High-Entropy Oxide Derived from Metal-Organic Framework as a Bifunctional Electrocatalyst for Efficient Urea Oxidation and Oxygen Evolution Reactions.

High-entropy oxides (HEOs) offer unique features through a combination of incompatible metal cations to a single crystalline lattice. Owing to their special characteristics such as abundant cation compositions, high entropy stabilization, chemical and thermal stability, and lattice distortion effect, they have drawn ever-increasing attention for various applications. However, very few studies have been reported for catalytic application, and developing HEOs with large surface areas for efficient catalytic application is still in infancy. Herein, we design nanostructured HEO of (FeNiCoCrCu)3O4 using metal-organic frameworks (MOFs) as sacrificial templates to achieve a large surface area, high density of exposed active sites, and more oxygen vacancies. Single-crystalline phase HEOs with surface area as large as 206 m2 g-1 are produced and further applied as bifunctional electrocatalysts for the urea oxidation reaction (UOR) and oxygen evolution reaction (OER). Benefiting from enhanced oxygen vacancies and a large surface area with abundant exposed active sites, the optimized HEO exhibited excellent electrocatalytic activity toward UOR with a very low potential of 1.35 V at the current density of 10 mA cm-2 and showed long-term stability for 36 h operation, making a significant catalytic performance over previously reported HEOs. Moreover, the HEO demonstrated an efficient catalytic performance toward OER with a low overpotential of 270 mV at 10 mA cm-2 and low Tafel slope of 49 mV dec-1. The excellent catalytic activity is ascribed to the starting MOF precursor and favorable high-entropy effect.

Silver-enhanced fluorescence of bimetallic Au/Ag nanoclusters as ultrasensitive sensing probe for the detection of folic acid.

Folic acid (FA) is the natural form of water-soluble vitamins widely found in most plants and animal products and its deficiency leads to several human body abnormalities. The advancements of metal nanoclusters are highly increasing due to their molecule-like optical properties and attractive applications. Because of increasingly demand of noble metal nanoclusters as sensing templates, different synthesis methods have been developed for facile synthesis of noble metal nanoclusters. Herein, red-emitting fluorescent bovine serum albumin (BSA)-capped Au-Ag bimetallic NCs are facilely synthesized through green one-pot synthetic approach. The effect of silver on the fluorescence properties of Au NCs was investigated and it was found that introduction of silver can enhance the fluorescence intensity. The fluorescence intensity of the as-prepared Au-Ag nanoclusters gets quenched in the presence of folic acid in an aqueous medium and it was used as ultrasensitive sensing probe for FA detection. The developed Au-Ag NCs-based sensing probe shows linear response in the wide range of 0-100 µM and the detection limit is as low as 0.47 nM. Its applicability has also been confirmed successfully in real human serum, urine and FA tablet samples. Due to the high stability, sensitivity and selectivity, the developed bimetallic cluster sensing system is highly promising to be applied in the pharmaceutical and clinical laboratories.

Pd-Doping-Induced Oxygen Vacancies in One-Dimensional Tungsten Oxide Nanowires for Enhanced Acetone Gas Sensing.

Metal oxide semiconductors (MOS) with different nanostructures have been widely used as gas sensing materials due to the tunable interface structures and properties. However, further improvement of the sensing sensitivity and selectivity is still challenging in this area. Constructing appropriate heterogeneous interface structures and oxygen vacancies is one of the important strategies to tune the sensing properties of MOS. In the present study, interfacial heterostructures in PdxW18O49 nanowires (PdxW18O49 NWs) were fabricated and manipulated by doping different Pd contents through a simple hydrothermal process. Relevant characterization proved that the structure and composition of the one-dimensional (1D) nanomaterial can be effectively changed by Pd doping. It was found that the oxygen vacancy concentration increases first with the increase of Pd content, and when the Pd content increases to 7.18% (Pd7.18%W18O49 NWs), the oxygen vacancy content reaches the maximum (52.5%). If the Pd content continues to increase, the oxygen vacancy ratio decreases. The gas sensing investigations illustrated that the PdxW18O49 NWs exhibited enhanced sensing properties than pure W18O49 NWs toward acetone. Among the as-prepared catalysts, the Pd7.18%W18O49 NWs showed the best sensing response and the fastest response-recovery speeds (5 and 10 s, respectively) at a working temperature of 175 °C. In addition, this 1D nanostructure with fabricated heterostructures also delivers a good sensing selectivity and a wide detection range from 100 ppb to 300 ppm, with maintaining excellent performance in the presence of high concentrations of ethanol and carbon dioxide. The excellent gas sensing behavior could be attributed to the generated oxygen vacancies and the heterostructures upon Pd doping. This study offers a novel strategy for the design of high-performance gas sensors for ppb-level acetone sensing.

"Turn-off" sensing probe based on fluorescent gold nanoclusters for the sensitive detection of hemin.

Balanced level of hemin in the body is fundamentally important for normal human organ function. Therefore, environmentally benign, stable, and fluorescent metal nanoclusters (NCs) for selective and sensitive detection of hemin have been investigated and reported. Herein, highly orange red emissive gold NCs are successfully synthesized using glutathione as a reducing and stabilizing agent (GSH-Au NCs). The clusters are characterized using various techniques like Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), UV-vis spectroscopy, and fluorescence spectrometer. The fluorescence intensity of as-synthesized Au NCs strongly quenched upon addition of different concentrations of hemin. The decrease in fluorescence intensity of GSH-Au NCs has been applied for determination of hemin concentration in the linear range from 1 to 25 nM with a low limit of detection (LOD) of 0.43 nM. The method was also successfully applied for quantification of hemin in human serum sample. In view of this reality, the system can be considered as a possible strategy and excellent platform for determination of hemin in various areas of application.