Nitrogen Doped Carbon as Efficient Catalyst toward Oxygen Reduction Reaction

A kind of nitrogen-doped carbon(NC) nanomaterials was prepared via calcining the nitrogen-rich organic molecular glycoluril under nitrogen atmosphere. Elemental analysis result indicates the N content of the obtained NC is 13.9 wt.%. Electrochemical measurement demonstrated that the obtained NC catalyst is an efficient ORR electrocatalyst in alkaline electrolyte. The process of ORR is dominated by a four-electron transfer pathway with the most efficient catalytic activity. In addition, the NC catalyst exhibits excellent stability and good resistance to methanol poisoning. After 10000 s of chronoamperometric durability test, the relative current of NC catalyst retained as high as 95%. This work provides a new strategy for the preparation of cost-effective ORR catalysts with high catalytic performance.     

瓜环基金属纳米催化剂的电化学研究进展（英文）

金属纳米材料在电催化应用中展示出良好的性能,但是它们依旧面临着稳定性差和调控策略有限的问题。引入第二组分是一种有效的策略,能够很好的改善其催化活性与稳定性。在这篇综述中,我们概述了结合金属纳米材料和瓜环（CB[n]）用于电催化应用。瓜环是一系列的具有刚性结构、高稳定性、与金属配位的官能团的大环,它们适合稳定金属纳米材料并对其进行调控。本文讨论按照瓜环的功能分类,包含瓜环作为保护剂、瓜环基的超分子自组装体以及瓜环作为前驱体制备氮掺杂多孔碳。多种金属纳米催化剂,包括金属纳米颗粒（Pt,Ir,Pd,Ru,Au）、金属单原子（Fe,Co,Ni）以及过渡金属碳化物（TMCs）成功与瓜环或瓜环衍生的碳材料复合,这些复合材料在许多电催化反应中展示出优异的性能和稳定性,反应包括了氧还原反应（ORR）、析氧反应（OER）、析氢反应（HER）、二氧化碳还原反应（CO2RR）、甲烷氧化反应（MOR）、乙醇氧化反应（EOR）。其中,一些金属-瓜环复合物可进一步作为双功能催化剂用于全水解和燃料电池中。瓜环基的纳米催化剂具有媲美商用催化剂的性能,甚至其稳定性可优于商用催化剂。实验分析以及密度泛函理论（DFT）计算...     

Synthesis and Crystal Structure of a New Noble Metalcontaining Supramolecular Self-assembly with Decamethylcucurbit[5]uril

A new supramolecular self-assembly [Li(H2 O)2]2[(H2 O@Me10 CB[5])][PtC l6]·7 H2 O(1, Me10 CB[5] = decamethylcucurbit[5]uril), has been successfully constructed with Me10 CB[5] and [PtCl6]^2- anion in the presence of lithium cation(Li+). Single-crystal X-ray diffraction study reveals that compound 1 crystallizes in monoclinic space group P21/n with a = 11.1681(18), b = 28.5425(4), c = 18.9342(3) ?, β = 99.0143(15)°, V = 5961.02(16) ?~3, Z = 4, F(000) = 3224, μ = 2.714 mm^-1, R = 0.0470 and wR = 0.1076(I > 2σ(I)). In the supramolecular self-assembly, two of the portal carbonyl oxygen atoms of Me10 CB[5] are coordinated to Li+ cation, yielding a "half-open" molecular capsule. Then adjacent molecular capsules are connected with each other through hydrogen-bonding to form a one-dimensional(1 D) supramolecular chain structure. The [PtCl6]^2- anions are fixed on one side of the 1 D supramolecular chain through supramolecular interactions. The thermal stability, electronic valence and morphology of compound 1 are also investigated.     

一个新的双核锌配合物Zn2(dhaash)2(py)4的合成及晶体结构

The crystal of binuclear zinc complex Zn₂(dhaash)₂(py)₄ was obtained in DMF and pyridine, where H₂dhaash is 2,4-dihydroxy-5-acetylacetophenone-N-salicylhydrazone. It has been characterized by IR, UV, element analysis and X-ray single crystal diffraction. The crystallographic data were as follows: monoclinic system, space group P2₁/c, a=1.108 98(11) nm, b=1.640 84(16) nm, c=1.445 14(14) nm, β=108.617(2)°, Z=2, V=2.492 1(4) nm³, D_c=1.466 g·cm^-3, M_r=1 099.74, μ=1.031 mm^-1, F(000)=1 136 and the final R=0.044 8 and wR=0.105 8 for 4 143 observed reflections with I≥2σ(I), respectively. The X-ray crystal structure analysis revealed that, in the centrosymmetric binuclear complex molecule, two zinc(Ⅱ) centers are linked by two oxygen atoms (O(3) and O(3A)), respectively. Zn(1)…Zn(1A) distance is 0.314 81(6) nm, O(3)…O(3A) distance is 0.270 4(2) nm. Every zinc(Ⅱ) ion has an elongated octahedral coordination. For example, the two pyridine nitrogen atoms, one oxygen atom and one nitrogen atom from salicylhydrazone, one oxygen atom from 2,4-dihydroxy-5-acetylacetophenone in one dhaash^2- ligand and one oxygen atom from 2,4-dihydroxy-5-acetylacetophenone in another dhaash^2- ligand coordinated to zinc(Ⅱ) ion, respectively. Two zinc(Ⅱ) ions and all the 72 non-hydrogen atoms in the two dhaash^2- ligands are in the same plane. CCDC: 261929.