General and Scalable Synthesis of Mesoporous 2D MZrO2 (M = Co, Mn, Ni, Cu, Fe) Nanocatalysts by Amorphous‐to‐Crystalline Transformation

Abstract

AbstractIn modern heterogeneous catalysis, it remains highly challenging to create stable, low‐cost, mesoporous 2D photo‐/electro‐catalysts that carry atomically dispersed active sites. In this work, a general shape‐preserving amorphous‐to‐crystalline transformation (ACT) strategy is developed to dope various transition metal (TM) heteroatoms in ZrO2, which enabled the scalable synthesis of TMs/oxide with a mesoporous 2D structure and rich defects. During the ACT process, the amorphous MZrO2 nanoparticles (M = Fe, Ni, Cu, Co, Mn) are deposited within a confined space created by the NaCl template, and they transform to crystalline 2D ACT‐MZrO2 nanosheets in a shape‐preserving manner. The interconnected crystalline ACT‐MZrO2 nanoparticles thus inherit the same structure as the original MZrO2 precursor. Owing to its rich active sites on the surface and abundant oxygen vacancies (OVs), ACT‐CoZrO2 gives superior performance in catalyzing the CO2‐to‐syngas conversion as demonstrated by experiments and theoretical calculations. The ACT chemistry opens a general route for the scalable synthesis of advanced catalysts with precise microstructure by reconciliating the control of crystalline morphologies and the dispersion of heteroatoms.