Doping Stabilizing Isolated Active Sites in Perovskite Lattice for Stable H 2 O 2 Electroproduction

ABSTRACT Developing the efficient catalysts with both high 2e − selectivity and stability remains challenging for on‐site hydrogen peroxide (H 2 O 2 ) synthesis. Perovskite oxides possess dense isolated active sites to convert O 2 into H 2 O 2 , yet their intrinsic structural instability is also equally noteworthy. In this work, one kind of silver‐based perovskites, AgNbO 3 , and the structure stabilization approach are proposed for H 2 O 2 electrosynthesis. The Ag exsolution from the perovskite phase, which triggers the metallic Ag assemblies on surface, is identified as a key origin of electrochemical destabilization for the 2e − ORR process. Simultaneously, the Zr‐doping‐induced stabilization approach is put forward. The introduction of high‐oxyphilic Zr 4+ leads charge delocalization of oxygen in the [NbO 6 ] octahedra toward Ag‐site region, thereby enhancing Ag–O covalency as evidenced by the increased integrated crystal orbital Hamilton population values and the suppressed exsolution thermodynamics, while the sharply declined phase‐transition constant reconfirms that the Zr incorporation retards the Ag‐migration kinetics in terms of experimentation. The resulting Zr‐doped AgNbO 3 shows outstanding structural stability maintaining the above 90% Faradaic efficiency even at high‐current and long‐term operation. This work unveils the origination of perovskite destabilization during the 2e − ORR process, and offers a general strategy for stabilizing isolated active sites in electrochemical application.