Solid-state crystallization of metal organic frameworks within mesoporous materials methods and hybrid materials thereof

A method, comprising:

• first, contacting an aqueous solution of an organic ligand salt of the formula Ax(L−x) with a mesoporous material (MPM) to form an impregnated mesoporous salt material of the formula Ax(L−x)/MPM where A is a counter ion, each x is independently a whole number, and L is an organic ligand;
• second, treating the impregnated mesoporous salt material with a nitrogen flow saturated with an aqueous acidic solution to form an impregnated mesoporous acid material of the formula Hx(L−x)/MPM where H is hydrogen;
• third, contacting an aqueous solution of a metal precursor of the formula M+y(B)y with the impregnated mesoporous acid material to form an impregnated mesoporous metal organic framework precursor of the formula [M+Y(B)y][Hx(L−x)]/MPM where M is a metal, each y is independently a whole number, and B is an anion;
• finally, drying the impregnated mesoporous metal organic framework precursor by heating or under vacuum;
• and
• at least one of 1) heating the impregnated mesoporous metal organic framework precursor in the absence of a solvent to a temperature between 120 and 300° C. or 2) exposing the impregnated mesoporous metal organic framework precursor to a volatile vapor in the absence of a solvent such that the heating or the exposing forms a hybrid material of the formula (M+yL−x)-MPM;
• wherein the hybrid material comprises a nano-crystalline metal organic framework (MOF) embedded within the mesoporous material;
• wherein the mesoporous material is at least one selected from the group consisting of a mesoporous metal oxide, a mesoporous silica, a mesoporous carbon, a mesoporous polymer, a mesoporous silicoalumina (zeolite), a mesoporous organosilica, and a mesoporous aluminophosphate;
• wherein the organic ligand (L−x) of the organic ligand salt is at least one selected from the group consisting of terephthalates, benzene-1,3,5-tricarboxylates, 2,5-dioxibenzene dicarboxylates, biphenyl-4,4′-dicarboxylates, and derivatives thereof;
• wherein the metal (M+y) of the metal precursor is at least one transition metal selected from the group consisting of Mg, V, Cr, Mo, Zr, Hf, Mn, Fe, Co, Cu, Ni, Zn, Ru, Al, and Ga;
• and
• wherein the hybrid material comprises mesopores with an average diameter in the range of 2-50 nm and micropores with an average diameter in the range of 0.5-5.0 nm.