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This invention is directed to a porous sorbent comprising a modified metal-organic framework (MOF) having a hierarchical pore structure. The MOF is modified by plasma-enhanced chemical vapor deposition with air, fluorocarbons, or other sources of fluorine. In preferred embodiments the MOFs are zirconium based. The modified MOF, while surprisingly retaining its crystal structure, comprises a mixture of micropores and mesopores and embedded fluorine atoms.