Understanding the effects of cationic dopants on α-MnO2 oxygen reduction reaction electrocatalysis

Lambert, Timothy N.; Vigil, Julian A.; White, Suzanne E.; Delker, Collin J.; Davis, Danae J.; Kelly, Maria; Brumbach, Michael T.; Rodriguez, Mark A.; Swartzentruber, Brian S.

doi:10.1021/acs.jpcc.6b11252

Title: Understanding the effects of cationic dopants on α-MnO₂ oxygen reduction reaction electrocatalysis

Journal Article · Mon Jan 09 00:00:00 EST 2017 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.6b11252· OSTI ID:1343628

^[1];

^[1]; White, Suzanne E. ^[1]; Delker, Collin J. ^[1]; Davis, Danae J. ^[1]; Kelly, Maria ^[1]; Brumbach, Michael T. ^[1]; Rodriguez, Mark A. ^[1]; Swartzentruber, Brian S. ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Nickel-doped α-MnO₂ nanowires (Ni–α-MnO₂) were prepared with 3.4% or 4.9% Ni using a hydrothermal method. A comparison of the electrocatalytic data for the oxygen reduction reaction (ORR) in alkaline electrolyte versus that obtained with α-MnO₂ or Cu–α-MnO₂ is provided. In general, Ni-α-MnO₂ (e.g., Ni-4.9%) had higher n values (n = 3.6), faster kinetics (k = 0.015 cm s^–1), and lower charge transfer resistance (R_CT = 2264 Ω at half-wave) values than MnO₂ (n = 3.0, k = 0.006 cm s^–1, R_CT = 6104 Ω at half-wave) or Cu–α-MnO₂ (Cu-2.9%, n = 3.5, k = 0.015 cm s^–1, R_CT = 3412 Ω at half-wave), and the overall activity for Ni–α-MnO₂ trended with increasing Ni content, i.e., Ni-4.9% > Ni-3.4%. As observed for Cu–α-MnO₂, the increase in ORR activity correlates with the amount of Mn³⁺ at the surface of the Ni–α-MnO₂ nanowire. Examining the activity for both Ni–α-MnO₂ and Cu–α-MnO₂ materials indicates that the Mn³⁺ at the surface of the electrocatalysts dictates the activity trends within the overall series. Single nanowire resistance measurements conducted on 47 nanowire devices (15 of α-MnO₂, 16 of Cu–α-MnO₂-2.9%, and 16 of Ni–α-MnO₂-4.9%) demonstrated that Cu-doping leads to a slightly lower resistance value than Ni-doping, although both were considerably improved relative to the undoped α-MnO₂. As a result, the data also suggest that the ORR charge transfer resistance value, as determined by electrochemical impedance spectroscopy, is a better indicator of the cation-doping effect on ORR catalysis than the electrical resistance of the nanowire.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1343628

Report Number(s):: SAND2017-1258J; 651017

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 5; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 71 works

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