Lithiation-Induced Defect Engineering to Promote Oxygen Evolution Reaction

Exploring efficient electrocatalysts for oxygen evolution reaction (OER) is an urgent need to advance the development of sustainable energy conversion. Though defect engineering is considered an effective strategy to regulate catalyst activity for enhanced OER performance, the controllable synthesis of defective oxides electrocatalysts remains challenging. Here, oxygen defects are introduced into NiCo₂O₄ nanorods by an electrochemical lithiation strategy. By tuning in situ lithiation potentials, the concentration of oxygen defects and the corresponding catalytic activity can be feasibly regulated. In addition, the relationship between the changes in the defect density and electronic structure and the lithiation cut-off voltages is revealed. The results show that NiCo₂O₄ nanorods undertook intercalation and two-step conversion reaction, in which the lithiation-induced conversion reaction gives rise to a CoO@NiO-based structure with higher defect density and lower oxidation states. As a result, the defective CoO@NiO-based catalyst exhibits exceptional OER activity with an overpotential of 270 mV at 10 mA cm⁻², which is about 74 mV below the pristine nanomaterials. This research proposes a novel strategy to explore high-performance catalysts with structural stability and defect control.     

Template‐Free Fabrication of Mesoporous Alumina Nanospheres Using Post‐Synthesis Water‐Ethanol Treatment of Monodispersed Aluminium Glycerate Nanospheres for Molybdenum Adsorption

This work reports the template‐free fabrication of mesoporous Al₂O₃ nanospheres with greatly enhanced textural characteristics through a newly developed post‐synthesis “water‐ethanol” treatment of aluminium glycerate nanospheres followed by high temperature calcination. The proposed “water‐ethanol” treatment is highly advantageous as the resulting mesoporous Al₂O₃ nanospheres exhibit 2–4 times higher surface area (up to 251 m² g^?1), narrower pore size distribution, and significantly lower crystallization temperature than those obtained without any post‐synthesis treatment. To demonstrate the generality of the proposed strategy, a nearly identical post‐synthesis “water treatment” method is successfully used to prepare mesoporous monometallic (e.g., manganese oxide (MnO₂)) and bimetallic oxide (e.g., CuCo₂O₄ and MnCo₂O₄) nanospheres assembled of nanosheets or nanoplates with highly enhanced textural characteristics from the corresponding monometallic and bimetallic glycerate nanospheres, respectively. When evaluated as molybdenum (Mo) adsorbents for potential use in molybdenum‐99/technetium‐99m (⁹⁹Mo/^99mTc) generators, the treated mesoporous Al₂O₃ nanospheres display higher molybdenum adsorption performance than non‐treated Al₂O₃ nanospheres and commercial Al₂O₃, thereby suggesting the effectiveness of the proposed strategy for improving the functional performance of oxide materials. It is expected that the proposed method can be utilized to prepare other mesoporous metal oxides with enhanced textural characteristics and functional performance.     

Effect of Powder Processing and Sintering Conditions on the Microstructural,Thermal, and Mechanical Properties of Reticulated Zinc Oxide Ceramic Foams

Ceramic foams are made of zinc oxide using different amounts of Sb₂O₃ and Bi₂O₃ as sintering aids. The effect of a ball milling processing of the starting powders and the sintering temperature on the microstructure and the properties of the ZnO foams is investigated. The focus is set on the evolution of the secondary phases formed within the microstructure of ZnO. A determining effect is identified in the amount of an Al₂O₃ impurity which is introduced by abrasion of the milling vessels during ball milling. Alumina is partially dissolved in a spinel α–Zn₇Sb₂O₁₂ secondary phase which is stabilized by a reduction of the unit cell volume. Remaining Al₂O₃ is incorporated into zinc oxide under formation of a defect wurtzite phase. The phase evolution is a complex function of the content of sintering aids, the Al₂O₃ impurity level and the sintering temperature. The shrinkage during sintering and the porosity evolution are correlated to the phase composition within the ZnO material. The thermal conductivity and the compressive strength of the foams are determined, normalized with respect to their porosity, and correlated to the microstructure and phase composition of the ZnO strut material.     

ROS scavenging Manganese-loaded mesoporous silica nanozymes for catalytic anti-inflammatory therapy

Reactive oxygen species (ROS) are reactive substances closely related to the inflammatory response, and previous studies have shown that anti-inflammatory therapy can achieve significant effects by scavenging ROS. Nanozymes are synthetic mimics of natural enzymes that are more stable, customizable, inexpensive, and catalytic for ROS. Therefore, we prepared a novel manganese-loaded mesoporous silica nanozyme (MnMSN) by template method and KMnO₄ oxidation surfactant templates. The physicochemical properties of the nanomaterials were investigated by XRD, TEM, SEM, size, Zeta potential and BET, etc. The results showed that MnMSN contains MnO₂ (Mn⁴⁺) and MnSiO₃ (Mn²⁺), and the particle size of MnMSN is smaller with the increase of KMnO₄ oxidation surfactant templates time, and the in vitro scavenging of ROS (H₂O₂, ·OH and ·O₂^–) is more effective. MnMSN has good cytocompatibility, scavenging intracellular ROS and inducing a shift from M1 to anti-inflammatory M2 phenotype. Furthermore, the intrinsic mechanism of MnMSN regulation of macrophage polarization was investigated by ELISA and qPCR, and the results showed that MnMSN is through scavenging ROS, leading to the down-regulation of NF-κB, which further leads to the down-regulation of TNF-α and IL-Iβ. The results of this work highlight the potential of MnMSN in catalyzing anti-inflammatory therapy.     

Manganese-based coordination framework derived manganese sulfide nanoparticles integrated with carbon sheets for application in supercapacitor

Manganese sulfide (MnS) with high specific capacitance and low-cost merits, has been investigated as a potential electroactive material for supercapacitor. However, in practical application, MnS has been suffering from some disadvantageous issues such as insufficient electrical conductivity, serious particle agglomeration as well as huge volume change during continuous charges and discharges, which resulted in a limited specific capacitance, shortened working life and inferior rate performance. Engineering electrode materials with controlled nanostructure and composition is pivotal to improve electrichemical performance of supercapacitors. This paper introduces a facile in situ sulfuration method to fabricate MnS/NSC composite with Mn-hexamethylene tetramine coordination framework as precursor. The results indicated that MnS nanoparticles were highly dispersed and incorporated into nitrogen, sulfur-doped carbon microsheets in MnS/NSC composite. Carbon matrix effectively dispersed and confined the MnS nanoparticles, thus inhibiting aggregation, relieving volume change and retaining structural integrity. Moreover, the 2D conductive carbon matrix reduced the diffusion distance for ions and ensured fast electron delivery. As a result, MnS/NSC electrode delivered a tremendously boosted electrochemical performance for supercapacitor. A large capacitance value about 1881.8F/g was achieved at 1A/g. Even cycling for 3000 loops at 40 A/g, MnS/NSC electrode retained a large capacitance of 404.3F/g. Furthermore, an asymmetric capacitor based on assembly of MnS/NSC composite cathode and activated carbon anode was fabricated. As tested under a current density of 0.1 A/g, it delivered a capacitance of ～ 110.1F/g and achieved an energy density of 12.4 Wh kg^?1 along with a power density of 3.03 kW kg^?1. These results demonstrate the potential utilization of MnS/NSC composite as electrodes for energy conversion and storage devices and open up a route for material design for future energy storage devices.     

Screen-printed carbon electrode for choline based on MnO2 nanoparticles and choline oxidase/polyelectrolyte layers

This paper presents the amperometric biosensor that determines choline and cholinesterase activity using a screen printed graphite electrode. In order to detect H₂O₂ we have blanket modified the electrode material with manganese dioxide nanoparticles layer. Using layer-by-layer technique on the developed hydrogen peroxide sensitive electrode surface choline oxidase was incorporated into the interpolyelectrolyte nanofilm. Its ability to serve as a detector of choline in bulk analysis and cholinesterase assay was investigated. We examined the interferences from red-ox species and heavy metals in the blood and in the environmental sample matrixes. The sensor exhibited a linear increase of the amperometric signal at the concentration of choline ranging from 1.3 × 10⁻⁷ to 1.0 × 10⁻⁴ M, with a detection limit (evaluated as 3σ) of 130 nM and a sensitivity of 103 mA M⁻¹ cm⁻² under optimized potential applied (480 mV vs. Ag/AgCl). The biosensor retained its activity for more than 10 consecutive measurements and kept 75% of initial activity for three weeks of storage at 4 °C. The R.S.D. was determined as 1.9% for a choline concentration of 10⁻⁴ M (n = 10) with a typical response time of about 10 s. The developed choline biosensor was applied for butyrylcholinesterase assay showing a detection limit of 5 pM (3σ). We used the biosensor to develop the cholinesterase inhibitor assay. Detection limit for chlorpyrifos was estimated as 50 pM.     

PdO修饰的SnO2纳米球的制备及其气敏特性研究

通过溶剂热法和退火处理制备了不同浓度(0 mol％,2 mol％,5 mol％,10 mol％)PdO修饰的SnO2纳米球.采用X射线衍射仪(XRD)、X射线能谱分析仪(EDS)和扫描电子显微镜(SEM)等测试手段对材料的物相、元素种类和形貌进行了表征,并制成气敏元件,对氢气(H2)进行气敏测试.实验结果表明:5 mol％PdO修饰的SnO2纳米球气体传感器最佳工作温度为175℃,其对100×10-6氢气灵敏度达到19,是纯的SnO2纳米球的灵敏度的3倍.最后,对PdO修饰氧化锡纳米球气体传感器气敏机理进行了分析讨论.     

Reduction of NOx Stored at Low Temperatures on a NOx Adsorbing Catalyst

Isothermal storage and reduction of NO₂ with CO, C₃H₆ and H₂ as reducing agents on a lean NO _x adsorber was investigated by temperature programmed desorption (TPD) and temperature programmed reduction (TPR) studies. The reduction of NO _x was clearly favoured with H₂ as reducing agent. Carbon monoxide and C₃H₆ showed fairly low reduction of NO _x . The NO _x reduction at low temperatures with H₂ as reducing agent was found to be effective, clearly much more effective than for CO.