Preparation of PCN-6（M） Bimetallic Organic Framework Materials by Steam-assisted Method and Their CO2 and CH4 Adsorption Performance

doi:10.19894/j.issn.1000-0518.220341

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (6): 896-903.DOI: 10.19894/j.issn.1000-0518.220341

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Preparation of PCN-6（M） Bimetallic Organic Framework Materials by Steam-assisted Method and Their CO₂ and CH₄ Adsorption Performance

Ning YUAN¹, Jie MA¹, Jin-Ling ZHANG¹, Jian-Sheng ZHANG¹^,²()

^1.Shanxi Research Institute for Clean Energy，Tsinghua University，Taiyuan 030032，China
^2.Department of Energy and Power Engineering，Tsinghua University，Beijing 100084，China

Received:2022-10-20 Accepted:2023-03-09 Published:2023-06-01 Online:2023-06-27
Contact: Jian-Sheng ZHANG
About author:zhang-jsh@tsinghua.edu.cn

Abstract

Abstract:

In this work， a steam-assisted method is used to prepare bimetallic organic framework materials （bimetallic MOFs）. Co， Fe， Mn， Zn， and Ni as the secondary metals are exchanged in the structure of PCN-6 which has large specific surface area and high porosity， and a series of PCN-6（M）（M=Co/Fe/Mn/Zn/Ni） bimetallic materials are obtained. Their structure， morphology， composition， and adsorption properties are characterized by powder X-ray diffraction（PXRD）， scanning electron microscopy（SEM）， energy dispersive spectroscopy（EDS）， inductively coupled plasma-atomic emission spectroscopy（ICP-OES）， and gas adsorption methods. The results show that the diffraction peaks and morphology of the PCN-6（M） series bimetallic materials are consistent with the parent material PCN-6， and the exchanged metals content reaches 12.1% for Co， 22.0% for Fe， 16.1% for Mn， 17.5% for Zn， and 16.8% for Ni， respectively，which is much higher than the metal exchange capacity of solvothermal method （about 5.0%） under the same conditions. In terms of gas adsorption performance， PCN-6（Zn）， PCN-6（Ni） and PCN-6（Co） have better adsorption capacity for CH₄ and CO₂ than the parent material， especially at low pressure. In addition， the adsorption selectivity of V（CO₂）∶V（CH₄）=50∶50， PCN-6（Fe） is superior to the parent material by theoretical ideal adsorption solution theory （IAST） calculation. The preparation of bimetallic MOFs by steam-assisted method can improve the exchange capacity of metals and change the affinity of MOFs to different gas molecules， thereby improving the gas adsorption performance and selectivity of materials. The steam-assisted method provides a new idea for the preparation of bimetallic MOFs， which is expected to be used in the preparation of other materials.

Key words: Gas adsorption, CO₂/CH₄ separation, Steam-assisted method, Bimetallic organic framework materials

CLC Number:

O611.4

Ning YUAN, Jie MA, Jin-Ling ZHANG, Jian-Sheng ZHANG. Preparation of PCN-6（M） Bimetallic Organic Framework Materials by Steam-assisted Method and Their CO₂ and CH₄ Adsorption Performance[J]. Chinese Journal of Applied Chemistry, 2023, 40(6): 896-903.

Figures/Tables 9

Fig.1 Reaction device of steam-assisted method

Fig.2 Effect of reaction temperature and m（PCN-6）/m（CoCl2） on Co exchange capacity

Fig.3 PXRD pattern of PCN-6 and PCN-6（M）

Fig.4 SEM and EDS of PCN-6 and PCN-6（M）

Table 1 Comparison of metals exchange capacity between steam-assisted method and solvent-assisted method

Sample	wt（M）∶wt（Cu）（steam-assisted）	wt（M）∶wt（Cu）（solvothermal）
PCN-6（Co）	12.1∶87.9	3.9∶96.1
PCN-6（Mn）	16.1∶89.3	4.2∶95.8
PCN-6（Ni）	16.8∶83.2	6.5∶93.5

Fig.5 N2 adsorption desorption isotherm at 77 K of PCN-6 and PCN-6（M）

Table 2 Specific surface area and average pore diameter of PCN-6 and PCN-6（M）

Sample	PCN-6	PCN-6（Co）	PCN-6（Fe）	PCN-6（Mn）	PCN-6（Zn）	PCN-6（Ni）
BET surface area/（m²·g^-1）	3 770.7	868.5	1 155.0	1 208.6	1 124.3	1 097.3
Langmuir surface area/（m²·g^-1）	5 285.6	1 202.2	1 599.5	1 674.1	1 557.4	1 521.4
Average pore diameter/nm	2.07	2.13	2.14	2.15	2.09	2.19

Fig.6 （A） CH4 sorption isotherms at 273 K of PCN-6 and PCN-6（M）（The illustration shows the CH4 adsorption isotherm at low pressure）；（B） CO2 sorption isotherms at 273 K of PCN-6 and PCN-6（M）（The illustration shows the CO2 adsorption isotherm at low pressure）

Fig.7 CO2/CH4 adsorption selectivity of PCN-6 and PCN-6（M） at 273 K

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Preparation of PCN-6（M） Bimetallic Organic Framework Materials by Steam-assisted Method and Their CO₂ and CH₄ Adsorption Performance

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