微波合成MOF-808及其水蒸气捕集特性

doi:10.16085/j.issn.1000-6613.2023-0171

摘要/Abstract

摘要：

金属有机骨架（MOFs）作为新型多孔材料，在干燥领域极具应用前景。本研究提供了一种MOF-808微波加热快速合成法，合成温度为140℃，甲酸浓度12.83mol/L。通过X射线衍射仪、场发射扫描电子显微镜、物理吸附仪等对MOF-808的样品组成、结构、比表面积以及形貌等进行表征分析。合成MOF-808材料的水蒸气吸附量随甲酸浓度增加而提高(由0.521g/g提高到0.810g/g），随吸附温度升高而降低，高湿度下MOF-808表现出较快的吸附速率，最佳的吸附工况为30℃、90%相对湿度。含湿混合气中CO₂浓度变化时，MOF-808平衡吸附量均值0.529g/g，标准差0.018，表明材料对水蒸气具有良好吸附选择性，CO₂不会对MOF-808捕集水蒸气能力产生影响。在较低再生温度（70℃）下MOF-808经过8次循环后再生效率仍高于90%，说明MOF-808材料用于干燥过程节能潜力较大，循环稳定性好。

关键词: 微波加热, 金属有机骨架, 水蒸气, 吸附, 干燥, 二氧化碳, 选择性

Abstract:

Metal organic frameworks (MOFs) as one of new porous materials, have promising application in drying field. In this study, a rapid microwave synthesis of MOF-808 at 140℃ and 12.83mol/L formic acid concentration was reported. The obtained MOF-808 was thoroughly characterized by X-ray diffractometer, field emission scanning electron microscope and physical adsorption instrument. The water vapor adsorption capacity of MOF-808 increased with increasing formic acid concentration (0.521g/g to 0.810g/g), decreased with the increase of adsorption temperature, and the optimal adsorption working conditions were 30℃ and 90% relative humidity. MOF-808 showed a higher rate of adsorption at high humidity. The average water vapor adsorption capacity of MOF-808 was 0.529g/g with standard deviation 0.018 under the conditions of various CO₂ concentrations, which indicated that MOF-808 had a good adsorption selectivity for water vapor. The variation of CO₂ concentration did not affect its water vapor uptake performance. The regeneration efficiency of MOF-808 was higher than 90% after eight cycles at lower temperature (70℃), which indicated that MOF-808 had a great energy conservation potential and much better cycle stability.

Key words: microwave heating, MOF, water vapor, adsorption, drying, carbon dioxide, selectivity

中图分类号:

TQ021.4

陈飞, 丁玉栋, 马丽娇, 朱恂, 程旻, 廖强. 微波合成MOF-808及其水蒸气捕集特性[J]. 化工进展, 2023, 42(12): 6461-6468.

CHEN Fei, DING Yudong, MA Lijiao, ZHU Xun, CHENG Min, LIAO Qiang. Microwave synthesis of MOF-808 and its water vapor uptake characteristics[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6461-6468.

图/表 8

图1 水蒸气吸附实验系统图1—CO2气瓶；2—N2气瓶；3~6—阀门；7~8—气体质量流量控制器；9~10—温度控制器；11—反应器；12—相对湿度测点；13—微型液体注射泵；14—蒸发段；15—数据采集系统

图2 MOF-808的表征结果

图3 不同合成温度下MOF-808水蒸气吸附量及其产量

图4 甲酸浓度对MOF-808水蒸气吸附量及产量的影响

图5 水蒸气吸附曲线

图6 CO2对MOF-808水蒸气吸附量的影响

图7 MOF-808的循环再生效率

表1 常见干燥剂特性参数

样品	再生温度/℃	比表面积 /m²·g^-1	水蒸气吸附量 /g·g^-1
MOF-808（本研究）	70	1100~1600	0.776
硅胶^[34]	90~150	650	0.03~0.1^[35]
沸石3A/4A^[9]	200	800~1000	0.227^[36]
F-200活性氧化铝^[37]	290	360	1.71^[38]
CaCl₂/MCM-41^[39]	80	—	1.75^[39]
LiNO₃/硅胶^[40]	65~75	—	0.06^[40]

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