尖晶石LiMn2O4的改性研究

由于资源丰富、价格便宜、易制备、对环境无污染、可回收利用等优点,尖晶石型LiMn2O4成为锂离子二次电池中最有希望的正极材料[1~3]。然而,在高电压充、放电条件下,由于电极中锰的溶解和Jahn鄄Teller效应的发生,会造成LiMn2O4容量迅速衰减[4~6]。为了改善LiMn2O4的电化学性能,研究者主要通过优化合成条件及合成方法来控制产品的粒径分布与形貌,以利于锂离子的脱、嵌[7,8];用掺杂的方法以稳定其结构,抑制Jahn鄄Teller效应的发生[9,10];用表面修饰的方式来减少活性物质与电解液的直接接触从而降低Mn的溶解[11,12]。掺杂方面,Co3 不仅有…     

Impact of carbon coating thickness on the electrochemical properties of Li<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>/C composites

A series of Li₃V₂(PO₄)₃/C composites with different amounts of carbon are synthesized by a combustion method. The physical and electrochemical properties of the Li₃V₂(PO₄)₃/C composites are investigated by X-ray diffraction, element analysis, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy and electrochemical measurements. The effects of carbon content of Li₃V₂(PO₄)₃/C composites on its electrochemical properties are conducted with cyclic voltammetry and electrochemical impedance. The experiment results clearly show that the optimal carbon content is 4.3 wt %, and more or less amount of carbon would be unfavorable to electrochemical properties of the Li₃V₂(PO₄)₃/C electrode materials. The results would provide some basis for further improvement on the Li₃V₂(PO₄)₃ electrode materials.     

Electrochemical reduction of NO2 studied by the use of cone-shaped electrodes

The electrochemical reduction, in an all solid state cell, of NO₂ and O₂ on LSF (strontium substituted lanthanum ferrite) based electrodes has been studied using the cone-shaped electrode technique. It was shown that the reduction of NO₂ occurs much faster on LSF based electrodes than the reduction of O₂. The electrochemical reduction of NO₂ on LSF compounds is probably catalyzed by Fe(III) and oxide ion vacancies. The same seems to be true for the electrochemical reduction of O₂. The largest difference in current densities for the electrochemical reduction of NO₂ and O₂ was found for the compound LSF70 (La_0.3Sr_0.7FeO_3−δ).     

Precise Tuning of the Charge Transfer Kinetics and Catalytic Properties of MoS2 Materials via Electrochemical Methods

MoS₂ has become particularly popular for its catalytic properties towards the hydrogen evolution reaction (HER). It has been shown that the metallic 1T phase of MoS₂, obtained by chemical exfoliation after lithium intercalation, possesses enhanced catalytic activity over the semiconducting 2H phase due to the improved conductivity properties which facilitate charge‐transfer kinetics. Here we demonstrate a simple electrochemical method to precisely tune the electron‐transfer kinetics as well as the catalytic properties of both exfoliated and bulk MoS₂‐based films. A controlled reductive or oxidative electrochemical treatment can alter the surface properties of the film with consequently improved or hampered electrochemical and catalytic properties compared to the untreated film. Density functional theory calculations were used to explain the electrochemical activation of MoS₂. The electrochemical tuning of electrocatalytic properties of MoS₂ opens the doors to scalable and facile tailoring of MoS₂‐based electrochemical devices.     

Enhanced electrochemical reduction of rare earth oxides in simulated oxide fuel via co-reduction of NiO in Li2O–LiCl salt

Rare earth oxides in spent oxide fuel from nuclear plants have poor reducibility in the electrochemical reduction process due to their high oxygen affinity and thermodynamic stability. Here, we demonstrate that the extent of their reduction can be enhanced via co-reduction of NiO in a Li₂O–LiCl electrolyte for the electrochemical reduction of a simulated oxide fuel (simfuel). First, the electrochemical behaviors of Nd₂O₃, NiO, and Nd₂O₃–NiO were studied by cyclic voltammetry and voltage control electrolysis. Then, the electrochemical reduction of the simfuel containing UO₂ and rare earth oxides (Nd₂O₃, La₂O₃, and CeO₂) was conducted in molten LiCl salt with 1 wt.% Li₂O via the co-reduction of NiO. The extent of reduction of the rare earth oxides was found to be significantly improved.     

Recent progress in advanced core-shell metal-based catalysts for electrochemical carbon dioxide reduction

Electrochemical carbon dioxide reduction（CO₂RR） plays an important role in solving the problem of high concentration of CO₂in the atmosphere and realizing carbon cycle. Core-shell structure has many unique features including tandem catalysis, lattice strain effect, defect engineering, which exhibit great potential in electrocatalysis. In this review, we focus on the advanced core-shell metal-based catalysts（CMCs） for electrochemical CO₂RR. The recent progress of ...     

Metal–Organic Frameworks for Electrocatalytic Sensing of Hydrogen Peroxide

The electrochemical detection of hydrogen peroxide (H₂O₂) has become more and more important in industrial production, daily life, biological process, green energy chemistry, and other fields (especially for the detection of low concentration of H₂O_2). Metal organic frameworks (MOFs) are promising candidates to replace the established H₂O₂ sensors based on precious metals or enzymes. This review summarizes recent advances in MOF-based H₂O₂ electrochemical sensors, including conductive MOFs, MOFs with chemical modifications, MOFs-composites, and MOF derivatives. Finally, the challenges and prospects for the optimization and design of H₂O₂ electrochemical sensors with ultra-low detection limit and long-life are presented.     

High-Resolution Electrochemical Mapping of the Hydrogen Evolution Reaction on Transition-Metal Dichalcogenide Nanosheets

High-resolution scanning electrochemical cell microscopy (SECCM) is used to image and quantitatively analyze the hydrogen evolution reaction (HER) catalytically active sites of 1H-MoS₂ nanosheets, MoS₂, and WS₂ heteronanosheets. Using a 20 nm radius nanopipette and hopping mode scanning, the resolution of SECCM was beyond the optical microscopy limit and visualized a small triangular MoS₂ nanosheet with a side length of ca. 130 nm. The electrochemical cell provides local cyclic voltammograms with a nanoscale spatial resolution for visualizing HER active sites as electrochemical images. The HER activity difference of edge, terrace, and heterojunction of MoS₂ and WS₂ were revealed. The SECCM imaging directly visualized the relationship of HER activity and number of MoS₂ nanosheet layers and unveiled the heterogeneous aging state of MoS₂ nanosheets. SECCM can be used for improving local HER activities by producing sulfur vacancies using electrochemical reaction at the selected region.     

High‐Resolution Electrochemical Mapping of the Hydrogen Evolution Reaction on Transition‐Metal Dichalcogenide Nanosheets

High‐resolution scanning electrochemical cell microscopy (SECCM) is used to image and quantitatively analyze the hydrogen evolution reaction (HER) catalytically active sites of 1H‐MoS₂ nanosheets, MoS₂, and WS₂ heteronanosheets. Using a 20 nm radius nanopipette and hopping mode scanning, the resolution of SECCM was beyond the optical microscopy limit and visualized a small triangular MoS₂ nanosheet with a side length of ca. 130 nm. The electrochemical cell provides local cyclic voltammograms with a nanoscale spatial resolution for visualizing HER active sites as electrochemical images. The HER activity difference of edge, terrace, and heterojunction of MoS₂ and WS₂ were revealed. The SECCM imaging directly visualized the relationship of HER activity and number of MoS₂ nanosheet layers and unveiled the heterogeneous aging state of MoS₂ nanosheets. SECCM can be used for improving local HER activities by producing sulfur vacancies using electrochemical reaction at the selected region.     

Electrochemical determination of riboflavin using a synthesized ethyl[(methythio)carbonothioyl] glycinate monolayer modified gold electrode

The surface of a gold disk electrode, for the first time, was modified with a self-assembled monolayer of a synthesized compound, ethyl [(methythio)carbonothioyl] glycinate (ECTG), for construction of an electrode sensitive to riboflavin (vitamin B₂). The electrochemical properties of the monolayer assembled on the gold disk were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. Under the optimized conditions, the voltammetric peak currents resulting from vitamin B₂ (VB₂) species were linear for VB₂ concentrations in the range from 10^–6 to 10^–2 M. The effect of pH, type of buffer solution and scan rate on the response of the modified electrode was studied. The constructed electrochemical sensor responses very well to VB₂ in the presence of most common vitamins. Finally, the performance of the Au–ECTG modified electrode was successfully tested for electrochemical detection of VB₂ in a pharmaceutical sample.     

Nanoflake-like cobalt hydroxide/ordered mesoporous carbon composite for electrochemical capacitors

Nanocomposites consisting of mesoporous carbon CMK-3 and cobalt hydroxide nanoflakes are synthesized by a chemical precipitation method. The successful growth of nanometer-sized Co(OH)₂ flakes on the surface of CMK-3 is confirmed by scanning electron microscopy. The Co(OH)₂/CMK-3 composite electrodes are investigated for its use in the electrochemical capacitors with cyclic voltammograms, chronopotentiometric measurements, and electrochemical impedance spectroscopy. Experimental studies reveal that the Co(OH)₂/CMK-3 composite electrode with the 20 wt.% CMK-3 presents excellent electrochemical performance with specific capacitance of 750 F/g (or 910 F/g after being corrected for the weight percentage of the Co(OH)₂ phase). The overall improved electrochemical behavior accounts for the unique structure design in the Co(OH)₂/CMK-3 composite in terms of porous nanostructure, large specific surface area, and good electrical conductance. The Co(OH)₂/CMK-3 composite electrode also shows better rate capability and cyclic stability, suggesting its potential applications as the electrode materials for electrochemical capacitors.     

Future perspectives for the advancement of electrochemical hydrogen peroxide production

Hydrogen peroxide (H₂O₂)is an important chemical with multiple uses across domestic and industrial settings. With a global need for wider adoption of green synthetic methods, there has been a growing interest in the electrochemical synthesis of H₂O₂ from oxygen reduction or water oxidation. State-of-the-art catalyst and reactor developments are beginning to advance to a stage where electrochemical synthesis is discussed as a viable alternative to current industrial methods. In this review, we highlight some of the most promising candidates for H₂O₂ electrosynthesis technologies and what further advancements are needed before the electrochemical route could challenge the ubiquitous anthraquinone process.     

Spectroelectrochemical Study of N‐Substituted Phenoxazines as Electrochemical Labels of Biomolecules

The electrochemical conversion of N‐substituted phenoxazines (NSP's) bearing a CH₂CH₂? X substitute (where X?OH, COOH, CH₂NH₂, CH₂SO₃H, CH₂NHCOR) was investigated using cyclic voltammetry on a bulk gold electrode and a thin‐layer spectroelectrochemical cell. The electrochemical oxidation of NSP's on the gold electrode was quasi‐reversible and proceeded in a diffusion‐controlled regime. The formal redox potential of NSP's covered the range from 0.39 to 0.45 V vs. SCE. The electrochemical oxidation of NSP's in the thin‐layer spectroelectrochemical cell produced radical cations that showed absorbance at 385, 410 and 530 nm. Electrochemical conversion fitted the general voltammetric current‐potential equation of a reversible wave, whereas electrolysis at constant potential showed a typical Cottrell behavior. Combining of NSP's with a biologically‐relevant theophylline molecule did not change electrochemical and spectral properties of the phenoxazine core. Theophylline enlarged with NSP's demonstrated electrochemical and biocatalytic behavior similar to that of NSP's. The investigated NSP's possess electrochemical and spectral properties that are useful as biomolecular labels for electroanalysis.     

Electrochemical cardiac troponin I immunosensor based on nitrogen and boron-doped graphene quantum dots electrode platform and Ce-doped SnO2/SnS2 signal amplification

The detection of acute myocardial infarction directly depends on the concentration of the cardiac troponin I (CTnI) in human blood plasma. In this study, the sensitive, selective, and fast sandwich-type electrochemical CTnI immunosensor was developed by using nitrogen and boron-dopped graphene quantum dots -as electrode platform and two-dimensional Ce-dopped SnO₂/SnS₂ (Ce–SnO₂/SnS₂) as signal amplification. In preparation of electrochemical CTnI immunosensor, the coordinated covalent bond between capture antibody (anti-CTnI-Ab₁) and nitrogen and boron-dopped graphene quantum dots as electrode platform led to immobilization of anti-CTnI-Ab₁, and the strong esterification between the secondary antibody (anti-CTnI-Ab₂) and thioglycolic acid-modified Ce–SnO₂/SnS₂ resulted in anti-CTnI-Ab₂ conjugation. Finally, the resultant electrochemical CTnI immunosensor was formed via antigen-antibody interaction. High-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, UV–Vis spectroscopy and Raman spectroscopy, as well as some electrochemical characterization techniques, including cyclic voltammetry, differential pulse voltammetry and electrochemical impedance spectroscopy were used to characterize the prepared immunosensor. The detection limit of CTnI in plasma samples was calculated as 2.00 fg mL^?1, making it an effective tool for acute myocardial infarction testing.     

不同组分下富锂正极材料xLi_2MnO_3·(1-x)LiNi_(0.5)Mn_(0.5)O_2(x=0.1-0.8)的晶体结构与电化学性能

采用溶胶-凝胶法制备了一系列富锂锰基正极材料xLi2MnO3?(1-x)LiNi0.5Mn0.5O2(x=0.1-0.8),通过X射线衍射(XRD)仪,扫描电子显微镜(SEM)和电化学测试等检测手段表征了所得样品的晶体结构与电化学性能,研究了不同组分下富锂材料的结构与电化学性能.结果表明:Li2MnO3组分含量较高时,材料的首次放电容量较高,但循环稳定性较差;该组分含量较少时,所得样品中出现尖晶石杂相,且放电容量较低,但循环稳定性较好;综合来看,x=0.5时材料的电化学性能最优.x=0.4,0.6时材料也表现出了较好的电化学性能,值得关注.     

Oxygen isotope exchange between the gas-phase and the electrochemical cell O<Subscript>2</Subscript>, Pt | YSZ | Pt,O<Subscript>2</Subscript> under conditions of applied potential difference

The kinetics of oxygen isotope exchange between gas-phase oxygen and the electrochemical cell O₂, Pt | ZrO₂ + 10 mol % Y₂O₃ (YSZ) | Pt, O₂ with applied potential difference (ΔU = ±1.2 V) is studied in the temperature range of 600–800°С and the oxygen pressure interval of 3–13 kPa. An original design of a vacuum electrochemical cell with the separated gas space is put forward for studying how the potential difference on the electrochemical cell influences the kinetics of interaction of gas-phase oxygen with the gas electrode O₂, Pt | YSZ in the electrochemical cell. It is shown that the oxygen interphase exchange rate is the higher the more negative the charge on the electrode studied; moreover, the mechanism of gas-phase oxygen exchange with the gas electrode O₂, Pt | YSZ in the electrochemical cell depends fundamentally on the electrode charge sign. The possible reasons for the revealed differences are discussed; the corresponding models are proposed.     

Facile Synthesis of Ultra‐wide Two Dimensional Bi2S3 Nanosheets: Characterizations,Properties and Applications in Hydrogen Peroxide Sensing and Hydrogen Storage

The ultra‐wide two dimensional Bi₂S₃ nanosheets (2D Bi₂S₃ Ns) as non‐toxic graphene‐like nanomaterials have been prepared through solvothermal decomposition of a single‐source precursor, Bi(S₂CNEt₂)₃, in ethylenediamine media for 2 h in 180 °C. The morphology, structure, properties and catalytic activity of prepared 2D Bi₂S₃ Ns were characterized with XRD, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), UV‐Visible spectroscopy, cyclic voltammetry (CV), amperometry, electrochemical charge/discharge technique and electrochemical impedance spectroscopy (EIS). The SEM image showed the 2D Bi₂S₃ Ns with a thickness of 15±4 nm and lengths of several micrometers is synthesized. The UV−Vis spectrum of 2D Bi₂S₃ Ns showed high sensitivity to visible‐near infrared light with its direct energy band gap of ≈1.22 eV. These Bi₂S₃ Ns showed high electron transfer ability and good electrochemical behavior and also exhibited electro‐catalytic activity toward the reduction‐oxidation of hydrogen peroxide. It is found that Bi₂S₃ Ns could detect H₂O₂ at wide linear concentration range (50.0 μM–8.0 mM) with detection limit 8 μM, using amperometry as measuring technique. Also the synthesized Bi₂S₃ Ns exhibited excellent electrochemical H₂ storage properties. As a result, based on above properties, the Bi₂S₃ Ns can be used as a valuable and useful nanomaterial for H₂ storage, high‐energy batteries, electrocatalytic fields and electrochemical sensing.     

Sensitive Electrochemical Detection of Pb(II) and H2O2 via a Dual-functional Sn-doped Defective Bi2S3 Microspheres

In this work, a dual-functional electrochemical sensor has been proposed based on Sn-doped defective Bi₂S₃ (TDDB) microspheres, which exhibited the excellent electrochemical performance on Pb(II) and H₂O₂ detection. The TDDB offered a satisfied detection limit of 8.0 nM towards Pb(II) with a sensitivity of 96.7 μA ⋅ μM⁻¹. As a H₂O₂ sensor, a high sensitivity of 3540 μA mM⁻¹ cm⁻² was obtained in a linear range from 0.45 mM to 10 mM with a detection limit of 10 nM. Moreover, the electrochemical detection of Pb(II) in Taihu Lake and H₂O₂ in human serum was achieved with high reliability and good recovery.     

Electrochemical properties of La0.8Sr0.2FeO3 − δ –La0.45Ce0.55O2 − δ composite cathodes for intermediate temperature SOFC

The electrochemical properties of La_0.8Sr_0.2FeO_3???δ (LSF)–La_0.45Ce_0.55O_2???δ (LDC) composite cathodes coated on LSGM electrolyte were studied by electrochemical impedance spectroscopy and cathodic polarization technique. Results showed that the composite cathodes possessed superior electrochemical performance compared to that of pure LSF cathode. The cathodic overpotential of Cathode C was only 100 mV at 0.3 A cm^?2, and the charge transfer resistance and the gas phase diffusion resistance were decreased to 0.105 Ω cm² and 0.257 Ω cm², respectively at 800 °C. The improvement of the electrochemical performance is contributed to the increase of the triple-phase boundary, enlargement of the effective area for electrode reaction, and increase of the porosity of the cathode by adding LDC to the cathode material.     

Review on electrochemical carbon dioxide capture and transformation with bipolar membranes

Anthropogenic carbon dioxide(CO₂ ) emission from the combustion of fossil fuels aggravates the global greenhouse effect. The implementation of CO₂ capture and transformation technologies have recently received great attention for providing a pathway in dealing with global climate change. Among these technologies, electrochemical CO₂ capture technology has attracted wide attention because of its environmental friendliness and flexible operating processes. Bipolar ...