Nanostructuration Effect of Carbon‐Based Phenylene Vinylene Conjugated Porous Polymers on TiO2 Hybrid Materials for Artificial Photosynthesis

This work examines the role of polymer nanostructuration of phenylene vinylene (PV) conjugated porous polymers (PV‐CPPs) as highly active photocatalysts for both hydrogen production and CO2 photoreduction reactions. It is found that nanostructured PV‐CPP hybrids with TiO2 show a high increase in H2 production being the most active example, the n‐IEP‐20@T‐10 sample with an evolution rate of 3.24 mmol g−1 h−1 (ξ = 1.20%), that is, 8 times higher than that of its non‐nanostructured and 65‐fold higher than TiO2. In contrast, CO2 photoreduction in both nanostructured polymers shows a significant improvement in CH4 production compared with bare TiO2, and a clear change of selectivity toward C2+ products. In particular, C2+/C1 ratios are obtained with n‐IEP‐20‐based hybrids increased by one order of magnitude that obtained for TiO2. The beneficial effect of this synthetic strategy is associated with an increase of the dispersion on nanostructured CPPs over TiO2 leading to an improvement on the surface interaction between them that favors longer‐lived photogenerated carriers in spatially separated redox active sites, which favor the production and selectivity to highly electron demanding products. The use of these nanostructuration strategies opens new opportunities for the production of more processable polymers for different energy technologies. The nanostructuration by means of miniemulsion synthesis of carbon‐based phenylene vinylene conjugated porous polymers is described. The approach allows the obtention of the polymer as colloidal dispersion opening the door to their processability. Thankfully to that, hybrids with TiO2 show improvement in the performance for hydrogen production and CO2 photoreduction.