一体化电极电催化二氧化碳还原研究进展

电催化二氧化碳还原反应(E-CO₂RR)可在温和条件下将CO₂转化成高附加值燃料或化学品,近年来受到广泛关注,其在实际反应中涉及到气体扩散和多电子转移等复杂过程,构筑高效、稳定的催化电极是其发展的核心之一。然而,传统涂敷电极制备时,需要将催化剂与粘结剂混合涂覆于集流体表面,此过程会造成活性位点包埋和传质过程受限,致使催化剂活性位利用率下降,同时在反应过程中电极表面容易粉化,造成稳定性下降,难以重复利用。因此,如何调控电极反应界面,提升催化剂活性位的利用率仍面临挑战。将催化剂原位生长于集流体上得到的一体化电极可直接应用于电催化反应,不仅有利于提升活性位利用率以及电荷传输能力,还能有效调控三相界面处的微观反应环境(如pH、反应物及反应中间体的浓度等),从而实现电催化性能强化。本文综述了一体化电极用于E-CO₂RR的最新进展,分析了结构和表界面调控对E-CO₂RR性能的影响规律,并对该领域仍然存在的挑战和未来一体化E-CO₂RR电极的发展进行了评述与展望。     

Synergistic effect of aluminum trihydrate and zirconium hydroxide nanoparticles on mechanical properties,flammability, and thermal degradation of polyester/jute fiber composite

Cellulose - This study focuses on the synergistic effects of hydroxide based nanoparticles namely aluminum trihydrate (ATH) and zirconium hydroxide (ZHO) on the mechanical characteristics, thermal...     

石墨烯包覆天然球形石墨作为锂离子电池的负极材料，是否需要乙炔黑导电剂？

我们通过包覆炭化的方法制备得到了石墨烯包覆的天然球形石墨(G/SG)材料,并使用扫描电子显微镜、X射线衍射仪以及多种电化学测试手段考察了不同石墨烯含量的复合材料的形貌结构及电化学性能。我们发现,在不添加乙炔黑(AB)的情况下,G/SG复合材料表现出较高的首次库伦效率,很好的循环稳定性和高倍率性能。当石墨烯包覆量为1%时,材料50次循环后的可逆容量可与添加10%AB的天然石墨电极(SG)等同;当石墨烯包覆量为2.5%时,材料的比容量完全高于添加10%AB的石墨电极。材料电化学性能的改善归因于石墨烯的包覆。一方面,石墨烯的柔软可变性可以保证天然石墨颗粒在充放电过程中的结构完整性,从而有效改善材料的循环稳定性;另一方面,石墨烯的存在提高了电极的导电性,促进更好导电网络的形成。因此,石墨烯包覆天然球形石墨材料中,石墨烯不仅是活性物质,也发挥导电剂的作用。当添加5%的乙炔黑时,在50 mA·g^-1电流循环50次后,5%G/SG电极的可逆容量从381.1 mAh·g^-1提高到404.5 mAh·g^-1,在1 A·g^-1电流时可逆容量从82.5 mAh·g^-1提高到101.9 mAh·g^-1,这表明G/SG电极仍然需要乙炔黑导电剂。乙炔黑颗粒填充在复合材料的空隙中,通过点接触的形式连接到G/SG颗粒,与石墨烯协同作用形成了更加有效的导电网络。尽管石墨烯包覆和乙炔黑添加对天然石墨电极具有积极的影响,例如增加了天然石墨电极的导电性和储锂性能(包括可逆容量,倍率性能和循环性能),但随着石墨烯或乙炔黑的增加,电极密度通常会降低。因此,在实际应用中应考虑石墨负极材料的质量和体积容量的平衡。这些结果对天然石墨的进一步商业应用具有重要意义。我们的工作为天然石墨电极在锂电池中的电化学行为提供了一种新的认识,并且有助于制备更高性能的负极材料。     

低共熔溶剂分散液液微萃取-悬浮固化-高效液相色谱法测定水产品中3种内分泌干扰物的含量北大核心CSCD

将癸酸和香叶醇在10 mL玻璃管中以2∶1的物质的量之比混合,然后将混合物在80℃水浴锅中加热,直至形成稳定的低共熔溶剂(DES)。该溶剂易合成、低成本、低毒性且具有高生物降解性,是一种新型的疏水性DES,可用于水产品中内分泌干扰物的微萃取。取已粉碎的水产品样品1 g和乙腈2 mL置于5 mL离心管中,以转速2 000 r·min^(-1)涡旋振荡3 min。取上清液400μL,经0.45μm滤膜过滤,滤液与100μL DES混合,并迅速注入装有5 mL 80 g·L^(-1)氯化钠溶液的10 mL离心管中,以完成DES的分散。将上述离心管以转速3 500 r·min^(-1)离心5 min,然后置于冰浴中进行固化。将固化后所得样品溶解于150μL甲醇中,以Eclipse Plus C;色谱柱为分离柱,以体积比90∶10的甲醇-水的混合液为流动相,在激发波长228 nm,发射波长305 nm处测定双酚A、4-叔辛基苯酚和壬基酚等3种内分泌干扰物的含量。结果表明,DES在冰浴中固化,可促进其从水溶液中分离,简单且快速,利于萃取剂的收集。3种内分泌干扰物的质量分数均在0.25~10μg·g^(-1)内与其对应的峰面积呈线性关系,检出限(3S/N)均为0.075μg·g^(-1)。用此法对空白加标样品进行测定,测定值的日内和日间相对标准偏差(n=5)均小于4.0%。以空白样品为基体进行加标回收试验,所得回收率为78.7%~91.6%。     

Graphene Nanocomposites Based Electrochemical Sensing Platform for Simultaneous Detection of Multi-drugs

Three reduced graphene oxide nanocomposites were employed to achieve the simultaneous electrochemical determination of multi-drugs including acetaminophen (ACTM), carbendazim (CB) and ciprofloxacin (CFX). All nanocomposite modified electrodes showed improved current responses for three drugs. Notably cauliflower-like platinum nanoparticles decorated reduced graphene oxide modified electrode (or Pt−RGO/GCE) exhibited the best performance in terms of electrochemical stability. Using Pt−RGO/GCE, the linear detect ranges of 30–120 μM, 25–115 μM and 10–25 μM, and detection limit values of 3.49, 2.96, and 1.53 μM were achieved for ACTM, CB and CFX respectively. The electrode was further used for the successful determination of above drugs in tap and river water using differential pulse voltammetry. From the obtained results, we believe that Pt-RGO/GCE is highly promising for the fabrication of robust electrochemical sensors for simultaneously determining ACTM, CB and CFX or similar types of drugs in the future.     

“Ghost peaks” of olmesartan medoxomil: Two solution degradation products of olmesartan medoxomil via oxidation mediated by metal ions

Two unknown solution degradants were found during the dissolution testing in 0.1-M HCl for olmesartan medoxomil (OLM) tablets. The structure of the degradants was identified and characterized by liquid chromatography–ultraviolet (LC–UV), liquid chromatography with tandem mass spectrometry (LC–MS/MS), and nuclear magnetic resonance (NMR) and demonstrated to be cyclization of tetrazole and benzene in the olmesartan (OL) and OLM structures. A series of studies including stress studies, simulation studies, and mechanism-based studies were performed to reveal the potential mechanisms that lead to the formation of the unknown degradants. The study results demonstrated that the degradation was catalyzed with radicals that originated from the metal ions leached from the inner surface of high-performance liquid chromatography (HPLC) glass vials with dissolved oxygen under acidic condition. Prerinsing the glass vials with acidic solution dissolved with EDTA can effectively avoid the generation of such oxidative impurities. The present work provides new insights into the understanding of degradation pathways of OLM, which might support the development of OLM tablets.     

High-performance liquid chromatography quantitative analysis of ephedrine alkaloids in Ephedrae Herba on a perfluorooctyl stationary phase

Ephedrae Herba is one of the most commonly used herbal medicines, and it has been shown that most of the clinical efficacy for cold and asthma is exerted by its alkaloidal components. A simple and sensitive high-performance liquid chromatography method was developed using a perfluorooctyl column for the simultaneous determination of five alkaloids (norephedrine, norpseudoephedrine, ephedrine, pseudoephedrine, and methylephedrine) in Ephedrae Herba. The mobile phase comprising acetonitrile and 15 mM ammonium trifluoroacetate was used to elute the targets in isocratic elution mode. The method was validated for linearity (R² > 0.999), repeatability, intraday and interday precision, recoveries with trueness (93.87–110.99%), limits of detection (5.35–5.76 µg/mL), and limits of quantification (20 µg/mL). The quantitative results revealed that the developed method was precise and accurate. Then it was successfully applied to determine the difference in the contents of three batches of Ephedrae Herba from three pharmaceutical companies.     

Extraction of parabens by melamine sponge with determination by high-performance liquid chromatography

In the present study, we propose a novel method for the extraction of parabens in personal care products. A new, simple adsorptive material was obtained by combining metal-organic frameworks and melamine sponges using the adhesive property of polyvinylidene fluoride. This new material, metal-organic frameworks/melamine sponges, was found to be particularly suitable for solid-phase extraction. The structural characteristics of metal-organic frameworks/melamine sponges were first analyzed by scanning electron microscopy. Subsequently, solid-phase extraction was performed on sample solutions, and the extracted substances were then analyzed by high-performance liquid chromatography. Following optimization of important experimental conditions, excellent recovery rates were obtained. Our novel method was then applied to the extraction of four parabens (methylparahydroxybenzoates, ethylparahydroxybenzoates, propylparahydroxybenzoates, and butylparahydroxybenzoates) from real samples. The results yielded limits of detection of 0.26–0.41 ng/mL. The inter- and intra-day recoveries were 104.0–109.7% and 91.2–98.1%, respectively (relative standard deviation, <13.8%).     

还原-氧化协同降解全/多卤代有机污染物

全/多卤代有机污染物大多具有生态毒性、生物蓄积性、环境持久性及长距离迁移性,不仅危害环境与生态安全,而且可经食物链传递威胁人类健康。由于卤原子是吸电子基团且取代数目多,这类物质的最高占据分子轨道能较低,难于被氧化降解,相反较易被还原法脱卤降解。随卤原子取代数减少,脱卤产物难被进一步还原,而其毒性甚至高于母体污染物。注意到低卤代有机物更容易发生氧化降解,一些研究构建了还原-氧化接力降解体系,即先利用还原法将全/多卤代有机污染物还原为低卤代产物,再利用氧化法降解这些中间产物,从而实现深度/完全脱卤和矿化。本文根据催化反应类型对还原-氧化联用法进行了归纳,分类介绍了基于传统化学催化、光催化、电化学、光电化学及机械化学等构建还原-氧化协同降解体系的原理及应用,以期为开发高效的处置技术提供思路和建议。     

A Unique Layered Cu-formate Hydrate of Cu(HCOO) 2·1/3H2O: Structures,Dehydration, and Thermal and Magnetic Properties

Anew layered Cu-formate hydrate of Cu(HCOO)₂·1/3H₂O is unique in its water content and the strongly waved (4,4) Cu-formate layers held by interlayer weak axial Cu-O_formate bonds and O-H_water···O_formate hydrogen bonds. The crystal is in orthorhombic space group Pbcn, with cell parameters at 80 K:a=7.9777(2) Å, b=7.3656(2) Å, c=21.0317(5) Å(1 Å=10⁻¹ nm), and V=1235.83(5) ų. The Cu²⁺ ions are in the environments of a square pyramid and elongated octahedron, in a ratio of 1/2 within the structure. In the layer, Cu²⁺ ions are connected by anti-anti formates via short basal Cu-O bonds. The structure remains unchanged until the dehydration that produces the layered anhydrous β-Cu(HCOO)₂, and the possible transformation mechanism, supported by diffraction evidence, is the reorganization of the Cu-O_formate bonds across the parent layers after dehydration. The two phases exhibit anisotropic thermal expansion behaviors closely relevant to the transverse thermal vibrations of the constituents. Cu(HCOO)₂·1/3H₂O is a 2-dimensional Heisenberg antiferromagnet, and exhibits a global spin-canted antiferromagnetism with the Néel temperature of 32.1 K. This is not only higher than that of the magnetically denser β-Cu(HCOO)₂, but also the highest among the copper formate frameworks.