Integrating Hybrid Perovskite Nanocrystals into Metal–Organic Framework as Efficient S-Scheme Heterojunction Photocatalyst for Synergistically Boosting Controlled Radical Photopolymerization under 980 nm NIR Light

S-scheme heterojunction photocatalyst MAPbI 3 @PCN-222 with light absorption extending to the NIR region is constructed by embedding organic–inorganic hybrid perovskite (MAPbI 3 ) into porphyrinic Zr-MOF (PCN-222). Both in situ X-ray photoelectron spectroscopy, ultraviolet photoelectron spectral characterization, and photocatalytic polymerization experiment prove the formation of S-scheme heterojunction. MAPbI 3 @PCN-222 with a low dosage (90 ppm) displays an impressive photocatalytic ability for 980 nm light-mediated photoinduced electron/energy-transfer-reversible addition–fragmentation chain-transfer (PET–RAFT) polymerization in air. The well-defined controllable-molecular weight polymers including block copolymers and ultrahigh-molecular weight polymers can be achieved with narrow distributions ( M w / M n < 1.20) via rapid photopolymerization. The industrial application potential of the photocatalyst also has been proved by scale-up synthesis of polymers with low polydispersity under NIR light-induced photopolymerization in a large-volume reaction system (200 mL) with high monomer conversion up to 99%. The penetration photopolymerization through the 5 mm polytetrafluoroethylene plate and excellent photocontrollable behavior illustrate the existence of long-term photogenerated electron transfer of heterojunction and abundant free radicals in photopolymerization. The photocatalyst still retains high catalytic activity after 10 cycles of photopolymerization in air. It is revealed for the first time that the special PET–RAFT polymerization pathway is initiated by the aldehyde-bearing α-aminoalkyl radical derived from the oxidization of triethanolamine (TEOA) by the heterojunction photocatalyst. This research offers a new insight into understanding the NIR-light-activated PET–RAFT polymerization mechanism in the presence of TEOA.