RESUMEN

The most frequently used sulfonamide is sulfamethazine (SMZ) because it is often found in foods made from livestock, which is hazardous for individuals. Here, we have developed an easy, quick, selective, and sensitive analytical technique to efficiently detect SMZ. Recently, transition metal oxides have attracted many researchers for their excellent performance as a promising sensor for SMZ analysis because of their superior redox activity, electrocatalytic activity, electroactive sites, and electron transfer properties. Further, Cu-based oxides have a resilient electrical conductivity; however, to boost it to an extreme extent, a composite including two-dimensional (2D) graphitic carbon nitride (g-C3N4) nanosheets needs to be constructed and ready as a composite (denoted as g-C3N4/Cu2Y2O5). Moreover, several techniques, including X-ray diffraction analysis, scanning electron microscopy analysis, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy were employed to analyze the composites. The electrochemical measurements have revealed that the constructed g-C3N4/Cu2Y2O5 composites exhibit great electrochemical activity. Nevertheless, the sensor achieved outstanding repeatability and reproducibility alongside a low limit of detection (LOD) of 0.23 µM, a long linear range of 2 to 276 µM, and an electrode sensitivity of 8.86 µA µM-1 cm-2. Finally, the proposed GCE/g-C3N4/Cu2Y2O5 electrode proved highly effective for detection of SMZ in food samples, with acceptable recoveries. The GCE/g-C3N4/Cu2Y2O5 electrode has been successfully applied to SMZ detection in food and water samples.

Asunto(s)

RESUMEN

Metal-insulator transitions (MITs) in resistive switching materials can be triggered by an electric stimulus that produces significant changes in the electrical response. When these phases have distinct magnetic characteristics, dramatic changes in the spin excitations are also expected. The transition metal oxide La0.7Sr0.3MnO3 (LSMO) is a ferromagnetic metal at low temperatures and a paramagnetic insulator above room temperature. When LSMO is in its metallic phase, a critical electrical bias has been shown to lead to an MIT that results in the formation of a paramagnetic resistive barrier transverse to the applied electric field. Using spin-transfer ferromagnetic resonance spectroscopy, we show that even for electrical biases less than the critical value that triggers the MIT, there is magnetic phase separation, with the spin-excitation resonances varying systematically with applied bias. Therefore, voltage-triggered MITs in LSMO can alter magnetic resonance characteristics, offering an effective method for tuning synaptic weights in neuromorphic circuits.

RESUMEN

The Jahn-Teller effect (JTE) arising from lattice-electron coupling is a fascinating phenomenon that profoundly affects important physical properties in a number of transition-metal compounds. Controlling JT distortions and their corresponding electronic structures is highly desirable to tailor the functionalities of materials. Here, we propose a local coordinate strategy to regulate the JTE through quantifying occupancy in the [Formula: see text] and [Formula: see text] orbitals of Mn and scrutinizing the symmetries of the ligand oxygen atoms in MnO6 octahedra in LiMn2O4 and Li0.5Mn2O4. The effectiveness of such a strategy has been demonstrated by constructing P2-type NaLi x Mn1 - x O2 oxides with different Li/Mn ordering schemes. In addition, this strategy is also tenable for most 3d transition-metal compounds in spinel and perovskite frameworks, indicating the universality of local coordinate strategy and the tunability of the lattice-orbital coupling in transition-metal oxides. This work demonstrates a useful strategy to regulate JT distortion and provides useful guidelines for future design of functional materials with specific physical properties.

RESUMEN

Low-cost sodium-ion batteries have demonstrated great prospects in energy storage, among which layered transition metal oxides hold great potential as a cathode material. However, the notorious phase transition in layered cathode materials has greatly hampered their cycle life due to large volume changes upon desodiation/sodiation. In this study, by adopting an O3-type NaNi1/3Fe1/3Mn1/3O2 (NFM) with controlled synthesis temperatures, we have revealed that the grain size is closely related to its phase transition behaviors. The layered material with a smaller grain size and more distorted lattice tends to experience a shorter plateau of the O3-P3-O3 phase transitions during the charge/discharge process. Despite having a lower nominal discharge capacity without the phase transition plateau, its cycling stability increases from 77.4% to 96.2% after 100 cycles with greatly reduced intragranular cracks. The smaller grain size and lattice distortion act as a barrier that prevents the smooth layer from gliding upon sodium intercalation and deintercalation. This study focuses on the influence of grain size on battery cycle stability and provides a basis for future analysis of the structural instability of layered materials.

RESUMEN

The facile sonochemical synthesis is reported of zinc cobalt oxide (ZnCo2O4) composited with carbon nanofiber (CNF). Structural, chemical, and morphological were characterized by X-ray diffraction (XRD), X-ray photoluminescent spectroscopy (XPS), field emission scanning electron microscopy (FESEM), and transmittance electron microscopy (TEM), respectively. ZnCo2O4/CNF-modified GCE was applied to the detection of bisphenol A (BPA). The modified GCE shows enhanced sensing performance towards BPA, which includes a linear range (0.2 to 120 µM L-1) alongside a low limit of detection (38.2 nM L-1), low interference, and good stability. Detection of lower concentrations of BPA enables real sample analysis in the food industries (milk, orange juice, yogurt, tap water, and baby feeding bottles). Surprisingly, the BPA was detected in milk 510 nM L-1, orange juice 340 nM L-1, yogurt 1050 nM L-1, and tap water 140 nM L-1. Moreover, an interaction mechanism between the BPA analyte and ZnCo2O4 was discussed.

Asunto(s)

RESUMEN

Surface reconstruction determines the fate of catalytic sites on the near-surface during the oxygen evolution reaction. However, deciphering the conversion mechanism of various intermediate-states during surface reconstruction remains a challenge. Herein, we employed an optical imaging technique to draw the landscape of dynamic surface reconstruction on individual Co3O4 nanoparticles. By regulating the surface states of Co3O4 nanoparticles, we explored dynamic growth of the CoOx(OH)y sublayer on single Co3O4 nanoparticles and directly identified the conversion between two dynamics. Rich oxygen vacancies induced more active sites on the surface and prolonged surface reconstruction, which enhanced electrochemical redox and oxygen evolution. These results were further verified by in situ electrochemical extinction spectroscopy of single Co3O4 nanoparticles. We elucidate the heterogeneous evolution of surface reconstruction on individual Co3O4 nanoparticles and present a unique perspective to understand the fate of catalytic species on the nanosurface, which is of enduring significance for investigating the heterogeneity of multielectron-transfer events.

RESUMEN

Transition metal oxide (TMO)-based nanozymes have appeared as hopeful tools for antitumor applications due to their unique catalytic properties and ability to modulate the tumor microenvironment (TME). The purpose of this review is to provide an overview of the latest progress made in the field of TMO-based nanozymes, focusing on their enzymatic activities and participating metal ions. These nanozymes exhibit catalase (CAT)-, peroxidase (POD)-, superoxide dismutase (SOD)-, oxidase (OXD)-, and glutathione oxidase (GSH-OXD)-like activities, enabling them to regulate reactive oxygen species (ROS) levels and glutathione (GSH) concentrations within the TME. Widely studied transition metals in TMO-based nanozymes include Fe, Mn, Cu, Ce, and the hybrid multimetallic oxides, which are also summarized. The review highlights several innovative nanozyme designs and their multifunctional capabilities. Despite the significant progress in TMO-based nanozymes, challenges such as long-term biosafety, targeting precision, catalytic mechanisms, and theoretical supports remain to be addressed, and these are also discussed. This review contributes to the summary and understanding of the rapid development of TMO-based nanozymes, which holds great promise for advancing nanomedicine and improving cancer treatment.

RESUMEN

In this study, an original molecularly imprinted electrochemical sensor (MIECS) is prepared using layer-by-layer modification of sensitization nanomaterials (CuCo2O4/BPC-E) coupled with molecularly imprinted polymers (MIPs) for the ultrasensitive and rapid determination of dimetridazole (DMZ) contaminants. The biomass waste of eggshell (ES) powders subtly introduced in situ in the carbonization process of psyllium husk (PSH) substantially promotes the physicochemical properties of the resulting biomass-derived porous carbon (BPC-E). The large specific surface area and abundant pores provide a favourable surface for loading mesoporous CuCo2O4 with a spinel structure. The assembly of CuCo2O4/BPC-E on the gold electrode (GE) surface enhances the electrochemical sensing signal. The MIPs constructed using DMZ and o-phenylenediamine (oPD) as templates and functional monomers boost the targeted recognition performance of the analyte. The combined DMZ targets then undergo an electrochemical reduction reaction in situ with the transfer of four electrons and four protons. Under optimum conditions, the current response of differential pulse voltammetry (DPV) exhibits two linear ranges for DMZ detection, 0.01-10 µM and 10-200 µM. The limit of detection (LOD) is 1.8 nM (S/N = 3) with a sensitivity of 5.724 µA µM-1 cm-2. The obtained MIECS exhibits excellent selectivity, reproducibility, repeatability and stability. This electrochemical sensing system is applied to the detection of real samples (tap water, coarse fodder and swine urine), yielding satisfactory recoveries (90.6%-98.1 %), which are consistent with those obtained via HPLC. This finding verifies that the utility of MIECS for monitoring pharmaceutical and environmental contaminants and ensuring food safety.

Asunto(s)

RESUMEN

We investigate the effect of alloying at the 3dtransition metal site of a rare-earth-transition metal oxide, by considering NdFe0.5Cr0.5O3mixed perovskite with two equal and random distribution of 3d ions, Cr and Fe, interacting with an early 4f rare earth ion, Nd. Employing temperature- and field- dependent magnetization measurements, temperature-dependent x-ray diffraction, neutron powder diffraction, and Raman spectroscopy, we characterize its structural and magnetic properties. Our study reveals bipolar magnetic switching (arising from negative magnetization) and magnetocaloric effect which underline the potential of the studied mixed perovskite in device application. The neutron diffraction study shows the absence of spin reorientation transition over the entire temperature range of 1.5-320 K, although both parent compounds exhibit spin orientation transition. We discuss the microscopic origin of this curious behavior. The neutron diffraction results also reveal the ordering of Nd spins at an unusually high temperature of about 40 K, which is corroborated by Raman measurements.

RESUMEN

Formaldehyde (FA), a carcinogenic oxygenated volatile organic compound, is present ubiquitously in indoor air. As such, it is generally regarded as a critical target for air quality management. The oxidative removal of FA under dark and room-temperature (RT) conditions is of practical significance. A series of ternary nickel-cobalt-manganese oxide-supported platinum catalysts (Pt/NiCoMnO4) have been synthesized for FA oxidative removal at RT in the dark. Their RT conversion values for 50 ppm FA (XFA) at 5,964 h-1 gas hourly space velocity (GHSV) decrease in the following order: 1 wt% Pt/NiCoMnO4 (100 %) > 0.5 wt% Pt/NiCoMnO4 (25 %) > 0.05 wt% Pt/NiCoMnO4 (14 %) > NiCoMnO4 (6 %). The catalytic performance of 1 wt% Pt/NiCoMnO4 has been examined further under the control of various process variables (e.g., catalyst mass, flow rate, relative humidity, FA concentration, time on stream, and molecular oxygen content). The catalytic oxidation of FA at low temperatures (e.g., RT and 60 °C) is accounted for by Langmuir-Hinshelwood mechanism (single-site competitive-adsorption), while Mars van Krevelen kinetics is prevalent at higher temperatures. In situ diffuse-reflectance infrared Fourier-transform spectroscopy reveals that FA oxidation proceeds through a series of reaction intermediates such as DOM, HCOO-, and CO32-. Based on the density functional theory simulations, the unique electronic structures of the nearest surface atoms (platinum and nickel) are suggested to be responsible for the superior catalytic activity of Pt/NiCoMnO4.

RESUMEN

The intrinsic activity assessment of transition metal oxides (TMOs) as key electrocatalysts for the oxygen evolution reaction (OER) has not been standardized due to uncertainties regarding their structure and composition, difficulties in accurately measuring their electrochemically active surface area (ECSA), and deficiencies in mass-transfer (MT) rates in conventional measurements. To address these issues, we utilized an electrodeposition-thermal annealing method to precisely synthesize single-particle TMOs with well-defined structure and composition. Concurrently, we engineered low roughness, spherical surfaces for individual particles, enabling precise measurement of their ECSA. Furthermore, by constructing a conductor-core semiconductor-shell structure, we evaluated the inherent OER activity of perovskite-type semiconductor materials, broadening the scope beyond just conductive TMOs. Finally, using single-particle nanoelectrode technique, we systematically measured individual TMO particles of various sizes for OER, overcoming MT limitations seen in conventional approaches. These improvements have led us to propose a precise and reliable approach to evaluating the intrinsic activity of TMOs, not only validating the accuracy of theoretical calculations but also revealing a strong correlation of OER activity on the melting point of TMOs. This discovery holds significant importance for future high-throughput material research and applications, offering valuable insights in electrocatalysis.

RESUMEN

The niobium oxide dihalides have recently been identified as a new class of van der Waals materials exhibiting exceptionally large second-order nonlinear optical responses and robust in-plane ferroelectricity. In contrast to second-order nonlinear processes, third-order optical nonlinearities can arise irrespective of whether a crystal lattice is centrosymmetric. Here, we report third harmonic generation (THG) in two-dimensional (2D) transition metal oxide iodides, namely NbOI2 and TaOI2. We observe a comparable THG intensity from both materials. By benchmarking against THG from monolayer WS2, we deduce that the third-order susceptibility is approximately on the same order. THG resonances are revealed at different excitation wavelengths, likely due to enhancement by excitonic states and band edge resonances. The THG intensity increases for material thicknesses up to 30 nm, owing to weak interlayer coupling. After this threshold, it shows saturation or a decrease, due to optical interference effects. Our results establish niobium and tantalum oxide iodides as promising 2D materials for third-order nonlinear optics, with intrinsic in-plane ferroelectricity and thickness-tunable nonlinear efficiency.

RESUMEN

Layered transition metal oxides are extensively considered as appealing cathode candidates for potassium-ion batteries (PIBs) due to their abundant raw materials and low cost, but their further implementations are limited by slow dynamics and impoverished structural stability. Herein, a layered composite having a P2 and P3 symbiotic structure is designed and synthesized to realize PIBs with large energy density and long-term cycling stability. The unique intergrowth of P2 and P3 phases in the obtained layered oxide is plainly characterized by X-ray diffraction refinement, high-angle annular dark field and annular bright field-scanning transmission electron microscopy at atomic resolution, and Fourier transformation images. The synergistic effect of the two phases of this layered P2/P3 composite is well demonstrated in K+ intercalation/extraction process. The as-prepared layered composite can present a large discharge capacity with the remarkable energy density of 321 Wh kg-1 and also manifest excellent capacity preservation after 600 cycles of K+ uptake/removal.

RESUMEN

Owing to the high economic efficiency and energy density potential, manganese-based layer-structured oxides have attracted great interests as cathode materials for potassium ion batteries. In order to alleviate the continuous phase transition and K+ re-embedding from Jahn-Teller distortion, the [Mn-Co-Mo]O6 octahedra are introduced into P3-K0.45MnO2 herein to optimize the local electron structure. Based on the experimental and computational results, the octahedral center metal molybdenum in [MoO6] octahedra proposes a smaller ionic radius and higher oxidation state to induce second-order JTE (pseudo-JTE) distortion in the adjacent [MnO6] octahedra. This distortion compresses the [MnO6] octahedra along the c-axis, leading to an increased interlayer spacing in the K+ layer. Meanwhile, the Mn3+/Mn4+ is balanced by [CoO6] octahedra and the K+ diffusion pathway is optimized as well. The proposed P3-K0.45Mn0.9Co0.05Mo0.05O2 cathode material shows an enhanced cycling stability and rate performance. It demonstrates a high capacity of 80.2 mAh g-1 at 100 mAh g-1 and 77.3 mAh g-1 at 500 mAh g-1. Furthermore, it showcases a 2000 cycles stability with a 59.6% capacity retention. This work presents a promising solution to the challenges faced by manganese-based layered oxide cathodes and offers a deep mechanism understanding and improved electrochemical performance.

RESUMEN

Transition metal spinel oxides were engineered with active elements as bifunctional water splitting electrocatalysts to deliver superior intrinsic activity, stability, and improved conductivity to support green hydrogen production. In this study, we reported the ternary metal Ni-Fe-Co spinel oxide electrocatalysts prepared by defect engineering strategy with rich and deficient Na+ ions, termed NFCO-Na and NFCO, which suggest the formation of defects with Na+ forming tensile strain. The Na-rich NiFeCoO4 spinel oxide reveals lattice expansion, resulting in the formation of a defective crystal structure, suggesting higher electrocatalytic active sites. The spherical NFCO-Na electrocatalysts exhibit lower OER and HER overpotentials of 248 mV and 153 mV at 10 mA cm-2 and smaller Tafel slope values of about 78 mV dec-1 and 129 mV dec-1, respectively. Notably, the bifunctional NFCO-Na electrocatalyst requires a minimum cell voltage of about 1.67 V to drive a current density of 10 mA cm-2. The present work highlights the significant electrochemical activity of defect-engineered ternary metal oxides, which can be further upgraded as highly active electrocatalysts for water splitting applications.

RESUMEN

The search for highly efficient and inexpensive electrocatalysts is crucial to the advancement of environmentally friendly and sustainable energy sources. Here, adopting a one-step hydrothermal method, we have effectively fabricated a self-supported multi-metal molybdenum-based oxide (FeCoNi-MoO4) on nickel foam (NF). In addition to changing the catalyst's microstructure, the introducing of Fe and Co, enhanced its active center count, improved its electronic structure, and in turn reduced the difficulty for high-valence Ni and Fe species to form, which accelerates the oxygen evolution reaction (OER) kinetics by promoting the development of the actual active materials, NiOOH and FeOOH. FeCoNi-MoO4 has outstanding OER performance, requiring just 204 mV overpotentials at 10 mA cm-2 and 271 mV at 100 mA cm-2. Its exceptional OER kinetics at both low and high currents are indicated by a Tafel slope of 50.6 mV dec-1, which is attributed to the combined effect of its multi-metal composition and a higher number of active sites. Moreover, the FeCoNi-MoO4 electrode was operated continuously for over 48 h. Furthermore, the density functional theory (DFT) results demonstrated that the introducing of Fe and Co, which quickens the rate of electron transfer during the electrocatalytic process, improves the ability of oxygen intermediate species to adsorb, and ultimately lowers the overpotential, is responsible for the increased electrocatalytic activity of FeCoNi-MoO4. This work offers hope for further developments in the sector by proposing an efficient approach for creating multi-active electrocatalysts that are stable, economical, and efficient.

RESUMEN

The design and synthesis of efficient, inexpensive, and long-term stable heterostructured electrocatalysts with high-density dislocations for hydrogen evolution reaction in alkaline media and seawater are still a great challenge. An amorphous/crystalline/amorphous sandwiched structure with abundant dislocations were synthesized through thermal phosphidation strategies. The dislocations play an important role in the hydrogen evolution reactions. Copious dislocation defects, combined with cracks, and the synergistic interfacial effect between crystalline phase and amorphous phase regulate the electronic structure of electrocatalyst, provide more active sites, and thus endow the electrocatalysts with excellent catalytic activity under alkaline water and seawater. The overpotentials of P-NiMoO4 at 10 mA/cm2 in 1 M KOH aqueous solution and seawater are 45 and 75 mV, respectively. Additionally, the P-NiMoO4 electrocatalyst exhibits long-term stability over 100 h. This study provides a simple approach for synthesizing amorphous/crystalline/amorphous sandwiched non-noble-metal electrocatalysts with abundant dislocations for hydrogen evolution reaction.

RESUMEN

Methane as the main component in natural gas is a promising chemical raw material for synthesizing value-added chemicals, but its harsh chemical conversion process often causes severe energy and environment concerns. Photocatalysis provides an attractive path to active and convert methane into various products under mild conditions with clean and sustainable solar energy, although many challenges remain at present. In this review, recent advances in photocatalytic methane conversion are systematically summarized. As the basis of methane conversion, the activation of methane is first elucidated from the structural basis and activation path of methane molecules. The study is committed to categorizing and elucidating the research progress and the laws of the intricate methane conversion reactions according to the target products, including photocatalytic methane partial oxidation, reforming, coupling, combustion, and functionalization. Advanced photocatalytic reactor designs are also designed to enrich the options and reliability of photocatalytic methane conversion performance evaluation. The challenges and prospects of photocatalytic methane conversion are also discussed, which in turn offers guidelines for methane-conversion-related photocatalyst exploration, reaction mechanism investigation, and advanced photoreactor design.

RESUMEN

Hierarchically nanostructured binary transition metal oxide-based materials with high conductivity and catalytic activity are quite attractive for the electrochemical quantitative detection of environmental pollutants due to their natural abundance, variable oxidation state, and excellent synergies between metal sites. Herein, a new hierarchical MnO-Fe3O4@C/expanded graphite (EG) composite is designed and synthesized through a simple and in situ annealing method with the utilization of bimetallic organic framework (FeMn-MOF)/EG precursor. The synthesized MnO-Fe3O4@C/EG composite possesses a unique hierarchical nanoarchitecture that small-sized bimetallic oxide nanoparticles of 10-40 nm completely encapsulated by amorphous carbon layers of 2-4 nm are uniformly distributed on the EG platform. This distinctive structure combines the advantages of high conductivity, excellent catalytic activity, and strong stability. Resultantly, when it is applied to monitor environmental endocrine disruptors, the sensor exhibits a significant catalytic effect on the electrochemical oxidation of bisphenol A (BPA), inducing an amplified response current. In addition, the sensor shows a wide linear range of 1-50 µM and 50-400 µM for the BPA monitor, giving a sensitivity of 5208.8 and 1641.9 µA mM-1 cm-2, respectively. This study offers a new approach to design hierarchical binary metal oxide-based sensing materials as well as to explore their electrochemical properties and applications for the determination of emerging contaminants.

RESUMEN

Alumina surface coatings are commonly applied to layered oxide cathode particles for lithium-ion battery applications. Atomic layer deposition (ALD) is one such surface coating technique, and ultrathin alumina ALD films (<2 nm) are shown to improve the electrochemical performance of LiNixMnyCo1-x-yO2 materials, with groups hypothesizing that a beneficial Li-Al-O product is being formed during the alumina ALD process. However, the atomic structure of these films is still not well understood, and quantifying the interface of ultrathin (∼1 nm) ALD films is an arduous experimental task. Here, we perform molecular dynamics simulations of amorphous alumina films of varying thickness in contact with the (0001) LiCoO2 (LCO) surface to quantify the film nanostructure. We calculate elemental mass density profiles through the films and observe that the Li-Al-O interphase extends ∼2 nm from the LCO surface. Additionally, we observe layering of Al and O atoms at the LCO-film interface that extends for ∼1.5 nm. To access the short-range order of the amorphous film, we calculated the Al coordination numbers through the film. We find that while [4]Al is the prevailing coordination environment, significant amounts of [6]Al exist at the interface between the LiCoO2 surface and the film. Taken together, these principal findings point to a pseudomorphic Li-Al-O overlayer that approximates the underlying layered LiCoO2 lattice but does not exactly replicate it. Additionally, with sufficient thickness, the Li-Al-O film transitions to an amorphous alumina structure. We anticipate that our findings on the ALD-like, Li-Al-O film nanostructure can be applied to other layered LiNixMnyCo1-x-yO2 materials because of their shared crystal structure with LiCoO2. This work provides insight into the nanostructure of amorphous ALD alumina films to help inform their use as protective coatings for Li-ion battery cathode active materials.