Polyethylenimine (PEI) has been grafted on a 2D hexagonal mesostructured porous silica of MCM-41 type (LUS silica) using 3-glycidoxypropyltrimethoxysilane (GTMS) as a grafting agent to develop sorbents for CO₂ capture. The advantage of this tether is to create ethanolamine units upon reaction of the epoxy group with the amine functions of PEI. Two synthetic routes have been explored: (1) reaction of GTMS and PEI and then grafting on a calcined MCM-41 silica (M-1), and (2) grafting of GTMS on the silica and then reaction with PEI (M-2). In both cases, the grafted solids are well structured according to the XRD patterns. The amounts of glycidoxypropylsilane (GS) and PEI are 14 and 9 wt%, and 21 and 16 wt%, respectively, for samples M-1 and M-2. The CO₂ adsorption capacity of both materials has been tested at 303 K and 101 kPa and compared to a bare LUS silica sample impregnated with 25 wt% PEI (M-3-25). Samples M-1 and M-2 containing ethanolamine groups show higher CO₂ adsorption capacities, with loading of about 150 and 134 mgCO₂ / gPEI (36 and 43 mgCO₂ / g-sorbent), respectively, while the CO₂ adsorption capacity was about 55 mgCO₂ / gPEI (14 mgCO₂ / g-sorbent) for the impregnated solid M-3-25.

The molecular stencil patterning (MSP) technique is a new surface molecular engineering technique developed for cation-templated porous silicas to graft several functions with vicinity control. First, tetramethylammonium ions (TMA⁺) are introduced by ion exchange of the cetyltrimethyl-ammonium template (CTA⁺). Then, the coverage is controlled to create a masking array of cations, the pattern of which is produced by mutual electrostatic repulsion. A first function is grafted, here monopodal trimethylsilyl groups (TMS) or dipodal ethyl-1,2-bis(dimethylsilyl) (EBDMS) groups. After the removal of the masking cations, a second function is grafted using here N-(2-aminoethyl)-3-amino-propyltrimethoxysilane precursor. The distribution of N-(2-aminoethyl)-3-amino-propylsilyl functions (AAPS) is probed by complexation to Cu(II) ions. X-Ray diffraction, N₂ adsorption–desorption isotherms, ¹³C solid-state NMR, IR, UV-visible and electron paramagnetic resonance (EPR) techniques show that MSP can produce isolation of AAPS by TMS, or even better by EBDMS groups, with preservation of the silica pore structure.