分级胺改性MOF-74的CO2吸附性能及机理研究

doi:10.11949/0438-1157.20251032

摘要/Abstract

摘要：

提升金属有机框架材料（MOF-74）的CO₂吸附容量与稳定性是碳捕集领域的关键挑战。研究制备了不同金属中心（Mg、Ni）和不同配体的MOF-74，并进行胺改性，筛选短链乙醇胺（MEA）、长链四乙烯五胺（TEPA）及TEPA&Py（1：1）复合胺三类改性剂，并系统评价了CO₂吸附性能。改性后材料性能显著提升：MEA、TEPA及TEPA：Py（1：1）分别将CO₂吸附容量提升至原始MOF-74的1.4倍、1.9倍和5.0倍。五次吸附-脱附循环后，改性吸附剂保持>95%的初始容量，证实其优异的循环稳定性与空气稳定性。本研究揭示了胺改性可显著强化MOF-74的CO₂捕集性能，但需控制负载量以避免过量胺引发的强碱性环境导致的性能衰减，为设计高效胺改性MOF吸附剂提供了理论依据与优化策略。

关键词: MOF-74, 胺功能化, CO₂捕集, 吸附剂

Abstract:

Enhancing the CO₂ adsorption capacity and stability of metal-organic frameworks (MOFs) is crucial for advancing carbon capture technologies. In this study, MOF-74 with different metal centers (Mg/Ni) and organic ligands was synthesized and subsequently modified with amines. Three amine modifiers-short-chain monoethanolamine (MEA), long-chain tetraethylenepentamine (TEPA), and a composite amine system (TEPA:Py = 1:1)—were screened and systematically evaluated for their influence on CO₂ adsorption performance. The modified materials markedly improved the CO₂ uptake: MEA, TEPA, and TEPA:Py (1:1) enhanced the adsorption capacity to 1.4, 1.9, and 5.0 times that of the pristine MOF-74, respectively. Moreover, all amine-modified adsorbents retained >95% initial capacity after five adsorption-desorption cycles under ambient conditions, demonstrating excellent cyclic stability. This work confirms that amine functionalization can significantly enhance the CO₂ capture performance of MOF-74, while also highlighting the need to optimize amine loading to prevent performance degradation caused by an excessively alkaline environment. These findings provide a theoretical foundation and practical strategy for designing highly efficient amine-modified MOF adsorbents.

Key words: MOF-74, amine-functionalization, CO₂ capture, adsorbents

中图分类号:

O647.3

肖翩翩, 卓超越, 张跃飞, 李子怡, 罗潇, 梁志武. 分级胺改性MOF-74的CO₂吸附性能及机理研究[J]. 化工学报, DOI: 10.11949/0438-1157.20251032.

Pianpian XIAO, Chaoyue ZHUO, Yuefei ZHANG, Ziyi LI, Xiao LUO, Zhiwu LIANG. Research on the CO₂ Adsorption Performance and Mechanism of Hierarchically Amine-Modified MOF-74[J]. CIESC Journal, DOI: 10.11949/0438-1157.20251032.

图/表 10

图1 实验流程图

Fig.1 Experimental flowchart

图2 CO2常压吸附与循环吸附示意图

Fig.2 Schematic of CO2 adsorption at ambient pressure and cyclic adsorption

图3 胺功能化改性的红外光谱图

Fig.3 FT-IR spectras of amine-functionalized modification

图4 胺功能化XRD图谱

Fig.4 XRD spectras of amine-functionalized modification

图5 胺功能化扫描电镜照片

Fig.5 SEM photographs of amine-functionalized modification

图6 改性MOF-74的DTG曲线

Fig.6 DTG curve of amine-functionalized MOF-74

图7 CO2常压吸附平衡曲线

Fig.7 Summary of CO₂ adsorption capacity under atmospheric conditions

图8 CO2常压吸附容量汇总图

Fig.8 Summary of CO₂ adsorption capacity under atmospheric conditions

图9 循环吸附曲线

Fig.9 Cyclic adsorption performance curves

图10 胺改性前后吸附模拟图注:(d)CO₂ Uptake in MOF-74 at 298 K and 100 kPa (e)Simulated CO₂ Isosteric Heat

Fig.10 Simulation diagram of amine-modified adsorption

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分级胺改性MOF-74的CO₂吸附性能及机理研究

Research on the CO₂ Adsorption Performance and Mechanism of Hierarchically Amine-Modified MOF-74

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