An Investigation on the Production of Random Copolymer with Monothiocarbonate and Trithiocarbonate Units over Cyclic Thiocarbonate via Metal‐free Catalysis

Synthesis of poly(thiocarbonate)s from the copolymerization of epoxides and carbon disulfide (CS₂) remains a tough challenge, due to inevitable oxygen‐sulfur atom scrambling process. In this work, we utilized the oxygen‐sulfur exchange reaction (O‐S ER) to synthesize a random copolymer with monothiocarbonate and trithiocarbonate units from CS₂ and phenyl glycidyl ether (PGE) via metal‐free Lewis pairs. The copolymers contained monothiocarbonate and trithiocarbonate units of which the molar fraction could be tuned by varying either the types of Lewis pairs or the reaction temperature. Keeping track on the intermediate provided an insight in the process of O‐S ER and thus gave a hint to control the product structure. Production and consumption of phenyl thioglycidyl ether was the key process to regulate the chain structure. Remarkably, the oxygen atoms of PGE could be excluded out of the chain, resulting in the nearly complete production of poly(trithiocarbonate)s. Correspondingly, the refractive index of this kind of copolymer could be regulated in a wide range of 1.73—1.79 (at 590 nm).     

活性位高度暴露的钴/氮/碳电催化剂的构建及氧还原性能研究

金属/氮/碳催化剂（M/N/C，M=Fe、Co等）是最有发展前景的非贵金属电催化剂之一，其性能依赖于催化剂表面的活性物种密度.通过常规的热解含氮前驱物与金属盐的方法制得的催化剂往往存在金属活性物种被包埋而不能有效利用的缺点.考虑到石墨相氮化碳（g-C₃N₄）富含类吡啶氮和亚纳米孔腔结构，将g-C₃N₄包覆在高导电性碳纳米笼（hCNC）表面，进而利用表层g-C₃N₄的配位和限域作用锚定大量Co²⁺离子，获得的Co/g-C₃N₄/hCNC复合物经热解后形成了活性位高度暴露、导电性好、孔结构丰富的Co/N/C催化剂.800℃热解得到的最优化催化剂在碱性介质中展现出优异氧还原活性，其起始电位（0.97 V）与商业Pt/C催化剂相当，且抗甲醇干扰性能和稳定性优异.此项研究提供了一种构建具有高度暴露活性位的M/N/C催化剂的有效策略.     

K/Ru(10ī0)表面上的CO-4a1轨道对称性确定

用同步辐射角分辨偏振紫外光电子谱对Ｋ／Ｒｕ（１０１０）面上吸附分子轨道的对称性测量发现：结合能在１１、．２ｅＶ的ＣＯ－４ａ１（４σ）分子轨道对ｓ偏振光（在沿〈１２１０〉的人射面）是禁戒的。结果表明由于Ｋ的强烈影响,ＣＯ的分子轨道重新排列（ｓＰ＾２杂化）。依据选择定则和分子轨道的对称性６说明,ｓｐ＾２再杂化的ＣＯ分子吸附的桥位取向是〈１２１０〉晶向。     

甲烷在Ni表面及La薄膜上激活解离化学吸附

利用分子束技术改变甲烷的平动能E_k来研究E_k及其法向分量E_n对甲烷在Ni表面及La薄膜上激活解离吸附的影响。对CH_4/Ni及CH_4/La系统, 当甲烷的平动能E_k分别低于58.5 kJ·mol~(-1)及52.3 kJ·mol~(-1)时, 没观察到甲烷的解离吸附。当甲烷的平动能超过此阈值时, 即对CH_4/Ni系统, 当Ek=58.5增至63.8 kJ·mol~(-1)时, 初始沾着几率s_0由0至0.54线性增加; 对CH_4/La系统, 当E_k=52.3增至63.8 kJ·mol~(-1)时, S_0由0至0.49线性增加。这些结果表明, 两个系统的化学吸附是不经过前趋态的直接化学吸附。最后求出CH_4/Ni, CH_4/La系统的表观活化能分别为46.8 kJ·mol~(-1)和38.1 kJ·mol~(-1)。     

2,2-二羟甲基-1,3-丙二醇在275-510 K间的热容和相变

许多多元醇在270-500K间具有相变焓很大的固-固相变,是一类潜在的固-固相变低温储能物质。2,2-二羟甲基-1,3-丙二醇是一种重要的多元醇,除在化工方面有广泛的应用外,在低温储能方面也有相当乐观的开发前景。它的有关热性质虽已有一些DSC研究报道,但数据精度较差并缺乏系统性。作为系统研究多元醇及其固体溶液热力学性质工作的一部份,本文将报道2,2-二羟甲基-1,3-丙二醇在275—500K间的热容和相变,并根据所测其固-固相变焓数据讨论该物质被破坏的平均氢键键能。     

聚对苯二甲酸乙二酯非晶区反式构象结构的探讨

<正> 聚对苯二甲酸乙二酯(PET)的重复单元中有乙撑基。它的碳碳键内旋转产生反式构象(T)和左右式构象(G)。用其不同的构象来表征PET的聚集态结构,对研究结构与性能的关系是十分重要的。许多工作都已指出,乙撑基反式构象的谱带热处理时随结晶度的增加而增加。X-射线衍射的结果证实     

Photorearrangement of photocycloadducts from arenes and 1,3-cyclohexadiene

The 4π_s+π_s photoadduct from an arene and 1,3-cyclohexadiene may undergo a photochemical rearrangement to the 4π_s+π_s adduct.     

Synthesis and Crystal Structure of Complex of Sodium Perrhenate with Tetraethyl p-tert-Butylcalix[4]arene Tetraacetate

Recently,theconformationofthecalixarenehasbeenshowntobeimportantincontrollingtheseIectivityofthereceptor.Forexample,sodiumioncouldbeboundverystronglybyesterderivativesofcalix[4]areneintheconeconformationl.Wehavefoundthatinthepresenceofcertainamountofsodiumion,microamountofReO4-canbequantitativelyextractedintol,2-dichloroethanebytheligandtetraethylp-tert-butylcalix[4]arenetetraacetate(L).ItshowsthatthepresenceofNa inaqueoussolutioncanpromotetheformationofhydrophobiccomplex[NaL] .ReO'-whichc…     

Hydrothermal Syntheses and Structural Characterization of Two Novel Arsenic–Vanadium Clusters: [Co(2,2′-bpy)3]2[As8V14O42(H2O)]·3H2O and [2,2′-bpy][Ni(2,2′-bpy)3]2[As8V14O42(H2O)]·3H2O

Two new arsenic–vanadium clusters, [Co(2,2- bpy)₃]₂[As₈V₁₄O₄₂(H₂O)] · 3H₂O (1), [2,2-bpy][Ni(2,2-bpy)₃]₂[As₈V₁₄O₄₂(H₂O)] · 3H₂O (2) (2,2-bpy=2,2-bipyridine), have been hydrothermally synthesized and characterized by IR, elemental analysis, UV–VIS, EPR, TGA, XPS, and single crystal X-ray diffraction analysis. Crystal data: 1, triclinic, P1, a=14.368(3) Å, b=16.753(3) Å, c=24.632(5) Å, =94.15(3)°, =93.16(3)°, =113.05(3)°, Z=2; 2, monoclinic, P2₁/c, a= 30.2150(4) Å, b=14.0690(3) Å, c=26.0536(3) Å, =106.8960(10)°, Z=4. X-ray crystallographic studies showed that crystals 1 and 2 are both composed of discrete cluster anion [As₈V₁₄O₄₂(H₂O)]^4– and transition metal coordination complexes [M(2,2-bpy)₃]²⁺ (M=Co or Ni). Interestingly, compound 2 contains another neutral organic space filler of 2,2-bpy. To the best of our knowledge, compounds 1 and 2 are the first examples of structurally characterized vanadium/2,2-bpy/arsenate polyoxometallates.     

A first-principles study of (R)- and (S)-PPA Molecules on Cu(111)

The adsorption of (R)- and (S)-2-phenylpropionamide (PPA, C(9)H(11)ON) molecules on a Cu(111) surface has been investigated using the density functional method with supercell models. The adsorption orientations of both (R)- and (S)-PPA molecules on the surface are the same: the phenyl rings are approximately parallel to the Cu(111) surface and positioned in the hollow sites, the amino and methyl groups occupy two-bridge sites, and the carbonyl occupies the top site. After the adsorption, the bond lengths in the two enantiomers are almost unchanged, but the changes for two dihedral angles show differences, especially for (R)-PPA molecule. The first angles between the (N,C9,C7) plane and the (C9,C7,C6) plane are 19.4 and 0.7 degrees for (R)- and (S)-PPA molecules, respectively, and the second angles between the (C8,C7,C6) plane and the (C7,C6,C5) plane are 74.8 and 0.4 degrees for (R)- and (S)-PPA molecules, respectively. The adsorption energies of (R)- and (S)-PPA molecules are calculated to be -34 and -26 kJ mol(-1), respectively. The simulated scanning tunneling microscopy (STM) images of (R)- and (S)-PPA molecules on the Cu(111) surface display different features and are coincident with the experimental ones. The interaction between the adsorption molecule and the metal surface is found to be responsible for the discrimination of (R)- and (S)-PPA molecules on the surface.