Photochemical versus Thermal Synthesis of Cobalt Oxyhydroxide Nanocrystals

Photochemical methods facilitate the generation, isolation, and study of metastable nanomaterials having unusual size, composition, and morphology. These harder-to-isolate and highly reactive phases, inaccessible using conventional high-temperature pyrolysis, are likely to possess enhanced and unprecedented chemical, electromagnetic, and catalytic properties. We report a fast, low-temperature and scalable photochemical route to synthesize very small (~3 nm) monodisperse cobalt oxyhydroxide (Co(O)OH) nanocrystals. This method uses readily and commercially available pentaamminechlorocobalt(III) chloride, [Co(NH3) 5Cl]Cl2, under acidic or neutral pH and proceeds under either near-UV (350 nm) or Vis (575 nm) illumination. Control experiments showed that the reaction proceeds at competent rates only in the presence of light, does not involve a free radical mechanism, is insensitive to O 2, and proceeds in two steps: (1) Aquation of [Co(NH3) 5Cl] 2+ to yield [Co(NH3) 5(H2O)] 3+, followed by (2) slow photoinduced release of NH3 from the aqua complex. This reaction is slow enough for Co(O)OH to form but fast enough so that nanocrystals are small (ca. 3 nm). The alternative dark thermal reaction proceeds much more slowly and produces much larger (~250 nm) polydisperse Co(O)OH aggregates. UV-Vis absorption measurements and ab initio calculations yield a Co(O)OH band gap of 1.7 eV. Fast thermal annealing of Co(O)OH nanocrystals leads to Co3O4 nanocrystals with overall retention of nanoparticle size and morphology. Thermogravimetric analysis shows that oxyhydroxide to mixed-oxide phase transition occurs at significantly lower temperatures (up to T = 64 degrees C) for small nanocrystals compared with the bulk

Ozonation: A unique route to prepare nickel oxyhydroxides. Synthesis optimization and reaction mechanism study

This paper details the reacting paths involved during the oxidation of αII-Ni(OH)2 and βII-Ni(OH)2 with ozone, which is compared to the oxidation process conducted in aqueous solution. The main advantage of the ozone method lies in the control of the reaction medium steps owing to the feasibility of operating in the presence or absence of alkaline cations. This enables the preparation of the pure βIII-NiOOH phase, well-known to be difficult to obtain in aqueous media without γIII-NiOOH traces. The reaction mechanisms for both oxidation processes were found to be similar, and to yield the same final products, except for αII-Ni(OH) 2, where ozonation allowed the preparation of a new oxidized phase that was isolated and characterized by means of complementary techniques such as X-ray diffraction, chemical analysis, HRTEM, TGA, and FT-IR. A mechanism to account for the formation of this phase is proposed