Single-Source Materials for Metal-Doped Titanium Oxide: Syntheses, Structures, and Properties of a Series of Heterometallic Transition-Metal Titanium Oxo Cages

“…[7] We first assessed the hydrolytic decomposition of TiNi into TiO 2 and the electroactivity of NiO x . A water-oxidizing electrode (FTO|TiNi) was assembled by drop-casting TiNi in toluene (10 μL of a 5 m m solution) on a fluoride-doped tin oxide (FTO)-coated glass substrate with an exposed geometrical surface area of 0.5 cm 2 .…”

mentioning

confidence: 99%

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

Lai

King

Wright

et al. 2013

Chemistry A European J

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“…53 Although the detailed formation mechanism is not fully understood yet, there is no doubt that the morphology of deposited films is highly dependent on the L-POT precursor cage used, especially the presence of a functional ligand. This conclusion is further supported by the interesting behaviour of crystalline blocks of [Ti 6 O 3 (O i Pr) 14 (TTF) 2 ]ˑ0.5H 2 O (9), which self-exfoliate upon exposure to air or oxygen, giving rise to stacks of 'floorboardlike' plates (Figure 8e,f). 24 The ready oxidation and exfoliation of the crystalline blocks can be attributed to catalysed reaction of 9 upon TTF oxidation and self-condensation of the POT core.…”

Section: Photocatalystsmentioning

confidence: 65%

“…Using recently developed synthetic approaches, the successful synthesis of atomically well-defined polyoxotitanate (POT) cages has allowed chemists to gain new insights into molecular activation using TiO 2 . [7][8][9] Resembling the fragments of bulk TiO 2 , POT cages of the type [Ti x O y (OR) z ] (OR = alkoxide), consisting of Ti x O y inorganic titanium oxide cores encapsulated within an alkoxide ligand periphery, can be considered as models for studying the structural chemistry of bulk TiO 2 , including its crystal growth mechanism, 10,11 the electronic and structural effects of heterometallic doping, [12][13][14][15][16][17][18][19][20][21] and the influence of surface functional ligand modification. [22][23][24][25][26][27][28][29][30][31] While their excellent solubility in common organic solvents allows POTs to be studied using various standard methods (e.g., NMR, 32-34 mass spectrometry 35 ), single-crystal X-ray diffraction is perhaps the preeminent tool for their characterisation (allowing unambiguous characterisation of structural features which can be related to that of bulk TiO 2 itself).…”

Section: Introductionmentioning

confidence: 99%

Novel properties and potential applications of functional ligand-modified polyoxotitanate cages

et al. 2016

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Functional ligand-modified polyoxotitanate (L-POT) cages of the general type [TixOy(OR)z(L)m] (OR = alkoxide, L = functional ligand) can be regarded as molecular fragments of surface-sensitized solid-state TiO2, and are of value as models for studying the interfacial charge and energy transfer between the bound functional ligands and a bulk semiconductor surface. These L-POTs have also had a marked impact in many other research fields, such as single-source precursors for TiO2 deposition, inorganic-organic hybrid material construction, photocatalysis, photoluminescence, asymmetric catalysis and gas adsorption. Their atomically well-defined structures provide the basis for the understanding of structure/property relationships and ultimately for the rational design of new cages targeting specific uses. This highlight focuses on recent advances in L-POTs research, with emphasis on their novel properties and potential applications.

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“…[19][20][21][22][23][24] These molecular species can be regarded as models for the incorporation of metal ions into TiO 2 and are useful as organically-soluble single-source precursors for the stoichiometrically controllable deposition of metal-doped TiO 2 . [24] The cages are also of interest as organically soluble photocatalytic redox systems in organic synthesis.…”

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confidence: 99%

Dipole‐Induced Band‐Gap Reduction in an Inorganic Cage

Cheng

Steiner

et al. 2014

Angewandte Chemie

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Metal-doped polyoxotitanium cages are a developing class of inorganic compounds which can be regarded as nanoand sub-nano sized molecular relatives of metal-doped titania nanoparticles. These species can serve as models for the ways in which dopant metal ions can be incorporated into metal-doped titania (TiO 2 ), a technologically important class of photocatalytic materials with broad applications in devices and pollution control. In this study a series of cobalt(II)-containing cages in the size range ca. 0.7-1.3 nm have been synthesized and structurally characterized, allowing a coherent study of the factors affecting the band gaps in well-defined metal-doped model systems. Band structure calculations are consistent with experimental UV/Vis measurements of the Ti x O y absorption edges in these species and reveal that molecular dipole moment can have a profound effect on the band gap. The observation of a dipole-induced band-gap decrease mechanism provides a potentially general design strategy for the formation of low band-gap inorganic cages.Titanium dioxide (titania, TiO 2 ) is a technologically important, high band-gap semiconductor which is used in a wealth of green applications, most importantly in photocatalytic water splitting and the photocatalytic degradation of environmental pollutants. [1][2][3] However, because of the high band gap (ca. 3.20 eV) only the ultraviolet region of the solar radiation (< 5 % of solar flux on Earth) can be harnessed in photoexcitation processes. To facilitate real-world applications using the full range of ambient sunlight it is therefore necessary to dope TiO 2 with non-metal atoms (such as N or B [4,5] ) or metal ions (lanthanides [6][7][8][9][10][11][12] and transition metals [13][14][15][16][17][18] ) which extend the absorption by the photocatalysts into visible region. Although very few studies have attempted to elucidate the way in which metal ions are incorporated into titania, it is well known that the photoactivity of metal-doped titania depends substantially on both the metal ion and its concentration [4,5] and seems to be closely related to the structure and binding mode of the dopant metal ions within titania.Our interest in this area has focused on the exploration of a broad family of heterometallic polyoxotitanium (POT) cage compounds containing transition-metal and lanthanide ions, [Ti x O y (OR) z M n X m ] (M is a dopant metal ion, X an inorganic anion). [19][20][21][22][23][24] These molecular species can be regarded as models for the incorporation of metal ions into TiO 2 and are useful as organically-soluble single-source precursors for the stoichiometrically controllable deposition of metal-doped TiO 2 . [24] The cages are also of interest as organically soluble photocatalytic redox systems in organic synthesis. Herein we address the major issue of what structural and physical factors influence the band gaps in molecular transition-metal-doped POT cages. In the current study we pinpoint a new effect in the area of metal-doped POT cages, that the introd...

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Single-Source Materials for Metal-Doped Titanium Oxide: Syntheses, Structures, and Properties of a Series of Heterometallic Transition-Metal Titanium Oxo Cages

Cited by 69 publications

References 51 publications

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

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

Novel properties and potential applications of functional ligand-modified polyoxotitanate cages

Dipole‐Induced Band‐Gap Reduction in an Inorganic Cage

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Single-Source Materials for Metal-Doped Titanium Oxide: Syntheses, Structures, and Properties of a Series of Heterometallic Transition-Metal Titanium Oxo Cages

Cited by 69 publications

References 51 publications

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

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

Novel properties and potential applications of functional ligand-modified polyoxotitanate cages

Dipole‐Induced Band‐Gap Reduction in an Inorganic Cage

Contact Info

Product

Resources

About

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

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