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

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

23 Scopus citations

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 (US)
Pages (from-to)	8380-8388
Number of pages	9
Journal	ACS Catalysis
Volume	6
Issue number	12
DOIs	https://doi.org/10.1021/acscatal.6b02046
State	Published - Dec 2 2016

Funding

This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DOE DE-FG02-03ER15457. This work also made use of instruments at the IMSERC center at Northwestern University, which were supported by the National Science Foundation under NSF CHE-9871268 (1998), NSF CHE-1048773, and NSF DMR-0521267 (2005). The CleanCat Core facility acknowledges funding from the Department of Energy (DE-FG02-03ER15457 and DE-AC02-06CH11357) used for the purchase of the Nicolet 6700 FT-IR, Harrick DRIFTS accessory, and Altamira AMI-200. This work made use of the JEOL JEM-ARM200CF in the Electron Microscopy Service (Research Resources Center, UIC). The acquisition of the UIC JEOL JEM-ARM200CF was supported by a MRI-R2 grant from the National Science Foundation (DMR-0959470). This work made use of the Keck-II facility of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN.

Keywords

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

ASJC Scopus subject areas

Catalysis
General Chemistry

Access to Document

10.1021/acscatal.6b02046

Cite this

@article{b2039a4950614c14ba01b33276b3c3da,

title = "Direct synthesis of low-Coordinate pd catalysts supported on SiO2 via surface organometallic chemistry",

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.}",

note = "Funding Information: This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DOE DE-FG02-03ER15457. This work also made use of instruments at the IMSERC center at Northwestern University, which were supported by the National Science Foundation under NSF CHE-9871268 (1998), NSF CHE-1048773, and NSF DMR-0521267 (2005). The CleanCat Core facility acknowledges funding from the Department of Energy (DE-FG02-03ER15457 and DE-AC02-06CH11357) used for the purchase of the Nicolet 6700 FT-IR, Harrick DRIFTS accessory, and Altamira AMI-200. This work made use of the JEOL JEM-ARM200CF in the Electron Microscopy Service (Research Resources Center, UIC). The acquisition of the UIC JEOL JEM-ARM200CF was supported by a MRI-R2 grant from the National Science Foundation (DMR-0959470). This work made use of the Keck-II facility of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = dec,

day = "2",

doi = "10.1021/acscatal.6b02046",

language = "English (US)",

volume = "6",

pages = "8380--8388",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "12",

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T1 - Direct synthesis of low-Coordinate pd catalysts supported on SiO2 via surface organometallic chemistry

AU - Liu, Shengsi

AU - Tan, J. Miles

AU - Gulec, Ahmet

AU - Schweitzer, Neil M.

AU - Delferro, Massimiliano

AU - Marks, Laurence D.

AU - Stair, Peter C.

AU - Marks, Tobin J.

N1 - Funding Information: This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DOE DE-FG02-03ER15457. This work also made use of instruments at the IMSERC center at Northwestern University, which were supported by the National Science Foundation under NSF CHE-9871268 (1998), NSF CHE-1048773, and NSF DMR-0521267 (2005). The CleanCat Core facility acknowledges funding from the Department of Energy (DE-FG02-03ER15457 and DE-AC02-06CH11357) used for the purchase of the Nicolet 6700 FT-IR, Harrick DRIFTS accessory, and Altamira AMI-200. This work made use of the JEOL JEM-ARM200CF in the Electron Microscopy Service (Research Resources Center, UIC). The acquisition of the UIC JEOL JEM-ARM200CF was supported by a MRI-R2 grant from the National Science Foundation (DMR-0959470). This work made use of the Keck-II facility of the NUANCE Center at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205); the MRSEC program (NSF DMR-1121262) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. Publisher Copyright: © 2016 American Chemical Society.

PY - 2016/12/2

Y1 - 2016/12/2

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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JO - ACS Catalysis

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