Positively Photo‐Responsive Adsorption Over Binary Copper Porphyrin Framework and Graphene Film Sorbents

Abstract Photo‐responsive adsorption has emerged as a vibrant area because it provides a promising route to reduce the energy consumption of the traditional adsorption separation. However, the current methodology to fabricate photo‐responsive sorbents is still subject to the photo‐deforming molecular units. In this study, a new initiative of photo‐dissociated electron‐hole pairs is proposed to generate amazing adsorption activity, and prove its feasibility. Employing CuPP [PP = 5,10,15,20‐tetrakis(4‐carboxyphenyl)porphyrin] framework nanosheets compounded with graphene, binary film (BF) sorbents are successfully fabricated. The paradigmatic BF nanostructure brings about efficiently photo‐excited electron‐hole pairs with durable enough lifetime to meet the needs of microscopic adsorption equilibrium, which ultimately alters the electron density distribution of adsorption surface, and thus markedly modulates the adsorption activity. Therefore, an amazing photo‐enhanced adsorption capability for the index gas CO can be gotten. Once exposed to the visible‐light at 420 nm, the CO adsorption capacity (0 °C, 1 bar) is risen from 0.23 mmol g⁻¹ in the darkness to 1.66 mmol g⁻¹, changed by + 622%. This is essentially different from majority of current photo‐responsive sorbents based on photo‐deforming molecular units, of which adsorption capability is only decreased with photo‐induction, and the maximum rate of change reported is just −54%.