Synthesis, X-ray crystal structures, and gas sorption properties of pillared square grid nets based on paddle-wheel motifs: implications for hydrogen storage in porous materials

A systematic modulation of organic ligands connecting dinuclear paddle-wheel motifs leads to a series of isomorphous metal-organic porous materials that have a three-dimensional connectivity and interconnected pores. Aromatic dicarboxylates such as 1,4-benzenedicarboxylate (1,4-bdc), tetramethylterephthalate (tmbdc), 1,4-naphthalenedicarboxylate (1,4-ndc), tetrafluoroterephthalate (tfbdc), or 2,6-naphthalenedicarboxylate (2,6-ndc) are linear linkers that form two-dimensional layers, and diamine ligands, 4-diazabicyclo[2.2.2]octane (dabco) or 4,4'-dipyridyl (bpy), coordinate at both sides of Zn(2) paddle-wheel units to bridge the layers vertically. The resulting open frameworks [Zn(2)(1,4-bdc)(2)(dabco)] (1), [Zn(2)(1,4-bdc)(tmbdc)(dabco)] (2), [Zn(2)(tmbdc)(2)(dabco)] (3), [Zn(2)(1,4-ndc)(2)(dabco)] (4), [Zn(2)(tfbdc)(2)(dabco)] (5), and [Zn(2)(tmbdc)(2)(bpy)] (8) possess varying size of pores and free apertures originating from the side groups of the 1,4-bdc derivatives. [Zn(2)(1,4-bdc)(2)(bpy)] (6) and [Zn(2)(2,6-ndc)(2)(bpy)] (7) have two- and threefold interpenetrating structures, respectively. The non-interpenetrating frameworks (1-5 and 8) possess surface areas in the range of 1450-2090 m(2)g(-1) and hydrogen sorption capacities of 1.7-2.1 wt % at 78 K and 1 atm. A detailed analysis of the sorption data in conjunction with structural similarities and differences concludes that porous materials with straight channels and large openings do not perform better than those with wavy channels and small openings in terms of hydrogen storage through physisorption.     

Photochemical Synthesis and Spectral-Optical Characteristics of ZnO/Cu and ZnO/Ag/Cu Nanoheterostructures

The photoreduction of Cu²⁺ at the surface of ZnO nanoparticles and ZnO/Ag nanostructures was investigated. The spectral characteristics of the obtained ZnO/Cu and ZnO/Ag/Cu composites were studied in relation to the reaction conditions. It was shown that the ZnO/Ag nanoparticles have higher photocatalytic activity in the reduction of Cu²⁺ ions than the individual ZnO particles.     

Elucidation of the Role of the Complex in Hydride Transfer Reaction between Methylene Blue and 1-Benzyl-1,4-dihydronictinamide by Effect of γ-Cyclodextrin

The kinetics of the hydride transfer reaction between Methylene Blue (MB⁺) and 1-benzyl-1,4-dihydronicotinamide (BNAH) were studied in 10% ethanol-90% water mixed solvents containing β- and γ-cyclodextrins (β-CD and γ-CD). The pseudo-first order rate constant shows kinetic saturation at high initial concentration of BNAH. This indicates the formation of a complex between MB⁺ and BNAH. The reaction was suppressed by addition of β-CD, but enhanced by addition of γ-CD. MB⁺ and BNAH were separately accommodated within the β-CD cavity and the cavity walls may protect the activity site of the reactants. On the other hand, in the MB⁺-BNAH-γ-CD system, the inclusion of the complex between MB⁺ and BNAH with γ-CD occurred. This effect of γ-CD can distinguish between the productive and non-productive nature of the complex.     

含铜三元类水滑石化合物的合成及其性质

 以Cu（NO3）2，Zn（NO3）2和Al（NO3）3为原料，以NaOH为沉淀剂，利用共沉淀法合成了含铜三元类水滑石化合物CuZnAl－HTLcs．从不同Cu／Zn／Al比的混合原料溶液的滴定曲线入手，详细探讨了溶液pH值、原料加入方式、组分配比及水热处理条件对类水滑石合成的影响，利用XRD，ICP及比表面积测定对合成物进行了表征，并以苯酚羟基化为探针反应评价了催化剂的催化性能．结果表明，在体系pH＝5．0～6．2，（Cu＋Zn）／Al摩尔比＝2．0，Cu／Zn摩尔比≤1．0及室温条件下共沉淀后，于100℃水热处理3h，即可得到晶相单一和结晶度高的CuZnAl－HTLcs．变化pH法合成的样品的相对结晶度为100％，低过饱和法为76．5％，高过饱和法为75．9％．合成的CuZnAl－HTLcs中Cu2＋的含量均比原料液中Cu2＋的含量有所增加，这可能是由于在pH＝5．8时Cu2＋对Al（OH）3的同晶取代能力比Zn2＋强．随着CuZnAl－HTLcs中Cu含量的增加，催化剂对苯酚羟化反应的催化活性逐渐增大．     

Nitro-PAPS分光光度法测定葡萄糖酸锌

为建立一种快速、简便、灵敏分光光度法测定葡萄糖酸锌方法,在非离子型表面活性剂聚氧乙烯失水山梨醇油酸单脂(Tween-80)及聚氧乙烯异辛基苯基醚(TritonX-100)存在下,用水溶性试剂2-(5-硝基-2-吡啶偶氮)-5-[N-正丙基-N-(3-磺酸丙基)氨基]苯酚二钠(简称Nitro-PAPS)作显色剂直接光度法测定葡萄糖酸锌。结果表明,该法显色络合物最大吸收波长为580nm,本法线性范围为0~1μg/mL,表观摩尔吸光数为1.41×105L.mol-1.cm-1,回收率为98.5%~102.8%。该法具有操作快速、简便、结果灵敏可靠等优点,应用本法直接测定补锌口服液葡萄糖酸锌含量,结果满意。     

Synthesis and Characterization of Novel Orange-emitting Iridium（Ⅲ） Complexes with Diphenylquinoline Ligands Containing Fluorinated Substituent

Three new cyclometalated iridium（m） complexes based on ligands of diphenylquinoline with fluorinated subsfituents were prepared, and characterized by elemental analysis （EA）, ^1H NMR, and mass spectroscopy （MS）. The photophysical and electrophosphorescent properties of the complexes were briefly discussed.     

Synthesis and X-ray crystal structures of six [TeL4][MF6] salts, where L is ethylene- or trimethylene-thiourea, and M is Si, Ge or Sn. Five Te(II) complexes with a novel type of structure linked together by unusual N–HF hydrogen bonds

The complexes [Te(etu)₄][SiF₆] (1), [Te(etu)₄][SiF₆] · H₂O (2), [Te(trtu)₄][SiF₆] (3), [Te(etu)₄][GeF₆] · H₂O (4), [Te(trtu)₄][GeF₆] (5) and [Te(etu)₄][SnF₆] (6) (etu = ethylenethiourea, trtu = trimethylenethiourea) have been prepared and their crystal structures determined by X-ray crystallographic methods. The crystals of 1, 3 and 5 are tetragonal; space groups P4cc (No. 103) with Z = 4 for 1, P4nc (No. 104) with Z = 2 for 3, and I4 (No. 79) with Z = 2 for 5. The crystals of 2, 4 and 6 are orthorhombic, space group Pccn (No. 56) with Z = 8 for 2 and 4 and Z = 4 for 6; those of 2 and 4 being isomorphous. The cations contain square planar or slightly distorted square planar TeS₄ coordination groups. In 1, 3 and 5 the Te atoms are located on fourfold rotation axes; the cations have fourfold rotational symmetry and the four thiourea ligands extend to the same side of the TeS₄ plane. These are the first examples of [TeL₄]²⁺ conformers of this type. In 2 and 4 the Te atoms lie on general positions; the cations are distorted versions of those in 1, and also in these the four ligands extend to the same side of the TeS₄ plane. In 6 the Te atoms are located on twofold rotation axes, the conformation of the cations corresponds to the point group C₂ with two neighbouring ligands extending to one side of the coordination plane and the remaining two to the opposite side. In 1–5 each of the four ligands forms a N–HF bond to the same F atom in the counter ion. The crystals of 1–5 are red, and those of 6 are yellow. The red colour is attributed to interactions of Te and S lone electron pairs caused by ligand TeS₄/TeSC tilt angles markedly different from 90°.     

酯交换法合成碳酸二苯酯用氧化铅－氧化锌催化剂的研究

 制备了一种用于苯酚与碳酸二甲酯酯交换合成碳酸二苯酯的新型氧化铅－氧化锌多相催化剂．研究了制备方法、焙烧温度、不同母体和母体配比对催化剂催化性能的影响．应用XRD，TPR和原子吸收光谱对催化剂结构进行了表征，发现Pb3O4是主活性物相，ZnO为助催化剂，并以非晶态或微晶态存在于催化剂体系中．当焙烧温度为500℃，n（Pb）／n（Zn）≈2时，催化剂的活性最高，碳酸二苯酯产率可达45．6％．考察了催化剂的重复使用效果，并对失活原因进行了探讨．     

Conductance Study of the Binding of K+ by Dibenzo-pyridino-18-crown-6 and 1,10-N,N′-didecyl-diaza-18-crown-6 in Acetonitrile

The binding of K+ by dibenzo-pyridino-18-crown-6 (B2-py-18-C-6) and1,10-N,N-didecyl-diaza-18-crown-6 (22-DD) has been studiedconductometrically at 10, 15, 20 and 25 °C in acetonitrile. Thecomplexes formed were assumed to have 1 : 1 stoichiometry. The complexes ofK+ with 18-crown-6 (18-C-6) and dibenzo-18-crown-6 (B2-18-C-6) were alsostudied for comparison purposes. The stability constant, K, of a givencomplex and its molar conductance, c, were obtained by subjectingthe conductance data to a non-linear least-squares curve fitting procedure.The values of the enthalpy change, H, the entropy change, Sand the Gibbs free energy, G, associated with the formation of the 1: 1 complexes were derived and compared with relevant literature data. Thevalues of G at 25 °C indicate that the binding capacity of thefour macrocycles follows the order 18-C-6 > 22-DD > B2-18-C-6 >B2-py-18-C-6. The difference between the molar ionic conductance of the freeK+ cation and that of the bound cation, KL+, was estimated and the trend insuch differences correlates with the molecular size of the macrocycle, L.