Tuning catalytic performance of platinum single atoms by choosing the shape of cerium dioxide supports†

The local coordination environment of single atom catalysts (SACs) often determines their catalytic performance. To understand these metal–support interactions, we prepared Pt SACs on cerium dioxide (CeO₂) cubes, octahedra and rods, with well-structured exposed crystal facets. The CeO₂ crystals were characterized by SEM, TEM, pXRD, and N₂ sorption, confirming the shape-selective synthesis, identical bulk structure, and variations in specific surface area, respectively. EPR, XPS, TEM and XANES measurements showed differences in the oxygen vacancy density following the trend rods > octahedra > cubes. AC-HAADF-STEM, XPS and CO-DRIFTS measurements confirmed the presence of only single Pt²⁺ sites, with different surface platinum surface concentrations. We then compared the performance of the three catalysts in ammonia borane hydrolysis. Precise monitoring of reaction kinetics between 30–80 °C gave Arrhenius plots with hundreds of data points. All plots showed a clear inflection point, the temperature of which (rods > octahedra > cubes) correlates to the energy barrier of ammonia borane diffusion to the Pt sites. These activity differences reflect variations in the – facet dependent – degree of stabilization of intermediates by surface oxygen lone pairs and surface–metal binding strength. Our results show how choosing the right macroscopic support shape can give control over single atom catalysed reactions on the microscopic scale.