Speciation of Arsenic in Drinking Water by Dispersive Liquid–Liquid Microextraction,Graphite Furnace Atomic Absorption Spectrometry,and Orthogonal Array Design

Orthogonal array design was used to optimize arsenic speciation in drinking water in contact with materials by dispersive liquid–liquid microextraction followed by graphite furnace atomic absorption spectrometry. Arsenic speciation was achieved by the formation of an arsenic(III) hydrophobic complex with a new chelating agent, 1,2,6-hexanetriol trithioglycolate, at neutral pH. The complex was extracted into the organic phase, while arsenic(V) remained in aqueous solution. The concentration of As(V) was determined by subtracting As(III) from the total arsenic following the reduction of As(V) to As(III) by L-cysteine. Orthogonal array design with OA₁₆ (44) and OA₉ (33) matrices was used to optimize the efficiency of dispersive liquid–liquid microextraction and the reduction of As(V) to As(III), respectively. Under the optimal conditions, the detection limit was 0.03?µg?L^?1 for As(III) and the relative standard deviation was 5.9% with an enhancement factor of 87. The calibration curve was linear from 0.19 to 3.0?µg?L^?1 with a correlation coefficient of 0.9996. The developed method was used for arsenic speciation in solutions of drinking water that contacted materials. The recoveries of fortified samples were in an acceptable range from 92.0 to 113.3%.     

Characterization of Sixteenth to Nineteenth Century Ottoman Silk Brocades by Scanning Electron Microscopy–Energy Dispersive X-Ray Spectroscopy and High-Performance Liquid Chromatography

Historical textiles in the Topkap? Museum, which are called silk kaftans and brocades by art historians from the sixteenth and nineteenth were characterized by scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM–EDX) and high-performance liquid chromatography with diode array detection for identification of metal threads and dyestuffs. In the most Ottoman textiles, metal threads, especially belonging to the sultans, were used as the gold gild. Although the chemical composition of the samples on the surface may easily be obtained by SEM–EDX, the thickness of the thin gold layer on metal threads cannot be obtained directly. Hence, the goal of this project is to describe whether metal threads are gilded or not and to measure coating thickness. A new method was developed for measuring the thickness of gold layer, and the modeling was reformed. The SEM–EDX results were interpreted in accordance with the theoretical models. The coating thickness of metal threads was subsequently measured in ancient textiles. The thickness, depth, and valuable metal composition in the threads of the artistic objects were obtained by this approach. Dye analysis was used to characterize the presence of indigotin, carminic acid, ellagic acid, and luteolin in the historical textiles.     

Fabrication of urchin‐like Ag/ZnO hierarchical nano/microstructures based on galvanic replacement mechanism and their enhanced photocatalytic properties

Urchin‐like Ag/ZnO hierarchical nano/microstructures have been synthesized through a facile low‐temperature hydrothermal growth method based on galvanic replacement mechanism. The experimental results show that the urchin‐like Ag/ZnO heterostructures are formed through the epitaxial growth of ZnO nanorods on the {111} facets of Ag nanoparticles along their own c‐axis. The photocatalytic properties of the products were evaluated by the degradation of RhB dye solution under ultraviolet irradiation, and the results show that the products exhibit significantly enhanced photocatalytic properties comparing with pure ZnO nanorods. The products with a Ag content of 35.64 atom % prepared with a Ag⁺ concentration in solution of 5 mM exhibit surprisingly high degradation rate (99.5%) for RhB dye solution (4 mg/L) after photocatalytic reaction for only 14 min under ultraviolet irradiation. The Schottky barrier formed at the metal‐semiconductor interfaces improves the segregation of charges and prevents the charge recombination, and thus significantly enhances the photocatalytic activities of the products. On the other hand, the high stability of the urchin‐like Ag/ZnO hierarchical nano/microstructures can effectively prevent the aggregation of nanostructures with simultaneously preserving high photocatalytic properties due to the existence of nanosized unites. Copyright © 2016 John Wiley & Sons, Ltd.     

Biomimetic superhydrophobic UHMWPE/nanosilica films with different sticky behavior on several metals

A kind of organic–inorganic composite film with biomimetic superhydrophobic performance was prepared on several metals including steel, aluminum, and copper. The organic matrix was ultrahigh‐molecular‐weight polyethylene (UHMWPE), and the inorganic filler was nanosilica. Scanning electron microscope observation indicated addition of nanosilica greatly changed the topography of the UHMWPE film. Special convexities were formed on the surfaces of the composite films, which made the composite films rougher than that of pure UHMWPE film. The nanosilica randomly scattered on the surface of the convexities and formed hierarchical structure similar to that of some plant leaves with superhydrophobic characteristics. Interestingly, it was found that there were remarkable differences between the sliding angles (SA) of water droplet on the composite films on different metals although the contact angles (CA) of water droplet on these films were quite close. The CA on the composite films on steel was about 157°, and the SA was larger than 90°, which demonstrated obvious superhydrophobic and sticky characteristic. But to the films on aluminum and copper, the CAs on them were larger than 160° and the SAs were between 3° and 4°, which meant excellent superhydrophobic and roll‐off performance. Scanning electron microscope observation indicated that there were some micro‐orifices in the film on steel and these micro‐orifices were connected to some extent. It was believed that these micro‐orifices provided capillary force and restrained sliding of water droplet. A sticky model based on capillary mechanism was proposed. Copyright © 2017 John Wiley & Sons, Ltd.     

Well Oriented ZnO Nanorods Array: Negative Resistance and Optical Switching

Well‐oriented ZnO nanorods (NRs) arrays were grown on Si, alumina, quartz, and FTO substrates through a ZnO seed layer followed by low temperature wet chemical process. The influence of sputtered ZnO seed layer thickness (100, 50, 32, and 16 nm), annealing temperature and CuO_x coverage on the characteristics of ZnO NRs were investigated in this study. The crystalline structural, chemical, morphological, optical, and electrical properties of ZnO NRs arrays were studied by X‐ray diffraction (XRD), field emission‐ scanning electron microscopy equipped by energy dispersive X‐ray spectroscopy (FE‐SEM/EDX), Raman scattering, UV/Vis ‐ near IR absorption spectroscopy and current‐voltage characteristic. XRD and Raman spectra measurement revealed that the synthesize ZnO displayed hexagonal wurtzite structure. The individual rod diameter, density, and orientation can be controlled by varying the seed layer thickness. The mean diameter and maximum length of ZnO NRs are around 55–66 nm and 282 nm, respectively. ZnO NRs/ ZnO thin film structure shows optical switching and negative differential resistance behavior as applicable to ON/OFF gate and memory devices.     

Flexible and powerful strategy for qualitative and quantitative analysis of valepotriates in Valeriana jatamansi Jones using high‐performance liquid chromatography with linear ion trap Orbitrap mass spectrometry

Valeriana jatamansi Jones is an important medicinal plant and its quality is closely related to its region of origin. In the current study, we utilized a flexible and powerful strategy for comprehensive evaluation of the quality diversity for 15 regions in China. The method was based on a hybrid linear ion trap‐Orbitrap mass spectrometry platform. For structure characterization, fragmentation patterns were detected by analyzing a series of standard compounds using data dependent multistage mass spectrometry acquisition. A fragment ion database for valepotriates was established, and the acquired data were high throughput filtered by fragment ion search for compound identification. For quantitative purposes, we normalized the mass spectrometry data of 15 samples using SIEVE 2.0 and the differences in composition were analyzed using principal component analysis combined with hierarchical clustering analysis. The results identified a total of 92 compounds from Valeriana jatamansi Jones. Samples from Dali, Kunming, and Baoshan have better qualities and concentrations of the main active constituents. To verify our strategy, we compared the valtrate, acevaltrate, and baldrinal contents using high‐performance liquid chromatography with diode array detector. We developed and validated a comprehensive qualitative and quantitative analytical method to achieve quality control of Valeriana jatamansi Jones.     

Rapid separation and simultaneous quantitative determination of 13 constituents in Psoraleae Fructus by a single marker using high‐performance liquid chromatography with diode array detection

Psoraleae Fructus is one of the most popular traditional Chinese medicines. Coumarins, flavonoids, and meroterpenes are the main contributors to the biological activity of Psoraleae Fructus. In this study, a new method for the quality control of Psoraleae Fructus was developed, through the quantitative analysis of multicomponents by single marker with diode array detector. Thirteen components, including psoralenoside, isopsoralenoside, psoralen, isopsoralen, psoralidin, neobavaisoflavone, bavachin, corylin, isobavachalcone, corylifol A, bavachinin, bavachalcone, and bakuchiol were rapidly separated and identified within 12 min by the newly developed method. The feasibility and reliability of this method were corroborated. The method was also compared to the external standard method and detection by corona charged aerosol detector. The results of percent difference (%) and cos (θ) have shown that there were no significant differences observed between the quantitative analysis of multicomponents by single marker and external standard method analyses; psoralen and isopsoralen were undetectable with the corona charged aerosol detector due to their but the sensitivity for all the compounds except bakuchiol detected by corona charged aerosol detector are higher than those obtained by diode array detector. In addition, the newly method developed was applied to the quality evaluation of Chinese patent medicines containing Psoraleae Fructus.     

复合材料柔软性对倒金字塔微结构阵列传感器性能的影响

采用模压成型方法制备了2种柔软性不同的热塑性聚氨酯/短切碳纤维/碳纳米管(TPU/SCF-CNT)复合材料复制物, 其表面上具有倒金字塔微结构阵列, 内部有SCF与CNT共同构成的导电通路. 将复合材料复制物和相应的复合材料平整片封装成柔性传感器. 结果表明, 压力作用下传感器内复制物和平整片之间的接触电阻因倒金字塔底棱的形变而显著降低. 对使用柔软性较高的复合材料封装的传感器, 虽然其相对迟滞稍大, 但压力作用下倒金字塔底棱形变量较大, 且复制物和平整片内导电通路增加量较大, 因此其在0~2.5 kPa的线性区内具有较高的灵敏度(0.32 kPa^?1). 制备的2种传感器均具有快速响应特性, 且能在500 s(约1580次)的循环压缩/释放测试(峰值压力约3 kPa)中保持较稳定的电阻响应. 研究表明, 利用模压成型的表面倒金字塔结构复合材料复制物封装成的柔性压力传感器具有良好的传感性能.     

钼酸根阴离子在增强聚苯胺包覆的镍钴层状氢氧化物的电容和析氧行为中的关键作用

理论容量大且过电位低的层状氢氧化物(LDHs)是极有前景的超级电容电池和析氧反应的电极材料;然而,体相LDHs的低电导率和活性位点不足增加了电极的内阻,降低了电极容量和产氧效率.本文采用两步法制备了聚苯胺包覆的MoO42?插层的镍钴层状双金属氢氧化物复合电极(M-LDH@PANI).随着LDH中MoO42?含量的增加,针状的LDH微球逐渐演化为具有较高比表面积的片状M-LDH微球,这为整个电极提供了更多的电化学位点.此外,非晶态的聚苯胺包覆提高了复合电极的电导率.在引入适量MoO42?插层离子时,M-LDH@PANI表现出显著强化的储能和催化性能.所获得的M-LDH@PANI-0.5在析氧反应中表现出优越的电催化活性(10 mA cm?2时的过电位为266 mV),作为超级电容电池电极则具有864.8 C g?1的高容量.采用M-LDH@PANI-0.5作为正极及以活性炭作为负极组装的超级电容电池在功率密度为8,300.0 W kg?1时能量密度为44.6 Wh kg?1,且具有优异的循环稳定性(10000次循环后保留83.9％的初始容量).本文为LDH基材料的阴离子插层改性增强材料性能的机理提供了一个非传统的解释.在上述研究基础上,采用射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、高分辨透射电镜(HRTEM)和比表面积测试(BET)等手段对样品进行了深入表征.XRD结果表明,MoO42?插层的LDH材料的层间晶面(003)的峰随着MoO42?含量的增加而逐渐消失,这是由于晶面间距越大越容易受到晶粒细化的影响,间距大的晶格更容易受到破坏,导致晶格的展宽和弱化,从而间接证明MoO42?的成功插层.SEM、HRTEM和BET测试结果表明,MoO42?的含量对材料的形貌和比表面积具有重大影响.利用XPS对样品的价态进行了研究,发现随着MoO42?含量的增加,Co和Ni的价态没有明显变化.电化学测试结果表明,电极的储能和催化性能随MoO42?含量的增加而先增加后减小.利用理论计算分析了MoO42?在LDH中的插层行为,发现少量的MoO42?有利于扩大LDH的层间间距,而过量的MoO42?则会与LDH的H原子结合,从而与电解液中的OH?竞争,导致复合电极的电化学性能下降.此外,MoO42?插层的片状微球能有效调节材料的去质子化能,大大加速电极表面的氧化还原反应.因此,MoO42?插层能够显著强化LDH基材料的超级电容电池电极和OER催化剂电化学性能.     

CeO2修饰Ni3S2纳米片用于高效电催化析氧

电化学水分解制氢作为重要的生产氢能的新能源技术,包括氢气析出反应(HER)和氧气析出反应(OER).然而,OER进行的是多步电子转移过程,动力学过程缓慢且过电位高,严重制约了电解水制氢的发展.因此开发低成本、高效稳定的非贵金属催化剂替代贵金属催化剂(RuO2,IrO2)来降低过电位,减少能源消耗十分必要.Ni₃S₂由于其高导电性、高活性、低成本等优点,具有作为贵金属催化剂替代品的广阔应用前景,但其OER性能仍需进一步提高.对已有的有效OER催化剂进行表界面调控是提高催化剂性能的一种有效策略.CeO₂中的Ce3+和Ce4+价态之间可以灵活过渡,使其具有良好的电子/离子导电性、可逆的表面氧离子交换和较高的储氧能力.CeO₂的多价性使其有机会与其它基质产生强烈的电子相互作用,良好的电子/离子导电性和较高的储氧能力是提高催化剂析氧活性的有利因素.因此,用CeO₂对Ni₃S₂进行修饰是提高其析氧活性的有效途径.基于此,本文运用水热和电沉积相结合的方法将CeO₂修饰到Ni₃S₂纳米片上,制备得到生长于泡沫镍上的Ni₃S₂-CeO₂纳米片阵列(Ni₃S₂-CeO₂/NF),并运用X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)等手段进行了表征,以三电极系统测试了其电催化析氧性能及稳定性,并通过密度泛函理论计算进行了验证.XRD结果表明,复合材料中确实存在Ni₃S₂和CeO₂.通过SEM发现,泡沫镍基底上均匀分布着Ni₃S₂纳米片阵列;电沉积CeO₂后,Ni₃S₂-CeO₂仍保持其纳米片特性,但表面变得粗糙.Ni₃S₂-CeO₂的TEM结果也证实了纳米片结构的形成,高分辨率TEM图像清晰的显示出Ni₃S₂和CeO₂之间具有明显的界面.XPS结果表明,Ni₃S₂-CeO₂的Ni 2p的结合能与Ni₃S₂相比出现负位移.与纯CeO₂的Ce 3d谱图相比,Ni₃S₂-CeO₂杂化体系中Ce4+的比例明显增加,表明Ce的价态发生了重排,部分电子转移给了Ni元素.这些结果均说明Ni₃S₂与CeO₂之间存在着较强的电子相互作用.相应的电催化测试结果显示,在1.0 M KOH中,当电流密度达到20 mA cm^–2时,Ni₃S₂/NF需提供356 mV的过电位,Ni₃S₂-CeO₂/NF只需264 mV的过电位,仅次于RuO2/NF.而且,Ni₃S₂-CeO₂/NF在中性条件下也显示出了较理想的析氧活性.Ni₃S₂-CeO₂/NF的Tafel斜率明显低于CeO₂/NF和Ni₃S₂/NF,表明其具有良好的OER反应动力学.循环伏安法和计时电位法结果均表明,Ni₃S₂-CeO₂/NF具有良好的电化学稳定性.电化学阻抗谱测试结果表明,与Ni₃S₂/NF和CeO₂/NF相比,Ni₃S₂-CeO₂/NF明显具有更小的半圆直径,说明其电荷转移阻抗更小,进一步表明CeO₂的修饰有助于催化过程中电子的快速转移.在非法拉第区域的循环伏安扫描曲线以及拟合扫描速度对电容电流曲线结果显示,Ni₃S₂-CeO₂/NF的最大电容值大于CeO₂/NF和Ni₃S₂/NF,表明其暴露了更多的活性位点,具有更大的电化学活性表面积;而且,Ni₃S₂-CeO₂/NF在400和500 mV时的电催化析氧转换频率明显高于Ni₃S₂/NF和CeO₂/NF,进一步说明Ni₃S₂-CeO₂/NF具有更高的本征催化活性.密度泛函理论计算表明,由于^*OH,^*O和^*OOH与Ni₃S₂-CeO₂中的Ni和Ce原子相互作用的存在,使得反应中间产物与Ni₃S₂-CeO₂之间的结合强度较纯Ni₃S₂或CeO₂强,使其显示出了更高的OER性能.在经过24 h连续电解后,SEM和TEM结果均表明,Ni₃S₂-CeO₂/NF材料仍保持了其纳米片形貌.稳定性测试后的XPS结果表明,Ni 2p对应的峰强度降低,而与氧化镍物种对应的峰强度增强;S元素在Ni₃S₂-CeO₂表面的信号强度明显降低.根据文献报道,在强烈的氧化环境下,过渡金属硫化物会部分转化为氧化物或氢氧化物,这通常被认为是OER过程的实际催化物种.