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

Soto-Pérez, Joesene; Betancourt, Luis E.; Trinidad, Pedro; Larios, Eduardo; Rojas-Pérez, Arnulfo; Quintana, Gerardo; Sasaki, Kotaro; Pollock, Christopher J.; Debefve, Louise M.; Cabrera, Carlos R.

doi:10.1021/acsomega.1c00792

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

Journal Article · Thu Jul 01 00:00:00 EDT 2021 · ACS Omega

DOI:https://doi.org/10.1021/acsomega.1c00792· OSTI ID:1804933

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

^[1]; Quintana, Gerardo ^[1];

^[2];

^[4]; Debefve, Louise M. ^[4];

^[1]

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

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 the 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.

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

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

Grant/Contract Number:: SC0012704; DMR-1827622; DMR-1719875

OSTI ID:: 1804933

Alternate ID(s):: OSTI ID: 1807785; OSTI ID: 1812514

Report Number(s):: BNL-221973-2021-JAAM

Journal Information:: ACS Omega, Journal Name: ACS Omega Vol. 6 Journal Issue: 27; ISSN 2470-1343

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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

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

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