Here, the use of high-performance microfluidic techniques (HPMT) is reportedto afford conjugated porous polymer (CPPs) with smaller particle size and narrower particle size dispersion than the obtained by miniemulsion methodology. Specifically, polymers based on BODIPY or BOPHY dyes are synthesized by HPMT conditions and conventional miniemulsion conditions. The polymer textural properties from HPMT are notably improved, giving rise to high-quality thin films that are photoelectrochemically characterized. Furthermore, hybrid materials of CPPs synthesized by HPMT and TiO2 inorganic semiconductor revealed enhanced photocatalytic activity in the hydrogen evolution reaction (HER). The most active hybrid UN_IEP-7@T-10 photocatalyst, containing 10 wt% polymer loading, achieved a hydrogen evolution rate of 3.10 mmol g−1 h−1 (ƺ = 1.13%), which is threefold higher than that of its non-nanostructured from bulk synthesis, two-times greater than its nanostructured by conventional miniemulsion techniques and even surpassed by 39-times the performance of bare TiO2. It is noteworthy that both photoluminescence lifetime (τPL) and transient lifetime (τT) are not affected by the nanoestructuration of CPPs, which agrees with the preservation of the chemical structure by both synthetic methodologies. The employment of HPMT as nanostructuration strategy clearly supports the obtaining of more processable polymers for a wide range of energy applications.

The work was funded by HySolChem project, which has received funding from the European Unions's Horizon 2020 research and innovation programme (101017928). The work was funded by European Research Council though ERC-PoC grants NanoCPP (899773) and DEMONIA (101069268). Financial support was received from the national projects N-GREEN (PID2022-141688OB-I00), SOL-Future (PLEC2021-007906), SOLARCHEM 5.0 (TED2021-130173B-C41), novaCO2 (PID2020-118593RB-C22), SolarCPP-Bat (CNS2022-135380) funded by MCIN/AEI/10.13039/501100011033. MB thanks the RYC2022-038157-I grant funded by MCIN/AEI/ 10.13039/501100011033. S.P. R. thanks the PIPF-2022/ECO-26069 grant funded by regional government of Comunidad de Madrid.