skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis of Supported Pd 0 Nanoparticles from a Single-Site Pd 2+ Surface Complex by Alkene Reduction

Abstract

Here, a surface metal–organic complex, (-AlO x)Pd(acac) (acac = acetylacetonate), is prepared by chemically grafting the precursor Pd(acac) 2 onto γ-Al 2O 3 in toluene at 25 °C. The resulting surface complex is characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and dynamic nuclear polarization surface-enhanced solid-state nuclear magnetic resonance spectroscopy (DNP SENS). This surface complex is a precursor in the direct synthesis of size-controlled Pd nanoparticles under mild reductive conditions and in the absence of additional stabilizers or pretreatments. Indeed, upon exposure to gaseous ethylene or liquid 1-octene at 25 °C, the Pd 2+ species is reduced to form Pd 0 nanoparticles with a mean diameter of 4.3 ± 0.6 nm, as determined by scanning transmission electron microscopy (STEM). These nanoparticles are catalytically relevant using the aerobic 1-phenylethanol oxidation as a probe reaction, with rates comparable to a conventional Pd/Al 2O 3 catalyst but without an induction period. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed reaction mass spectrometry (TPR-MS) reveal that the surface complex reduction with ethylene coproduces H 2, acetylene, and 1,3-butadiene. This process reasonably proceeds via an olefin activation/coordination/insertion pathway, followed by β-hydride elimination to generatemore » free Pd 0. Lastly, the well-defined nature of the single-site supported Pd 2+ precursor provides direct mechanistic insights into this unusual and likely general reductive process.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [1];  [4]; ORCiD logo [4]; ORCiD logo [3]; ORCiD logo [1];  [5]; ORCiD logo [6]
  1. Northwestern Univ., Evanston, IL (United States). Department of Chemistry
  2. Northwestern Univ., Evanston, IL (United States). Department of Chemical & Biological Engineering
  3. Northwestern Univ., Evanston, IL (United States). Department of Materials Science & Engineering
  4. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  5. Northwestern Univ., Evanston, IL (United States). Department of Chemistry; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences & Engineering Division
  6. Northwestern Univ., Evanston, IL (United States). Department of Chemistry and Department of Chemical & Biological Engineering
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1427728
Alternate Identifier(s):
OSTI ID: 1461330
Report Number(s):
IS-J-9596
Journal ID: ISSN 0897-4756
Grant/Contract Number:  
AC02-07CH11358; FG02-03ER154757; AC02-06CH11357; FG02-03ER15457
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 3; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Mouat, Aidan R., Whitford, Cassandra L., Chen, Bor-Rong, Liu, Shengsi, Perras, Frédéric A., Pruski, Marek, Bedzyk, Michael J., Delferro, Massimiliano, Stair, Peter C., and Marks, Tobin J. Synthesis of Supported Pd0 Nanoparticles from a Single-Site Pd2+ Surface Complex by Alkene Reduction. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.7b04909.
Mouat, Aidan R., Whitford, Cassandra L., Chen, Bor-Rong, Liu, Shengsi, Perras, Frédéric A., Pruski, Marek, Bedzyk, Michael J., Delferro, Massimiliano, Stair, Peter C., & Marks, Tobin J. Synthesis of Supported Pd0 Nanoparticles from a Single-Site Pd2+ Surface Complex by Alkene Reduction. United States. doi:10.1021/acs.chemmater.7b04909.
Mouat, Aidan R., Whitford, Cassandra L., Chen, Bor-Rong, Liu, Shengsi, Perras, Frédéric A., Pruski, Marek, Bedzyk, Michael J., Delferro, Massimiliano, Stair, Peter C., and Marks, Tobin J. Fri . "Synthesis of Supported Pd0 Nanoparticles from a Single-Site Pd2+ Surface Complex by Alkene Reduction". United States. doi:10.1021/acs.chemmater.7b04909.
@article{osti_1427728,
title = {Synthesis of Supported Pd0 Nanoparticles from a Single-Site Pd2+ Surface Complex by Alkene Reduction},
author = {Mouat, Aidan R. and Whitford, Cassandra L. and Chen, Bor-Rong and Liu, Shengsi and Perras, Frédéric A. and Pruski, Marek and Bedzyk, Michael J. and Delferro, Massimiliano and Stair, Peter C. and Marks, Tobin J.},
abstractNote = {Here, a surface metal–organic complex, (-AlOx)Pd(acac) (acac = acetylacetonate), is prepared by chemically grafting the precursor Pd(acac)2 onto γ-Al2O3 in toluene at 25 °C. The resulting surface complex is characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and dynamic nuclear polarization surface-enhanced solid-state nuclear magnetic resonance spectroscopy (DNP SENS). This surface complex is a precursor in the direct synthesis of size-controlled Pd nanoparticles under mild reductive conditions and in the absence of additional stabilizers or pretreatments. Indeed, upon exposure to gaseous ethylene or liquid 1-octene at 25 °C, the Pd2+ species is reduced to form Pd0 nanoparticles with a mean diameter of 4.3 ± 0.6 nm, as determined by scanning transmission electron microscopy (STEM). These nanoparticles are catalytically relevant using the aerobic 1-phenylethanol oxidation as a probe reaction, with rates comparable to a conventional Pd/Al2O3 catalyst but without an induction period. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed reaction mass spectrometry (TPR-MS) reveal that the surface complex reduction with ethylene coproduces H2, acetylene, and 1,3-butadiene. This process reasonably proceeds via an olefin activation/coordination/insertion pathway, followed by β-hydride elimination to generate free Pd0. Lastly, the well-defined nature of the single-site supported Pd2+ precursor provides direct mechanistic insights into this unusual and likely general reductive process.},
doi = {10.1021/acs.chemmater.7b04909},
journal = {Chemistry of Materials},
number = 3,
volume = 30,
place = {United States},
year = {Fri Feb 02 00:00:00 EST 2018},
month = {Fri Feb 02 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on February 2, 2019
Publisher's Version of Record

Save / Share: