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951.
The closo‐dodecaborate [B12H12]2? is degraded at room temperature by oxygen in an acidic aqueous solution in the course of several weeks to give B(OH)3. The degradation is induced by Ag2+ ions, generated from Ag+ by the action of H2S2O8. Oxa‐nido‐dodecaborate(1?) is an intermediate anion, that can be separated from the reaction mixture as [NBzlEt3][OB11H12] after five days in a yield of 18 %. The action of FeCl3 on the closo‐undecaborate [B11H11]2? in an aqueous solution gives either [B22H22]2? (by fusion) or nido‐B11H13(OH)? (by protonation and hydration), depending on the concentration of FeCl3. In acetonitrile, however, [B11H11]2? is transformed into [OB11H12]? by Fe3+ and oxygen. The radical anions [B12H12] ˙ ? and [B11H11] ˙ ? are assumed to be the primary products of the oxidation with the one‐electron oxidants Ag2+ and Fe3+, respectively. These radical anions are subsequently transformed into [OB11H12]? by oxygen. The crystal structure analysis shows that the structure of [OB11H12]? is derived from the hypothetical closo‐oxaborane OB12H12 by removal of the B3 vertex, leaving a non‐planar pentagonal aperture with a three‐coordinate O vertex, as predicted by NMR spectra and theory. 相似文献
952.
A pure calcium borate Ca2[B2O4(OH)2]·0.5H2O has been synthesized under hydrothermal condition and characterized by XRD, FT-IR and TG as well as by chemical analysis. The molar enthalpy of solution of Ca2[B2O4(OH)2]·0.5H2O in HC1·54.582H2O was determined. From a combination of this result with measured enthalpies of solution of H3BO3 in HC1·54.561H2O and of CaO in (HCl + H3BO3) solution, together with the standard molar enthalpies of formation of CaO(s), H3BO3(s) and H2O(l), the standard molar enthalpy of formation of −(3172.5 ± 2.5) kJ mol−1 of Ca2[B2O4(OH)2]·0.5H2O was obtained. 相似文献
953.
An accurate global potential-energy surface (PES) is reported for H5(+) based on more than 100,000 CCSD(T)/aug-cc-pVTZ ab initio energies. This PES has full permutational symmetry with respect to interchange of H atoms and dissociates to H3(+) and H2. Ten known stationary points of H5(+) are characterized and compared to previous ab initio calculations. Quantum diffusion Monte Carlo calculations are performed on the PES to obtain the zero-point energy of H5(+) and the anharmonic dissociation energy (D0) of H5(+) --> H3(+) + H2. The rigorous zero-point state of H4D+ is also calculated and discussed within the context of a strictly classical approach to obtain the branching ratio of the reaction H4D+ --> H3(+) + HD and H2D+ + H2. Such an approach is taken using the PES and critiqued based on the properties of the quantum zero-point state. Finally, a simple procedure for adding the long range-interaction energy is described. 相似文献
954.
955.
随着环境污染和能源短缺的加剧,无污染环境修复技术及清洁能源替代工程已成为一项重要而紧迫的任务。作为层状结构的过渡金属硫化物,二硫化钼带隙较窄,边缘具有高的反应活性,容易与其他物质形成复合结构,是近年来光催化环境修复及清洁能源领域的研究热点。本文详细介绍了半导体二硫化钼及其复合物的合成方法和光催化降解与产氢行为,重点阐述了二硫化钼及其复合物的具体复合方式、光催化降解污染物活性、光催化产氢活性以及具体的降解与产氢机理等方面的内容,并举例说明。二硫化钼及其复合物在光催化降解污染物和光催化产氢方面具有绿色、廉价、高效等优点,在环境修复及清洁能源领域具有巨大的潜力和应用发展前景。 相似文献
956.
The reaction pathways and energetics for the reaction of methane with CaO are discussed on the singlet spin state potential energy surface at the B3LYP/6-311+G(2df,2p) and QCISD/6-311++G(3df,3pd)//B3LYP/6-311+G(2df,2p) levels of theory. The reaction of methane with CaO is proposed to proceed in the following reaction pathways: CaO + CH4 → CaOCH4 → [TS] → CaOH + CH3, CaO + CH4 → OCaCH4 → [TS] → HOCaCH3 → CaOH + CH3 or [TS] → CaCH3OH → Ca + CH3OH, and OCaCH4 → [TS] → HCaOCH3 → CaOCH3 + H or [TS] → CaCH3OH → Ca + CH3OH. The gas-phase methane–methanol conversion by CaO is suggested to proceed via two kinds of important reaction intermediates, HOCaCH3 and HCaOCH3, and the reaction pathway via the hydroxy intermediate (HOCaCH3) is energetically more favorable than the other one via the methoxy intermediate (HCaOCH3). The hydroxy intermediate HOCaCH3 is predicted to be the energetically most preferred configuration in the reaction of CaO + CH4. Meanwhile, these three product channels (CaOH + CH3, CaOCH3 + H and Ca + CH3OH) are expected to compete with each other, and the formation of methyl radical is the most preferable pathway energetically. On the other hand, the intermediates HCaOCH3 and HOCaCH3 are predicted to be the energetically preferred configuration in the reaction of Ca + CH3OH, which is precisely the reverse reaction of methane hydroxylation. 相似文献
957.
把取代基电性、立体及疏水性物化参数组合建立一种新取代基描述方法, 对环尿素类和N,N-二甲基-2-溴苯乙胺类衍生物进行结构表征. 对训练样本集通过逐步回归筛选变量, 所建多元线性回归方程R2分别为0.853和0.960, 留一法交互检验Rcv2分别为0.723和0.901;用预测集样本作外部预测, 所得Qext2分别为0.7617和0.7653. 结果显示:环尿素类化合物结构中苯环邻位立体、间位疏水、对位疏水及立体因素对该类药物抗HIV活性产生阻抑作用; N,N-二甲基-2-溴苯乙胺类苯环上取代基立体因素及对位给电子效应有利于提高肾上腺素能阻断活性. 相似文献
958.
ZHANG Xingwen HU Lijiang HUANG Yudong SUN Dezhi & SUN Yi . Department of Applied Chemistry Harbin Institute of Technology HUANG Yudong Harbin China . Department of Environmental Engineering Harbin Institute of Technology Harbin China . Department of Experimental Mechanics Harbin Institute of Technology Harbin China 《中国科学B辑(英文版)》2004,47(5):388-395
Silsesquioxanes (SSO) or polyhedral oligomericsilsesquioxanes (POSS) are generally prepared frommolecular precursors using the hydrolytic condensa-tion of trialkoxysilane, RSi(OR')3. They are organic/inorganic hybrid nanostructural blocks with theircomplete general formula Tn(T = RSiO1.5, n = 1,2, …), and the incomplete generic formula is Tn-(OH)x(OR')y[x, y = 0, 1, 2, …, T= RSiO1.5 ?(x+y)/2n][1,2].Each VSSO, possessing a certain structural formulaand molecular weight, may h… 相似文献
959.
Gold nanotubule membranes were prepared by using electroless deposition of gold within the pores and surfaces of polycarbonate track-etched membranes.And the gold nanotubule membrane was used as an electrode for determination of uric acid in urine samples for the first time.In Britton-Robinson buffer of pH 4.56,uric acid exhibited well-defined differential pulse voltammograms.And the interference between coexistent ascorbic acid and uric acid was overcome owing to the attractive ability of the gold nanotubule electrode to yield a large anodic peak difference ca.0.404 V(vs.SCE).The proposed method was then applied to the determination of uric acid in urine without any pretreatment. 相似文献
960.
Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance of these devices relies on the understanding and optimization of several complementary processes. Our goal is to discuss the relationship between the molecular stacking structures and their optoelectronic properties that are of importance in all these areas. The concept of intermolecular interaction should be taken here in the special sense that is inter-dipole coupling. Specifically, we will address the impact of inter-dipole interaction between adjacent molecules in aggregate state on the solid-state emission properties. 相似文献