Porphyrins as nanoreactors in the carbon dioxide capture and conversion: a review

Abstract

7Uniqueness of properties and robustness of structure makes porphyrins nature's favorite catalysts. 8 They have grabbed human attention since decades due to its intense colours and in modern times the 9 interest in these molecules has sharply increased, owing to their use for handling some tough 10 problems, including medical and environmental issues. Nowadays much attention is being focused 11 on the development of materials for the capture and conversion of CO 2 into value added products and 12 porphyrins are not lagging behind in extending their favor. The idea that porphyrins are poor 13 absorption materials since are generally plnar compounds has been belied by the development of new 14 efficient porphyrin-based materials, and the development of reliable synthetic routes for porphyrin 15 based nanoreactors such as covalent-organic frameworks (COF) and metal-organic frameworks 16 (MOF) as porous materials has facilitated to overcome the underlying CO 2 reactivity challenges.17Porphyrin-based materials behaving as nanoreactors are very promising for CO 2 capture and 18 conversion due to the presence of basic pyrrole containing macrocyclic cavity and large aromatic 19 rings which facilitates strong interactions with CO 2 . This review is intended to provide an overview 20 of up-to-date progress made in the area of the CO 2 capture and conversion involving porphyrin-based 21 molecular materials and nanoreactors, bearing important structural features in terms of surface area, 22 porosity, CO 2 uptake and the possibility of its catalytic conversion to chemically valuable products.

Metal–Organic‐Framework‐Based Catalysts for Photoreduction of CO2

“…Electron-rich conjugated linkers show high CO 2 adsorption capacity due to their strong interactions with CO 2 , [64,157] which has proven to be beneficial for the photocatalytic CO 2 reduction reaction. [136,141,142] Moreover, electron-rich conjugated linkers can generate photoinduced charges through radical formation under light irradiation.…”

Beryllium subphthalocyanines self-assembling properties

“…This survey has also been extended to dimers including water and pyridine molecules, which can form a stable network of non-covalent interactions between monomers. Taking BeSubPz as a good model for BeSubPc, the aggregate formed by three monomer units ((BeSubPzH 2 O) 3 ) has large dipole moment and interaction energy values, which are clear driven forces for the selfassembling. Again, nitrogens are essential for the formation of hydrogen bonds between neighboring units along the molecular wire.…”

“…1-2 From a structural point of view, porphyrines are highly conjugated systems that generate nowadays as much interest as in the early years, in particular in material science and medicine. [3][4][5][6][7] Many analogues of porphyrins have been obtained in the last years in the search for new materials, as for instance subphthalocyanines (SubPc) or subporphyrazines (SubPz). [8][9][10][11] These SubPc compounds (see Figure 1) are non-planar contracted porphyrinoids containing a 14 π electron aromatic core and present a very promising photochemical behavior.…”

Three dimensional metal/N-doped nanoplate carbon catalysts for oxygen reduction, the reason for using a layered nanoreactor

“…Nanoreactors are nano size matrices, confining discrete chemical reactions from the surrounding bulk media 16–18 . These nanosized containers are either synthetically produced (for instance, nano porous, tubular and hollow nanomaterials with various geometries and diameters) or they are inherently composed of nano pores and channels (for instance, proteins, lipids and zeolites, etc) 16–20 . This confinement offers the control of a chemical reaction to make a particular product such as a new class of nanomaterials and/or gains a new insight into fundamental basics of physics and chemistry of the material 16,19 .…”