Polarization engineering of porous organic polymers for superior photocatalytic synthesis of disulfides and CO2 reduction

Abstract

The coupling of benzyl mercaptans to disulfide compounds is an important reaction in the production of pharmaceuticals, life medicine and other valuable fine chemicals. However, the coupling of benzyl mercaptans to disulfide compounds under aerobic and mild conditions remains a great challenge. Herein, we use cyclotriphosphazene as the basic skeleton to connect pyrimidine rings through ether bonds to form porous organic polymers (OBCPs). Research shows that OBCP samples not only exhibit fast carrier mobility, but also build up more negative reduction potential as well as low oxidation potential. In the photocatalytic reaction of benzyl mercaptans, OBCP sample generates the coupling of benzyl mercaptan to disulfide compounds rather than thiol oxidation products. Meanwhile, OBCPs also showed excellent photocatalytic reduction of CO₂ to produce CH₄. This work highlights that the dipole modulation of monomer molecules is important for designing polymers for excellent photocatalytic reactions.