Lerf-Klinowski-type models of graphene oxide and reduced graphene oxide are robust in analyzing non-covalent functionalization with porphyrins

Graphene-based nanohybrids are good candidates for various applications. However, graphene exhibits some unwanted features such as low solubility in an aqueous solution or tendency to aggregate, limiting its potential applications. On the contrary, its derivatives, such as graphene oxide (GO) and reduced graphene oxide (RGO), have excellent properties and can be easily produced in large quantities. GO/RGO nanohybrids with porphyrins were shown to possess great potential in the field of photocatalytic hydrogen production, pollutant photodegradation, optical sensing, or drug delivery. Despite the rapid progress in experimental research on the porphyrin-graphene hybrids some fundamental questions about the structures and the interaction between components in these systems still remain open. In this work, we combine detailed experimental and theoretical studies to investigate the nature of the interaction between the GO/RGO and two metal-free porphyrins 5,10,15,20-tetrakis(4-aminophenyl) porphyrin (TAPP) and 5,10,15,20-tetrakis(4-hydroxyphenyl) porphyrin (TPPH)]. The two porphyrins form stable nanohybrids with GO/RGO support, although both porphyrins exhibited a slightly higher affinity to RGO. We validated finite, Lerf-Klinowski-type (Lerf et al. in J Phys Chem B 102:4477, 1998) structural models of GO (C59O26H26) and RGO (C59O17H26) and successfully used them in ab initio absorption spectra simulations to track back the origin of experimentally observed spectral features. We also investigated the nature of low-lying excited states with high-level wavefunction-based methods and shown that states' density becomes denser upon nanohybrid formation. The studied nanohybrids are non-emissive, and our study suggests that this is due to excited states that gain significant charge-transfer character. The presented efficient simulation protocol may ease the properties screening of new GO/RGO-nanohybrids.

Automated summary

Graphene-based nanohybrids show potential for various applications, but challenges such as low solubility and aggregation limit graphene's usefulness. Derivatives like GO and RGO have great properties and can be produced in large quantities. Nanohybrids of GO/RGO with porphyrins have potential in fields like photocatalysis and drug delivery, but questions remain about their structure and interaction. Experimental and theoretical studies on the interaction between GO/RGO and metal-free porphyrins suggest that the nanohybrids are non-emissive due to significant charge-transfer character in excited states. Efficient simulation methods may help in screening properties of new GO/RGO nanohybrids.