Mixed valence Zn-Co-layered double hydroxides and their exfoliated nanosheets with electrode functionality

Abstract

New phases of Zn-Co-layered double hydroxides (Zn-Co-LDHs) were synthesized for the first time via a co-precipitation reaction using hydrogen peroxide as an oxidant. According to powder X-ray diffraction and field emission-scanning electron microscopy, both nitrate- and sulfate-forms of the Zn-Co-LDHs crystallized with the brucite-type layer structure having interlayer nitrate and sulfate anions, respectively, and commonly showed plate-like morphology with a crystal size of several hundred nanometers. dc magnetic susceptibility measurements revealed that the Zn-Co-LDHs displayed ferromagnetic/ antiferromagnetic transitions below 15 K and the magnetic moment calculated from the paramagnetic region (30-300 K) indicated the co-existence of weak field Co 2+ and strong field Co 3+ ions. The mixed oxidation state of Co 2+/Co 3+ was confirmed by the results of iodometry and X-ray absorption near-edge structure spectroscopy. The heat-treatment for the Zn-Co-LDHs at elevated temperatures produced mixed metal oxide nanocomposites composed of spinel ZnCo 2O 4 and wurzite ZnO phases. The colloidal suspension of exfoliated Zn-Co-LDH nanosheets could be synthesized by dispersion of the pristine LDH materials in formamide, which was confirmed by the Tyndall phenomenon, high resolution-transmission electron microscopy/selected area electron diffraction, and UV-vis spectroscopy. The Zn-Co-LDH film fabricated with the restacked nanosheets exhibited pseudocapacitive behavior with a large specific capacitance and a good capacitance retention. The present findings underscore that the newly synthesized mixed valence Zn-Co-LDH phases showed promising functionality as a supercapacitor electrode material and also showed interesting magnetic coupling behavior. © 2011 The Royal Society of Chemistry.