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

doi:10.1021/acscatal.6b02046

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

Northwestern University

Research output: Contribution to journal › Article

5 Citations (Scopus)

Abstract

Highly dispersed low-coordinate Pd sites on SiO₂ are fabricated by grafting the Pd^II PCP-pincer complex (^tBuPCP)Pd−OH (^tBuPCP = 2,6-C₆H₃(CH₂P^tBu₂)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 language	English
Journal	ACS Catalysis
Volume	6
Issue number	12
DOIs	https://doi.org/10.1021/acscatal.6b02046
Publication status	Published - Jan 1 2016

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Keywords

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

ASJC Scopus subject areas

Catalysis

Cite this

Liu, S., Tan, J. M., Gulec, A., Schweitzer, N. M., Delferro, M., Marks, L. D., Stair, P. C., & Marks, T. J. (2016). Direct synthesis of low-Coordinate pd catalysts supported on SiO₂ via surface organometallic chemistry. ACS Catalysis, 6(12). https://doi.org/10.1021/acscatal.6b02046

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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.",

keywords = "Benzyl alcohol oxidation, DRIFTS, Heterogeneous catalysis, Palladium nanoparticles, Solution-phase grafting, Surface organometallic chemistry",

author = "Shengsi Liu and Tan, {J. Miles} and Ahmet Gulec and Schweitzer, {Neil M.} and Massimiliano Delferro and Marks, {Laurence D.} and Stair, {Peter C} and Marks, {Tobin J}",

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AU - Schweitzer, Neil M.

AU - Delferro, Massimiliano

AU - Marks, Laurence D.

AU - Stair, Peter C

AU - Marks, Tobin J

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N2 - 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.

AB - 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.

KW - Benzyl alcohol oxidation

KW - DRIFTS

KW - Heterogeneous catalysis

KW - Palladium nanoparticles

KW - Solution-phase grafting

KW - Surface organometallic chemistry

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Access to Document

10.1021/acscatal.6b02046