Mesoporous Silica Encapsulated Platinum–Tin Intermetallic Nanoparticles Catalyze Hydrogenation with an Unprecedented 20% Pairwise Selectivity for Parahydrogen Enhanced Nuclear Magnetic Resonance

• Published in: The journal of physical chemistry letters 2022-05, Vol.13 (18), p.4125-4132
• Main Authors: Du, Yong, Behera, Ranjan K., Maligal-Ganesh, Raghu V., Chen, Minda, Zhao, Tommy Yunpu, Huang, Wenyu, Bowers, Clifford R.
• Format: Article
• Language: English
• Subjects: Physical Insights into Chemistry, Catalysis, and Interfaces
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.2c00581

Supported noble metals offer key advantages over homogeneous catalysts for in vivo applications of parahydrogen-based hyperpolarization. However, their performance is compromised by randomization of parahydrogen spin order resulting from rapid hydrogen adatom diffusion. The diffusion on Pt surfaces can be suppressed by introduction of Sn to form Pt–Sn intermetallic phases. Herein, an unprecedented pairwise selectivity of 19.7 ± 1.1% in the heterogeneous hydrogenation of propyne using silica encapsulated Pt–Sn intermetallic nanoparticles is reported. This high level of selectivity exceeds that of all supported metal catalysts by at least a factor of 3. Moreover, the pairwise selectivity for alkyne hydrogenation is about 2 times higher than for alkene hydrogenation, an observation attributed to the higher coverage of the former and its effect on diffusion. Lastly, PtSn@mSiO2 nanoparticles exhibited improved coking resistance, and any loss of activity is shown to be fully reversible through high-temperature oxidation–reduction cycling.