Direct synthesis of low-Coordinate pd catalysts supported on SiO2 via surface organometallic chemistry

Shengsi Liu, J. Miles Tan, Ahmet Gulec, Neil M. Schweitzer, Massimiliano Delferro, Laurence D. Marks, Peter C Stair, Tobin J Marks

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Highly dispersed low-coordinate Pd sites on SiO2 are fabricated by grafting the PdII PCP-pincer complex (tBuPCP)Pd−OH (tBuPCP = 2,6-C6H3(CH2PtBu2)2) on SiO2, followed by calcination with ozone (100 °C) and reduction with H2 (300 °C). The chemisorption process and structure of this organometallic complex on SiO2 is established by solution-phase1H and31P NMR and solid-state31P CPMAS NMR spectroscopy, XPS, DRIFTS, and AC-HAADF-STEM. The CO adsorption properties of the Pd centers reveal a surprisingly high fraction of adsorption sites where CO is bound in a linear fashion, indicative of low-coordinate Pd. Furthermore, enhanced selectivity of these catalyst centers in aerobic alcohol oxidation versus a control catalyst argues that these low-coordinate sites are the catalytically active sites.

Original languageEnglish
JournalACS Catalysis
Volume6
Issue number12
DOIs
Publication statusPublished - Jan 1 2016

Fingerprint

Organometallics
Carbon Monoxide
Catalyst supports
Adsorption
Catalysts
Catalyst selectivity
Ozone
Chemisorption
Calcination
Nuclear magnetic resonance spectroscopy
Alcohols
X ray photoelectron spectroscopy
Nuclear magnetic resonance
Oxidation

Keywords

  • Benzyl alcohol oxidation
  • DRIFTS
  • Heterogeneous catalysis
  • Palladium nanoparticles
  • Solution-phase grafting
  • Surface organometallic chemistry

ASJC Scopus subject areas

  • Catalysis

Cite this

Direct synthesis of low-Coordinate pd catalysts supported on SiO2 via surface organometallic chemistry. / Liu, Shengsi; Tan, J. Miles; Gulec, Ahmet; Schweitzer, Neil M.; Delferro, Massimiliano; Marks, Laurence D.; Stair, Peter C; Marks, Tobin J.

In: ACS Catalysis, Vol. 6, No. 12, 01.01.2016.

Research output: Contribution to journalArticle

Liu, Shengsi ; Tan, J. Miles ; Gulec, Ahmet ; Schweitzer, Neil M. ; Delferro, Massimiliano ; Marks, Laurence D. ; Stair, Peter C ; Marks, Tobin J. / Direct synthesis of low-Coordinate pd catalysts supported on SiO2 via surface organometallic chemistry. In: ACS Catalysis. 2016 ; Vol. 6, No. 12.
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