Ultrathin 2D nanosheets of transition metal (hydro)oxides as prospective materials for energy storage devices: A short review

The ultrathin two-dimensional (2D) transition metal oxides and hydroxides (TMO and TMH) nanosheets are attractive for creating high-performance energy storage devices due to a set of unique physical and chemical properties. Flat 2D structure of such materials provides a sufficient number of active adsorption centers, and the ultra-small thickness, on the order of several nanometers, provides fast charge transfer, which significantly improves electronic conductivity. This brief review summarizes recent progress in the synthesis of materials based on ultrathin 2D nanosheets for energy storage applications, including pseudocapacitors, lithium-ion batteries, and other rechargeable devices. The review also presents examples of representative work on the synthesis of ultrathin 2D nanomaterials based on TMO and TMH for various power sources. In conclusion, the article discusses possible prospects and directions for further development of methods and routes for the synthesis of ultrathin two-dimensional transition metal oxides and hydroxides.keywords: two-dimensional materials, transition metal oxides, layered double hydroxides, nanosheets, energy storage devicesDOI: https://doi.org/10.15726/elmattech.2022.1.00

A Novel Oxidation–Reduction Route for the Morphology-Controlled Synthesis of Manganese Oxide Nanocoating as Highly Effective Material for Pseudocapacitors

In recent years, pseudocapacitors have been receiving much attention as low-cost and safe energy storage technology for emerging applications in flexible and safe devices. However, creating high-energy-density electrode materials is now the main limit for high-performance pseudocapacitors. In this work, we propose a novel reduction route for the synthesis of uniform MnO2 nanocoating with porous morphology on nickel foam via the SILD method as electrode material for high-effective pseudocapacitors. The obtained nanocoatings were characterized by SEM, TEM, EDX, XRD, XPS, and electrochemical techniques. Comparisons of MnO2 coatings were conducted to obtain the reduction and oxidative routes of synthesis. The influence of the oxidation–reduction reaction type on the structures, morphologies, and capacity performance of manganese oxide was investigated. The results show that the nanocoatings synthesized via the reduction route were formed of amorphous uniform ultra-thick coating MnO2 with a porous morphology of “nanoflakes.” Due to the unique morphology and uniform coating of nanosized manganese oxide, electrodes based on this process have shown a high specific capacity (1490 F/g at 1 A/g) and excellent cycling stability (97% capacity retention after 1000 charge–discharge cycles)

A Novel Oxidation–Reduction Route for the Morphology-Controlled Synthesis of Manganese Oxide Nanocoating as Highly Effective Material for Pseudocapacitors

In recent years, pseudocapacitors have been receiving much attention as low-cost and safe energy storage technology for emerging applications in flexible and safe devices. However, creating high-energy-density electrode materials is now the main limit for high-performance pseudocapacitors. In this work, we propose a novel reduction route for the synthesis of uniform MnO2 nanocoating with porous morphology on nickel foam via the SILD method as electrode material for high-effective pseudocapacitors. The obtained nanocoatings were characterized by SEM, TEM, EDX, XRD, XPS, and electrochemical techniques. Comparisons of MnO2 coatings were conducted to obtain the reduction and oxidative routes of synthesis. The influence of the oxidation–reduction reaction type on the structures, morphologies, and capacity performance of manganese oxide was investigated. The results show that the nanocoatings synthesized via the reduction route were formed of amorphous uniform ultra-thick coating MnO2 with a porous morphology of “nanoflakes.” Due to the unique morphology and uniform coating of nanosized manganese oxide, electrodes based on this process have shown a high specific capacity (1490 F/g at 1 A/g) and excellent cycling stability (97% capacity retention after 1000 charge–discharge cycles)

Synthesis and Structure of ZnO-Decorated Graphitic Carbon Nitride (g-C₃N₄) with Improved Photocatalytic Activity under Visible Light

The volume of dye production in the chemical industry is growing rapidly every year. Given the global importance of clean water resources, new wastewater treatment solutions are required. Utilizing photocatalysis by harvesting solar energy represents a facile and promising solution for removing dangerous pollutants. This study reports the possibility of increasing the photocatalytic activity of g-C3N4 by creating nanocomposites with ZnO. Exfoliated g-C3N4/ZnO nanocomposites were synthesized by heat treatment of urea and subsequent ultrasonic exfoliation of the colloidal solution by introducing zinc acetate. The uniformity of the distribution of ZnO nanoparticles is confirmed by the method of elemental mapping. The obtained X-ray diffractograms of the obtained nanocomposites show typical X-ray reflections for g-C3N4 and ZnO. It was found that the introduction of oxide into g-C3N4 leads to an increase in the specific surface area values due to the developed ZnO surface. The maximum value of the specific surface area was obtained for a sample containing 7.5% ZnO and was 75.2 m2/g. The g-C3N4/7.5% ZnO sample also demonstrated increased photocatalytic activity during the decomposition of methylene blue under the influence of visible light, which led to a twofold increase in the reaction rate compared to initial g-C3N4

The effect of barium titanate admixture on the stability of potassium nitrate ferroelectric phase in (1–x)KNO3 + (x)BaTiO3 composites

The study of temperature evolution of the KNO3 structure in ferroelectric (1 – x)KNO3 + (x)BaTiO3 composites at х = 0.25 and 0.50 has been carried out on cooling and on heating using X-ray diffraction. It was shown that on cooling the phase transition temperature (Tc) from the high-temperature paraelectric phase into the ferroelectric one did not depend on barium titanate concentration and practically coincided with Tc for the pure KNO3. Simultaneously the admixture of BaTiO3 essentially enlarged the temperature interval of the KNO3 ferroelectric phase stability in these composites. Structure refinement did not confirm the suppression of the ferroelectric phase of potassium nitrate proposed previously for (0.5)KNO3 + (0.5)BaTiO3 sample on the basis of dielectric spectroscopy data. The transition from the ferroelectric phase into the low-temperature paraelectric α-phase was not observed in this composite on cooling down to 348 K

The Influence of Co-Precipitation Technique on the Structure, Morphology and Dual-Modal Proton Relaxivity of GdFeO3 Nanoparticles

Nanocrystals of gadolinium orthoferrite (GdFeO3) with morphology close to isometric and superparamagnetic behavior were successfully synthesized using direct, reverse and microreactor co-precipitation of gadolinium and iron(III) hydroxides with their subsequent heat treatment in the air. The obtained samples were investigated by PXRD, FTIR, low-temperature nitrogen adsorption-desorption measurements, HRTEM, SAED, DRS and vibration magnetometry. According to the X-ray diffraction patterns, the GdFeO3 nanocrystals obtained using direct co-precipitation have the smallest average size, while the GdFeO3 nanocrystals obtained using reverse and microreactor co-precipitation have approximately the same average size. It was shown that the characteristic particle size values are much larger than the corresponding values of the average crystallite size, which indicates the aggregation of the obtained GdFeO3 nanocrystals. The GdFeO3 nanocrystals obtained using direct co-precipitation aggregate more than the GdFeO3 nanocrystals obtained using reverse co-precipitation, which, in turn, tend to aggregate more strongly than the GdFeO3 nanocrystals obtained using microreactor co-precipitation. The bandgap of the obtained GdFeO3 nanocrystals decreases with decreasing crystallite size, which is apparently due to their aggregation. The colloidal solutions of the obtained GdFeO3 nanocrystals with different concentrations were investigated by 1H NMR to measure the T1 and T2 relaxation times. Based on the obtained r2/r1 ratios, the GdFeO3 nanocrystals obtained using microreactor, direct and reverse co-precipitation may be classified as T1, T2 and T1–T2 dual-modal MRI contrast agents, respectively

Synthesis, Characterization and Photocatalytic Activity of Spherulite-like <i>r</i>-TiO₂ in Hydrogen Evolution Reaction and Methyl Violet Photodegradation

Synthesis and characterization of spherulite-like nanocrystalline titania with rutile structure (r-TiO2) are described herein. The r-TiO2 particles were synthesized via the convenient and low-cost hydrothermal treatment of TiO(C6H6O7) titanyl citrate. The r-TiO2 spherulites are micron-sized agglomerates of rod-shaped nanocrystals with characteristic sizes of 7(±2) × 43(±10) nm, oriented along (101) crystallographic direction, and separated by micropores, as revealed by SEM and TEM. PXRD and Raman spectroscopy confirmed the nanocrystalline nature of r-TiO2 crystallites. BET analysis showed a high specific surface area of 102.6 m2/g and a pore volume of 6.22 mm3/g. Photocatalytic performances of the r-TiO2 spherulites were investigated for the processes of methyl violet (MV) degradation in water and hydrogen evolution reaction (HER) in aqueous solutions of ethanol. The (MV) degradation kinetics was found to be first-order and the degradation rate coefficient is 2.38 × 10−2 min−1. The HER was performed using pure r-TiO2 spherulites and nanocomposite r-TiO2 spherulites with platinum deposited on the surface (r-TiO2/Pt). It was discovered that the r-TiO2/Pt nanocomposite has a 15-fold higher hydrogen evolution rate than pure r-TiO2; their rates are 161 and 11 nmol/min, respectively. Thus, the facile synthesis route and the high photocatalytic performances of the obtained nanomaterials make them promising for commercial use in such photocatalytic processes as organic contamination degradation and hydrogen evolution

Synthesis, Characterization and Photocatalytic Activity of Spherulite-like r-TiO2 in Hydrogen Evolution Reaction and Methyl Violet Photodegradation

Synthesis and characterization of spherulite-like nanocrystalline titania with rutile structure (r-TiO2) are described herein. The r-TiO2 particles were synthesized via the convenient and low-cost hydrothermal treatment of TiO(C6H6O7) titanyl citrate. The r-TiO2 spherulites are micron-sized agglomerates of rod-shaped nanocrystals with characteristic sizes of 7(&plusmn;2) &times; 43(&plusmn;10) nm, oriented along (101) crystallographic direction, and separated by micropores, as revealed by SEM and TEM. PXRD and Raman spectroscopy confirmed the nanocrystalline nature of r-TiO2 crystallites. BET analysis showed a high specific surface area of 102.6 m2/g and a pore volume of 6.22 mm3/g. Photocatalytic performances of the r-TiO2 spherulites were investigated for the processes of methyl violet (MV) degradation in water and hydrogen evolution reaction (HER) in aqueous solutions of ethanol. The (MV) degradation kinetics was found to be first-order and the degradation rate coefficient is 2.38 &times; 10&minus;2 min&minus;1. The HER was performed using pure r-TiO2 spherulites and nanocomposite r-TiO2 spherulites with platinum deposited on the surface (r-TiO2/Pt). It was discovered that the r-TiO2/Pt nanocomposite has a 15-fold higher hydrogen evolution rate than pure r-TiO2; their rates are 161 and 11 nmol/min, respectively. Thus, the facile synthesis route and the high photocatalytic performances of the obtained nanomaterials make them promising for commercial use in such photocatalytic processes as organic contamination degradation and hydrogen evolution