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61.
利用自组装的方法,实现碳纳米管的有序排列可以充分有效的促进碳纳米管在各个领域的应用。本文从自组装所依赖的驱动力着手,介绍了国内外近几年来基于功能化碳纳米管的自组装开展的研究工作及取得的成果,重点介绍了通过配位作用、静电力及氢键、亲水/疏水相互作用等实现的自组装。 相似文献
62.
Cycloaddition of carbon dioxdie and propylene oxide to propylene carbonate catalyzed by tetra-tert-butyl metal phthalocyanine in the presence of tributylamine(TBA) shows higher yield than catalyzed by unsubstituted metal phthalocyanine.Comparing different catalysts of diverse metals,(t-Bu)4PcMg is more active than (t-Bu)PcFe ,But(t-Bu)4PcCo and (t-Bu)4PcNi only have low catalytic activities towards the reaction.Moreover,the yield will increase as the temperature increases. 相似文献
63.
Xiu Hui Lu Hai Bin Yu Wei Rong Wu Yue Hua Xu 《International journal of quantum chemistry》2007,107(2):451-457
Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
64.
Lin Yan Wengang Chai Guanghui Wang Guanli Wu Kaijuan Lu Yue Luo 《Journal of mass spectrometry : JMS》1987,22(5):279-282
During a comparison study of the fast atom bombardment (FAB) and electron impact mass spectra of 1-organyl-2,9,10-trioxa-6-aza-1-silatricyclo[4.3.3.01,6]dodecanes, an unusual ion peak at m/z 164 was noticed in the FAB spectra. Accurate mass measurement indicated that m/z 164 corresponds to protonated 1-[N,N-bis(2-hydroxyethyl)amino]-1-propanol (BHAP), which is produced by a ring-rupture reaction. Further experiment showed that the intensity of the [BHAP + H]+ ion peak increased markedly as the 7keV Ar0 bombardment proceeded, suggesting a FAB-induced reaction. The possible mechanism is also discussed. 相似文献
65.
The coordination of silver cation to diphosphene Mes*P=PMes* ( 1 , Mes* = tBu3C6H2) was investigated in detail. The reaction of 1 with Ag[Al(ORF)4] (ORF = OC(CF3)3) in the ratios of 2 : 1, 3 : 2 and 1 : 2 led to the formation of the first cationic silver linked diphosphene complexes 2 — 4 . Complexes 2 and 3 contain two and three diphosphene molecules linked by the linear Ag(I) cation, respectively, and they feature unusual zig‐zag topologies. Complex 4 is a dinuclear silver complex, and each Ag(I) center features a tetrahedral geometry, coordinated by one phosphorus atom of diphosphene 1 and three chloro atoms of two CH2Cl2 molecules. 相似文献
66.
CuO/活性炭和Fe2O3/活性炭催化还原NO 总被引:4,自引:0,他引:4
CuO/活性炭和Fe_2O_3/活性炭催化还原NO高志明,赵震,杨向光,吴越(中国科学院长春应用化学研究所长春130022)关键词活性炭,还原,NO,氧化铜,氧化铁目前,对固定源的NO处理是采用V2O5/TiO2作催化剂,NH3作还原剂的选择催化还原方... 相似文献
67.
68.
Different from Rh(II) catalysts, X-H (X = O, S, N) insertion of methyl styryldiazoacetate catalyzed by Lewis acids including Cu(I), Cu(II) and Ag(I) complexes occurred at γ-position preferably. Only (E)-isomer was observed in the reactions. This method provides an alternative for the synthesis of γ-hydroxyl or γ-amino acid derivatives. 相似文献
69.
A nickel catalyst was nodeled with ligand L^2,[NH=CH-CH=CH-0]^-,which should have potential use as a syndiotactic plyolefin catalyst,and the reaction mechanism was studied by theoretical calculations using the density functinal method at the B3LYP/LANL2MB level.The mechanism involves the formation of the intermediate [NiL^2Me]^ ,in which the metal occupies a T-shaped geometry.This intermediate has two possible structures with the methyl group trans either to the oxygen or to the nitrogen atom of L^2.The results show that both structures can lead to the desired product via similar reaction paths,A and B.Thus,the polymerization could be considered as taking place either with the alkyl group occupying the position trans to the Ni-0 or trans to the Ni-N bond in the catalyst.The polymerization process thus favors the catalysis of syndiotactic polyolefins.The syndiotactic synthesis effects could also be enhanced by varations in the ligand substituents.From energy considerations,we can conclude that it is more favorable for the methyl ttrans-O position to form a complex than to occupy the trans-N position.From bond length considerations,it is also more favoured for ethene to occupy the trans-O position than to occupy the trans-N position. 相似文献
70.
photoelectron-photoion coincidence spectroscopy and density functional theory calculations have been used to investigate the dissociation kinetics of the benzene chromium tricarbonyl ion, BzCr(CO)3+ (Bz = C6H6). The dissociation of the BzCr(CO)3+ ion proceeds by the sequential loss of three CO and benzene ligands. The first and third CO and the benzene loss reactions were associated with metastable precursor ions (lifetimes in the microsecond range). By simulating the resulting asymmetric time-of-flight peak shapes and breakdown diagram, the 0 K appearance energies of the four product ions were determined to be 8.33 +/- 0.05, 8.93 +/- 0.05, 9.97 +/- 0.06, and 11.71 +/- 0.06 eV, respectively. Combined with the ionization energy of BzCr(CO)3, 7.30 +/- 0.05 eV, the three successive Cr-CO bond energies in the BzCr(CO)3+ were found to alternate, with values of 1.03 +/- 0.05, 0.60 +/- 0.05, and 1.04 +/- 0.05 eV, respectively, and the Bz-Cr bond energy in BzCr+ is 1.74 +/- 0.05 eV, a trend confirmed by the density functional theory (DFT) calculations. Using the heats of formation of the fully dissociated products, C6H6, Cr+, and CO, the 298 K heats of formation the ionic BzCr(CO)n+ (n = 03) species were determined. By scaling the DFT calculated bond energies for the neutral molecules, the heats of formation of the neutral BzCr(CO)n (n = 03) were also obtained. 相似文献