Understanding the effects of cationic dopants on α-MnO2 oxygen reduction reaction electrocatalysis
Abstract
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 (RCT = 2264 Ω at half-wave) values than MnO2 (n = 3.0, k = 0.006 cm s–1, RCT = 6104 Ω at half-wave) or Cu–α-MnO2 (Cu-2.9%, n = 3.5, k = 0.015 cm s–1, RCT = 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 bothmore »
- Authors:
-
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA)
- OSTI Identifier:
- 1343628
- Report Number(s):
- SAND2017-1258J
Journal ID: ISSN 1932-7447; 651017
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 5; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Lambert, Timothy N., Vigil, Julian A., White, Suzanne E., Delker, Collin J., Davis, Danae J., Kelly, Maria, Brumbach, Michael T., Rodriguez, Mark A., and Swartzentruber, Brian S. Understanding the effects of cationic dopants on α-MnO2 oxygen reduction reaction electrocatalysis. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.6b11252.
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. Understanding the effects of cationic dopants on α-MnO2 oxygen reduction reaction electrocatalysis. United States. https://doi.org/10.1021/acs.jpcc.6b11252
Lambert, Timothy N., Vigil, Julian A., White, Suzanne E., Delker, Collin J., Davis, Danae J., Kelly, Maria, Brumbach, Michael T., Rodriguez, Mark A., and Swartzentruber, Brian S. Mon .
"Understanding the effects of cationic dopants on α-MnO2 oxygen reduction reaction electrocatalysis". United States. https://doi.org/10.1021/acs.jpcc.6b11252. https://www.osti.gov/servlets/purl/1343628.
@article{osti_1343628,
title = {Understanding the effects of cationic dopants on α-MnO2 oxygen reduction reaction electrocatalysis},
author = {Lambert, Timothy N. and Vigil, Julian A. and White, Suzanne E. and Delker, Collin J. and Davis, Danae J. and Kelly, Maria and Brumbach, Michael T. and Rodriguez, Mark A. and Swartzentruber, Brian S.},
abstractNote = {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 (RCT = 2264 Ω at half-wave) values than MnO2 (n = 3.0, k = 0.006 cm s–1, RCT = 6104 Ω at half-wave) or Cu–α-MnO2 (Cu-2.9%, n = 3.5, k = 0.015 cm s–1, RCT = 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.},
doi = {10.1021/acs.jpcc.6b11252},
journal = {Journal of Physical Chemistry. C},
number = 5,
volume = 121,
place = {United States},
year = {Mon Jan 09 00:00:00 EST 2017},
month = {Mon Jan 09 00:00:00 EST 2017}
}
Web of Science
Works referenced in this record:
Carbon-air electrode with regenerative short time overload capacity: Part 1. Effect of manganese dioxide
journal, November 1973
- Żółtowski, P.; Dražić, D. M.; Vorkapić, L.
- Journal of Applied Electrochemistry, Vol. 3, Issue 4
Carbon-Supported Manganese Oxide Nanoparticles as Electrocatalysts for the Oxygen Reduction Reaction (ORR) in Alkaline Medium: Physical Characterizations and ORR Mechanism
journal, December 2006
- Roche, I.; Chaînet, E.; Chatenet, M.
- The Journal of Physical Chemistry C, Vol. 111, Issue 3
Durability of carbon-supported manganese oxide nanoparticles for the oxygen reduction reaction (ORR) in alkaline medium
journal, March 2008
- Roche, I.; Chaînet, E.; Chatenet, M.
- Journal of Applied Electrochemistry, Vol. 38, Issue 9
Recent Insights into Manganese Oxides in Catalyzing Oxygen Reduction Kinetics
journal, September 2015
- Stoerzinger, Kelsey A.; Risch, Marcel; Han, Binghong
- ACS Catalysis, Vol. 5, Issue 10
Electrocatalytic activity of manganese oxides prepared by thermal decomposition for oxygen reduction
journal, March 2007
- Lima, Fabio H. B.; Calegaro, Marcelo L.; Ticianelli, Edson A.
- Electrochimica Acta, Vol. 52, Issue 11
New multi-electron high capacity anodes based on nanoparticle vanadium phosphides
journal, January 2011
- Lambert, Timothy N.; Davis, Danae J.; Limmer, Steven J.
- Chemical Communications, Vol. 47, Issue 34
Poly(3,4-ethylenedioxythiphene) (PEDOT)-Modified Anodes: Reduced Methanol Crossover in Direct Methanol Fuel Cells
journal, May 2010
- Stanis, Ronald J.; Lambert, Timothy N.; Yaklin, Melissa A.
- Energy & Fuels, Vol. 24, Issue 5
Graphene–Ni–α-MnO2 and –Cu–α-MnO2 nanowire blends as highly active non-precious metal catalysts for the oxygen reduction reaction
journal, January 2012
- Lambert, Timothy N.; Davis, Danae J.; Lu, Wei
- Chemical Communications, Vol. 48, Issue 64
Investigations of the catalytic properties of manganese oxides for the oxygen reduction reaction in alkaline media
journal, May 2006
- Lima, Fabio H. B.; Calegaro, Marcelo L.; Ticianelli, Edson A.
- Journal of Electroanalytical Chemistry, Vol. 590, Issue 2
Ionic liquid modified graphene nanosheets anchoring manganese oxide nanoparticles as efficient electrocatalysts for Zn–air batteries
journal, January 2011
- Lee, Jang-Soo; Lee, Taemin; Song, Hyun-Kon
- Energy & Environmental Science, Vol. 4, Issue 10
α-MnO2 nanorods grown in situ on graphene as catalysts for Li–O2 batteries with excellent electrochemical performance
journal, January 2012
- Cao, Yong; Wei, Zhikai; He, Jiao
- Energy & Environmental Science, Vol. 5, Issue 12
Oxygen Reduction Reaction Using MnO 2 Nanotubes/Nitrogen-Doped Exfoliated Graphene Hybrid Catalyst for Li-O 2 Battery Applications
journal, December 2012
- Park, Hey Woong; Lee, Dong Un; Nazar, Linda F.
- Journal of The Electrochemical Society, Vol. 160, Issue 2
MnO 2 -Based Nanostructures as Catalysts for Electrochemical Oxygen Reduction in Alkaline Media †
journal, February 2010
- Cheng, Fangyi; Su, Yi; Liang, Jing
- Chemistry of Materials, Vol. 22, Issue 3
Electrodeposited MnO x /PEDOT Composite Thin Films for the Oxygen Reduction Reaction
journal, October 2015
- Vigil, Julian A.; Lambert, Timothy N.; Eldred, Kaitlyn
- ACS Applied Materials & Interfaces, Vol. 7, Issue 41
Conducting CoMn2O4 - PEDOT nanocomposites as catalyst in oxygen reduction reaction
journal, February 2014
- Chowdhury, Ankan Dutta; Agnihotri, Nidhi; Sen, Pintu
- Electrochimica Acta, Vol. 118
A dual-metal–organic-framework derived electrocatalyst for oxygen reduction
journal, January 2016
- Guan, Bu Yuan; Yu, Le; (David) Lou, Xiong Wen
- Energy & Environmental Science, Vol. 9, Issue 10
Boron- and Nitrogen-Substituted Graphene Nanoribbons as Efficient Catalysts for Oxygen Reduction Reaction
journal, February 2015
- Gong, Yongji; Fei, Huilong; Zou, Xiaolong
- Chemistry of Materials, Vol. 27, Issue 4
Electrodeposited Ni x Co 3−x O 4 nanostructured films as bifunctional oxygen electrocatalysts
journal, January 2015
- Lambert, Timothy N.; Vigil, Julian A.; White, Suzanne E.
- Chemical Communications, Vol. 51, Issue 46
Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal–air batteries
journal, June 2011
- Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki
- Nature Chemistry, Vol. 3, Issue 7, p. 546-550
Review—Recent Progress in Electrocatalysts for Oxygen Reduction Suitable for Alkaline Anion Exchange Membrane Fuel Cells
journal, January 2015
- He, Qinggang; Cairns, Elton J.
- Journal of The Electrochemical Society, Vol. 162, Issue 14
Role of Cu-Ion Doping in Cu-α-MnO 2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction
journal, July 2014
- Davis, Danae J.; Lambert, Timothy N.; Vigil, Julian A.
- The Journal of Physical Chemistry C, Vol. 118, Issue 31
Insight into the Effect of Oxygen Vacancy Concentration on the Catalytic Performance of MnO 2
journal, July 2015
- Li, Li; Feng, Xianghong; Nie, Yao
- ACS Catalysis, Vol. 5, Issue 8
Shape-Controlled Synthesis of MnO 2 Nanostructures with Enhanced Electrocatalytic Activity for Oxygen Reduction
journal, December 2009
- Xiao, Wei; Wang, Deli; Lou, Xiong Wen
- The Journal of Physical Chemistry C, Vol. 114, Issue 3
Carbon-supported manganese oxide nanoparticles as electrocatalysts for oxygen reduction reaction (orr) in neutral solution
journal, September 2008
- Roche, I.; Scott, K.
- Journal of Applied Electrochemistry, Vol. 39, Issue 2
Oxygen Reduction Properties of Bifunctional α-Manganese Oxide Electrocatalysts in Aqueous and Organic Electrolytes
journal, October 2011
- Benbow, E. M.; Kelly, S. P.; Zhao, L.
- The Journal of Physical Chemistry C, Vol. 115, Issue 44
Framework Doping of Indium in Manganese Oxide Materials: Synthesis, Characterization, and Electrocatalytic Reduction of Oxygen
journal, March 2008
- Liu, Zhenxin; Xing, Yu; Chen, Chun-Hu
- Chemistry of Materials, Vol. 20, Issue 6
Structure–Property Relationship of Bifunctional MnO 2 Nanostructures: Highly Efficient, Ultra-Stable Electrochemical Water Oxidation and Oxygen Reduction Reaction Catalysts Identified in Alkaline Media
journal, August 2014
- Meng, Yongtao; Song, Wenqiao; Huang, Hui
- Journal of the American Chemical Society, Vol. 136, Issue 32
The mechanism of oxygen reduction on MnO2-catalyzed air cathode in alkaline solution
journal, October 2003
- Cao, Y. L.; Yang, H. X.; Ai, X. P.
- Journal of Electroanalytical Chemistry, Vol. 557
Rationalizing the Influence of the Mn(IV)/Mn(III) Red-Ox Transition on the Electrocatalytic Activity of Manganese Oxides in the Oxygen Reduction Reaction
journal, January 2016
- Ryabova, Anna S.; Napolskiy, Filipp S.; Poux, Tiphaine
- Electrochimica Acta, Vol. 187
Preparation and physical properties of the solid solutions Cu1+xMn1−xO2 ()
journal, September 2005
- Trari, M.; Töpfer, J.; Dordor, P.
- Journal of Solid State Chemistry, Vol. 178, Issue 9
Effect of Surface Manganese Valence of Manganese Oxides on the Activity of the Oxygen Reduction Reaction in Alkaline Media
journal, December 2013
- Tang, Qiwen; Jiang, Luhua; Liu, Jing
- ACS Catalysis, Vol. 4, Issue 2
Core-level satellites and outer core-level multiplet splitting in Mn model compounds
journal, July 2000
- Nelson, A. J.; Reynolds, John G.; Roos, Joseph W.
- Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 18, Issue 4
Influence of Microstucture on the Charge Storage Properties of Chemically Synthesized Manganese Dioxide
journal, September 2002
- Toupin, Mathieu; Brousse, Thierry; Bélanger, Daniel
- Chemistry of Materials, Vol. 14, Issue 9
Works referencing / citing this record:
Mn x (PO 4 ) y /NPC As a High Performance Bifunctional Electrocatalyst for Oxygen Electrode Reactions
journal, January 2019
- Wang, Shuai; Nam, Gyutae; Li, Ping
- ChemCatChem, Vol. 11, Issue 4
Transition-Metal-Doped α-MnO 2 Nanorods as Bifunctional Catalysts for Efficient Oxygen Reduction and Evolution Reactions
journal, March 2018
- Lübke, Mechthild; Sumboja, Afriyanti; McCafferty, Liam
- ChemistrySelect, Vol. 3, Issue 9
Recent Progress on Transition Metal Oxides as Bifunctional Catalysts for Lithium‐Air and Zinc‐Air Batteries
journal, October 2018
- Pan, Jing; Tian, Xin Long; Zaman, Shahid
- Batteries & Supercaps, Vol. 2, Issue 4
Synthesis of Large Surface-Area g-C 3 N 4 Comodified with MnO x and Au-TiO 2 as Efficient Visible-Light Photocatalysts for Fuel Production
journal, September 2017
- Raziq, Fazal; Sun, Liqun; Wang, Yuying
- Advanced Energy Materials, Vol. 8, Issue 3
Nanoscale Perovskites as Catalysts and Supports for Direct Methanol Fuel Cells
journal, April 2019
- Li, Luyao; Tan, Sha; Salvatore, Kenna L.
- Chemistry – A European Journal, Vol. 25, Issue 33
Insights into the spontaneous formation of hybrid PdO x /PEDOT films: electroless deposition and oxygen reduction activity
journal, January 2018
- Vigil, Julian A.; Brumbach, Michael T.; Duay, Jonathon
- RSC Advances, Vol. 8, Issue 43
Electrochemical Oxygen Reduction Reaction Performance Boosted by N, P Doped Carbon Layer over Manganese Dioxide Nanorod
journal, August 2019
- Pei, Chengang; Ding, Ruifu; Yu, Xu
- ChemCatChem, Vol. 11, Issue 18
Nanostructured MnO2 as Electrode Materials for Energy Storage
journal, November 2017
- Julien, Christian M.; Mauger, Alain
- Nanomaterials, Vol. 7, Issue 11, p. 396
A Pt-free graphenaceous composite as an electro-catalyst for efficient oxygen reduction reaction
journal, January 2019
- Sravani, Bathinapatla; Maseed, H.; Y., Chandrasekhar
- Nanoscale, Vol. 11, Issue 28
Transition metal oxide-based oxygen reduction reaction electrocatalysts for energy conversion systems with aqueous electrolytes
journal, January 2018
- Xue, Yejian; Sun, Shanshan; Wang, Qin
- Journal of Materials Chemistry A, Vol. 6, Issue 23
Waste minimized synthesis of pharmaceutically active compounds via heterogeneous manganese catalysed C–H oxidation in flow
journal, January 2020
- Ferlin, Francesco; Luque Navarro, Pilar María; Gu, Yanlong
- Green Chemistry, Vol. 22, Issue 2
One-pot achievement of MnO 2 /Fe 2 O 3 nanocomposites for the oxygen reduction reaction with enhanced catalytic activity
journal, January 2019
- Jiang, Lingling; Zhang, Guodong; Li, Dehua
- New Journal of Chemistry, Vol. 43, Issue 43
Heterogeneous Manganese‐Catalyzed Oxidase C−H/C−O Cyclization to Access Pharmaceutically Active Compounds
journal, November 2019
- Ferlin, Francesco; Marini, Alberto; Ascani, Nicola
- ChemCatChem, Vol. 12, Issue 2
Heterojunctions of silver–iron oxide on graphene for laser-coupled oxygen reduction reactions
journal, January 2018
- Chen, Wei-Quan; Chung, Min-Chuan; Valinton, Joey Andrew A.
- Chemical Communications, Vol. 54, Issue 57