石墨烯复合功能材料及其在重金属离子检测的电化学研究与应用

石墨烯(GR)是典型的单原子碳纳米材料,具有独特的二维共辄平面结构,其高活性的比表面积和突出的导电性能,在电催化和敏感材料制备领域已得到广泛的应用。氧化石墨烯(GO)作为GR的前驱体,存在大量的含氧官能团,具有良好的水溶分散性。大量GO含氧官能团的介入会破坏其K-7T共辘结构,导致其电学性能变差。GO通过化学、水热合成或直接电化学还原方法可有效修复其共辄平面结构,得到导电性良好的还原氧化石墨烯(rGO),即GR.单组分的GR材料在实际应用中仍存在某些局限性,如电学活性相对较弱,与其它材料加工复合性能较差等。将GR、G O材料与其它功能材料进行复合,可进一步改善复合物的物理或化学性能,如分散性、加工修饰和电催化活性等。综述了石墨烯材料与金属及其氧化物纳米粒子、聚合物、掺杂原子、导电离子液体、碳纳米材料等功能材料复合后,能形成可调控的微结构,具有改性的化学性质和协同发挥的电学效应,表现出显著的电子传递能力及其功能性作用。论述了GR功能化修饰的复合材料作为敏感界面,构筑基于重金属离子检测的电化学生物传感器,可以实现对Pb2+,Hg2+,C『+等多种重金属离子的同时或分别检出,提出了GR复合制备材料的纳米结构特征、功能修饰作用对于提高传感器的电催化活性和选择性性能等方面的应用,并对该研究领域进行了总结与展望。     

300M超高强钢在中性盐雾环境中的腐蚀行为及机制

摘要：为了研究300M超高强钢在中性盐雾环境中的腐蚀行为及腐蚀机制，采用失重法，宏观、微观腐蚀形貌分析，三维表面轮廓分析及电化学分析的研究方法，来表征腐蚀实验现象并进行分析。结果表明：300M超高强钢在中性盐雾环境中的腐蚀产物为FeOOH、Fe2O3、Fe(OH)3和Fe3O4；腐蚀速率随着腐蚀时间逐渐降低，腐蚀后期（72h）腐蚀速率降低50%；腐蚀初期以点蚀为主，点蚀坑通过横向扩展，逐渐发展为后期的均匀腐蚀，腐蚀表面形貌呈沟壑状；外腐蚀层对基体的保护能力很弱，Cr元素在锈层靠近基体的一侧偏聚使内腐蚀层具有一定的抗腐蚀性。     

Estimates of pollutant temporal and spatial variability in commercial buildings from the joint urban 2003 field experiments

In this paper, we report on the indoor concentrations from a suite of full-scale outdoor tracer-gas point releases conducted in the downtown area of Oklahoma City in 2003. A point release experiment consisted of releases of sulfur hexafluoride (SF₆) in multiple buildings and from different outdoor locations. From the measurements, we are able to estimate the concentration variations indoors for a building operating under “typical” operating conditions. The mean indoor spatial coefficients of variation are 30% to 45% from a daytime outdoor release are around 80% during an outdoor evening release. Having estimates of the spatial coefficient of variation provides stakeholders, including first responders, with the likely range of concentrations in the building when little is known about the building characteristics and operating behavior, such as developing urban-scale hazard and consequence analyses. We show differences in indoor measurements at different distances to the release points, floors of the building, and heating, ventilation, and air conditioning system (HVAC) operation. We also show estimates at different time resolutions. The statistics show that in the studied medium to large commercial buildings, spatial differences would result in peak indoor concentrations in certain parts of the buildings that may be substantially higher than the building average. To our knowledge, very few tracer gas measurements have been conducted in buildings of this scope, particularly with measurements on multiple floors and within a floor. The resulting estimates of spatial variability provide a unique opportunity for hazard assessment, and comparison to multi-zone models.     

Optimization of BiVO4 photoelectrodes made by electrodeposition for sun-driven water oxidation

In this work, the synthesis of cheap BiVO₄ photoanodes for the photoelectrochemical water splitting reaction was optimized via the scalable thin film electrodeposition method. Factors affecting the photoelectrochemical activity, such as the electrodeposition time, the ratio of the Bi-KI to benzoquinone-EtOH in the deposition bath, and the calcination temperature, have been investigated by using the Central Composite Design of Experiments. Pristine monoclinic scheelite BiVO₄ photoanodes having a photocurrent density of 0.45 ± 0.05 mA/cm² at 1.23 V vs RHE have been obtained. It was shown that a high photocurrent density is generally dictated by the following physico-chemical properties: a higher crystallite size, optimal thickness and a porous morphology, which give rise to a low charge transfer resistance, low onset potential and a high donor density. Moreover, to the best of our knowledge, this is the first report on the depth profile XPS analysis performed in BiVO₄ photoanodes made by electrodeposition technique, from which it was concluded that the surface V species exist as V⁴⁺ while the bulk V species are V⁵⁺. The V⁴⁺ induces a higher amount of surface oxygen vacancies, which was found to be beneficial for the photoactivity.     

Development and monitoring of an integrated bioprocess for production of a potential malaria vaccine with Pichia pastoris

An engineered variant of the yeast Pichia pastoris was used to produce the potential malaria vaccine D1M1. This paper describes the implementation of an expanded bed adsorption chromatography step into a sequential cultivation process of the yeast in order to link protein expression, cell release, and product capture of the secreted protein in a fully automated plant. The process is operated with a semi-continuous strategy for an integrated production. Process improvements have been achieved using design of experiments. Resulting purities of product achieved up to 87% with recoveries of 51% in a single downstream operation. Furthermore, a multivariate analysis of historical batch data was used to develop a golden batch model for process monitoring.     

A Polyallylamine Anchored Amine‐Rich Laser‐Ablated Graphene Platform for Facile and Highly Selective Electrochemical IgG Biomarker Detection

Current immunosensors have an insufficient number of binding sites for the recognition of biomolecules, which leads to false positive or negative results. In this research, a facile, cost‐effective, disposable, and highly selective electrochemical immunosensing platform is developed based on cationic polyelectrolyte polyallylamine (PAAMI) anchored laser‐ablated graphene (LAG). Here, for the first time, PAAMI is introduced to stabilize LAG flakes, while retaining the intrinsic thermal and electronic properties of the substrate by noncovalent π–π interaction and electrostatic physical absorption. The sensing platform offers a suitable number of anchoring sites for the immobilized antibodies by providing ? NH₂ functional groups. The proper grafting of PAAMI is confirmed through X‐ray photoelectron spectroscopy and Raman spectroscopy. The immunosensing platform is applied to detect immunoglobulin (IgG) biomarkers as a proof of concept. Under optimized conditions, the sensing platform exhibits a linear range of 0.012–15 and 15–352 ng mL^?1 with a limit of detection of 6 pg mL^?1 for IgG detection with high selectivity. Based on the analysis, the developed immunosensing platform can be used for point‐of‐care detection of IgG in clinical diagnostic centers. Furthermore, the developed strategy is well suited for the detection of other cancer biomarkers after immobilizing the relevant antibodies.     

扫描隧道显微镜钨针尖的制备与表征

采用直流电化学刻蚀方法制备扫描隧道显微镜钨针尖,研究了电化学刻蚀过程中NaOH溶液浓度、钨丝浸入长度和刻蚀电压对针尖形貌的影响。通过扫描电子显微镜(SEM)测量针尖曲率半径和针尖纵横比值,以表征针尖的尺寸和形状;通过能谱仪(EDS)分析针尖表面成分,以表征表面清洁度;通过场发射显微镜(FEM)得到Fowler-Nordheim (F-N)曲线来检测针尖发射性能。实验结果表明,当溶液浓度为2 mol/L、钨丝浸入长度为4 mm、刻蚀电压为3 V时,可以得到曲率半径约为100 nm、纵横比值为13的针尖,且表面无钨的氧化层。FEM结果显示当对针尖施加500 V的负偏压时,针尖可以稳定发射50 nA量级的电流,且针尖性能具有良好的一致性。