用于动力学研究的开源电化学通道流动池装置。应用于氧气电催化研究。

IF 5.5 3区 材料科学 Q1 ELECTROCHEMISTRY Electrochimica Acta Pub Date : 2024-11-17 DOI:10.1016/j.electacta.2024.145365
Alessandro Brega, Sylvain Brimaud
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引用次数: 0

摘要

本文详细介绍了一种电化学通道流动池装置,该装置可在最高温度 80°C 和最高压力 3 bar 的气体环境下进行电化学研究,包括技术图纸和零件清单,以方便社会各界采用这种装置进行电化学/电催化动力学研究。氧还原反应(ORR)在商用铂/铂催化剂上的反应被选为模型反应进行研究,以证明实验装置的可靠性,包括流体动力学特性,为开展实验提供实用指南,另一方面也说明该电化学装置在评估基本量方面的能力。在通过实验确定的 ORR 的各种量中,随着 ORR 过电位的增加,活化焓呈单调衰减,活化熵呈钟形变化。这些基本热力学/动力学数据是在已建立的反应机理框架内进行简要讨论的,可作为理论/计算模型输出结果的基准。此外,通过流动池设置确定的 ORR 激活自由吉布斯能的变化,与在氢质子交换膜燃料电池阴极中嵌入相同 Pt/C 催化剂所获得的燃料电池极化曲线动力学区域之间,也取得了显著的一致。这有可能弥补在与液态电解质接触的活性材料层面进行的模型实验与在实际设备中使用的嵌入相同活性材料的多孔气体扩散电极实验之间存在的环境差距。
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An open source electrochemical channel flow cell setup for kinetics studies. Application to investigations on oxygen electrocatalysis.
Herein, an electrochemical channel flow cell setup that allows for conducting electrochemical investigations up to 80°C and pressurized gases up to 3 bar is presented in details, including technical drawings and list of parts, in an attempt to facilitate the adoption of such setup by the community for electrochemical/electrocatalytic kinetic studies. The oxygen reduction reaction (ORR) on a commercial Pt/C catalyst, chosen as a model reaction, was investigated to demonstrate the reliability of the experimental setup, including the hydrodynamic properties, to provide hands on practical guidelines to carry out experiments, and, on the other hand, to illustrate the capabilities of this electrochemical setup for an assessment of basic quantities. Among the various quantities that have be determined experimentally for the ORR, a monotonic decay of the activation enthalpy and bell-shaped variation of the entropy of activation were resolved as the overpotential for the ORR increases. These fundamental thermodynamic/kinetic data are briefly discussed within the frame of the established reaction mechanism and can serve as a feed for the benchmarking of the outputs from theoretical/computational models. Furthermore, a remarkable agreement was obtained between the change in the activation free Gibbs energy determined for the ORR with the flow cell setup and the kinetic region of fuel cell polarization curve obtained with the same Pt/C catalyst embedded in the cathode of an a hydrogen proton exchange membrane fuel cell. This enables potentially a bridge of the environmental gap existing between model experiments conducted at active material level in contact with liquid electrolyte and experiments with porous gas diffusion electrode embedding the same active material that are employed in practical device.
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来源期刊
Electrochimica Acta
Electrochimica Acta 工程技术-电化学
CiteScore
11.30
自引率
6.10%
发文量
1634
审稿时长
41 days
期刊介绍: Electrochimica Acta is an international journal. It is intended for the publication of both original work and reviews in the field of electrochemistry. Electrochemistry should be interpreted to mean any of the research fields covered by the Divisions of the International Society of Electrochemistry listed below, as well as emerging scientific domains covered by ISE New Topics Committee.
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