ABSTRACT
The crystal nucleation and growth mechanism of monodispersed metal-organic framework nanoparticles were studied using time-resolved light dynamic, electrokinetic, and powder X-ray diffraction methods. We confirmed that zeolitic imidazolate framework-8 (ZIF-8) nanocrystals follow a nonclassical crystal growth pathway, where a fast nucleation occurs with dense liquid clusters or nanocrystals forming spontaneously when two precursors are mixed. We also explored the zeta potential and solvodynamic size changes of ZIF-8 prepared by a surfactant-assisted synthesis. Three modulators, including 1-methylimidazole (1-mIm), tris(hydroxymethyl)aminomethane (THAM), and (1-hexadecyl)trimethylammonium bromide (CTAB), were studied. We found that 1-mIm dramatically increases the rate of nucleation of ZIF-8. With an increasing amount of 1-mIm, which functions as a coordination modulator, the size increases, and the zeta potential of ZIF-8 decreases. Whereas THAM, as both a coordination and a deprotonation modulator, increases the size and zeta potential of ZIF-8 simultaneously, CTAB, as a long alkyl cationic surfactant, mainly adsorbs on the surface of ZIF-8, and the zeta potential of the formed ZIF-8 is controlled by the amount of CTAB in solution compared with its critical micelle concentration. Overall, we reveal that the modulator type and concentration can be used to control the size and zeta potential of the dispersed ZIF-8 nanocrystals in a colloid system. The experiments also enable identification of the nucleation and crystal growth processes of ZIF-8. The findings will be applicable to other nanocrystals in colloid systems, which are used for heterogeneous catalysis and guest molecular loadings.
ABSTRACT
Two new transition metal oxides with the nominal chemical compositions of Li4NiOsO6 and Li3Ni2OsO6 were successfully synthesized. Both compounds crystallize in an ordered rock salt structure type in the monoclinic C2/m space group. The crystal structures were determined using both synchrotron X-ray and time-of-flight neutron, powder diffraction data. In both phases, Ni2+ ions are present while oxidation states of osmium are +6 and +5 in Li4NiOsO6 and Li3Ni2OsO6, respectively. Ni2+ ions in the hypothetical fully ordered phase form a honeycomb arrangement in the ab crystallographic plane and these hexagons are centered by osmium ions. The magnetic layers are separated along the c axis by the octahedra, which are centered by Li+ (or Li+/Ni2+, depending on the chemical compositions). Crystal structure refinements reveal that there is some degree of mixed occupancy in cationic positions. Temperature dependent magnetic susceptibility data for both phases show ferrimagnetic transitions with predominant antiferromagnetic (AFM) interactions among 3d electrons of nickel and 5d electrons of osmium. Iso-thermal magnetization loops as a function of the applied magnetic field below the transition temperatures confirm the ferrimagnetic nature in magnetic transitions. Temperature dependent heat capacity data, however, did not exhibit any anomaly in either phase, indicating the absence of long-range magnetic ordering. The lack of long-range order for both Os5+ and Os6+-based compounds was also confirmed by low temperature neutron diffraction data down to 10 K. Temperature dependent AC magnetic susceptibility data in various frequencies for both samples indicate that Li4NiOsO6 exhibits spin-glass-like behavior, while the transition temperature for Li3Ni2OsO6 is nearly frequency independent.
ABSTRACT
This article reports the effects of heating temperature and composition of nanoparticle multilayer films on the morphology, stability, and optical property of gold nanoisland films prepared by nanoparticle self-assembly/heating method. First, nanoparticle-polymer multilayer films are prepared by the layer-by-layer assembly. Nanoparticle multilayer films are then heated at temperature ranging from 500 °C to 625 °C in air to induce an evaporation of organic matters from the films. During the heating process, the nanoparticles on the solid surface undergo coalescence, resulting in the formation of nanostructured gold island arrays. Characterization of nanoisland films using atomic force microscopy and UV-vis spectroscopy suggests that the morphology and stability of gold island films change when different heating temperatures are applied. Stable gold nanoisland thin film arrays can only be obtained after heat treatments at or above 575 °C. In addition, the results show that the use of nanoparticles with different sizes produces nanoisland films with different morphologies. Multilayer films containing smaller gold nanoparticles tend to produce more monodisperse and smaller island nanostructures. Other variables such as capping ligands around nanoparticles and molecular weight of polymer linkers are found to have only minimal effects on the structure of island films. The adsorption of streptavidin on the biotin-functionalized nanoisland films is studied for examining the biosensing capability of nanoisland arrays.
