P‐P Hybrids Antimony Single‐Atom Anchored Covalent Organic Framework for Efficient High‐Selectivity H <sub>2</sub> O <sub>2</sub> Piezosynthesis
Yimu Jiao, Qiyu Lian, Zhi Li, Muke Lin, Dingren Ma, Zhuoyun Tang, Dehua Xia, Mingshan Zhu
Abstract
Abstract The p orbital electrons in main‐group metals are generally underrated in the catalytic activity. Herein, an antimony (Sb) single‐atom bipyridine‐based covalent organic framework (SASb‐TpBpy‐COF) with the Sb─N coordination is successfully synthesized via 5p‐2p orbitals hybridizarion for accomplishing the highly selective piezosynthesis of hydrogen peroxide (H 2 O 2 ) by the non‐radical oxygen reduction reaction (ORR). Notably, the synthesized SASb‐TpBpy‐COF achieved an impressive H 2 O 2 piezosynthesis yield of 1500.58 µmol g −1 h −1 , which is up to more than 7‐times higher than the reported catalysts. Moreover, the characterization results confirmed that the 5p‐2p orbitals hybrid Sb single‐atom can intrinsically drive the local polarization level, charge migration dynamics, electron‐hole pairs separation, and affinity toward O 2 , consequently enhancing the piezoactivity and selective Pauling‐type O 2 adsorption. Besides, experimental results clarified that the fast H 2 O 2 piezosynthesis is selectively dominated by the non‐radical ORR. Furthermore, the dynamic Sb‐OOH* intermediate is directly detected, proving the selective Pauling‐type O 2 adsorption on the Sb single‐atom sites. Moreover, this system can achieve an in situ degradation efficiency of over 80% for various emerging pollutants even in the real water samples. Conclusively, this study broadens the fundamental understanding for the fast H 2 O 2 piezosynthesis and provides a highly potential candidate technology for in situ water purification.