Low temperature in situ immobilization of nanoscale fcc and hcp polymorphic nickel particles in polymer-derived Si-C-O-N(H) to promote electrocatalytic water oxidation in alkaline media.

We synthesized nickel (Ni) nanoparticles (NPs) in a high specific surface area (SSA) p-block element-containing inorganic compound prepared via the polymer-derived ceramics (PDC) route to dispatch the obtained nanocomposite towards oxygen evolution reaction (OER). The in situ formation of Ni NPs in an amorphous silicon carboxynitride (Si-C-O-N(H)) matrix is allowed by the reactive blending of a polysilazane, NiCl2 and DMF followed by the subsequent thermolysis of the Ni : organosilicon polymer coordination complex at a temperature as low as 500 °C in flowing argon. The final nanocomposite displays a BET SSA as high as 311 m2 g-1 while the structure of the NPs corresponds to face-centred cubic (fcc) Ni along with interstitial-atom free (IAF) hexagonal close-packed (hcp) Ni as revealed by XRD. A closer look into the compound through FEG-SEM microscopy confirms the formation of pure metallic Ni, while HR-TEM imaging reveals the occurrence of Ni particles featuring a fcc phase and surrounded by carbon layers; thus, forming core-shell structures, along with Ni NPs in an IAF hcp phase. By considering that this newly synthesized material contains only Ni without doping (e.g., Fe) with a low mass loading (0.15 mg cm-2), it shows promising OER performances with an overpotential as low as 360 mV at 10 mA cm-2 according to the high SSA matrix, the presence of the IAF hcp Ni NPs and the development of core-shell structures. Given the simplicity, the flexibility, and the low cost of the proposed synthesis approach, this work opens the doors towards a new family of very active and stable high SSA nanocomposites made by the PDC route containing well dispersed and accessible non-noble transition metals for electrocatalysis applications.

Mechanistic Investigation of the Formation of Nickel Nanocrystallites Embedded in Amorphous Silicon Nitride Nanocomposites.

Herein, we report the mechanistic investigation of the formation of nickel (Ni) nanocrystallites during the formation of amorphous silicon nitride at a temperature as low as 400 °C, using perhydropolysilazane (PHPS) as a preformed precursor and further coordinated by nickel chloride (NiCl2); thus, forming the non-noble transition metal (TM) as a potential catalyst and the support in an one-step process. It was demonstrated that NiCl2 catalyzed dehydrocoupling reactions between Si-H and N-H bonds in PHPS to afford ternary silylamino groups, which resulted in the formation of a nanocomposite precursor via complex formation: Ni(II) cation of NiCl2 coordinated the ternary silylamino ligands formed in situ. By monitoring intrinsic chemical reactions during the precursor pyrolysis under inert gas atmosphere, it was revealed that the Ni-N bond formed by a nucleophilic attack of the N atom on the Ni(II) cation center, followed by Ni nucleation below 300 °C, which was promoted by the decomposition of Ni nitride species. The latter was facilitated under the hydrogen-containing atmosphere generated by the NiCl2-catalyzed dehydrocoupling reaction. The increase of the temperature to 400 °C led to the formation of a covalently-bonded amorphous Si3N4 matrix surrounding Ni nanocrystallites.

Low temperature in situ formation of cobalt in silicon nitride toward functional nitride nanocomposites.

This work highlights the first demonstration of a low-temperature in situ formation of Co nanocrystallites embedded within an amorphous silicon nitride matrix through careful control of the chemistry behind material design using perhydropolysilazane (PHPS) as a Si3N4 precursor further coordinated with CoCl2 and ammonia as a pyrolysis atmosphere. The Co nucleation was allowed to proceed at temperatures as low as 400 °C via thermal decomposition of Co2N pre-formed in situ by the reaction of CoCl2 with the Si centers of PHPS at the early stage of pyrolysis (220-350 °C).