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胺功能化席夫碱共价有机框架负载的钯金铱纳米颗粒作为甲酸脱氢和六价铬还原的高性能催化剂。

Amine-functionalized Schiff base covalent organic frameworks supported PdAuIr nanoparticles as high-performance catalysts for formic acid dehydrogenation and hexavalent chromium reduction.

作者信息

Guo Xiaosha, Di Xixi, Tang Tian, Shi Yixuan, Liu Dong, Wang Wei, Liu Zhifeng, Ji Xiaohui, Shao Xianzhao

机构信息

Shaanxi Key Laboratory of Catalysis, School of Chemistry and Environment Science, Shaanxi University of Technology, Hanzhong 723001, PR China.

Shaanxi Key Laboratory of Catalysis, School of Chemistry and Environment Science, Shaanxi University of Technology, Hanzhong 723001, PR China; State Key Laboratory of Qinba Bio-Resource and Ecological Environment, Shaanxi University of Technology, Hanzhong 723001, PR China.

出版信息

J Colloid Interface Sci. 2024 Mar 15;658:362-372. doi: 10.1016/j.jcis.2023.12.085. Epub 2023 Dec 16.

Abstract

Formic acid (FA) holds significant potential as a liquid hydrogen storage medium. However, it is important to improve the reaction rates and extend the practical applications of FA dehydrogenation and Cr(VI) reduction through the development of efficient heterogeneous catalysts. This study reports the synthesis of a uniformly dispersed PdAuIr nanoparticles (NPs) catalyst loaded with amine groups covalent organic frameworks (COFs). The alloyed NPs demonstrated exceptional effectiveness in FA dehydrogenation rate and Cr(VI) reduction. The initial turnover of frequency (TOF) value for FA dehydrogenation without additives was 9970 h at 298 K, the apparent activation energy (E) was 30.3 kJ/mol and the rate constant (k) for Cr(VI) reduction was 0.742 min. Additionally, it showcased the ability to undergo recycling up to six times with minimal degradation in performance. The results indicate that its remarkable catalytic performance can be attributed primarily to the favorable mass transfer attributes of the aminated COFs supports, the strong metal-support interaction (SMSI), and the synergistic effects among the metals. This study offers a novel perspective on the advancement of efficient and durable heterogeneous catalysts with diverse capabilities, thereby making significant contributions to the fields of energy and environmental preservation.

摘要

甲酸(FA)作为一种液态储氢介质具有巨大潜力。然而,通过开发高效的非均相催化剂来提高反应速率并扩展FA脱氢和Cr(VI)还原的实际应用至关重要。本研究报道了一种负载胺基共价有机框架(COF)的均匀分散的PdAuIr纳米颗粒(NP)催化剂的合成。合金化的NP在FA脱氢速率和Cr(VI)还原方面表现出卓越的效果。在298 K下,无添加剂时FA脱氢的初始频率转换(TOF)值为9970 h⁻¹,表观活化能(Ea)为30.3 kJ/mol,Cr(VI)还原的速率常数(k)为0.742 min⁻¹。此外,它还展示了能够循环使用多达六次且性能降解最小的能力。结果表明,其卓越的催化性能主要可归因于胺化COF载体有利的传质属性、强金属-载体相互作用(SMSI)以及金属之间的协同效应。本研究为开发具有多种功能的高效耐用非均相催化剂提供了新的视角,从而为能源和环境保护领域做出了重大贡献。

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