Application of pore-expanded MCM-41 (PE-MCM-41) mesoporous silica coated with 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (TRI) has been extensively examined for the adsorption of CO2 from N-2. A systematic study of the amine loading as a function of the relative amounts of TRI and water used during the grafting procedure and the temperature of the grafting reaction was carried out. Extremely high levels of active amine content were achieved using prehydrated silica surfaces at grafting temperatures below reflux in order to facilitate thermally controlled water-aided surface polymerization of the aminosilanes. The CO2 adsorption capacities and rates were determined for all materials as a function of the amount of TRI and water per gram of support added to the grafting mixture. The optimal TRI grafted PE-MCM-41 adsorbent exhibited a 2.65 mmol/g adsorption capacity at 25 degrees C and 1.0 atm for a dry 5% CO2 in N-2 feed mixture, which exceeded all literature reported values, for both meso- and microporous materials under the conditions used in this study. Further, the apparent adsorption and desorption rates with the amine functionalized materials were exceedingly high. When considering the grafted amine quantity, the adsorption capacity and rate were found to be mutually dependent on each other, exhibiting an apparent optimal combination. In comparison to zeolite 13X, the optimally loaded TRI-PE-MCM-41 was far superior in terms of dynamic adsorption and desorption performance. These results were further enhanced when the adsorbents were challenged with a humid stream of 5% CO2/N-2. The TRI-PE-MCM-41 exhibited a 10% increase in CO2 adsorption capacity, whereas the 13X zeolite did not retain any significant CO2 adsorption capacity.