Modifying structure-sensitive reactions by addition of Zn to Pd

David J. Childers, Neil M. Schweitzer, Seyed Mehdi Kamali Shahari, Robert M. Rioux, Jeffrey T. Miller, Randall J. Meyer

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

Silica-supported Pd and PdZn nanoparticles of a similar size were evaluated for neopentane hydrogenolysis/isomerization and propane hydrogenolysis/ dehydrogenation. Monometallic Pd showed high neopentane hydrogenolysis selectivity. Addition of small amounts of Zn to Pd lead Pd-Zn scatters in the EXAFS spectrum and an increase in the linear bonded CO by IR. In addition, the neopentane turnover rate decreased by nearly 10 times with little change in the selectivity. Increasing amounts of Zn lead to greater Pd-Zn interactions, higher linear-to-bridging CO ratios by IR and complete loss of neopentane conversion. Pd NPs also had high selectivity for propane hydrogenolysis and thus were poorly selective for propylene. The PdZn bimetallic catalysts, however, were able to preferentially catalyze dehydrogenation, were not active for propane hydrogenolysis, and thus were highly selective for propylene formation. The decrease in hydrogenolysis selectivity was attributed to the isolation of active Pd atoms by inactive metallic Zn, demonstrating that hydrogenolysis requires a particular reactive ensemble whereas propane dehydrogenation does not.

Original languageEnglish (US)
Pages (from-to)75-84
Number of pages10
JournalJournal of Catalysis
Volume318
DOIs
StatePublished - Oct 2014

Fingerprint

hydrogenolysis
Hydrogenolysis
neopentane
Propane
propane
Dehydrogenation
dehydrogenation
selectivity
Carbon Monoxide
propylene
Propylene
Isomerization
Silicon Dioxide
isomerization
isolation
Lead
Silica
Nanoparticles
silicon dioxide
catalysts

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Childers, D. J., Schweitzer, N. M., Shahari, S. M. K., Rioux, R. M., Miller, J. T., & Meyer, R. J. (2014). Modifying structure-sensitive reactions by addition of Zn to Pd. Journal of Catalysis, 318, 75-84. https://doi.org/10.1016/j.jcat.2014.07.016
Childers, David J. ; Schweitzer, Neil M. ; Shahari, Seyed Mehdi Kamali ; Rioux, Robert M. ; Miller, Jeffrey T. ; Meyer, Randall J. / Modifying structure-sensitive reactions by addition of Zn to Pd. In: Journal of Catalysis. 2014 ; Vol. 318. pp. 75-84.
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Childers, DJ, Schweitzer, NM, Shahari, SMK, Rioux, RM, Miller, JT & Meyer, RJ 2014, 'Modifying structure-sensitive reactions by addition of Zn to Pd', Journal of Catalysis, vol. 318, pp. 75-84. https://doi.org/10.1016/j.jcat.2014.07.016

Modifying structure-sensitive reactions by addition of Zn to Pd. / Childers, David J.; Schweitzer, Neil M.; Shahari, Seyed Mehdi Kamali; Rioux, Robert M.; Miller, Jeffrey T.; Meyer, Randall J.

In: Journal of Catalysis, Vol. 318, 10.2014, p. 75-84.

Research output: Contribution to journalArticle

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AU - Childers, David J.

AU - Schweitzer, Neil M.

AU - Shahari, Seyed Mehdi Kamali

AU - Rioux, Robert M.

AU - Miller, Jeffrey T.

AU - Meyer, Randall J.

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N2 - Silica-supported Pd and PdZn nanoparticles of a similar size were evaluated for neopentane hydrogenolysis/isomerization and propane hydrogenolysis/ dehydrogenation. Monometallic Pd showed high neopentane hydrogenolysis selectivity. Addition of small amounts of Zn to Pd lead Pd-Zn scatters in the EXAFS spectrum and an increase in the linear bonded CO by IR. In addition, the neopentane turnover rate decreased by nearly 10 times with little change in the selectivity. Increasing amounts of Zn lead to greater Pd-Zn interactions, higher linear-to-bridging CO ratios by IR and complete loss of neopentane conversion. Pd NPs also had high selectivity for propane hydrogenolysis and thus were poorly selective for propylene. The PdZn bimetallic catalysts, however, were able to preferentially catalyze dehydrogenation, were not active for propane hydrogenolysis, and thus were highly selective for propylene formation. The decrease in hydrogenolysis selectivity was attributed to the isolation of active Pd atoms by inactive metallic Zn, demonstrating that hydrogenolysis requires a particular reactive ensemble whereas propane dehydrogenation does not.

AB - Silica-supported Pd and PdZn nanoparticles of a similar size were evaluated for neopentane hydrogenolysis/isomerization and propane hydrogenolysis/ dehydrogenation. Monometallic Pd showed high neopentane hydrogenolysis selectivity. Addition of small amounts of Zn to Pd lead Pd-Zn scatters in the EXAFS spectrum and an increase in the linear bonded CO by IR. In addition, the neopentane turnover rate decreased by nearly 10 times with little change in the selectivity. Increasing amounts of Zn lead to greater Pd-Zn interactions, higher linear-to-bridging CO ratios by IR and complete loss of neopentane conversion. Pd NPs also had high selectivity for propane hydrogenolysis and thus were poorly selective for propylene. The PdZn bimetallic catalysts, however, were able to preferentially catalyze dehydrogenation, were not active for propane hydrogenolysis, and thus were highly selective for propylene formation. The decrease in hydrogenolysis selectivity was attributed to the isolation of active Pd atoms by inactive metallic Zn, demonstrating that hydrogenolysis requires a particular reactive ensemble whereas propane dehydrogenation does not.

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