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超声化学法制备用于碱性介质中乙醇氧化的高性能 Pd@CuNWs/MWCNTs-CH 电催化剂。

Sonochemical synthesis of high-performance Pd@CuNWs/MWCNTs-CH electrocatalyst by galvanic replacement toward ethanol oxidation in alkaline media.

机构信息

Department of Applied Chemistry, University of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan, Iran.

Department of Chemistry, Organic and Polymer Research Laboratory, University of Sistan and Baluchestan, Zahedan, Iran.

出版信息

Ultrason Sonochem. 2019 Mar;51:478-486. doi: 10.1016/j.ultsonch.2018.06.011. Epub 2018 Jun 15.

Abstract

In this paper, a fast and effective method for the palladium (Pd) wire nanostructures synthesis with the great surface area through galvanic replacement reaction utilizing copper nanowires (CuNWS) as a template by the assistance of ultrasound under room temperature condition is proposed. A multifunctional catalyst with the mentioned nanostructure, Pd@CuNWs, and multi walled carbon nanotubes (MWCNTs) and chitosan (CH) as a binder was fabricated. To investigate the morphology and bulk composition of the prepared catalyst, Field Emission Scanning Electron Microscopy (FE-SEM), Energy Dispersive X-ray Spectroscopy (EDS), X-ray Powder Diffraction (XRD), and Inductively Coupled Plasma atomic Emission Spectroscopy (ICP-AES) were utilized. Various electrochemical techniques including chronoamperometry and cyclic voltammetry were employed for the electrocatalytic activity of ethanol electrooxidation and durability in basic solution. Electrochemical catalytic activity and durability evaluation results proved that the as-synthesized Pd@CuNWs/MWCNTs-CH has a super electrocatalytic activity compared to Pd/MWCNTs and Pd/C electrocatalysts for ethanol electrooxidation. Pd@CuNWs/MWCNTs-CH catalyst demonstrated substantially enhanced performance and long-term stability for ethanol electrooxidation in the basic solution in comparison to Pd/MWCNTs and commercial Pd/C demonstrated the potential in utilizing Pd@CuNWs/MWCNTs-CH as an efficient catalyst for ethanol oxidation. Additionally, thermodynamic and kinetic evaluations revealed that the Pd@CuNWs/MWCNTs-CH catalyst has lower activation energy compared to Pd/MWCNTs and Pd/C which leads to a lower energy barrier and an excellent charge transfer rate towards ethanol oxidation. Noticeably, the Pd@CuNWs/MWCNTs-CH presented excellent catalytic activities with high peak current density which was 9.5 times more than Pd/C, and more negative onset potential in comparison to Pd/C is acquired for ethanol electrooxidation denoting synergistic effect between CuNWs/MWCNs-CH and Pd. The Pd@CuNWs/MWCNTs-CH can be considered as a valid candidate among available electrocatalysts in direct ethanol fuel cells (DEFCs).

摘要

本文提出了一种在室温条件下,通过在超声辅助下利用铜纳米线(CuNWS)作为模板的电置换反应,快速有效地合成具有大表面积的钯(Pd)线纳米结构的方法。制备了一种多功能催化剂,该催化剂具有上述纳米结构、Pd@CuNWs、多壁碳纳米管(MWCNTs)和壳聚糖(CH)作为粘结剂。为了研究制备催化剂的形貌和体相组成,采用场发射扫描电子显微镜(FE-SEM)、能谱(EDS)、X 射线粉末衍射(XRD)和电感耦合等离子体原子发射光谱(ICP-AES)。采用计时电流法和循环伏安法等各种电化学技术研究了乙醇电氧化的电催化活性和碱性溶液中的耐久性。电化学催化活性和耐久性评价结果表明,与 Pd/MWCNTs 和 Pd/C 电催化剂相比,合成的 Pd@CuNWs/MWCNTs-CH 对乙醇电氧化具有超强的电催化活性。与 Pd/MWCNTs 和商业 Pd/C 相比,Pd@CuNWs/MWCNTs-CH 催化剂在碱性溶液中对乙醇电氧化具有显著提高的性能和长期稳定性,表明 Pd@CuNWs/MWCNTs-CH 作为乙醇氧化的有效催化剂具有潜力。此外,热力学和动力学评价表明,与 Pd/MWCNTs 和 Pd/C 相比,Pd@CuNWs/MWCNTs-CH 催化剂具有更低的活化能,这导致更低的能量势垒和对乙醇氧化的优异电荷转移速率。值得注意的是,与 Pd/C 相比,Pd@CuNWs/MWCNTs-CH 表现出优异的催化活性,具有更高的峰值电流密度,是 Pd/C 的 9.5 倍,并且在乙醇电氧化方面获得了更负的起始电位,这表明 CuNWs/MWCNs-CH 与 Pd 之间存在协同效应。Pd@CuNWs/MWCNTs-CH 可被认为是直接乙醇燃料电池(DEFCs)中可用电催化剂中的有效候选物。

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