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51.
P. V. Snytnikov K. V. Yusenko S. V. Korenev Yu. V. Shubin V. A. Sobyanin 《Kinetics and Catalysis》2007,48(2):276-281
The performance of a Co-Pt powder and of Co-Pt catalysts supported on γ-Al2O3 and on the graphite-like carbon material Sibunit in selective CO oxidation in hydrogen-containing mixtures is considered. Fine particles of metal-metal solid solutions and intermetallides were obtained by the decomposition of a Co- and Pt-containing double complex salt in a hydrogen atmosphere at ~400°C. As compared to their Pt and Co monometallic counterparts, the bimetallic catalysts are more active and allow the CO concentration in hydrogen-containing mixtures to be reduced from 1 to 10?3 vol %. This effect is likely due to the formation of bimetallic particles of a Co-Pt solid solution on the support surface. 相似文献
52.
53.
A. M. Genaev G. E. Sal’nikov V. G. Shubin 《Russian Journal of Organic Chemistry》2007,43(8):1134-1138
By DFT method energy barriers were calculated for carousel rearrangements of bicyclo[3.1.0]hexenyl, cyclobutenyl, and homotropylium cations. A plausible agreement between calculated and experimental findings was found. 相似文献
54.
Yong Li Xiao-Bing Cui Ji-Qing Xu Ke-Chang Li Guang-Hua Li Qing-Xin Yang 《Journal of solid state chemistry》2005,178(1):363-369
Both the homometal cluster [P(ph4)]2[Mo2O2(μ-S)2(S2)2] (1) and [Mo2O2(μ-S)2(Et2dtc)2] (2) (Et2dtc=diethyl-dithiocarbamate) were successfully synthesized by low-temperature solid-state reactions. X-ray single-crystal diffraction studies suggest that compound (1) is a dinuclear anion cluster, and compound (2) is a dinuclear neutral cluster. The two compounds were characterized by elemental analyses, IR spectra and UV-Vis spectra. The third-order non-linear optical (NLO) properties of the clusters were also investigated and all exhibited nice non-linear absorption and self-defocusing performance with moduli of the hyperpolarizabilities 5.145×10−30 esu for (1) and 5.428×10−30 esu for (2). 相似文献
55.
Zubarev DY Boldyrev AI Li X Cui LF Wang LS 《The journal of physical chemistry. A》2005,109(50):11385-11394
Photoelectron spectroscopy and ab initio calculations are used to investigate the electronic structure and chemical bonding of Si5(-) and Si5(2-) in NaSi5(-). Photoelectron spectra of Si5(-) and NaSi5(-) are obtained at several photon energies and are compared with theoretical calculations at four different levels of theory, TD-B3LYP, R(U)OVGF, UCCSD(T), and EOM-CCSD(T), all with 6-311+G(2df) basis sets. Excellent agreement is observed between experiment and theory, confirming the obtained ground-state structures for Si5(-) and Si5(2-), which are both found to be trigonal bipyramid with D3h symmetry at several levels of theory. Chemical bonding in Si5, Si5(-), and Si5(2-) is analyzed using NPA, molecular orbitals, ELF, and NICS indices. The bonding in Si5(2-) is compared with that in the isoelectronic and isostructural B5H5(2-) species, but they are found to differ due to the involvement of electron densities, which are supposed to be lone pairs in the skeletal bonding in Si5(2-). 相似文献
56.
Cui X Delgado R Carapuça HM Drew MG Félix V 《Dalton transactions (Cambridge, England : 2003)》2005,(20):3297-3306
A tetraazamacrocycle containing ferrocene moieties has been synthesized and characterized. The tetraprotonated form of this compound was evaluated as a receptor (R) for anion recognition of several substrates (S), Cl(-), PF(6)(-), HSO(4)(-), H(2)PO(4)(-) and carboxylates, such as p-nitrobenzoate (p-nbz(-)), phthalate (ph(2-)), isophthalate (iph(2-)) and dipicolinate (dipic(2-)). (1)H NMR titrations in CD(3)OD indicated that this receptor is not suitable for recognizing HSO(4)(-) and H(2)PO(4)(-), but weakly binds p-nbz(-), and strongly interacts with ph(2-), dipic(2-), and iph(2-) anions forming 1 : 2 assembled species. The largest beta(2) binding constant was determined for ph(2-), followed by dipic(2-) and finally iph(2-). The effect of the anionic substrates on the electron-transfer process of the ferrocene units of R was evaluated using cyclic voltammetry (CV) and square wave voltammetry (SWV) in methanol solution and 0.1 mol dm(-3)(CH(3))(4)NCl as the supporting electrolyte. Titrations of the receptor were undertaken by addition of anion solutions in their tetrabutylammonium or tetramethylammonium forms. The protonated ligand exhibits a reversible voltammogram, which shifts cathodically in the presence of the substrates. The data revealed kinetic constraints in the formation of the receptor/substrate entity for dipic(2-), ph(2-) and iph(2-) anions, but not for p-nbz(-). In spite of the slow kinetics of assembled species formation with the ph(2-) substrate, this anion provides the largest redox-response when the supramolecular entity is formed, followed by dipic(2-), iph(2-) and finally p-nbz(-) anions. This trend is in agreement with the (1)H NMR results and the values of the binding constants. Single crystal X-ray structures of the receptor with PF(6)(-), ph(2-), iph(2-) and p-nbz(-) were carried out and showed that supermolecules with a RS(2) stoichiometry are formed with the first three anions, but RS(4) with p-nbz(-). In all cases the binding occurs outside the macrocyclic cavity via N-H...O=C hydrogen bonds for carboxylate anions and N-H...F hydrogen bonds for the PF(6)(-) anion, which is in agreement with the solution results. The macrocyclic framework adopts different conformations in order to interact with each substrate having Fe...Fe intramolecular distances ranging from 10.125(14) to 12.783(15)A. 相似文献
57.
钇对Ti-1100高温钛合金热稳定性和蠕变行为的影响 总被引:3,自引:1,他引:3
量了Ti1100和Ti1100/01%Y(质量分数)高温钛合金在600℃/100h空气中暴露后的拉伸性能及在600℃/150MPa/100h条件下的蠕变性能,利用透射电镜观察了合金室温及蠕变后的组织。结果表明,Ti1100合金加入01%的Y后,由于原始β晶粒得到细化,明显改善了其热稳定性;固溶在基体中的硅原子阻碍位错滑移和攀移,使蠕变中的回复过程难于实现;稀土还抑制α2相的长大,所形成的氧化物也阻碍位错的运动。这些均有利于提高Ti1100合金的抗蠕变性能。 相似文献
58.
59.
Determination of tripolyphosphate in frozen cod and scallop adductor by ion chromatography 总被引:4,自引:0,他引:4
We introduce a method for the determination of tripolyphosphate in frozen cod and scallop adductor by using ion chromatography. The tripolyphosphate was extracted from minced cod and scallop adductor with deionized water by ultrasonic leaching, and then the proteins soluble in water were precipitated with trichloroacetic acid and removed by filtering. An ion chromatograph with an ionpac AS11-HC anion-exchange column, an ASRS (Anion Self Regenerating Suppression), a conductivity detector and a gradient pump (sodium hydroxide gradient) was used. The detection limit was below 5 mg tripolyphosphate/kg cod or scallop adductor. This method is applicable to the determination of polyphosphates in aquatic products and the procedures are easy to implement. 相似文献
60.
Cui C Brynda M Olmstead MM Power PP 《Journal of the American Chemical Society》2004,126(21):6510-6511
Reaction of Ar'GeGeAr' (1) with an excess of Me3SiN3 gives the non-Kekulé, biradicaloid Ar'Ge(mu-NSiMe3)2GeAr' (3, Ar' = 2,6-Dipp2C6H3, Dipp = 2,6-i-Pr2C6H3) which has a planar Ge2N2Si2 array and pyramidal geometry at the germaniums. DFT calculations for the model MeGe(mu-NSiH3)2GeMe indicate no Ge-Ge bonding and a singlet ground state. The calculated energy difference between the optimized singlet and triplet states is 17.51 kcal/mol. 相似文献