Tuning the Supramolecular Structures of Metal-Free Porphyrin via Surfactant Assisted Self-Assembly to Enhance Photocatalytic Performance

Abstract

Metal-free porphyrin with good planarity is beneficial to π–π stack interactions, which promotes electron coupling and the separation and transfer of photogenerated carriers. It is necessary to develop metal-free porphyrin-based photocatalysts and exploit the photocatalytic mechanism. Herein, metal–free porphyrin (5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin, TCPP) was self-assembled through an acid-based neutralization reaction and mixing dual-solvents under surfactants to form different aggregates. Morphology structures, optical and optoelectronic properties of the TCPP aggregates were characterized in detail. TCPP self-assemblies showed higher photocatalytic activities for the degradation of phenol under visible light than untreated TCPP powders, and the aggregates of nanorods formed through the acid-based neutralization reaction in the presence of hexadecyl trimethyl ammonium bromide (CTAB) possessed 2.6 times more activity than the nanofiber aggregates formed through mixing dual-solvents. It was proved that self-assembly methods are crucial for controlling the aggregation of porphyrins to form different aggregations, which have a profound impact on the photocatalytic activity.

Supramolecular Porphyrin Nanostructures Based on Coordination-Driven Self-Assembly and Their Visible Light Catalytic Degradation of Methylene Blue Dye

“…Therefore, the formation of well-defined, discrete (isolable) porphyrin nanostructures with a definite size, shape, and dimension is a challenging task. In the self-assembly of porphyrins, a variety of intermolecular non-covalent interactions (e.g., hydrogen bonding, ligand coordination, hydrophobic, π-π stacking, van der Waals forces, and electrostatic interactions) have been utilized [ 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 ]. In recent years, Sn(IV) porphyrins have been widely used as a building block for the construction of useful porphyrin nanostructures, including nanocomposites, nanosheets, nanotubes, or thin stripes on surfaces [ 31 , 32 , 33 , 34 ].…”

Porphyrin in prebiotic catalysis: Ascertaining a route for the emergence of early metalloporphyrins

“…Upon formation of J-aggregates and H-aggregates, the soret absorption band of porphyrin is known to undergo red-shift and blue shift, respectively 57,59,63,64 . The absorption λmax of J-aggregates of TPPS was reported to be near ~ 490 nm in aqueous solution 57,59,63,64 .…”

Covalently Conjugated Gold–Porphyrin Nanostructures

“…[ 14 , 15 , 16 ]. Actually, different particle dimensions and additional structural factors, such as aggregation and shape irregularity, may also considerably affect the overall properties, as the surface plasmon resonance that appears at different wavelengths depending on the abovementioned reasons [ 9 , 10 , 11 , 12 , 13 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ].…”

“…This porphyrin molecule is well suited to act as a bridge for Au NPs in order to obtain an extensive and organized network of Au NPs, covalently linked by organic and emissive connections. To our knowledge, this represents one of the first few cases of an Au NPs–porphyrin organized, plasmonic, and emissive network [ 26 , 27 , 41 , 42 , 43 , 44 , 45 ].…”