Enhancing Electrocatalysis: Engineering the Fe–Nx–C Electrocatalyst for Oxygen Reduction Reaction Using Fe-Functionalized Silica Hard Templates

IF 5.4 3区 材料科学 Q2 CHEMISTRY, PHYSICAL
Mohsin Muhyuddin, Silvia Mostoni, Hilah Clara Honig, Lorenzo Mirizzi, Lior Elbaz, Roberto Scotti, Massimiliano D’Arienzo* and Carlo Santoro*, 
{"title":"Enhancing Electrocatalysis: Engineering the Fe–Nx–C Electrocatalyst for Oxygen Reduction Reaction Using Fe-Functionalized Silica Hard Templates","authors":"Mohsin Muhyuddin,&nbsp;Silvia Mostoni,&nbsp;Hilah Clara Honig,&nbsp;Lorenzo Mirizzi,&nbsp;Lior Elbaz,&nbsp;Roberto Scotti,&nbsp;Massimiliano D’Arienzo* and Carlo Santoro*,&nbsp;","doi":"10.1021/acsaem.4c0121510.1021/acsaem.4c01215","DOIUrl":null,"url":null,"abstract":"<p >The availability of robust and accessible active sites in iron–nitrogen-carbon (Fe–N<sub><i>x</i></sub>-C) electrocatalysts is essential to optimize the oxygen reduction reaction (ORR), which is the main obstacle in the commercial realization of fuel cells. Herein, a modified hard templating method to develop efficient Fe–N<sub><i>x</i></sub>-C has been presented that not only ensured the generation of a porous architecture but also helped in the homogeneous distribution of Fe throughout the structure. First, silica nanoparticles (NPs) were grown via the Stöber process and then functionalized atomically with iron through two different types of silane chains, i.e., (3-aminopropyl)triethoxysilane (APTES) and N-(2-Aminoethyl)-3-aminopropyltriethoxysilane (EDTMS). The Fe-functionalized silica simultaneously acting as a sacrificial template as well as an iron source was then impregnated with nicarbazin, which was a carbon and nitrogen precursor. The dried mix was subject to pyrolysis (H1) followed by acid washing to dissolve silica templates, and then, again, it was subjected to another pyrolysis treatment (H2). At each proceeding step, ORR activity in both acidic and alkaline media was improved and the samples obtained at the last stage (i.e., H2) outperformed the other counterparts collected at the initial stages of the fabrication pathway. Eventually, the electrocatalyst developed using EDTMS-type silane attached to silica NPs (E_FeNC_H2) demonstrated the highest onset potentials of 990 mV vs RHE in alkaline media and 862 mV vs RHE in acidic media. Moreover, the lower peroxide yield of E_FeNC_H2 signifying nearly direct 4e<sup>–</sup> ORR was attributed to the highest specific surface area (627 m<sup>2</sup> g<sup>–1</sup>) and the optimum combination of active moieties dispersed in the porous carbonaceous framework.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"7 24","pages":"11691–11702 11691–11702"},"PeriodicalIF":5.4000,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsaem.4c01215","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Energy Materials","FirstCategoryId":"88","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsaem.4c01215","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

Abstract

The availability of robust and accessible active sites in iron–nitrogen-carbon (Fe–Nx-C) electrocatalysts is essential to optimize the oxygen reduction reaction (ORR), which is the main obstacle in the commercial realization of fuel cells. Herein, a modified hard templating method to develop efficient Fe–Nx-C has been presented that not only ensured the generation of a porous architecture but also helped in the homogeneous distribution of Fe throughout the structure. First, silica nanoparticles (NPs) were grown via the Stöber process and then functionalized atomically with iron through two different types of silane chains, i.e., (3-aminopropyl)triethoxysilane (APTES) and N-(2-Aminoethyl)-3-aminopropyltriethoxysilane (EDTMS). The Fe-functionalized silica simultaneously acting as a sacrificial template as well as an iron source was then impregnated with nicarbazin, which was a carbon and nitrogen precursor. The dried mix was subject to pyrolysis (H1) followed by acid washing to dissolve silica templates, and then, again, it was subjected to another pyrolysis treatment (H2). At each proceeding step, ORR activity in both acidic and alkaline media was improved and the samples obtained at the last stage (i.e., H2) outperformed the other counterparts collected at the initial stages of the fabrication pathway. Eventually, the electrocatalyst developed using EDTMS-type silane attached to silica NPs (E_FeNC_H2) demonstrated the highest onset potentials of 990 mV vs RHE in alkaline media and 862 mV vs RHE in acidic media. Moreover, the lower peroxide yield of E_FeNC_H2 signifying nearly direct 4e ORR was attributed to the highest specific surface area (627 m2 g–1) and the optimum combination of active moieties dispersed in the porous carbonaceous framework.

强化电催化:利用铁功能化二氧化硅硬模板设计用于氧还原反应的Fe-Nx-C电催化剂
铁氮碳(Fe-Nx-C)电催化剂中活性位点的可用性是优化氧还原反应(ORR)的关键,而氧还原反应是燃料电池商业化实现的主要障碍。本文提出了一种改进的硬模板方法来开发高效的Fe - nx - c,不仅确保了多孔结构的产生,而且有助于Fe在整个结构中的均匀分布。首先,通过Stöber工艺培养二氧化硅纳米颗粒(NPs),然后通过(3-氨基丙基)三乙氧基硅烷(APTES)和N-(2-氨基乙基)-3-氨基丙基三乙氧基硅烷(EDTMS)两种不同类型的硅烷链进行铁原子功能化。然后用碳氮前驱体尼卡巴嗪浸渍铁功能化二氧化硅,同时作为牺牲模板和铁源。将干燥后的混合物进行热解(H1),然后进行酸洗以溶解二氧化硅模板,然后再次进行热解(H2)处理。在每个步骤中,ORR在酸性和碱性介质中的活性都得到了提高,并且在最后阶段(即H2)获得的样品优于在制造途径的初始阶段收集的其他对应样品。最终,利用edtms型硅烷与二氧化硅NPs (E_FeNC_H2)结合制备的电催化剂在碱性介质中表现出990 mV vs RHE的最高起始电位,在酸性介质中表现出862 mV vs RHE的最高起始电位。此外,E_FeNC_H2的过氧化物产率较低,几乎直接表示4e - ORR,这归因于其最高的比表面积(627 m2 g-1)和分散在多孔碳质框架中的活性基团的最佳组合。
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 求助全文
来源期刊
ACS Applied Energy Materials
ACS Applied Energy Materials Materials Science-Materials Chemistry
CiteScore
10.30
自引率
6.20%
发文量
1368
期刊介绍: ACS Applied Energy Materials is an interdisciplinary journal publishing original research covering all aspects of materials, engineering, chemistry, physics and biology relevant to energy conversion and storage. The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrate knowledge in the areas of materials, engineering, physics, bioscience, and chemistry into important energy applications.
×
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
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
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 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术官方微信