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 › peer-review

7 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

Keywords

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

ASJC Scopus subject areas

Catalysis

Access to Document

10.1021/acscatal.6b02046

Fingerprint Dive into the research topics of 'Direct synthesis of low-Coordinate pd catalysts supported on SiO<sub>2</sub> via surface organometallic chemistry'. Together they form a unique fingerprint.

Cite this

@article{91f7fb679b15424bb1d33233e20fb448,

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}",

year = "2016",

month = jan,

day = "1",

doi = "10.1021/acscatal.6b02046",

language = "English",

volume = "6",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

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

PY - 2016/1/1

Y1 - 2016/1/1

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

UR - http://www.scopus.com/inward/record.url?scp=85046810481&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85046810481&partnerID=8YFLogxK

U2 - 10.1021/acscatal.6b02046

DO - 10.1021/acscatal.6b02046

M3 - Article

AN - SCOPUS:85046810481

VL - 6

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

IS - 12

ER -