In some embodiments, the present disclosure pertains to methods of capturing CO2 from an environment by hydrating a porous material with water molecules to the extent thereby to define a preselected region of a plurality of hydrated pores and yet to the extent to allow the preselected region of a plurality of pores of the porous material to uptake gas molecules; positioning the porous material within a CO2 associated environment; and capturing CO2 by the hydrated porous material. In some embodiments, the pore volume of the hydrated porous material includes between 90% and 20% of the pre-hydrated pore volume to provide unhydrated pore volume within the porous material for enhanced selective uptake of CO2 in the CO2 associated environment. In some embodiments, the step of capturing includes forming CO2-hydrates within the pores of the porous material, where the CO2.nH2O ratio is n<4.