Browsing by Author "Amirzhanova, Assel"
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Item Open Access Mesoporous MnCo2O4 NiCo2O4 and ZnCo2O4 thin-film electrodes as electrocatalysts for the oxygen evolution reaction in alkaline solutions(American Chemical Society, 2021-03-22) Amirzhanova, Assel; Akmanşen, Nesibe; Karakaya, Irmak; Dağ, ÖmerThe oxygen evolution reaction (OER) is the bottleneck of the electrochemical water-splitting process, where the use of porous metal oxide electrodes is beneficial. In this work, we introduce a one-pot synthesis method to fabricate a series of mesoporous metal cobaltite (m-MCo2O4, M = Mn, Ni, and Zn) electrodes for the OER. The method involves preparation and coating of a homogeneous clear solution of all ingredients (metal salts and surfactants) over a fluorine-doped tin oxide surface as a thin lyotropic liquid crystalline film and calcination (as low as 250 °C) to obtain a 400 nm thick crystalline m-MCo2O4 electrode with a spinel structure. Mesophases and m-MCo2O4 films are characterized using structural and electrochemical techniques. All electrodes are stable during the electrochemical test in 1 M KOH aqueous solution and perform at as low as 204 mV overpotential at 1 mA/cm2 current density; the m-MnCo2O4 electrode works at current densities of 1, 10, and 100 mA/cm2 at 227, 300, and 383 mV overpotentials after compensating the IR drop, respectively. The Tafel slope is 60 mV/dec for the m-NiCo2O4 and m-ZnCo2O4 electrodes, but it gradually increases to 85 mV/dec in the m-MnCo2O4 electrode by thermal treatment, indicating a change in the OER mechanism.Item Open Access Synthesis and characteization of mesoporous nickel oxide and nickel cobaltite thin films(Bilkent University, 2019-09) Amirzhanova, AsselIn this thesis work, molten-salt assisted self-assembly (MASA) approach was adopted to synthesize mesoporous nickel oxide (m-NiO) and nickel cobaltite (m-NiCo2O4) thin films. The m-NiO and m-NiCo2O4 films were obtained by coating clear ethanol solutions of nickel salt and two surfactants (charged, CTAB and neutral, 10-lauryl ether), and nickel and cobalt salts with the same surfactants, respectively, followed by calcination at different temperatures (between 250 and 500 oC). The method has been established in a very broad range of salt concentrations in the lyotropic liquid crystalline (LLC) mesophase that can be calcined to produce mesoporous thin films. Both Ni(II) and Ni(II)/Co(II) systems form stable and oriented LLC mesophases in a broad range of salt concentrations (salt surfactant mole ratio of 2-8) upon evaporation of ethanol from the media. This can be achieved by either spin coating of the clear solutions (this ensure immediate evaporation of ethanol, leaving the LLC gel phase as thin film) or drop casting and evaporation of ethanol (the gelation process takes more time). At higher salt concentrations (10-30 salt/surfactant mole ratios), the mesophase is disordered and leach out salt crystals. However, those compositions can still be used for the synthesis of mesoporous metal oxides, if the samples are calcined immediately after the gelation step. The mesophase is 2D hexagonal at low salt concentrations and disordered or cubic at higher salt concentrations. The calcined films were characterized by recording x-ray diffraction (XRD), N2-adsorption desorption measurements, imaging (SEM, TEM, and POM) and spectroscopic (UV-Vis, XPS, EDX, and ATR-FTIR) techniques. The N2 adsorption-desorption isotherms are type IV and characteristic for mesoporous materials. The XRD data show that the crystalline m-NiO and m-NiCo2O4 form at around 300 and 250 oC, respectively, with a pore-wall thickness of around 3-4 nm. The pore-walls grow with increasing the calcination/annealing temperature up to 20 nm at around 500 oC. It accords well with the BET surface area that decreases with increasing calcinations temperature; it is 223 m2/g at 300 oC and drops to 20 m2/g at 500oC in mesoporous nickel oxide, and 223 m2/g at 250 oC and drops to 31 m2/g at 500 oC in mesoporous nickel cobaltite. The observed diffraction patterns can be indexed to rock salt cubic structure of NiO and cubic spinel structure of NiCo2O4. The diffraction lines gradually become sharper indicating crystallization and growth of the pore-walls that accord well with the reduction on the surface area. The m-NiO and m-NiCo2O4 films can be coated over FTO glass to use as an electrochromic electrode (oxidation dark-reduction clear) and electrode for water oxidation reactions (WOR) and WOR, respectively. In nickel oxide case, during cyclic voltammograms cycling, water oxidation process, and electrochromic switching, a few atomic layer of nanocrystalline NiO pore-wall is converted to NiOOH in oxidation and Ni(OH)2 upon reduction processes; initially formed nanocrystalline NiO (after calcination) pore-walls become NiO coated Ni(OH)2 (core-shell structure) upon electrochemical treatments. Both NiO and NiCo2O4 having high surface area and electrochemical stability show promising capacitive properties and can be used as electrocatalysts. From the Tafel slope analysis, it has been shown that nickel cobaltite can oxidize water at low overpotentials and therefore can be used as a promising water splitting catalyst.Item Open Access Synthesis and water oxidation electrocatalytic and electrochromic behaviours of mesoporous nickel oxide thin film electrodes(Royal Society of Chemistry, 2019) Amirzhanova, Assel; Karakaya, Irmak; Uzundal, Can Berk; Karaoğlu, Gözde; Karadaş, Ferdi; Ülgüt, Burak; Dağ, ÖmerNickel oxide (NiO) thin film with a high surface area is an important material in electrochemical applications. Spin coating of a preformed clear solution of ethanol, nickel nitrate, and surfactants (C12H25(OCH2CH2)10OH, C12E10 and C16H33N(CH3)3Br, CTAB) over a substrate produces a lyotropic liquid crystalline phase that is calcined into a transparent mesoporous NiO (m-NiO) thin film with a uniform film morphology and high porosity and surface area. m-NiO, coated over FTO glass, can be used as an electrode in an electrochromic device and electrocatalytic water oxidation processes with excellent efficiency (Tafel slope of 62 mV dec−1 and a low overpotential of 0.200 V at 1 mA cm−2 current density). Repetitive cyclic voltammetry and chronopotentiometry measurements convert the NiO pore walls into a NiO/Ni(OH)2 core–shell structure. In the water oxidation process, various Ni2+ surface species on the pore-walls are oxidized to Ni3+ and further to Ni4+ electrocatalytic active species. In an electrochromic device, the oxidation of the Ni2+ species to Ni3+ species reversibly contributes to the electrochromic behaviour, but if the electrochromic device is run at more positive potentials (such as those beyond water oxidation potentials), then electrochromic switching takes place between the Ni(OH)2 and NiOOH surface species.