干盐图、氯图和水图. 研究结果表明, 在298.16 K下氯化钠饱和时, 该五元体系投影干盐图由8个二盐共饱和的双变面、13条三盐共饱的单变线和6个四盐共饱的零变点构成, 存在两种复盐, 8个二盐共饱双变面分别对应于NaCl+NaNO3, NaCl+Na2SO4, NaCl+MgCl2·6H2O, NaCl+MgSO4·Na2SO4·4H2O, NaCl+Mg(NO3)2·6H2O, NaCl+NaNO3·Na2SO4·2H2O, NaCl+MgSO4·7H2O 和NaCl+MgSO4·(1—6)H2O. 讨论了该相图在新疆硝酸盐矿开发利用过程中的应用.     

Synthesis and characterization of octa- and hexanuclear polyoxomolybdate wheels: role of the inorganic template and of the counterion

Eight new compounds based on [O3PCH2PO3]4- ligands and {MoV2O4} dimeric units have been synthesized and structurally characterized. Octanuclear wheels encapsulating various guests have been isolated with different counterions. With NH4+, a single wheel was obtained, as expected, with the planar CO32- guest, (NH4)12[(MoV2O4)4(O3PCH2PO3)4(CO3)2].24H2O (1a), while with the pyramidal SO32- guest, only the syn isomer (NH4)12[(MoV2O4)4(O3PCH2PO3)4(SO3)2].26H2O (2a) was characterized. The corresponding anti isomer was obtained with Na+ as counterions, Na12[(MoV2O4)4(O3PCH2PO3)4(SO3)2]39H2O (2b), and with mixed Na+ and NH4(+) counterions, Na+(NH4)11[(MoV2O4)4(O3PCH2PO3)4(SO3)2].13H2O (2d). With [O3PCH2PO3]4- extra ligands, the octanuclear wheel Li12(NH4)2[(MoV2O4)4(O3PCH2PO3)4(HO3PCH2PO3)2].31H2O (4a) was isolated with Li+ and NH4+ counterions and Li14[(MoV2O4)4(O3PCH2PO3)4(HO3PCH2PO3)2].34H2O (4c) as a pure Li+ salt. A new rectangular anion, formed by connecting two MoV dimers and two MoVI octahedra via methylenediphosphonato ligands with NH4+ as counterions, (NH4)10[(MoV2O4)2(MoVIO3)2(O3PCH2PO3)2(HO3PCH2PO3)2].15H2)O (3a), and Li9(NH4)2Cl[(MoV2O4)2(MoVIO3)2(O3PCH2PO3)2]. 22H2O (3d) as a mixed NH4+ and Li+ salt have also been synthesized. The structural characterization of the compounds, combined with a study of their behavior in solution, investigated by 31P NMR, has allowed a discussion on the influence of the counterions on the structure of the anions and their stability. Density functional theory calculations carried out on both isomers of the [(MoV2O4)4(O3PCH2PO3)4(SO3)2]12- anion (2), either assumed isolated or embedded in a continuum solvent model, suggest that the anti form is favored by approximately 2 kcal mol(-1). Explicit insertion of two solvated counterions in the molecular cavity reverses this energy difference and reduces it to less than 1 kcal mol(-1), therefore accounting for the observed structural versatility.     

Self-assembly of a series of extended architectures based on polyoxometalate clusters and silver coordination complexes

Three unusual compounds based on polyoxometalate building blocks, [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2][Ag2IMo6O24(H2O)4] x 6.25H2O (1), [(H2O)4Na2(C6NO2H5)6Ag3][IMo6O24] x 6H2O (2), and (C6NO2H6)2[(C6NO2H5)2Ag][Cr(OH)6Mo6O18] x 4H2O (3), have been synthesized and characterized by elemental analysis; IR, XPS, and ESR spectroscopy; TG analysis; and single-crystal X-ray diffraction. Compound 1 is constructed from the cationic two-dimensional (2D) coordination polymer sheets which are constituted of [(H2O)5Na2(C6NO2H4)(C6NO2H5)3Ag2]3+ and anionic [Ag2IMo6O24(H2O)4]3- chains as pillars, forming a three-dimensional (3D) supramolecular framework via weak Ag-O interactions. Compound 2 is composed of the well-defined [IMo6O24]5- building blocks, which are linked through trinuclear Ag-pyridine-3-carboxylic acid, [(C6NO2H5)6Ag3]3+, fragments into a one-dimensional (1D) hybrid chain; adjacent chains are further connected by sodium cations to yield a novel 2D network. Compound 3 has a 1D chainlike structure constructed from [Cr(OH)6Mo6O18]3- building blocks and Ag-pyridine-4-carboxylic acid coordination units. The crystal data for these compounds are the following: 1, triclinic, P1, a = 13.280(3) A, b = 13.641(3) A, c = 16.356(3) A, alpha = 89.68(3) degrees, beta = 88.31(3) degrees, gamma = 75.87(3) degrees, Z = 2; 2, triclinic, P1, a = 11.978(2) A, b = 12.008(2) A, c = 13.607(3) A, alpha = 116.14(3) degrees, beta = 108.85(3) degrees, gamma = 93.86(3) degrees, Z = 1; 3, triclinic, P1, a = 10.458(2) A, b = 10.644(2) A, c = 12.295(3) A, alpha = 97.40(3) degrees, beta = 112.38(3) degrees, gamma = 113.59(3) degrees, Z = 1.     

单斜层状LiMn0.97Al0.03O2-x(PO4)x材料的合成及其电化学性能

以Na₂CO₃, (CH₃CO₂)₂Mn·4H₂O, Al₂O₃, Na₃PO₄·12H₂O和CH₃COOLi·2H₂O为原料, 通过2次高温固相法和一步水热离子交换法得到一系列铝和磷掺杂的LiMn_0.97Al_0.03O₂, LiMnO_1.99(PO₄)_0.01和LiMn_0.97Al_0.03O_2-x(PO₄)_x(x=0.01, 0.03, 0.05)化合物. 用X射线衍射(XRD)表征了前驱体及交换产物的晶体结构, 用扫描电镜(SEM) 测定了晶体的形貌. 通过X射线光电子能谱(XPS)、傅里叶红外光谱及恒电流充放电测试, 研究了掺杂离子对合成材料结构及电化学性能的影响. 研究结果表明, Al-PO₄复合掺杂综合了Al³⁺掺杂提高材料的电化学反应活性和减低材料的电化学反应阻抗以及PO₄^3-掺杂增大材料的晶胞体积的特点, 提高材料中Li⁺的扩散能力, 有效地抑制了材料由于Jahn-Teller效应引起的结构畸变, 改性后的LiMnO₂正极材料既保持了较高的容量又获得了良好的电化学循环性能.     

Synthesis and characterization of protonated zirconium trisilicate and its exchange phases with strontium

A partially protonated form of the mineral umbite has been prepared by ion exchange of K2ZrSi3O9 x H2O with acetic acid. The protonated phase, compound 1, is assigned the formula H1.45K0.55ZrSi3O9 x 2 H2O and crystallizes in the space group P2(1)/c with unit cell dimensions of a = 7.1002(2), b = 10.1163(3), c = 13.1742(5), and beta = 91.181(1) degrees. The characteristic building blocks of the acid phase are almost identical to those of the parent compound. The framework is composed of polymeric chains of trisilicate groups linked by zirconium atoms, resulting in zeolite-type channels. When viewed down the a axis, two unique ion-exchange channels can be seen. Site 1 is marked by a 12-membered ring and contains 2 cations. Site 2, a 16-membered ring, contains 4 water molecules. Compound 2, consists of a mixed Sr2+ and K+ phase synthesized from 1 by ion exchange with Sr(NO3)2. Compound 2 has the formula K0.34Sr0.83ZrSi3O9 x 1.8 H2O and crystallizes in the same space group P2(1)/c. It has cell dimensions of a = 7.1386(3), b = 10.2304(4), c = 13.1522(4), and beta = 90.222(1) degrees. The Sr2+ cations are distributed evenly among the two exchange sites, showing no preference for either cavity. Compound 3 is the fully substituted Sr phase, SrZrSi3O9 x 2 H2O, and retains the same space group as that of the previous two compounds having unit cell dimensions of a = 7.1425(5), b = 10.2108(8), c = 13.0693(6), and beta = 90.283(1) degrees. The strontium cations show a slight affinity for ion-exchange site 2, having a higher occupancy of 0.535, while site 1 is occupied by the remainder of the Sr2+ cations with an occupancy of 0.465. Batch uptake studies demonstrate a selectivity series among alkaline earth cations of Ba2+ > Sr2+ > Ca2+ > Mg2+.     

A computational study on the kinetics and mechanism for the unimolecular decomposition of o-nitrotoluene

The kinetics and mechanism for the unimolecular decomposition of o-nitrotoluene (o-CH(3)C(6)H(4)NO(2)) have been studied computationally at the G2M(RCC, MP2)//B3LYP/6-311G(d, p) level of theory in conjunction with rate constant predictions with RRKM and TST calculations. The results of the calculations reveal 10 decomposition channels for o-nitrotoluene and its six isomeric intermediates, among them four channels give major products: CH(3)C(6)H(4) + NO(2), C(6)H(4)C(H)ON (anthranil) + H(2)O, CH(3)C(6)H(4)O (o-methyl phenoxy) + NO, and C(6)H(4)C(H(2))NO + OH. The predicted rate constants in the 500-2000 K temperature range indicate that anthranil production, taking place initially by intramolecular H-abstraction from the CH(3) group by NO(2) followed by five-membered ring formation and dehydration, dominates at temperatures below 1000 K, whereas NO(2) elimination becomes predominant above 1100 K and CH(3)C(6)H(4)O formation by the nitro-nitrite isomerization/decomposition process accounts for only 5-11% of the total product yield in the middle temperature range 800-1300 K. The branching ratio for CH(2)C(6)H(4)NO formation by the decomposition process of CH(2)C(6)H(4)N(O)OH is negligible. The predicted high-pressure-limit rate constants with the rate expression of 4.10 x 10(17) exp[-37000/T] s(-1) for the NO(2) elimination channel and 9.09 x 10(12) exp[-25800/T] s(-1) for the H(2)O elimination channel generally agree reasonably with available experimental data. The predicted high-pressure-limit rate constants for the NO and OH elimination channels are represented as 1.49 x 10(14) exp[-30000/T] and 1.31 x 10(15) exp[-38000/T] s(-1), respectively.     

Reactions of POxCly- ions with H and H2 from 298 to 500 K

Rate constants and product branching ratios for POxCly- ions reacting with H and H2 were measured in a selected ion flow tube (SIFT) from 298 to 500 K. PO2Cl-, PO2Cl2-, POCl2-, and POCl3- were all unreactive with H2, having a rate constant with an upper limit of <5 x 10(-12) cm3 s(-1). PO2Cl2- did not react with H atoms either, having a similar rate constant limit of <5 x 10(-12) cm3 s(-1). The rate constants for PO2Cl-, POCl2-, and POCl3- reacting with H showed no temperature dependence over the limited range of 298-500 K and were approximately 10-20% of the collision rate constant. Cl abstraction by H to form HCl was the predominant product channel for PO2Cl-, POCl2-, and POCl3-, with a small amount of Cl- observed from POCl2- + H. Reactions of O2 and O3 with the POCl- products ions from the reaction of POCl2- + H were observed to yield predominantly PO3- and PO2-, respectively. POCl- reacted with O2 and O3 with rate constants of 8.9 +/- 1.1 x 10(-11) and 5.2 +/- 3.3 x 10(-10) cm3 s(-1), respectively. No associative electron detachment in the reactions with H atoms was observed with any of the reactant ions; however, detachment was observed with a PO- secondary product ion at high H atom concentrations. Results of new G3 theoretical calculations of optimized geometries and energies for the products observed are discussed.