High Lithium Capacity MxV2O5Ay·nH2O for Rechargeable Batteries

The aqueous synthesis and electrochemical properties of nanocrystalline M_xV₂O₅A_y·nH₂O are described. It is easily and quickly prepared by precipitation from acidified vanadate solutions. M_xV₂O₅A_y·nH₂O has been characterized by X-ray powder diffraction, electron microscopy, TGA, chemical analyses, and electrochemical studies. The atomic structure is related to that of xerogel-derived V₂O₅·nH₂O. In M_xV₂O₅A_y·nH₂O, M is a cation from the starting vanadate salt and A is an anion from the mineral acid. This material exhibits high, reversible Li capacity and may be considered for use in a cathode in primary and secondary batteries. The lithium capacity of an electrode composed of M_xV₂O₅A_y·nH₂O/EPDM/carbon (88/4/8) is ∼380(mA h)/g (C/80 rate) and the energy density is ∼1000(W h)/kg (120-μm-thick cathode, 4-1.5 V, versus Li metal anode). Critical parameters identified in the synthesis of M_xV₂O₅A_y·nH₂O, with respect to achieving high Li-ion insertion capacity, are acid/vanadium ratio, starting vanadate salt, and temperature. Inclusion of carbon black in the synthesis yields a composite that maintains the high Li capacity, lowers the electrochemical-cell polarization, and preserves the lithium capacity at higher discharge rates. Li-ion coin cells, using pre-lithiated graphite anodes, exhibit electrochemical performance comparable to that of Li-metal coin cells.     

INTRAPARTICLE DIFFUSION EFFECTS IN FISCHER-TROPSCH SYNTHESIS Ⅰ. MODELING OF DIFFUSION AND REACTION

IntroductionCatal}ticrcactionsaffcctcdb}'diffosionaIlimitationincatal}'stporcshavcbccnextensive1}dcaltx`ithinlit.rat.rcll~5I.Scvcraltcchniqucsonthcspccialcase0fFischcr-Tropschs}'nthcsis(FTS)t\crcapplicdtocxplorcthebchaviorofthiscatal}ticrcactionundercxpcrimcntalandopcrationaIconditionsI3~5l.It`"ouldbeofvaluctoindicatchcrcthatthcseinvcstigationsx"ercmainl}'bascdonthesimplcstkineticsofthcfirstordcrinH2proposedbyAndersonl6]attheearIystages.However-thesetboents,striCtlyspeaking,areinvalidfor…     

Laponite clay in homopolymer and tri-block copolymer matrices

Macromolecule/laponite nanomaterials were studied by DSC and X-ray diffraction techniques. The matrices are poly(ethylene) glycols at various molecular masses and poly(ethylene oxides)-poly(propylene oxides)-poly(ethylene oxides) tri-block copolymers. The latter were tuned by modulating the molecular masses, at constant hydrophilic/hydrophobic ratio, and the hydrophilicity. For all the investigated systems, the enthalpy of melting (ΔH _m) is nearly constant up to a given composition thereafter it increases monotonically reaching the value of the pure macromolecule. We proposed a model to interpret the DSC data. Briefly, it was invoked a mechanism of interaction following which some segments of the adsorbed macromolecule are anchored to the laponite (RD) particles and the remaining segments are radiating away from the surface. The portion of the macromolecule in contact with RD does not contribute to ΔH _m whereas that radiating away from the clay does. Once that the RD surface is saturated, the excess of the macromolecule behaves like the pure one. The proposed model allowed to compute successfully the ΔH _m values. The X-ray diffraction experiments ruled out the polymer intercalation between the silicate sheets.     

Rhodium-catalyzed addition of arylboron compounds to nitriles, ketones, and imines

The rhodium-catalyzed addition reactions of sodium tetraphenylborate and arylboronic acids to nitriles, ketones, and imines were examined. The reaction of nitriles could be carried out efficiently in the presence of a catalyst system of [RhCl(cod)]₂-dppp and H₂O to give the corresponding monoarylated products selectively. Although unactivated ketones and imines are known to be poor electrophiles for rhodium-catalyzed arylation, the phenylation of them with use of sodium tetraphenylborate proceeded smoothly in the presence of [RhCl(cod)]₂ and Rh(acac)(cod) as catalysts, respectively. The addition of NH₄Cl was found to be crucial to effectively conduct the reaction of ketones and imines.     

La-Ba系氧化物催化剂用于甲烷氧化偶联

以La_2O_3为基础,碱土金属作为第二组分的二元氧化物催化剂均具有较高的生成C_2活性,特别是La-Ba-O系催化剂具有优良的甲烷氧化偶联活性和稳定性,当La/Ba原子比为2.5时,C_2收率可达20.3％。第三组分的添加有助于提高C_2选择性,特别是添加碱金属,可以抑制完全氧化反应,并提高乙烯/乙烷比。在La:Ba:Na=2.5:1:0.1的催化剂上进行了500/小时的寿命实验,在整个反应期间,催化剂的活性和选择性相当稳定。X-射线物相分析表明,新鲜催化剂除有少量的碳酸钡外,主要是氧化镧和氧化钡的混合物。500小时后的物相基本上是氧化镧和碳酸钡。使用前后催化剂的比表面积及表面La和Ba的分布均无改变。较高的CH_4/O_3比对提高C_2选择性有利,当CH_4:O_2=4:1时,C_2选择性和收率分别为65.1％和19.1％。     

Osmotic and activity coefficients at 25°C for tetraalkylammonium bromides in deuterium oxide

Earlier work by Lindenbaum and Boyd has demonstrated the important role of hydrophobic interactions involving the water solvent in determining the osmotic coefficients and properties of aqueous solutions of the tetraalkylammonium halides. Osmotic coefficients of solutions of tetramethyl-, tetraethyl-, tetrapropyl-, and tetrabutylammonium bromides in the more highly structured solvent D₂O have now been determined by the gravimetric isopiestic method, using reference solutions of NaCl in D₂O. The data were fitted to the Rush-Johnson and Pitzer equations. Satisfactory agreement with the results for aqueous solutions at comparable concentrations indicates that the solution chemistry of these quaternary ammonium bromides is not highly dependent on the degree of structure of the pure solvents. Supplementary data for mixtures of Me₄NBr with Et₄NBr, Pr₄NBr, or Bu₄NBr in both H₂O and D₂O are consistent with this conclusion.On leave 1980–82 from Banaras Hindu University, India     

希土元素与三甲胺氧化物配合物的制备及光谱性质

尽管文献报道了三甲胺氧化物与Mn、Co、Ni、Zn、Cd、Cu等多种离子在有机溶剂中形成较稳定的配合物。但对其金属配合物的研究远不如芳香族杂环化合物那样引起人们广泛的注意。本文研究了它与希土元素形成配合物的合成和光谱性质。     

超临界二氧化碳中卟啉与钴(II)、镍(II)、锌(II)配合物反应动力学

用紫外-可见光谱研究了钴(II)、镍(II)、锌(II)的1, 1, 1, 5, 5, 5-六氟-2, 4-戊二酮-二水配合物[M(hfac)2(H₂O)₂, M=Co、Ni、Zn]与5, 10, 15, 20-四(五氟苯基)卟啉[H2tpfpp]在超临界二氧化碳中反应生成金属卟啉[M(tpfpp)]的反应动力学. 在金属配合物大大过量时, 反应对卟啉为一级. 其表观一级速率常数随钴(II)、镍(II)配合物的浓度增加先增加、而后趋于稳定, 而表观一级速率常数随锌(II)配合物的浓度增加线形增加. 根据实验事实, 讨论了反应的机理, 得到了相应的热力学和动力学参数.     

INFLUENCE OF DIALKYLZINC IN RARE-EARTH TERNARY CATALYST ON THE COPOLYMERIZATION OF CARBON DIOXIDE AND PROPYLENE OXIDE

Rare-earth ternary catalysts Y（CCl3COO）3-ZnR2-glycerin were prepared for the copolymerization of carbon dioxide and propylene oxide （PO）, where dialkylzincs （ZnR2） were diethylzinc, di（n-propyl）zinc, di（n-butyl）zinc, di（i-propyl）zinc, di（i-butyl）zinc, di（s-butyl）zinc,respectively. The Y（CCl3COO）3-ZnR2-glycerin catalysts displayed the highest catalytic activity at the molar ratio of Y（CCl3COO）3：ZnR2：glycerin = 1：20：10. In the same copolymerization condition, catalysts containing dialkylzincs with branched alkyl group showed lower catalytic activity than that with primary alkyl group. For those catalysts including dialkylzincs with primary alkyl group, their catalytic activity decreases with increasing number of carbon atom in the alkyl group with the following sequence： Y（CCl3COO）3-ZnEt2-glycerin 〉 Y（CCl3COO）3-Zn（n- Pr）2-glycerin〉Y（CCl3COO）3-Zn（n-Bu）2-glycerin. However, the alkyl group in the dialkylzinc does not influence the insertion of PO into the propagation chain end.