Browsing by Subject "Molten salt assisted self-assembly"

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Open Access
Modification of mesoporous LiMn2O4 and LiMn2−xCoxO4 by SILAR method for highly efficient water oxidation electrocatalysis
(Wiley, 2020-06) Karakaya, Irmak; Karadaş, Ferdi; Ulgut, Burak; Dağ, Ömer
Iridium, ruthenium, and cobalt oxides are target materials as efficient and stable mesoporous metal oxide electrocatalysts for oxygen evolution reaction (OER). However, they are costly, toxic, and not practical for an efficient OER process. Here, a two‐step method is introduced, based on earth‐abundant manganese; molten salt‐assisted self‐assembly process to prepare mesoporous LiMn2−xCoxO4 (x = 0–0.5) modified electrodes, in which a systematic incorporation of Co(II) into the structure is performed using successive ionic layer adsorption and reaction followed by an annealing (SILAR‐AN) process. Applying SILAR‐AN over a stable m‐LiMn1.6Co0.4O4 electrode improves the OER performance; the Tafel slope and overpotential drop from 66 to 46 mV dec−1 and 304 to 265 mV (at 1.0 mA cm−2), respectively. The performance of the modified electrodes is comparable to benchmark IrO2 and RuO2 catalysts and much better than cobalt oxide electrodes. Electronic interactions between the neighboring Mn and Co sites synergistically amplify the OER performance of the m‐LiMn2−xCoxO4 electrodes. The data are compatible with an eight steps nucleophilic acid‐base reaction mechanism during OER.
Open Access
Molten salt assisted self-assembly: synthesis of mesoporous LiCoO2 and LiMn2O4 thin films and investigation of electrocatalytic water oxidation performance of lithium cobaltate
(Wiley-VCH Verlag, 2018) Saat, G.; Balci, F. M.; Alsaç, E. P.; Karadas, F.; Dağ, Ömer
Mesoporous thin films of transition metal lithiates (TML) belong to an important group of materials for the advancement of electrochemical systems. This study demonstrates a simple one pot method to synthesize the first examples of mesoporous LiCoO2 and LiMn2O4 thin films. Molten salt assisted self-assembly can be used to establish an easy route to produce mesoporous TML thin films. The salts (LiNO3 and [Co(H2O)6](NO3)2 or [Mn(H2O)4](NO3)2) and two surfactants (10-lauryl ether and cethyltrimethylammonium bromide (CTAB) or cethyltrimethylammonium nitrate (CTAN)) form stable liquid crystalline mesophases. The charged surfactant is needed for the assembly of the necessary amount of salt in the hydrophilic domains of the mesophase, which produces stable metal lithiate pore-walls upon calcination. The films have a large pore size with a high surface area that can be increased up to 82 m2 g−1. The method described can be adopted to synthesize other metal oxides and metal lithiates. The mesoporous thin films of LiCoO2 show promising performance as water oxidation catalysts under pH 7 and 14 conditions. The electrodes, prepared using CTAN as the cosurfactant, display the lowest overpotentials in the literature among other LiCoO2 systems, as low as 376 mV at 10 mA cm-2 and 282 mV at 1 mA cm-2.
Open Access
Synthesis and characteization of mesoporous nickel oxide and nickel cobaltite thin films
(2019-09) Amirzhanova, Assel
In 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.