RESUMO
We report here on the controlled synthesis, characterization, and electrochemical properties of different polymorphs of niobium pentoxide grown by CVD of new single-source precursors. Nb2O5 films deposited at different temperatures showed systematic phase evolution from low-temperature tetragonal (TT-Nb2O5, T-Nb2O5) to high temperature monoclinic modifications (H-Nb2O5). Optimization of the precursor flux and substrate temperature enabled phase-selective growth of Nb2O5 nanorods and films on conductive mesoporous biomorphic carbon matrices (BioC). Nb2O5 thin films deposited on monolithic BioC scaffolds produced composite materials integrating the high surface area and conductivity of the carbonaceous matrix with the intrinsically high capacitance of nanostructured niobium oxide. Heterojunctions in Nb2O5/BioC composites were found to be beneficial in electrochemical capacitance. Electrochemical characterization of Nb2O5/BioC composites showed that small amounts of Nb2O5 (as low as 5%) in conjunction with BioCarbon resulted in a 7-fold increase in the electrode capacitance, from 15 to 104 F g(-1), while imparting good cycling stability, making these materials ideally suited for electrochemical energy storage applications.
RESUMO
The synthesis and characterization of nine new heteroleptic alkoxides of niobium is described. Metathesis reactions of Nb(2)Cl(10) with (t)BuCH(2)OH and pyridine (py) or 4-dimethylaminopyridine (DMAP) affords monomeric octahedral complexes Nb(OCH(2)(t)Bu)(5)py (1) and Nb(OCH(2)(t)Bu)(5)DMAP (2), respectively, in high yields (>60%). The same reaction with (t)BuOH resulted in a chloro functionalized alkoxide Nb(O(t)Bu)(4)pyCl (3) and could not be pushed to complete removal of remaining Cl(-) ligand. The introduction of a chelating bidental ligand 3,3,3-trifluoro-1-(pyridine-2-yl)propen-2-ol (2-PyCHCOHCF(3)) (4'') in the dimeric framework of Nb(2)(O(i)Pr)(10) (4') produced a heteroleptic, monomeric niobium complex Nb(O(i)Pr)(4)(2-PyCHCOCF(3)) (4) with significantly enhanced stability and volatility. As a comparison to (4), five different heteroaryl systems (5-9) with the same side chain have been synthesized and examined in order to understand the influence upon physio-chemical properties. All the new compounds (1-9) have been characterized by microanalysis, variable temperature multinuclear NMR spectroscopy, mass spectrometry, thermal analysis and single crystal X-ray diffraction studies ((3), (4) and (9)). The molecular structure of (3) revealed mononuclear species with Nb atoms present in the distorted octahedral environment of four (t)BuO, one chloride and one pyridine ligand. Compounds (4) and (9) consisting of four (i)PrO and a trifluoroheteroarylenolate exhibited a stronger distortion in the molecular geometry due to the rigidity of chelating ß-alkenolate moiety.
RESUMO
Nanosized (20-30 nm) colloidal gold, silver and their alloys were obtained by reductive transformation of corresponding metal salts. Dispersions of metal nanoparticles (σ < 4%) in aqueous solutions were obtained by appropriate surface functionalization which led to inorganic inks with solid fraction ranging from 0.01-4%. Judicious choice of a polymer additive (polyethylene glycol or carboxymethyl cellulose) was found to be crucial to avoid the agglomeration of nanocrystals in the ink-jetted structures upon solvent evaporation. The versatility of the nanoparticle-based printing technology was demonstrated by fabrication of dot-matrices and circuitry patterns on different substrates. Characterization of printed structures showed a homogeneous topography (AFM) and uniform distribution of metallic nanoparticles (SEM/TEM) within the ink-jetted microdrops. The site-specific patterning on silicon (001) substrates with nanoparticle (mono)layers could also be achieved by printing the linker molecule, aminopropyltriethoxysilane, followed by selective attachment of gold nanoparticles. Positionally ordered and chemically bonded gold catalyst patterns were used for the chemical vapour deposition (CVD) of nanowires, which led to site-specific growth of nanowires via the vapour-liquid-solid (VLS) mechanism and unlike in the case of spin-coated metal colloids no significant lateral diffusion of metal nanoparticles was observed, in chemically anchored Au nanoparticles. Nanoparticle containing inks allow a user-defined dilution to vary the density of CVD grown nanowires, which was utilized to show the differences in catalytic activities of silver and gold catalysts in the VLS growth.
