Fast Li-ion Storage and Dynamics in TiO2 Nanoparticle Clusters Probed by Smart Scanning Electrochemical Cell Microscopy

Anatase TiO₂ is a promising material for Li-ion (Li⁺) batteries with fast charging capability. However, Li⁺ (de)intercalation dynamics in TiO₂ remain elusive and reported diffusivities span many orders of magnitude. Here, we develop a smart protocol for scanning electrochemical cell microscopy (SECCM) with in situ optical microscopy (OM) to enable the high-throughput charge/discharge analysis of single TiO₂ nanoparticle clusters. Directly probing active nanoparticles revealed that TiO₂ with a size of ≈50 nm can store over 30 % of the theoretical capacity at an extremely fast charge/discharge rate of ≈100 C. This finding of fast Li⁺ storage in TiO₂ particles strengthens its potential for fast-charging batteries. More generally, smart SECCM-OM should find wide applications for high-throughput electrochemical screening of nanostructured materials.     

Electrode-Potential-Driven Dissociation of N-Heterocycle/BF3 Adducts: A Possible Manifestation of the Electro-Inductive Effect

Recently, non-Faradaic effects were used to modify the electronic structure and reactivity of electrode-bound species. We hypothesize that these electrostatic perturbations could influence the chemical reactivity of electrolyte species near an electrode in the absence of Faradaic electron transfer. A prime example of non-Faradaic effects is acid-base dissociation near an interface. Here, we probed the near-electrode dissociation of N-heterocycle-BF₃ Lewis adducts upon electrode polarization, well outside of the redox potential window of the adducts. Using scanning electrochemical microscopy and confocal fluorescence spectroscopy, we detected a potential-dependent depletion of the adduct near the electrode. We propose an electro-inductive effect where a more positive potential leads to electron withdrawal on the N-heterocycle. This study takes a step forward in the use of electrostatics at electrochemical interfaces for field-driven electrocatalytic and electro-synthetic processes.     

表面应力效应调控钯纳米晶二氧化碳电催化还原性能

<正>目前,与人们日常生活密切相关的液体燃料、化学品、电和热等主要依赖石油、煤和天然气等化石能源经过工业炼制或高效燃烧等过程转化。在转化过程中二氧化碳的大量排放对人们赖以生存的生态环境造成了严重威胁。电催化还原二氧化碳提供了一条将作为排放物的CO_2高效转变为高值化学品新途径~1。简单地说,利用可再生电     

Comparative Permeation Study of Different Types of Myoglobin Layer‐by‐Layer Films and the Effect of Film Permeability on Their Electrochemistry and Electrocatalysis

Three different types of myoglobin (Mb) layer‐by‐layer films were assembled respectively with TiO₂ sol‐gel by vapor‐surface deposition, TiO₂ nanoparticles, and poly(styrenesulfonate), designated as {SG‐TiO₂/Mb}_n, {NP‐TiO₂/Mb}_n, and {PSS/Mb}_n. The permeability of the films was studied and compared by rotating disk voltammetry (RDV) and electrochemical impedance spectroscopy (EIS) with different electroactive probes, showing a general permeability sequence of {SG‐TiO₂/Mb}_n>{NP‐TiO₂/Mb}_n>{PSS/Mb}_n. The electrochemical and electrocatalytic activity of Mb in these films were also investigated and compared by cyclic voltammetry (CV), RDV, and amperometry, indicating that among the three Mb films, {SG‐TiO₂/Mb}_n films demonstrated the highest maximum surface concentration of electroactive Mb and the best electrocatalytic performances toward reduction of H₂O₂. All these advantages could be attributed to the unique architecture and porous structure of {SG‐TiO₂/Mb}_n films, which could greatly facilitate the mass transport of small counterions and catalytic substrates within the films. The various influencing factors on the permeability, electrochemistry, and electrocatalysis of the Mb films were also investigated in detail.     

单粒子表面增强拉曼光谱的二维成像研究

以单个椭球形Fe₂O₃@Au核壳粒子作为SERS活性基底, 苯硫酚(TP)作为探针分子, 研究了椭球形粒子表面SERS效应的分布, 对比了粒子尖端以及中间SERS效应的差别. 为了得到单个粒子表面不同部分对SERS强度的贡献差别, 通过数学模拟和解析了探针分子SERS的二维成像(2D-mapping)信号, 获得了粒子边缘不同点的SERS效应. 模拟分析结果表明, 当xy平面内粒子在垂直入射(z轴)平面波作用下, 单个椭球形Fe₂O₃@Au核壳粒子表面单位面积上的SERS强度相差极大, 粒子长轴方向端点附近单位面积上的SERS效应最大, 而其它表面部分较弱, 其中与短轴平行方向的表面附近为最弱, 差异可达到约2~3个数量级. 若考虑SERS增强主要为电磁场增强的尖端效应, 则单个椭球形粒子尖端的局域感应电磁场为垂直方向的5倍.     

Single nucleotide polymorphism detection in the hMSH2 gene using conformation-sensitive CE

CE allows for highly reproducible analysis of DNA fragments which can be used to detect DNA mutations including SNPs. We have utilized a simple and direct CE analysis method for SNP analysis called conformation-sensitive CE (CSCE), based on the principle of single nucleotide different to produce conformational changes in the mildly denaturing solvent system. This method was applied to analysis of a mutation in the promoter region of the hMSH2 gene. This gene belongs to the human DNA mismatch repair system, which is responsible for recognizing and repairing mispaired nucleotides, and mutations in the hMSH2 gene are known to cause hereditary nonpolyposis colorectal cancer (HNPCC). PCR fragments generated from the promoter region of the hMSH2 gene, displaying either a C/C homozygote, C/T heterozygote, or T/T homozygote genotype, did not require further pretreatment before electrokinetic injection. The CE separation, using a 1xTris-borate-EDTA (TBE) buffer containing 3% w/v hydroxylethyl cellulose (HEC) and 6 M urea, was performed under reverse polarity with a separation temperature of 15 degrees C. The genotypes of 204 healthy volunteers and 13 colorectal cancer patients were determined using CSCE, and the results confirmed by DNA sequencing. While the CSCE separations were shown to be highly reproducible and sensitive for screening large populations, no correlation was observed between cancer patients and this hMSH2 gene polymorphism.     

Strain hardening test on the limits of Slow Crack Growth evaluation in high resistance polyethylene resins: Effect of comonomer type

Long term performance assessment of polyethylene pipes is an issue that has greatly increased in importance in recent years due to the incorporation in the market of high resistance to crack polyethylene grades (PE100RC), where established Slow Crack Growth (SCG) evaluation using traditional tests such as Full Notch Creep Test (FNCT) or Pennsylvania Notch Tensile (PENT) Test is insufficient. The development in recent years of fast evaluation techniques such as Strain Hardening (SH) modulus has opened an important alternative for quick SCG evaluation since it correlates well with other conventional tests such as FNCT and PENT. In this work, a large number of commercial and experimental polyethylene pipe resins with different comonomer types were evaluated in order to define their SH values to rank the resins as PE100 or PE100RC. A relationship is proposed that utilizes SH test results to estimate the SCG resistance of PE pipes. 1-Butene copolymer resins display threshold SH values of 38 and 53 MPa that have been assigned to PE100 and 100RC grades, respectively. Moreover, dependence of the SH values on comonomer type used has been demonstrated. The experimental results show that 1-hexene copolymer resins exhibit higher SH values than 1-butene comonomer based resins.