Electrochemical activity

电化学活性
  • 文章类型: Journal Article
    这里,全固体扫描电化学电池显微镜(SECCM)首先是通过将聚丙烯酰胺(PAM)填充到纳米毛细管中作为固体电解质而建立的。纳米毛细管尖端处的固体PAM纳米球接触石墨烯,并充当用于同时测量形态和电化学活性的电化学电池。与基于液滴的SECCM相比,这种固体纳米球是稳定的,在接触区域不会留下任何电解质,这允许在没有任何间隔的情况下对表面进行精确和连续的扫描。因此,横向(x-y)和垂直(z)方向的分辨率提高到~10nm。石墨烯上皱纹的完整扫描记录了皱纹的两个侧壁处的低电流和皱纹中心处的相对高电流。皱纹的电化学活性的异质性说明了不同曲率的表面上不同的电子转移特征,这是目前的电化学或光学方法很难观察到的。这种高空间电化学显微镜的成功建立克服了当前在纳米尺度上研究材料电化学活性的挑战,这对于更好地理解材料中的电子转移具有重要意义。
    Here, all-solid scanning electrochemical cell microscopy (SECCM) is first established by filling polyacrylamide (PAM) into nanocapillaries as a solid electrolyte. A solid PAM nanoball at the tip of a nanocapillary contacts graphene and behaves as an electrochemical cell for simultaneously measuring the morphology and electrochemical activity. Compared with liquid droplet-based SECCM, this solid nanoball is stable and does not leave any electrolyte at the contact regions, which permits accurate and continuous scanning of the surface without any intervals. Accordingly, the resolutions in the lateral (x-y) and vertical (z) directions are improved to ∼10 nm. The complete scanning of the wrinkles on graphene records low currents at the two sidewalls of the wrinkles and a relatively high current at the center of the wrinkles. The heterogeneity in the electrochemical activity of the wrinkle illustrates different electron transfer features on surfaces with varied curvatures, which is hardly observed by the current electrochemical or optical methods. The successful establishment of this high spatial electrochemical microscopy overcomes the current challenges in investigating the electrochemical activity of materials at the nanoscale, which is significant for a better understanding of electron transfer in materials.
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  • 文章类型: Journal Article
    在这项研究中,从先前运行的单室微生物燃料电池(SCMFC)中分离出属于Brevundimonasdiminuta(OK287021,OK287022)属的高度耐亚硒酸盐菌株。中心复合材料设计表明,小型双歧杆菌可以减少亚硒酸盐。在最佳条件下,15.38LogCFUmL-1微生物生长,99.08%Se(IV)还原,化学需氧量(COD)去除率为89.94%。此外,紫外可见光谱(UV)和傅里叶变换红外光谱(FTIR)分析证实了元素硒纳米颗粒(SeNPs)的合成。此外,透射电子显微镜(TEM)和扫描电子显微镜(SEM)显示了纳米球的形成。此外,B.diminuta在SCMFC中的生物电化学性能表明,亚硒酸盐SCMFC的最大功率密度高于无菌对照SCMFC的最大功率密度。此外,生物电化学阻抗谱和循环伏安法表征说明了确定的细胞外氧化还原介体的产生,这些介体可能参与亚硒酸盐还原过程中的电子转移进程。总之,B.diminuta的电化学活性从未被报道过,可能是亚硒酸盐生物还原和废水处理的合适和强大的生物催化剂,生物发电,以及在MFC中经济地合成SeNPs。
    In this study, highly selenite-resistant strains belonging to Brevundimonas diminuta (OK287021, OK287022) genus were isolated from previously operated single chamber microbial fuel cell (SCMFC). The central composite design showed that the B. diminuta consortium could reduce selenite. Under optimum conditions, 15.38 Log CFU mL-1 microbial growth, 99.08% Se(IV) reduction, and 89.94% chemical oxygen demand (COD) removal were observed. Moreover, the UV-visible spectroscopy (UV) and Fourier transform infrared spectroscopy (FTIR) analyses confirmed the synthesis of elemental selenium nanoparticles (SeNPs). In addition, transmission electron microscopy (TEM) and scanning electron microscope (SEM) revealed the formation of SeNPs nano-spheres. Besides, the bioelectrochemical performance of B. diminuta in the SCMFC illustrated that the maximum power density was higher in the case of selenite SCMFCs than those of the sterile control SCMFCs. Additionally, the bioelectrochemical impedance spectroscopy and cyclic voltammetry characterization illustrated the production of definite extracellular redox mediators that might be involved in the electron transfer progression during the reduction of selenite. In conclusion, B. diminuta whose electrochemical activity has never previously been reported could be a suitable and robust biocatalyst for selenite bioreduction along with wastewater treatment, bioelectricity generation, and economical synthesis of SeNPs in MFCs.
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  • 文章类型: Journal Article
    硫化焦耳杆菌DL1是一种金属还原异化细菌,通常用于在生物电化学系统(BES)中产生电能。电极上形成的生物膜是有效电子转移的最重要因素之一;这是可能的,因为IV型菌毛和c型细胞色素的产生使其能够进行细胞外电子转移(EET)到最终受体。在这项研究中,我们分析了在不同支撑材料(玻璃,赤铁矿(Fe2O3)在玻璃上,掺氟氧化锡(FTO)半导体玻璃,Fe2O3对FTO,石墨,和不锈钢)通过G.硫还原DL1(WT)和GSU1771缺陷型菌株突变体(Δgsu1771)。GSU1771是转录调节因子,其控制参与电子转移的若干基因的表达。用生长在不同支撑材料上的生物膜进行了不同的方法和实验测试,包括通过共聚焦激光扫描显微镜(CLSM)进行结构分析,电化学活性的表征,并通过RT-qPCR定量相对基因表达。分析了参与EET的所选基因的基因表达,观察到pgcA的过度表达,omcS,omcM,和来自Δgsu1771生物膜的omcF与来自WT的omcF相比,epsH基因的过度表达,参与胞外多糖合成。尽管我们观察到对于Δgsu1771突变株,相关的氧化还原过程与WT菌株相似,产生更多的电流,我们认为,这可能与EET和胞外多糖生产中涉及的某些基因的较高相对表达有关,尽管生物膜发展的化学环境。这项研究支持G.硫还原能够适应其生长的电化学环境。
    Geobacter sulfurreducens DL1 is a metal-reducing dissimilatory bacterium frequently used to produce electricity in bioelectrochemical systems (BES). The biofilm formed on electrodes is one of the most important factors for efficient electron transfer; this is possible due to the production of type IV pili and c-type cytochromes that allow it to carry out extracellular electron transfer (EET) to final acceptors. In this study, we analyzed the biofilm formed on different support materials (glass, hematite (Fe2O3) on glass, fluorine-doped tin oxide (FTO) semiconductor glass, Fe2O3 on FTO, graphite, and stainless steel) by G. sulfurreducens DL1 (WT) and GSU1771-deficient strain mutant (Δgsu1771). GSU1771 is a transcriptional regulator that controls the expression of several genes involved in electron transfer. Different approaches and experimental tests were carried out with the biofilms grown on the different support materials including structure analysis by confocal laser scanning microscopy (CLSM), characterization of electrochemical activity, and quantification of relative gene expression by RT-qPCR. The gene expression of selected genes involved in EET was analyzed, observing an overexpression of pgcA, omcS, omcM, and omcF from Δgsu1771 biofilms compared to those from WT, also the overexpression of the epsH gene, which is involved in exopolysaccharide synthesis. Although we observed that for the Δgsu1771 mutant strain, the associated redox processes are similar to the WT strain, and more current is produced, we think that this could be associated with a higher relative expression of certain genes involved in EET and in the production of exopolysaccharides despite the chemical environment where the biofilm develops. This study supports that G. sulfurreducens is capable of adapting to the electrochemical environment where it grows.
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  • 文章类型: Journal Article
    碳基电极用于液流电池中,为钒氧化还原反应提供活性中心。然而,关于这些中心的确切起源存在强烈争议。本研究系统地探讨了结构和官能团对碳表面钒氧化还原反应的影响。吡啶,含苯酚和丁基的基团连接到碳毡电极上。为了在模型和现实世界的行为之间建立独特的比较,非活化的和商业上使用的热活化的毛毡作为基底。结果显示在引入亲水官能团的非活化毡中增强的半电池性能。然而,这不能转移到热活化毛毡。除了电化学活性下降之外,可以观察到降低的长期稳定性。这项工作表明,热处理产生的活性位点超过了官能团的作用,甚至受到官能团引入的阻碍。
    Carbon-based electrodes are used in flow batteries to provide active centers for vanadium redox reactions. However, strong controversy exists about the exact origin of these centers. This study systematically explores the influence of structural and functional groups on the vanadium redox reactions at carbon surfaces. Pyridine, phenol and butyl containing groups are attached to carbon felt electrodes. To establish a unique comparison between the model and real-world behavior, both non-activated and commercially used thermally activated felts serve as a substrate. Results reveal enhanced half-cell performance in non-activated felt with introduced hydrophilic functionalities. However, this cannot be transferred to the thermally activated felt. Beyond a decrease in electrochemical activity, a reduced long-term stability can be observed. This work indicates that thermal treatment generates active sites that surpass the effect of functional groups and are even impeded by their introduction.
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  • 文章类型: Journal Article
    在物联网时代,迫切需要满足可穿戴设备的严格要求的技术,自供电,和无缝集成的设备。当前开发基于MXene的电化学传感器的方法涉及刚性或不透明组件,限制它们在利基应用中的使用。这项研究调查了原始Ti3C2Tx电极用于柔性和透明电化学传感的潜力,通过探索材料特性(薄片尺寸,薄片取向,胶片几何,和均匀性)使用循环伏安法影响外球氧化还原探针钌六胺的电化学活性。由堆叠的大Ti3C2Tx薄片制成的优化电极表现出优异的再现性和耐弯曲条件,建议它们用于可靠,健壮,和灵活的传感器。减少电极厚度导致放大的法拉第电容信号,这对于这种应用是有利的。这导致透明的Ti3C2Tx薄膜的沉积,它保持了高达73%的透明度的最佳性能。这些发现强调了它对高性能的承诺,定制的传感器,标志着在下一代电化学传感技术中推进MXene利用的重大进展。结果鼓励分析电化学领域利用原始Ti3C2Tx电极可以通过更多参数研究在感测中提供的独特性质。
    In the era of the internet of things, there exists a pressing need for technologies that meet the stringent demands of wearable, self-powered, and seamlessly integrated devices. Current approaches to developing MXene-based electrochemical sensors involve either rigid or opaque components, limiting their use in niche applications. This study investigates the potential of pristine Ti3C2Tx electrodes for flexible and transparent electrochemical sensing, achieved through an exploration of how material characteristics (flake size, flake orientation, film geometry, and uniformity) impact the electrochemical activity of the outer sphere redox probe ruthenium hexamine using cyclic voltammetry. The optimized electrode made of stacked large Ti3C2Tx flakes demonstrated excellent reproducibility and resistance to bending conditions, suggesting their use for reliable, robust, and flexible sensors. Reducing electrode thickness resulted in an amplified faradaic-to-capacitance signal, which is advantageous for this application. This led to the deposition of transparent thin Ti3C2Tx films, which maintained their best performance up to 73% transparency. These findings underscore its promise for high-performance, tailored sensors, marking a significant stride in advancing MXene utilization in next-generation electrochemical sensing technologies. The results encourage the analytical electrochemistry field to take advantage of the unique properties that pristine Ti3C2Tx electrodes can provide in sensing through more parametric studies.
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  • 文章类型: Journal Article
    与传统火力发电厂相比,高温固体氧化物燃料电池(SOFC)是由氢基燃料发电的最有效和绿色的转换技术。已经做出了许多努力来将SOFC中的高工作温度(>800°C)降低到中/低工作温度(400°C The high-temperature solid oxide fuel cells (SOFCs) are the most efficient and green conversion technology for electricity generation from hydrogen-based fuel as compared to conventional thermal power plants. Many efforts have been made to reduce the high operating temperature (>800 °C) to intermediate/low operating temperature (400 °C
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  • 文章类型: Journal Article
    背景:在双室微生物燃料电池(DCMFC)中应用产生胞外多糖的细菌(EPS)是关键的,其可以最小化具有生物电生产的糖蜜的化学需氧量(COD)。因此,我们的研究旨在通过使用糖蜜废物来评估新型菌株比西芽孢杆菌的EPS产量。因此,统计建模用于优化EPS产量。其结构由UV,FTIR,NMR,和单糖组合物。最终,为了强调B.piscis在能源应用中的适应性,在优化的糖蜜培养基饲喂的BCMFC中研究了该生物的生物电生产。
    结果:B.以16SrRNA为特征的piscisOK324045是一种有效的EPS形成生物,在补充糖蜜(5%)后增加了6.42倍,MgSO4(0.05%),和接种物大小(4%)。由芽孢杆菌属产生的新型胞外多糖。通过结构分析证实了(EPS-BP5M)。结果表明,MFC的最大闭路电压(CCV)为265mV。该菌株提高了DCMFC的性能,最大功率密度(PD)为31.98mWm-2,COD去除率为90.91%,颜色去除率为27.68%。此外,循环伏安法(CV)表明,阳极生物膜可以直接将电子转移到阳极,而无需使用外部氧化还原介体。此外,在各种扫描扫描速率下进行的CV测量以评估动力学研究表明,电子电荷转移是不可逆的。SEM图像显示生物膜生长分布在电极表面。
    结论:本研究为EPS-BP5M生产提供了一种新的双歧杆菌菌株,COD去除,脱色,优化糖蜜培养基在MFC中的发电。由比西芽孢杆菌菌株生物合成EPS-BP5M及其电化学活性以前从未被记录过。采用的方法将通过使用糖蜜作为燃料产生生物电并提供改善糖蜜废水处理的可行方法,从而为制糖工业带来重大利益。
    BACKGROUND: The application of exopolysaccharide-producing bacteria (EPS) in dual chamber microbial fuel cells (DCMFC) is critical which can minimize the chemical oxygen demand (COD) of molasses with bioelectricity production. Hence, our study aimed to evaluate the EPS production by the novel strain Bacillus piscis by using molasses waste. Therefore, statistical modeling was used to optimize the EPS production. Its structure was characterized by UV, FTIR, NMR, and monosaccharides compositions. Eventually, to highlight B. piscis\' adaptability in energy applications, bioelectricity production by this organism was studied in the BCMFC fed by an optimized molasses medium.
    RESULTS: B. piscis OK324045 characterized by 16S rRNA is a potent EPS-forming organism and yielded a 6.42-fold increase upon supplementation of molasses (5%), MgSO4 (0.05%), and inoculum size (4%). The novel exopolysaccharide produced by Bacillus sp. (EPS-BP5M) was confirmed by the structural analysis. The findings indicated that the MFC\'s maximum close circuit voltage (CCV) was 265 mV. The strain enhanced the performance of DCMFC achieving maximum power density (PD) of 31.98 mW m-2, COD removal rate of 90.91%, and color removal of 27.68%. Furthermore, cyclic voltammetry (CV) revealed that anodic biofilms may directly transfer electrons to anodes without the use of external redox mediators. Additionally, CV measurements made at various sweep scan rates to evaluate the kinetic studies showed that the electron charge transfer was irreversible. The SEM images showed the biofilm growth distributed over the electrode\'s surface.
    CONCLUSIONS: This study offers a novel B. piscis strain for EPS-BP5M production, COD removal, decolorization, and electricity generation of the optimized molasses medium in MFCs. The biosynthesis of EPS-BP5M by a Bacillus piscis strain and its electrochemical activity has never been documented before. The approach adopted will provide significant benefits to sugar industries by generating bioelectricity using molasses as fuel and providing a viable way to improve molasses wastewater treatment.
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  • 文章类型: Journal Article
    MXene,一种新的嵌入假电容电极材料,具有用于超级电容器应用的高理论电容。然而,有限的可访问的层间空间和活性位点是在实际应用中实现这种高电容的主要挑战。为了在更大程度上刺激MXene的电化学活性,在这里,首先提出了一种用还原剂柠檬酸在NaOH溶液中进行水热处理的方法。经过这种治疗,MXene的重量电容显着增强,大约是原始价值的250%,在2mVs-1时达到543Fg-1。这种改善的电化学性能归因于夹层结构和表面化学状态的定制。创建了扩展和均匀化的层间空间,这为电解质离子的储存提供了足够的空间。-F末端被含O的基团取代,这增强了亲水性,促进电解质进入MXene表面,并使MXene对电解质离子H+表现出更强的吸附作用,提供足够的电化学活性位点。终止的变化进一步导致Ti化合价的增加,变得更容易减少。这项工作建立了对电化学储能应用的合理MXene设计的全面了解。
    MXene, a new intercalation pseudocapacitive electrode material, possesses a high theoretical capacitance for supercapacitor application. However, limited accessible interlayer space and active sites are major challenges to achieve this high capacitance in practical application. In order to stimulate the electrochemical activity of MXene to a greater extent, herein, a method of hydrothermal treatment in NaOH solution with reducing reagent-citric acid is first proposed. After this treatment, the gravimetric capacitance of MXene exhibits a significant enhancement, about 250% of the original value, reaching 543 F g-1 at 2 mV s-1. This improved electrochemical performance is attributed to the tailoring of an interlayer structure and surface chemistry state. An expanded and homogenized interlayer space is created, which provides enough space for electrolyte ions storage. The -F terminations are replaced with O-containing groups, which enhances the hydrophilicity, facilitating the electrolyte\'s accessibility to MXene\'s surface, and makes MXene show stronger adsorption for electrolyte ion-H+, providing sufficient electrochemical active sites. The change in terminations further leads to the increase in Ti valence, which becomes more prone to reduction. This work establishes full knowledge of the rational MXene design for electrochemical energy storage applications.
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  • 文章类型: Journal Article
    这项研究证明了在甲基紫(MV)染料存在下一步合成聚(3,4-亚乙基二氧噻吩)(PEDOT)。使用拉曼和MALDI-TOF光谱法研究了PEDOT:过氧二硫酸盐的结构性质。在聚合过程中使用MV染料导致PEDOT的典型不规则形态发生了变化:过氧二硫酸盐,导致球形图案的形成。SEM和TEM分析表明,增加染料浓度可以产生更大的球形聚集体,这可能是由于疏水和π-π相互作用。这些较大的聚集体阻碍了电荷传输并降低了电导率。有趣的是,在较高的染料浓度(0.05和0.075M),PEDOT:过氧二硫酸盐/MV膜对金黄色葡萄球菌和大肠杆菌的抗菌活性显著提高。此外,具有并入的MV染料的PEDOT:过氧二硫酸盐膜表现出明确的和可重复的氧化还原行为。它们光学的显著融合,电化学和抗菌性能为PEDOT:过氧二硫酸盐/MV材料提供了非常多样化的应用范围,包括光学传感器和医疗设备。
    This study demonstrates a one-step synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) in the presence of the methyl violet (MV) dye. The structural properties of PEDOT:peroxodisulfate were studied using Raman and MALDI-TOF spectroscopies. The use of the MV dye in the polymerization process resulted in a change in the typical irregular morphology of PEDOT:peroxodisulfate, leading to the formation of spherical patterns. SEM and TEM analyses revealed that increasing the dye concentration can produce larger spherical aggregates probably due to the hydrophobic and π-π interactions. These larger aggregates hindered the charge transport and reduced the electrical conductivity. Interestingly, at higher dye concentrations (0.05 and 0.075 M), the PEDOT:peroxodisulfate/MV films exhibited significantly improved antibacterial activity against Staphylococcus aureus and Escherichia coli. Furthermore, the PEDOT:peroxodisulfate films with the incorporated MV dye exhibited a well-defined and repeatable redox behavior. The remarkable amalgamation of their optical, electrochemical and antibacterial properties provides the PEDOT:peroxodisulfate/MV materials with an immensely diverse spectrum of applications, including in optical sensors and medical devices.
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  • 文章类型: Journal Article
    在过去的几十年里,钛(IV)氧化物基材料由于其稳定性而受到特别关注,耐腐蚀性,紫外光下的光催化活性,和修改的可能性。在各种结构中,在Ti箔或玻璃基板上生长并通过简单的阳极氧化过程获得的TiO2纳米管(NT)被广泛用作光催化剂或光阳极。在阳极氧化过程中,纳米管的几何形状(长度,分布,直径,壁厚,等。)易于控制,尽管获得的样品是无定形的。需要热处理以将无定形材料转变为晶体材料。然而,而不是耗时和成本的炉子处理,快速和精确的激光退火是一个有前途的替代应用。尽管如此,激光处理会导致TiO2NTs的几何形状变化,因此改变,它们的电化学活性。此外,用过渡金属对TiO2NTs表面进行改性和进一步的激光处理可以产生具有独特光电化学性能的材料。在这方面,我们为这篇综述论文收集了激光处理二氧化钛领域的最新成果。我们主要关注脉冲激光退火引起的单一结构和形态变化及其对二氧化钛电化学性能的影响。最后,还讨论了激光和金属改性的理论基础和组合及其对电化学水分解可能性的影响。
    Over the last few decades, titanium(IV) oxide-based materials have gained particular attention due to their stability, corrosion resistance, photocatalytic activity under UV light, and possibilities for modification. Among various structures, TiO2 nanotubes (NTs) grown on Ti foil or glass substrates and obtained through a simple anodization process are widely used as photocatalysts or photoanodes. During the anodization process, the geometry of the nanotubes (length, distribution, diameter, wall thickness, etc.) is easily controlled, though the obtained samples are amorphous. Heat treatment is required to transform the amorphous material into crystalline material. However, instead of time- and cost-consuming furnace treatment, fast and precise laser annealing is applied as a promising alternative. Nonetheless, laser treatment can result in geometry changes of TiO2 NTs, consequently altering, their electrochemical activity. Moreover, modification of the TiO2 NTs surfaces with transition metals and further laser treatment can result in materials with unique photoelectrochemical properties. In this regard, we gathered the latest achievements in the field of laser-treated titania for this review paper. We mainly focused on single structural and morphological changes resulting from pulsed laser annealing and their influence on the electrochemical properties of titania. Finally, the theoretical basis for and combination of laser- and metal-modifications and their impact on the resulting possibilities for electrochemical water splitting are also discussed.
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