One‐Pot Functionalization of Graphene with Porphyrin through Cycloaddition Reactions

Abstract

Two types of graphene-based hybrid materials, graphene-TPP (TPP=tetraphenylporphyrin) and graphene-PdTPP (PdTPP=palladium tetraphenylporphyrin), were prepared directly from pristine graphene through one-pot cycloaddition reactions. The hybrid materials were characterized by thermogravimetric analysis (TGA), by TEM, by UV/Vis, FTIR, Raman, and luminescence spectroscopy, and by fluorescence/phosphorescence lifetime measurements. The presence of the covalent linkages between graphene and porphyrin was confirmed by FTIR and Raman spectroscopy and further supported by control experiments. The presence of TPP (or PdTPP) in the hybrid material was demonstrated by UV/Vis spectroscopy, with TGA results indicating that the graphene-TPP and graphene-PdTPP hybrid materials contained approximately 18 % TPP and 20 % PdTPP. The quenching of fluorescence (or phosphorescence) and reduced lifetimes suggest excited state energy/electron transfer between graphene and the covalently attached TPP (or PdTPP) molecules.

One-pot synthesis of manganese porphyrin covalently functionalized graphene oxide for enhanced photocatalytic hydrogen evolution

“…Furthermore, the intensity ratio of D-and G-bands of GO is 1.1; while it changes to 1.2 for GO-MnTPP. This change is consistent with the functionalization of graphene oxide through covalent bonding [46]. Besides, the Raman spectrum of the nanocomposite also includes peaks of MnTPP centered at 374, 578, 851, and 999 cm -1 .…”

Probing the origin of fluorescence quenching of a graphene-porphyrin hybrid material

“…In addition, graphene-based hybrid nanomaterials, which combine the unique optical, electrical, magnetic and chemical properties of each component have the potential applications in solar cells, sensors and catalysis. Such a hybrid material combining graphene with porphyrin, namely graphene-TPP (tetraphenylporphyrin), has been recently synthesized by cycloaddition reactions [1]. Further, fluorescence spectroscopic studies [1] on graphene-TPP and free TPP-CHO (5-(4-Formylphenyl)-10,15,20-triphenylporphyrin) in dimethylformamide (DMF) (containing similar concentration of porphyrin) have shown that while TPP-CHO shows strong fluorescence (λ peak : 650 nm and 710 nm), fluorescence of porphyrin is quenched significantly in graphene-TPP.…”

“…Such a hybrid material combining graphene with porphyrin, namely graphene-TPP (tetraphenylporphyrin), has been recently synthesized by cycloaddition reactions [1]. Further, fluorescence spectroscopic studies [1] on graphene-TPP and free TPP-CHO (5-(4-Formylphenyl)-10,15,20-triphenylporphyrin) in dimethylformamide (DMF) (containing similar concentration of porphyrin) have shown that while TPP-CHO shows strong fluorescence (λ peak : 650 nm and 710 nm), fluorescence of porphyrin is quenched significantly in graphene-TPP. The reduced fluorescence lifetime (< 500ps) of the graphene-TPP as compared to that of free TPP-CHO (∼ 10ns) further confirms the fast quenching of the porphyrin singlet excited state in the hybrid material.…”

“…We report transient absorption spectroscopic studies on the hybrid material composed of porphyrin molecules covalently attached to graphene for investigating the mechanism underlying the reported fluorescence quenching of porphyrin in the hybrid [1]. Excited state dynamics of pure graphene suspension and porphyrin have also been studied as reference samples.…”

Nanocarbon-based electrochemical systems for sensing, electrocatalysis, and energy storage

“…by pyrene derivatives, [97,98] covalent bonding with dienophiles, [99,100] oxygen plasma treatment, [101] doping with 27 heteroatoms, [102][103][104][105] and creation of graphene-inorganic oxide hybrids. [106][107][108] …”