{"title":"High-performance ammonium perchlorate propellants enabled by ferrocene-functionalized carbon nanotube catalysts","authors":"","doi":"10.1016/j.jorganchem.2024.123401","DOIUrl":null,"url":null,"abstract":"<div><div>Ferrocene-based burning rate catalysts (BRCs) are essential for controlling the combustion of ammonium perchlorate (AP)-based composite solid propellants. However, their efficacy is often limited by migration during storage, leading to performance degradation. This work reports a novel class of covalently grafted ferrocene-functionalized multi-walled carbon nanotubes (CNT-Fc-n, <em>n</em> = 1, 2, 3) exhibiting enhanced catalytic activity and anti-migration properties. Structural characterization confirmed successful functionalization, while electrochemical analysis revealed facilitated electron transfer during AP decomposition due to π-π conjugation within the CNT-Fc-n structure. Consequently, CNT-Fc-n catalysts significantly reduced the AP decomposition activation energy, with CNT-Fc-3 (highest ferrocene loading) demonstrating the most pronounced catalytic effect. Specifically, CNT-Fc-3 lowered the AP decomposition temperature by 103 °C and 39 °C compared to pure AP and Catocene-catalyzed AP, respectively. Kinetic analysis revealed a 28-fold increase in the rate constant for CNT-Fc-3 catalyzed AP decomposition compared to pure AP. Moreover, the unique architecture of CNT-Fc-3 significantly reduced migration during a 50 °C simulation. This work presents a promising strategy for developing high-performance, migration-resistant BRCs for next-generation solid propellants.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":null,"pages":null},"PeriodicalIF":2.1000,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Organometallic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0022328X24003966","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Ferrocene-based burning rate catalysts (BRCs) are essential for controlling the combustion of ammonium perchlorate (AP)-based composite solid propellants. However, their efficacy is often limited by migration during storage, leading to performance degradation. This work reports a novel class of covalently grafted ferrocene-functionalized multi-walled carbon nanotubes (CNT-Fc-n, n = 1, 2, 3) exhibiting enhanced catalytic activity and anti-migration properties. Structural characterization confirmed successful functionalization, while electrochemical analysis revealed facilitated electron transfer during AP decomposition due to π-π conjugation within the CNT-Fc-n structure. Consequently, CNT-Fc-n catalysts significantly reduced the AP decomposition activation energy, with CNT-Fc-3 (highest ferrocene loading) demonstrating the most pronounced catalytic effect. Specifically, CNT-Fc-3 lowered the AP decomposition temperature by 103 °C and 39 °C compared to pure AP and Catocene-catalyzed AP, respectively. Kinetic analysis revealed a 28-fold increase in the rate constant for CNT-Fc-3 catalyzed AP decomposition compared to pure AP. Moreover, the unique architecture of CNT-Fc-3 significantly reduced migration during a 50 °C simulation. This work presents a promising strategy for developing high-performance, migration-resistant BRCs for next-generation solid propellants.
二茂铁基燃烧速率催化剂(BRC)对于控制高氯酸铵(AP)基复合固体推进剂的燃烧至关重要。然而,它们的功效往往受到储存过程中迁移的限制,从而导致性能下降。本研究报告了一类新型共价接枝二茂铁功能化多壁碳纳米管(CNT-Fc-n,n = 1、2、3),它们具有更强的催化活性和抗迁移特性。结构表征证实了功能化的成功,而电化学分析表明,CNT-Fc-n 结构中的π-π共轭作用促进了 AP 分解过程中的电子转移。因此,CNT-Fc-n 催化剂显著降低了 AP 分解活化能,其中 CNT-Fc-3(二茂铁负载量最高)的催化作用最为明显。具体而言,与纯 AP 和二茂铁催化的 AP 相比,CNT-Fc-3 将 AP 分解温度分别降低了 103 ℃ 和 39 ℃。动力学分析表明,与纯 AP 相比,CNT-Fc-3 催化 AP 分解的速率常数增加了 28 倍。此外,CNT-Fc-3 的独特结构大大减少了 50 °C 模拟期间的迁移。这项工作为开发用于下一代固体推进剂的高性能、抗迁移 BRC 提供了一种前景广阔的策略。
期刊介绍:
The Journal of Organometallic Chemistry targets original papers dealing with theoretical aspects, structural chemistry, synthesis, physical and chemical properties (including reaction mechanisms), and practical applications of organometallic compounds.
Organometallic compounds are defined as compounds that contain metal - carbon bonds. The term metal includes all alkali and alkaline earth metals, all transition metals and the lanthanides and actinides in the Periodic Table. Metalloids including the elements in Group 13 and the heavier members of the Groups 14 - 16 are also included. The term chemistry includes syntheses, characterizations and reaction chemistry of all such compounds. Research reports based on use of organometallic complexes in bioorganometallic chemistry, medicine, material sciences, homogeneous catalysis and energy conversion are also welcome.
The scope of the journal has been enlarged to encompass important research on organometallic complexes in bioorganometallic chemistry and material sciences, and of heavier main group elements in organometallic chemistry. The journal also publishes review articles, short communications and notes.