多孔胺基化氧化石墨烯基材料对CO2的吸附性能研究

doi:10.11949/j.issn.0438-1157.20190018

摘要/Abstract

摘要：

以乙二胺(EDA)、二乙烯三胺(DETA)、四乙烯五胺(TEPA)、聚乙烯亚胺(PEI)等多胺基化合物为表面改性剂，氧化石墨烯(GO)材料为载体，采用嫁接法辅以超声处理制备了表面胺基功能化多孔吸附材料，用于CO₂气体的吸附捕集。所制备的多孔吸附材料孔径约为1.35~4.34 nm，比表面积约为98.032~210.465 m²/g。制备的四种吸附材料中，以PEI功能化吸附材料对CO₂的吸附容量最大，70℃下达到了1.5 mmol/g，且经过20次循环吸附/脱附实验后，其CO₂吸附量基本不变。吸附过程的吸附等温线线型为Ⅰ型优惠型，另外吸附实验数据与Avrami模型模拟结果符合性较好。

关键词: 石墨烯, 胺基功能化, 吸附, 二氧化碳捕集, 制备

Abstract:

CO₂ adsorbents were prepared by chemical grafting ethylenediamine(EDA), diethylenetriamine(DETA), tetraethylenepentamime(TEPA), and polyethyleneimine(PEI) onto surface of graphene oxide combined with the ultrasound treatment. The pore diameter of amine functionalized GO is 1.35—4.34 nm, and the surface area is 98.032—210.465 m²/g. Among the four amine functionalized GO, the PEI functionalized GO has the largest CO₂ adsorption capacity, reaching 1.5 mmol/g at 70°C. Besides, the adsorbent also exhibited stable cyclic adsorption-regeneration performance with almost unchanged adsorption capacity after 20 cycles. The type of isothermal adsorption line is type Ⅰ, and the Avrami simulation results agree well with the adsorption experimental data.

Key words: graphene oxide, amine functionalization, adsorption, CO₂ capture, preparation

中图分类号:

TQ 465.92

刘亚敏, 彭蕾, 苏凤英, 王湘湘, 黄艺真, 林在春, 喻晓静, 裴义山. 多孔胺基化氧化石墨烯基材料对CO₂的吸附性能研究[J]. 化工学报, 2019, 70(5): 2016-2024.

Yamin LIU, Lei PENG, Fengying SU, Xiangxiang WANG, Yizhen HUANG, Zaichun LIN, Xiaojing YU, Yishan PEI. Study of CO₂ adsorption on amine functionalized graphene oxide porous materials[J]. CIESC Journal, 2019, 70(5): 2016-2024.

图/表 13

图1 GO的拉曼光谱图

Fig.1 Raman spectra of GO

图2 GO、EDA-GO、DETA-GO、TEPA-GO、PEI-GO的XRD谱图

Fig.2 XRD patterns of GO, EDA-GO, DETA-GO, TEPA-GO and PEI-GO

表1 GO及EDA-GO、DETA、TEPA-GO、PEI-GO的结构参数

Table 1 Textural properties of GO, EDA-GO, DETA, TEPA-GO and PEI-GO

样品	比表面积/(m²/g)	孔容/(cm³/g)	孔径(BJH)/nm
GO	289.028	0.046	1.91
EDA-GO	98.032	0.016	4.34
DETA-GO	210.465	0.043	1.73
TEPA-GO	194.484	0.042	1.69
PEI-GO	162.042	0.031	1.35

表2 GO和胺基功能化GO样品元素分析结果

Table 2 Elemental analysis of GO and amine functionalized GO

Sample	C/%(mass)	N/%(mass)	O/%(mass)
GO	62.17	0.08	20.24
EDA-GO	59.37	2.34	18.06
DETA-GO	53.52	4.18	14.84
TEPA-GO	52.68	4.84	14.66
PEI-GO	51.06	5.42	13.08

图3 GO以及EDA-GO、TEPA-GO、PEI-GO的扫描电镜图

Fig.3 SEM images of GO, EDA-GO, TEPA-GO and PEI-GO

图4 样品的TGA曲线

Fig.4 TGA curves of samples

图5 GO及EDA-GO、TEPA-GO、PEI-GO的FTIR谱图

Fig.5 FTIR spectrums of GO, EDA-GO, DETA-GO and PEI-GO

表3 样品的CO2吸附量

Table 3 Adsorption capacity of samples

Sample	Adsorption capacity/(mmol CO₂/g)
Sample	30℃	50℃	70℃
PEI-GO	0.3	1.2	1.5
TEPA-GO	0.3	0.9	1.3
DETA-GO	0.3	0.8	1.2
EDA-GO	0.1	0.5	0.7
GO	0.2	0.1	0

表4 Langmuir方程对实验数据的拟合结果

Table 4 Constants of Langmuir model for CO2 adsorption on PEI-GO

T/℃	q _m /(mmol/g)	k _L/min^?1	R ²
70	1.8523	0.3737	0.997
50	1.59147	0.2257	0.988
30	0.50101	0.15023	0.979

图6 30℃、50℃及70℃条件下PEI-GO的CO2等温吸附线

Fig.6 CO2 adsorption isotherms of PEI-GO at 30℃, 50℃ and 70℃

图7 Avrami 模型对30℃、50℃及70℃温度下PEI-GO吸附CO2实验数据模拟曲线

Fig.7 Avrami models on experimental CO2 uptake of PEI-GO at various adsorption temperatures

表5 Avrami模型模拟结果参数

Table 5 Constants of Avrami model for CO2 adsorption on PEI-GO

T/℃	q _e/(mmol/g)	k _a/min^-1	n	R ²	q _a/(mmol/g)
30	0.35096	0.46997	1.12044	0.998	0.3
50	1.28668	0.27768	1.28763	0.998	1.2
70	1.61234	0.272	1.05424	0.999	1.5

图8 PEI-GO样品循环吸附性能

Fig.8 Recycle adsorption/desorption runs of PEI-GO

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多孔胺基化氧化石墨烯基材料对CO₂的吸附性能研究

Study of CO₂ adsorption on amine functionalized graphene oxide porous materials

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