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摘要: 为比较不同物理吸附材料的结构参数对其储氢性能的影响，制备和选取了具有超高比表面积的活性炭、石墨烯以及金属有机骨架（MOFs）作为低温吸附储氢的典型材料。首先，利用77 K下氮气在材料上的吸附数据确定了其BET比表面积以及孔径分布的主要结构参数。其次，利用3Flex全自动微孔吸附仪在77-87 K测试了0-0.1 MPa低压下氢在各材料上的吸附量，而后在0.1-8 MPa高压条件下利用PCTPro测试了氢在各材料上的过剩吸附量。最后，分析了各材料的储氢量与其结构参数间的关系。结果表明，在低压下，影响物理吸附材料储氢量的主要因素为孔径分布小于1 nm的微孔；而高压下，氢在多孔材料上的最大过剩吸附量与材料的BET比表面积呈正相关关系，斜率为0.0059 mmol/m2。Abstract: For comparing the effects of the structural properties of adsorbents on the capability for hydrogen storage, three kinds of adsorbents, including activated carbon, graphene sheets (GF) and metal-organic frameworks (MOFs), were synthesized and undertaken adsorption equilibrium tests of hydrogen at temperature of liquid nitrogen. The structural characterization of the prepared samples were firstly conducted employing Micromeritics 3Flex for the adsorption data of nitrogen at 77 K. Then, the adsorption equilibrium tests of hydrogen on those adsorbents had been respectively measured under low pressure of 0-0.1 MPa at temperature of 77-87 K and under high pressure of 0.1-8 MPa at 77 K. Lastly, the relationships of the hydrogen uptake and the structural properties of the adsorbents were analyzed. Results show that the hydrogen uptake of the physical absorbents is mainly affected by the micro-pores with pore size less than 1nm under low pressure, but under high pressure, the maximum amount of excess hydrogen adsorption on the porous material is positively correlated with the BET specific surface area of the material, and the slope is 0.0059 mmol/m2.
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Key words:
- cryo-adsorbed hydrogen storage /
- activated carbon /
- graphene sheets /
- MOFs
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图 1 77 K下活性炭、GS和MOFs材料的氮气吸附等温线
Figure 1 Adsorption/desorption isotherms of nitrogen at 77 K on the activated carbon, GS and MOFs
图 2 通过运用H-K方法分析氮气在77 K温度下吸附等温线得到活性炭、GS和MOFs材料的PSD
Figure 2 PSD of the activated carbon, GS and MOFs determined by analyzing adsorption isotherms of nitrogen at 77 K by H-K method
图 3 77 K、0-0.1 MPa条件下，活性炭、GS和MOFs材料的氢气过剩吸附等温线
Figure 3 Isotherms of excess amount of hydrogen absorbed on the activated carbon, GS and MOFs at 77 K and 0-0.1 MPa
图 4 87 K、0-0.1 MPa条件下，活性炭、GS和MOFs材料的氢气过剩吸附等温线
Figure 4 Isotherms of excess amount of hydrogen absorbed on the activated carbon, GS and MOFs at 87 K and 0-0.1 MPa
图 5 77 K、0.1-8 MPa条件下，活性炭、GS和MOFs材料的氢气过剩吸附等温线
Figure 5 Isotherms of excess amount of hydrogen absorbed on the activated carbon, GS and MOFs at 77 K and 0.1-8 MPa
图 6 活性炭、GS和MOFs材料上的氢过剩吸附量与其平均孔宽的关系(77 K和0.1 MPa)
Figure 6 Excess hydrogen uptake of the activated carbon, GS and MOFs vs mean pore width (77 K and 0.1 MPa) : excess uptake piont
图 7 活性炭、GS和MOFs在77 K时氢的最大过剩吸附量与BET比表面积的关系
Figure 7 Maximum excess capacity of the activated carbon, GS and MOFs at 77 K vs BET surface area
表 1 活性炭、GS和MOFs材料的结构表征参数
Table 1 Structural properties of the activated carbon, GS and MOFs
Sample ABET(a) /(m2·g-1) vmico(b)/(cm3·g-1) Mean pore width(b) d/nm SAC-02F 1730 0.62 0.96 AC-042 2310 0.71 0.95 GS2D 2000 0.61 0.93 GS 220 0.07 1.1 HKUST-1 1850 0.77 0.7 MOF-5(M) 3320 1.26 1.05 MOF-5(S) 1100 0.42 0.63 MIL-101(Cr) 3200 1.05 1.04 MIL-53(Al) 1500 0.6 0.73 ZIF-8 1620 0.54 1.07 note：(a): ABET was determined by the equilibrium data in the range of p/p0=0.05-0.15; (b): H-K method 
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表 2 氢在多孔材料上的极限吸附热和吸附量
Table 2 Isosteric heat of adsorption and hydrogen adsorption capacity on porous materials
Sample qst0/(kJ·mol-1) H2 uptake at low pressure/(mmol·g-1)(a) Maximum excess adsorption/(mmol·g-1)(b) SAC-02F 6.28 8.58(6.06) 14.82 AC-042 7.17 10.16(6.65) 21.78 GS2D 6.82 8.34(6.39) 17.45 GS 6.40 1.12(0.73) 5.02 HKUST-1 7.59 10.31(6.38) 19.69 MOF-5(M) 7.86 5.68(3.48) 25.65 MOF-5(S) 8.52 10.17(6.36) 12.18 MIL-101(Cr) 7.20 8.67(5.54) 20.76 MIL-53(Al) 6.08 9.11(5.92) 14.07 ZIF-8 5.25 6.46(3.28) 15.76 (a): H2 uptake at 77 K(87 K) and 0.1MPa; (b)：maximum excess adsorption can be accurately determined by the toth equation[27]
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