Cubic Cuprous Oxide-Based Nanocomposites for Photocatalytic Hydrogen Generation

Abstract

Semiconductor nanophotocatalysts with high performance for hydrogen (H2) generation require well-designed and optimized interfaces. This work aimed at the rational design and facile assembly of a highly efficient 5,10,15,20-tetrakis­(4-sulfophenyl)­porphyrin/Cu2O (TSPP/Cu2O) heteroarchitectural nanocomposite photocatalyst. The assembly mechanism was explored in detail by spectroscopy and calculation. It was confirmed that the excellent photoactive conjugate molecule TSPP was strongly anchored onto the cubic Cu2O by facilely combined coordination with a hydrogen bond, which was profitable for inhibiting the oxidation of Cu2O and aggregation among TSPP molecules. Importantly, it was shown that the TSPP/Cu2O nanocomposite possessed higher activity. On the basis of the results of fluorescence spectroscopy, X-ray photoelectron spectroscopy, and electrochemical measurements, the increased optical structure and dual interfacial interaction between TSPP and Cu2O were beneficial to improving the transfer of charge carriers. Therefore, the performance was greatly improved. It could provide a convenient approach for exploring highly efficient nanophotocatalysts for H2 generation.

Porphyrins and phthalocyanines as biomimetic tools for photocatalytic H2production and CO2reduction

“…35). 160 Since porphyrins with sulfonyl groups possess stronger electron-withdrawing abilities they were used as an alternative dye. Therefore, the combination of light-harvesting TSPP porphyrin (electron donor) and Cu 2 O cubic phase (electron acceptor) improved the photocatalytic performance towards hydrogen production.…”

Photocatalytic activity enhancement of Cu2O cubes functionalized with 2-ethynyl-6-methoxynaphthalene through band structure modulation

“…Beyond the typical metal, graphene, and semiconductor deposition, as well as metal–semiconductor core–shell formation, to create semiconductor heterostructures for enhanced photocatalytic performance, 25–31 surface molecular functionalization may be a new approach for increased photocatalytic activity. 32 Recent surface functionalization of Cu 2 O crystals with conjugated 4-ethynylaniline (4-EA) showed an unexpected excellent photocatalytic activity for Cu 2 O cubes, while rhombic dodecahedra gave a notably improved activity and octahedra presented a moderate activity enhancement. 33 DFT calculations have revealed a 4-EA-derived band within the band gap of Cu 2 O.…”

4-Nitrophenylacetylene-modified Cu2O cubes and rhombic dodecahedra showing superior photocatalytic activity through surface band structure modulation

“…3 The next untapped strategy to increasing photocatalytic activity should be surface molecular functionalization. 29 Previously, surface modification of Cu 2 O crystals with 4-ethynylaniline (4-EA) showed an unexpected good photocatalytic activity for Cu 2 O cubes, while rhombic dodecahedra exhibited a clearly improved activity and octahedra presented a smaller activity enhancement. 30 DFT calculations have disclosed a 4-EA-derived band within the Cu 2 O band gap.…”