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Title: Multiscale Morphology of Nanoporous Copper Made from Intermetallic Phases

Many application-relevant properties of nanoporous metals critically depend on their multiscale architecture. For example, the intrinsically high step-edge density of curved surfaces at the nanoscale provides highly reactive sites for catalysis, whereas the macroscale pore and grain morphology determines the macroscopic properties, such as mass transport, electrical conductivity, or mechanical properties. Here, in this work, we systematically study the effects of alloy composition and dealloying conditions on the multiscale morphology of nanoporous copper (np-Cu) made from various commercial Zn–Cu precursor alloys. Using a combination of X-ray diffraction, electron backscatter diffraction, and focused ion beam cross-sectional analysis, our results reveal that the macroscopic grain structure of the starting alloy surprisingly survives the dealloying process, despite a change in crystal structure from body-centered cubic (Zn–Cu starting alloy) to face-centered cubic (Cu). The nanoscale structure can be controlled by the acid used for dealloying with HCl leading to a larger and more faceted ligament morphology compared to that of H 3PO 4. Finally, anhydrous ethanol dehydrogenation was used as a probe reaction to test the effect of the nanoscale ligament morphology on the apparent activation energy of the reaction.
Authors:
 [1] ; ORCiD logo [2] ;  [3] ;  [4] ;  [5] ;  [4] ; ORCiD logo [2] ;  [6] ;  [4]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Nanoscale Synthesis and Characterization Laboratory; Harvard Univ., Cambridge, MA (United States). John A. Paulson School of Engineering and Applied Sciences and Department of Chemistry and Chemical Biology
  2. Harvard Univ., Cambridge, MA (United States). John A. Paulson School of Engineering and Applied Sciences and Department of Chemistry and Chemical Biology
  3. Harvard Univ., Cambridge, MA (United States). Department of Chemistry and Chemical Biology
  4. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Nanoscale Synthesis and Characterization Laboratory
  5. Harvard Univ., Cambridge, MA (United States). Center for Nanoscale Systems
  6. Harvard Univ., Cambridge, MA (United States). John A. Paulson School of Engineering and Applied Sciences and Center for Nanoscale Systems
Publication Date:
Report Number(s):
LLNL-JRNL-733718
Journal ID: ISSN 1944-8244; TRN: US1702015
Grant/Contract Number:
AC52-07NA27344; SC0012573
Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 9; Journal Issue: 30; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Research Org:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; anhydrous ethanol dehydrogenation; dealloying; EBSD; intermetallic phase; morphology; nanoporous copper; Zn−Cu
OSTI Identifier:
1393327

Egle, Tobias, Barroo, Cédric, Janvelyan, Nare, Baumgaertel, Andreas C., Akey, Austin J., Biener, Monika M., Friend, Cynthia M., Bell, David C., and Biener, Juergen. Multiscale Morphology of Nanoporous Copper Made from Intermetallic Phases. United States: N. p., Web. doi:10.1021/acsami.7b05648.
Egle, Tobias, Barroo, Cédric, Janvelyan, Nare, Baumgaertel, Andreas C., Akey, Austin J., Biener, Monika M., Friend, Cynthia M., Bell, David C., & Biener, Juergen. Multiscale Morphology of Nanoporous Copper Made from Intermetallic Phases. United States. doi:10.1021/acsami.7b05648.
Egle, Tobias, Barroo, Cédric, Janvelyan, Nare, Baumgaertel, Andreas C., Akey, Austin J., Biener, Monika M., Friend, Cynthia M., Bell, David C., and Biener, Juergen. 2017. "Multiscale Morphology of Nanoporous Copper Made from Intermetallic Phases". United States. doi:10.1021/acsami.7b05648. https://www.osti.gov/servlets/purl/1393327.
@article{osti_1393327,
title = {Multiscale Morphology of Nanoporous Copper Made from Intermetallic Phases},
author = {Egle, Tobias and Barroo, Cédric and Janvelyan, Nare and Baumgaertel, Andreas C. and Akey, Austin J. and Biener, Monika M. and Friend, Cynthia M. and Bell, David C. and Biener, Juergen},
abstractNote = {Many application-relevant properties of nanoporous metals critically depend on their multiscale architecture. For example, the intrinsically high step-edge density of curved surfaces at the nanoscale provides highly reactive sites for catalysis, whereas the macroscale pore and grain morphology determines the macroscopic properties, such as mass transport, electrical conductivity, or mechanical properties. Here, in this work, we systematically study the effects of alloy composition and dealloying conditions on the multiscale morphology of nanoporous copper (np-Cu) made from various commercial Zn–Cu precursor alloys. Using a combination of X-ray diffraction, electron backscatter diffraction, and focused ion beam cross-sectional analysis, our results reveal that the macroscopic grain structure of the starting alloy surprisingly survives the dealloying process, despite a change in crystal structure from body-centered cubic (Zn–Cu starting alloy) to face-centered cubic (Cu). The nanoscale structure can be controlled by the acid used for dealloying with HCl leading to a larger and more faceted ligament morphology compared to that of H3PO4. Finally, anhydrous ethanol dehydrogenation was used as a probe reaction to test the effect of the nanoscale ligament morphology on the apparent activation energy of the reaction.},
doi = {10.1021/acsami.7b05648},
journal = {ACS Applied Materials and Interfaces},
number = 30,
volume = 9,
place = {United States},
year = {2017},
month = {7}
}