Elucidating the Nanoparticle–Metal Organic Framework Interface of Pt@ZIF-8 Catalysts
2017
Whitford, Cassandra L. | Stephenson, Casey J. | Gómez-Gualdrón, Diego A. | Hupp, Joseph T. | Farha, Omar K. | Snurr, Randall Q. | Stair, Peter C.
Composites of metal nanoparticles encapsulated in metal–organic frameworks (NP@MOFs) have emerged as heterogeneous catalysts for regioselective reactions. While numerous NP@MOF composite combinations have been synthesized, characterization of the nanoparticle–MOF interface and the encapsulated nanoparticle surface have yet to be determined. In this work, Pt@ZIF-8 synthesized by the controlled encapsulation method was chosen as a representative NP@MOF, and in situ characterization methods coupled with density functional theory (DFT) calculations were used to probe the nanoparticle surface. CO adsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) revealed that Pt@ZIF-8 exhibits red-shifted linear- and bridge-bound CO peaks and a linear peak associated with cationic Pt. DFT calculations and ¹H NMR suggest that these sites arise from the binding and electronic donation of the MOF linker, 2-methylimidazole, to the Pt surface. DRIFTS under argon reveals that linker fragments may be present on the Pt nanoparticle surface, suggesting a reaction between the nanoparticle and the MOF linker during controlled encapsulation synthesis. Finally, CO oxidation reveals via DRIFTS that the red-shifted linear CO and bridging CO sites are active sites, while the cationic Pt is not. Overall, these results show that Pt@ZIF-8 contains unique Pt surface sites and indicate that the nanoparticle–MOF interface contains a heterogeneous mixture of framework 2-methylimidazole, free-standing 2-methylimidazole, and linker fragments. These findings expose the complex nature of the nanoparticle surface in NP@MOF composites and demonstrate the importance of characterizing their surface to understand their catalytic behavior.
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