Origin of Electronic Modification of Platinum in a Pt ₃ V Alloy and Its Consequences for Propane Dehydrogenation Catalysis

Journal Article · Mon Jan 06 23:00:00 EST 2020 · ACS Applied Energy Materials

DOI:https://doi.org/10.1021/acsaem.9b01373· OSTI ID:1633306

Purdy, Stephen C. ^[1]; Ghanekar, Pushkar ^[1]; Mitchell, Garrett ^[1]; Kropf, A. Jeremy ^[2]; Zemlyanov, Dmitry Y. ^[1]; Ren, Yang ^[2]; Ribeiro, Fabio ^[1]; Delgass, W. Nicholas ^[1]; Greeley, Jeffrey ^[1]; Miller, Jeffrey T. ^[1]

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1. Purdue Univ., West Lafayette, IN (United States)
2. Argonne National Lab. (ANL), Argonne, IL (United States)

We demonstrate the synthesis of a Pt₃V alloy and Pt/Pt₃V core/shell catalysts, which are highly selective for propane dehydrogenation. The selectivity is a result of the Pt₃V intermetallic phase, which was characterized by in situ synchrotron XRD and XAS. Formation of a continuous alloy surface layer 2-3 atomic layers thick was sufficient to obtain identical catalytic properties between a core-shell and full alloy catalyst, which demonstrates the length scale over which electronic effects pertinent to dehydrogenation act. Electronic characterization of the alloy phase was investigated by using DFT, XPS, XANES, and RIXS, all of which show a change in the energy of the filled and unfilled Pt 5d states resulting from Pt-V bonding. The electronic modification leads to a change in the most stable binding site of hydrocarbon fragments, which bind to V containing ensembles despite the presence of 3-fold Pt ensembles in Pt3V. In addition, electronic modification destabilizes deeply dehydrogenated species thought to be responsible for hydrogenolysis and coke formation.

• Research Organization: Argonne National Laboratory (ANL), Argonne, IL (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES)
• Grant/Contract Number: AC02-06CH11357
• OSTI ID: 1633306
• Journal Information: ACS Applied Energy Materials, Journal Name: ACS Applied Energy Materials Journal Issue: 2 Vol. 3; ISSN 2574-0962
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
Pt3V nanoparticle
dehydrogenation selectivity
electronic effects in alloy catalysts
in-situ synchrotron x-ray diffraction
in-situ x-ray absorption spectroscopy
intermetallic alloy catalyst
propane dehydrogenation
resonant inelastic x-ray scattering