CO2 adsorption and separation on phloroglucinol-melamine -formaldehyde polymeric nanofibers
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摘要: 以三聚氰胺、间苯三酚和甲醛为原料，通过水热缩聚反应合成了三聚氰胺酚醛纤维（PMF），考察了温度对PMF合成的影响。以扫描电子显微镜（SEM）、透射电子显微镜（TEM）、N2吸脱附和傅里叶变换红外（FT-IR）光谱等表征了PMF的形貌和结构，并采用体积法测定不同温度下CO2和N2在PMF上的单组分吸附平衡等温线。结果表明，在393 K下合成的PMF具有较大的比表面积（64 m2/g）和较高的CO2吸附量（1.83 mmol/g，298 K、118 kPa）。穿透柱实验表明，在298 K、200-600 kPa，CO2-N2混合气在PMF上均可实现有效分离。将PMF在873 K下，N2、H2及水蒸气等多种气氛中进行后处理，其比表面积和微孔孔容均显著增加，其中，在15% H2O气氛中处理后，样品CO2吸附量提高至2.83 mmol/g（298 K、118 kPa）。Abstract: Phloroglucinol-melamine-formaldehyde polymeric nanofibers (PMF) were hydrothermally synthesized by a polycondensation method using melamine, phloroglucinol and formaldehyde as starting materials. The effect of temperature on the PMF synthesis was investigated. The morphology and structure of the as-synthesized PMF were characterized by the scanning electron microscope (SEM), transmission electron microscope (TEM), N2 adsorption-desorption and Fourier-transform infrared spectrometer (FT-IR) etc. Pure gas adsorption equilibrium isotherms of CO2 and N2 were determined by the volumetric method. The PMF sample synthesized at 393 K presented a higher specific surface area (64 m2/g) and a higher adsorption capacity of CO2 (1.83 mmol/g@118 kPa, 298 K). Breakthrough column experiments indicated that efficient separation of CO2-N2 mixtures could be achieved on the PMF at 298 K and various pressures ranging from 200 to 600 kPa. After the PMF was thermally treated at 873 K in various atmospheres such as N2, H2, water vapor, etc., it was found that the specific surface area and micropore volume were greatly increased. Among the posttreated PMF samples, the one treated in 15% H2O stream showed an improved CO2 adsorption amount up to 2.83 mmol/g at 298 K and 118 kPa.
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Key words:
- melamine /
- nanofiber /
- CO2 adsorption /
- breakthrough column /
- nitrogen-rich carbon nanofiber
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图 1 PMF样品的SEM照片
Figure 1 SEM images of the PMF samples
(a): T1; (b): T2; (c): T3; (d): T4
图 2 PMF样品的TEM照片
Figure 2 TEM images of the PMF samples
(a): T1; (b): T2; (c): T3; (d): T4
图 4 77 K下PMF的N2吸脱附曲线
Figure 4 N2 adsorption-desorption isotherms of the PMF samples at 77 K T1-T4 curves were shifted up by 20, 40, 60 and 80 cm3/g, respectively
图 5 298 K下CO2在PMF上的吸脱附等温线
Figure 5 Adsorption-desorption isotherms of CO2 on the PMF samples at 298 K
图 6 298 K，不同压力下CO2-N2在T3上的穿透曲线和解吸曲线
Figure 6 Breakthrough curves of CO2-N2 on T3 at different pressures and desorption curves in He at 298 K
图 7 不同气氛中热处理后PMF样品的SEM照片
Figure 7 SEM images of the PMF samples after thermal treatment at various gas streams
(a): T3-N2; (b): T3-H2; (c): T3-5%H2O; (d): T3-15%H2O
图 8 77 K下热处理后样品的N2吸脱附曲线
Figure 8 N2 adsorption-desorption isotherms of the samples after thermal treatment at 77 K
图 9 298 K下CO2在热处理后样品上的吸脱附等温线
Figure 9 Adsorption-desorption isotherms of CO2 on the samples after thermal treatment at 298 K
表 1 PMF样品的孔结构数据
Table 1 Porosity data of the PMF samples
Sample ABET/
(m2·g-1)Smicro/
(m2·g-1)vtotal/
(cm3·g-1)vmicro/
(cm3·g-1)T1 39 2 0.29 0.000 T2 48 9 0.11 0.004 T3 64 16 0.19 0.008 T4 54 10 0.19 0.005 
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表 2 热处理后PMF的孔结构数据
Table 2 Porosity data of the PMF samples after thermal treatment
Sample ABET/
(m2·g-1)Smicro/
(m2·g-1)vtotal/
(cm3·g-1)vmicro/
(cm3·g-1)T3-N2 354 313 0.18 0.13 T3-H2 490 414 0.25 0.16 T3-5%H2O 406 375 0.17 0.14 T3-15%H2O 369 330 0.17 0.14
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表 3 XPS谱图N 1s分峰拟合结果
Table 3 Curve fitting results of N 1s XPS spectra
N 1s chemical state T3-H2 T3-15%H2O EB/eV content w/% EB/eV content w/% Nitride 396.8 5.9 397.3 5.4 Pyridinic 397.6 39.6 398.1 40.1 Amine 398.1 0.0 398.6 0.0 Pyrolic 399.5 48.1 400.0 51.8 Graphic N-O 401.1 6.4 401.6 2.7
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