Intermetallic Compounds as an Alternative to Single-atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X-ray Spectroscopies and Computational Studies

Wegener, Evan C.; Bukowski, Brandon C.; Yang, Dali; Wu, Zhenwei; Kropf, A. Jeremy; Delgass, W. N.; Greeley, Jeffrey; Zhang, Guanghui; Miller, Jeffrey T.

doi:10.1002/cctc.201901869

Intermetallic Compounds as an Alternative to Single-atom Alloy Catalysts: Geometric and Electronic Structures from Advanced X-ray Spectroscopies and Computational Studies

Journal Article · Sun Dec 08 23:00:00 EST 2019 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.201901869· OSTI ID:1763427

Wegener, Evan C. ^[1]; ^[1]; Yang, Dali ^[2]; Wu, Zhenwei ^[1]; Kropf, A. Jeremy ^[3]; ^[1]; Greeley, Jeffrey ^[1]; ^[4]; ^[1]

Purdue Univ., West Lafayette, IN (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Chemical Sciences and Engineering Division Argonne National Laboratory 9700 South Cass Avenue Lemont IL 60439 USA
Purdue Univ., West Lafayette, IN (United States); Dalian Univ. of Technology (China)

Pt-Fe intermetallic compound (IMC) catalysts, including Pt₃Fe, PtFe and PtFe₃, are shown to have advantageous catalytic properties similar to those reported for single-atom alloy catalysts. Elimination of the Pt ensembles responsible for C-C bond cleavage yields high selectivity toward C-H bond activation during propane dehydrogenation. In situ Resonant Inelastic X-ray Scattering (RIXS) measurements and density functional theory calculations, in turn, show that these changes are associated with a decrease in the average energy of the filled 5d states of Pt in the Pt-Fe intermetallic compound structures compared to monometallic Pt, accompanied by an increase in the average energy of the unfilled valance bands. The decrease in energy of the filled Pt 5d orbitals increases with increasing Fe content in the IMC, PtFe₃ > PtFe > Pt₃Fe. These results demonstrate that by altering the stoichiometry of IMC catalysts it is possible to control both the ensemble size and electronic properties of active sites, which affords another mechanism for tuning catalytic properties, in addition to changing promoter metals. The present study demonstrates the potential of ordered intermetallic compounds as an alternative to traditional solid-solution single-atom alloys, to serve as catalysts with well-defined and uniform active sites.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); National Natural Science Foundation of China (NNSFC); Fundamental Research Funds for Central Universities

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1763427

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 5 Vol. 12; ISSN 1867-3880

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

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