Linear sweep voltammetry

Abstract: Scanning electron microscopy, X-ray diffraction, cyclic voltammetry, chronoamperometry, in situ Raman spectroscopy, and X-ray absorption near-edge structure spectroscopy (XANES) were used to investigate the electrochemical oxygen evolution reaction (OER) on Cu, Cu2O, Cu(OH)2, and CuO catalysts. Aqueous 0.1 M KOH was used as the electrolyte. All four catalysts were oxidized or converted to CuO and Cu(OH)2 during a slow anodic sweep of cyclic voltammetry and exhibited similar activities for the OER. A Raman peak at 603 cm–1 appeared for all the four samples at OER-relevant potentials, ≥1.62 V vs RHE. This peak was identified as the Cu–O stretching vibration band of a CuIII oxide, a metastable species whose existence is dependent on the applied potential. Since this frequency matches well with that from a NaCuIIIO2 standard, we suggest that the chemical composition of the CuIII oxide is CuO2–-like. The four catalysts, in stark contrast, did not oxidize the same way during direct chronoamperometry measurement...

Abstract: A metal-rich form of Ni-selenide, nickel subselenide, Ni3Se2 has been investigated as a potential oxygen evolution electrocatalyst under alkaline conditions for the first time. The Ni3Se2 phase has a structure similar to the sulfur mineral heazlewoodite, which contains metal–metal bonding. The electrocatalytic activities of Ni3Se2 towards OER were seen to be at par with or even superior to the transition metal oxide based electrocatalyst in terms of onset overpotential for O2 evolution as well as overpotential to reach a current density of 10 mA cm−2 (observed at 290 mV). The electrocatalytic Ni3Se2 films were grown by electrodeposition on conducting substrates and the deposition parameters including the pH of the electrolytic bath, deposition potential, and substrate composition were seen to have some influence on the catalytic activity. So far, Ni3Se2 films deposited on the Au-coated Si substrate was seen to have the lowest overpotential. Annealing of the as-deposited electrocatalytic films in an inert atmosphere, enhanced their catalytic efficiencies by decreasing the overpotential (@10 mA cm−2) as well as increasing the current density. The structure and morphology of these films has been characterized by powder X-ray diffraction, scanning and transmission electron microscopy, Raman, and X-ray photoelectron spectroscopy. Catalytic activities were investigated through detailed electrochemical studies under alkaline conditions, including linear sweep voltammetry, chronoamperometric studies at constant potential, electrochemical surface area determination and calculation of the Tafel slope. The Faradaic efficiency of this catalyst has been estimated by reducing the evolved O2 in a RRDE set-up which also confirmed that the evolved gas was indeed O2. In addition to low overpotentials, these Ni3Se2 electrodeposited films were seen to be exceptionally stable under conditions of continuous O2 evolution for an extended period (42 h).

Abstract: In this work, three types of MnO2 nanostructures, viz., microsphere/nanosheet core−corona hierarchical architectures, one-dimensional (1D) nanorods, and nanotubes, have been synthesized employing a simple hydrothermal process. The formation mechanisms have been rationalized. The materials have been thoroughly characterized by X-ray diffraction, Brunauer−Emmett−Teller spectrometry, field-emission scanning electron miscroscopy, energy dispersive spectroscopy, and transmission electron microscopy. The microsphere/nanosheet core−corona hierarchical structures are found to be the layered birnessite-type MnO2, while 1D nanorods and nanotubes are of the α-MnO2 phase. These MnO2 nanostructures are used as a model system for studying the shape/phase-dependent electrocatalytic properties for the oxygen reduction reaction, which have be investigated by cyclic and linear sweep voltammetry. It is found that α-MnO2 nanorods/tubes possess largely enhanced electrocatalytic activity compared to birnessite-type MnO2 core−c...