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This corrects the article DOI: 10.1038/srep44763.
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SnO2 nanocrystals were prepared by precipitation in dodecylamine at 100 °C, then they were reacted with vanadium chloromethoxide in oleic acid at 250 °C. The resulting materials were heat-treated at various temperatures up to 650 °C for thermal stabilization, chemical purification and for studying the overall structural transformations. From the crossed use of various characterization techniques, it emerged that the as-prepared materials were constituted by cassiterite SnO2 nanocrystals with a surface modified by isolated V(IV) oxide species. After heat-treatment at 400 °C, the SnO2 nanocrystals were wrapped by layers composed of vanadium oxide (IV-V mixed oxidation state) and carbon residuals. After heating at 500 °C, only SnO2 cassiterite nanocrystals were obtained, with a mean size of 2.8 nm and wrapped by only V2O5-like species. The samples heat-treated at 500 °C were tested as RhB photodegradation catalysts. At 10-7 M concentration, all RhB was degraded within 1 h of reaction, at a much faster rate than all pure SnO2 materials reported until now.
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TiO2 anatase nanocrystals were prepared by solvothermal processing of Ti chloroalkoxide in oleic acid, in the presence of W chloroalkoxide, with W/Ti nominal atomic concentration (R(w)) ranging from 0.16 to 0.64. The as-prepared materials were heat-treated up to 500 °C for thermal stabilization and sensing device processing. For R(0.16), the as-prepared materials were constituted by an anatase core surface-modified by WO(x) monolayers. This structure persisted up to 500 °C, without any WO3 phase segregation. For R(w) up to R(0.64), the anatase core was initially wrapped by an amorphous WO(x) gel. Upon heat treatment, the WO(x) phase underwent structural reorganization, remaining amorphous up to 400 °C and forming tiny WO3 nanocrystals dispersed into the TiO2 host after heating at 500 °C, when part of tungsten also migrated into the TiO2 structure, resulting in structural and electrical modification of the anatase host. The ethanol sensing properties of the various materials were tested and compared with pure TiO2 and WO3 analogously prepared. They showed that even the simple surface modification of the TiO2 host resulted in a 3 orders of magnitude response improvement with respect to pure TiO2.
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Titanium solid-state NMR spectroscopy data for a series of organic-inorganic titanium MCM-41 based materials have been collected. These materials have been synthesized by first modifying the mesoporous silica MCM-41 in one step with a mixture of silanes: a triazine propyl triethoxysilane acting as functional linker and methyltrimethoxysilane or hexamethyldisilizane as capped agents to mask the remaining silanol groups. Second, the appropiate titanium precursor Ti(OPr(i))(4), [{Ti(OPr(i))(3)(OMent)}(2)] (OMent = 1R,2S,5R-(-)-menthoxo), Ti(OPr(i))(4), or [Ti(eta(5)-C(5)HMe(4))Cl(3)], has been immobilized by reaction with the modified MCM-41. Finally, after Ti(OPr(i))(4) immobilization onto the organomodified support the reaction with the chiral (+)-diethyl-l-tartrate was accomplished. The materials without functional linker have been also prepared by reaction in one step of the capped agent and the titanium precursor with the mesoporous silica. Relevant correlations of titanium NMR resonance chemical shifts and line widths can be inferred depending on different factors. The immobilization procedure used to prepare titanium-based MCM-41 hybrid materials and the choice of the silylating reagents employed to mask the silanol groups present on the silica surfaces produce significant differences in the Ti NMR spectra. Furthermore, depending on the electronic and sterical influence of the substituents directly attached to the titanium center, chemical shifts and line widths are modified providing novel information about titanium structure.
