Fe doping promotes water splitting activity of nickel-based catalysts in steam reforming of tar model compound

IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL
Tingwei An , Zixuan Zhang , Xu Ren , Keliang Wang , Ziwei Li , Min Li
{"title":"Fe doping promotes water splitting activity of nickel-based catalysts in steam reforming of tar model compound","authors":"Tingwei An ,&nbsp;Zixuan Zhang ,&nbsp;Xu Ren ,&nbsp;Keliang Wang ,&nbsp;Ziwei Li ,&nbsp;Min Li","doi":"10.1016/j.apcata.2025.120424","DOIUrl":null,"url":null,"abstract":"<div><div>Steam reforming of tar represents a cost-effective approach for tar removal in biomass gasification. Here, we developed a Ni-Fe/CeO<sub>2</sub>/CNT catalyst and unveil the effect of Fe for steam reforming of toluene (SRT) which is a representative tar model compound. The catalyst demonstrated exceptional stability (above 80 % toluene conversion, 3000 mmol/g<sub>cat</sub>/h H<sub>2</sub> yield) over 50 h. The outstanding performance is attributed to the effect of Fe in forming Ni-Fe alloy with the highest reducibility, dispersion, Ni<sup>0</sup> ratio, and increased sintering resistance, alongside enhanced electron transfer between Ni and Fe. Fe also promotes H<sub>2</sub>O adsorption, providing active oxygen for toluene conversion and carbon elimination. Finally, reaction mechanism was explored based on the <em>in-situ</em> DRIFTS and DFT calculations. DFT calculations revealed that Fe sites exhibit higher density of states, electrostatic potential, and <em>d</em>-band center than Ni sites, facilitating H<sub>2</sub>O coordination. Fe doping reduces energy barriers for H<sub>2</sub>O splitting and methyl dehydrogenation, while Ni promotes H<sub>2</sub> desorption. The synergistic Ni-Fe interaction enables distinct activation of toluene and H<sub>2</sub>O, respectively. Comparative studies showed Ni/CeO<sub>2</sub>/CNT suffers from carbon deposition, while Fe/CeO<sub>2</sub>/CNT exhibits limited activity due to poor reducibility and low Fe<sup>0</sup> content. These findings provide critical insights for designing stable Fe-based catalysts for efficient tar removal.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"705 ","pages":"Article 120424"},"PeriodicalIF":4.8000,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis A: General","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926860X25003254","RegionNum":2,"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

Abstract

Steam reforming of tar represents a cost-effective approach for tar removal in biomass gasification. Here, we developed a Ni-Fe/CeO2/CNT catalyst and unveil the effect of Fe for steam reforming of toluene (SRT) which is a representative tar model compound. The catalyst demonstrated exceptional stability (above 80 % toluene conversion, 3000 mmol/gcat/h H2 yield) over 50 h. The outstanding performance is attributed to the effect of Fe in forming Ni-Fe alloy with the highest reducibility, dispersion, Ni0 ratio, and increased sintering resistance, alongside enhanced electron transfer between Ni and Fe. Fe also promotes H2O adsorption, providing active oxygen for toluene conversion and carbon elimination. Finally, reaction mechanism was explored based on the in-situ DRIFTS and DFT calculations. DFT calculations revealed that Fe sites exhibit higher density of states, electrostatic potential, and d-band center than Ni sites, facilitating H2O coordination. Fe doping reduces energy barriers for H2O splitting and methyl dehydrogenation, while Ni promotes H2 desorption. The synergistic Ni-Fe interaction enables distinct activation of toluene and H2O, respectively. Comparative studies showed Ni/CeO2/CNT suffers from carbon deposition, while Fe/CeO2/CNT exhibits limited activity due to poor reducibility and low Fe0 content. These findings provide critical insights for designing stable Fe-based catalysts for efficient tar removal.
在焦油模型化合物蒸汽重整过程中,铁的掺杂提高了镍基催化剂的水裂解活性
蒸汽重整焦油是一种经济有效的生物质气化脱除焦油的方法。本文开发了一种Ni-Fe/CeO2/CNT催化剂,揭示了Fe在蒸汽重整甲苯(SRT)中的作用,甲苯是一种典型的焦油模型化合物。催化剂在50 h以上表现出优异的稳定性(甲苯转化率超过80 %,H2产率3000 mmol/gcat/h)。优异的性能是由于Fe在Ni-Fe合金中的作用,使其具有最高的还原性、分散性、Ni0比和烧结阻力,同时增强了Ni和Fe之间的电子转移。铁还促进水吸附,为甲苯转化和碳消除提供活性氧。最后,基于原位漂移和DFT计算,探讨了反应机理。DFT计算表明,Fe位点比Ni位点具有更高的态密度、静电势和d带中心,有利于水的配位。Fe掺杂降低了H2O分裂和甲基脱氢的能垒,而Ni则促进了H2的脱附。协同的Ni-Fe相互作用分别对甲苯和H2O具有明显的活化作用。对比研究表明,Ni/CeO2/CNT容易发生碳沉积,而Fe/CeO2/CNT由于还原性差和Fe0含量低,活性有限。这些发现为设计稳定的铁基催化剂以有效去除焦油提供了重要的见解。
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
Applied Catalysis A: General
Applied Catalysis A: General 化学-环境科学
CiteScore
9.00
自引率
5.50%
发文量
415
审稿时长
24 days
期刊介绍: Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications. Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.
×
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