Lattice-Disordered High-Entropy Alloy Engineered by Thermal Dezincification for Improved Catalytic Hydrogen Evolution Reaction.

A disordered crystal structure is an asymmetrical atomic lattice resulting from the missing atoms (vacancies) or the lattice misarrangement in a solid-state material. It has been widely proven to improve the electrocatalytic hydrogen evolution reaction (HER) process. In the present work, due to the special physical properties (the low evaporation temperature of below 900 °C), Zn is utilized as a sacrificial component to create senary PtIrNiCoFeZn high-entropy alloy (HEA) with highly disordered lattices. The structure of the lattice-disordered PtIrNiCoFeZn HEA is characterized by the thermal diffusion scattering (TDS) in transmission electron microscope. Density functional theory calculations reveal that lattice disorder not only accelerates both the Volmer step and Tafel step during the HER process but also optimizes the intensity and distribution of projected density of states near the Fermi energy after the H2O and H adsorption. Anomalously high alkaline HER activity and stability are proven by experimental measurements. This work introduces a novel approach to preparing irregular lattices offering highly efficient HEA and a TDS characterization method to reveal the disordered lattice in materials. It provides a new route toward exploring and developing the catalytic activities of materials with asymmetrically disordered lattices.

Confining Co1.11Te2 nanoparticles within mesoporous hollow carbon combination sphere for fast and ultralong sodium storage.

Co1.11Te2 nanoparticles are in-situ uniformly grown within mesoporous hollow carbon combination sphere (MHCCS@Co1.11Te2) using a hard-template and spray drying process, solution impregnation and pyrolysis tellurization. Material characterizations reveal that Co1.11Te2, with a diameter of âˆ¼ 20 nm, is attached to the internal walls of the unit spheres or embedded in the mesopore shells of the unit spheres, presenting a distinctive "ships-in-combination-bottles" nanoencapsulation structure. In sodium-ion half-cells, MHCCS@Co1.11Te2 exhibits excellent cycling stability, achieving reversible capacities of 257 mAh/g at 0.5 A/g after 250 cycles, 235 mAh/g at 1.0 A/g after 300 cycles and 161 mAh/g at 10.0 A/g after 1900 cycles. Electrochemical kinetic analyses and ex-situ characterizations reveal rapid electron/Na+ transport kinetics, prominent surface pseudocapacitive behavior, robust nanocomposite structure, and multi-step conversion reactions of sodium polytellurides. In sodium-ion full-cells, MHCCS@Co1.11Te2 still demonstrates stable cycling performance at 1.0 and 5.0 A/g and excellent rate capability. The superior electrochemical performance is associated with the nanoencapsulation structure based on mesoporous hollow carbon combination spheres, which promotes electron conduction and Na+ transport. The space-confined effect maintains the high electrochemical activity and cycling stability of Co1.11Te2.

PEC/Colorimetric Dual-Mode Lab-on-Paper Device via BiVO4/FeOOH Nanocomposite In Situ Modification on Paper Fibers for Sensitive CEA Detection.

A dual-mode lab-on-paper device based on BiVO4/FeOOH nanocomposites as an efficient generating photoelectrochemical (PEC)/colorimetric signal reporter has been successfully constructed by integration of the lab-on-paper sensing platform and PEC/colorimetric detection technologies for sensitive detection of carcinoembryonic antigen (CEA). Concretely, the BiVO4/FeOOH nanocomposites were in situ synthesized onto the paper-working electrode (PWE) through hydrothermal synthesis of the BiVO4 layer on cellulose fibers (paper-based BiVO4) which were initially modified by Au nanoparticles for improving the conductivity of three dimensional PWE, and then the photo-electrodeposition of FeOOH onto the paper-based BiVO4 to construct the paper-based BiVO4/FeOOH for the portable dual-mode lab-on-paper device. The obtained nanocomposites with an FeOOH needle-like structure deposited on the BiVO4 layer exhibits enhanced PEC response activity due to its effective separation of the electron-hole pair which could further accelerate the PEC conversion efficiency during the sensing process. With the introduction of CEA targets onto the surface of nanocomposite-modified PWE assisted by the interaction with the CEA antibody from a specific recognition property, a signal-off PEC signal state with a remarkable photocurrent response decreasing trend can be achieved, realizing the quantitative detection of CEA with the PEC signal readout mode. By means of a smart origami paper folding, the colorimetric signal readout is achieved by catalyzing 3,3',5,5'-tetramethylbenzidine (TMB) to generate blue oxidized TMB in the presence of H2O2 due to the satisfied enzyme-like catalytic activity of the needle-like structure, FeOOH, thereby achieving the dual-mode signal readout system for the proposed lab-on-paper device. Under the optimal conditions, the PEC and colorimetric signals measurement were effectively carried out, and the corresponding linear ranges were 0.001-200 ng·mL-1 and 0.5-100 ng·mL-1 separately, with the limit of detection of 0.0008 and 0.013 ng·mL-1 for each dual-mode. The prepared lab-on-paper device also presented a successful application in serum samples for the detection of CEA, providing a potential pathway for the sensitive detection of target biomarkers in clinical application.

A Paper-Based Photoelectrochemical Sensing Platform Based on In Situ Grown ZnO/ZnIn2S4 Heterojunctions onto Paper Fibers for Sensitively Detecting AFP.

Nowadays, developing a cost-effective, easy-to-operate, and efficient signal amplification platform is of important to microfluidic paper-based analytical devices (µPAD) for end-use markets of point-of-care (POC) assay applications. Herein, an ultrasensitive, paper-based photoelectrochemical (PEC) bioassay platform is constructed by in situ grown ZnO/ZnIn2S4 heterojunctions onto paper fibers, which acted as photoactive signal amplification probes for enhancing the sensitivity of antibodies-based diagnostic assays, for the sensitive detection of alpha-fetoprotein (AFP) targets. The crystalline flake-like ZnIn2S4 composited with hexagonal nanorods (NRs) morphology of ZnO is an in situ grown, at the first time, onto cellulose fibers surface supported with Au nanoparticle (Au NP) modification to improve conductivity of the device working zone. The obtained composites on paper fibers are implemented as a flexible paper-based photoelectrode to realize remarkable performance of the fabricated µPAD, resulting from the enhanced PEC activity of heterojunctions with effective electron-hole pair separation for accelerating photoelectric conversion efficiency of the sensing process under light irradiation. Once the target AFP was introduced into the biosensing interface assistant, with a specific recognition interaction of AFP antibody, a drastically photocurrent response was generated, in view of the apparent steric effects. With the concentration increase of AFP targets, more immune conjugates could be confined onto the biosensing interface, eventually leading to the quantitative decrease of photocurrent intensity. Combined with an ingenious origami design and permitting the hydrophobic/hydrophilic conversion procedure in the bioassay process, the ultrasensitive PEC detection of AFP targets was realized. Under the optimized conditions, the level of AFP could be sensitively tracked by the prepared µPAD with a liner range from 0.1 to 100 ng mL-1 and limit of detection of 0.03 ng mL-1. This work provides a great potential application for highly selective and sensitive POC testing of AFP, and finally, developments for clinical disease diagnosis.

In situ growth of WO3/BiVO4 nanoflowers onto cellulose fibers to construct photoelectrochemical/colorimetric lab-on-paper devices for the ultrasensitive detection of AFP.

In this work, novel dual-mode lab-on-paper devices based on in situ grown WO3/BiVO4 heterojunctions onto cellulose fibers, as signal amplification probes, were successfully fabricated by the integration of photoelectrochemical (PEC)/colorimetric analysis technologies into a paper sensing platform for the ultrasensitive detection of alpha-fetoprotein (AFP). Specifically, to achieve an impressive PEC performance of the lab-on-paper device, the WO3/BiVO4 heterojunction was in situ grown onto the surface of cellulose fibers assisted with Au nanoparticle (Au NP) functionalization for enhancing the conductivity of the working zone of the device. With the target concentration increased, more immune conjugates could be captured by the proposed paper photoelectrode, which could lead to a quantitative decrease in the photocurrent intensity, eventually realizing the accurate PEC signal readout. To meet the requirement of end-user application, a colorimetric signal readout system was designed for the lab-on-paper device based on the color reaction of 3,3'5,5'-tetramethylbenzidine (TMB) oxidized by WO3/BiVO4 nanoflowers in the presence of H2O2. Noticeably, it is the first time that the WO3/BiVO4 heterojunction is in situ grown onto cellulose fibers, which enhances the sensitivity in view of both their PEC activity and catalytic ability. By controlling the conversion process of hydrophobicity and hydrophilicity on the lab-on-paper device combined with diverse origami methods, the dual-mode PEC/colorimetric signal output for the ultrasensitive AFP detection was realized. Under optimal conditions, the proposed dual-mode lab-on-paper device could enable the sensitive PEC/colorimetric diagnosis of AFP in the linear range of 0.09-100 ng mL-1 and 5-100 ng mL-1 with the limit of detection of 0.03 and 1.47 ng mL-1, respectively.