Decoupling the roles of carbon and metal oxides on the electrocatalytic reduction of oxygen on La1-xSrxCoO3-δ perovskite composite electrodes.

Perovskite oxides are active room-temperature bifunctional oxygen electrocatalysts in alkaline media, capable of performing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with lower combined overpotentials relative to their precious metal counterparts. However, their semiconducting nature necessitates the use of activated carbons as conductive supports to generate applicably relevant current densities. In efforts to advance the performance and theory of oxide electrocatalysts, the chemical and physical properties of the oxide material often take precedence over contributions from the conductive additive. In this work, we find that carbon plays an important synergistic role in improving the performance of La1-xSrxCoO3-δ (0 ≤ x ≤ 1) electrocatalysts through the activation of O2 and spillover of radical oxygen intermediates, HO2- and O2-, which is further reduced through chemical decomposition of HO2- on the perovskite surface. Through a combination of thin-film rotating disk electrochemical characterization of the hydrogen peroxide intermediate reactions (hydrogen peroxide reduction reaction (HPRR), hydrogen peroxide oxidation reaction (HPOR)) and oxygen reduction reaction (ORR), surface chemical analysis, HR-TEM, and microkinetic modeling on La1-xSrxCoO3-δ (0 ≤ x ≤ 1)/carbon (with nitrogen and non-nitrogen doped carbons) composite electrocatalysts, we deconvolute the mechanistic aspects and contributions to reactivity of the oxide and carbon support.

[1]  R. Sarpong,et al.  Bio-inspired synthesis of xishacorenes A, B, and C, and a new congener from fuscol† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c9sc02572c , 2019, Chemical science.

[2]  Litao Yan,et al.  Recent Progress and Perspectives of Bifunctional Oxygen Reduction/Evolution Catalyst Development for Regenerative Anion Exchange Membrane Fuel Cells , 2018 .

[3]  K. Stevenson,et al.  Role of the Carbon Support on the Oxygen Reduction and Evolution Activities in LaNiO3 Composite Electrodes in Alkaline Solution , 2018 .

[4]  Lei Wang,et al.  Nanocarbon/oxide composite catalysts for bifunctional oxygen reduction and evolution in reversible alkaline fuel cells: A mini review , 2018 .

[5]  E. Savinova,et al.  Further insights into the role of carbon in manganese oxide/carbon composites in the oxygen reduction reaction in alkaline media , 2017 .

[6]  Artem M. Abakumov,et al.  Study of Hydrogen Peroxide Reactions on Manganese Oxides as a Tool To Decode the Oxygen Reduction Reaction Mechanism , 2016 .

[7]  William G. Hardin,et al.  Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts , 2016, Nature Communications.

[8]  M. Nachtegaal,et al.  Superior Bifunctional Electrocatalytic Activity of Ba0.5Sr0.5Co0.8Fe0.2O3‐δ/Carbon Composite Electrodes: Insight into the Local Electronic Structure , 2015 .

[9]  X. Duan,et al.  High-performance transition metal–doped Pt3Ni octahedra for oxygen reduction reaction , 2015, Science.

[10]  R. Kötz,et al.  Electrocatalysis of Perovskites: The Influence of Carbon on the Oxygen Evolution Activity , 2015 .

[11]  G. Kéranguéven,et al.  Synthesis of efficient Vulcan–LaMnO3 perovskite nanocomposite for the oxygen reduction reaction , 2015 .

[12]  Dan Xu,et al.  Oxygen electrocatalysts in metal-air batteries: from aqueous to nonaqueous electrolytes. , 2014, Chemical Society reviews.

[13]  T. Poux,et al.  Electrocatalytic oxygen reduction reaction on perovskite oxides: series versus direct pathway. , 2014, Chemphyschem : a European journal of chemical physics and physical chemistry.

[14]  Junjie Gu,et al.  An overview of metal oxide materials as electrocatalysts and supports for polymer electrolyte fuel cells , 2014 .

[15]  William G. Hardin,et al.  Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes. , 2014, Nature materials.

[16]  T. Poux,et al.  Electrocatalysis of hydrogen peroxide reactions on perovskite oxides: experiment versus kinetic modeling. , 2014, Physical chemistry chemical physics : PCCP.

[17]  William G. Hardin,et al.  Tuning the Electrocatalytic Activity of Perovskites through Active Site Variation and Support Interactions , 2014 .

[18]  R. Kötz,et al.  Composite Electrode Boosts the Activity of Ba0.5Sr0.5Co0.8Fe0.2O3-δ Perovskite and Carbon toward Oxygen Reduction in Alkaline Media , 2014 .

[19]  Hai-Ping Cheng,et al.  Oxygen Reduction Activity on Perovskite Oxide Surfaces: A Comparative First-Principles Study of LaMnO3, LaFeO3, and LaCrO3 , 2012, 1210.1554.

[20]  S. Narayanan,et al.  Electrocatalytic Activity of Transition Metal Oxide-Carbon Composites for Oxygen Reduction in Alkaline Batteries and Fuel Cells , 2013 .

[21]  E. Antipov,et al.  Dual role of carbon in the catalytic layers of perovskite/carbon composites for the electrocatalytic oxygen reduction reaction , 2012 .

[22]  Jun Chen,et al.  Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts. , 2012, Chemical Society reviews.

[23]  J. Sunarso,et al.  Oxygen reduction reaction activity of la-based perovskite oxides in alkaline medium: A thin-film rotating ring-disk electrode study , 2012 .

[24]  H. Dai,et al.  Covalent hybrid of spinel manganese-cobalt oxide and graphene as advanced oxygen reduction electrocatalysts. , 2012, Journal of the American Chemical Society.

[25]  Y. Shao-horn,et al.  Synthesis and Activities of Rutile IrO2 and RuO2 Nanoparticles for Oxygen Evolution in Acid and Alkaline Solutions. , 2012, The journal of physical chemistry letters.

[26]  W. Marsden.  I and J , 2012 .

[27]  S. Woo,et al.  On the mechanism of enhanced oxygen reduction reaction in nitrogen-doped graphene nanoribbons. , 2011, Physical chemistry chemical physics : PCCP.

[28]  Jaclyn D. Wiggins-Camacho,et al.  Mechanistic Discussion of the Oxygen Reduction Reaction at Nitrogen-Doped Carbon Nanotubes , 2011 .

[29]  H. Dai,et al.  Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. , 2011, Nature materials.

[30]  J. Goodenough,et al.  Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries. , 2011, Nature chemistry.

[31]  Ting Yu,et al.  Pyridinic N doped graphene: synthesis, electronic structure, and electrocatalytic property , 2011 .

[32]  Jiujun Zhang,et al.  Electrocatalytic Activities of La0.6Ca0.4CoO3 and La0.6Ca0.4CoO3-Carbon Composites Toward the Oxygen Reduction Reaction in Concentrated Alkaline Electrolytes , 2011 .

[33]  T. Fukutsuka,et al.  Single-step synthesis of nano-sized perovskite-type oxide/carbon nanotube composites and their electrocatalytic oxygen-reduction activities , 2011 .

[34]  T. Jaramillo,et al.  A bifunctional nonprecious metal catalyst for oxygen reduction and water oxidation. , 2010, Journal of the American Chemical Society.

[35]  Jun Liu,et al.  Ammonia-Treated Ordered Mesoporous Carbons as Catalytic Materials for Oxygen Reduction Reaction , 2010 .

[36]  Wei Qu,et al.  A review on air cathodes for zinc–air fuel cells , 2010 .

[37]  Keith J. Stevenson,et al.  Effect of Nitrogen Concentration on Capacitance, Density of States, Electronic Conductivity, and Morphology of N-Doped Carbon Nanotube Electrodes , 2009 .

[38]  Nigel P. Brandon,et al.  Review of gas diffusion cathodes for alkaline fuel cells , 2009 .

[39]  Junliang Zhang,et al.  Catalytic Activity−d-Band Center Correlation for the O2 Reduction Reaction on Platinum in Alkaline Solutions , 2007 .

[40]  V. Osinniy,et al.  Investigation of epitaxial LaNiO3−x thin films by high-energy XPS , 2006 .

[41]  Thomas Lippert,et al.  Ln1-xAxCoO3 (Ln = Er, La; A = Ca, Sr)/carbon nanotube composite materials applied for rechargeable Zn/air batteries , 2002 .

[42]  M. A. Peña,et al.  Chemical structures and performance of perovskite oxides. , 2001, Chemical reviews.

[43]  C. Comninellis,et al.  Mechanistic studies of oxygen reduction at La0.6Ca0.4CoO3-activated carbon electrodes in a channel flow cell , 2000 .

[44]  K. Striebel,et al.  Thermal treatment of La{sub 0.6}Ca{sub 0.4}CoO{sub 3} perovskites for bifunctional air electrodes , 1997 .

[45]  Hubert A. Gasteiger,et al.  Oxygen reduction of platinum low-index single-crystal surfaces in alkaline solution: Rotating ring disk{sub Pt(hkl)} studies , 1996 .

[46]  John L. Falconer,et al.  Spillover in Heterogeneous Catalysis , 1995 .

[47]  N. Yamazoe,et al.  Bi‐Functional Oxygen Electrode Using Large Surface Area La1 − x Ca x CoO3 for Rechargeable Metal‐Air Battery , 1990 .

[48]  E. Sato,et al.  Electrocatalytic properties of transition metal oxides for oxygen evolution reaction , 1986 .

[49]  J. Bockris,et al.  The Electrocatalysis of Oxygen Evolution on Perovskites , 1984 .

[50]  J. Bockris,et al.  Mechanism of oxygen evolution on perovskites , 1983 .

[51]  Allen J. Bard,et al.  Electrochemical Methods: Fundamentals and Applications , 1980 .

[52]  E. Sato,et al.  Oxygen evolution on SrFeO3 electrode , 1979 .

[53]  E. Sato,et al.  Oxygen evolution on La1-xSrxMnO3 electrodes in alkaline solutions , 1979 .

[54]  Y. Matsumoto,et al.  The Mechanism of Oxygen Reduction at a LaNiO3 Electrode , 1978 .

[55]  Y. Matsumoto,et al.  Influence of the nature of the conduction band of transition metal oxides on catalytic activity for oxygen reduction , 1977 .

[56]  Y. Matsumoto,et al.  Catalytic activity for electrochemical reduction of oxygen of lanthanum nickel oxide and related oxides , 1977 .

[57]  Ernest Yeager,et al.  KINETIC STUDIES OF THE OXYGEN-PEROXIDE COUPLE ON PYROLYTIC GRAPHITE , 1970 .

[58]  D. Meadowcroft,et al.  Low-cost Oxygen Electrode Material , 1970, Nature.