Halogen-Dependent Surface Confinement Governs Selective Alkane Functionalization to Olefins

Guido Zichittella, Matthias Scharfe, Begoña Puértolas, Vladimir Paunović, Patrick Hemberger, Andras Bodi, L. Szentmiklósi, Núria López, Javier Pérez-Ramírez

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The product distribution in direct alkane functionalization by oxyhalogenation strongly depends on the halogen of choice. We demonstrate that the superior selectivity to olefins over an iron phosphate catalyst in oxychlorination is the consequence of a surface-confined reaction. By contrast, in oxybromination alkane activation follows a gas-phase radical-chain mechanism and yields a mixture of alkyl bromide, cracking, and combustion products. Surface-coverage analysis of the catalyst and identification of gas-phase radicals in operando mode are correlated to the catalytic performance by a multi-technique approach, which combines kinetic studies with advanced characterization techniques such as prompt-gamma activation analysis and photoelectron photoion coincidence spectroscopy. Rationalization of gas-phase and surface contributions by density functional theory reveals that the molecular level effects of chlorine are pivotal in determining the stark selectivity differences. These results provide strategies for unraveling detailed mechanisms within complex reaction networks.

Original languageEnglish
JournalAngewandte Chemie - International Edition
DOIs
Publication statusPublished - Jan 1 2019

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Halogens
Alkanes
Alkenes
Paraffins
Olefins
Gases
Activation analysis
Catalysts
Catalyst selectivity
Chlorine
Surface analysis
Photoelectrons
Bromides
Density functional theory
Phosphates
Iron
Chemical activation
Spectroscopy
Kinetics

Keywords

  • density functional theory
  • hydrogen halides
  • olefin selectivity
  • operando spectroscopies
  • reaction mechanisms

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Zichittella, G., Scharfe, M., Puértolas, B., Paunović, V., Hemberger, P., Bodi, A., ... Pérez-Ramírez, J. (2019). Halogen-Dependent Surface Confinement Governs Selective Alkane Functionalization to Olefins. Angewandte Chemie - International Edition. https://doi.org/10.1002/anie.201811669

Halogen-Dependent Surface Confinement Governs Selective Alkane Functionalization to Olefins. / Zichittella, Guido; Scharfe, Matthias; Puértolas, Begoña; Paunović, Vladimir; Hemberger, Patrick; Bodi, Andras; Szentmiklósi, L.; López, Núria; Pérez-Ramírez, Javier.

In: Angewandte Chemie - International Edition, 01.01.2019.

Research output: Contribution to journalArticle

Zichittella, Guido ; Scharfe, Matthias ; Puértolas, Begoña ; Paunović, Vladimir ; Hemberger, Patrick ; Bodi, Andras ; Szentmiklósi, L. ; López, Núria ; Pérez-Ramírez, Javier. / Halogen-Dependent Surface Confinement Governs Selective Alkane Functionalization to Olefins. In: Angewandte Chemie - International Edition. 2019.
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