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Title: Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation

Abstract

The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu- based catalysts are not practical for this chemistry due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Utilizing Pt/Cu single atom alloys (SAAs) we examine C-H activation in a number of systems including methyl groups, methane, and butane using a combination of simulations, surface science, and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke resistant C-H activation chemistry with the added economic benefit that the precious metal is diluted at the atomic limit.

Authors:
 [1];  [2];  [3];  [3];  [1];  [4];  [5];  [3];  [6]; ORCiD logo [1]
  1. Tufts Univ., Medford, MA (United States). Dept. of Chemistry
  2. Univ. College London, London (United Kingdom). Thomas Young Centre and Dept. of Chemical Engineering
  3. Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering
  4. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
  5. Univ. College London, London (United Kingdom). Thomas Young Centre, London Centre for Nanotechnology and Dept. of Physics and Astronomy
  6. Univ. College London, London (United Kingdom). Thomas Young Centre and Dept. of Chemical Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); European Union (EU); Engineering and Physical Sciences Research Council (EPSRC); Royal Society
OSTI Identifier:
1426229
Grant/Contract Number:  
AC02-06CH11357; FG02-10ER16170; FG02-05ER15730; AC05-00OR22725; SC0012573; 616121
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 10; Journal Issue: 3; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Marcinkowski, Matthew D., Darby, Matthew T., Liu, Jilei, Wimble, Joshua M., Lucci, Felicia R., Lee, Sungsik, Michaelides, Angelos, Flytzani-Stephanopoulos, Maria, Stamatakis, Michail, and Sykes, E. Charles H. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation. United States: N. p., 2018. Web. doi:10.1038/NCHEM.2915.
Marcinkowski, Matthew D., Darby, Matthew T., Liu, Jilei, Wimble, Joshua M., Lucci, Felicia R., Lee, Sungsik, Michaelides, Angelos, Flytzani-Stephanopoulos, Maria, Stamatakis, Michail, & Sykes, E. Charles H. Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation. United States. doi:10.1038/NCHEM.2915.
Marcinkowski, Matthew D., Darby, Matthew T., Liu, Jilei, Wimble, Joshua M., Lucci, Felicia R., Lee, Sungsik, Michaelides, Angelos, Flytzani-Stephanopoulos, Maria, Stamatakis, Michail, and Sykes, E. Charles H. Mon . "Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation". United States. doi:10.1038/NCHEM.2915. https://www.osti.gov/servlets/purl/1426229.
@article{osti_1426229,
title = {Pt/Cu single-atom alloys as coke-resistant catalysts for efficient C–H activation},
author = {Marcinkowski, Matthew D. and Darby, Matthew T. and Liu, Jilei and Wimble, Joshua M. and Lucci, Felicia R. and Lee, Sungsik and Michaelides, Angelos and Flytzani-Stephanopoulos, Maria and Stamatakis, Michail and Sykes, E. Charles H.},
abstractNote = {The recent availability of shale gas has led to a renewed interest in C-H bond activation as the first step towards synthesis of fuels and fine chemicals. Heterogeneous catalysts based on Ni and Pt can perform this chemistry, but deactivate easily due to coke formation. Cu- based catalysts are not practical for this chemistry due to high C-H activation barriers, but their weaker binding to adsorbates offers resilience to coking. Utilizing Pt/Cu single atom alloys (SAAs) we examine C-H activation in a number of systems including methyl groups, methane, and butane using a combination of simulations, surface science, and catalysis studies. We find that Pt/Cu SAAs activate C-H bonds more efficiently than Cu, are stable for days under realistic operating conditions, and avoid the problem of coking typically encountered with Pt. Pt/Cu SAAs therefore offer a new approach to coke resistant C-H activation chemistry with the added economic benefit that the precious metal is diluted at the atomic limit.},
doi = {10.1038/NCHEM.2915},
journal = {Nature Chemistry},
issn = {1755-4330},
number = 3,
volume = 10,
place = {United States},
year = {2018},
month = {1}
}

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