A flux‐splitting solver for shallow water equations with source terms

This paper introduces a stable flux‐splitting solver for one‐dimensional (1D) shallow water equations. This solver is specifically designed to satisfy a strengthened consistency condition for stationary solutions that ensures the stability and accuracy of the scheme. It applies to channels with variable depth and width, including terms modelling friction at bottom and vertical walls. Some numerical tests by comparison to both analytical solutions and experimental measurements show the good performances of the scheme. Copyright © 2003 John Wiley & Sons, Ltd.     

A note on asymptotic splitting and its applications

Explicit forms of the remainder terms of the asymptotic splitting formulae associated with the first order splitting, Strange's splitting, and the parallel splitting are derived. Using the identities obtained, we establish the global error estimates for the asymptotic splitting formulae. Both the theoretical investigation and numerical experiments indicate that it is a more efficient and accurate way to use the asymptotic splitting than the conventional splitting formulae.     

Crossover finite-size scaling at first-order transitions

In a recent paper we developed a method which allows one to control rigorously the finite-size behavior in long cylinders near first-order phase transitions at low temperature. Here we apply this method to asymmetric transitions with two competing phases, and to theq-state Potts model as a typical model of a temperature-driven transition, whereq low-temperature phases compete with one high-temperature phase. We obtain the finite-size scaling of the firstN eigenvalues (whereN is the number of competing phases) of the transfer matrix in a periodic box of volumeL × ... ×L ×t, and, as a corollary, the finite-size scaling of the shape of the order parameter in a hypercubic box (t=L), the infinite cylinder (t=), and the crossover regime from hypercubic to cylindrical scaling. For the two-phase case (N=2 we find that the crossover length _L is given by O(L^w)exp(L^v), where is the inverse temperature, is the surface tension, and w=1/2 if v+1=2 whilew=0 if v+1 >2. For the standard Ising model we also consider free boundary conditions, showing that _L=exp[L^v+O(L^v– 1)] for any dimension v+12. For v+1=2 we finally discuss a class of boundary conditions which interpolate between free (corresponding to the interpolating parameter g=0) and periodic boundary conditions (corresponding to g=1), finding that _L=O(L^w)exp(L ^v) withw=0 forg=0 andw=1/2 for 0<g1.     

Syringe-to-syringe-dispersive liquid–phase microextraction combined with flame atomic absorption spectrometry for pre-concentration and determination of cobalt with the aid of experimental design

A rapid and selective technique has been proposed for the extraction, pre-concentration and determination of trace amounts of cobalt in water and pharmaceutical samples by syringe-to-syringe-dispersive liquid–phase microextraction (SS-DLPME) combined with flame atomic absorption spectrometry (FAAS). In the developed method, 1-nitroso-2-naphthol was used as a selective complexing agent and 1-octanol was selected as the extraction solvent. Factors such as pH of the sample solution, concentration of the complexing agent, volume of the extraction solvent, number of injections and centrifugation time affecting the extraction efficiency were screened using a Plackett–Burman design (PBD) and optimised using a Box–Behnken design (BBD). Under optimum conditions, a dynamic linear range of 2.5–650 μg L^?1 with the coefficient of determination r² = 0.997 was obtained. The resultant limit of detection (LOD) was 0.68 μg L^?1, whereas the enrichment factor (EF), intraday precision and inter-day precision were 281, 1.43% and 1.93%, respectively. This method was used successfully for pre-concentration and determination of the analyte in environmental water and drug samples.     

Fast determination of β-endosulfan, α-hexachlorocyclohexane and pentachlorobenzene in the river water from northeast of China

A magnetic solid-phase extraction method for the preconcentration of three organochlorine pesticides (OCPs) from water samples has been proposed, based on magnetic phosphatidylcholine (MPC) as adsorbents. The extraction procedure was carried out in a single step by stirring the mixture of MPC and water samples. Subsequently, the MPC was collected by an external magnetic field without additional centrifugation or filtration. The analytes were desorbed from the MPC and finally analysed by gas chromatography–tandem mass spectrometry. The influence of various parameters on OCPs recoveries was studied. Results show that phosphatidylcholine amount and extraction time were critical in enhancing extraction performance, and the presence of humic acid was shown to significantly reduce the extraction efficiency. The limits of detection obtained were in the range of 0.1–0.15 ng L^?1. Recoveries of spiked water samples ranged from 76.2% to 101.5% with relative standard deviations varying from 3.8% to 7.7%. The proposed method was employed for analysis of pentachlorobenzene, α-hexachlorocyclohexane and β-endosulfan in the surface water from two rivers in northeast China.     

Dispersive liquid–liquid microextraction using the freezed floating organic drop for rapid,fast, and sensitive determination of lead

A rapid, simple, and sensitive method was developed for lead preconcentration and separation in various real samples by dispersive liquid–liquid microextraction based on the freezing of floating organic drop. In this method, a suitable extraction solvent dissolved in a dispersive solvent was quickly syringed into the water sample so that the solution became turbid. Then, two phases were separated by centrifugation. The floating extractant droplet can be easily solidified on an ice bath and taken out of the water sample. Then, it can be liquefied instantly at room temperature, and analyte can be determined in it. In the creation of a hydrophobic complex with lead, 1-(2-pyridylazo)-2-naphthole (PAN) was used as the chelating agent. 1-Undecanol and acetone were used as extraction and disperser solvent. To achieve the highest recovery, some factors (type and volume of dispersive and extraction solvent, pH, PAN concentration, and salt concentration) were optimised. Under optimised conditions (pH = 9, 1.0 × 10^–3 mol L^?1 PAN, 15% w/v NaCl, 100 µL 1-undecanol, and 0.3 mL acetone), the lead calibration graph was linear from 1.5 to 80 μg L^?1. The detection limit and preconcentration factor were 0.5 μg L^?1 and 50, respectively. Lead was successfully determined in water and food (spinach, rice, potato, carrot, and black tea bag) samples by this method.     

通过温和的镍腐蚀制备珊瑚状FeNi(OH)x/Ni作为一种一体化高效水分解电极

高效稳定并可同时催化析氧反应(OER)和析氢反应(HER)的非贵金属催化剂对于实现廉价水分解电解槽的商业化十分重要.虽然众多研究表明FeNi(OH)x是一种极具潜力的催化剂,但是在基础研究与更有实用前景的电极之间仍有许多空白亟待填补.比如,基础研究多基于薄膜电极,其催化剂内部导电性的影响通常可以忽略.而基于实用化的电极则需要负载较厚的催化剂膜以获得更多的活性位,与此同时,其催化剂内部导电性的不利影响将会增大.此外,物质传递方面也会出现类似的情况.因此,一些在基础研究中显示出高本征活性的催化剂,在更加接近实际应用的体系下难以表现出预期的高活性.对于这一问题,目前鲜有相关的研究报道.基于上述分析,本文报道了一种经济且环保的方法,以制备珊瑚状的FeNi(OH)x/Ni催化剂.在碱性条件下,该催化剂具有同时催化OER和HER,从而实现全水分解的能力.在催化剂的制备过程中,具有高本征活性的FeNi(OH)x纳米片借助Fe(NO3)3对Ni温和的腐蚀过程,被原位负载到珊瑚状镍骨架上.这些纳米片与电沉积制备的珊瑚镍骨架以及3D泡沫镍基底一起构成了一体化的析气电极.这样的电极结构有助于暴露活性位、电解质快速传递和气体产物的迅速释放.此外,与珊瑚状金属镍骨架的复合也有利于减轻较厚的催化剂薄膜所带来的导电性降低的负面影响.在1.0mol L-1 KOH溶液中,以FeNi(OH)x/Ni同时作为阳极和阴极而构建的对称电解槽表现出了优异的催化活性,只需要施加1.52 V的槽压即获得10 mA cm-2的催化电流密度.其活性甚至优于当前最佳的由贵金属催化剂RuO2和Pt/C构建的非对称电解槽所表现出来的活性(10 mA cm-2的槽压为1.55 V).本文提供了一种简便易行且十分可靠的制备更加实用、具有潜力且可负担的水分解装置的策略.     

基于掺Zn氮化碳和BiVO4构建Z型光催化系统实现完全分解水

随着现代工业的迅猛发展和化石燃料的过量使用, 全球范围内能源和环境问题日益严峻, 因此利用丰富的太阳光能分解水来直接制取清洁的氢气具有诱人的应用前景. 目前, 聚合物半导体石墨相氮化碳(g-C3N4)因其廉价、稳定、不含金属组分和独特的电子能带结构已被广泛应用于光解水产氢研究. 然而, 氮化碳具有结晶度差、光生载流子易复合的缺点.众所周知, Z型体系可以很好地减少电子和空穴的复合问题. 同时, 催化剂只需分别满足光解水过程的一端, 这使得半导体光催化剂的选择非常丰富, 可以大大拓宽材料体系. 因此, 将g-C3N4运用到Z型体系中的研究得到了广泛关注. 然而, 这些研究多集中在如何增强g-C3N4的产氢能力方面, 对实现水的完全分解的研究鲜见报道.本实验设计了这样一种Z型体系: 使用掺Zn的g-C3N4作为产氢端, BiVO4作为产氧端, Fe3+/Fe2+作为氧化还原对. 实验结果表明, 该体系可以在全波段下实现水的完全分解(氢氧比为2:1), 并且保持相当高的稳定性.实验所使用的氮化碳为固相法烧结尿素制得, Zn的掺杂采用浸渍法, 同时通过水热法合成BiVO4, 使用Pt作为助催化剂. 通过搭建含有不同组成成分的Z型体系, 将它们的性能和表征结果进行比较分析.通过XRD, UV-Vis, SEM和XPS等测试手段对催化剂进行表征. XRD分析结果表明成功合成了掺杂Zn的石墨相氮化碳. UV-Vis则显示随着Zn浓度的提高, 吸收边发生变化. 通过改变掺杂Zn的浓度, 得到了能够实现完全分解水的Z型体系,其最佳掺杂比例为: ZnCl2和氮化碳的质量比为1:10. 为了排除单催化剂和Pt颗粒对完全分解水性能的影响, 分别作了单独产氢端、单独产氧端、预负载Pt和光沉积Pt的性能测试. 从SEM中没有发现g-C3N4和BiVO4的异质结结构. 这些结果表明所搭建的是典型的利用氧化还原离子对为中间电子传输载体的Z型体系, 经长达12 h的持续测试证明其具有较高的稳定性.为了研究Zn在构建Z型中所起的作用, 分别采用文献中报道的原位和浸渍法实现Zn的掺杂. 对这两种掺杂方式的性能测试表明, 只有采用浸渍法时, 所构建的Z型体系具有完全分解水的能力. 对这两种方法得到的掺Zn氮化碳进行表面化学组成和价态(XPS)的分析. 结果显示, 两种掺杂方法都可以通过形成Zn=N键的形式实现Zn的掺杂, 但浸渍法使Zn在g-C3N4表面分布更均匀, 同时对氮化碳原本三嗪环的破坏较小, 因此具有更好的还原能力, 可以与BiVO4匹配以构成Z型体系.实验通过采用掺杂Zn的氮化碳作为产氢催化剂, BiVO4作为产氧催化剂, Fe3+/Fe2+作为氧化还原中间体, 构建了典型的Z型体系. 该体系在Zn的掺杂浓度为10%时能够实现长时间稳定的完全分解水.     

三维百合花状的CoNi2S4作为先进的双功能电催化剂用于氢析出和氧析出反应

为简化电解水催化剂的合成过程和优化电解水操作系统, 双功能电解水催化剂的研究, 特别是在碱性条件下同时具有优异催化氢析出和氧析出反应性能的双功能电催化剂的研究尤为重要. 其中, 过渡金属硫化物, 特别是 CoNi 硫化物, 被报道有与氢化酶类似的催化活性中心, 从而具有优异的催化氢析出和催化氧析出反应性能. 虽然有关对过渡金属硫化物的研究很多, 但主要集中在具有一维纳米线和二维纳米片形貌结构的过渡金属硫化物. 不幸的是, 这些形貌结构的过渡金属硫化物在电催化过程中容易聚集和受限于电荷传输能力. 三维纳米结构的材料具有较大的比表面积以分布更多的活性位点和拥有良好的电子传输能力, 所以, 开发三维纳米结构的过渡金属硫化物材料可能是改进其催化电解水性能的一个好途径. 本文采用简单的两步水热法, 通过硫化合成的 CoNi 前体得到了长于泡沫镍上的三维百合花状的 CoNi2S4(Co-Ni2S4/Ni). 它只需要 54 mV 的过电位即可获得 10 mA cm-2的催化氢析出反应电流, 是最好的碱性催化氢析出反应电极材料之一. 它在驱动 100 mA cm-2的催化氧析出反应电流时也只需要 328 mV 的过电位. 另外, 把 CoNi2S4/Ni 分别作为阴极和阳极组装成双电极碱性水电解槽时, 它只需要 1.56 V 的电压即可获取 10 mA cm-2的催化全电解水电流并具有良好的催化全电解水稳定性.扫描电子显微镜、透射电子显微镜和 N2吸脱附曲线测试结果表明, 该三维百合花状的 CoNi2S4/Ni 的表面粗糙度高和拥有多孔特性. 多孔结构的 CoNi2S4/Ni 可提供更多可接触的催化活性位点, 也有利于催化过程中的电解质和生成的气体的扩散与传递. 交流阻抗图谱测试结果表明, CoNi2S4/Ni 具有良好的电子传输能力. 另外, 不同于前期对尖晶石结构的硫化物 AB2S4的研究结果, XPS 结果表明, CoNi2S4/Ni 中含有 Niб+和 Sб-活性物种, 表明 CoNi2S4具有与活性氢化酶类似的活 性中心. Niδ+和 Sδ-可分别作为氢氧根和质子的接收体, 协助促进吸附的水分子的分离, 从而提高材料的催化性能. 所以, Niδ+和 Sδ-活性物种的出现, 大比表面积的三维百合花状多孔结构和良好的电荷传输能力等特性集合于 CoNi2S4/Ni 上使得CoNi2S4/Ni 具有优异的催化氢析出和催化氧析出反应性能.     

A Graphene‐based Electrochemical Sensor for the Individual,Selective and Simultaneous Determination of Total Chlorogenic Acids,Vanillin and Caffeine in Food and Beverage Samples

An electrochemical sensor based on the electrocatalytic activity of graphene (GR) was prepared, and used for the individual, selective and simultaneous determination of 5‐O‐Caffeoylquinic acid (5‐CQA) that is major compound of chlorogenic acids in coffee, vanillin (VAN) and caffeine (CAF). The electrochemical behaviors of these compounds on GR modified glassy carbon electrode (GR/GCE) were investigated by cyclic voltammetry and square‐wave adsorptive stripping voltammetry. By using stripping conditions after 30 s accumulation under open‐circuit voltage, the electrochemical oxidation peaks appeared at +0.53, 0.83 and 1.39 V in phosphate buffer pH 2.5, and good linear current responses were obtained with detection limits of 4.4×10⁻⁹, 5.0×10⁻⁷, and 3.0×10⁻⁷ M for 5‐CQA, VAN and CAF, respectively. The potential applicability of the proposed method was illustrated in commercial food and beverage samples.