锆基金属有机骨架材料用于氨吸附性能的研究

doi:10.11949/0438-1157.20220021

摘要/Abstract

摘要：

近年来，金属有机骨架材料（MOF）在气体吸附和储存领域得到了迅速发展，但由于结构的不稳定性，其在强腐蚀性气体氨（NH₃）的吸附方面并不令人满意。考虑到NH₃是唯一的无碳排放的氢能源载体，开发高效的储氨技术来载氢是有效的降低二氧化碳排放的手段。利用MOF材料具有的高比表面积和结构多样的特性，在NH₃的吸附和储存方面具有广阔的应用前景。而NH₃具有孤对电子，会攻击金属与配体之间形成的配位键，使MOF材料的结构遭到破坏。锆基金属有机骨架材料是公认结构稳定性较好的MOF材料，但其是否能胜任干燥NH₃及含水条件下的稳定性仍未深入考察，由此需探究该系列材料在NH₃吸附领域的适用性。在此，通过实验和计算模拟研究锆基系列的金属有机骨架UiO-66、NU-1000、MOF-801和 MOF-808的结构特征、稳定性和NH₃吸附性能。结果表明，UiO-66、NU-1000和MOF-808在纯NH₃环境下的稳定性较好，并且显示出高吸附量且可循环的氨吸附性能（13.04、6.38、9.65 mmol/g）。受限于水和氨对结构的协同破坏作用，NU-1000和MOF-801的结构均不能维持，而UiO-66和MOF-808的结构非常稳定，无论在干燥NH₃环境及含水NH₃环境下均能胜任而应用于NH₃吸附和储存。

关键词: 金属有机骨架材料, 锆基系列, 氨吸附, 稳定性, 循环性

Abstract:

Metal-organic framework (MOF) has been developed rapidly in the fields of gas adsorption and storage in recent years, but they are unsatisfactory in the adsorption of strong corrosive gas ammonia (NH₃) due to structural instability. Considering NH₃ is the only carbon-free chemical energy carrier, developing efficient ammonia storage technology to carry hydrogen is an effective technology to reduce carbon dioxide emissions. MOFs exhibit great prospects for adsorption and storage of NH₃ due to their high surface area and structural diversity advantages. NH₃ has a lone pair of electrons, which will attack the coordination bond formed between the metal ion and the ligand, resulting in the structural destruction of MOFs. Herein, the structural characteristics, stability, and NH₃ adsorption properties of Zr-based metal-organic frameworks, including UiO-66, NU-1000, MOF-801, and MOF-808, were investigated by experiments and computational simulations. The results showed that UiO-66 has excellent structural stability in NH₃ adsorption with a high uptake of 13.04, 6.38 and 9.65 mmol/g. However, Due to the limited stability and low adsorption capacity, NU-1000 and MOF-801 are not suitable for ammonia adsorption under the humid environment. Conversely, the structure of UiO-66 and MOF-808 is very stable, which can be used in NH₃ adsorption and storage applications both in dry and humid NH₃ environments.

Key words: metal-organic framework, Zr-based series, NH₃ adsorption, stability, cycling ability

中图分类号:

TQ 536.9

王毅, 熊启钊, 陈杨, 杨江峰, 李立博, 李晋平. 锆基金属有机骨架材料用于氨吸附性能的研究[J]. 化工学报, 2022, 73(4): 1772-1780.

Yi WANG, Qizhao XIONG, Yang CHEN, Jiangfeng YANG, Libo LI, Jinping LI. Research on Zr-based metal-organic frameworks for NH₃ adsorption[J]. CIESC Journal, 2022, 73(4): 1772-1780.

图/表 8

图1 UiO-66、MOF-801、MOF-808的孔笼结构和 NU-1000的直通道结构

Fig.1 The structures of UiO-66, MOF-801 and MOF-808 with cages and NU-1000 with channels

图2 合成的 UiO-66、NU-1000、MOF-801和MOF-808的形貌及其NH3/H2O共吸附之后的形貌

Fig.2 SEM images of synthesized UiO-66, NU-1000, MOF-801, and MOF-808 and after NH3/H2O co-adsorption

图3 UiO-66、NU-1000、MOF-801和MOF-808的PXRD谱图

Fig.3 PXRD patterns of UiO-66, NU-1000, MOF-801 and MOF-808

图4 UiO-66、NU-1000、MOF-801和MOF-808的TGA曲线

Fig.4 TGA curves of UiO-66, NU-1000, MOF-801 and MOF-808

图5 UiO-66、NU-1000、MOF-801和MOF-808的N2 (77 K)吸脱附等温线

Fig.5 N2 (77 K) ad/desorption isotherms of UiO-66, NU-1000, MOF-801 and MOF-808

图6 25℃下UiO-66、NU-1000、MOF-801和MOF-808的NH3吸脱附循环曲线

Fig.6 Cycles NH3 ad/desorption curves of UiO-66, NU-1000, MOF-801 and MOF-808 at 25℃

表1 孔结构及吸附性能

Table 1 Pore structure and adsorption performance of the samples

材料	BET比表面积/(m²/g)	孔径/?	孔体积/(cm³/g)	298 K NH₃吸附量/(mmol/g)
UiO-66	916	8.4,7.4	0.49	13.04
NU-1000	1567	31	1.4	6.38
MOF-801	873	7.4,5.6,4.8	0.45	9.85
MOF-808	1512	4.8,18.4	0.84	9.65

图7 在1 bar、25℃下使用 GCMC 计算的UiO-66、NU-1000、MOF-801和MOF-808中NH3分子(红点)的吸附分布

Fig.7 The adsorbed NH3 molecule density (red points) in UiO-66, NU-1000, MOF-801 and MOF-808 obtained from the GCMC simulations at 1 bar and 25℃

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