Sinter-resistant Platinum Catalyst Supported by Metal-Organic Framework

Kim, I. S.; Li, Z.; Zheng, J.; Platero-Prats, A.; Mavrandonakis, A.; Pellizzeri, S.; Ferrandon, M.; Vjunov, A.; Gallington, L. C.; Webber, T.; Vermeulen, N. A.; Penn, R. L.; Getman, R. B.; Cramer, C. J.; Chapman, K. W.; Camaioni, D. M.; Fulton, J. L.; Lercher, J. A.; Farha, O. K.; Hupp, J. T.; Martinson, A. B. F.
Angew. Chem. Int. Ed. 2018, 59, 909 (doi:10.1002/anie.201708092).

Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapour-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favourable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.