通过琥珀酸功能化的二氧化硅提高钌的利用率,支持在甲苯基LOHC系统中高效储氢

IF 4.8 2区 化学 Q2 CHEMISTRY, PHYSICAL
Tatiana M. Bustamante , Santiago Bedoya , Yenlis Rodríguez-Aballi , Diego Sanhueza-Rosales , J.N.Díaz de León , Cristian H. Campos
{"title":"通过琥珀酸功能化的二氧化硅提高钌的利用率,支持在甲苯基LOHC系统中高效储氢","authors":"Tatiana M. Bustamante ,&nbsp;Santiago Bedoya ,&nbsp;Yenlis Rodríguez-Aballi ,&nbsp;Diego Sanhueza-Rosales ,&nbsp;J.N.Díaz de León ,&nbsp;Cristian H. Campos","doi":"10.1016/j.apcata.2025.120518","DOIUrl":null,"url":null,"abstract":"<div><div>Toluene is a representative liquid organic hydrogen carrier (LOHC) with favorable thermodynamic and physical properties for reversible hydrogen storage. In this study, we report the synthesis of Ru-based catalysts supported on SiO₂ materials (SBA-15 and commercial SiO₂), surface-functionalized with succinamic acid to improve nanoparticle anchoring and metal utilization. Characterization confirmed the successful incorporation of carboxylic groups via a ring-opening grafting approach, leading to significant enhancements in Ru dispersion and stabilization. The Ru/SBA15-AC catalyst exhibited a narrow particle size distribution centered at 4 nm and a dispersion of 32 %. Catalytic tests revealed high activity and total toluene hydrogenation, with the Ru/SBA15-AC system achieving, after 3 h of reaction, a hydrogen storage capacity of 5.2 wt% and a TOF of 639 min⁻¹—outperforming most reported Ru-based catalysts under comparable conditions. Apparent activation energies (Eₐₐ) for all catalysts, determined from Arrhenius analysis, revealed that Ru/SBA15-AC exhibited the lowest value (41 kJ mol⁻¹). The combination of mesoporosity and carboxylic functionality appears to synergistically promote both Ru dispersion and the stabilization of highly active Ru species, which is reflected in the lower energy barrier for hydrogenation. Notably, the catalyst retained its structural integrity and activity over ten consecutive reaction cycles, as confirmed by post-reaction HR-TEM and recyclability assays. In addition to toluene, the Ru/SBA15-AC catalyst also demonstrated effective hydrogenation of other relevant LOHCs, including naphthalene, 2-methylindole, and 9-ethylcarbazole, highlighting its versatility across structurally diverse hydrogen carriers. While a complete LOHC cycle requires both hydrogenation and dehydrogenation steps, this work focused on the hydrogenation half-cycle to elucidate the role of support functionalization on catalyst efficiency and durability.These findings demonstrate that succinamic acid-modified SiO₂ supports represent a robust platform for designing recyclable, atom-efficient Ru catalysts, offering a promising pathway for practical hydrogen storage in LOHC systems.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"707 ","pages":"Article 120518"},"PeriodicalIF":4.8000,"publicationDate":"2025-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Enhanced ruthenium utilization via succinamic acid-functionalized SiO₂ supports for efficient hydrogen storage in toluene-based LOHC systems\",\"authors\":\"Tatiana M. Bustamante ,&nbsp;Santiago Bedoya ,&nbsp;Yenlis Rodríguez-Aballi ,&nbsp;Diego Sanhueza-Rosales ,&nbsp;J.N.Díaz de León ,&nbsp;Cristian H. Campos\",\"doi\":\"10.1016/j.apcata.2025.120518\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Toluene is a representative liquid organic hydrogen carrier (LOHC) with favorable thermodynamic and physical properties for reversible hydrogen storage. In this study, we report the synthesis of Ru-based catalysts supported on SiO₂ materials (SBA-15 and commercial SiO₂), surface-functionalized with succinamic acid to improve nanoparticle anchoring and metal utilization. Characterization confirmed the successful incorporation of carboxylic groups via a ring-opening grafting approach, leading to significant enhancements in Ru dispersion and stabilization. The Ru/SBA15-AC catalyst exhibited a narrow particle size distribution centered at 4 nm and a dispersion of 32 %. Catalytic tests revealed high activity and total toluene hydrogenation, with the Ru/SBA15-AC system achieving, after 3 h of reaction, a hydrogen storage capacity of 5.2 wt% and a TOF of 639 min⁻¹—outperforming most reported Ru-based catalysts under comparable conditions. Apparent activation energies (Eₐₐ) for all catalysts, determined from Arrhenius analysis, revealed that Ru/SBA15-AC exhibited the lowest value (41 kJ mol⁻¹). The combination of mesoporosity and carboxylic functionality appears to synergistically promote both Ru dispersion and the stabilization of highly active Ru species, which is reflected in the lower energy barrier for hydrogenation. Notably, the catalyst retained its structural integrity and activity over ten consecutive reaction cycles, as confirmed by post-reaction HR-TEM and recyclability assays. In addition to toluene, the Ru/SBA15-AC catalyst also demonstrated effective hydrogenation of other relevant LOHCs, including naphthalene, 2-methylindole, and 9-ethylcarbazole, highlighting its versatility across structurally diverse hydrogen carriers. While a complete LOHC cycle requires both hydrogenation and dehydrogenation steps, this work focused on the hydrogenation half-cycle to elucidate the role of support functionalization on catalyst efficiency and durability.These findings demonstrate that succinamic acid-modified SiO₂ supports represent a robust platform for designing recyclable, atom-efficient Ru catalysts, offering a promising pathway for practical hydrogen storage in LOHC systems.</div></div>\",\"PeriodicalId\":243,\"journal\":{\"name\":\"Applied Catalysis A: General\",\"volume\":\"707 \",\"pages\":\"Article 120518\"},\"PeriodicalIF\":4.8000,\"publicationDate\":\"2025-08-21\",\"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/S0926860X25004193\",\"RegionNum\":2,\"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":"Applied Catalysis A: General","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926860X25004193","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

摘要

甲苯是一种典型的液态有机氢载体(LOHC),具有良好的热力学和物理性质,可用于可逆储氢。在这项研究中,我们报道了在二氧化硅材料(SBA-15和商用二氧化硅)上负载钌基催化剂的合成,并用琥珀酸进行表面功能化,以提高纳米颗粒的锚定和金属利用率。表征证实了通过开环接枝方法成功结合羧基,导致Ru的分散和稳定性显著增强。Ru/SBA15-AC催化剂的粒径分布较窄,以4 nm为中心,分散度为32 %。催化测试显示,Ru/SBA15-AC体系具有高活性和总甲苯加氢,反应3 h后,储氢容量为5.2 wt%, TOF为639 min -毒葫芦-优于大多数报道的Ru基催化剂。根据阿伦尼乌斯分析,Ru/SBA15-AC的表观活化能(E)是最低的(41 kJ mol⁻¹)。介孔性和羧基官能团的结合似乎协同促进了Ru的分散和高活性Ru物种的稳定,这反映在较低的氢化能垒上。值得注意的是,通过反应后的HR-TEM和可回收性分析,该催化剂在连续10个反应周期中保持了其结构完整性和活性。除甲苯外,Ru/SBA15-AC催化剂还能有效加氢其他相关的lohc,包括萘、2-甲基吲哚和9-乙基咔唑,突出了其在不同结构的氢载体上的通用性。虽然一个完整的LOHC循环需要加氢和脱氢步骤,但这项工作主要集中在加氢半循环上,以阐明支撑功能化对催化剂效率和耐久性的作用。这些发现表明,琥珀酸修饰的SiO₂载体为设计可回收的、原子高效的Ru催化剂提供了一个强大的平台,为LOHC系统的实际储氢提供了一条有希望的途径。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Enhanced ruthenium utilization via succinamic acid-functionalized SiO₂ supports for efficient hydrogen storage in toluene-based LOHC systems
Toluene is a representative liquid organic hydrogen carrier (LOHC) with favorable thermodynamic and physical properties for reversible hydrogen storage. In this study, we report the synthesis of Ru-based catalysts supported on SiO₂ materials (SBA-15 and commercial SiO₂), surface-functionalized with succinamic acid to improve nanoparticle anchoring and metal utilization. Characterization confirmed the successful incorporation of carboxylic groups via a ring-opening grafting approach, leading to significant enhancements in Ru dispersion and stabilization. The Ru/SBA15-AC catalyst exhibited a narrow particle size distribution centered at 4 nm and a dispersion of 32 %. Catalytic tests revealed high activity and total toluene hydrogenation, with the Ru/SBA15-AC system achieving, after 3 h of reaction, a hydrogen storage capacity of 5.2 wt% and a TOF of 639 min⁻¹—outperforming most reported Ru-based catalysts under comparable conditions. Apparent activation energies (Eₐₐ) for all catalysts, determined from Arrhenius analysis, revealed that Ru/SBA15-AC exhibited the lowest value (41 kJ mol⁻¹). The combination of mesoporosity and carboxylic functionality appears to synergistically promote both Ru dispersion and the stabilization of highly active Ru species, which is reflected in the lower energy barrier for hydrogenation. Notably, the catalyst retained its structural integrity and activity over ten consecutive reaction cycles, as confirmed by post-reaction HR-TEM and recyclability assays. In addition to toluene, the Ru/SBA15-AC catalyst also demonstrated effective hydrogenation of other relevant LOHCs, including naphthalene, 2-methylindole, and 9-ethylcarbazole, highlighting its versatility across structurally diverse hydrogen carriers. While a complete LOHC cycle requires both hydrogenation and dehydrogenation steps, this work focused on the hydrogenation half-cycle to elucidate the role of support functionalization on catalyst efficiency and durability.These findings demonstrate that succinamic acid-modified SiO₂ supports represent a robust platform for designing recyclable, atom-efficient Ru catalysts, offering a promising pathway for practical hydrogen storage in LOHC systems.
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
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