规整Mn-Zn-Mg-Al-CO3四元LDHs层状材料的水热合成、结构及性能

以Mn(NO3)2.6H2O、Zn(NO3)2.6H2O、Mg(NO3)2.6H2O和Al(NO3)3.9H2O为原料,采用水热合成法,一步合成了Mn-Zn-Mg-Al-CO3四元LDHs层状材料。采用ICP、元素分析仪、XRD、FTIR、TG-DSC、SEM、低温氮吸附-脱附等对样品进行了表征。探讨了pH值、反应温度、反应时间和原料配比对Mn-Zn-Mg-Al-CO3四元LDHs层状材料合成的影响。结果表明,在pH=10、反应温度控制在140℃、反应时间为24 h的条件下,可以合成出结构规整、晶形良好、各层间排列紧密有序的含不同比例金属阳离子的Mn-Zn-Mg-Al-CO3四元LDHs层状材料。其吸附等温线符合V型吸附,H3滞后环,晶体内层间存在2 nm以上的孔,晶体内部结构的有序性高,层间碳酸根离子的排列整齐,通道内孔密度大、孔径小、比表面积大。     

MgAl-EDTA柱撑水滑石的制备及其应用

以MgAl-CO3型水滑石为前体,由离子交换法进行插层组装,合成了EDTA柱撑的MgAl-EDTA水滑石,并用X射线衍射、红外光谱对样品进行了表征。探讨了n(Mg)/n(Al)摩尔比、pH、反应温度、EDTA与前体水滑石配比对插层反应的影响,结果表明,当n(Mg)/n(Al)摩尔比为2～3、pH在4.5左右、反应温度控制在150℃以上、同时保证过量的EDTA时,EDTA可以插入MgAl-CO3水滑石层间,取代CO23-,形成结构完好的EDTA柱撑水滑石。MgAl-EDTA柱撑水滑石通过层间EDTA对Cu2+的螯合作用,可以在较短的时间内吸附溶液中的Cu2+,溶液中Cu2+的去除率在96%以上。     

类凝胶法制备锂离子二次电池正极材料镍钴酸锂

以LiOH.H2O,Ni(NO3)2,6H2O,Co(NO3)2.6H2O,NH3.H2O为原料,在不同条件下以类凝胶法制备层状化合物LiNixCo1-xO2,并以此作正极材料进行电化学测试,结果表明,首次充电比容量达192mAh/g,首次放电比容量达140mAh/g,循环22次后其放电比容量保持在119mAh/g。     

钴镍铁水滑石的合成、表征及衍生复合氧化物酸碱催化活性研究

水滑石(Layered Double Hydroxides,简称LDHs)是一类具有层状结构的阴离子型粘土[1],其结构类似于水镁石,化学通式为x/n ·mH2O ,其中M2+和M3+分别代表层板上占据八面体氢氧化物中心位置的二价和三价金属离子,An-为层间阴离子.以半径相似的二价、三价过渡金属阳离子部分或全部取代Mg、Al可合成多种二元、三元甚至四元水滑石类化合物HTLcs(Hydrotalcite-like compounds);将较大的阴离子基团(如杂多阴离子等) 引入层间则可合成柱撑水滑.     

锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的低温燃烧合成

以LiNO3、Ni(NO3)2·6H2O、Co(NO3)2·6H2O、Mn(NO3)2、CO(NH2)2为原料,通过低温燃烧法在空气中合成了锂离子正极材料LiNi1/3Mn1/3Co1/3O2.采用XRD研究了合成产物的物相与结构,用SEM研究了合成产物的形貌,考察了点火温度、回火温度,回火时间以及锂过量对合成产物电化学性能的影响.研究结果表明,合成产物与层状LiNiO2的结构相同,属α-NaFeO2型层状结构,合成产物的粒度较小且比较均匀,并具有良好的电化学性能.采用低温燃烧法在空气中合成LiNi1/3Mn1/3Co1/3O2的最佳条件为:500℃点火,850℃回火20h,锂过量为15mol%.在此条件下得到的合成产物首次放电比容量达到158.9mAh/g.     

氧化硅柱层状铁钛酸盐的制备

层柱材料（如层柱粘土、金属磷酸盐等）因其有独特的物理化学性质而倍受人们青睐，并其中；层柱金属氧化物是一类近年来才开发的新型层柱材料．由于制备上的困难，迄今所报导的层柱金属氧化物为数甚少，K0.8Ti1.2O4是一个典型的层状金属氧化物，但由于期没有遇水溶胀性，用常规方法无法制备热稳定的无机氧化物柱层状铁钛酸盐．本文通过先将K0.8Ti1.2O4同n-CH3(CH2)5NH3Cl反应得到正已铵离子柱撑的层状铁钛酸盐，然后再与NH2(CH2)3Si(OC2HO)3（以下简称APS）反应，最后将所得产物在空气中焙烧可得新型氧化硅柱层状铁钛酸盐，该新材…     

杂多酸阴离子[Co_2Bi_2W_(20)O_(70)]~(10-)柱撑水滑石光催化降解甲基橙

采用离子交换法合成了一种新型的杂多酸阴离子[Co2Bi2W20O70]10-柱撑水滑石类层状化合物,利用X射线衍射仪和傅立叶变换红外光谱仪分析了其晶相结构;研究了[Co2Bi2W20O70]10-柱撑水滑石光催化降解甲基橙的活性.结果表明,合成的[Co2Bi2W20O70]10-杂多酸阴离子柱撑水滑石较好地保持了水滑石原有的晶体形貌,具有较高的离子交换度.与此同时,杂多酸阴离子替换NO3-后,可以在一定程度上提高催化剂的催化活性.这主要归因于水滑石材料中杂多酸阴离子和水滑石层板之间的协同效应.     

高比表面Al2O3柱撑纳米钛酸盐的制备

0引言近年来,柱撑法由于可以调节孔道结构和产物性能而被广泛用于制备高比表面的多孔催化剂及催化剂载体材料[1~3]。柱撑是指在无机层状主体化合物中引入客体聚合物阳离子,经热处理而形成二维多孔材料的过程[4]。以柱撑法在层状钛酸盐层间引入Keggin离子([Al13O4(OH)24(H2O)12]     

新型超分子化合物[ Co( L-alanato)2(phen) ]NO3·4H2O的水热合成及其晶体结构

以Co( NO3)2.6H2O,邻菲罗啉(phen)与L-丙氨酸(L-alanine)为原料,通过水热法合成了新型超分子化合物[ Co(L-alanato)2(phen)] NO3.4H2O(1),其结构经IR,元素分析和X-射线单晶衍射分析表征.1属三斜晶系,空间群P-1,晶胞参数a=10.121 9(5)(A),b...     

钴镁铁水滑石的合成、表征及衍生复合氧化物酸碱催化活性研究

以Co(NO3)2.6(H2O)、Mg(NO3)2.6(H2O)和Fe(NO3)3.9(H2O)为原料,以NaOH和Na2CO3为沉淀剂采用低过饱和共沉淀法合成了CoMgFe系列的碳酸根水滑石,通过XRD,IR,TG-DTA,等手段对样品进行测试和表征,X-衍射结果显示,其M2 /M3 投料物质的量比为2-4得到的水滑石为理想构型。经焙烧后,发现其复合氧化物对乙醇催化脱水、脱氢反应有一定的活性。     

2-Aminoisobutyric acid in Co(II) and Co(II)/Ln(III) chemistry: homometallic and heterometallic clusters

The synthesis and magnetic properties of 13 new homo- and heterometallic Co(II) complexes containing the artificial amino acid 2-amino-isobutyric acid, aibH, are reported: [Co(II)(4)(aib)(3)(aibH)(3)(NO(3))](NO(3))(4)·2.8CH(3)OH·0.2H(2)O (1·2.8CH(3)OH·0.2H(2)O), {Na(2)[Co(II)(2)(aib)(2)(N(3))(4)(CH(3)OH)(4)]}(n) (2), [Co(II)(6)La(III)(aib)(6)(OH)(3)(NO(3))(2)(H(2)O)(4)(CH(3)CN)(2)]·0.5[La(NO(3))(6)]·0.75(ClO(4))·1.75(NO(3))·3.2CH(3)CN·5.9H(2)O (3·3.2CH(3)CN·5.9H(2)O), [Co(II)(6)Pr(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Pr(NO(3))(5)]·0.41[Pr(NO(3))(3)(ClO(4))(0.5)(H(2)O)(1.5)]·0.59[Co(NO(3))(3)(H(2)O)]·0.2(ClO(4))·0.25H(2)O (4·0.25H(2)O), [Co(II)(6)Nd(III)(aib)(6)(OH)(3)(NO(3))(2.8)(CH(3)OH)(4.7)(H(2)O)(1.5)]·2.7(ClO(4))·0.5(NO(3))·2.26CH(3)OH·0.24H(2)O (5·2.26CH(3)OH·0.24H(2)O), [Co(II)(6)Sm(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Sm(NO(3))(5)]·0.44[Sm(NO(3))(3)(ClO(4))(0.5)(H(2)O)(1.5)]·0.56[Co(NO(3))(3)(H(2)O)]·0.22(ClO(4))·0.3H(2)O (6·0.3H(2)O), [Co(II)(6)Eu(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)OH)(4.87)(H(2)O)(1.13)](ClO(4))(2.5)(NO(3))(0.5)·2.43CH(3)OH·0.92H(2)O (7·2.43CH(3)OH·0.92H(2)O), [Co(II)(6)Gd(III)(aib)(6)(OH)(3)(NO(3))(2.9)(CH(3)OH)(4.9)(H(2)O)(1.2)]·2.6(ClO(4))·0.5(NO(3))·2.58CH(3)OH·0.47H(2)O (8·2.58CH(3)OH·0.47H(2)O), [Co(II)(6)Tb(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·[Tb(NO(3))(5)]·0.034[Tb(NO(3))(3)(ClO(4))(0.5)(H(2)O)(0.5)]·0.656[Co(NO(3))(3)(H(2)O)]·0.343(ClO(4))·0.3H(2)O (9·0.3H(2)O), [Co(II)(6)Dy(III)(aib)(6)(OH)(3)(NO(3))(2.9)(CH(3)OH)(4.92)(H(2)O)(1.18)](ClO(4))(2.6)(NO(3))(0.5)·2.5CH(3)OH·0.5H(2)O (10·2.5CH(3)OH·0.5H(2)O), [Co(II)(6)Ho(III)(aib)(6)(OH)(3)(NO(3))(3)(CH(3)CN)(6)]·0.27[Ho(NO(3))(3)(ClO(4))(0.35)(H(2)O)(0.15)]·0.656[Co(NO(3))(3)(H(2)O)]·0.171(ClO(4)) (11), [Co(II)(6)Er(III)(aib)(6)(OH)(4)(NO(3))(2)(CH(3)CN)(2.5)(H(2)O)(3.5)](ClO(4))(3)·CH(3)CN·0.75H(2)O (12·CH(3)CN·0.75H(2)O), and [Co(II)(6)Tm(III)(aib)(6)(OH)(3)(NO(3))(3)(H(2)O)(6)]·1.48(ClO(4))·1.52(NO(3))·3H(2)O (13·3H(2)O). Complex 1 describes a distorted tetrahedral metallic cluster, while complex 2 can be considered to be a 2-D coordination polymer. Complexes 3-13 can all be regarded as metallo-cryptand encapsulated lanthanides in which the central lanthanide ion is captivated within a [Co(II)(6)] trigonal prism. dc and ac magnetic susceptibility studies have been carried out in the 2-300 K range for complexes 1, 3, 5, 7, 8, 10, 12, and 13, revealing the possibility of single molecule magnetism behavior for complex 10.     

EDTA辅助水热法合成硫化铋晶体

以Bi(NO3)3·5H2O和Na2S2O3·5H2O为原料,用乙二胺四乙酸(EDTA)辅助水热法合成了纳米或微米级的Bi2S3晶体(1),其结构、形貌和光谱性能经XRD,FE-SEM和UV-Vis表征。结果表明:溶液的pH对1的形貌有显著的影响,随着pH的增大,1由纳米棒组成的微米球逐渐转变为微米级片状结构;1出现蓝移。     

水热法制纳米CeO2膜及紫外吸收性能研究

以Ce(NO3)3.6H2O和CO(NH2)2为原料,采用水热法在玻璃基质上制备了CeO2纳米膜。研究了水热温度和时间对所制备纳米CeO2薄膜的抗紫外性能的影响。采用XRD、FT-IR、SEM、UV-Vis以及自动椭圆偏振仪等测试手段对CeO2纳米膜及粉体进行了表征。结果表明,水热法制备的薄膜,最佳的水热工艺条件为水热温度130℃加热7 h。在此条件下,制备的薄膜厚度达100nm,晶型较好,膜表面平整度较高,且具有优异的可见光透过性和紫外吸收特性。     

Co掺杂ZnO纳米棒的水热法制备及其光致发光性能

以Zn(NO3)2·6H2O 和Co(NO3)2·6H2O为原料, 通过水热法在较低温度下制备了纯ZnO和Co掺杂的ZnO(ZnO:Co)纳米棒. 利用XRD、EDS、TEM和HRTEM对样品进行了表征, 结合光致发光(PL)谱研究了样品的PL性能. 结果表明, 水热法制备纯ZnO和ZnO:Co纳米棒均具有较好的结晶度. Co2+是以替代的形式进入ZnO晶格, 掺入量为2%(原子分数)左右. 纯的ZnO纳米棒平均直径约为20 nm, 平均长度约为180 nm; 掺杂样品的平均直径值约为15 nm, 平均长度约为200 nm左右; Co掺杂轻微地影响ZnO纳米棒的生长. 另外, Co掺杂能够调整ZnO纳米棒的能带结构、提高表面态含量, 进而使得ZnO:Co纳米棒的紫外发光峰位红移, 可见光发光能力增强.     

Synthesis, structure, and characterization of a new thorium-organic framework material, Th3F5[(C10H14)(CH2CO2)2]3(NO3)

A new three-dimensional cubic thorium-organic framework material, Th3F5[(C10H14)(CH2CO2)2]3(NO3) has been synthesized under mild hydrothermal reaction conditions using Th(NO3)4 x 6H2O, 1,3-adamantanediacetic acid, and aqueous HF as reagents.     

Mutual sensitization of the oxidation of nitric oxide and a natural gas blend in a JSR at elevated pressure: experimental and detailed kinetic modeling study

The mutual sensitization of the oxidation of NO and a natural gas blend (methane-ethane 10:1) was studied experimentally in a fused silica jet-stirred reactor operating at 10 atm, over the temperature range 800-1160 K, from fuel-lean to fuel-rich conditions. Sonic quartz probe sampling followed by on-line FTIR analyses and off-line GC-TCD/FID analyses were used to measure the concentration profiles of the reactants, the stable intermediates, and the final products. A detailed chemical kinetic modeling of the present experiments was performed yielding an overall good agreement between the present data and this modeling. According to the proposed kinetic scheme, the mutual sensitization of the oxidation of this natural gas blend and NO proceeds through the NO to NO2 conversion by HO2, CH3O2, and C2H5O2. The detailed kinetic modeling showed that the conversion of NO to NO2 by CH3O2 and C2H5O2 is more important at low temperatures (ca. 820 K) than at higher temperatures where the reaction of NO with HO2 controls the NO to NO2 conversion. The production of OH resulting from the oxidation of NO by HO2, and the production of alkoxy radicals via RO2 + NO reactions promotes the oxidation of the fuel. A simplified reaction scheme was delineated: NO + HO2 --> NO2 + OH followed by OH + CH4 --> CH3 + H2O and OH + C2H6 --> C2H5 + H2O. At low-temperature, the reaction also proceeds via CH3 + O2 (+ M) --> CH3O2 (+ M); CH3O2 + NO --> CH3O + NO2 and C2H5 + O2 --> C2H5O2; C2H5O2 + NO --> C2H5O + NO2. At higher temperature, methoxy radicals are produced via the following mechanism: CH3 + NO2 --> CH3O + NO. The further reactions CH3O --> CH2O + H; CH2O + OH --> HCO + H2O; HCO + O2 --> HO2 + CO; and H + O2 + M --> HO2 + M complete the sequence. The proposed model indicates that the well-recognized difference of reactivity between methane and a natural gas blend is significantly reduced by addition of NO. The kinetic analyses indicate that in the NO-seeded conditions, the main production of OH proceeds via the same route, NO + HO2 --> NO2 + OH. Therefore, a significant reduction of the impact of the fuel composition on the kinetics of oxidation occurs.     

双吡啶化合物3，7-di(3-pyridyl)-1，5-dioxa-3，7-diazacyclooctane构建的四个过渡金属配合物的合成、结构及热稳定性

采用准刚性的双吡啶化合物3,7-di(3-pyridyl)-1,5-dioxa-3,7-diazacyclooctane(L),合成了4个过渡金属配合物[Co(NO3)(H2O)2(L)2]NO3(1)、[Co2Cl4(L)2]·CH2Cl2(2)、[Cd2(AcO)4(L)2]·4CH3OH(3)和[Cd2(NO3)2(CH3OH)2(H2O)2(L)2](NO3)2·2H2O(4)。单晶衍射分析表明,配合物1是单核结构,配合物2是24-元环状双核结构,而配合物3和4为多边形双核结构。在这些配合物中,双吡啶配体分别采用了单齿、trans-和cis-桥连3种不同配位方式。配合物经过了元素分析、红外、热重和X射线单晶结构分析表征。     

pH-dependent H2-activation cycle coupled to reduction of nitrate ion by CpIr complexes.

This paper reports a pH-dependent H2-activation [H2 (pH 1-4) --> H+ + H- (pH -1) --> 2H+ + 2e-] promoted by CpIr complexes [Cp = eta5-C5(CH3)5]. In a pH range of about 1-4, an aqueous HNO3 solution of [CpIr(III)(H2O)3]2+ (1) reacts with 3 equiv of H2 to yield a solution of [(CpIr(III))2(mu-H)3]+ (2) as a result of heterolytic H2-activation [2[1] + 3H2 (pH 1-4) --> [2] + 3H+ + 6H2O]. The hydrido ligands of 2 display protonic behavior and undergo H/D exchange with D+: [M-(H)3-M]+ + 3D+ <==>[M-(D)3-M]+ + 3H+ (where M = CpIr). Complex 2 is insoluble in a pH range of about -0.2 (1.6 M HNO3/H2O) to -0.8 (6.3 M HNO3/H2O). At pH -1 (10 M HNO3/H2O), a powder of 2 drastically reacts with HNO3 to give a solution of [CpIr(III)(NO3)2] (3) with evolution of H2, NO, and NO2 gases. D-labeling experiments show that the evolved H2 is derived from the hydrido ligands of 2. These results suggest that oxidation of the hydrido ligands of 2 [[2] + 4NO3- (pH -1) --> 2[3] + H2 + H+ + 4e-] couples to reduction of NO3- (NO3- --> NO2- --> NO). To complete the reaction cycle, complex 3 is transformed into 1 by increasing the pH of the solution from -1 to 1. Therefore, we are able to repeat the reaction cycle using 1, H2, and a pH gradient between 1 and -1. A conceivable mechanism for the H2-activation cycle with reduction of NO3- is proposed.     

Reflected shock tube studies of high-temperature rate constants for OH + CH4 --> CH3 + H2O and CH3 + NO2 --> CH3O + NO

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm has been used to study the reactions OH + CH(4) --> CH(3) + H(2)O and CH(3) + NO(2) --> CH(3)O + NO. Over the temperature range 840-2025 K, the rate constants for the first reaction can be represented by the Arrhenius expression k = (9.52 +/- 1.62) x 10(-11) exp[(-4134 +/- 222 K)/T] cm(3) molecule(-1) s(-1). Since this reaction is important in both combustion and atmospheric chemistry, there have been many prior investigations with a variety of techniques. The present results extend the temperature range by 500 K and have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range 195-2025 K. A three-parameter expression describes the rate behavior over this temperature range, k = (1.66 x 10(-18))T(2.182) exp[(-1231 K)/T] cm(3) molecule(-1) s(-1). Previous theoretical studies are discussed, and the present evaluation is compared to earlier theoretical estimates. Since CH(3) radicals are a product of the reaction and could cause secondary perturbations in rate constant determinations, the second reaction was studied by OH radical production from the fast reactions CH(3)O --> CH(2)O + H and H + NO(2) --> OH + NO. The measured rate constant is 2.26 x 10(-11) cm(3) molecule(-1) s(-1) and is not dependent on temperature from 233 to 1700 K within experimental error.