One-Dimensional Porphyrin Nanoassemblies Assisted via Graphene Oxide: Sheetlike Functional Surfactant and Enhanced Photocatalytic Behaviors

Abstract

Surfactant-assisted self-assembly (SAS) has received much attention for supramolecular nanoassemblies, due to its simplicity and easiness in realizing a controllable assembly. However, in most of the existing SAS protocols, the employed surfactants work only as a regulator for a controllable assembly but not as active species for function improvement. In this paper, we report that a porphyrin, zinc 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (ZnTPyP), could be assembled to form one-dimensional (1D) supramolecular nanostructures via a SAS method, wherein graphene oxide (GO) plays a fascinating role of sheetlike surfactant. We show that, when a chloroform or tetrahydrofuran solution of ZnTPyP is injected into an aqueous dispersion of GO, 1D supramolecular nanoassemblies of ZnTPyP with well-defined internal structures could be easily formulated in a controllable manner. Our experimental facts disclose that the complexation of ZnTPyP with the two-dimensional GO nanosheets plays an important role in this new type of SAS. More interestingly, compared with the 1D ZnTPyP nanoassemblies formulated via a conventional SAS, wherein cetyltrimethylammonium bromide is used as surfactant, those constructed via our GO-assisted SAS display distinctly enhanced photocatalytic activity for the photodegradation of rhodamine B under visible-light irradiation. Our new findings suggest that GO could work not only as an emergent sheetlike surfactant for SAS in terms of supramolecular nanoassembly but also as functional components during the performance of the assembled nanostructures.

Arginine-Mediated Self-Assembly of Porphyrin on Graphene: A Photocatalyst for Degradation of Dyes

“…Free-standing TCPP aggregates in the presence of arginine reveal a Soret absorption peak at 417 nm and the four weak absorption peaks of Q bands in the TCPP monomer are replaced by a strong peak at 666 nm also with three weak Q-bands in its original TCPP. The distinct bathochromic and hypsochromic shifts by 3 nm in Soret band of the TCPP confirm aggregation formation in comparison with monomeric TCPP, which indicates that most of the TCPP building blocks form J-type supramolecular assemblies with induction of arginine [15,37,42]. Similarly, the UV-vis spectrum of GNPs@TCPP nanofibers also show a Soret peak at approximately 420 nm and one strong peak at 666 nm along with three relatively weak peaks in Q-band region.…”

“…When GNPs were used as photocatalyst, while a decrease in RhB concentration of approximately 25% was observed, there is an insignificant decrease in the concentration of MO. This is likely due to good adsorption affinity of graphene toward RhB rather than MO [37]. When using free-standing TCPP aggregate photocatalysts, the concentration of RhB and MO are decreased by 90% and 30% respectively after 180 min of irradiation time under simulated sunlight.…”

“…For example, Chen et al employed vacuum filtration methods to integrate porphyrin nanoparticles into reduced graphene oxide (RGO) for use in photocatalysis [24]. In another study, Guo's group studied visible-light photocatalytic activity of a one-dimensional porphyrin formed by self-assembly assisted by graphene oxide [37]. However, these studies faced disadvantages, being poor integration or poor distribution of the porphyrin nanostructures on the graphene substrate.…”

Enhanced photo-electrochemical performances of graphene-based composite functionalized by Zn2+ tetraphenylporphyrin

“…On the other hand, the conductive structure of graphene affords facile charge transport channel to FTO, therefore leading to a low resistance and offering high capacitance [26]. Moreover, the resistance of G/ZnTPP is lower than that of other graphene-based composites [27]. All of these indicate the reduction in the solid state interface resistance and the charge transfer resistance on the G/ZnTPP composite.…”

Bilayer Porphyrin-Graphene Templates for Self-Assembly of Metal-Organic Frameworks on the Surface

“…Это указывает на существование в монослоях ZnTPyP и ZnTСPP двух типов структур с различным расположением моментов перехода. [52][53][54] Поскольку при сжатии монослоя увели-чивается только интенсивность полос, а форма спек-тров практически не изменяется, можно утверждать, что при растекании монослоя на поверхности воды обра-зуются два типа доменов, в одном из которых ориентация плоскостей порфирина близка к параллельной поверх-ности субфазы, а в другом перпендикулярной. Четкость проявления этих полос определяется расположением элементов оптоволоконного спектрометра.…”