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富氟介孔碳作为高效氧还原催化剂:了解多孔基质中的缺陷及在燃料电池中的应用

Fluorine-enriched mesoporous carbon as efficient oxygen reduction catalyst: understanding the defects in porous matrix and fuel cell applications.

作者信息

Parthiban V, Bhuvaneshwari Balasubramaniam, Karthikeyan J, Murugan P, Sahu A K

机构信息

CSIR - Central Electrochemical Research Institute-Madras Unit, CSIR Madras Complex Taramani Chennai 600113 India

Academy of Scientific and Innovative Research (AcSIR), CSIR - Central Electrochemical Research Institute Karaikudi 630003 India.

出版信息

Nanoscale Adv. 2019 Nov 20;1(12):4926-4937. doi: 10.1039/c9na00572b. eCollection 2019 Dec 3.

Abstract

Herein, fluorine enrichment in mesoporous carbon (F-MC) was explored to introduce maximum charge polarization in the porous matrix, which is beneficial for the preferential orientation of O molecules and their subsequent reduction. doping of F to porous carbon derived from phloroglucinol-formaldehyde resin using Pluronic F-127 as a structure-directing agent is standardized. The optimized F-MC catalyst exhibited excellent electrocatalytic activity towards the oxygen reduction reaction (ORR) in alkaline media (0.1 M KOH) with an onset potential of -0.10 V SCE and diffusion-limiting current of 4.87 mA cm, while displaying only about 50 mV overpotential in the half-wave region compared to Pt-C (40 wt%). In the stability test, the catalyst showed only 10 mV negative shift in its half-wave potential after 10 000 potential cycles. The rotating ring disk electrode (RRDE) experiments revealed that F-MC follows the most preferable 4 pathway ( = 3.61) with a moderate peroxide (HO ) yield. This was further supported by density functional theory calculations and also deeply explains the existence of defects being beneficial for the ORR. The F-MC catalyst owing to its promising ORR activity and long-term electrochemical stability can be viewed as a potential alternative ORR catalyst for anion exchange membrane fuel cell applications.

摘要

在此,研究了介孔碳中的氟富集(F-MC),以在多孔基质中引入最大电荷极化,这有利于O分子的优先取向及其随后的还原。 使用Pluronic F-127作为结构导向剂,对源自间苯三酚-甲醛树脂的多孔碳进行F掺杂已标准化。 优化后的F-MC催化剂在碱性介质(0.1 M KOH)中对氧还原反应(ORR)表现出优异的电催化活性,起始电位为-0.10 V SCE,扩散极限电流为4.87 mA cm,而在半波区域与Pt-C(40 wt%)相比仅显示约50 mV的过电位。 在稳定性测试中,该催化剂在10000次电位循环后其半波电位仅负移10 mV。 旋转环盘电极(RRDE)实验表明,F-MC遵循最优选的4电子途径(n = 3.61),过氧化物(HO)产率适中。 密度泛函理论计算进一步支持了这一点,并且也深入解释了缺陷的存在对ORR有益。 由于其有前景的ORR活性和长期电化学稳定性,F-MC催化剂可被视为用于阴离子交换膜燃料电池应用的潜在替代ORR催化剂。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/62b6/9416892/1401812e602b/c9na00572b-f1.jpg

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