Oxide Research Articles

Photocatalytic degradation of naphthalene, using various nanocomposite materials mostly based on metal oxides

Photocatalytic degradation of naphthalene, using various nanocomposite materials mostly based on metal oxides

Emerging Low Detection Limit of Optically Activated Gas Sensors Based on 2D and Hybrid Nanostructures

Gas sensing is essential for detecting and measuring gas concentrations across various environments, with applications in environmental monitoring, industrial safety, and healthcare. The integration of two-dimensional (2D) materials, organic materials, and metal oxides has significantly advanced gas sensor technology, enhancing its sensitivity, selectivity, and response times at room temperature. This review examines the progress in optically activated gas sensors, with emphasis on 2D materials, metal oxides, and organic materials, due to limited studies on their use in optically activated gas sensors, in contrast to other traditional gas-sensing technologies. We detail the unique properties of these materials and their impact on improving the figures of merit (FoMs) of gas sensors. Transition metal dichalcogenides (TMDCs), with their high surface-to-volume ratio and tunable band gap, show exceptional performance in gas detection, especially when activated by UV light. Graphene-based sensors also demonstrate high sensitivity and low detection limits, making them suitable for various applications. Although organic materials and hybrid structures, such as metal–organic frameworks (MoFs) and conducting polymers, face challenges related to stability and sensitivity at room temperature, they hold potential for future advancements. Optically activated gas sensors incorporating metal oxides benefit from photoactive nanomaterials and UV irradiation, further enhancing their performance. This review highlights the potential of the advanced materials in developing the next generation of gas sensors, addressing current research gaps and paving the way for future innovations.

Studying the productivity of sewage sludge (SS) components for photocatalytic CO2 transformation to CO and methane

AbstractEnergy-efficient photocatalytic CO2 conversion to sustainable solar fuels is a promising approach for simultaneously resolving energy and environmental concerns. The increased growth of sewage sludge necessitates research and innovation to propose more commercially viable options for lowering the socioeconomic and environmental complications associated with its current treatment. Sewage sludge can be applied to valuable products or used as a feedstock for energy production. According to the characterization results, the sewage sludge contains several metallic oxides (M), including Ni, Al, Mn, and Cu, and semiconductors (Fe2O3 and ZnO). According to the proposed mechanism, ZnO acts as an electron conductor between the Fe2O3 and the active sewage sludge due to forming an n–n type heterojunction. Under visible-light irradiation, photocatalytic CO2 reduction of sewage sludge was investigated using a fixed bed reactor. The CO2 reduction produced CO and CH4, with production rates of 9.76 and 4.20 µmol g−1 h−1, respectively, via the electrical conductivity in the sewage sludge elements. Furthermore, the impacts of photocatalyst loading, system reforming, light effect and pressure range were examined, where the methane yield at 0.1 g was 4.23 and 2.26 times significantly higher than at 0.05 and 0.2 g, correspondingly. With catalyst loadings of 0.1 and 0.2 g, the mono-oxide productivity was 1.69 and 2.58, notably greater, respectively. Moreover, the best yield of the CO and methane was obtained by using 0.3 bar as pressure and 10% methanol in H2O/CO2 as a reducing agent. Finally, using sewage sludge to produce a solar fuel based on the presence of active metallic oxide and semi-conductor heterojunctions provides novel insights from molecular and engineering perspectives into converting CO2 to a green fuel using wastewater sludge. Graphical abstract

High performance chemiresistive carbon-nanotube ammonia gas sensor surface modified by tantalum oxide (Ta2O5) metal nanoparticles

High performance chemiresistive carbon-nanotube ammonia gas sensor surface modified by tantalum oxide (Ta2O5) metal nanoparticles

Topological phases driven by orbital entanglement in Transition Metal Oxide Perovskite interfaces

Topological phases driven by orbital entanglement in Transition Metal Oxide Perovskite interfaces

Direct Precursor Route for the Fabrication of LLZO Composite Cathodes for Solid-State Batteries.

Solid-state batteries based on Li7La3Zr2O12 (LLZO) garnet electrolyte are a robust and safe alternative to conventional lithium-ion batteries. However, the large-scale implementation of ceramic composite cathodes is still challenging due to a complex multistep manufacturing process. A new one-step route for the direct synthesis of LLZO during the manufacturing of LLZO/LiCoO2 (LCO) composite cathodes based on cheap precursors and utilizing the industrially established tape casting process is presented. It is shown that Al, Ta:LLZO can be formed directly in the presence of LCO from metal oxide precursors (LiOH, La2O3, ZrO2, Al2O3, and Ta2O5) by heating to 1050°C, eliminating the time- and energy-consuming synthesis of preformed LLZO powders. In addition, performance-optimized gradient microstructures can be produced by sequential casting of slurries with different compositions, resulting in dense and flat phase-pure cathodes without unwanted ion interdiffusion or secondary phase formation. Freestanding cathodes with a thickness of 85µm, a relative density of 95%, and an industrial relevant LCO loading of 15mg show an initial capacity of 82 mAh g-1 (63% of the theoretical capacity of LCO) in a solid-state cell with Li metal anodes, which is comparable to conventional LCO/LLZO cathodes and can be further improved in the future.

Luminescence and dielectric investigations of crystalline niobate nanoceramics prepared through aqueous chemical process

The present study reflects the synthesis of MgNb2O6 using hydrofluoric acid via a wet chemical approach, followed by characterizations involving XRD, electron microscopy, Raman spectroscopy, optical analyses, and impedance spectroscopy. The crystallite size of the synthesized material was determined to be 44 nm through XRD analysis. The lattice parameters of MgNb2O6 a, b, and c, were found to be 14.1998 Å, 5.6844 Å, and 4.9813 Å, respectively. Raman spectroscopy identified molecular bonds ranging from 253 to 1011 cm−1, mainly indicating the presence of metal oxide bonds. EDX spectra confirmed the presence of Mg, Nb, and O atoms in the prepared ceramics, indicating phase purity. FESEM analysis revealed a grain size of approximately 48 nm, with the presence of agglomerated grains. Bright spots in the SAED pattern observed by HRTEM confirmed the crystallinity of the prepared niobate materials, with the HRTEM microstructure showing a particle size near 49 nm. The crystallite size by XRD, grain size by FESEM, and particle size by HRTEM are in accordance with each other. The direct band gap was determined to be approximately 2.76 eV using UV-Visible spectroscopy. Additionally, MgNb2O6 materials exhibited a broad and strong photoluminescence emission near 445 nm with excitation at 270 nm, possibly indicating the presence of radiative defects in the crystalline nanostructure. Furthermore, impedance studies conducted between 40 and 110 MHz demonstrated a decrease in the dielectric constant at higher frequencies, reaching 21.06 at 110 MHz. A low dielectric loss was also observed at 110 MHz. The moderate band gap and strong room-temperature photoluminescence in the visible range make magnesium niobates suitable for possible applications in optical devices. This investigation shows that a dielectric constant near 21 and low dielectric loss can be achieved in the high-frequency range around 110 MHz.

An Enhanced LPRAFF with Tri-State Inverter Embedded Non-Clock Gating via the CT-GWO Algorithm

Since a long time ago, it has been understood how radiation affects digital circuits, particularly those using the Complementary Metal Oxide Semiconductor (CMOS) model. Total Ionisation Dose (TID) and Single Event Effects (SEE) are the two most significant radiation effects. Depending on the gate input count, the complexity of the circuit will rise, which will worsen the radiation and raise the cumulative dose levels. The incremental dose level affects the circuit parameter failure, which affects how well the logic design functions. Many authors concentrate on minimising the effects of radiation while preventing function loss, but these extra efforts use excess energy. To improve the efficiency of the Low Power Radiation Aware (LPRA) circuit, this paper introduces optimisation concepts in a Flip Flop (FF) architecture named Chaos Theory-based Grey Wolf Optimised FF (CT-GWOFF). First, compute each component's radiation response using a physics-based modelling strategy. To minimise undesirable latches and disable the inverter chain when the input data remain constant, a tri-state inverter, incorporating a non-clocked gating mechanism, is provided. This prevents repeated transitions of delayed clock signals. Moreover, the proposed model is implemented in FFs for simulation purposes, making it more cognizant of radiation effects and power consumption. Using the HSPICE tool, the performance of the suggested circuit design is evaluated at the 16 nm CMOS Predictive Technology Model (PTM).

An intriguing way to synthesize a TiO2–ZnO hybrid nanostructure for the pragmatic application as a photocatalyst

In an attempt to counter the problem of treating wastewater more efficiently, we report the study on photocatalytic properties of metal oxide nanostructures under different light sources. A novel sonication-assisted refluxing method was employed to synthesize a binary heterostructure consisting of TiO2 and ZnO. XRD and EDS analysis of synthesized materials confirm the presence of both TiO2 and ZnO. Also, the change in the intensity of XRD peaks and elemental composition are well observed with a change in molar concentration of Ti and Zn. HR-TEM micrographs show nanostructures having hybrid Janus and Core-shell type structures. The XPS spectra were probed to identify the surface chemical species associated with the prepared heterostructures. Raman spectra confirm the smaller ZnO particles attached over agglomerated TiO2 as a shell layer as depicted in TEM results. Optical studies exhibit the modification in the band structure of the materials due to the formation of the heterostructure. The synthesized hybrid catalyst shows impressive results in photocatalytic performance. The catalytic potency of the prepared heterostructures under UV light is reminiscent of Anatase while it gets convalescent with an increment of Zn content under visible light. The photocatalytic performance of synthesized materials under sunlight shows their potential to be utilized as commercial catalysts for direct application in wastewater treatment. The kinetic study of the degradation data reveals interesting facets of the catalysis. It suggests that the photo-corrosion of the catalyst inordinately changes the rate of photocatalytic reaction which ultimately affects the photocatalytic efficiency of the catalyst. The study also discusses the role of kinetic and validation parameters in the selection of the best-fitted kinetic model with realistic arguments.

Remarkable performance of Co3O4 anode coated with hard-soft carbon 2D nanosheets prepared from single pavement petroleum asphalt precursor

Incorporating extraneous carbonaceous materials to coat transitional metal oxide (TMO) anodes emerges as a viable strategy to mitigate the pulverization of TMO anode during Li-ion insertion/extraction processes. Herein, hard-soft carbon coated Co3O4 (HC-SC@Co3O4) composites were synthesized by employing a facile NaCl-mediated pyrolysis with Co(NO3)2·6 H2O as the oxide precursor and pavement petroleum asphalt as the single hard-soft carbon source. Microscopic structure characterizations revealed that HC-SC@Co3O4 exhibited a core-shell structure with a fluffy nanoflower-like S/O co-doped carbon shell. Benefiting from its distinctive coating structure, the HC-SC@Co3O4 anode demonstrated remarkable cycling stability and significant initial coulombic efficiency (ICE) of 71 %, after 150 cycles at 100 mA g−1, it still maintained a capacity of 742 mAh g−1. Moreover, introduction of soft carbon delivered outstanding rate capability upon HC-SC@Co3O4 anode, evidenced by discharge capacities of 1108 and 571 mA h g−1 at 100 and 1000 mA g−1, respectively. This study not only presents the potential to effectively solve the challenge of TMO anodes in lithium-ion batteries (LIBs), but also introduces an economically and environmentally approach for the efficient utilization of pavement petroleum asphalt.

Hydrothermal Carbonization of Biomass for Electrochemical Energy Storage: Parameters, Mechanisms, Electrochemical Performance, and the Incorporation of Transition Metal Dichalcogenide Nanoparticles

Given the pressing climate and sustainability challenges, shifting industrial processes towards environmentally friendly practices is imperative. Among various strategies, the generation of green, flexible materials combined with efficient reutilization of biomass stands out. This review provides a comprehensive analysis of the hydrothermal carbonization (HTC) process as a sustainable approach for developing carbonaceous materials from biomass. Key parameters influencing hydrochar preparation are examined, along with the mechanisms governing hydrochar formation and pore development. Then, this review explores the application of hydrochars in supercapacitors, offering a novel comparative analysis of the electrochemical performance of various biomass-based electrodes, considering parameters such as capacitance, stability, and textural properties. Biomass-based hydrochars emerge as a promising alternative to traditional carbonaceous materials, with potential for further enhancement through the incorporation of extrinsic nanoparticles like graphene, carbon nanotubes, nanodiamonds and metal oxides. Of particular interest is the relatively unexplored use of transition metal dichalcogenides (TMDCs), with preliminary findings demonstrating highly competitive capacitances of up to 360 F/g when combined with hydrochars. This exceptional electrochemical performance, coupled with unique material properties, positions these biomass-based hydrochars interesting candidates to advance the energy industry towards a greener and more sustainable future.

Chemistry of Formate and Water Ligands on Metal Oxide Cluster Nodes of Metal-Organic Framework hcp Hf-UiO-66: Keys to Understanding Reactivity of Paired μ2-OH and Defect Sites.

Many metal-organic frameworks (MOFs) incorporate nodes that are metal oxide clusters, and ligands that have been observed on these nodes include formates, acetates, water, hydroxyl groups, and others, all of which are potentially important in affecting reactivities for applications in separations, catalysis, and sensing. Formate is a common node ligand, arising from formic acid used as a modulator and from N,N-dimethylformamide used as a solvent in MOF syntheses. Yet only little work has been reported characterizing the reactivities of node formate ligands. Infrared spectra reported here show that formate bonds to two types of sites on the paired Hf6O8 nodes of hcp UiO-66, namely, defect and μ2-OH sites. Quantifying the number of formate ligands by 1H NMR spectroscopy of digested samples showed an almost equal number of formate ligands on the two sites, indicating the likelihood that they neighbor each other. These formate ligands interact with water molecules, reversibly switching their bonding from bidentate to monodentate. The formates on μ2-OH sites of hcp Hf-UiO-66 interact much more strongly with water than those on defect sites of the same node, and both interact more strongly than isolated defect sites of Hf-UiO-66. Correspondingly, the catalytic activities of hcp UiO-66 determined as turnover frequencies on each site are approximately twofold higher than those on UiO-66, bolstering the inference that methanol dehydration is catalyzed by a node defect site and a neighboring node μ2-OH site. The results show how MOFs, with their well-defined node structures, provide unprecedented opportunities to understand details of reactivities and catalysis on metal oxide clusters, in contrast to bulk metal oxide surfaces.

Mineralogical characterization of magnesium-based nanoparticles recovered from a swirl-stabilized magnesium flame by analytical and scanning/transmission electron microscopy

Abstract. The current climate emergency and the related energy transition require the development of technology producing zero-carbon energy. One viable option entails the utilization of recyclable metal fuels. The primary energy stored by the reduction in metal oxides can be transported and later released by metal combustion. Mg is among the most promising metal as a regenerable energetic vector, having an energy density of 25 MJ kg−1. The exploitation of the Mg oxidation and reduction loop has recently been demonstrated, and the loop combustion products are made of metal oxides. The mineralogical characterization of the MgO crystals generated by the Mg combustion is of utter importance for the optimization of the particle trapping capacity in the combustion system during the closed oxidation and reduction loop. In this paper we characterize MgO particles generated in a swirl-stabilized Mg flame by using powder X-ray diffraction, transmission electron microscopy and selected area electron diffraction, and atomic-resolution microscopy combined with energy-dispersive X-ray spectroscopy and dual-electron energy-loss spectroscopy. The MgO combustion products were chemically homogeneous at this level of investigation. Three representative morphologies (cubic, truncated octahedron, and spherical) and two isostructural phases were identified in the MgO combustion product. These findings may contribute to the optimization of system development, particularly in terms of the collection efficiency of the combustion end product.

Oxygen vacancies kinetics in TaO2−h/Ta2O5−x memristive interfaces

Abstract Oxygen vacancies (OV) are pervasive in metal oxides and play a pivotal role in the switching behaviour of oxide-based memristive devices. In this study we address OV dynamics in Pt/TaO 2 − h /Ta2O 5 − x /TaO 2 − y /Pt devices, through a combination of experiments and theoretical simulations, In particular, we focus on the RESET transition (from low to high resistance) induced by the application of electrical pulse(s), by choosing different initial OV profiles and studying their kinetics during the mentioned process. We demonstrate that by selecting specific OV profiles it is possible to tune the characteristic time-scale of the RESET. Finally, we show that the implementation of gradual RESETs, induced by applying many (small) successive pulses, allows estimating the activation energies involved in the OV electromigration process. Our results help paving the way for OV engineering aiming at optimizing key memristive figures such as switching speed or power consumption, which are highly relevant for neuromorphic or in-memory computing implementations.

Construction of hierarchical and core-shell structured Co3O4@MnO2@NiO nanoarrays as binder-free electrodes for high-performance asymmetric supercapacitors

Remarkable specific capacity and excellent cycle stability of the electrode materials are vital prerequisites for their practical applications. Transition metal oxide-based materials have been extensively explored and employed as electrode materials for asymmetric supercapacitors. However, the actual specific capacitances of these materials are still far lower than their theoretically predicted values. Thus, it is essential to design transition metal oxide with novel structures in order to maximize their specific capacity and cycle stability. Herein, we constructs hierarchical and core-shell structured Co3O4@MnO2@NiO arrays on nickel foam (Co3O4@MnO2@NiO/NF) through a three-step hydrothermal-annealing process, and use them as a direct binder-free electrode for pseudocapacitors. The as-prepared layered hierarchical Co3O4@MnO2@NiO/NF electrode exhibits an impressive specific capacitance of 6.42 F cm−2 (2054 F g−1) at 1 mA cm−2 in a three-electrode configuration, which is largely because of the synergistic effect among Co3O4, MnO2 and NiO. Furthermore, the 3D nanoarray structure can provides a larger specific surface area, a rapid diffusion path, and more active sites that allow to achieve improved electrochemical performance. In addition, the assembled Co3O4@MnO2@NiO/NF//AC/NF ASC all-solid-state asymmetric supercapacitor (ASC) displays a remarkable energy density (30.7 Wh kg−1 at 400.4 W kg−1), demonstrating that this all-solid-state ASC owns considerable potential for practical applications in such high-performance energy storage devices.

Construction of "Metal Defect/Oxygen Defect Junction" in ZnFe2O4-NiCo2O4 Heterostructures for Enhancing Electrocatalytic Oxygen Evolution.

Defect engineering is a promising approach to improve the conductivity and increase the active sites of transition metal oxides used as catalysts for the oxygen evolution reaction (OER). However, when metal defects and oxygen defects coexist closely within the same crystal, their compensating charges can diminish the benefits of both defect structures on the catalyst's local electronic structure. To address this limitation, a novel strategy that employs the heterostructure interface of ZnFe2O4-NiCo2O4 to spatially separate the metal defects from the oxygen defects is proposed. This configuration positions the two types of defects on opposite sides of the heterojunction interface, creating a unique structure termed the "metal-defect/oxygen-defect junction". Physical characterization and simulations reveal that this configuration enhances electron transfer at the heterostructure interface, increases the oxidation state of Fe on the catalyst surface, and boosts bulk charge carrier concentration. These improvements enhance active site performance, facilitating hydroxyl adsorption and deprotonation, thereby reducing the overpotential required for the OER.

Innovative Charge-Tuning for Highly Dispersed Pt Catalysts: Achieving Deep CO Removal in Industrial H2 Purification for Fuel Cells.

Proton exchange membrane fuel cells have strict requirements for the CO concentration in H2-rich fuel gas. Here, from the perspective of industrial practicability, a highly dispersed Pt catalyst (2-4 nm) supported on activated carbon (AC), which was modified by electronic promoters (K+) and structural promoters (isopropanol), is studied in detail. Compared with traditional metal oxide supports, the K-Pt/AC catalysts, which benefit from the tuned charge distribution, achieve a significant reduction of CO (from 1% to <0.1 ppb) under H2-rich conditions and show potential for used in large-scale industrial hydrogen purification. Experimental results and theoretical calculations reveal that the K atom, with its lower electronegativity, contributes to the shift of surface Pt2+ to a lower binding energy due to the presence of oxygen species on the AC surface. This facilitates oxygen activation and accelerates desorption of the CO2 product, thereby accelerating the reaction process and enabling the deep removal of CO in a hydrogen-rich atmosphere.

Green synthesis of silver and gold-doped zinc oxide nanocomposite with propolis extract for enhanced anticancer activity

Metal and metal oxide nanocomposites have unique properties and are promising for antibacterial and anticancer applications. In this work, we aimed to highlight the relationship between the biosynthesis ways of silver and gold-doped zinc oxide nanocomposites and their functions as anticancer on cell lines (MCF-7 and HepG2). The propolis was used to biosynthesize four different nanoparticles with the same components, including zinc, gold and silver. The nanocomposites were characterized using various techniques, including ultraviolet–visible spectroscopy (UV–Vis), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Energy Dispersive X-ray analysis (EDX) and cytotoxicity assays. The result of this study showed that formed nanocomposites have a similar level of Zn, Au, and Ag, ranging from 23–34%, 2–6%, and 2–3%, respectively. In addition, adding the components simultaneously produces the fastest color change, and the fabricated nanoparticles have spherical shapes with different layers. In addition, the prepared nanoparticles influenced the cell viability of the cancer cell lines, with the most effective one when Zn, Au, and Ag were added spontaneously to form a nanocomposite called (All) with IC50 of 24.5 µg/mL for MCF7 cells and 29.1 µg/mL for HepG2 cells. Thus, the study illustrates that the preparation of nanocomposite generated through green synthesis with different methods significantly affects the structure and function and may improve the synthesis of nanocomposite to be developed into an efficacious therapeutic agent for cancers. In addition, this study opens the door toward a novel track in the field of nanocomposites as it links the synthesis with structure and function. Further anti-cancer properties, as well as animal testing are needed for those nanocomposites.

Highly Active Photoreduction of Atmospheric-Concentration CO2 into CH3COOH over Palladium Particles on Nb2O5 Nanosheets.

The endeavor to drive CO2 photoreduction towards the synthesis of C2 products is largely thwarted by the colossal energy hurdle inherent in C-C coupling. Herein, we load active metal particles on metal oxide nanosheets to build the dual metal pair sites for steering C-C coupling to form C2 products. Taking Pd particles anchored on the Nb2O5 nanosheets as an example, the high-angle annular dark-field image and X-ray photoelectron spectroscopy demonstrate the presence of Pd-Nb metal pair sites on the Pd-Nb2O5 nanosheets. Density functional theory calculations reveal these sites exhibit a low reaction energy barrier of only 1.02 eV for C-C coupling, implying that the introduction of Pd particles effectively tailors the reaction step to form C2 products. Therefore, the Pd-Nb2O5 nanosheets achieve a CH3COOH evolution rate of 13.5 μmol g-1 h-1 in photoreduction of atmospheric-concentration CO2, outshining all other single photocatalysts reported to date under analogous conditions.

Highly Active Photoreduction of Atmospheric‐Concentration CO2 into CH3COOH over Palladium Particles on Nb2O5 Nanosheets

The endeavor to drive CO2 photoreduction towards the synthesis of C2 products is largely thwarted by the colossal energy hurdle inherent in C−C coupling. Herein, we load active metal particles on metal oxide nanosheets to build the dual metal pair sites for steering C−C coupling to form C2 products. Taking Pd particles anchored on the Nb2O5 nanosheets as an example, the high‐angle annular dark‐field image and X‐ray photoelectron spectroscopy demonstrate the presence of Pd−Nb metal pair sites on the Pd‐Nb2O5 nanosheets. Density functional theory calculations reveal these sites exhibit a low reaction energy barrier of only 1.02 eV for C−C coupling, implying that the introduction of Pd particles effectively tailors the reaction step to form C2 products. Therefore, the Pd‐Nb2O5 nanosheets achieve a CH3COOH evolution rate of 13.5 μmol g−1 h−1 in photoreduction of atmospheric‐concentration CO2, outshining all other single photocatalysts reported to date under analogous conditions.