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Title: Probing the Behavior of Composition‐Tunable Ultrathin PtNi Nanowires for CO Oxidation and Small‐Molecule Electrocatalytic Reactions

Abstract

Abstract We have successfully synthesized ultrathin nanowires of pure Pt, Pt 99 Ni 1 , Pt 9 Ni 1 , and Pt 7 Ni 3 using a modified room‐temperature soft‐template method. Analysis of both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) results found that the Pt 7 Ni 3 samples yielded the best performance with specific activities of 0.36 and 0.34 mA/cm 2 respectively. Additionally, formic acid oxidation reaction (FAOR) tests noted that both Pt and PtNi nanowires oxidize small organic molecules (SOMs) via an indirect pathway. CO oxidation data suggests little measurable performance without any pre‐reduction treatment; however, after annealing in H 2 , we detected significantly improved CO 2 formation for both Pt 9 Ni 1 and Pt 7 Ni 3 motifs. These observations highlight the importance of pre‐treating these nanowires under a reducing atmosphere to enhance their performance for CO oxidation. To explain these findings, we collected extended x‐ray adsorption fine structure (EXAFS) spectroscopy data, consistent with the presence of partial alloying with a tendency for Pt and Ni to segregate, thereby implying the formation of a Pt‐rich shell coupled with a Ni‐rich core. We also observed that the degree of alloying within the nanowires increasedmore » after annealing in a reducing atmosphere, a finding deduced through analysis of the coordination numbers and calculations of Cowley's short range order parameters.« less

Authors:
 [1];  [1];  [2];  [1];  [1];  [3];  [3];  [4];  [5]; ORCiD logo [1]
  1. Department of Chemistry Stony Brook University Stony Brook, New York 11794-3400 USA
  2. Department of Chemistry Fordham University Bronx NY 10458 USA
  3. Department of Materials Science and Chemical Engineering Stony Brook University Stony Brook New York 11794-2275 USA
  4. Center for Functional Nanomaterials, Building 735 Brookhaven National Laboratory Upton New York 11973 USA
  5. Department of Materials Science and Chemical Engineering Stony Brook University Stony Brook New York 11794-2275 USA, Chemistry Division, Building 555 Brookhaven National Laboratory Upton New York 11973 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
2229002
Grant/Contract Number:  
SC-00112704
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
ChemNanoMat
Additional Journal Information:
Journal Name: ChemNanoMat Journal Volume: 10 Journal Issue: 2; Journal ID: ISSN 2199-692X
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Hurley, Nathaniel, Gallagher, Michael, Koenigsmann, Christopher, Stephanie, Elena, Davoudi, Monireh, Plonka, Anna M., Wang, Haodong, Zhang, Lihua, Frenkel, Anatoly I., and Wong, Stanislaus S. Probing the Behavior of Composition‐Tunable Ultrathin PtNi Nanowires for CO Oxidation and Small‐Molecule Electrocatalytic Reactions. Germany: N. p., 2023. Web. doi:10.1002/cnma.202300356.
Hurley, Nathaniel, Gallagher, Michael, Koenigsmann, Christopher, Stephanie, Elena, Davoudi, Monireh, Plonka, Anna M., Wang, Haodong, Zhang, Lihua, Frenkel, Anatoly I., & Wong, Stanislaus S. Probing the Behavior of Composition‐Tunable Ultrathin PtNi Nanowires for CO Oxidation and Small‐Molecule Electrocatalytic Reactions. Germany. https://doi.org/10.1002/cnma.202300356
Hurley, Nathaniel, Gallagher, Michael, Koenigsmann, Christopher, Stephanie, Elena, Davoudi, Monireh, Plonka, Anna M., Wang, Haodong, Zhang, Lihua, Frenkel, Anatoly I., and Wong, Stanislaus S. Wed . "Probing the Behavior of Composition‐Tunable Ultrathin PtNi Nanowires for CO Oxidation and Small‐Molecule Electrocatalytic Reactions". Germany. https://doi.org/10.1002/cnma.202300356.
@article{osti_2229002,
title = {Probing the Behavior of Composition‐Tunable Ultrathin PtNi Nanowires for CO Oxidation and Small‐Molecule Electrocatalytic Reactions},
author = {Hurley, Nathaniel and Gallagher, Michael and Koenigsmann, Christopher and Stephanie, Elena and Davoudi, Monireh and Plonka, Anna M. and Wang, Haodong and Zhang, Lihua and Frenkel, Anatoly I. and Wong, Stanislaus S.},
abstractNote = {Abstract We have successfully synthesized ultrathin nanowires of pure Pt, Pt 99 Ni 1 , Pt 9 Ni 1 , and Pt 7 Ni 3 using a modified room‐temperature soft‐template method. Analysis of both methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR) results found that the Pt 7 Ni 3 samples yielded the best performance with specific activities of 0.36 and 0.34 mA/cm 2 respectively. Additionally, formic acid oxidation reaction (FAOR) tests noted that both Pt and PtNi nanowires oxidize small organic molecules (SOMs) via an indirect pathway. CO oxidation data suggests little measurable performance without any pre‐reduction treatment; however, after annealing in H 2 , we detected significantly improved CO 2 formation for both Pt 9 Ni 1 and Pt 7 Ni 3 motifs. These observations highlight the importance of pre‐treating these nanowires under a reducing atmosphere to enhance their performance for CO oxidation. To explain these findings, we collected extended x‐ray adsorption fine structure (EXAFS) spectroscopy data, consistent with the presence of partial alloying with a tendency for Pt and Ni to segregate, thereby implying the formation of a Pt‐rich shell coupled with a Ni‐rich core. We also observed that the degree of alloying within the nanowires increased after annealing in a reducing atmosphere, a finding deduced through analysis of the coordination numbers and calculations of Cowley's short range order parameters.},
doi = {10.1002/cnma.202300356},
journal = {ChemNanoMat},
number = 2,
volume = 10,
place = {Germany},
year = {Wed Dec 06 00:00:00 EST 2023},
month = {Wed Dec 06 00:00:00 EST 2023}
}

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