电解水金属单原子催化剂的研究进展

氢能因其能量密度高、清洁无污染等特点,作为替代化石燃料的能源载体得到了广泛的研究.如何清洁高效地制备氢气受到了大量研究者的关注.当前,以化石能源的热反应所得副产氢气是主要来源.然而,采用该类方法不仅不能摆脱化石能源的使用以及温室气体的排放,还会造成生产氢气的纯度不高,碳氧化物杂质浓度过高的问题,严重影响氢气的后续使用.采用可再生能源(太阳能、风能等)所产富余电,进行电解水制氢,产生的氢气不含碳氧化合物杂质,纯度很高,可以真正实现碳的零排放,被认为是未来氢气来源的重要方式.目前,电解水制氢在制氢市场的所占份额较小,而造成这样局面的主要因素是该过程中的高能耗问题.为了降低能耗,开发高效催化剂加速两个电极上的电解反应的动力学尤为重要.近年,金属单原子催化剂(SACs)因其独特的结构,在很多研究中被用作电解水催化剂,进而开发出大量高性能的金属单原子电解水催化剂.本文综述了近年SACs在电解水催化方面的应用.首先,针对电解水反应本身,总结了阴阳极两侧的电极反应机制以及影响电极催化性能的关键吸附中间物种;然后,根据载体的不同,即合金、碳以及其它化合物将SACs分为三类,总结了相关电解水催化研究现状,并且针对不同类型SACs目前的发展情况,提出了它们各自存在的问题.其次,进一步总结了影响SACs电解水催化活性的因素,提出了四种决定SACs催化性能的影响因子,分别为金属原子的固有元素性质、配位环境、几何结构和负载量;同时讨论了这四类影响因素对SACs催化活性的影响机制,总结了调控各类影响因素的方法,为SACs的设计提出了一些建议.最后,展望了SACs在电解水催化中的应用,探讨了SACs在催化剂设计及催化机制研究方面的问题,提出了SACs在电解水催化中的未来发展方向.     

Photochemically Produced Superhydrophobic Silane@polystyrene-Coated Polypropylene Fibrous Network for Oil/Water Separation

Cost-effective separation of oil and immiscible organic contaminants from water has become an urgent challenge to protect aquatic and human life from devastating effects. Therefore, it has become imperative to develop super-selective materials for efficiently separating oil from water. In this work, a superhydrophobic surface has been formed that consists of a silane@polystyrene-coated polypropylene fibrous network (silane@PS-PPF) for efficient separation of accidentally spilled oil from water. The superhydrophobic PPFs were designed by a simple, cost-effective two-step process that includes photochemically controlled polymerization of styrene and subsequent dip coating in octadecyltrichlorosilane solution. The hydrophobic surface (CA=129°±4°) of the PS coated PPF after treating with silane was turned into a superhydrophobic body (CA=161°±2°). The achieved silane@PS-PPF fibrous network selectively allowed the fast permeation of the oils and non-polar organic liquids by altogether rejecting water during operation. The separation efficiency for various oils from the contaminated water was 96 to 99%, with a high flux in the range of 7606±312 L m⁻²h⁻¹ to 9870±151 L m⁻²h⁻¹. Apart from being used as a filter, the silane@PS-PPF was also used as an oil absorber and has shown an absorption capacity in the range of 1185 to 1535% for various oils. We anticipate that the developed silane@PS-PPF, due to its facile synthetic route, cost-effectiveness, and high performance, can be effectively used in oily wastewater treatment and clean-up of large oil spills from water.     

微波消解-ICP-MS测定电镀污泥中的重金属

采用微波消解系统对某电镀污泥进行消解,利用ICP-MS对污泥中的重金属进行测定。称取制备后样品,置于消解罐中充分反应后,赶酸、定容后利用电感耦合等离子体质谱法进行测定。电镀污泥中的铬为18845.2mg/kg、镉为10.3mg/kg、镍为5200.0mg/kg、铅为189.7mg/kg、铜为3271.7mg/kg、锌为49632.6mg/kg。测定结果表明所检测项目工作曲线线性关系好,相关系数r均大于0.999。铬加标回收率在91.6～97.7%之间、镉加标回收率在92.0～97.0%之间、镍加标回收率在95.1～98.0%之间、铅加标回收率在94.3～95.2%之间、铜加标回收率在97.1～102%之间、锌加标回收率在96.3～98.7%之间,均满足相关测定要求。计算的潜在生态危害系数、潜在生态危害指数结果表明,电镀污泥中的铬、镉、铅、铜、锌为轻微生态危害,镍为强生态危害;潜在生态危害指数RI计算值为216.69,属于中等生态危害。     

Tutorial review on validation of liquid chromatography–mass spectrometry methods: Part I

This is the part I of a tutorial review intending to give an overview of the state of the art of method validation in liquid chromatography mass spectrometry (LC–MS) and discuss specific issues that arise with MS (and MS/MS) detection in LC (as opposed to the “conventional” detectors). The Part I briefly introduces the principles of operation of LC–MS (emphasizing the aspects important from the validation point of view, in particular the ionization process and ionization suppression/enhancement); reviews the main validation guideline documents and discusses in detail the following performance parameters: selectivity/specificity/identity, ruggedness/robustness, limit of detection, limit of quantification, decision limit and detection capability. With every method performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to determine it, specifically in the case of LC–MS methods.     

表面解吸常压化学电离质谱法直接分析牙齿微区表面

采用纳升取样表面解吸常压化学电离质谱法(nano-SDAPCI-MS)结合主成分分析(PCA),建立了一种采用具有微米级针尖的金属取样针直接对龋齿不同部位取样并进行快速质谱分析的方法.数据分析结果表明,同一颗龋齿不同部位的质谱指纹谱图之间存在差异;在不需要样品预处理的前提下通过串联质谱快速测定了龋齿中的乳酸、丙酮酸、苯乙酸和丙酸等成分.采用PCA方法可较好地将龋齿病灶位置与邻近正常组织进行区分,也可对不同牙病及健康牙齿进行区分.本方法可方便地对牙齿进行直接微区分析,为鉴别牙齿疾病及观测治疗效果提供了一种快速、简单的方法,为生物体中微细部位的快速取样及直接质谱分析提供了一种可能的解决方案.     

Trace metal analyses in honey samples from selected countries. A potential use in bio-monitoring

Honey is a sweet product made by bees using nectar from flowers. Concentrations of Ca, K, Mg, Fe, Zn, Mn, Cu, Pb and Cd were determined in 13 honey samples from the selected regions around the world. Levels of Ca, Mg, Cu, Fe, Zn and Mn were measured using flame atomic absorption spectrometry (FAAS). Potassium concentration was determined via flame photometry. Concentrations of Cd and Pb were determined using the electrothermal technique (ETAAS). It was estimated that the examined samples of honey from Greece, Turkey, Spain, Poland, Mexico, Argentina and Italy were of good quality in terms of metal concentrations (compliant with the norms referring to food products – WHO, Fifty-third Report of the joint FAO/WHO Expert Committee on Food Additives; Technical Report Series 776, Geneva), although the analysed samples were not free of heavy metals. The concentrations of the elements in the honey samples ranged from 2.38 to 9.31 μg · g^?1 for Zn, from 3.86 to 35.10 μg · g^?1 for Fe, from 0.19 to 21.64 μg · g^?1 for Mn, from 49.53 to 1006.90 μg · g^?1 for Ca, from 388.25 to 4761.50 μg · g^?1 for K and from 0.20 to 1.53 μg · g^?1 for Cu and regarding heavy metals from 0.11 to 2.78 μg · g^?1 for Pb and from 0.02 to 0.44 μg · g^?1 for Cd. According to these results it was found that the concentrations of heavy metals in the honey samples (except for alfalfa honey and eucalyptus honey from Italy) were under the acceptable limits for foods set out by the FAO/WHO. It was confirmed that the application of chemometric tools supports the extraction of significant information from analytical data, even though the availability of samples is not fully sufficient (this problem is often encountered in environmental analyses).     

氧化环境和比例对改性Hummers法制备GO的影响

以鳞片石墨(GR)为原料,采用改性Hummers法液相氧化方法制备氧化石墨,通过超声剥离的方法剥离出片状的氧化石墨烯(GO),探讨了H₂SO₄环境与H₂SO₄+H₃PO₄混酸环境和KMnO₄与GR的比例对GO制备的影响。采用FTIR、UV、TG、XRD、SEM和XPS等分析手段对制备的GO进行分析。结果表明：GO外貌是呈褶皱片状,在片层上主要有C=O、C-OH、-COOH和C-O-C等官能团,以共价键形式存在石墨层间;通过TG与XPS数据分析表明在H₂SO₄ H₃PO₄混酸环境下制备的GO含氧官能团较多,并且(KMnO₄)与鳞片石墨的最佳比例是1:4。     

Laser Machined Plastic Laminates: Towards Portable Diagnostic Devices for Use in Low Resource Environments

Despite significant progress in development of bioanalytical devices cost, complexity, access to reagents and lack of infrastructure have prevented use of these technologies in resource‐limited regions. To provide a sustainable tool in the global effort to combat infectious diseases the diagnostic device must be low cost, simple to operate and read, robust, and have sensitivity and specificity comparable to laboratory analysis. In this mini‐review we describe recent work using laser machined plastic laminates to produce diagnostic devices that are capable of a wide variety of bioanalytical measurements and show great promise towards future use in low‐resource environments.     

Impact of singularity of Navier-Stokes equation upon atmospheric motion equations

Some conclusions about the smooth function classes stability for the basic system of equations of atmospheric motion and instability for Navier-Stokes equation are summarized. On the basis of this, by taking the basic system of equations of atmospheric motion via Boussinesq approximation as example to explain in detail that the instability about some simplified models of the basic system of equations for atmospheric motion is caused by the instability of Navier-Stokes equation, thereby, a principle to guarantee the stability of simplified equation is drawn in simplifying the basic system of equations.     

Numerical and experimental study of turbulent impinging twin-jet flow

The two dimensional impinging circular twin-jet flow with no-cross flow is studied numerically and experimentally. The theoretical predications are carried out through numerical procedure based on finite volume method to solve the governing mass, momentum, turbulent kinetic energy and turbulent kinetic energy dissipation rate. The parameters studied were jet Reynolds number (9.5 × 10⁴  Re  22.4 × 10⁴), nozzle to plate spacing (3  h/d  12), nozzle to nozzle centerline spacing (l/d = 3, 5 and 8) and jet angle (0°  θ  20°). It is concluded that the stagnation primary point moves away in the radial main flow direction by increasing the jet angle. This shift becomes stronger by increasing the nozzle to nozzle centerline spacing (l/d). A secondary stagnation point is set up between two jets. The value of pressure at this point decreases by decreasing Reynolds number and/or increasing the jet angle.

The sub atmospheric region occurs on the impingement plate. It increases strongly by increasing Reynolds number and decreases as the jet angle and/or a nozzle to plate spacing increases. The spreading of jet decreases by increasing nozzle to plate spacing. The intensity of re-circulation zone between two jets decreases by increasing of h/d and jet angle. The increase of turbulence kinetic energy occurs within high gradient velocity.