Dual Promotion of Oxygen Reduction on Pt in Membrane Electrode Assembly by Hydroxyphenyl Metal Porphyrins

IF 32.4 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Energy & Environmental Science Pub Date : 2024-11-08 DOI:10.1039/d4ee04320k
Meihua Tang, Chunping Wang, Zhenying Zheng, Xiaoxiao Wang, Fulong Zhu, Shengli Chen
{"title":"Dual Promotion of Oxygen Reduction on Pt in Membrane Electrode Assembly by Hydroxyphenyl Metal Porphyrins","authors":"Meihua Tang, Chunping Wang, Zhenying Zheng, Xiaoxiao Wang, Fulong Zhu, Shengli Chen","doi":"10.1039/d4ee04320k","DOIUrl":null,"url":null,"abstract":"The oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) is severely hindered by the strong adsorption of sulfonate groups in perfluorinated sulfonic acid (PFSA) ionomers on Pt, which not only blocks the catalytic sites, but also induces dense PFSA films resisting O2 toward Pt. Herein, we address this issue with hydroxyphenyl metal porphyrins (MPOHs) as an additive in cathodic catalyst layers (CCLs). Detailed physical and electrochemical characterizations and molecular dynamics simulations reveal that MPOHs dually enables ORR-favorite Pt/ionomer interfaces, by forming hydrogen-bonding networks with hydronium and sulfonates to break the sulfonate-Pt interaction and enlarge the O2-diffusive hydrophilic domains in ionomer films, and enriching and carrying O2 molecules through adsorption/desorption processes. Consequently, the fuel cells with MPOHs-added CCLs exhibit marked reduction in the local oxygen transport resistance of ionomer films and notable improvements in the output power accordingly, with CuPOH, which is suggested by density functional theory calculations as an optimal O2 carrier due to the near zero O2 adsorption free energy, showing more pronounced improvement. These results should inspire more molecule-level strategies to boost PEMFC efficiency through regulating Pt/ionomer interfaces and stimulate electrode optimization-oriented materials development in broad areas spanning various electrochemical energy technologies.","PeriodicalId":72,"journal":{"name":"Energy & Environmental Science","volume":null,"pages":null},"PeriodicalIF":32.4000,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Energy & Environmental Science","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d4ee04320k","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

The oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) is severely hindered by the strong adsorption of sulfonate groups in perfluorinated sulfonic acid (PFSA) ionomers on Pt, which not only blocks the catalytic sites, but also induces dense PFSA films resisting O2 toward Pt. Herein, we address this issue with hydroxyphenyl metal porphyrins (MPOHs) as an additive in cathodic catalyst layers (CCLs). Detailed physical and electrochemical characterizations and molecular dynamics simulations reveal that MPOHs dually enables ORR-favorite Pt/ionomer interfaces, by forming hydrogen-bonding networks with hydronium and sulfonates to break the sulfonate-Pt interaction and enlarge the O2-diffusive hydrophilic domains in ionomer films, and enriching and carrying O2 molecules through adsorption/desorption processes. Consequently, the fuel cells with MPOHs-added CCLs exhibit marked reduction in the local oxygen transport resistance of ionomer films and notable improvements in the output power accordingly, with CuPOH, which is suggested by density functional theory calculations as an optimal O2 carrier due to the near zero O2 adsorption free energy, showing more pronounced improvement. These results should inspire more molecule-level strategies to boost PEMFC efficiency through regulating Pt/ionomer interfaces and stimulate electrode optimization-oriented materials development in broad areas spanning various electrochemical energy technologies.
查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
羟苯基金属卟啉对膜电极组装中铂上氧还原的双重促进作用
质子交换膜燃料电池(PEMFCs)中的氧还原反应(ORR)因全氟磺酸(PFSA)离子体中的磺酸基团在铂上的强烈吸附而受到严重阻碍,这不仅会阻塞催化位点,还会导致致密的 PFSA 薄膜阻挡 O2 向铂移动。详细的物理和电化学表征以及分子动力学模拟显示,MPOHs 可与氢离子和磺酸盐形成氢键网络,从而打破磺酸盐与铂之间的相互作用,扩大离子膜中的 O2 扩散亲水域,并通过吸附/解吸过程富集和携带 O2 分子,从而实现有利于 ORR 的铂/离子膜界面。因此,添加了 MPOHs 的 CCL 燃料电池明显降低了离子膜的局部氧气传输阻力,输出功率也相应得到显著提高,其中 CuPOH 因其接近零的氧气吸附自由能而被密度泛函理论计算认为是最佳的氧气载体。这些结果应能启发更多分子层面的策略,通过调节铂/离子膜界面来提高 PEMFC 的效率,并在跨越各种电化学能源技术的广泛领域中促进以电极优化为导向的材料开发。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 去求助
来源期刊
Energy & Environmental Science
Energy & Environmental Science 化学-工程:化工
CiteScore
50.50
自引率
2.20%
发文量
349
审稿时长
2.2 months
期刊介绍: Energy & Environmental Science, a peer-reviewed scientific journal, publishes original research and review articles covering interdisciplinary topics in the (bio)chemical and (bio)physical sciences, as well as chemical engineering disciplines. Published monthly by the Royal Society of Chemistry (RSC), a not-for-profit publisher, Energy & Environmental Science is recognized as a leading journal. It boasts an impressive impact factor of 8.500 as of 2009, ranking 8th among 140 journals in the category "Chemistry, Multidisciplinary," second among 71 journals in "Energy & Fuels," second among 128 journals in "Engineering, Chemical," and first among 181 scientific journals in "Environmental Sciences." Energy & Environmental Science publishes various types of articles, including Research Papers (original scientific work), Review Articles, Perspectives, and Minireviews (feature review-type articles of broad interest), Communications (original scientific work of an urgent nature), Opinions (personal, often speculative viewpoints or hypotheses on current topics), and Analysis Articles (in-depth examination of energy-related issues).
期刊最新文献
Anti-Freezing Hydrogel Electrolyte with Regulated Hydrogen Bond Network Enables High-Rate and Long Cycling Zinc Batteries A Review on Organic Nanoparticle-based Optoelectronic Devices: From Synthesis to Applications Surface-deprotonated ultra-small SnO2 quantum dots for high-performance perovskite solar cells Self-assembled porous salt crystals for solar-powered crystallization Decoupling Capacity Fade and Voltage Decay of Li-rich Mn-rich Cathodes by Tailoring Surface Reconstruction Pathways
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1