Timothy C. King

Formation of Ti28Ln Cages, the Highest Nuclearity Polyoxotitanates (Ln=La, Ce)

The solvothermal reactions of Ti(OEt)(4) with LnCl(3) (Ln = La, Ce) produced new Ti(28) Ln cages, in which the Ln(3+) ions are coordinated within a metallocrown arrangement, which represents the highest nuclearity cages of this type (see figure).

Scalable One‐Step Assembly of an Inexpensive Photoelectrode for Water Oxidation by Deposition of a Ti‐ and Ni‐Containing Molecular Precursor on Nanostructured WO3

Photoactive in one step! A nanocomposite water-oxidation photocatalyst was assembled by a straightforward and one-step spin-coating procedure of a Ti- and Ni-containing molecule on nanostructured WO3. The photoanode oxidizes water to O2 with good activity and stability in alkaline solution, and thereby features light absorption, charge separation and water-oxidation catalysis (see scheme).

A study of the optical properties of metal-doped polyoxotitanium cages and the relationship to metal-doped titania

To what extent the presence of transition metal ions can affect the optical properties of structurally well-defined, metal-doped polyoxotitanium (POT) cages is a key question in respect to how closely these species model technologically important metal-doped TiO2. This also has direct implications to the potential applications of these organically-soluble inorganic cages as photocatalytic redox systems in chemical transformations. Measurement of the band gaps of the series of closely related polyoxotitanium cages [MnTi14(OEt)28O14(OH)2] (1), [FeTi14(OEt)28O14(OH)2] (2) and [GaTi14(OEt)28O15(OH)] (3), containing interstitial Mn(II), Fe(II) and Ga(III) dopant ions, shows that transition metal doping alone does not lower the band gaps below that of TiO2 or the corresponding metal-doped TiO2. Instead, the band gaps of these cages are within the range of values found previously for transition metal-doped TiO2 nanoparticles. The low band gaps previously reported for 1 and for a recently reported related Mn-doped POT cage appear to be the result of low band gap impurities (most likely amorphous Mn-doped TiO2).

Theory and Practice: Bulk Synthesis of C3B and its H2‐ and Li‐Storage Capacity

Previous theoretical studies of C3B have suggested that boron-doped graphite is a promising H2- and Li-storage material, with large maximum capacities. These characteristics could lead to exciting applications as a lightweight H2-storage material for automotive engines and as an anode in a new generation of batteries. However, for these applications to be realized a synthetic route to bulk C3B must be developed. Here we show the thermolysis of a single-source precursor (1,3-(BBr2)2C6H4) to produce graphitic C3B, thus allowing the characteristics of this elusive material to be tested for the first time. C3B was found to be compositionally uniform but turbostratically disordered. Contrary to theoretical expectations, the H2- and Li-storage capacities are lower than anticipated, results that can partially be explained by the disordered nature of the material. This work suggests that to model the properties of graphitic materials more realistically, the possibility of disorder must be considered.

Development Strategy and Investment Criteria: Complementary or Competitive?

Introduction, 108. — I. The three approaches and the issues facing them, 109. — II. Similar objectives will require different policies, 114. — III. Contrast between development strategy and benefit-cost analysis, 117. — IV. Conclusion, 119.

Synthesis and extensive characterisation of phosphorus doped graphite

The pyrolysis of 1,2-diphosphinobenzene at 800 °C gives a phosphorus-doped graphite (P-DG) with an unprecedented high phosphorus content, ca. 20 at%. In contrast with previously studied boron and nitrogen doped graphite materials, thorough characterisation and analysis of this material demonstrates that it is extensively disordered and contains substitutional P-atoms along with PO units in the host graphitic lattice, as well as P4 molecules trapped between the graphitic sheets. This represents a stabilised form of P4, which has been shown to covalently bind to lithium as Li3P in this material.

Chapter 7:Group 2 (Be–Ba) and Group 12 (Zn–Hg)

This review presents a perspective of the important structural and synthetic studies reported in 2011. The strict definition of an organometallic compound as one containing at least one C-metal bond or contact has been used throughout the literature survey. The review is not intended to be comprehensive, although it is based on a comprehensive search. Individual topics are highlighted in bold in the text in order to facilitate rapid access to a particular area of the literature. The year 2011 has seen a large number of structural studies of Group 2 and Group 12 organometallics, which dominate the review for this year. A particular highlight was the structural characterisation of Me2Zn and Et2Zn in the solid state.