Title: In Situ X-ray Absorption Spectroscopy of PtNi-Nanowire/Vulcan XC-72R under Oxygen Reduction Reaction in Alkaline Media

Abstract

Studying the oxygen reduction reaction (ORR) in the alkaline electrolyte has proven to promote better catalytic responses and accessibility to commercialization. Ni-nanowires (NWs) were synthesized via the solvothermal method and modified with Pt using the spontaneous galvanic displacement method to obtain PtNi-NWs. Carbon Vulcan XC-72R (V) was used as the catalyst support, and they were doped with NH₃ to obtain PtNi-NWs/V and PtNi-NWs/V–NH₃. Their electrocatalytic response for the ORR was tested and PtNi-NWs/V provided the highest specific activity with logarithmic values of 0.707 and 1.01 (mA/cm²_Pt) at 0.90 and 0.85 V versus reversible hydrogen electrode (RHE), respectively. PtNi-NWs showed the highest half-wave potential (E_1/2 = 0.89 V) at 1600 rpm and 12 μgPt/cm² in 0.1 M KOH at 25.00 ± 0.01 °C. Additionally, the catalysts followed a four-electron pathway according to the Koutecký–Levich analysis. Moreover, durability experiments demonstrated that the PtNi-NW/V performance loss was like that of commercial Pt/V along 10,000 cycles. Electrochemical ORR in situ X-ray absorption spectroscopy results showed that the Pt L₃ edge white line in the PtNi-NW catalysts changed while the electrochemical potential was lowered to negatives values, from 1.0 to 0.3 V versus RHE. The Pt/O region in the in situ Fourier transforms remained themore » same as the potentials were applied, suggesting an alloy formation between Pt and Ni, and Pt/Pt contracted in the presence of Ni. These results provide a better understanding of PtNi-NWs in alkaline electrolytes, suggesting that they are active catalysts for ORR and can be tuned for fuel cell studies.« less

Authors:

Soto-Pérez, Joesene ^[1]; Betancourt, Luis E. ^[2]; Trinidad, Pedro ^[1]; Larios, Eduardo ^[3]; Rojas-Pérez, Arnulfo  ^[1];

• Search DOE PAGES for author "Rojas-Pérez, Arnulfo"
• Search DOE PAGES for ORCID "0000-0002-3804-6309"

Quintana, Gerardo ^[1]; Sasaki, Kotaro  ^[2];

• Search DOE PAGES for author "Sasaki, Kotaro"
• Search DOE PAGES for ORCID "0000-0003-2474-8323"

Pollock, Christopher J.  ^[4];

• Search DOE PAGES for author "Pollock, Christopher J."
• Search DOE PAGES for ORCID "0000-0001-5736-513X"

Debefve, Louise M. ^[4]; Cabrera, Carlos R.  ^[1]

• Search DOE PAGES for author "Cabrera, Carlos R."
• Search DOE PAGES for ORCID "0000-0002-3342-8666"

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+ Show Author Affiliations

1. Department of Chemistry, University of Puerto Rico, Río Piedras Campus, San Juan 00925-2537, Puerto Rico
2. Chemistry Division, Brookhaven National Laboratory, Upton, New York 11973, United States
3. Departamento de Ingeniería Química y Metalurgia, Universidad de Sonora, Hermosillo 83000, Mexico
4. Cornell High Energy Synchrotron Source (CHESS), Wilson Laboratory, Cornell University, Ithaca, New York 14853, United Sates

Publication Date:

Thu Jul 01 00:00:00 EDT 2021

Research Org.:

Univ. of Puerto Rico, San Juan, PR (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation NSF-PREM, Center for Interfacial Electrochemistry of Energy Materials (CiE2M); NSF MRSEC

OSTI Identifier:

1804933

Alternate Identifier(s):

OSTI ID: 1807785; OSTI ID: 1812514

Report Number(s):

BNL-221973-2021-JAAM
Journal ID: ISSN 2470-1343

Grant/Contract Number:  

SC0012704; DMR-1827622; DMR-1719875

Resource Type:

Published Article

Journal Name:

ACS Omega

Additional Journal Information:

Journal Name: ACS Omega Journal Volume: 6 Journal Issue: 27; Journal ID: ISSN 2470-1343

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Redox reactions; Oxides; Platinum; Electrodes; Catalysts