A Full‐Spectrum Metal‐Free Porphyrin Supramolecular Photocatalyst for Dual Functions of Highly Efficient Hydrogen and Oxygen Evolution

Abstract

A full‐spectrum (300–700 nm) responsive porphyrin supramolecular photocatalyst with a theoretical solar spectrum efficiency of 44.4% is successfully constructed. For the first time, hydrogen and oxygen evolution (40.8 and 36.1 µmol g−1 h−1) is demonstrated by a porphyrin photocatalyst without the addition of any cocatalysts. The strong oxidizing performance also presents an efficient photodegradation activity that is more than ten times higher than that of g‐C3N4 for the photodegradation of phenol. The high photocatalytic reduction and oxidation activity arises from a strong built‐in electric field due to molecular dipoles of electron‐trapping groups and the nanocrystalline structure of the supramolecular photocatalyst. The appropriate band structure of the supramolecular photocatalyst adjusted via the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of the porphyrin gives rise to thermodynamic driving potential for H2 and O2 evolution under visible light irradiation. Controlling the energy band structure of photocatalysts via the ordered assembly of structure‐designed organic molecules could provide a novel approach for the design of organic photocatalysts in energy and environmental applications.

Directed self-assembly of viologen-based 2D semiconductors with intrinsic UV–SWIR photoresponse after photo/thermo activation

“…10 and 11). The photoresponse ranges for both 1B-T and 2B-T exceed all known reported values for single-component organic-based semiconductors 5,10,12,37,38 .…”

Photocatalytic activity enhanced via surface hybridization

“…At the same time, by adding cyanophosphoric acid to anchor zinc porphyrin on TiO 2 surface, the surface hybrid has long-term stability in reducing CO 2 . 129 In reviewing the application of surface hybrids based on small organic molecule semiconductors in the field of photocatalysis, we found that although some phthalocyanine or porphyrin derivatives exhibit catalysis activity, 175 there are not many reports of phthalocyanines and porphyrins as a part of photocatalysts to participate in photogenerated charge transport, and research at present pay less attention to tightly connected and large contact area interfaces. Nano-assembly takes porphyrin heterogeneity a step forward.…”

Functionalization of Graphene Oxide with Porphyrins: Synthetic Routes and Biological Applications

“…As a well-known class of naturally occurring macrocycles with pivotal roles in life, porphyrins and their derivatives are highly colored compounds used in diverse fields, such as medicine [e. g. photodynamic therapy (PDT) of cancer, [125,126] antimicrobial PDT [127,128] ) sensors, [129] environmental remediation, [130,131] photocatalysis [132] and solar cells. [133] These "pigments of life" are made of four pyrrole-type subunits connected by methinic bridges in a cyclic fashion.…”