Photocatalytic Water Splitting Promoted by 2D and 3D Porphyrin Covalent Organic Polymers Synthesized by Suzuki-Miyaura Carbon-Carbon Coupling.

This work deals with the synthesis of metal-free and porphyrin-based covalent organic polymers (COPs) by the Suzuki-Miyaura coupling carbon-carbon bond forming reaction to study the photocatalytic overall water splitting performance. Apart from using 5,10,15,20-Tetrakis-(4-bromophenyl)porphyrin, we have chosen different cross-linker monomers to induce 2-dimensional (2D) or 3-dimensional (3D) and different rigidity in their resulting polymeric molecular structure. The synthesised COPs were extensively characterised to reveal that the dimensionality and flexibility of the molecular structure play an intense role in the physical, photochemical, and electronic properties of the polymers. Photoinduced excited state of the COPs was evaluated by nanosecond time-resolved laser transient absorption spectroscopy (TAS) by analysing excited state kinetics and quenching experiments, photocurrent density measurements and photocatalytic deposition of Ru3+ to RuO2, and photocatalysis. In summary, TAS experiments demonstrated that the transient excited state of these polymers has two decay kinetics and exhibit strong interaction with water molecules. Moreover, photocurrent and photocatalytic deposition experiments proved that charges are photoinduced and are found across the COP molecular network, but more important charges can migrate from the surface of the COP to the medium. Among the various COPs tested, COP-3 that has a flexible and 3D molecular structure reached the best photocatalytic performances, achieving a photocatalytic yield of 0.4 mmol H2 × gCOP-3-1 after 3 h irradiation.

Study of the Photothermal Catalytic Mechanism of CO2 Reduction to CH4 by Ruthenium Nanoparticles Supported on Titanate Nanotubes.

The Sabatier reaction could be a key tool for the future of the renewable energy field due to the potential of this reaction to produce either fuels or to stabilize H2 in the form of stable chemicals. For this purpose, a new composite made of ruthenium oxide nanoparticles (NPs) deposited on titanate nanotubes (TiNTs) was tested. Titanate nanotubes are a robust semiconductor with a one-dimensional (1D) morphology that results in a high contact area making this material suitable for photocatalysis. Small ruthenium nanoparticles (1.5 nm) were deposited on TiNTs at different ratios by Na+-to-Ru3+ ion exchanges followed by calcination. These samples were tested varying light power and temperature conditions to study the reaction mechanism during catalysis. Methanation of CO2 catalyzed by Ru/TiNT composite exhibit photonic and thermic contributions, and their ratios vary with temperature and light intensity. The synthesized composite achieved a production rate of 12.4 mmol CH4·gcat-1·h-1 equivalent to 110.7 mmol of CH4·gRu-1·h-1 under 150 mW/cm2 simulated sunlight irradiation at 210 °C. It was found that photo-response derives either from Ru nanoparticle excitation in the visible (VIS) and near-infrared (NIR) region (photothermal and plasmon excitation mechanism) or from TiNT excitation in the ultraviolet (UV) region leading to electron-hole separation and photoinduced electron transfer.