A three-dimensional coordination polymer based on a manganese-doped polyoxotitanate nanocluster, {Ti13Mn4O16[MeC(CH2O)3]4(OEt)12Br4}∞, has been synthesized under solvothermal conditions. It is the first framework of doped polyoxotitanate nanoclusters reported in the literature. Compared with anatase, its band gap is reduced from 3.19 to 2.57 eV.
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http://dx.doi.org/10.1039/c3dt52218k | DOI Listing |
Dalton Trans
January 2017
Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China.
We present a novel strategy to improve the stability and optical absorption of polyoxotitanates (POTs) via concurrently fully carboxylate-coordinating and hetero-metal-doping, and illustrate the strategy by an indium doped hetero-polyoxotitanate (h-POT) of a [TiInO(OOCCH)] (POTi12In6) nanocluster, which possesses ultrahigh stability in both acid and base aqueous solutions. The nanocluster structurally features a core-shell double wheel structure and a polar cavity. Both experiments and theoretical calculations confirm the semiconductive properties of the nanocluster.
View Article and Find Full Text PDFChemistry
August 2015
Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260-3000 (USA).
Homodisperse doped polyoxotitanate nanoclusters with formulae Ti11 (MX)O14 (OiPr)17 (M=Mn, Fe or Co; X=Cl, Br or I, OiPr=isopropoxide) display strongly dopant-dependent properties. Spectroscopic solution and reflectance measurements backed up by density of states and time-dependent DFT calculations based on the determined structures, show the prominent effect of FeX substitution by decreasing the HOMO-LUMO gap of the particles. The effect is attributed to the presence of an occupied Fe β orbital halfway up the bandgap, leading to long-wavelength absorption with electron transfer to the titanium atoms of the cluster.
View Article and Find Full Text PDFPhys Chem Chem Phys
August 2014
Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, NY 14260-3000, USA.
Whereas a large number of sensitized polyoxotitanate clusters have been reported, information on the electrochemical properties of the fully structurally defined nanoparticles is not available. Bridging of this gap will allow a systematic analysis of the relation between sensitizer-cluster binding geometry, electronic structure and electron injection properties. Ti17O28(O(i)Pr)16(Fe(II)Phen)2 is a member of a doubly-doped series of nanoclusters in which the phenanthroline is attached to the surface-located transition metal atom.
View Article and Find Full Text PDFChem Rev
October 2014
Chemistry Department, University at Buffalo, SUNY , Buffalo, New York 14260-3000, United States.
Dalton Trans
March 2014
Chemistry Department, University at Buffalo, SUNY, Buffalo, New York 14260-3000, USA.
A large manganese-doped polyoxotitanate nanocluster Ti28MnO38(OEt)40H2, has been synthesized solvothermally. Its structure is arranged around the four-coordinate Mn(2+) dopant atom in a Keggin-type structure. A significant reduction of the band gap relative to that of undoped polyoxotitanate clusters is observed.
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