title: Solvothermal Metal Metathesis on a Metal-Organic Framework with Constricted Pores and the Study of Gas Separation.
abstract: Metal-organic frameworks (MOFs) with constricted pores can increase the adsorbate density of gas and facilitate effective CO2 separation from flue gas or natural gas due to their enhanced overlapping of potential fields of the pores. Herein, an MOF with constricted pores, which was formed by narrow channels and blocks of functional groups, was fabricated from the assembly of a methyl-functionalized ligand and Zn(II) centers (termed NPC-7-Zn). Structural analysis of the as-synthesized NPC-7-Zn reveals a series of zigzag pores with pore diameters of ∼0.7 nm, which could be favorable for CO2 traps. For reinforcing the framework stability, a solvothermal metal metathesis on the pristine MOF NPC-7-Zn was performed, and a new Cu(II) MOF (termed NPC-7-Cu) with an identical framework was produced. The influence of the reaction temperatures on the metal metathesis process was investigated. The results show that the constricted pores in NPC-7-Zn can induce kinetic issues that largely slow the metal metathesis process at room temperature. However, this kinetic issue can be solved by applying higher reaction temperatures. The modified MOF NPC-7-Cu exhibits significant improvements in framework stability and thus leads to a permanent porosity for this framework. The constricted pore structure enables enhanced potential fields for these pores, rendering this MOF with high adsorbate densities for CO2 and high adsorption selectivity for a CO2/N2 gas mixture. The adsorption kinetic studies reveal that CH4 has a faster diffusion rate constant than CO2, showing a surface diffusion controlled mechanism for CO2 and CH4 adsorption.
authors.affiliation: Research Institute of Unconventional Petroleum and Renewable Energy, China University of Petroleum (East China) , Qingdao 266580, China.
authors.forename: Liangjun
authors.initials: L
authors.lastname: Li
authors.affiliation: Research Institute of Unconventional Petroleum and Renewable Energy, China University of Petroleum (East China) , Qingdao 266580, China.
authors.forename: Haitao
authors.initials: H
authors.lastname: Xue
authors.affiliation: Research Institute of Unconventional Petroleum and Renewable Energy, China University of Petroleum (East China) , Qingdao 266580, China.
authors.forename: Ying
authors.initials: Y
authors.lastname: Wang
authors.affiliation: Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences , Qingdao 266101, China.
authors.forename: Pinhui
authors.initials: P
authors.lastname: Zhao
authors.affiliation: Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences , Qingdao 266101, China.
authors.forename: Dandan
authors.initials: D
authors.lastname: Zhu
authors.affiliation: Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences , Qingdao 266101, China.
authors.forename: Min
authors.initials: M
authors.lastname: Jiang
authors.affiliation: Research Institute of Unconventional Petroleum and Renewable Energy, China University of Petroleum (East China) , Qingdao 266580, China.
authors.forename: Xuebo
authors.initials: X
authors.lastname: Zhao
keywords: adsorbate density; adsorption kinetics; constricted pores; gas selectivity; metal metathesis; metal−organic frameworks