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.
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.
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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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 -