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The location and function of dopants in metal oxide nanoparticles have been poorly characterized for many systems. We have performed heat capacity measurements, electron energy-loss spectroscopy (EELS), and X-ray diffraction (XRD) on 10 TiO2 nanoparticle samples that have different amounts of Al dopant to determine the location and function of the Al3+ cations. From the heat capacity data, lattice vacancies are observed to increase significantly with the addition of the Al dopant, suggesting Al3+ cations enter the TiO2 lattice and create vacancies due to the charge difference between Al3+ and Ti4+. The presence of gapped terms in fits of the low-temperature heat capacity data also suggests that small regions of short-range order are created within the TiO2 lattice. Entropies at T = 298.15 K were determined from the heat capacity data and show effects related to the entropy of mixing, suggesting that a solid solution of Al/TiO2 is formed. EELS data confirm that Al enters the TiO2 lattice but also indicates...

A new stationary phase for reversed-phase high performance liquid chromatography (RP HPLC) was created by coating spherical 3 μm carbon core particles in a layer-by-layer (LbL) fashion with poly(allylamine) (PAAm) and nanodiamond. Unfunctionalized core carbon particles were characterized by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and Raman spectroscopy. After LbL of PAAm and nanodiamond, which yields ca. 4 μm core-shell particles, the particles were simultaneously functionalized and cross-linked using a mixture of 1,2-epoxyoctadecane and 1,2,7,8-diepoxyoctane to obtain a mechanically stable C(18)/C(8) bonded outer layer. Core-shell particles were characterized by SEM, and their surface area, pore diameter, and volume were determined using the Brunauer-Emmett-Teller (BET) method. Short stainless steel columns (30 × 4.6 mm i.d.) were packed and the corresponding van Deemter plots obtained. The Supporting Information contains a MATLAB program used to fit the van Deemter data. The retentions of a suite of analytes were investigated on a conventional HPLC at various organic solvent compositions, pH values of mobile phases, including extreme pH values, and column temperatures. At 60 °C, a chromatogram of 2,6-diisopropylphenol showed 71,500 plates/m (N/m). Chromatograms obtained under acidic conditions (pH 2.7) of a mixture of acetaminophen, diazepam, and 2,6-diisopropylphenol and a mixture of phenol, 4-methylphenol, 2-chlorophenol, 4-chlorophenol, 4-bromophenol, and 1-tert-butyl-4-methylphenol are presented. Retention of amitriptyline, cholesterol, and diazinon at temperatures ranging from 35 to 80 °C and at pH 11.3 is reported. A series of five basic drugs was also separated at this pH. The stationary phase exhibits considerable hydrolytic stability at high pH (11.3) and even pH 13 over extended periods of time. An analysis run on a UHPLC with a "sandwich" injection appeared to reduce extra column band broadening and gave best efficiencies of 110,000-120,000 N/m.

Porous graphitic carbon (PGC) particles were functionalized/passivated in situ in packed beds at elevated temperature with neat di- tert -amylperoxide (DTAP) in a column oven. The performance of these particles for high performance liquid chromatography (HPLC) was assayed before and after this chemistry with the following analytes: benzene, toluene, ethyl benzene, n -propyl benzene, n -butyl benzene, p -xylene, phenol, 4-methylphenol, phenetole, 3,5-xylenol, and anisole. After the first functionalization/passivation, the retention factors, k , of these compounds decreased by about 5% and the number of theoretical plates ( N ) increased by ca. 15%. These values of k then remained roughly constant after a second functionalization/passivation but a further increase in N was noticed. In addition, after each of the reactions, the peak asymmetries decreased by ca. 15%, for a total of ca. 30%. The columns were then subjected twice to methanol at 100 °C for 5 h at 1 mL/min. After these stability tests, the values of k remained roughly constant, the number of plates increased, which is favorable, and the asymmetries rose and then declined, where they remained below the initial values for the unfunctionalized columns. Functionalized and unfunctionalized particles were characterized by scanning electron microscopy and BET measurements, which showed no difference between the functionalized and unfunctionalized materials, and X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS), where ToF-SIMS suggested some chemical differences between the functionalized and unfunctionalized materials. In particular ToF-SIMS suggested that the expected five-carbon fragments from DTAP exist at higher concentrations on DTAP-functionalized PGC. First principle calculations on model graphitic surfaces suggest that the first addition of a DTAP radical to the surface proceeds in an approximately isothermal or slightly favorable fashion, but that subsequent DTAP additions are then increasingly thermodynamically favorable. Thus, this analysis suggests that the direct functionalization/passivation of PGC with DTAP is plausible. Chemometric analyses of the chromatographic and ToF-SIMS data are also presented.

The effects of iron catalyst thickness on the fabrication and performance of microfabricated, binder-free, carbon nanotube (CNT)-templated, thin layer chromatography (TLC) plates are demonstrated. The iron catalyst was deposited at thicknesses ranging from 4 to 18 nm in increments of 2 nm. Its thickness plays a key role in governing the integrity and separation capabilities of microfabricated TLC plates, as determined using a test dye mixture. Atomic force microscopy and scanning electron microscopy show that smaller and more numerous catalyst nanoparticles are formed from thinner Fe layers, which in turn govern the diameters and densities of the CNTs. The average diameter of the Fe nanoparticles, Dp, is approximately six times the initial Fe film thickness, tFe: Dp ≈ 6tFe. After deposition of relatively thick silicon layers on CNTs made with different Fe thicknesses, followed by oxidation, all of the resulting CNT-templated SiO2 wires had nearly the same diameter. Consequently, their surface areas were v...

We present low temperature (11 K) inelastic neutron scattering (INS) data on four hydrated nanoparticle systems: 10 nm CoO·0.10H(2)O (1), 16 nm Co(3)O(4)·0.40H(2)O (2), 25 nm Co(3)O(4)·0.30H(2)O (3) and 40 nm Co(3)O(4)·0.026H(2)O (4). The vibrational densities of states were obtained for all samples and from these the isochoric heat capacity and vibrational energy for the hydration layers confined to the surfaces of these nanoparticle systems have been elucidated. The results show that water on the surface of CoO nanoparticles is more tightly bound than water confined to the surface of Co(3)O(4), and this is reflected in the reduced heat capacity and vibrational entropy for water on CoO relative to water on Co(3)O(4) nanoparticles. This supports the trend, seen previously, for water to be more tightly bound in materials with higher surface energies. The INS spectra for the antiferromagnetic Co(3)O(4) particles (2-4) also show sharp and intense magnetic excitation peaks at 5 meV, and from this the magnetic contribution to the heat capacity of Co(3)O(4) nanoparticles has been calculated; this represents the first example of use of INS data for determining the magnetic contribution to the heat capacity of any magnetic nanoparticle system.