Changes in Catalytic and Adsorptive Properties of 2 nm Pt3Mn Nanoparticles by Subsurface Atoms
- 7 November 2018
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 140 (44), 14870-14877
- https://doi.org/10.1021/jacs.8b08162
Abstract
Supported multimetallic nanoparticles (NPs) are widely used in industrial catalytic processes, where the relation between surface structure and function is well-known. However, the effect of subsurface layers on such catalysts remains mostly unstudied. Here, we demonstrate a clear subsurface effect on supported 2 nm core-shell NPs with atomically precise and high temperature stable Pt3Mn intermetallic surface measured by in situ synchrotron X-ray Diffraction, difference X-ray Absorption Spectroscopy, and Energy Dispersive X-ray Spectroscopy. The NPs with a Pt3Mn subsurface have selectivity to C-H over C-C bond activation during propane dehydrogenation at 550 degrees C compared with 82% for core-shell NPs with a Pt subsurface. The difference is correlated with significant reduction in the heats of reactant adsorption due to the Pt3Mn intermetallic subsurface as discerned by theory as well as experiment. The findings of this work highlight the importance of subsurface for supported NP catalysts, which can be tuned via controlled intermetallic formation. Such approach is generally applicable to modifying multimetallic NPs, adding another dimension to the tunability of their catalytic performance.Funding Information
- Division of Engineering Education and Centers (EEC-1647722)
- Davidson School of Chemical Engineering, Purdue University
This publication has 44 references indexed in Scilit:
- Density Functional Theory Study on Propane and Propene Adsorption on Pt(111) and PtSn Alloy SurfacesThe Journal of Physical Chemistry C, 2011
- Alloy catalysts designed from first principlesNature Materials, 2004
- Heats of Adsorption of Linear and Multibound Adsorbed CO Species on a Pt/Al2O3 Catalyst Using in Situ Infrared Spectroscopy under Adsorption EquilibriumJournal of Catalysis, 2000
- Microcalorimetric, Infrared Spectroscopic, and DFT Studies of Ethylene Adsorption on Pt/SiO2 and Pt−Sn/SiO2 CatalystsThe Journal of Physical Chemistry B, 1999
- From ultrasoft pseudopotentials to the projector augmented-wave methodPhysical Review B, 1999
- Projector augmented-wave methodPhysical Review B, 1994
- Microcalorimetric, Spectroscopic, and Kinetic Studies of Silica Supported Pt and Pt/Sn Catalysts for Isobutane DehydrogenationJournal of Catalysis, 1994
- Ab initiomolecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germaniumPhysical Review B, 1994
- Chemical and electronic properties of ultrathin metal films: The Pd/Re(0001) and Pd/Ru(0001) systemsPhysical Review B, 1992
- Catalysis by alloys and bimetallic clustersAccounts of Chemical Research, 1977