Electrochemistry

电化学
  • 文章类型: Journal Article
    磺化的三(1-苯基吡唑)铱(III)配合物([Ir(sppz)3]3-)用作广泛使用的三(2,2'-联吡啶)钌(II)([Ru(bpy)3]2)与三正丙胺(TPrA)共反应物的ECL检测系统的概念证明非发射增强剂,通过TPrA氧化的电催化和发光体的有效化学激发作用。使用自干扰ECL光谱,我们表明,增强剂从电极表面扩展了所需的电生成前体的扩散。先前报道的通过这些途径的增强已被增强子的固有ECL混淆,但是使用[Ir(sppz)3]3-获得了[Ru(bpy)3]2ECL强度的增加,而没有伴随发射。最显著的增强(11倍)发生在与“间接”共反应物ECL途径相关的低电位下,当发光体固定在微珠上作为增强的ECL测定的一般模型时,其转化为2至6倍的增强。
    A sulfonated tris(1-phenylpyrazolato)iridium(III) complex ([Ir(sppz)3]3-) serves as a proof-of-concept non-emissive enhancer of the widely used ECL detection system of tris(2,2\'-bipyridine)ruthenium(II) ([Ru(bpy)3]2+) with tri-n-propylamine (TPrA) co-reactant, acting through electrocatalysis of TPrA oxidation and efficient chemi-excitation of the luminophore. Using self-interference ECL spectroscopy, we show that the enhancer extends diffusion of the required electrogenerated precursors from the electrode surface. Previously reported enhancement through these pathways has been confounded by the inherent ECL of the enhancer, but the increase in [Ru(bpy)3]2+ ECL intensity using [Ir(sppz)3]3- was obtained without its concomitant emission. The most prominent enhancement (11-fold) occurred at low potentials associated with the \'indirect\' co-reactant ECL pathway, which translated to between 2- and 6-fold enhancement when the luminophore was immobilised on microbeads as a general model for enhanced ECL assays.
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  • 文章类型: Journal Article
    由于其独特的层结构,2D材料已被证明是用于可再充电电池的有前途的电极材料。然而,单个2D材料不能满足能量密度的所有性能要求,功率密度,和循环寿命。构建基于2D材料的异质结构提供了协同处理单个2D材料的缺陷并调节物理和电化学性质的机会。增加的层间距离和增加的结合能与异质结构的离子可以促进电荷转移,提高电化学反应性,导致可充电电池性能增强。在这里,我们总结了由2D材料组成的异质结构的最新发展及其在可充电电池中的应用。首先,系统地介绍了基于二维材料的异质结构的不同制备策略和优化结构工程策略。其次,分别讨论了基于二维材料的异质结构在可充电电池中的独特功能。最后,提出了挑战和观点,以激发基于2D材料的异质结构的未来研究。
    Because of their unique layer structure, 2D materials have demonstrated to be promising electrode materials for rechargeable batteries. However, individual 2D materials cannot meet all the performance requirements of energy density, power density, and cycle life. Constructing 2D materials-based heterostructures offers an opportunity to synergistically handle the deficiencies of individual 2D materials and modulate the physical and electrochemical properties. The enlarged interlayer distance and increased binding energy with ions of heterostructures can facilitate charge transfer, boost electrochemical reactivities, resulting in an enhanced performance in rechargeable batteries. Here we summarize the latest development of heterostructures consisted of 2D materials and their applications in rechargeable batteries. Firstly, different preparation strategies and optimized structure engineering strategies of 2D materials-based heterostructures are systematically introduced. Secondly, the unique functions of 2D materials-based heterostructures in rechargeable batteries are discussed respectively. Finally, challenges and perspectives are presented to inspire the future study of 2D materials-based heterostructures.
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  • 文章类型: Journal Article
    高毒性是传统缓蚀剂应用受限的主要原因。在这里,找到绿色是至关重要的,高效,和长期稳定的替代替代危险和常规腐蚀抑制剂。三裂AmbrosisL作为入侵植物在中国广泛分布于田间和河边湿地。根据变废为宝的概念,三叶AmbrosiaL叶(ATL)的提取物由于其天然来源和杂环有机物的丰富存在而具有解决这一问题的潜力。因此,ATL,作为绿色缓蚀剂,首次通过简单的水基提取方法制备。FT-IR(傅里叶变换红外光谱)和UV-Vis(紫外-可见)表明ATL萃取物含有丰富的共轭结构的杂环有机物,具有成为高效抑制剂的潜力。值得注意的是,通过理论计算揭示了ATL分子的活性位点及其与Q235钢在分子/原子水平上的相互作用。ATL提取物中主要成分的最高结合值为259.66kcal/mol,意味着显著的吸附能力。电化学结果验证了微剂量ATL提取物能显著抑制钢的腐蚀,最高抑制效率(η)为97.5%(1000mg/L)。浸泡24小时后,η值提高到99.0%,表明一个可靠的和长期的ATL提取物保护膜形成在钢表面在苛刻的酸性溶液。减肥的结果,SEM(扫描电子显微镜),LSCM(激光扫描共聚焦显微镜)与上述结论一致。最后,本研究为开发新型绿色植物提取物抑制剂及其在工业酸洗环境中的应用提供了理论支持。
    High toxicity is the main reason for the limited application of traditional corrosion inhibitors. Herein, it is critical to find a green, efficient, and long-term stable alternative substitute for the hazardous and conventional corrosion inhibitor. Ambrosia trifida L is widely distributed in fields and riverside wetlands as an invasive plant in China. According to the concept of turning waste into treasure, the extract of Ambrosia trifida L leaves (ATL) has the potential to address this issue due to its natural origin and abundant presence of heterocyclic organics. Therefore, ATL, as a green corrosion inhibitor, is prepared for the first time via a simple water-based extraction method. FT-IR (Fourier transform infrared spectroscopy) and UV-Vis (UV-visible) indicate that ATL extract contains abundant heterocyclic organics with conjugated structures, which exhibit the potential to become a high-efficiency inhibitor. Notably, the active sites of ATL molecules and their interaction with Q235 steel at the molecular/atomic level are revealed via theoretical calculations. The highest Ebinding value observed for the major components in the ATL extract is 259.66 kcal/mol, implying a significant adsorption capacity. The electrochemical results verify that microdose ATL extract can prominently inhibit steel corrosion, and the highest inhibition efficiency (η) is 97.5% (1000 mg/L). Following immersion for 24 h, the η value is enhanced to 99.0%, indicating a reliable and long-term ATL extract protection film is formed on the steel surface in harsh acidic solutions. The results of the weight loss, SEM (scanning electron microscope), and LSCM (laser scanning confocal microscopy) are consistent with the above conclusions. Finally, this study anticipates providing theoretical support for developing novel green plant extract inhibitors and aiding in their application in industrial pickling environments.
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  • 文章类型: Journal Article
    活化PMS以产生活性物质是抗生素降解的有吸引力的技术,但受限于低反应动力学和高成本。在这项工作中,通过原位电沉积制备了钴基催化剂,以增强电激活的PMS降解抗生素的过程。在电活化的过氧单硫酸盐(PMS)工艺中,通过使用Co(OH)2作为催化剂,在10分钟内除去了几乎100%的培氟沙星(PFX),反应动力学常数达到0.52min-1。Co(OH)2催化剂中Co2和Co3的氧化还原过程被认为是PMS活化的主要途径。其中1O2是主要的活性物种。此外,该策略还可以实现对其他有机污染物的优异降解效率。该研究为污染物降解提供了一种有效且低成本的无二次污染策略。
    The activation of PMS to produce active species is an attractive technique for antibiotic degradation but is restricted to the low reaction kinetics and high costs. In this work, a cobalt-based catalyst was prepared by in situ electrodeposition to enhance the electrically activated PMS process for the degradation of antibiotics. Almost 100% of pefloxacin (PFX) was removed within 10 min by employing Co(OH)2 as the catalyst in the electrically activated peroxymonosulfate (PMS) process, and the reaction kinetic constant reached 0.52 min-1. The redox processes of Co2+ and Co3+ in Co(OH)2 catalysts were considered to be the main pathways for PMS activation, in which 1O2 was the main active species. Furthermore, this strategy could also achieve excellent degradation efficiency for other organic pollutants. This study provides an effective and low-cost strategy with no secondary pollution for pollutant degradation.
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  • 文章类型: Journal Article
    作为实现碳中和和以可用形式存储可再生能源的实用解决方案,二氧化碳(CO2)到有价值的化学品的电化学转化正受到极大关注。最近的研究越来越集中在设计专门将CO2转化为乙醇的电催化剂上,由于其高能量密度而成为理想的产品,易于存储,和便携性。然而,与乙烯(具有相似电子构型的竞争产物)相比,实现高效乙醇生产仍然是一个挑战。现有的电催化系统经常受到诸如低能量效率、稳定性差,对乙醇的选择性不足。受到该领域最新进展的启发,这篇综述探讨了CO2电还原的基本原理和材料进展,强调乙醇生产超过乙烯的策略。我们讨论电催化剂设计,反应机制,挑战,以及未来的研究方向。这些进步旨在弥合当前研究与该技术的工业化应用之间的差距。
    The electrochemical conversion of carbon dioxide (CO2) to valuable chemicals is gaining significant attention as a pragmatic solution for achieving carbon neutrality and storing renewable energy in a usable form. Recent research increasingly focuses on designing electrocatalysts that specifically convert CO2 into ethanol, a desirable product due to its high-energy density, ease of storage, and portability. However, achieving high-efficiency ethanol production remains a challenge compared to ethylene (a competing product with a similar electron configuration). Existing electrocatalytic systems often suffer from limitations such as low energy efficiency, poor stability, and inadequate selectivity toward ethanol. Inspired by recent progress in the field, this review explores fundamental principles and material advancements in CO2 electroreduction, emphasizing strategies for ethanol production over ethylene. We discuss electrocatalyst design, reaction mechanisms, challenges, and future research directions. These advancements aim to bridge the gap between current research and industrialized applications of this technology.
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  • 文章类型: Journal Article
    MicroRNA,作为一种独特的生物标志物,在许多严重疾病的早期预后和诊断中起着至关重要的作用。然而,由于其固有的特性,如低丰度,小尺寸,和高度的序列相似性,微小RNA的灵敏和准确检测仍然是一个重大挑战。在这里,开发了用于microRNA检测的双模式电化学生物传感平台,基于聚(3,4-亚乙基二氧噻吩)(PEDOT)掺杂氧化石墨烯-Fe3O4(GO-Fe3O4)纳米复合材料。GO-Fe3O4/PEDOT复合材料表现出多孔微观结构,出色的导电性,对亚硝酸盐具有强大的催化活性。使用循环伏安法(CV)以一步法将其电沉积到电极表面上。通过形成酰胺键将具有氨基的DNA锚定到GO-Fe3O4/PEDOT层来获得microRNA生物传感器。设计的双模式microRNA生物传感器表现出从10-15M到10-6M的宽线性范围,当使用计时库仑法(CC)和安培法i-t曲线(i-t)模式时,检测限低为5.18×10-15M和7.36×10-15M,分别。此外,双模式电化学生物传感器已成功开发并用于检测人血清中的microRNA,证明了其在精确和灵敏的microRNA检测中的潜力及其在临床医学中的实际应用价值。
    MicroRNA, as a distinctive biomarker, plays a crucial role in the early prognosis and diagnosis of numerous severe diseases. However, due to its inherent properties such as low abundance, small size, and high sequence similarity, the sensitive and accurate detection of microRNA remains a major challenge. Herein, a dual-mode electrochemical biosensing platform was developed for microRNA detection, based on poly(3,4-ethylenedioxythiophene) (PEDOT) doped with graphene oxide-Fe3O4 (GO-Fe3O4) nanocomposite. The GO-Fe3O4/PEDOT composite demonstrated a porous microstructure, outstanding conductivity, and robust catalytic activity towards nitrite. It was electrodeposited onto the electrode surface in a one-step process using the cyclic voltammetry method (CV). The microRNA biosensor was obtained by anchoring DNA with amino groups to the GO-Fe3O4/PEDOT layer through the formation of amide bonds. The designed dual-mode microRNA biosensor demonstrated a broad linear range spanning from 10-15 M to 10-6 M, with low detection limits of 5.18 × 10-15 M and 7.36 × 10-15 M when using chronocoulometry (CC) and amperometric i-t curve (i-t) modes, respectively. Furthermore, a dual-mode electrochemical biosensor has been successfully developed and utilized for the detection of microRNA in human serum, demonstrating its potential for precise and sensitive microRNA detection and its practical application value in clinical medicine.
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  • 文章类型: Journal Article
    细胞间的相互作用在许多生物过程中起着重要的作用。并且已经开发了用于控制细胞-细胞相互作用的各种方法。然而,细胞间相互作用的有效和快速控制仍然具有挑战性。在这里,我们报道了一部小说,快速,和有效的电化学策略,而不破坏通过脂质体融合动态控制细胞间相互作用的基本生命过程。在拟议的系统中,在脂质体融合的基础上,在活细胞表面修饰了生物正交化学基团和氢醌(HQ)-和氨基氧基(AO)-连接的配体,实现动态细胞间组装。在施加相应的氧化电势时,“关闭状态”HQ可以被氧化为“打开状态”醌(Q),其随后与AO系链配体反应以在生理条件下形成稳定的肟键。这种反应有效地缩短了细胞之间的距离,促进细胞簇的形成。当施加相应的反向还原电势时,肟键被切断,导致细胞的释放。此外,我们使用HQ和AO系链配体修饰线粒体,诱导线粒体聚集。这种非侵入性和无标记策略允许动态可逆调节细胞间相互作用,增强我们对蜂窝间通信网络的理解,具有提高抗肿瘤治疗疗效的潜力。
    Cell-cell interactions play an important role in many biological processes, and various methods have been developed for controlling the cell-cell interactions. However, the effective and rapid control of intercellular interactions remains challenging. Herein, we report a novel, rapid, and effective electrochemical strategy without destroying the basic life processes for the dynamic control of intercellular interactions via liposome fusion. In the proposed system, bioorthogonal chemical groups and hydroquinone (HQ)- and aminooxy (AO)-tethered ligands were modified on the surface of living cells on the basis of the liposome fusion, enabling dynamical intercellular assemblies. Upon application of the corresponding oxidative potential, the \"off-state\" HQ could be oxidized to the \"on-state\" quinone (Q), which subsequently reacts with AO-tethered ligands to form stable oxime linkages under physiological conditions. This reaction effectively shortens the distance between cells, promoting the formation of cell clusters. When the corresponding reverse reductive potential is applied, the oxime linkage is cleaved, resulting in the release of the cells. Furthermore, we employed HQ- and AO-tethered ligands to modify mitochondria, inducing mitochondrial aggregation. This noninvasive and label-free strategy allows for the dynamic reversible regulation of intercellular interactions, enhancing our understanding of intercellular communication networks, and has the potential for improving the antitumor therapy efficacy.
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  • 文章类型: Journal Article
    基于小分子的超分子粘附材料体系在结合强粘附性和可逆性之间的巨大矛盾方面显示出巨大的潜力。然而,这些材料系统具有低粘合强度/窄粘合跨度,有限的可设计性,和单一相互作用,由于小分子中共价键含量和作用位点较少。在这里,开发了一种通过支化低聚物可控自聚集策略实现的超高强度和大跨度可逆粘合剂。存在于支化低聚物中的致密共价键极大地增强粘合强度而不损害可逆性。所得粘合剂表现出约140倍的大跨度可逆粘附力,在交变温度下,在超强和坚韧的粘附强度(5.58MPa和5093.92Nm-1)和超低粘附力(0.04MPa和87.656Nm-1)之间切换。此外,可逆动态双交联赋予粘合剂稳定的可逆粘合过渡,即使在100个循环。这种可逆粘附特性也可以通过8V的电压进行远程控制,加载电压持续时间为45s。这项工作为使用共价聚合物设计具有长跨度出色性能的可逆粘合剂铺平了道路,并为合理设计具有强大韧性和出色可逆性的高性能粘合剂提供了途径。
    Supramolecular adhesion material systems based on small molecules have shown great potential to unite the great contradiction between strong adhesion and reversibility. However, these material systems suffer from low adhesion strength/narrow adhesion span, limited designability, and single interaction due to fewer covalent bond content and action sites in small molecules. Herein, an ultrahigh-strength and large-span reversible adhesive enabled by a branched oligomer controllable self-aggregation strategy is developed. The dense covalent bonds present in the branched oligomers greatly enhance adhesion strength without compromising reversibility. The resulting adhesive exhibits a large-span reversible adhesion of ≈140 times, switching between ultra-strong and tough adhesion strength (5.58 MPa and 5093.92 N m-1) and ultralow adhesion (0.04 MPa and 87.656 N m-1) with alternating temperature. Moreover, reversible dynamic double cross-linking endows the adhesive with stable reversible adhesion transitions even after 100 cycles. This reversible adhesion property can also be remotely controlled via a voltage of 8 V, with a loading voltage duration of 45 s. This work paves the way for the design of reversible adhesives with long-span outstanding properties using covalent polymers and offers a pathway for the rational design of high-performance adhesives featuring both robust toughness and exceptional reversibility.
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  • 文章类型: Journal Article
    研究老化机制与充电状态(SOC)之间的相关性可以优化锂离子电池(LIB)的循环条件并延长其寿命。通常采用某个SOC范围之间的长期循环来研究这种相关性。然而,这种方法需要很长的时间,从几个月到几年,显著延长研究时间。通过该方法获得的老化机制是各种SOC水平耦合的结果;特定SOC水平下的老化机制不是精确解耦和可分析的。提出的零和脉冲方法,使用SOC幅度变化较小的对称脉冲,可以探索LIB在特定SOC水平下的老化机制,并将时间减少到不到一周,这大大加快了研究进程。在30%的老化机制,50%,70%,90%的SOC水平,验证了该方法的准确性和时效性。
    Investigating the correlation between aging mechanisms and state of charge (SOC) can optimize cycling conditions and prolong the life cycle of lithium-ion batteries (LIBs). A long-term cycle between a certain SOC range is usually employed to study this correlation. However, this method necessitates a lengthy period, running from months to years, prolonging the research duration significantly. The aging mechanisms obtained through this method are a result of the coupling of various SOC levels; the aging mechanisms at a specific SOC level are not accurately decoupled and analyzable. The proposed Zero-sum pulse method, using symmetrical pulses with small SOC amplitude variations on SOC, can explore aging mechanisms of LIBs at a specific SOC level and reduce the time to less than a week, which significantly expedite the research process. The aging mechanisms at 30%, 50%, 70%, and 90% SOC levels are explored to verify the accuracy and timeliness of this method.
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  • 文章类型: Journal Article
    黄曲霉毒素B1(AFB1)是食品中的强效毒素,需要迅速,即时,和灵敏的检测。我们设计了一种电化学传感器,使用由Fe3O4-NH4/AuNP/apt-S1组成的系统来监测AFB1。适体特异性识别AFB1,而\'S1\'用亚甲基蓝官能化以增强电流。RecJf外切核酸酶促进电化学策略的形成。Fe3O4成分,凭借其磁铁特性,使固体和液体的快速分离无需仪器。传感器显示AFB1的线性范围为1ng至10μg。回归方程为I(nA)=446.8×logc+2085(其中I和c代表峰电流和AFB1浓度,分别)。相关系数为0.9508,检出限为3.447nM。花生油中AFB1的相对标准偏差为4.80%~6.80%。这些结果表明,该传感器具有很高的灵敏度,稳定性,重复性,和AFB1检测的特异性。
    Aflatoxin B1 (AFB1) is a potent toxin in food, necessitating rapid, instant, and sensitive detection. We have engineered an electrochemical sensor to monitor AFB1 using a system composed of Fe3O4-NH4/AuNPs/apt-S1. The aptamer specifically recognizes AFB1, while \'S1\' is functionalized with methylene blue to enhance the current. The RecJf exonuclease promotes the formation of the electrochemical strategy. The Fe3O4 component, with its magnet properties, enables a rapid separation of solids and liquids without the need for instrumentation. The sensor exhibits a linear range for AFB1 ranging from 1 ng to 10 μg. The regression equation is I(nA) = 446.8 × logc+2085 (where I and c represent the peak current and AFB1 concentration, respectively). The correlation coefficient is 0.9508, and the detection limit is 3.447 nM. The relative standard deviation of AFB1 in peanut oil ranges from 4.80% to 6.80%. These results demonstrate that the sensor has high sensitivity, stability, repeatability, and specificity for AFB1 detection.
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