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With the continuous tightening of automotive emission regulations and the increasing promotion of energy-efficient hybrid vehicles, new challenges have arisen for the low-temperature performance of three-way catalysts (TWCs). To guide the design of next-generation TWCs, it is essential to further develop our understanding of the relationships between microstructure and catalytic performance. Here, Rh/CeO2–ZrO2 catalysts were synthesized with different Rh metal dispersion by using a combination of the wet impregnation method and reduction treatment. These catalysts included Rh single-atom catalysts, cluster catalysts, and nanoparticle catalysts. The results showed that the Rh nanoparticle catalyst, with an average size of 1.9 nm, exhibited superior three-way catalytic performance compared to the other catalysts. Based on the catalytic activity in a series of simple reaction atmospheres such as CO + O2, NO + CO, and hydrocarbons (HCs) + O2 and operando infrared spectroscopy, we found that metallic Rh sites on Rh nanoparticles are the key factor responsible for the low-temperature catalytic performance.
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