Application of enriched stable 196Hg isotope for monitoring the stability of total mercury in water samples

A novel tool for the investigation of stability of total mercury in water samples is presented. The study focuses on the application of enriched ¹⁹⁶Hg stable isotopic reagent for the stability studies. Natural abundance of ¹⁹⁶Hg in water samples is only 0.15%. Thus, the use of the ¹⁹⁶Hg isotope spike represents a major advantage, when it can be assumed that all the measured isotope is the same as is accurately added by the analyst, and the change in its mass concentration can be followed simply and reliably. Tests were carried out with industrial waste water and two type of the natural water. Cold vapour (CV) inductively coupled plasma mass spectrometer (ICP-MS) technique was applied for the mercury measurements. Monitoring was continued for approximately 100 days. It is commonly advised that the measurement for total mercury in water samples should be carried out within 14 days. In this study the samples were observed to be stable for more than three months, if they were stored at a temperature of 4–6°C. The results of this stability study were in line with the guidance presented in EPA standard 1631. However, the samples were noticed to be stable for a much longer time than is presented in the standard method ISO 17852.     

Large Optical Nonlinearity Induced by Singlet Fission in Pentacene Films

By creating two triplet excitons from one photo‐excited singlet exciton, singlet fission in organic semiconductors has drawn tremendous attention for its potential applications in boosting the efficiency of solar conversion. Here, we show that this carrier‐multiplication effect can also be used to dramatically improve the nonlinear optical response in organic materials. We have observed large optical nonlinearity with a magnitude of χ⁽³⁾ up to 10^?9 esu in pentacene films, which is further shown to be a result of singlet fission by monitoring the temporal dynamics. The potential application of such efficient nonlinear optical response has been demonstrated with a singlet‐fission‐induced polarization rotation.     

Sensor–actuator system for dynamic chloride ion determination

Chloride is a crucial anion for various analytical applications from biological to environmental applications. In order to measure the chloride ion concentration, a measurement system is needed which can detect this concentration for prolonged times reliably. Chronopotentiometry is a technique which does not need a long term stable reference electrode and is therefore very suitable for prolonged ion concentration measurements. As the used electrode might be fouled by reaction products, this work focuses on a chronopotentiometric approach with a separated sensing electrode (sensor) and actuating electrode (actuator). Both actuation and sensor electrode are made of Ag/AgCl. A constant current is applied to the actuator and will start the reaction between Ag and Clˉ, while the resulting Clˉ ion concentration change is observed through the sensor, which is placed close to the actuator. The time it takes to locally deplete the Clˉ ions is called transition time. Experiments were performed to verify the feasibility of this approach. The performed experiments show that the sensor detects the local concentration changes resulting from the current applied to the actuator. A linear relation between the Clˉ ion concentration and the square root of the transition time was observed, just as was predicted by theory. The calibration curves for different chips showed that both a larger sensor and a larger distance between sensor and actuator resulted in a larger time delay between the transition time detected at the actuator and the sensor.     

Multivariate analysis of extremely large ToFSIMS imaging datasets by a rapid PCA method

Principal component analysis (PCA) and other multivariate analysis methods have been used increasingly to analyse and understand depth profiles in X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and secondary ion mass spectrometry (SIMS). These methods have proved equally useful in fundamental studies as in applied work where speed of interpretation is very valuable. Until now these methods have been difficult to apply to very large datasets such as spectra associated with 2D images or 3D depth‐profiles. Existing algorithms for computing PCA matrices have been either too slow or demanded more memory than is available on desktop PCs. This often forces analysts to ‘bin’ spectra on much more coarse a grid than they would like, perhaps even to unity mass bins even though much higher resolution is available, or select only part of an image for PCA analysis, even though PCA of the full data would be preferred. We apply the new ‘random vectors’ method of singular value decomposition proposed by Halko and co‐authors to time‐of‐flight (ToF)SIMS data for the first time. This increases the speed of calculation by a factor of several hundred, making PCA of these datasets practical on desktop PCs for the first time. For large images or 3D depth profiles we have implemented a version of this algorithm which minimises memory needs, so that even datasets too large to store in memory can be processed into PCA results on an ordinary PC with a few gigabytes of memory in a few hours. We present results from ToFSIMS imaging of a citrate crystal and a basalt rock sample, the largest of which is 134GB in file size corresponding to 67 111 mass values at each of 512 × 512 pixels. This was processed into 100 PCA components in six hours on a conventional Windows desktop PC. © 2015 The Authors. Surface and Interface Analysis published by John Wiley & Sons Ltd.     

Real‐time electro‐diffusion method to discriminate carbon nanomaterials

We report both the experimental and theoretical insights of differential electro‐diffusion behavior of carbon nanomaterials (e.g. single wall, multiwall carbon nanotubes, and graphene). We thus discriminate one from the other in a soft gel system. The differential mobility of such material depends on their intrinsic properties, both extend and rate of migration bearing the discriminatory signature. The mobility analysis is made by a real time monitoring of the respective bands.     

氧化石墨超声时间对三维还原氧化石墨烯结构及超级电容性能的影响

将氧化石墨凝胶超声不同时间制备氧化石墨烯(GO)溶胶,再以GO溶胶为前驱体采用一步水热法制备了三维还原氧化石墨烯(3DRGO),采用X射线衍射(XRD)、拉曼光谱、原子力显微镜(AFM)、扫描电子显微镜(SEM)和电化学测试等研究了不同超声时间对3DRGO的形貌、结构及超级电容性能的影响.结果表明,当超声时间不超过120 min时,经水热反应后还原氧化石墨烯均能形成稳定的三维结构,但随着超声时间的延长,三维结构尺寸不断减小,强度增加,样品的内部结构也由片状逐渐向多孔网状转化;当超声时间超过120 min时,还原氧化石墨烯虽具有网状结构,但在宏观上不利于形成稳定的三维结构.电化学测试结果表明,经不同超声时间所制备的还原氧化石墨烯均表现出较好的超级电容性能,其中超声时间为120 min时制备的3DRGO具有更均匀的多孔网状结构,表现出了最佳的超级电容性能,在1 A/g电流密度下其比电容可达328 F/g,即使在20 A/g的大电流密度条件下,其比电容仍可高达240 F/g.     

Localization and Dynamics of Long‐Lived Excitations in Colloidal Semiconductor Nanocrystals with Dual Quantum Confinement

Semiconductor nanocrystals consisting of a quantum dot (QD) core and a quantum well (QW) shell, where the QD and QW are separated by a tunneling barrier, offer a unique opportunity to engineer the photophysical properties of individual nanostructures. Using the thicknesses of the corresponding layers, the excitons of the first and second excited states can be separated spatially, localizing one state to the QD and the other to the QW. Thus the wave function overlap of the two states can be minimized, suppressing non‐radiative thermalization between the two wells, which in turn leads to radiative relaxation from both states. The molecular analogy to such dual emission would be the inhibition of internal conversion, a special case that violates Kasha′s rule. Using nanosecond time‐resolved spectroscopy of QDQW CdSe/ZnS onion‐like nanocrystals, an intermediate regime of exciton separation and suppressed thermalization is identified where the non‐radiative relaxation of the higher‐energy state is slowed, but not completely inhibited. In this intermediate thermalization regime, the temporal evolution of the delayed emission spectra resulting from trapped carriers mimic the dynamics of such states in nanocrystals that consist of only a QD core. In stark contrast, when a higher‐energy metastable state exists in the QW shell due to strongly suppressed interwell thermalization, the spectral dynamics of the long‐lived excitations in the QD and QW, which are spectrally distinct, are amplified and differ from each other as well as from those in the core‐only nanocrystals. This difference in spectral dynamics demonstrates the utility of exploiting well‐defined exciton localization to study the nature and spatial dependence of the intriguing photophysics of colloidal semiconductor nanocrystals, and illustrates the power of nanosecond gated luminescence spectroscopy in illuminating complex relaxation dynamics which are entirely masked in steady‐state or ultrafast spectroscopy.     

Sol‐to‐Gel Transition in Fast Evaporating Systems Observed by in Situ Time‐Resolved Infrared Spectroscopy

The in situ observation of a sol‐to‐gel transition in fast evaporating systems is a challenging task and the lack of a suitable experimental design, which includes the chemistry and the analytical method, has limited the observations. We synthesise an acidic sol, employing only tetraethylorthosilicate, SiCl₄ as catalyst and deuterated water; the absence of water added to the sol allows us to follow the absorption from the external environment and the evaporation of deuterated water. The time‐resolved data, obtained by attenuated total reflection infrared spectroscopy on an evaporating droplet, enables us to identify four different stages during evaporation. They are linked to specific hydrolysis and condensation rates that affect the uptake of water from external environment. The second stage is characterized by a decrease in hydroxyl content, a fast rise of condensation rate and an almost stationary absorption of water. This stage has been associated with the sol‐to‐gel transition.