Tuning the Electrocatalytic Oxygen Reduction Reaction Activity of PtCo Nanocrystals by Cobalt Concentration with Atomic-Scale Understanding

Lee, Jennifer D.; Jishkariani, Davit; Zhao, Yingrui; Najmr, Stan; Rosen, Daniel; Kikkawa, James M.; Stach, Eric A.; Murray, Christopher B.

doi:10.1021/acsami.9b06346

Title: Tuning the Electrocatalytic Oxygen Reduction Reaction Activity of PtCo Nanocrystals by Cobalt Concentration with Atomic-Scale Understanding

Abstract

The development of a suitable catalyst for the oxygen reduction reaction (ORR) – the cathode reaction of proton exchange membrane fuel cells (PEMFC) – is necessary to push this technology towards widespread adoption. There have been substantial efforts to utilize bimetallic Pt-M alloys that adopt the ordered face-centered tetragonal (L10) phase in order to reduce the usage of precious metal, enhance the ORR performance, and improve catalyst stability. In this work, monodisperse Pt-Co nanocrystals (NCs) with well-defined size (4-5 nm) and cobalt composition (25-75 at%) were synthesized via colloidal synthesis. The transformation from the chemically disordered A1 (face-centered cubic, fcc) to the L10 phase was achieved via thermal annealing using both a conventional oven and a rapid thermal annealing process. The structure of the Pt-Co catalysts was characterized by a variety of techniques, including transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy in high-angle annular dark-field scanning transmission electron microscopy (STEM-EDS), small-angle X-ray scattering (SAXS), X-ray diffraction (XRD), and inductively coupled plasma-optical emission spectrometry (ICP-OES). The effects of annealing temperature on the composition-dependent degree of ordering, and subsequent effect on ORR activity is described. This work provides insights regarding the optimal spatial distribution of elements at the atomic level tomore »« less

Authors:

^[1];

^[1]; Zhao, Yingrui ^[1];

^[1]; Rosen, Daniel ^[1]; Kikkawa, James M. ^[1];

^[1]; Murray, Christopher B. ^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)

Publication Date:: Mon Jul 08 00:00:00 EDT 2019

Research Org.:: Univ. of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office

Contributing Org.:: This research used resources of the Center for Functional Nanomaterials, Brookhaven National Laboratory (BNL), and was supported by the U.S. Department of Energy, Office of Science, Office of Workforce Development for Teachers and Scientists, Office of Science Graduate Student Research (SCGSR) program. J.D.L acknowledge the support from the SCGSR program, which is administered by the Oak Ridge Institute for Science and Education (ORISE) for the DOE. ORISE is managed by ORAU under contract number DE-SC0014664. Magnetic property measurements were supported by NSF MRSEC DMR-1720530. J.D.L acknowledges Dr. Kotaro Sasaki at the Brookhaven National Laboratory for the assistance with the RDE measurements at the Chemistry Division. C.B.M. acknowledges the Richard Perry University Professorship at the University of Pennsylvania.

OSTI Identifier:: 1532516

Alternate Identifier(s):: OSTI ID: 1532515

Grant/Contract Number:: AC52-06NA25396; SC0014664; DMR-1720530

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Materials and Interfaces

Additional Journal Information:: Journal Volume: 11; Journal Issue: 30; Journal ID: ISSN 1944-8244

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 77 NANOSCIENCE AND NANOTECHNOLOGY; nanocrystal electrocatalysis; platinum-cobalt alloy; structure-activity relationship; face-centered tetragonal structure; oxygen reduction reaction

Citation Formats


                    Lee, Jennifer D., Jishkariani, Davit, Zhao, Yingrui, Najmr, Stan, Rosen, Daniel, Kikkawa, James M., Stach, Eric A., and Murray, Christopher B. Tuning the Electrocatalytic Oxygen Reduction Reaction Activity of PtCo Nanocrystals by Cobalt Concentration with Atomic-Scale Understanding.  United States: N. p., 2019. 
Web.  doi:10.1021/acsami.9b06346.

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                    Lee, Jennifer D., Jishkariani, Davit, Zhao, Yingrui, Najmr, Stan, Rosen, Daniel, Kikkawa, James M., Stach, Eric A., & Murray, Christopher B. Tuning the Electrocatalytic Oxygen Reduction Reaction Activity of PtCo Nanocrystals by Cobalt Concentration with Atomic-Scale Understanding.  United States.  https://doi.org/10.1021/acsami.9b06346

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                    Lee, Jennifer D., Jishkariani, Davit, Zhao, Yingrui, Najmr, Stan, Rosen, Daniel, Kikkawa, James M., Stach, Eric A., and Murray, Christopher B. Mon .  
"Tuning the Electrocatalytic Oxygen Reduction Reaction Activity of PtCo Nanocrystals by Cobalt Concentration with Atomic-Scale Understanding".  United States.  https://doi.org/10.1021/acsami.9b06346.  https://www.osti.gov/servlets/purl/1532516.

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@article{osti_1532516,

  title        = {Tuning the Electrocatalytic Oxygen Reduction Reaction Activity of PtCo Nanocrystals by Cobalt Concentration with Atomic-Scale Understanding},

  author       = {Lee, Jennifer D. and Jishkariani, Davit and Zhao, Yingrui and Najmr, Stan and Rosen, Daniel and Kikkawa, James M. and Stach, Eric A. and Murray, Christopher B.},

  abstractNote = {The development of a suitable catalyst for the oxygen reduction reaction (ORR) – the cathode reaction of proton exchange membrane fuel cells (PEMFC) – is necessary to push this technology towards widespread adoption. There have been substantial efforts to utilize bimetallic Pt-M alloys that adopt the ordered face-centered tetragonal (L10) phase in order to reduce the usage of precious metal, enhance the ORR performance, and improve catalyst stability. In this work, monodisperse Pt-Co nanocrystals (NCs) with well-defined size (4-5 nm) and cobalt composition (25-75 at%) were synthesized via colloidal synthesis. The transformation from the chemically disordered A1 (face-centered cubic, fcc) to the L10 phase was achieved via thermal annealing using both a conventional oven and a rapid thermal annealing process. The structure of the Pt-Co catalysts was characterized by a variety of techniques, including transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy in high-angle annular dark-field scanning transmission electron microscopy (STEM-EDS), small-angle X-ray scattering (SAXS), X-ray diffraction (XRD), and inductively coupled plasma-optical emission spectrometry (ICP-OES). The effects of annealing temperature on the composition-dependent degree of ordering, and subsequent effect on ORR activity is described. This work provides insights regarding the optimal spatial distribution of elements at the atomic level to achieve enhanced ORR activity and stability.},

  doi          = {10.1021/acsami.9b06346},

  journal      = {ACS Applied Materials and Interfaces},

  number       = 30,

  volume       = 11,

  place        = {United States},

  year         = {Mon Jul 08 00:00:00 EDT 2019},

  month        = {Mon Jul 08 00:00:00 EDT 2019}

}

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Cited by: 30 works

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Figure 1: TEM images of as-synthesized (a) Pt₃Co, (b) PtCo, (c) PtCo₂ and (d) PtCo₃NCs, the corresponding (e) SAXS and (f) XRD patterns. The black circles in (e) and (f) represent the observed data. The solid lines in (e) and (f) represent the simulated fits for the size andmore »

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