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1.
Yussri Salem 《Surface and interface analysis : SIA》2022,54(7):775-785
The current study aims to characterize a heavily corroded bronze statue from Pharaonic Egypt, in terms of the morphology and mechanism of corrosion. The characterization was carried out by a combination of methods, including the scanning electron microscope equipped with energy dispersive X-ray spectroscopy (SEM–EDS), USB digital microscope, X-ray micro-diffraction, and Raman micro-spectroscopy. Insights into the morphology and corrosion mechanisms of two corrosion stages are presented. Specifically, the metallic-wall layer was first converted into grayish-brown corrosion mottled with green and gray spots in the central part, in which a greenish-white corrosion phase was formed in the second stage. The EDS analysis of the greenish-white phase revealed the predominance of tin, copper, oxygen, and carbon and a low chlorine content. The greenish-white phase consisted of four corrosion products: romarchite, cassiterite, malachite, and a small amount of atacamite. The morphology developed upon corrosion was attributed to the selective dissolution and depletion of copper in the central layer, internal oxidation of tin, and conversion of cuprite into malachite. Moreover, the usual bronze corrosion products were formed as a superficial layer on the statue. 相似文献
2.
烯烃是重要的化工原料,目前主要通过石油催化裂化得到.随着石油资源的消耗以及人们对烯烃需求的日益增长,开发非石油路线制取烯烃势在必行.合成气可以从煤、天然气和生物质等获得,由合成气作为重要的C1平台分子一步制取烯烃(STO)的过程受到了广泛关注.将合成气制甲醇/二甲醚的金属催化剂与甲醇制烯烃的分子筛催化剂耦合得到的混合双功能催化剂,可以使合成气高选择性地转化为烯烃.其中,ZnO/ZrO2金属氧化物催化剂被广泛应于合成气的活化,然而,该金属氧化物结构对混合双功能催化剂上合成气制烯烃反应的影响尚不明确.本文合成了单斜相ZrO2(m-ZrO2)和四方相ZrO2(t-ZrO2),并负载ZnO制成催化剂,再将其与SAPO-34分子筛物理混合得到混合双功能催化剂,用于合成气制烯烃反应中.在较优化的条件下,ZnO/m-ZrO2与SAPO-34分子筛组成的双功能催化剂CO转化率为27.9%,低碳烯烃选择性高达80.5%,性能明显优于ZnO/t-ZrO2+SAPO-34双功能催化剂.为研究ZrO2晶相对催化合成气制烯烃反应性能的影响,对ZnO/ZrO2进行红外光谱表征.结果表明,ZnO/m-ZrO2较ZnO/t-ZrO2具有更多的表面羟基和更多的路易斯酸性位点.金属氧化物表面的路易酸主要与催化剂表面不饱和的金属离子有关,而且Zr基催化剂表面羟基有助于缺陷氧的形成,因此,ZnO/m-ZrO2催化剂表面应该具有更高浓度的氧缺陷位.光电子能谱进一步证明了ZnO/m-ZrO2表面有更高浓度的氧缺陷位.另外,Zr基催化剂上表面羟基还有利于CO与其形成羧酸盐物种,在623-673 K条件下的CO原位吸附的红外光谱表明,ZnO/m-ZrO2催化剂上CO吸附的浓度及其表面羧酸盐浓度均明显高于ZnO/t-ZrO2催化剂,这与ZnO/m-ZrO2表现出更好的催化合成气转化性能一致.为了探究该催化剂体系上合成气制烯烃的反应路径,分别对两种晶相的ZnO/ZrO2和相应的双功能催化剂进行了原位红外监测.与CO红外漫反射相比,合成气氛围下金属氧化表面除了存在吸附态的CO和甲酸盐物种,还存在表面甲氧基物种,后者是合成气制甲醇/二甲醚过程重要的中间物种.对合成气制烯烃过程中分子筛上的停留物种进行分析,结果发现,停留物种中含有多甲基苯、多甲基萘等甲醇制烯烃过程中的烃池物种.另外,合成气氛围下双功能催化剂甲氧基信号峰明显弱于金属氧化物表面甲氧基的信号强度,表明STO过程应该是合成气制甲醇/二甲醚与甲醇制烯烃的串联过程.综上所述,在STO反应中,相较于ZnO/t-ZrO2催化剂,ZnO/m-ZrO2催化剂具有更高浓度的表面羟基物种、路易斯酸密度和表面氧缺陷位,从而有利于羧酸盐及甲氧基中间物种的形成,进而提高了混合双功能催化剂催化STO反应性能. 相似文献
3.
光催化完全分解水制氢是一个在粉末颗粒中实现多个串行物理化学步骤的复杂反应过程.这一过程在理论上具有体系简单、成本低、易操作等特点.然而,单步光激发系统中通常存在严重的光生载流子复合,这极大地制约了光催化的整体效率.利用能带结构不同的半导体合理构建异质结催化剂被认为是解决这一难题的重要途径之一.特别是近年来,S型异质结概念的提出为设计异质结结构以及分析不同半导体之间的载流子迁移问题提供了新的思路.本文以小粒径BiVO4/Bi0.6Y0.4VO4(BYV)为研究对象,首先利用"共沉淀-晶化"的方法制备了BYV固溶体纳米颗粒,随后利用压力诱导固溶体中四方相钒酸铋结构转变为单斜相,从而构建了BiVO4/Bi0.6Y0.4VO4复合光催化剂.XRD,Raman,HRTEM,HAADF-EDS的结果表明,经过高压后处理的BYV固溶体表面会出现粒径约为5 nm单斜钒酸铋纳米颗粒,实现了原位构建异质结结构.随后载流子动力学的相关表征以及Au选择性光沉积的结果表明,在光照条件下,所构建异质结中的光生电子主要分布在BYV固溶体上,而在表面形成的单斜相钒酸铋颗粒主要起到了类似"空穴"捕获的作用.这种在异质结中的载流子迁移路径符合S型异质结机理.电化学、稳态荧光光谱以及瞬态荧光光谱的表征结果表明,相比于单一固溶体,在S型异质结这种两步激发系统中所存在的载流子迁移路径能够大幅促进光生载流子分离,从而提高了小粒径BYV的光催化完全分解水性能.综上,构建S型异质结是一种解决小粒径光催化剂中载流子分离能力差的有效途径.同时,压力诱导材料晶型转变实现原位构建异质结的制备方法也为提高光生载流子分离效率提供了新的研究思路与机遇. 相似文献
4.
Yongjing Liu Qiang Chen Suxia Zhang Hua Zhang Wei Xu 《Biomedical chromatography : BMC》2022,36(3):e5293
Deep eutectic solvents (DESs) were applied as eco-friendly solvents in this study for the extraction of alkaloids from lotus leaf, including O-nornuciferine, N-nornuciferine, nuciferine and roemerine. A series of hydrophilic and hydrophobic DESs with different hydrogen bond donors and a acceptors were synthesized and screened for a suitable DESs for extraction of alkaloids from lotus leaf. The study results showed that the hydrophilic DES with choline chloride and propanediol had the highest extraction yield. The main factors affecting the extraction efficiency—choline chloride–propanediol ratio, water content in deep eutectic solvents, solid–liquid ratio and extraction time—were investigated via a single-factor experiment. The optimized extraction conditions were 30% of water in choline chloride–propanediol (1:4) for heated extraction for 30 min and solid–liquid ratio 1:100 g/ml. Under optimum conditions, the extraction yields of O-nornuciferine, N-nornuciferine, nuciferine and roemerine were 0.069, 0.152, 0.334 and 0.041 g/100 g respectively, which were higher than those of methanol in acidified aqueous solution. This study suggests considerable potential for DESs as promising materials for the green and efficient extraction solvents for bioactive alkaloids from natural sources. 相似文献
5.
Elnaz Marzi Khosrowshahi Behnaz Limuie Khosrowshahi Mir Ali Farajzadeh Abolghasem Jouyban Mustafa Tuzen Mohammad Reza Afshar Mogaddam Mahboob Nemati 《Biomedical chromatography : BMC》2022,36(7):e5371
A dispersive solid-phase extraction method based on a new sorbent has been performed on plasma and wastewater samples to determine metoprolol by high-performance liquid chromatography–tandem mass spectrometry. In this study, the analyte was adsorbed from the samples onto microcrystalline cellulose as a green and efficient sorbent and then eluted for use in the determination step. In the mass spectrometer, the analyte was detected in the positive mode and selectivity of the analysis was increased by sequential mass analysis through multiple reaction monitoring. All of the effective parameters in the extraction of metoprolol from plasma and wastewater were optimized. Under optimal conditions the method was linear in the ranges of 1–1,000 and 0.1–1,000 ng/ml in plasma and wastewater samples, respectively. The detection limits of the method were 0.30 and 0.03 ng/ml in plasma and wastewater samples, respectively. The data showed that the method provides low detection limit, wide linear range, good precision and high extraction recovery. Finally several plasma and wastewater samples were successfully analyzed using the method. The use of a small amount of a green and inexpensive sorbent and a low volume of plasma without the need for further pretreatment steps are the main advantages of the method. 相似文献
6.
Yuan Xiong Long Ye Chao Zhang 《Journal of polymer science. Part A, Polymer chemistry》2022,60(6):945-960
All-polymer solar cells (all-PSCs) exhibit great potentials in commercial applications. All-PSCs have observed steady performance gains with power conversion efficiency now reaching over 17% in the open literature. However, the current processing of all-PSCs relies predominantly on toxic, chlorinated solvents in moisture-free environments, representing a significant barrier for their commercialization due to the added costs to handle and dispose of such solvents. There is thus an urgent need for safe, environmentally benign, and sustainable ink-based processing methods to produce all-PSC devices reliably and reproducibly in ambient air. In this perspective, fundamental insights on the interplay between all-polymer blend morphologies and eco-friendly solvents are provided. Also, we discuss the recent successes of the green processing methods to manipulate the photoactive morphologies for high-efficiency all-PSCs. In the end, we provide an outlook on future challenges and opportunities of eco-friendly solvents processed all-PSCs for large-scale manufacturing. 相似文献
7.
Chelating resins based on biopolymers, specifically cellulose, offers a green analytical method for determination of metal ions at trace levels present in various samples. It offers a fast, accurate and simple method for separation and pre-concentration of metal ions at low concentrations, prior to their determination by instrumental method. Cellulose based chelating resin (CELL-GLY) has been synthesised by immobilising glycine on it. CELL-GLY was used for the determination of trace amounts of Cu2+ and Ni2+ from aqueous solutions before their determination by FAAS. The preparation of CELL-GLY involves simple steps, based on natural and easily available biopolymer cellulose, which makes its use as chelating resin is a green method. The Cu2+ and Ni2+ can be quantitatively recovered from the CELL-GLY in the pH range 4.8–6.9 and 6.9-7.8 respectively with a recovery of more than 95% for each of these metal ions. Recovery of these metal ions using CELL-GLY was quantitative up to 35 °C. The detection limits for copper and nickel by FAAS were 1.20 ppb and 1.40 ppb, respectively. The method was successfully employed for the determination of trace amounts of Cu2+ and Ni2+ in various samples. 相似文献
8.
Mark P. Stockham Alice Griffiths Dr. Bo Dong Prof. Peter R. Slater 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(6):e202103442
Lithium garnets are promising solid-state electrolytes for next-generation lithium-ion batteries. These materials have high ionic conductivity, a wide electrochemical window and stability with Li metal. However, lithium garnets have a maximum limit of seven lithium atoms per formula unit (e.g., La3Zr2Li7O12), before the system transitions from a cubic to a tetragonal phase with poor ionic mobility. This arises from full occupation of the Li sites. Hence, the most conductive lithium garnets have Li between 6–6.55 Li per formula unit, which maintains the cubic symmetry and the disordered Li sub-lattice. The tetragonal phase, however, forms the highly conducting cubic phase at higher temperatures, thought to arise from increased cell volume and entropic stabilisation permitting Li disorder. However, little work has been undertaken in understanding the controlling factors of this phase transition, which could enable enhanced dopant strategies to maintain room temperature cubic garnet at higher Li contents. Here, a series of nine tetragonal garnets were synthesised and analysed by variable temperature XRD to understand the dependence of site substitution on the phase transition temperature. Interestingly the octahedral site cation radius was identified as the key parameter for the transition temperature with larger or smaller dopants altering the transition temperature noticeably. A site substitution was, however, found to make little difference irrespective of significant changes to cell volume. 相似文献
9.
Jianfeng Zhang Dr. Marco Wenzel Johannes Steup Gerrit Schaper Dr. Felix Hennersdorf Prof. Dr. Hao Du Prof. Dr. Shili Zheng Prof. Dr. Leonard F. Lindoy Prof. Dr. Jan J. Weigand 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(1):e202103640
Effective receptors for the separation of Li+ from a mixture with other alkali metal ions under mild conditions remains an important challenge that could benefit from new approaches. In this study, it is demonstrated that the 4-phosphoryl pyrazolones, H L 2-H L 4, in the presence of the typical industrial organophosphorus co-ligands tributylphosphine oxide (TBPO), tributylphosphate (TBP) and trioctylphosphine oxide (TOPO), are able to selectively recognise and extract lithium ions from aqueous solution. Structural investigations in solution as well as in the solid state reveal the existence of a series of multinuclear Li+ complexes that include dimers (TBPO, TBP) as well as rarely observed trimers (TOPO) and represent the first clear evidence for the synergistic role of the co-ligands in the extraction process. Our findings are supported by detailed NMR, MS and extraction studies. Liquid-liquid extraction in the presence of TOPO revealed an unprecedented high Li+ extraction efficiency (78 %) for H L 4 compared to the use of the industrially employed acylpyrazolone H L 1 (15 %) and benzoyl-1,1,1-trifluoroacetone (52 %) extractants. In addition, a high selectivity for Li+ over Na+, K+ and Cs+ under mild conditions (pH ∼8.2) confirms that H L 2-H L 4 represent a new class of ligands that are very effective extractants for use in lithium separation. 相似文献
10.
Dr. Somnath Dey Dr. Andreas Schönleber Prof. Dr. Sander van Smaalen Dr. Wolfgang Morgenroth Prof. Dr. Finn Krebs Larsen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(13):e202104151
Phase transitions in molecular crystals are often determined by intermolecular interactions. The cage complex of [Co(C12H30N8)]3+ ⋅ 3 NO3− is reported to undergo a disorder-order phase transition at Tc1 ≈133 K upon cooling. Temperature-dependent neutron and synchrotron diffraction experiments revealed satellite reflections in addition to main reflections in the diffraction patterns below Tc1. The modulation wave vector varies as function of temperature and locks in at Tc3≈98 K. Here, we demonstrate that the crystal symmetry lowers from hexagonal to monoclinic in the incommensurately modulated phases in Tc1<T<Tc3. Distinctive levels of competitions: trade-off between longer N−H⋅⋅⋅O and shorter C−H⋅⋅⋅O hydrogen bonds; steric constraints to dense C−H⋅⋅⋅O bonds give rise to pronounced modulation of the basic structure. Severely frustrated crystal packing in the incommensurate phase is precursor to optimal balance of intermolecular interactions in the lock-in phase. 相似文献