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

In 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.