The reduction/oxidation behaviour of MnAPO-5 as studied by ESR spectroscopy

It is shown by ESR spectroscopy that Mn²⁺ ions in MnAPO-5 are oxidized to Mn³⁺ during calcination atT475 K. Mn²⁺ occupies variously distorted tetrahedral positions within the framework and in extra-lattice sites. Octahedrally coordinated Mn²⁺ presumably located in the channels becomes detectable after adsorption of water. The ESR spectra of reduced MnAPO-5 show line-narrowing due to spin exchange interactions. The material behaves reversible in redox cycles at temperatures near 500 K.     

镁质低品位铁镍硫化矿的活化工艺及机理

细菌浸出是镁质低品位铁镍硫化矿的潜在处理方案之一。针对该矿石浸出活性较低的问题,研究了硫酸预浸出和硫酸铵焙烧预浸出2种活化方案,并与细菌直接浸出(空白试验)做了比较。结果表明,2种活化方案都有利于金属回收,但硫酸铵焙烧预浸出方案的活化效果更优:浸出时间为8 d时,Ni、Cu和Mg的浸出率分别为90.2%、89.56%和61.19%,分别高于硫酸预浸出方案2.08%、12.2%和8.95%。矿石中的Mg主要在硫酸铵焙烧预浸出阶段进入溶液,细菌对Mg浸出的影响不大。XRD和能谱分析表明:浸出渣中Ni和Cu的残留量很低,Mg主要存在于难浸出的蛇纹石之中。     

Electrochemical and microstructural characterization of cyclic redox behaviour of SOFC anodes

The oxidation of Ni to NiO in solid oxide fuel cell (SOFC) anode will result in large bulk volume change, which may change the interfaces of the two phases in the anode cermet and thus may cause significant performance degradation. The reduction and oxidation (redox) of the Ni/YSZ cermet were studied at 800 ℃. Anodic polarization measurements were performed before and after redox cycles. The anode current density at an overpotential of 100 mV kept decreasing during the whole redox treatment. It decreased from 19.11 to 7.95 mA·cm-2 after two redox cycles. Anode supported unit cell was assembled for cell's discharge measurements. Cell performance declined after each redox cycle. The maximum power density decreased from 126.28 to 40.32 mW·cm-2 . The microstructural changes after redox cycling were recorded using scanning electron microscopy (SEM). The results reveal that after re-oxidation, the Ni gets coarse and has a higher porosity; the nickel network structure turns to be desultory.     

Characteristics of graphite felt electrode electrochemically oxidized for vanadium redox battery application

The graphite felt was oxidized at a positive electrode potential in sulfuric acid solution.The electrochemical performance of the treated graphite felt served as electrode for vanadium redox battery was investigated with FT-IR,SEM,XPS,BET,cyclic voltammetry and testing VRB system,respectively.The results show that the molar ratio of O to C increases from 0.085 to 0.15 due to the increase of—COOH functional groups during electrochemical oxidation treatment,and the GF surface is eroded by electrochemical oxidation,resulting in the surface area increase from 0.33 m2/g to 0.49 m 2/g.The VRB with modified GF electrode exhibits excellent performance under a current density of 30 mA/cm 2 .The average current efficiency reaches 94%and average voltage efficiency reaches 85%.The improvement of electrochemical activity for the electrode is ascribed to the increase of the number of—COOH group and the special surface of GF.     

用于无创检测皮下葡萄糖的新型生物传感器研究

以无创检测人体血糖为应用需求,采用高灵敏度锇氧化还原聚合物修饰在薄膜电极上,并通过戊二醛交联法固定酶分子制备成新型生物传感器。实验结果表明:在0~700μmol/L的葡萄糖标准浓度范围内,传感器灵敏度为23.955 nA/(μmol.L-1),最低检测限为0.3μmol/L,相关系数为0.999;在标准皮下葡萄糖浓度0~19mmol/L浓度范围内,被抽取出的葡萄糖电流响应值与皮下葡萄糖的浓度成线性关系,线性相关系数为0.994,灵敏度为4.03 nA/(mmol.L-1);单只传感器对100μmol/L葡萄糖检测的精度为4.07%(n=10),不同传感器之间对100μmol/L葡萄糖测量的精度为3.22%(n=10),在4℃条件下,传感器的寿命可达450 d。     

Recovery of chromium from tannery effluents using a redox–adsorption approach

Adsorption isotherms for sodium and trivalent chromium uptake from aqueous solutions onto Amberlite resin were prepared at 18°C. Adsorption of each cation followed the Langmuir model. The rate of uptake of each cation was found to be film diffusion controlled with sodium showing the most rapid uptake. In aqueous solutions containing both chromium and sodium as the only cationic species, it was found that with increasing initial concentration of sodium, the trivalent chromium uptake on the resin decreased substantially. To overcome this difficulty a four step redox–adsorption system has been developed for the removal of Cr³⁺ from tannery effluents. The first step comprises the oxidation of trivalent chromium to the hexavalent form using selected common oxidising agents. The liquid effluent is then passed through an Amberlite cation-exchange resin in step 2 where the sodium in the waste stream is completely removed. The anionic hexavalent form of chromium (Cr₂O) passes unaltered through the resin along with the waste stream. In the third stage the dichromate is reduced back to the trivalent cationic form which is subsequently removed from the waste stream by a second Amberlite ion-exchange bed in stage 4. Each step in this process is assessed in batch and flow mode using simulated and real tannery effluents.     

Engineering Transition Metal Layers for Long Lasting Anionic Redox in Layered Sodium Manganese Oxide

Oxygen-redox-based-layered cathode materials are of great importance in realizing high-energy-density sodium-ion batteries (SIBs) that can satisfy the demands of next-generation energy storage technologies. However, Mn-based-layered materials (P2-type Na-poor Na_y[A_xMn_1−x]O₂, where A = alkali ions) still suffer from poor reversibility during oxygen-redox reactions and low conductivity. In this work, the dual Li and Co replacement is investigated in P2-type-layered Na_xMnO₂. Experimentally and theoretically, it is demonstrated that the efficacy of the dual Li and Co replacement in Na_0.6[Li_0.15Co_0.15Mn_0.7]O₂ is that it improves the structural and cycling stability despite the reversible Li migration from the transition metal layer during de-/sodiation. Operando X-ray diffraction and ex situ neutron diffraction analysis prove that the material maintains a P2-type structure during the entire range of Na⁺ extraction and insertion with a small volume change of ≈4.3%. In Na_0.6[Li_0.15Co_0.15Mn_0.7]O₂, the reversible electrochemical activity of Co³⁺/Co⁴⁺, Mn³⁺/Mn⁴⁺, and O^2-/(O₂)^n- redox is identified as a reliable mechanism for the remarkable stable electrochemical performance. From a broader perspective, this study highlights a possible design roadmap for developing cathode materials with optimized cationic and anionic activities and excellent structural stabilities for SIBs.     

Local Electronic Structure Modulation Enables Fast-Charging Capability for Li-Rich Mn-Based Oxides Cathodes With Reversible Anionic Redox Activity

Anionic and cationic redox chemistries boost ultrahigh specific capacities of Li-rich Mn-based oxides cathodes (LRMO). However, irreversible oxygen evolution and sluggish kinetics result in continuous capacity decay and poor rate performance, restricting the commercial fast-charging cathodes application for lithium ion batteries. Herein, the local electronic structure of LRMO is appropriately modulated to alleviate oxygen release, enhance anionic redox reversibility, and facilitate Li⁺ diffusion via facile surface defect engineering. Concretely, oxygen vacancies integrated on the surface of LRMO reduce the density of states of O 2p band and trigger much delocalized electrons to distribute around the transition metal, resulting in less oxygen release, enhancing reversible anionic redox and the MnO₆ octahedral distortion. Besides, partially reduced Mn and lattice vacancies synchronously stimulate the electrochemical activity and boost the electronic conductivity, Li⁺ diffusion rate, and fast charge transfer. Therefore, the modified LRMO exhibits enhanced cyclic stability and fast-charging capability: a high discharging capacity of 212.6 mAh·g⁻¹ with 86.98% capacity retention after 100 cycles at 1 C is obtained and to charge to its 80%, SOC is shortened to 9.4 min at 5 C charging rate. This work will draw attention to boosting the fast-charging capability of LRMO via the local electronic structure modulation.     

In Situ Deformation Topology of COFs with Shortened Channels and High Redox Properties for Li–S Batteries

Covalent organic frameworks (COFs) with various topologies are typically synthesized by selecting and designing connecting units with rich shapes. However, this process is time-consuming and labour-intensive. Besides, the tight stacking of COFs layers greatly restrict their structural advantages. It is crucial to effectively exploit the high porosity and active sites of COFs by topological design. Herein, for the first time, inducing in situ topological changes in sub-chemometric COFs by adding graphene oxide (GO) without replacing the monomer, is proposed. Surprisingly, GO can slow down the intermolecular stacking and induce rearrangement of COFs nanosheets. The channels of D- [4+3] COFs are significantly altered while the stacking of periodically expanded framework is weakened. This not only maximizes the exposure of pore area and polar groups, but also shortens the channels and increases the redox activity, which enables high loading while enhancing host-guest interactions. This topological transformation to exhibit the structural features of COFs for efficient application is an innovative molecular design strategy.     

High-rate Decoupled Water Electrolysis System Integrated with α-MoO3 as a Redox Mediator with Fast Anhydrous Proton Kinetics

Hydrogen is a promising alternative to fossil fuels that can reduce greenhouse gas emissions. Decoupled water electrolysis system using a reversible proton storage redox mediator, where the oxygen evolution reaction and hydrogen evolution reaction are separated in time and space, is an effective approach to producing hydrogen gas with high purity, high flexibility, and low cost. To realize fast hydrogen production in such a system, a redox mediator capable of releasing protons rapidly is required. Herein, α-MoO₃, with an ultrafast proton transfer property that can be explained by a dense hydrogen bond network in the lattice oxygen arrays of HxMoO₃, is examined as a high-rate redox mediator for fast hydrogen production in acidic electrolytes. The α-MoO₃ redox mediator shows both a large capacity of 204 mAh g⁻¹ and fast hydrogen production at a current rate of 10 A cm⁻²(≈153 A g⁻¹), outperforming most of the previously reported solid-state redox mediators.