Nanostructuration Effect of Carbon‐Based Phenylene Vinylene Conjugated Porous Polymers on TiO<sub>2</sub> Hybrid Materials for Artificial Photosynthesis
Alejandro García‐Eguizábal, Miguel Gomez‐Mendoza, Mariam Barawi, Laura Collado, Antonio Sánchez‐Ruiz, Joaquín C. Garcı́a-Martı́nez, Marta Liras, Víctor A. de la Peña O’Shea
Abstract
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 CO 2 photoreduction reactions. It is found that nanostructured PV‐CPP hybrids with TiO 2 show a high increase in H 2 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 TiO 2 . In contrast, CO 2 photoreduction in both nanostructured polymers shows a significant improvement in CH 4 production compared with bare TiO 2 , and a clear change of selectivity toward C 2+ products. In particular, C 2+ /C 1 ratios are obtained with n‐IEP‐20 ‐based hybrids increased by one order of magnitude that obtained for TiO 2 . The beneficial effect of this synthetic strategy is associated with an increase of the dispersion on nanostructured CPPs over TiO 2 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.