Unraveling 1-Hexene Hydrogenation over Dilute Pd-in-Au Alloys

van der Hoeven, Jessi S.; Ngan, Hio Tong; Yan, George; Aizenberg, Joanna; Madix, Robert J.; Sautet, Philippe; Friend, Cynthia M.

doi:10.1021/acs.jpcc.2c04982

Unraveling 1-Hexene Hydrogenation over Dilute Pd-in-Au Alloys

Journal Article · Wed Sep 14 00:00:00 EDT 2022 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.2c04982· OSTI ID:1903556

^[1]; Ngan, Hio Tong ^[2]; Yan, George ^[2]; ^[3]; ^[3]; ^[2]; ^[3]

Harvard Univ., Cambridge, MA (United States); Utrecht Univ. (Netherlands); Harvard
Univ. of California, Los Angeles, CA (United States)
Harvard Univ., Cambridge, MA (United States)

Dilute Pd-in-Au alloys are valuable materials for selectively hydrogenating alkynes and isomerizing alkenes. By diluting Pd in a Au host, the selectivity toward semihydrogenated alkene isomers can be significantly enhanced and the unfavorable overhydrogenation to alkanes is suppressed. However, a detailed mechanistic study on the origin of the enhanced alkene selectivity over dilute alloy catalysts is still missing. Here, we combine experiment and theory to unravel the reaction mechanism, identifying rate-limiting and selectivity-controlling steps in 1-hexene hydrogenation over dilute Pd-in-Au catalysts. Using isotope-exchange hydrogenation experiments, we show that 1-hexene and hydrogen over a bimetallic Pd4Au96 in silica catalyst preferentially form 1-hexene isomers, (trans and cis) 2- and 3-hexene and only a small amounts of hexane. The reaction is consistent with a Horiuti–Polanyi mechanism, similar to a monometallic Pd nanoparticle catalyst. Computation of the free-energy profiles for 1-hexene hydrogenation and isomerization over a single Pd atom in a Au surface using first principles calculations indicated that the isomerization of 1-hexene to 2-hexene is energetically favorable due to the relatively large barrier for H2 dissociation preventing hydrogenation to n-hexane. Microkinetic modeling established that H2 dissociation on the single-atom Pd sites and H spillover from these sites onto the Au host are rate-limiting and key in steering the selectivity of dilute Pd-in-Au alloys toward the hexene isomers. Furthermore, the mechanistic insights from this study contribute to the rational design of optimized dilute alloy catalysts for selective alkene isomerization.

View Accepted Manuscript (DOE)

Research Organization:: Harvard Univ., Cambridge, MA (United States)

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

Grant/Contract Number:: SC0012573

OSTI ID:: 1903556

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 37 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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