ABSTRACT
This paper describes a supercritical hydrothermal synthesis method as a green solvent process, along with products based on this method that can be used as green materials that contribute to solving environmental problems. The first part of this paper summarizes the basics of this method, including the mechanism of the reactions, specific features of the supercritical state for nanoparticle synthesis, the continuous flow-type reactor and applications; this provides a better understanding of the suitability of this method to synthesize green materials. The second part of the paper describes the method used to synthesize Cr-doped CeO(2) nanoparticles, which show an extremely high oxygen storage capacity, suggesting their high potential as an environmental catalyst. Transmission electron microscopy and scanning electron microscope images showed octahedral Cr-doped CeO(2) nanoparticles with sizes of 15-30 nm and cubic Cr-doped CeO(2) nanoparticles with sizes of 5-8 nm. Octahedral Cr-doped CeO(2) nanoparticles exposing (111) facets and cubic Cr-doped CeO(2) nanoparticles exposing (100) facets were determined by high-resolution transmission electron microscopy and selected area electron diffraction. The X-ray diffraction peaks shifted to a high angle because the radius of the Cr ion is smaller than that of the Ce ion.
ABSTRACT
A series of gadolinium hydroxide [Gd(OH)3] nanoclusters having different morphologies was synthesized in the presence of 3,4-dihydroxy hydrocinnamic acid (DHCA), an organic modifier, under subcritical water conditions. These well-shaped Gd(OH)3 clusters are composed of many nanorods in a parallel orientation, rather than a disordered aggregation of nanorods, which are linked together by organic DHCA molecules. Here DHCA works as an inter-linker to form these cluster-like structures through coordination bonds. All samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and SQUID magnetometry. We investigated the effect of the concentrations of DHCA and KOH on the size and morphology of the Gd(OH)3 clusters. Their possible formation mechanism is also briefly discussed.
ABSTRACT
Friedel-Crafts reactions of aromatic and heteroaromatic compounds with an N-acyliminium ion pool were studied. The reaction of 1,3,5-trimethylbenzene in a batch reactor gave rise to the selective formation of a monoalkylation product (69%). Presumably, the second alkylation is slower than the first alkylation because of the protonation of the monoalkylation product that decreases its reactivity. The reaction of 1,3,5-trimethoxybenzene, however, gave rise to the formation of both monoalkylation (37%) and dialkylation (32%) products. Disguised chemical selectivity due to faster reaction than mixing seems to be responsible for the lack of selectivity. The use of micromixing was found to be quite effective to solve this problem to increase the selectivity. The monoalkylation product was obtained in 92% yield together with a small amount of the dialkylation product (4%). The reaction with various aromatic and heteroaromatic compounds revealed that the low mono/dialkylation selectivity was observed only for highly reactive aromatics. In such cases, the use of micromixing was quite effective to improve the selectivity. On the basis of micromixing, the selective sequential dialkylation using two different N-acyliminium ions was achieved. CFD simulations using a laminar flow and finite-rate model are consistent with the experimental observations and clearly indicate the importance of mixing.
