Preparation of metal-organic frameworks Cu3(BTC)2 with amino-functionalization for CO2 adsorption
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摘要: 首先制备了嫁接氨基的均苯三甲酸，同时以其为原料通过溶剂热法合成了金属有机框架材料Cu3（NH2BTC）2，利用XRD、N2吸附-脱附、热重、红外、原位红外分析等表征手段对吸附剂进行了表征，并通过固定床测量穿透曲线的方法研究其CO2吸附性能。结果表明，氨基被成功引入Cu3（BTC）2骨架中。氨基修饰的Cu3（BTC）2对CO2有着较高的吸附容量，在10 kPa，50 ℃的条件下CO2吸附量为1.41 mmol/g，这源于材料对于CO2同时存在着物理吸附和化学吸附。Abstract: The metal-organic framework of Cu3(NH2BTC)2 was synthesized by solvothermal method with the prepared grafted amine-based trimesic acid as organic ligand. The synthesized adsorbent was characterized by XRD, N2 adsorption-desorption, thermogravimetry, FT-IR and in-situ FT-IR. The performance of the CO2 adsorption was studied by the breakthrough curve based on the fixed-bed reactor. The results showed that the amine groups had been successfully grafted into the skeleton of Cu3(BTC)2. The CO2 adsorption capacity of Cu3(NH2BTC)2 was improved to 1.41 mmol/g at 10 kPa and 50 ℃. The improvement of CO2 uptake might due to the effect of both the physical and chemical adsorption of CO2.
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Key words:
- amino-functionalized /
- Cu3(BTC)2 /
- CO2 adsorption
1) 本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813). -
图 1 氨基嫁接前后的Cu3(BTC)2的XRD谱图
Figure 1 XRD patterns of Cu3(BTC)2 before and after amino-functionalization
图 2 氨基嫁接前后配体的红外光谱谱图
Figure 2 FT-IR spectra of ligands before and after amino-functionalization
图 3 氨基嫁接前后Cu3(BTC)2的红外光谱谱图
Figure 3 FT-IR spectra of Cu3(BTC)2 before and after amino-functionalization
图 4 两种材料的N2吸附-脱附等温线
Figure 4 N2 adsorption-desorption isotherms of Cu3(BTC)2 before and after amino-functionalization
图 7 两种材料的原位透射红外光谱谱图
Figure 7 In-situ transmission infrared spectra of the two samples
(a): before adsorption; (b): after adsorption
表 1 两种材料的物性结构参数及在10 kPa，50 ℃下的CO2吸附量
Table 1 Structural properties and CO2 adsorption capacity (10 kPa, 50 ℃) of two samples
Sample BET surface area A/(m2·g-1) Pore volume v/(cm3·g-1) Micropore volume /% (t-plot) Average pore diameter d/nm Adsorption capacity mB /(mmol·g-1) Cu3(BTC)2 735 0.34 91.50 2.00 0.96 Cu3(NH2BTC)2 410 0.16 31.34 4.64 1.41 
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