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101.
The complexation of Keggin-type polyoxometalate [alpha-SiW 12O 40] (4-), macrocation [Cr 3O(OOCC 2H 5) 6(H 2O) 3] (+), and monovalent cation A (+) forms ionic crystals of A 2[Cr 3O(OOCC 2H 5) 6(H 2O) 3] 2[alpha-SiW 12O 40]. nH 2O [A = Na ( 1a), K ( 2a), Rb ( 3a), NH 4 ( 4a), Cs ( 5a), and tetramethylammonium (TMA) ( 6a)]. Single crystal (1a- 4a and 6a) and powder (5a) X-ray analyses have shown that the ionic crystals possess 2D layers of polyoxometalates and macrocations. Compounds 2a- 5a had almost the same structure, while the layers in 1a and 6a stack in different ways. The structures and sorption properties of 2b- 5b are investigated in more detail. The interlayer distances of guest free phases 2b- 5b increase with the increase in the ionic radii of the monovalent cations, which reside between the layers. Compounds 2b- 5b possess hydrophobic and hydrophilic channels, which exist between the layers and through the layers, respectively. The volumes of the hydrophobic channels increase in the order of 2b < 3b approximately 4b < 5b, and those of the hydrophilic channels increase in the order of 2b < or = 3b < or = 4b < 5b. Single-crystal X-ray structure analyses of 2a- 4a have shown that the water of crystallization resides in the hydrophilic channel. It is probable that the water of crystallization in 5a resides in the hydrophilic channel in the same manner as those in 2a- 4a since 2a- 5a have almost the same structure. The water vapor sorption profiles of 2b- 5b are approximately reproduced by a linear driving force model. Therefore, water molecules sorbed in 2b- 5b probably reside in the hydrophilic channel. The n-propanol sorption profiles are reproduced by the summation of the linear driving force model, showing that two independent barriers exist in the n-propanol sorption. The in situ IR spectra of n-propanol sorbed showed the presence of two n-propanol species. These data show that n-propanol is sorbed into both hydrophilic and hydrophobic channels. Compound 5b sorbs halocarbons in the hydrophobic channel, while 2b- 4b exclude them. 相似文献
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Humic substances that preferentially adsorb at the air/water interfaces of water or aerosols consist of both fulvic and humic acid. To investigate the chemical reactivity for the heterogeneous reaction of gaseous ozone, O(3)(g), with aqueous iodide, I(-)(aq), in the presence of standard fulvic acid, humic acid, or alcohol, cavity ring-down spectroscopy was used to detect gaseous products, iodine, I(2)(g) and an iodine monoxide radical, IO(g). Fulvic acid enhanced the I(2)(g) production yield, but not the IO(g) yield. Humic acid, n-hexanol, n-heptanol, and n-octanol did not affect the yields of I(2)(g) or IO(g). We can infer that the carboxylic group contained in fulvic acid promotes the I(2)(g) emission by supplying the requisite interfacial protons more efficiently than water on its surface. 相似文献
105.
Takanori Itoh Saori Shirasaki Hironori Ofuchi Sayaka Hirayama Tetsuo Honma Masanobu Nakayama 《Solid State Communications》2012,152(4):278-283
The oxygen partial pressure (P(O2)) dependence of in situ X-ray absorption spectroscopy (XAS) at the Co and Fe K edges was measured simultaneously and continuously at 900 and 1000 K. These experiments, which were performed during reduction, changing P(O2) from 1 to 10?4 atm, were used to investigate each valence related to Co and Fe in (La0.6Sr0.4)(Co0.2Fe0.8)O3?δ (LSCF). The absorption edge shift of the Co K edge was more than twice that of the Fe K edge at 1000 K during reduction. For quantitative analysis, X-ray absorption near-edge structure spectroscopy was carried out at the Co and Fe K edges; the results indicated that the Co valence decreased more easily than the Fe valence; that is, the oxygen preferentially left from the oxygen sites around Co. 相似文献
106.
The complexation of Keggin-type polyoxometalates [alpha-XW12O40]n- (X = P, Si, B, Co), macrocation [Cr3O(OOCH)6(H2O)3]+, and alkali-metal ions forms ionic crystals of Na2[Cr3O(OOCH)6(H2O)3][alpha-PW12O40].16H2O (1a), K3[Cr3O(OOCH)6(H2O)3][alpha-SiW12O40].16H2O (2a), Rb4[Cr3O(OOCH)6(H2O)3][alpha-BW12O40].16H2O (3a), and Cs5[Cr3O(OOCH)6(H2O)3][alpha-CoW12O40].7.5H2O (4a). The space volumes of the ionic crystals decrease in the order of 1a > 2a > 3a > 4a. The water of crystallization in 1a-3a is completely desorbed by evacuation at room temperature, while about 50% of the water of crystallization in 4a is desorbed. The respective 1a-4a after evacuation at room temperature are denoted by 1b-4b, which show the close packing of the constituent ions. The calculated cell volumes per formula decreased in the order of 1b > 2b > 3b > 4b, which would be related to the increase in n. Compound 1b sorbs various < or =C5 polar organic molecules such as 1-butanol, valeronitrile, and methyl propionate. Compound 2b sorbs ethanol, acetonitrile, and methyl formate. Compound 3b sorbs water and methanol, and 4b sorbs only water. Thus, the ionic crystals can discriminate < or =C5 polar organic molecules such as alcohols, nitriles, and esters by one methylene chain, and the decrease in n of [alpha-XW12O40]n- enables the sorption of molecules with the longer methylene chain. The nature of the sorption properties of 1b-4b can be explained by the lattice energy needed for the expansion of 1b-4b. The selective sorption properties of 1b-4b are successfully applied to the separation of mixtures of alcohols, nitriles, esters, and water. 相似文献
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Yasuto Tsuruta Hirofumi Inoue Keiko Fukunaga Sayaka Munemura Misa Ozaki Masaya Ohta Fumito Matsuura 《Analytical sciences》2005,21(6):697-699
A highly sensitive method for the determination of bisphenol-A in water with semi-micro column high-performance liquid chromatography using 2-methoxy-4-(2-phthalimidinyl)phenylsulfonyl chloride as a fluorescent labeling reagent has been developed. The labeling reaction was carried out at 70 degrees C for 20 min in borate buffer (pH 9.5). The derivative eluted at 11.6 min on a reversed-phase column with methanol-water (78:22, v/v) at a flow-rate of 0.2 ml/min. The fluorescence was monitored at 308 nm for excitation and 410 nm for emission. The detection limit (S/N = 3) was 10 fmol per injection. The labeling yield was about 95%. 相似文献
109.
Kazu Okumura Dr. Hirosuke Matsui Takuya Tomiyama Takashi Sanada Tetsuo Honma Dr. Sayaka Hirayama Miki Niwa Prof. 《Chemphyschem》2009,10(18):3265-3272
Structures of Pd/zeolites immersed in solvents were measured by in situ X‐ray absorption fine structure (XAFS). Systematic studies revealed that the selection of an appropriate support (USY‐zeolite), thermal treatment temperature of USY, solvent (o‐xylene), H2 partial pressure (6 %), and the use of a Pd amine complex affect the structure of Pd. As a result, we found that monomeric Pd can be obtained in the USY support with H2 bubbling in o‐xylene. The structural properties of Pd correlate well with its catalytic performance in the Suzuki–Miyaura coupling reactions; a very high TON of up to 11 000 000 was obtained over the monomeric Pd. 相似文献
110.
Pd was loaded on ultra stable Y (USY) zeolites prepared by steaming NH(4)-Y zeolite under different conditions. Heck reactions were carried out over the prepared Pd/USY. We found that H? bubbling was effective in improving not only the catalytic activity of Pd/USY, but also that of other supported Pd catalysts and Pd(OAc)?. Moreover, the catalytic activity of Pd/USY could be optimized by choosing appropriate steaming conditions for the preparation of the USY zeolites; Pd loaded on USY prepared at 873 K with 100% H?O gave the highest activity (TOF = 61,000 h?1), which was higher than that of Pd loaded on other kinds of supports. The prepared Pd/USY catalysts were applicable to the Heck reactions using various kinds of substrates including bromo- and chloro-substituted aromatic and heteroaromatic compounds. Characterization of the acid properties of the USY zeolites revealed that the strong acid site (OH(strong)) generated as a result of steaming had a profound effect on the catalytic activity of Pd. 相似文献