In situ and operando electrochemistry of redox enzymes

Understanding the biocatalytic or the interfacial electron transfer processes of redox enzymes is decisive to develop high-performance biofuel cells, mimetic catalysts, bioelectrosynthesis reactors, biosensors, and bioelectronic devices. The state-of-art of redox enzyme electrochemistry lies in using in situ and operando instrumentation, in which protein electrochemistry is resourcefully coupled to or hyphenated with numerous analytical techniques. Nevertheless, there is still a lot to research about the manipulation of redox proteins in the unusual sample holding environments, and bioelectrodes engineering emerges as a key. Here, we discuss these challenges in detail, focusing on contemporary instrumentation setups.     

金-石墨烯修饰电极电化学检测塑料瓶中双酚A

在离子液体碳糊电极(CILE)表面上采用一步电还原法制备了纳米金(nAu)-石墨烯(GR)复合膜修饰电极(nAu-GR/CILE)。研究了双酚A(BPA)在nAu-GR/CILE上的电化学行为,BPA的电极反应过程为受吸附控制的不可逆过程;采用示差脉冲伏安法研究了BPA氧化峰电流和浓度之间的关系,在0.08~400.0μmol/L范围内,检出限为0.021μmol/L(3σ)。将nAu-GR/CILE用于塑料瓶中BPA的检测,与采用高效液相色谱法(HPLC)进行对比,结果表明两种方法对BPA的检测结果相吻合。     

Halogen-Bonding Strapped Porphyrin BODIPY Rotaxanes for Dual Optical and Electrochemical Anion Sensing

Anion receptors employing two distinct sensory mechanisms are rare. Herein, we report the first examples of halogen-bonding porphyrin BODIPY [2]rotaxanes capable of both fluorescent and redox electrochemical sensing of anions. ¹H NMR, UV/visible and electrochemical studies revealed rotaxane axle triazole group coordination to the zinc(II) metalloporphyrin-containing macrocycle component, serves to preorganise the rotaxane binding cavity and dramatically enhances anion binding affinities. Mechanically bonded, integrated-axle BODIPY and macrocycle strapped metalloporphyrin motifs enable the anion recognition event to be sensed by the significant quenching of the BODIPY fluorophore and cathodic perturbations of the metalloporphyrin P/P^+. redox couple.     

三维钴基MOF[KCo7(OH)3(ip)6(H2O)4]·12H2O作为超级电容器的高容量电极材料

为了开发较高能量密度的超级电容器,我们通过简单的溶剂热反应合成了一种三维的钴基金属有机框架(MOF)化合物([KCo7(OH)3(ip)6(H2O)4]·12H2O,Co?ip;ip=间苯二甲酸根),并考察了其作为超级电容器电极材料的性能。Co?ip电极显示出高比电容、良好的循环稳定性和优良的倍率性能。在1 mol·L^-1 KOH溶液中,电流密度为1 A·g^-1时,其最大比电容为1660 F·g^-1。在电流密度为2 A·g^-1条件下,循环3000次后,其比电容的保持率为82.7%。优异的超级电容性能可归因于Co?ip具有纳米尺寸颗粒和三维的多孔结构。     

服役温度对多壁碳纳米管/Li1.18Ni0.15Co0.15Mn0.52O2复合正极材料性能的影响

通过煅烧的方式制得多壁碳纳米管(MWCNT)质量分数为3%的MWCNT/Li1.18Ni0.15Co0.15Mn0.52O2锂离子电池复合正极材料,并测试了复合正极材料在不同服役温度环境下的电化学性能:-20和60℃下服役时,其放电容量分别高达169、303 mAh·g^-1,且展示出良好的倍率性能和循环稳定性。结合电化学阻抗测试结果可知,MWCNT均匀附着在层状粒子的表面,有效减少了电解液对电极材料的侵蚀,阻碍了表面膜的生成,同时提高了材料的电子电导率。     

BiVO4的添加对Nd0.2Ce0.8O1.9电解质微观结构和性能的影响

采用溶胶凝胶法制备BiVO₄（BV）和Nd_0.2Ce_0.8O_1.9（NDC）粉末,研究BV的加入对NDC电解质结构、形貌及电性能的影响。实验结果表明,NDC-5BV电解质的微观结构更致密,700℃时总电导率（σ_t）提高至3.35×10^-2 S·cm^-1,极化电阻（R_p）降低34%以上。单电池在700℃时的最大功率密度（MPD）为514 mW·cm^-2,开路电压（OCV）在70 h内可以保持良好的长期稳定性。     

氮掺杂碳原位锚定铜纳米颗粒用于高效氧还原反应催化剂

与贵金属铂基电化学氧还原反应（ORR）催化剂相比,廉价的非贵金属催化剂引起了广泛的关注。本文以壳聚糖作为一种富含氮和碳元素的生物质资源,利用碳浴法成功制备了氮掺杂碳原位负载铜纳米颗粒（Cu/N-C）催化剂。纯壳聚糖碳化得到的样品N-C的比表面积为67.5 m²·g^-1、平均孔径0.14 nm、平均孔体积8.00 m²·g^-1,与之相比,Cu/N-C比表面积可达607.3 m²·g^-1、平均孔径为2.5 nm、平均孔体积为0.40 cm³·g^-1。通过密度泛函理论（DFT）进行计算表明,Cu(111)/N-C的自由能值低于N-C,更有利于氧还原催化进行。在0.1 mol·L^-1 KOH的介质中,Cu/N-C不仅表现出优异的起始和半波电势（分别为0.96 V和0.84 V）,而且还表现出了优异的抗甲醇性能和稳定性,并且Cu元素掺杂量达到1.67wt.%。     

应用镍超微电极的电化学表面增强拉曼光谱技术研究

镍（Ni）电极在电化学中应用广泛。原位表征Ni电极表面的吸附物种有益于帮助理解电极反应历程、指导发展高效电催化剂。应用超微电极作为工作电极的电化学表面增强拉曼光谱技术结合了超微电极表面的传质特性和分子水平的高灵敏度表征,是研究Ni电化学的有力手段。本文所述的研究工作通过在金（Au）超微电极表面电吸附具有SERS活性的Au纳米粒子并恒电流沉积金属Ni薄层,制备并表征了具有SERS活性的Ni超微电极。在氢氧化钠溶液中的循环伏安实验和以4-甲基苯硫酚分子作为探针分子的SERS实验结果表明,沉积速率和沉积电量是影响超微电极表面Ni的覆盖度和SERS活性的关键因素。在吸附了直径为55 nm Au纳米粒子的、直径为10 μm Au的超微电极表面,以100 μA·cm^-2电流密度电沉积厚度约为5个原子层Ni的条件下,可获得Ni覆盖完好的、具有最强SERS活性的Ni超微电极。     

Development of Pen-type Portable Electrochemical Sensor Based on Au-W Bimetallic Nanoparticles Decorated Graphene-chitosan Nanocomposite Film for the Detection of Nitrite in Water,Milk and Fruit Juices

The development and fabrication of a simple, portable, and sensitive detection tool to precisely monitor nitrite level is of growing importance in electrochemistry research, given the strong interest in the protection of drinking water quality, treatment of wastewater, food production, and control of remediation processes. This work describes the fabrication of a simple, cost-effective, pen-type electrochemical sensor based on bimetallic gold and tungsten nanoparticles electrochemically decorated on graphene-chitosan modified pencil graphite electrode (PGE) for the trace detection of nitrite in real samples. The prepared nanocomposite was characterized using XRD, SEM, and EDS. The electrochemical behavior of the sensor was evaluated by cyclic voltammetry (CV) and impedance electrochemical spectroscopy (EIS). Results revealed that the proposed sensor displayed excellent electrocatalytic activity towards electro-oxidation of nitrite with an irreversible redox reaction. The AuNPs-WNPs@Gr-Chi/PGE sensor exhibited excellent analytical performance with a wide linear range from 10 to 250 μM towards nitrite. The LOD and LOQ were calculated to be 0.12 μM and 0.44 μM, respectively. The designed electrochemical sensor was successfully applied for the detection of nitrite in water, milk, and natural fruit juice samples.     

Urea Detection of Electrochemical Transistor Sensors based on Polyanline (PANI)/MWCNT/Cotton Yarns

A cotton yarn biosensor based on electrochemical transistor functionalized with MWCNT and PANI was developed for the detection of urea. The transistors based on PANI/MWCNT/cotton yarns under optimized MWCNT concentration has been obtained, which exhibited high on/off current ratio, fast response time, and good operational stability. A transistor-based urea sensor was prepared from PANI/MWCNT/cotton yarns, which could monitor urea in the 1 nM–1 mM linear range with the correlation coefficient of 0.9716. Furthermore, the sensor showed superior reproducibility and high specificity. The practical applications of the proposed sensor were also confirmed. These results indicate the flexible transistor can be used as an efficient platform for biological detection in body fluids.