Low Temperature Synthesis of Large-Size Anatase TiO2 Nanosheets with Enhanced Photocatalytic Activities.

TiO2 nanosheets have continuously been intriguing due to their high surface activities as photocatalyst but still challenging to synthesis large-scale 2D nanostructures. A special microstructure evolution of TiO2 , ripening in aqueous solution at low temperature (≈4 °C), is found for the first time, i.e., from the initial aperiodic atom-networks gradually into low crystallized continuous spongy structure with small crystal facets and ultimately forming large-size anatase nanosheets with exposed (101) and (200) facets. Based on this finding, the synthesized anatase TiO2 nanosheets possess monodispersed large-scale 2D nanostructure so as to exhibit appreciable quantum size effects and remarkable enhanced optical absorption capacity. Using photocatalytic reduction of Cr (VI) to Cr (III) as the probe reaction to evaluate photocatalytic activities of the TiO2 nanosheets, the reductivity of Cr (VI) achieves 99.8% in 15 min under irradiation of 200-800 nm light. At the same time, an in situ Cr (III)-doping occurs spontaneously and triggers pronounced visible light driven photocatalysis, reducing 99% of Cr (VI) in 100 min under irradiation of 400-800 nm light.

Phosphine-iminopyridines as platforms for catalytic hydrofunctionalization of alkenes.

A series of phosphine-diimine ligands were synthesized by the condensation of 2-(diphenylphosphino)aniline (PNH2) with a variety of formyl and ketopyridines. Condensation of PNH2 with acetyl- and benzoylpyridine yielded the Ph2P(C6H4)N═C(R)(C5H4N), respectively abbreviated PN(Me)py and PN(Ph)py. With ferrous halides, PN(Ph)py gave the complexes FeX2(PN(Ph)py) (X = Cl, Br). Condensation of pyridine carboxaldehyde and its 6-methyl derivatives with PNH2 was achieved using a ferrous template, affording low-spin complexes [Fe(PN(H)py(R))2](2+) (R = H, Me). Dicarbonyls Fe(PN(R)py)(CO)2 were produced by treating PN(Me)py with Fe(benzylideneacetone)(CO)3 and reduction of FeX2(PN(Ph)py) with NaBEt3H under a CO atmosphere. Cyclic voltammetric studies show that the [FeL3(CO)2](0/-) and [FeL3(CO)2](+/0) couples are similar for a range of tridentate ligands, but the PN(Ph)py system uniquely sustains two one-electron reductions. Treatment of Fe(PN(Ph)py)X2 with NaBEt3H gave active catalysts for the hydroboration of 1-octene with pinacolborane. Similarly, these catalysts proved active for the addition of diphenylsilane, but not HSiMe(OSiMe3)2, to 1-octene and vinylsilanes. Evidence is presented that catalysis occurs via iron hydride complexes of intact PN(Ph)py.