Piezoelectric Zinc Oxides with High Polar Facets Ratios for Mechanically Controlled RAFT Polymerization†.

Comprehensive Summary: Mechanoredox chemistry that uses highly polarized piezoelectric materials as mechanoredox catalysts to promote redox reactions has emerged recently. It provides an alternative approach alongside the existing polymerization methods. Despite recent accomplishments, determining the quantitative relationship between the structure of ZnO and its catalytic performance for polymerization is still challenging. Herein, we prepared various ZnO crystals with different polar facets ratios to achieve efficient mechanically induced reversible addition‐fragmentation chain transfer polymerization (mechano‐RAFT). ZnO prepared from Zn(NO3)2 showed a high polar facet ratio of 1.66 and offered the highest catalytic activity among all ZnO samples. A near‐quantitative initiator efficiency of 99.5% and narrow molecular weight distribution were achieved for the polymerization of n‐butyl acrylate. Furthermore, the high chain‐end fidelity and chain extension capability were also evidenced by MALDI‐TOF MS and GPC analysis. This work highlighted the significant contribution of polar facets in ZnO to its catalytic activity and will guide the design of mechanoredox catalysis with superior catalytic performance in the future. [ABSTRACT FROM AUTHOR]