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.

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.

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.

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.

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.

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.

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.

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.

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.

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.