An Electrochemical Sensor Based on Three-Dimensional Porous Reduced Graphene and Ion Imprinted Polymer for Trace Cadmium Determination in Water.

Three-dimensional (3D) porous graphene-based materials have displayed attractive electrochemical catalysis and sensing performances, benefiting from their high porosity, large surface area, and excellent electrical conductivity. In this work, a novel electrochemical sensor based on 3D porous reduced graphene (3DPrGO) and ion-imprinted polymer (IIP) was developed for trace cadmium ion (Cd(II)) detection in water. The 3DPrGO was synthesized in situ at a glassy carbon electrode (GCE) surface using a polystyrene (PS) colloidal crystal template and the electrodeposition method. Then, IIP film was further modified on the 3DPrGO by electropolymerization to make it suitable for detecting Cd(II). Attributable to the abundant nanopores and good electron transport of the 3DPrGO, as well as the specific recognition for Cd(II) of IIP, a sensitive determination of trace Cd(II) at PoPD-IIP/3DPrGO/GCE was achieved. The proposed sensor exhibited comprehensive linear Cd(II) responses ranging from 1 to 100 µg/L (R2 = 99.7%). The limit of detection (LOD) was 0.11 µg/L, about 30 times lower than the drinking water standard set by the World Health Organization (WHO). Moreover, PoPD-IIP/3DPrGO/GCE was applied for the detection of Cd(II) in actual water samples. The satisfying recoveries (97-99.6%) and relative standard deviations (RSD, 3.5-5.7%) make the proposed sensor a promising candidate for rapid and on-site water monitoring.

Ion imprinted polymers integrated into a multi-functional microfluidic paper-based analytical device for trace cadmium detection in water.

A novel multi-functional microfluidic paper-based analytical device (µPAD) integrated with ion imprinted polymers (IIPs) was proposed for specific, portable and low-cost detection of cadmium (Cd(II)) in water. The IIP was grafted on paper and integrated into the µPAD for separation of Cd(II) through multi-layer design. The paper-based screen printed carbon electrode (pSPCE) modified with reduced graphene oxide was fabricated and combined with the µPAD for electrochemical sensing of the separated Cd(II). Reduced graphene oxide (rGO) was prepared via electroreduction on the working electrode surface of the pSPCE (rGO/pSPCE), which provided a sensitization effect with an improved signal for Cd(II) detection. The µPAD developed with the integrated IIP and combined with rGO/pSPCE is able to detect Cd(II) with a linear range from 1 ng ml-1 to 100 ng ml-1 and a detection limit of 0.05 ng ml-1. The accuracy of this µPAD was evaluated with spiked real water samples and compared with that of the inductively coupled plasma mass spectrometry (ICP-MS) method, from which the recovery values ranged from 96.5% to 114.2% with RSDs <10% between the two methods. This µPAD demonstrated its advantages of low-cost, portability, and suitability for highly sensitive detection of Cd(II), making it a valuable tool for on-site analysis.

Enhanced ion-electron mixing interface for high energy solid-state lithium metal batteries.

Solid-state Li metal batteries (SSLMBs) are famous for superior security and excellent energy density. Nevertheless, the poor interfacial contact between solid lithium and electrode is one key problem in the development of SSLMBs, resulting in high impedance and growth of lithium dendrites along the grain boundaries. Herein, an innovative and accessible approach has been applied to SSLMBs, which introduces an ion-electron mixing (IEM) interface on the surface of Li1.3Al0.3Ti1.7(PO4)3 (LATP). The IEM interlayer generates LixSn/LiI of fast lithium-ion conductor through an in-situ reaction. The existence of LiI would promote the quick transmission of Li+ at the interface and inhibit the electronic conduction, thus restraining the growth of lithium dendrites. The batteries with IEM@LATP electrolyte could stably cycle more than 1000 h at high current density of 0.1 mA cm-2. Even increasing the current density to 3.0 mA cm-2, the batteries still could work normally. This novel and viable approach offers a robust basis for the practical application of SSLMBs and has some general applicability to other solid-state batteries.

Enriching Oxygen Vacancy Defects via Ag-O-Mn Bonds for Enhanced Diffusion Kinetics of δ-MnO2 in Zinc-Ion Batteries.

Aqueous zinc-ion batteries (ZIBs) have received great attention due to their environmental friendliness and high safety. However, cathode materials with slow diffusion dynamics and dissolution in aqueous electrolytes hindered their further application. To address these issues, in this work, a MnO2-2 cathode doped with 1.12 wt % Ag was prepared, and after 1000 cycles of charge/discharge at 1 A·g-1, the capacity remained at 114 mA·h·g-1 (only 57.7 mA·h·g-1 for pristine MnO2). Cyclic voltammetry (CV), the galvanostatic intermittent titration technique (GITT), the electrochemical quartz crystal microbalance (EQCM) method, and density functional theory (DFT) calculation on pristine δ-MnO2 and MnO2-2 also proved the superior performance of MnO2-2. More investigation disclosed that its superior performance is attributed to the improved diffusion kinetics of the cathode brought by the enriched oxygen vacancy defects due to the formation of Ag-O-Mn bonds. Meanwhile, the kinetic mechanism of the Zn/MnO2-2 cell can be described as a reversible process of the dissolution/precipitation of the ZHS phase and consequent insertion/extraction of Zn2+ and H3O+. Herein, the primary issues of ZIB cathode materials have been addressed and solved to a certain extent. More importantly, such a modification in the design of the advanced manganese-based aqueous ZIB cathode materials can provide further insight and facilitate the development and application of this large-scale energy storage system in the near future.

A New Co-Free Ni-Rich LiNi0.8Fe0.1Mn0.1O2 Cathode for Low-Cost Li-Ion Batteries.

In recent years, with the rapid development of electric vehicles, the ever-fluctuating cobalt price has become a decisive constraint on the supply chain of the lithium-ion (Li-ion) battery industry. To address these challenges, a new and unreported cobalt-free (Co-free) material with a general formula of LiNi0.8Fe0.1Mn0.1O2 (NFM) is introduced. This Co-free material is synthesized via the coprecipitation method and examined by using scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) to investigate the morphological, crystal-structure, and electrochemical properties. The NFM cathode can deliver a specific capacity of 202.6 mA h g-1 (0.1C, 3.0-4.5 V), a specific energy capacity of 798.8 W h kg-1 in material level (0.1C, 3.0-4.5 V), a reasonable rate capability, and a stable cycling performance (81.1% discharge capacity retention after 150 cycles at 10C, 3.0-4.3 V). Although the research on this subject is still in its early stage, the capability of this novel cathode material as a practical candidate for applications in next-generation Co-free lithium-ion batteries (LIBs) is highlighted in this study.

Fine-Tuning Pyridinic Nitrogen in Nitrogen-Doped Porous Carbon Nanostructures for Boosted Peroxidase-Like Activity and Sensitive Biosensing.

Carbon materials have been widely used as nanozymes in bioapplications, attributing to their intrinsic enzyme-like activities. Nitrogen (N)-doping has been explored as a promising way to improve the activity of carbon material-based nanozymes (CMNs). However, hindered by the intricate N dopants, the real active site of N-doped CMNs (N-CMNs) has been rarely investigated, which subsequently retards the further progress of high-performance N-CMNs. Here, a series of porous N-CMNs with well-controlled N dopants were synthesized, of which the intrinsic peroxidase (POD)like activity has a positive correlation with the pyridinic N content. Density functional theory calculations also reveal that pyridinic N boosts the intrinsic POD-like activity of N-CMNs. Pyridinic-N dopant can effectively promote the first H2O desorption process in comparison with the graphitic and pyrrolic N, which is the key endothermic reaction during the catalytic process. Then, utilizing the optimized nanozymes with high pyridinic N content (NP-CMNs) and superior POD-like activity, a facile total antioxidant capacity (TAC) assay was developed, holding great promise in the quality assessment of medicine tablets and antioxidant food for healthcare and healthy diet.