Organic semiconductor for artificial photosynthesis: water splitting into hydrogen by a bioinspired C₃N₃S₃polymer under visible light irradiation

Abstract

A novel organic semiconductor photocatalyst mimicking natural light-harvesting antenna complexes in photosynthetic organisms, a disulfide (-S-S-) bridged C 3 N 3 S 3 polymer, was designed and developed to generate hydrogen from water under visible light irradiation. The artificial conjugated polymer shows high H 2 -producing activity from the half-reaction of water splitting without the aid of a sacrificial electron donor. The H 2 -producing efficiency and photo-stability of the catalyst could be improved greatly using Ru and single-wall carbon nanotubes as cocatalysts or by adding a sacrificial donor. The results represent a potential and prospective application of the C 3 N 3 S 3 polymer in solar energy conversion and offer significant guidance to develop more stable and efficient photocatalytic systems based on organic semiconductors.

Degradation of Organic Dyes over Polymeric Photocatalyst C3N3S3

“…The XRD pattern of C 3 N 3 S 3 polymer is shown in Figure 1, where it can be seen that only one broadened diffraction peak exist at 22.9°, indicating that the resulting solid is an amorphous material. The position of XRD pattern peak is same to that reported by Long's group [19], implying that the obtained substance was C 3 N 3 S 3 .…”

Tuning of photocatalytic activity by creating a tridentate coordination sphere for palladium

“…In addition, an excitation spectrum of Ru(bmptpphz) in acetonitrile was recorded to explore, whether the additional absorption at 416 nm, related to the arylated tpphz ligand, contributes to the population of the luminescent 3 MLCT state (ESI Fig. S3 †).…”

“…30 The cyclometallation in Ru(bmptpphz)PdCl will influence both, the redox properties of the Pd centre and the stability and reactivity of the metal centre in all oxidation states since Pd(0) forms stable bonds to organometallic ligands. 48 (3) Moreover, also the steric shielding by the anisyl-substituents might have an impact on the catalytic performance of the Pd centre. As reported in the literature, the catalytic activity of Pd as catalytic centre in a phen coordination sphere is significantly affected by the steric influence of substituents in 2,9-position (equivalent to the 2,17-position in bmptpphz).…”

Modelling materials for solar fuel synthesis by artificial photosynthesis; predicting the optical, electronic and redox properties of photocatalysts

“…The most well-known of these photocatalysts are the inorganic solids [1][2][3]6], mostly oxides but also sulfides and selenides, the former including titanium dioxide [13][14][15], the quintessential photocatalyst. Perhaps less well-known, a range of supramolecular systems [16,17] and even organic polymers [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] have also been reported to act as photocatalysts. In this mini-review we will discuss computational work on modelling such photocatalysts in terms of the relevant material properties and processes, as well as what we believe to be key aspects to consider when performing such calculations.…”