There is a special reason for reviewing this book at this time: it is the 50th edition of a compendium that is known and used frequently in most chemical and physical laboratories in many parts of the world. Surely, a publication that has been published for 56 years, withstanding the vagaries of science in this century, must have had something to offer. There is another reason: while the book is a standard fixture in most chemical and physical laboratories, including those in medical centers, it is not as frequently seen in the laboratories of physician's offices (those either in solo or group practice). I believe that the Handbook can be useful in those laboratories. One of the reasons, among others, is that the various basic items of information it offers may be helpful in new tests, either physical or chemical, which are continuously being published. The basic information may relate

Handbook of Chemistry and Physics

Oxide pyrochlores — A review

Fast Na+-ion transport in skeleton structures

Single crystals of TiO2 anatase containing 0.22% of Al and traces of V, Zr, Nb, and La were grown by chemical transport reactions employing TeCl4 as the transporting agent. Electrodes having the (101) face exposed doped by reduction with hydrogen were employed. The electrochemical and photoelectrochemical behavior of a single crystal of anatase were scrutinized for the first time. Properties were compared to those of single-crystal rutile having the (001) face exposed. Impedance analysis established that the flatband potential of anatase (101) is shifted negatively by 0.2 V with regards to that of rutile (001). Interfacial capacitance measurements under forward bias indicate smaller density of surface states on anatase. Photoelectrochemical oxidation of water occurs on both rutile and anatase with incident photon-to-current conversion efficiencies close to unity at λ = 300 nm. From the comparison of Ufb and Eg, it follows that anatase (101) and rutile (001) electrodes differ mainly in the position of the ...

Electrochemical and photoelectrochemical investigation of single-crystal anatase

Synthesis of nanocrystals with exposed high-energy facets is a well-known challenge in many fields of science and technology. The higher reactivity of these facets simultaneously makes them desirable catalysts for sluggish chemical reactions and leads to their small populations in an equilibrated crystal. Using anatase TiO2 as an example, we demonstrate a facile approach for creating high-surface-area stable nanosheets comprising nearly 100% exposed (001) facets. Our approach relies on spontaneous assembly of the nanosheets into three-dimensional hierarchical spheres, which stabilizes them from collapse. We show that the high surface density of exposed TiO2 (001) facets leads to fast lithium insertion/deinsertion processes in batteries that mimic features seen in high-power electrochemical capacitors.

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Constructing Hierarchical Spheres from Large Ultrathin Anatase TiO2 Nanosheets with Nearly 100% Exposed (001) Facets for Fast Reversible Lithium Storage

Oxide superconductors in the system Tl2Ba2Can–1CunO4+2n (ref. 1) have transition temperatures (Tc) above 100 K, increasing with n. So far, stacking sequences up to n = 3 have been found in small crystals, and sequences with n > 3 have been seen in electron microscopy studies1. For large n, the stoichiometry of Tl2Ba2Can–1CunO4+2n approaches CaCuO2, a structure expected to consist only of CuO2 planes separated by Ca atoms. By analogy with Tl2Ba2Can–1CunO4+2n, the unit cell of this hypothetical phase is expected to be tetragonal with a = 3.86 A. Such a compound is not known in the Ca–Cu–O system, but Roth2 recently reported that small amounts of Sr on the Ca site can stabilize this simple structure. Here we report the growth of small single crystals of this phase, with composition (Ca0.86Sr0.14)CuO2, and their characterization by single-crystal X-ray diffraction. The crystals are tetragonal with space group P4/mmm, and the structure contains planar [CuO2]∞ layers separated by Ca and Sr atoms. The structure is a simple defect perovskite with ordered oxygen vacancies and can be regarded as the n = ∞ parent of the A2B2Can–1CunO4+2n (A = Bi, Tl; B = Sr, Ba) superconductors.

The parent structure of the layered high-temperature superconductors

The crystal structures of the lithium-inserted metal oxides Li0.5TiO2 anatase, LiTi2O4 spinel, and Li2Ti2O4

The effect of small oxide additions on the polymorphism of Bi2O3 was studied by means of high-temperature x-ray diffractometry. Solidus and occasional liquidus temperatures were approximated, so that tentative partial phase diagrams for 33 oxide additions were constructed. Only the monoclinic and the cubic forms of Bi2O3 were found to be stable. Other phases, frequently reported by previous investigators, such as tetragonal and body-centered cubic (b.c.c.), were shown to form metastably from cooled liquid or cubic. An impure b.c.c. phase of distinct but variable composition appeared in systems of ZnO, PbO, B2O3, Al2O3, Ga2O3, Fe2O3, SiO2, GeO2, TiO2, and P2O5. The impure b.c.c. phase in the systems with SiO2, GeO2, and TiO2 melted congruently about 100 °C above the m.p. of Bi2O3. The impure b.c.c. phase was formed metastably in systems with Rb2O, NiO, MnO, CdO, V2O5, and Nb2O5; the conditions of formation were dependent on composition, preparation, and heating schedules. The impure b.c.c. phases, both stable and metastable, had smaller unit cell dimensions than that of pure Bi2O3.

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Polymorphism of Bismuth Sesquioxide. II. Effect of Oxide Additions on the Polymorphism of Bi2O3.

Barium titanate precursors with Ba/Ti ratios ranging from 2:1 to 1:9 were prepared by controlled hydrolysis of mixed barium and titanium species in an alcohol medium. Details of the synthesis and characterization of the resultant products are given. Amorphous powders precipitated by hydrolysis from ethanol solutions of barium and titanium alkoxides crystallize to single-or two-phase 1:2 and 1:5 compounds at ∼700°C. These compounds transform at higher temperatures to other known crystalline phases, the 1:5 phase being maintained metastably to ∼1100°C.

Robert S. Roth

Papers

The parent structure of the layered high-temperature superconductors

The crystal structures of the lithium-inserted metal oxides Li0.5TiO2 anatase, LiTi2O4 spinel, and Li2Ti2O4

Polymorphism of Bismuth Sesquioxide. II. Effect of Oxide Additions on the Polymorphism of Bi2O3.

Alkoxide Precursor Synthesis and Characterization of Phases in the Barium-Titanium Oxide System

A new layered cuprate structure-type, (A1−xA′x)14Cu24O41