Hollow polyhedron structure of amorphous Ni-Co-S/Co(OH)_2 for high performance supercapacitors

In power storage technology,ion exchange is widely used to modify the electronic structures of electrode materials to stimulate their electrochemical properties.Here,we proposed a multistep ion exchange(cation exchange and anion exchange) strategy to synthesize amorphous Ni-Co-S and β-Co(OH)_2 hybrid nanomaterials with a hollow polyhedron structures.The synergistic effects of different components and the remarkable superiorities of hollow structure endow Ni-Co-S/Co(OH)_2 electrode with outstanding electrochemical performance,including ultra-high specific capacity(1440.0 C/g at 1 A/g),superior capacitance retention rate(79.1% retention at 20 A/g) and long operating lifespan(81.4% retention after5000 cycles).Moreover,the corresponding hybrid supercapacitor enjoys a high energy density of 58.4 Wh/kg at the power density of 0.8 kW/kg,and a decent cyclability that the capacitances are maintained at80.8% compared with the initial capacitance.This research presents a high-performance electrode material and provides a promising route for the construction of electrode materials for supercapacitors with both structural and component advantages.     

Synthesis and Characterization of Flexible Hydrogel Electrodes for Electrochemical Impedance Measurements of Protective Coatings on Metal Sculptures

A novel conductive anionic hydrogel was synthesized for use as a solid electrolyte for electrochemical impedance spectroscopy (EIS) characterization of the barrier properties of protective coatings on outdoor metalworks, such as bronze sculptures. The AMPS‐co‐PAA hydrogel was soaked in a variety of aqueous salt solutions and characterized by swelling capacity and conductivity in order to determine the most appropriate gel/liquid electrolyte combination for use on culturally significant objects. K₂PIPES‐equilibrated hydrogels were selected as the preferred electrodes for this particular application and were used to measure the impedance of a coated substrate, yielding spectra similar to those from standard liquid cells.     

On a new FeOF polymorph: Synthesis and stability

A new polymorph of FeOF (up to now only known in its rutile type structure) was prepared by using a new synthesis approach formally based on anionic exchange using the well-known layered FeOCl as precursor. The synthesis was achieved using [CH₃C(CH₂O–)₂(COO–)B] to vehicle fluorine through the formation of soluble (CH₃)₄N⁺ [CH₃C(CH₂O–)₂(COO–)BF]⁻ and using N,N-dimethylformamide (DMF) as the reacting medium. The XRD pattern of layered FeOF can be indexed with an orthorhombic cell which doubles along the b axis (which is the direction perpendicular to the layers) with respect to that of pristine FeOCl (a = 3.792(1) Å, b = 12.699(1) Å, c = 3.321(1) Å). Both thermal analysis and diffraction indicate similar stability for the layered and rutile polymorphs. Such findings are rationalized through Density Functional Theory calculations. It is found that the energy difference between the more stable rutile and layered polymorphs is practically nul. The origin of the similar stability lies in the fact that although the number of Fe–F and Fe–O bonds is different in the two structures, the strength of both the total number of Fe–O as well as Fe–F bonds are found to be almost identical. Even if the crystal and electronic structures are considerably different, the total bonding and thus, the stability of the two polymorphs, is comparable. The stability of different FeOF rutile type structures is also analyzed.     

Simultaneous determination of peroxydisulfate and conventional inorganic anions by ion chromatography with the column‐switching technique

The application of ion chromatography with the column‐switching technique for the simultaneous analysis of peroxydisulfate and conventional inorganic anions in a single run is described. With this method, conventional inorganic anions were separated by consecutive elution through both the guard column and separation column, but peroxydisulfate that only passed through the guard column had a good peak shape and short retention time. A series of standard solutions consisting of target anions of various concentrations from 0.01 to 75 mg/L were analyzed, with a correlation coefficient (r) ≥ 0.9990. The limits of detection were in the range of 0.49–9.84 μg/L based on the S/N of 3 and a 25 μL injection volume. RSDs for retention time, peak area, and peak height were all <1.77%. A spiking study was performed with satisfactory recoveries between 97.6 and 103.4% for all anions. The quantitative determination of peroxydisulfate and conventional inorganic anions in surface waters was accomplished within 18 min by this column‐switching technique.     

Characterization of sequence variation at 30 autosomal STRs in Chinese Han and Tibetan populations

Massively parallel sequencing (MPS) technologies have the ability to reveal sequence variations within STR alleles as well as their nominal allele lengths, which have traditionally been detected by CE instruments. Recently, Thermo Fisher Scientific has updated the MPS-STR panel, named the Precision ID GlobalFiler next-generation sequencing (NGS) STR Panel version 2, with primers redesigned to add two pentanucleotide tandem repeat loci and profile interpretation supported by the Converge software. Using the Ion Chef System, the Ion S5XL System, and the Converge software, genetic variations were characterized within STR repeat and flanking regions of 30 autosomal STR markers in 115 unrelated individuals from two Chinese population groups (58 Tibetans and 57 Hans). Nineteen STRs demonstrated a relative increase in diversity with the variant sequence alleles compared with those of traditional nominal length alleles. In total, 390 alleles were identified by their sequences compared with 258 alleles that were identified by length. Of these 92 sequence variants found within the STR repeat regions, 40 variants were located in STR flanking regions. Additionally, the agreement of the results with CE data was evaluated, as was the ability of this new MPS panel to analyze case-type (11 samples) and artificially degraded samples (seven samples in triplicate). The results generated from this study illustrate that extensive sequence variation exists in commonly used STR markers in the selected population samples and indicate that this NGS STR panel has the potential to be used as an effective tool for human forensics.     

烯醇-酮互变异构型亚胺衍生物对Co2+的高选择性识别

设计合成了新型烯醇-酮互变异构型亚胺衍生物R, 考察了受体R对18种阳离子的紫外光谱及裸眼识别性能. 结果表明, 该受体对Co²⁺, Fe²⁺和Ni²⁺表现出良好的紫外光谱识别能力, 且可实现对Co²⁺相对明显的裸眼单一识别. Job曲线表明, 受体R与Co²⁺形成了1:1型金属配合物, 且检出限可达4.14×10^-7 mol/L. 制备了受体R裸眼比色识别试纸; 根据理论计算及核磁滴定实验结果阐述了Co²⁺离子识别过程中烯醇-酮互变异构机理.     

Polyanionic Frameworks in the Lithium Phosphidogermanates Li2GeP2 and LiGe3P3 – Synthesis,Structure, and Lithium Ion Mobility

Recently fast lithium ion conductors were discovered in compounds containing tetrahedral SiP₄^8– and GeP₄^8– units. In the context of material development for all solid state batteries the ternary Li/Ge/P phase system has been further investigated and two new lithium phosphidogermanates were discovered on the lithium poor side of the ternary composition diagram. Li₂GeP₂ crystallizes in space group I4₁/acd with unit cell parameters of a = 12.3069(1) Å and c = 19.0306(4) Å, consists of a framework of Ge₄P₁₀ supratetrahedra, and exhibits an ionic conductivity of 1.5(3)×10^–7 S · cm^–1 at 27 °C. LiGe₃P₃ crystallizes in Pbam with a = 9.8459(5) Å, b = 15.7489(7) Å, and c = 3.5995(2) Å. In LiGe₃P₃ Ge and P atoms form a two dimensional polyanion. The slabs consist of five- and six-membered heteroatomic rings comprising GeP₄ and Ge(P₃Ge) tetrahedra including homoatomic Ge–Ge bonds. A semiconducting behavior with an electronic conductivity of ∼10^–4 S · cm^–1 and a remarkable stability vs. air and moisture is observed.     

具有抗生物污染活性的分子筛膜用于高效油水分离

The development of the global economy has been accompanied by frequent oil spills caused by accidental leaks and industrial manufacturing, which have seriously threatened the aquatic environment and human health. Traditional methods for the treatment of oily wastewater include centrifugation, skimming, flotation, oil-absorbing technology, etc., which are limited by low separation efficiency as well as secondary pollution during the post-processing of oil absorption materials. Recently, separation technologies utilizing the special wettabilities of filtration membranes have been developed to enrich and recycle oils from wastewater. Among these, the fabrication of superhydrophilic/underwater superhydrophobic membranes have attracted intensive research interest, which can selectively allow the passage of water through the membrane while blocking the oils. However, microorganisms are more likely to breed on these hydrophilic surfaces, eventually leading to the blockage of the membranes. In this study, ZSM-5 zeolite crystals (MFI topological structure) were coated onto the stainless-steel meshes by means of seeding and secondary hydrothermal growth. Then, 70% of the total Na⁺ ions in the zeolite channels were substituted by Ag⁺ ions via an ion exchange process. The resultant membranes (Ag@ZCMFs) were superamphiphilic in air, with both water contact angle and oil contact angle of approximately 0°. However, they became superoleophobic when immersed in water, and the underwater oil contact angle reached 151.27° ± 4.34°. In terms of special wettability, Ag@ZCMF achieved efficient separation for various oil-water mixtures with separation efficiencies above 99%. The water flux and intrusion pressure of Ag@ZCMF depended on the diameter of pinholes in the membrane, which could be modulated by altering the time of secondary hydrothermal growth. For instance, the average diameter of pinholes in Ag@ZCMF with optimum secondary growth time of 14 h (Ag@ZCMF-14) reached approximately 21 μm, giving rise to the water flux and intrusion pressure of 54720 L·m^-2·h^-1 and 4357 Pa, respectively. The anti-corrosion test and rubbing test confirmed the high chemical and mechanical stability of Ag@ZCMF-14, respectively. The separation efficiency of Ag@ZCMF-14 remained stable during ten purification-regeneration cycles, and no obvious attenuation was observed, proving the high separation stability of Ag@ZCMF-14. Furthermore, the loaded Ag⁺ ions afforded the membrane excellent anti-biofouling activity, which could effectively inhibit the growth of both alga and bacteria in the operating environment, thus preventing membrane blockage during the oil-water separation process. In particular, the bacteriostatic rate of Ag@ZCMF-14 to Escherichia coli reached to 99.6%. These results demonstrate that Ag@ZCMFs with anti-biofouling activity has promising potential future applications in the removal of oil slicks from oily wastewater.     

基于FeWOx/SiO2载氧体的甲烷化学链部分氧化反应

甲烷具有价格低廉且储量丰富的优点,因此将甲烷转化为合成气(一种H2:CO为2的混合物),从而进一步合成有价值的化学品和液体燃料引起了人们的极大关注.化学链甲烷部分氧化(CLPOM)技术能避免甲烷与空气直接接触而引起爆炸的危险,可以降低后续对合成气与氮气分离操作所带来的费用,因此日益受到关注.CLOPM过程主要分为两步:第一步,CH4被载氧体所携带的氧部分氧化,载氧体被还原;第二步,利用氧化剂(例如空气)将被还原的载氧体再氧化恢复.因此,载氧体在CLOPM过程中起到至关重要的作用.载氧体的选择主要存在两个问题:(1)甲烷被活化所产生含碳产物的能力与晶格氧的给氧能力不匹配所带来的严重碳沉积;(2)金属离子间扩散速率不匹配而造成载氧体在氧化还原过程中结构的不可逆变化.基于上述两个问题,本文设计了FeWOx/SiO2载氧体用于CLPOM.与未改性的WO3/SiO2载氧体相比,甲烷的转化率和合成气的收率都有显著提高.FeWOx/SiO2在900℃、1 atm反应条件下表现出62%的甲烷转化率、93%的CO气相选择性、94%的H2选择性和2.4的H2/CO比值,同时在50个循环中表现出优异的催化活性和稳定性.本工作利用CH4脉冲反应研究了FeWOx/SiO2的甲烷表面反应过程;采用CH4-TPR和H2-TPR相结合探究了甲烷活化速率与晶格氧扩散速率之间的关系;通过XPS和XRD对FeWOx/SiO2在氧化还原过程中的结构稳定性进行了探讨.综合上述实验结果,对FeWOx/SiO2应用于CLPOM的反应机理进行了阐述.H2-TPR结果表明,在FeWOx/SiO2中,相较于Fe2O3/SiO2,Fe-O的活性受到抑制,使其更倾向于与甲烷发生部分氧化反应;相较于WO3/SiO2,W-O的活性得到明显提升,因此更多的晶格氧可以参与到部分氧化反应中来氧化积碳,从而使合成气收率大幅度提升.从CH4-TPR结果可以看出,对于FeWOx/SiO2,CO与H2的生成温度最接近,意味着晶格氧的传输速率较快并且能够与甲烷活化产生含碳中间物种的速率相匹配,将其及时氧化生成CO,避免由于积碳造成的催化剂失活.结合XPS和XRD结果可以得出,在甲烷还原过程中,FeWOx经历一步还原形成Fe-W合金,由于其间存在强相互作用,因而抑制了还原过程中催化剂相分离现象的发生.同时,根据铁钨离子在空气条件下扩散速率的公式计算可以得出,其相近的离子氧化速率也保证了在氧化过程中催化剂结构的稳定性.本工作为进一步构建用于甲烷化学链部分氧化制合成气的复合金属氧化物载氧体提供了研究思路.     

Thermodynamics,a suitable reporter in the design of mercury (II) ion selective electrodes

A fully functionalised calix[4]pyrrole derivative, namely, meso-tetramethyl-tetrakis[(diethylthiocarbamoyl)phenoxy] calix[4]-pyrrole, 1 has been synthesised and structurally characterised. Its complexing properties with metal cations in acetonitrile were investigated with particular emphasis on the thermodynamics of these systems. These data and those previously reported for a partially functionalised calix[4]arene based receptor, 5,11,17,23-tetra-tert-butyl[25,27 bis(diethylthiocarbamoyl)oxy]calix[4]arene, 2 were used to, i) further corroborate their use to predict the selectivity coefficients of carrier mediated mercury (II) ion selective electrodes (ISEs) and ii) to obtain approximate stability constant data from selectivity coefficients. The optimum working conditions of both electrodes were determined. It is shown that while the ISE based on 1 is characterised by a wider linear range and a lower mercury (II) detection than the one based on 2, the latter has the advantage of lower interference of other metal cations due to the much lower stability constants of bivalent cations relative to Hg(II). The response characteristics of these electrodes are compared with those found in the literature. SEM micrographs along with EDX spectra of the PVC membranes containing ionophore 1 or 2 unloaded and loaded with Hg(II) are reported.