mof衍生Ni₃Fe@C催化剂上气体脱出在CO₂甲烷化中的作用:原位XAS和PDF研究

IF 3.9 3区 化学 Q2 CHEMISTRY, PHYSICAL
ChemCatChem Pub Date : 2025-07-17 DOI:10.1002/cctc.202500859
Fabio Manzoni, Sven Strübbe, Leif Rohrbach, Maxime Boniface, Thomas Lunkenbein, Roland Schoch, Wolfgang Kleist, Matthias Bauer, Mirijam Zobel
{"title":"mof衍生Ni₃Fe@C催化剂上气体脱出在CO₂甲烷化中的作用:原位XAS和PDF研究","authors":"Fabio Manzoni,&nbsp;Sven Strübbe,&nbsp;Leif Rohrbach,&nbsp;Maxime Boniface,&nbsp;Thomas Lunkenbein,&nbsp;Roland Schoch,&nbsp;Wolfgang Kleist,&nbsp;Matthias Bauer,&nbsp;Mirijam Zobel","doi":"10.1002/cctc.202500859","DOIUrl":null,"url":null,"abstract":"<p>With industrial chemical processes facing the challenges of renewable energy supply, catalysts are needed that withstand fluctuations of operating conditions. For methanation reactions using hydrogen from electrocatalytic water splitting, dropouts of hydrogen are amongst the realistic scenarios. While Ni-based catalysts are the most widely used, bimetallic Ni/Fe-based catalysts recently emerged as superior. A new method of preparing highly active metallic catalysts is the decomposition of metal-organic frameworks. Even though it is difficult to control the particle size distribution and the homogeneity of the formed nanoparticles with this method, the carbonaceous features present between the nanoparticles permit avoiding the use of support, leading to a high-loading catalyst with superior stability. Here, we investigate with in situ X-ray absorption spectroscopy and pair distribution function analysis the structural details of a Ni<sub>3</sub>Fe@C methanation catalyst derived from a metal-organic framework during its activation and catalysis under H<sub>2</sub>-dropout conditions. Despite the similarity of these phases, it was possible to identify two fcc phases of Ni<sub>3</sub>Fe and Ni coexisting during catalytic cycling, with a Fe<sub>2</sub>NiO<sub>4</sub> spinel phase appearing during dropouts. This indicates oxidation of the particle surface in the absence of hydrogen, which can be fully recovered by reactivation in pure hydrogen atmosphere, providing high stability of the catalyst during an industrially relevant dropout scenario.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 18","pages":""},"PeriodicalIF":3.9000,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500859","citationCount":"0","resultStr":"{\"title\":\"Role of Gas Dropouts in CO₂ Methanation over MOF-Derived Ni₃Fe@C Catalysts: An In Situ XAS and PDF Study\",\"authors\":\"Fabio Manzoni,&nbsp;Sven Strübbe,&nbsp;Leif Rohrbach,&nbsp;Maxime Boniface,&nbsp;Thomas Lunkenbein,&nbsp;Roland Schoch,&nbsp;Wolfgang Kleist,&nbsp;Matthias Bauer,&nbsp;Mirijam Zobel\",\"doi\":\"10.1002/cctc.202500859\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>With industrial chemical processes facing the challenges of renewable energy supply, catalysts are needed that withstand fluctuations of operating conditions. For methanation reactions using hydrogen from electrocatalytic water splitting, dropouts of hydrogen are amongst the realistic scenarios. While Ni-based catalysts are the most widely used, bimetallic Ni/Fe-based catalysts recently emerged as superior. A new method of preparing highly active metallic catalysts is the decomposition of metal-organic frameworks. Even though it is difficult to control the particle size distribution and the homogeneity of the formed nanoparticles with this method, the carbonaceous features present between the nanoparticles permit avoiding the use of support, leading to a high-loading catalyst with superior stability. Here, we investigate with in situ X-ray absorption spectroscopy and pair distribution function analysis the structural details of a Ni<sub>3</sub>Fe@C methanation catalyst derived from a metal-organic framework during its activation and catalysis under H<sub>2</sub>-dropout conditions. Despite the similarity of these phases, it was possible to identify two fcc phases of Ni<sub>3</sub>Fe and Ni coexisting during catalytic cycling, with a Fe<sub>2</sub>NiO<sub>4</sub> spinel phase appearing during dropouts. This indicates oxidation of the particle surface in the absence of hydrogen, which can be fully recovered by reactivation in pure hydrogen atmosphere, providing high stability of the catalyst during an industrially relevant dropout scenario.</p>\",\"PeriodicalId\":141,\"journal\":{\"name\":\"ChemCatChem\",\"volume\":\"17 18\",\"pages\":\"\"},\"PeriodicalIF\":3.9000,\"publicationDate\":\"2025-07-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500859\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemCatChem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202500859\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemCatChem","FirstCategoryId":"92","ListUrlMain":"https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/cctc.202500859","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

摘要

随着工业化学过程面临可再生能源供应的挑战,需要能够承受操作条件波动的催化剂。对于使用电催化水裂解氢的甲烷化反应,氢的漏出是现实的情况之一。虽然镍基催化剂的应用最为广泛,但近年来双金属镍/铁基催化剂的优势逐渐显现。金属有机骨架分解是制备高活性金属催化剂的一种新方法。尽管用这种方法很难控制颗粒的大小分布和形成的纳米颗粒的均匀性,但纳米颗粒之间存在的碳质特征允许避免使用载体,从而产生具有优越稳定性的高负载催化剂。本文采用原位x射线吸收光谱和对分布函数分析研究了在H2-dropout条件下由金属-有机骨架衍生的Ni3Fe@C甲烷化催化剂的活化和催化过程中的结构细节。尽管这些相相似,但在催化循环过程中可以识别出Ni3Fe和Ni共存的两个fcc相,其中Fe2NiO4尖晶石相出现在dropouts过程中。这表明在没有氢的情况下,颗粒表面氧化,可以通过在纯氢气氛中再活化完全恢复,在工业相关的脱落情况下提供高稳定性的催化剂。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Role of Gas Dropouts in CO₂ Methanation over MOF-Derived Ni₃Fe@C Catalysts: An In Situ XAS and PDF Study

Role of Gas Dropouts in CO₂ Methanation over MOF-Derived Ni₃Fe@C Catalysts: An In Situ XAS and PDF Study

Role of Gas Dropouts in CO₂ Methanation over MOF-Derived Ni₃Fe@C Catalysts: An In Situ XAS and PDF Study

Role of Gas Dropouts in CO₂ Methanation over MOF-Derived Ni₃Fe@C Catalysts: An In Situ XAS and PDF Study

With industrial chemical processes facing the challenges of renewable energy supply, catalysts are needed that withstand fluctuations of operating conditions. For methanation reactions using hydrogen from electrocatalytic water splitting, dropouts of hydrogen are amongst the realistic scenarios. While Ni-based catalysts are the most widely used, bimetallic Ni/Fe-based catalysts recently emerged as superior. A new method of preparing highly active metallic catalysts is the decomposition of metal-organic frameworks. Even though it is difficult to control the particle size distribution and the homogeneity of the formed nanoparticles with this method, the carbonaceous features present between the nanoparticles permit avoiding the use of support, leading to a high-loading catalyst with superior stability. Here, we investigate with in situ X-ray absorption spectroscopy and pair distribution function analysis the structural details of a Ni3Fe@C methanation catalyst derived from a metal-organic framework during its activation and catalysis under H2-dropout conditions. Despite the similarity of these phases, it was possible to identify two fcc phases of Ni3Fe and Ni coexisting during catalytic cycling, with a Fe2NiO4 spinel phase appearing during dropouts. This indicates oxidation of the particle surface in the absence of hydrogen, which can be fully recovered by reactivation in pure hydrogen atmosphere, providing high stability of the catalyst during an industrially relevant dropout scenario.

求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
ChemCatChem
ChemCatChem 化学-物理化学
CiteScore
8.10
自引率
4.40%
发文量
511
审稿时长
1.3 months
期刊介绍: With an impact factor of 4.495 (2018), ChemCatChem is one of the premier journals in the field of catalysis. The journal provides primary research papers and critical secondary information on heterogeneous, homogeneous and bio- and nanocatalysis. The journal is well placed to strengthen cross-communication within between these communities. Its authors and readers come from academia, the chemical industry, and government laboratories across the world. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies, and is supported by the German Catalysis Society.
×
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:604180095
Book学术官方微信