Polyoxometallate Cluster Induced High-Entropy Oxide Sub-1 nm Nanosheets as Photoelectrocatalysts for Zn-Air Batteries.

The lack of highly efficient and inexpensive catalysts severely hinders the large-scale application of Zn-air batteries (ZABs). High-entropy oxides (HEOs) exhibit unique structures and attractive properties; thus, they are promising to be used in ZABs. However, conventional high-temperature synthesis methods tend to obtain microscale HEOs with a lower exposure rate of active sites. Here, we report a facile solvothermal strategy for preparing two-dimensional (2D) HEO sub-1 nm nanosheets (SNSs) induced by polyoxometalate (POM) clusters. Taking advantage of the special 2D sub-1 nm structure and precise element regulation, these 2D HEOs-POM SNSs exhibit enhanced bifunctional oxygen evolution and oxygen reduction reaction activity under light irradiation. Further applying these 2D HEOs-POM SNSs to ZABs as cathode catalysts, the CoFeNiMnCuZnOx-phosphomolybdic acid SNSs-based ZABs deliver a low charge/discharge voltage gap of 0.25 V at 2 mA cm-2 under light irradiation. Meanwhile, it could maintain an ultralong-term stability for 1600 h at 2 mA cm-2 and 930 h at 10 mA cm-2. The 2D sub-1 nm structure and fine element control in HEOs provide opportunities to solve the problems of low intrinsic activity, limited active sites, and instability of air cathodes in ZABs.