Dynamics at Electrode-Electrolyte Interfaces Down to the Nanosecond Domain

电极-电解质界面的动力学低至纳秒域

基本信息

批准号：
1808592
负责人：
Daniel Scherson
金额：
$ 50万
依托单位：
Case Western Reserve University
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2018
资助国家：
美国
起止时间：
2018-08-01 至 2023-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1808592&HistoricalAwards=false
关键词：
Dynamics Electrode Electrolyte Interfaces Down

项目摘要

This project is jointly funded by the Chemical Measurement and Imaging Program and the Chemical Structure, Dynamics and Mechanisms - A Program. Both are in the Division of Chemistry. Professor Daniel Scherson of Case Western Reserve University is developing and using hardware and electroanalytical methods for ultrafast charge injection across electrode/electrolyte interfaces. This capability enables fundamental studies of electrochemical phenomena at timescales down to the nanosecond (ns) regime. These new ultrafast electronics are combined with spectroscopic techniques such as second harmonic generation (SHG), sum frequency generation (SFG), and differential reflectance spectroscopy. This work will provide the means to answer fundamental questions about the dynamics of short-lived adsorbates and reactive intermediates. The behavior of electrode and electrolyte interfaces are highly relevant to a wide-range of electrochemical applications. Electrochemical surface science lies at the juncture of chemistry, physics and a wide number of engineering fields, such as materials and electronics. The scientific advances will impact wide ranging areas of practical importance such as energy conversion, corrosion mitigation and sensor technology. Students pursuing research in this area become exposed to a very broad range of both fundamental and applied disciplines. This type of training will produce students especially suited to face the challenges posed by a multitude of important and unresolved problems in environmental remediation, energy conversion, energy storage, biosciences, and microsensor technology. The primary objectives of this work are to develop and implement experimental techniques to achieve potential control across electrode/electrolyte interfaces in the nanosecond regime, and to monitor the subsequent time evolution of the interface using spectroscopic techniques with the highest sensitivity and specificity and temporal resolution. Attention is focused on ultrafast charge injection tactics employing electronic circuitry and electrochemical cell architectures designed in collaboration with Tektronix (Keithley). These is validated using selected model systems involving both well-defined single crystal metal substrates and adsorbate layers. The response of the systems to such fast electrical perturbations is monitored using linear and non-linear spectroscopic probes, including normalized differential reflectance, and second harmonic, (SHG) and sum frequency generation (SFG). The actual model systems investigated include: electron transfer in self-assembled monolayers bearing redox active terminal groups as a function of the distance from the electrode surface, order/disorder transitions in halide adsorbate layers on single crystal silver, and hydrogen adsorption/desorption on Pt(111) as a function of pH. Also explored is the use of ultrafast current pulses applied to the solution in order to modulate the electrostatic potential across the interface and thus the overpotential driving the interfacial events. It is expected that the experimental data resulting from this research will serve to validate theoretical predictions emerging from the fast developing field of interfacial dynamics.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

该项目由化学测量和成像程序以及化学结构，动力学和机制共同资助。两者都在化学划分中。 Case Western Reserve University的Daniel Scherson教授正在开发和使用硬件和电分析方法，用于跨电极/电解质界面的超快电荷注入。该能力使时间尺度的电化学现象至纳米秒（NS）制度进行了基本研究。这些新的超快电子产品与光谱技术（例如第二次谐波生成（SHG），总和频率产生（SFG）和差异反射率光谱）结合使用。这项工作将为回答有关短暂吸附物和反应性中间体动态的基本问题提供手段。电极和电解质界面的行为与广泛的电化学应用高度相关。电化学表面科学在于化学，物理和广泛的工程领域，例如材料和电子产品。科学的进步将影响实用重要性的广泛领域，例如能量转换，缓解腐蚀和传感器技术。从事这一领域的研究的学生将暴露于广泛的基本学科和应用学科。这种类型的培训将使学生特别适合面对众多在环境补救，能源转换，能源存储，生物科学和微传感器技术方面的重要和未解决的问题所带来的挑战。这项工作的主要目的是开发和实施实验技术，以在纳秒制度中跨电极/电解质界面之间实现潜在的控制，并使用具有最高敏感性，特异性和时间分辨率的光谱技术来监测界面的随后时间演变。注意力集中在与Tektronix（Keithley）合作设计的电子电路和电化学细胞体系结构的超快电荷注入策略上。使用选定的模型系统验证了这些系统，该模型系统涉及定义明确的单晶金属底物和吸附物层。使用线性和非线性光谱探针（包括归一化的差异反射率，第二个谐波）（SHG）和SUM频率产生（SFG），使用线性和非线性光谱探针（包括归一化的差分反射率）和非线性光谱探针（SFG）来监测系统对这种快速电扰动的响应。研究的实际模型系统包括：在自组装单层中具有氧化还原活性末端基团的电子转移，这是距电极表面距离的函数，单晶型银色的卤化物吸附层中的有序/无序转变以及pT（111）上的氢吸附/吸附/解吸收（111）的功能。还探讨了应用于溶液上的超快电流脉冲，以调节界面上的静电电势，从而使超电势驱动界面事件。预计这项研究产生的实验数据将有助于验证界面动力学快速发展领域的理论预测。该奖项反映了NSF的法定任务，并认为值得通过基金会的智力优点和更广泛的影响审查标准通过评估来获得支持。

项目成果

期刊论文数量（7）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

On the Mechanism of the Oxygen Reduction Reaction on Au(poly) in Aqueous Alkaline Electrolytes: A Critical Reassessment

DOI：
10.1021/acs.jpcc.1c02683
发表时间：
2021-06-17
期刊：
JOURNAL OF PHYSICAL CHEMISTRY C
影响因子：
3.7
作者：
Strobl, Jonathan R.;Scherson, Daniel
通讯作者：
Scherson, Daniel

The adsorption of perchlorate, sulfate, selenate and water on Au(111)-textured electrodes from aqueous solutions: Simultaneous voltammetric, optical and microgravimetric studies

Au(111) 纹理电极对水溶液中高氯酸盐、硫酸盐、硒酸盐和水的吸附：同时伏安、光学和微重量研究

DOI：
10.1016/j.electacta.2021.139107
发表时间：
2021
期刊：
Electrochimica Acta
影响因子：
6.6
作者：
Strobl, Jonathan R.;Scherson, Daniel
通讯作者：
Scherson, Daniel

A High-Speed Charge Injection Circuit for Nanosecond-Scale Electrochemical Measurements

用于纳秒级电化学测量的高速电荷注入电路

DOI：
10.1109/mercon50084.2020.9185286
发表时间：
2020
期刊：
2020 Moratuwa Engineering Research Conference (MERCon
影响因子：
0
作者：
Huan, Junjun;Liang, Jifu;Georgescu, Nicholas;Feng, Zhange;Scherson, Daniel;Mandal, Soumyajit
通讯作者：
Mandal, Soumyajit

Solution phase superoxide as an intermediate in the oxygen reduction reaction on glassy carbon in alkaline media