One‐Step Prepared Water‐Resistant Organic–Inorganic‐Hybrid Perovskite Quantum Dots with Zn–Oxygen Vacancies for Attempts at Nitrogen Fixation
Yixuan Gao, Xiao Su, Jiangwei Zhang, Hongwei Tan, Jianghui Sun, Jin Ouyang, Na Na
Abstract
Abstract Applying organic–inorganic hybrid perovskite quantum dots (PQDs) to photocatalytic nitrogen fixation is hindered long‐term by the inherent instability in water and tedious preparations. Here, to realize PQD‐catalyzed photocatalytic N 2 reduction reaction (NRR), water‐resistant PQDs are simply prepared through one‐step electrospray synthesis in microseconds. During the fast electrospray, PQDs of Zn/PbO‐doped methylammonium lead bromide (Zn/PbO/PC–Zn/MAPbBr 3 , MA: CH 3 NH 3 ) are prepared and part‐encapsulated by polycarbonate. The synthesis maintains good water resistance, whose restriction on charge transport is overcome skillfully. Simultaneously, substitution of Zn with Pb on water‐resistant surface is also achieved, which fabricates new Zn–oxygen vacancies (Zn‐OVs) with Zn/PbO–Zn/MAPbBr 3 type I heterojunction. This facilitates efficient electron transfer from internal heterojunction interface of Zn/MAPbBr 3 PQDs to the surface of Zn/PbO. Demonstrated by theoretical calculations, Zn‐OVs promote chemisorption and polarization of N 2 . In addition, s‐electrons in exposed Zn become active due to changes of electron filling of Zn orbitals under OVs’ co‐doping. Thus, photocatalytic N 2 reduction reaction catalyzed by organic–inorganic hybrid PQDs is first achieved in aqueous phase without sacrificial agents being added. This initiates possibilities for photocatalytic applications of organic–inorganic hybrid PQDs in aqueous phase.