A General Strategy for Synthesis of Binary Transition Metal Phosphides Hollow Sandwich Heterostructures

Abstract The hollow sandwich core–shell micro‐nanomaterials are widely used in materials, chemistry, and medicine, but their fabrication, particularly for transition metal phosphides (TMPs), remains a great challenge. Herein, a general synthesis strategy is presented for binary TMPs hollow sandwich heterostructures with vertically interconnected nanosheets on the inside and outside surfaces of polyhedron FeCoP x /C, demonstrated by a variety of transition metals (including Co, Fe, Cd, Mn, Cu, Cr, and Ni). Density functional theory (DFT) calculation reveals the process and universal mechanism of layered double hydroxide (LDH) growth on Prussian blue analog (PBA) surface in detail for the first time, which provides the theoretical foundations for feasibility and rationality of the synthesis strategy. This unique structure exhibits a vertical nanosheet‐shell‐vertical nanosheet configuration combining the advantages of sandwich, hollow and vertical heterostructures, effectively achieving their synergistic effect. As a proof‐of‐concept of their applications, the CoNiP x @FeCoP x /C@CoNiP x hollow sandwich polyhedron architectures (representative samples) show excellent catalytic performance for the oxygen evolution reaction (OER) in alkaline electrolytes. This work provides a general method for constructing hollow‐sandwich micro‐nanostructures, which provides more ideas and directions for design of micro‐nano materials with special geometric topology.