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Microwave-assisted heating methods have been used to synthesize oleylamine-capped Ge1–xSnx nanocrystals. By varying the reaction temperature while keeping the Ge and Sn precursor concentrations con...

Water-soluble poly(allylamine) Mn2+-doped Si (SiMn) nanoparticles (NPs) were prepared and show promise for biologically related applications. The nanoparticles show both strong photoluminescence and good magnetic resonance contrast imaging. The morphology and average diameter were obtained through transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM); spherical crystalline Si NPs with an average diameter of 4.2 ± 0.7 nm were observed. The doping maximum obtained through this process was an average concentration of 0.4 ± 0.3% Mn per mole of Si. The water-soluble SiMn NPs showed a strong photoluminescence with a quantum yield up to 13%. The SiMn NPs had significant T1 contrast with an r1 relaxivity of 11.1 ± 1.5 mM-1 s-1 and r2 relaxivity of 32.7 ± 4.7 mM-1 s-1 where the concentration is in mM of Mn2+. Dextran-coated poly(allylamine) SiMn NPs produced NPs with T1 and T2 contrast with a r1 relaxivity of 27.1 ± 2.8 mM-1 s-1 and r2 relaxivity of 1078.5 ± 1.9 mM-1 s-1. X-band electron paramagnetic resonance spectra are fit with a two-site model demonstrating that there are two types of Mn2+ in these NP's. The fits yield hyperfine splittings (A) of 265 and 238 MHz with significant zero field splitting (D and E terms). This is consistent with Mn in sites of symmetry lower than tetrahedral due to the small size of the NP's.

Inorganic semiconductor nanoparticles are of significant interest for applications that benefit from their size-dependent properties. The work presented here focuses on the characterization of solution-based microwave synthesized Ge nanocrystals (NCs). Three differently capped Ge NCs were investigated: oleylamine (OAM), dodecanethiol (DDT), and a functionalized N4,N4,N4′,N4′-tetraphenylbiphenyl-4,4′-diamine (TPD) ligand, which is commonly used as hole-transporting units. The optical gaps followed the expected trend for quantum confinement; however, the absolute value depended upon the ligand. We found that the DDT-capped Ge NCs feature consistently larger bandgaps than OAM-capped Ge NCs of a similar size. Cyclic voltammetry (CV) was used to determine the valence band energy for OAM-capped Ge NCs, and the conduction band energy was estimated from the optical gap. By contrast, DDT-capped Ge NCs and the OAM/DDT-capped Ge NCs did not exhibit an oxidative signal in the cyclic voltammetry. This was attributed t...

Ammonia borane (AB) is under significant investigation as a possible hydrogen storage material. While chemical additives have been shown to lower the temperature for hydrogen release from ammonia borane, many provide additional complications in the regeneration cycle. Mechanically alloyed hexagonal boron nitride (nano-BN) has been shown to facilitate the release of hydrogen from AB at lower temperature, with minimal induction time and less exothermicity, and inert nano-BN may be easily removed during any regeneration of the spent AB. The samples were prepared by mechanically alloying AB with nano-BN. Raman spectroscopy indicates that the AB/nano-BN samples are physical mixtures of AB and h-BN. The release of hydrogen from AB/nano-BN mixtures as well as the decomposition products was characterized by 11B magic angle spinning (MAS) solid state NMR spectroscopy, TGA/DSC/MS with 15N-labeled AB, and solution 11B NMR spectroscopy. The 11B MAS solid state NMR spectrum shows that diammoniate of diborane (DADB) is...

Nanoscale hexagonal BN additive for ammonia borane, AB, is shown to decrease the onset temperature for hydrogen release. Both the nano-BN and the AB:nano-BN samples are prepared by ball milling. The materials are characterized by X-ray powder diffraction, 11B muclear magnetic resonance, thermogravimetric analysis, differential scanning calorimetry, and mass spectrometry, and the hydrogen release is measured by a volumetric gas burette system. Several effects of the mixtures of AB:nano-BN are shown to be beneficial in comparison with neat AB. These are the decrease of the dehydrogenation temperature, the decrease in NH3 formation, as well as the decrease of the exothermicity of hydrogen release with increasing the nano-BN concentration.

The electronic conductivity of Langmuir−Blodgett monolayers of silane-passivated silicon nanoparticles (core diameter 3.86 ± 0.85 nm) was examined by electrochemical measurements within the context of photoirradiation and at controlled temperatures. Temperature dependence of the dark conductivity indicated that the interparticle charge transfer followed a thermal activation mechanism within the temperature range of 200−320 K; whereas at lower temperature, the ensemble conductance was determined by tunneling between (clusters of) nanoparticles that were of equivalent energy states. When exposed to photoexcitation with photon energy greater than the effective particle bandgap, the particle ensemble conductivity exhibited a drastic enhancement as compared to that in the dark; and, at a specific excitation wavelength, the conductivity became virtually independent of temperature. This suggested efficient ionization of the photoexcited quantum-confined electron−hole pairs by the applied electric field, most pro...