Facilitating Charge Separation of Donor–Acceptor Conjugated Microporous Polymers via Position Isomerism Strategy for Efficient CO[sub.2] Photoconversion

Photoreduction of CO[sub.2] into the chemical feedstocks of fuels provides a green way to help solve both the energy crisis and carbon emission issues. Nevertheless, undesirable charge separation and migration, as well as rapid reverse charge recombination results in the unsatisfactory photocatalytic activity of most conjugated microporous polymers (CMPs). Herein, a pair of donor–acceptor (D-A) CMPs for CO[sub.2] photoconversion was developed through position isomerism by altering linkage sites. The results show that Py-D[sub.27]F with 2,7-site linkage exhibits a completely conjugated structure and a large molecular dipole moment, thus significantly accelerating charge separation and transfer. As a result, Py-D[sub.27]F achieves a higher yield of 320.9 μmol g[sup.−1] h[sup.−1] for CO[sub.2]-to-CO photoreduction (without the addition of any photosensitizers and precious metals), which is about three-fold greater than that of Py-D[sub.36]F (3,6-site linkage). This study provides a valuable idea for exploring outstanding CMP photocatalysts for the efficient processing of photocatalysis.