Abstract: Methane (CH₄) as a substitute for other mineral fuels plays a crucial role in reducing energy consumption and preventing environmental pollution. The present study employs a solvothermal method to fabricate a porous framework Co-metal-organic framework (Co-MOF) containing two distinct secondary building units (SBUs): an anionic [Co₂(μ₂-OH)(COO)₄(H₂O)] and a neutral [CoN₂(COO)₂]. Notably, within the anionic SBUs, the coordinated water molecules induce the generation of divergent unsaturated Co(II) centers in the unidirectional porous channels, thereby creating open metal sites. The adsorption performance of Co-MOF towards pure component gases was systematically investigated. The results demonstrated that Co-MOF exhibits superior adsorption capacity for C₂-C₃ hydrocarbons compared to CH₄, which offers the potential for efficient adsorption and separation of CH₄ from C₂-C₃ hydrocarbons. The gas selectivity separation ratios of Co-MOF for C₂H₆/CH₄ and C₃H₈/CH₄ were calculated using the ideal adsorbed solution theory method at 273/298 K and 0.1 MPa. The results revealed that Co-MOF achieved remarkable equilibrium separation selectivity for CH₄ and C₂-C₃ hydrocarbon gases among non-modified MOFs, signifying the potential of the synthesized Co-MOF for efficient recovery and purification of CH₄ from C₂-C₃ hydrocarbons. Breakthrough experiments further demonstrate the ability of Co-MOF to purify methane from C₂-C₃ hydrocarbons in practical gas separation scenarios. Additionally, molecular simulation calculations further substantiate the propensity of anionic SBUs to interact with C₂-C₃ hydrocarbon compounds. This study provides a novel paradigm for the development of porous MOF materials in the application of gas mixture separation.

Key words: Co-MOF, Separation hydrocarbons, Dynamic breakthrough curves, Molecular simulations adsorbent, Monte Carlo simulation

摘要： Methane (CH₄) as a substitute for other mineral fuels plays a crucial role in reducing energy consumption and preventing environmental pollution. The present study employs a solvothermal method to fabricate a porous framework Co-metal-organic framework (Co-MOF) containing two distinct secondary building units (SBUs): an anionic [Co₂(μ₂-OH)(COO)₄(H₂O)] and a neutral [CoN₂(COO)₂]. Notably, within the anionic SBUs, the coordinated water molecules induce the generation of divergent unsaturated Co(II) centers in the unidirectional porous channels, thereby creating open metal sites. The adsorption performance of Co-MOF towards pure component gases was systematically investigated. The results demonstrated that Co-MOF exhibits superior adsorption capacity for C₂-C₃ hydrocarbons compared to CH₄, which offers the potential for efficient adsorption and separation of CH₄ from C₂-C₃ hydrocarbons. The gas selectivity separation ratios of Co-MOF for C₂H₆/CH₄ and C₃H₈/CH₄ were calculated using the ideal adsorbed solution theory method at 273/298 K and 0.1 MPa. The results revealed that Co-MOF achieved remarkable equilibrium separation selectivity for CH₄ and C₂-C₃ hydrocarbon gases among non-modified MOFs, signifying the potential of the synthesized Co-MOF for efficient recovery and purification of CH₄ from C₂-C₃ hydrocarbons. Breakthrough experiments further demonstrate the ability of Co-MOF to purify methane from C₂-C₃ hydrocarbons in practical gas separation scenarios. Additionally, molecular simulation calculations further substantiate the propensity of anionic SBUs to interact with C₂-C₃ hydrocarbon compounds. This study provides a novel paradigm for the development of porous MOF materials in the application of gas mixture separation.

关键词: Co-MOF, Separation hydrocarbons, Dynamic breakthrough curves, Molecular simulations adsorbent, Monte Carlo simulation