Reactivity of a model of B3P3-doped nanographene with up to three CO2 molecules

Abstract

The reactivity of a B3P3-doped hexa-cata-hexabenzocoronene, as a model of nanographene (B3P3-NG), towards carbon dioxide was studied at the DFT M06-2X/6-311++G(3df,3pd)//M06-2X/6-31+G* level of theory. This compound can be classified as a poly-cyclic poly-Frustrated Lewis Pair (FLP) system, as it presents more than one Lewis Acid/Lewis Base pair on its surface, making the capture of several carbon dioxide molecules possible. Two scenarios were considered to fully characterize the capture of CO2 by this multi-FLP system: (i) fixation of three CO2 molecules sequentially one by one; and (ii) simultaneous contact of three CO2 molecules with the B3P3-NG surface. The resulting adducts were analyzed as function of activation barriers and the relative stability of the CO2 capture. A cooperativity effect due to the π-delocalization of the hexa-cata-hexabenzocoronene is observed. The fixation of a CO2 molecule modifies the electronic properties. It enhances the capture of additional CO2 molecules by changing the acidy and basicity of the rest of the boron and phosphorus atoms in the B3P3-NG system.

A multi-FLP approach for CO2 capture: investigating nitrogen, boron, phosphorus and aluminium doped nanographenes and the influence of a sodium cation

“…These MEP maxima are not found for the nitrogen-containing NGs (B 3 N 3 -NG and Al 3 N 3 -NG). As previously reported, 32 this observation can be related to the angle between the a, b, and g centroids of the 6member rings (Fig. 1).…”

Advances in CO2 activation by frustrated Lewis pairs: from stoichiometric to catalytic reactions

“…This multi FLP device binds three CO 2 molecules sequentially or simultaneously on the B 3 P 3 ·NG surface. 165 For the CO 2 reduction via dissociative chemisorption of H 2 , nanocarbon-based FLP bifunctional catalysts are becoming promising due to their unquenched electron transport capability. One study proposes a nanocarbon-based FLP catalyst for the CO 2 reduction via the dissociative chemisorption of H 2 .…”

(Pyridin‐2‐ylmethyl)triel Derivatives as Masked Frustrated Lewis Pairs. Interactions and CO2‐Sequestration

“…Their ability to activate small molecules under mild conditions, along with their tunable reactivity, makes them valuable tools in synthetic chemistry, providing greener and more sustainable routes to various chemical transformations. [6][7][8][9] A number of theoretical studies have been carried out to explain and predict the reactivity of intermolecular [10][11][12] and intramolecular [13][14][15][16][17][18][19][20][21][22][23] reactions involving FLPs.…”