Structural trends in the dehydrogenation selectivity of palladium alloys

Purdy, Stephen C.; Seemakurthi, Ranga Rohit; Mitchell, Garrett  M.; Davidson, Mark; Lauderback, Brooke A.; Deshpande, Siddharth; Wu, Zhenwei; Wegener, Evan C.; Greeley, Jeffrey; Miller, Jeffrey T.

doi:10.1039/d0sc00875c

Structural trends in the dehydrogenation selectivity of palladium alloys

Journal Article · Tue May 05 00:00:00 EDT 2020 · Chemical Science

DOI:https://doi.org/10.1039/d0sc00875c· OSTI ID:1648337

^[1]; ^[1]; Mitchell, Garrett M. ^[1]; Davidson, Mark ^[1]; Lauderback, Brooke A. ^[1]; Deshpande, Siddharth ^[1]; Wu, Zhenwei ^[1]; Wegener, Evan C. ^[1]; ^[1]; ^[1]

Purdue Univ., West Lafayette, IN (United States)

Alloying is well-known to improve the dehydrogenation selectivity of pure metals, but there remains considerable debate about the structural and electronic features of alloy surfaces that give rise to this behavior. To provide molecular-level insights into these effects, a series of Pd intermetallic alloy catalysts with Zn, Ga, In, Fe and Mn promoter elements was synthesized, and the structures were determined using in situ X-ray absorption spectroscopy (XAS) and synchrotron X-ray diffraction (XRD). The alloys all showed propane dehydrogenation turnover rates 5–8 times higher than monometallic Pd and selectivity to propylene of over 90%. Moreover, among the synthesized alloys, Pd₃M alloy structures were less olefin selective than PdM alloys which were, in turn, almost 100% selective to propylene. This selectivity improvement was interpreted by changes in the DFT-calculated binding energies and activation energies for C–C and C–H bond activation, which are ultimately influenced by perturbation of the most stable adsorption site and changes to the d-band density of states. Furthermore, transition state analysis showed that the C–C bond breaking reactions require 4-fold ensemble sites, which are suggested to be required for non-selective, alkane hydrogenolysis reactions. These sites, which are not present on alloys with PdM structures, could be formed in the Pd₃M alloy through substitution of one M atom with Pd, and this effect is suggested to be partially responsible for their slightly lower selectivity.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1648337

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 19 Vol. 11; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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