Enhancing Electrocatalytic Activity of Perovskite Oxides by Tuning Cation Deficiency for Oxygen Reduction and Evolution Reactions

Development of cost-effective and efficient electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is of prime importance to emerging renewable energy technologies. Here, we report a simple and effective strategy for enhancing ORR and OER electrocatalytic activity in alkaline solution by introducing A-site cation deficiency in LaFeO3 perovskite; the enhancement effect is more pronounced for the OER than the ORR. Among the A-site cation deficient perovskites studied, La0.95FeO3-δ (L0.95F) demonstrates the highest ORR and OER activity and, hence, the best bifunctionality. The dramatic enhancement is attributed to the creation of surface oxygen vacancies and a small amount of Fe4+ species. This work highlights the importance of tuning cation deficiency in perovskites as an effective strategy for enhancing ORR and OER activity for applications in various oxygen-based energy storage and conversion processes.

[1]  L. Cadús,et al.  La1−xCaxCoO3 perovskite-type oxides: Identification of the surface oxygen species by XPS , 2006 .

[2]  Zongping Shao,et al.  A universal and facile way for the development of superior bifunctional electrocatalysts for oxygen reduction and evolution reactions utilizing the synergistic effect. , 2014, Chemistry.

[3]  F. Tietz,et al.  Activation of oxygen evolving perovskites for oxygen reduction by functionalization with Fe-N(x)/C groups. , 2014, Chemical communications.

[4]  Sean C. Smith,et al.  High activity and durability of novel perovskite electrocatalysts for water oxidation , 2015 .

[5]  Zongping Shao,et al.  Boosting oxygen reduction reaction activity of palladium by stabilizing its unusual oxidation states in perovskite , 2015 .

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

[7]  J. Sunarso,et al.  Enhancing bi-functional electrocatalytic activity of perovskite by temperature shock: a case study of LaNiO3-δ , 2013 .

[8]  M. Armand,et al.  Building better batteries , 2008, Nature.

[9]  R. D. Shannon.  Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .

[10]  Zongping Shao,et al.  High-performance SrNb0.1Co0.9−xFexO3−δ perovskite cathodes for low-temperature solid oxide fuel cells , 2014 .

[11]  Zongping Shao,et al.  Properties and performance of A-site deficient (Ba0.5Sr0.5)1−xCo0.8Fe0.2O3−δ for oxygen permeating membrane , 2007 .

[12]  I. Concina,et al.  Chemical Tuning versus Microstructure Features in Solid-State Gas Sensors: LaFe1-xGaxO3, a Case Study , 2014 .

[13]  Ho Won Jang,et al.  A new water oxidation catalyst: lithium manganese pyrophosphate with tunable Mn valency. , 2014, Journal of the American Chemical Society.

[14]  Ch. Ftikos,et al.  Properties of A-site-deficient La0.6Sr0.4Co0.2Fe0.8O3-δ-based perovskite oxides , 1999 .

[15]  L. Wan,et al.  Insight into the Effect of Oxygen Vacancy Concentration on the Catalytic Performance of MnO2 , 2015 .

[16]  Harry B Gray,et al.  Powering the planet with solar fuel. , 2009, Nature chemistry.

[17]  Jun Chen,et al.  Enhancing electrocatalytic oxygen reduction on MnO(2) with vacancies. , 2013, Angewandte Chemie.

[18]  D. Morgan,et al.  Ab initio GGA+U study of oxygen evolution and oxygen reduction electrocatalysis on the (001) surfaces of lanthanum transition metal perovskites LaBO₃ (B = Cr, Mn, Fe, Co and Ni). , 2015, Physical chemistry chemical physics : PCCP.

[19]  João A. Labrincha,et al.  Cathode materials for intermediate temperature SOFCs , 2000 .

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

[21]  Zongping Shao,et al.  Co‐doping Strategy for Developing Perovskite Oxides as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction , 2015, Advanced science.

[22]  X. D. Xu,et al.  Perovskite Oxides: Preparation, Characterizations, and Applications in Heterogeneous Catalysis , 2014 .

[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]  N. Bonanos,et al.  The role of dopant concentration, A-site deficiency and processing on the electrical properties of strontium- and titanium-doped lanthanum scandate , 2004 .

[25]  Zongping Shao,et al.  A High‐Performance Electrocatalyst for Oxygen Evolution Reaction: LiCo0.8Fe0.2O2 , 2015, Advanced materials.

[26]  Zongping Shao,et al.  SrNb(0.1)Co(0.7)Fe(0.2)O(3-δ) perovskite as a next-generation electrocatalyst for oxygen evolution in alkaline solution. , 2015, Angewandte Chemie.

[27]  Shuji Kawasaki,et al.  Ferromagnetic Properties of SrFe1−xCoxO3Synthesized under High Pressure , 1996 .

[28]  James R. McKone,et al.  Solar water splitting cells. , 2010, Chemical reviews.

[29]  Zongping Shao,et al.  Evaluation of A-site cation-deficient (Ba0.5Sr0.5)1−xCo0.8Fe0.2O3−δ (x > 0) perovskite as a solid-oxide fuel cell cathode , 2008 .

[30]  Chong Xiao,et al.  Low overpotential in vacancy-rich ultrathin CoSe2 nanosheets for water oxidation. , 2014, Journal of the American Chemical Society.

[31]  Yang Shao-Horn,et al.  Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution , 2013, Nature Communications.

[32]  Zongping Shao,et al.  Nonstoichiometric Oxides as Low-Cost and Highly-Efficient Oxygen Reduction/Evolution Catalysts for Low-Temperature Electrochemical Devices. , 2015, Chemical reviews.

[33]  Lei Liu,et al.  The role of oxygen vacancies in improving the performance of CoO as a bifunctional cathode catalyst for rechargeable Li–O2 batteries , 2015 .

[34]  Zongping Shao,et al.  An A-site-deficient perovskite offers high activity and stability for low-temperature solid-oxide fuel cells. , 2013, ChemSusChem.

[35]  A. Majumdar,et al.  Opportunities and challenges for a sustainable energy future , 2012, Nature.

[36]  Zhonghua Zhu,et al.  Highly defective CeO2 as a promoter for efficient and stable water oxidation , 2015 .

[37]  Dan Xu,et al.  3D ordered macroporous LaFeO3 as efficient electrocatalyst for Li–O2 batteries with enhanced rate capability and cyclic performance , 2014 .

[38]  Gang Wu,et al.  Oxygen-deficient BaTiO3−x perovskite as an efficient bifunctional oxygen electrocatalyst , 2015 .

[39]  Zongping Shao,et al.  Structural and oxygen-transport studies of double perovskites PrBa1−xCo2O5+δ (x = 0.00, 0.05, and 0.10) toward their application as superior oxygen reduction electrodes , 2014 .

[40]  Zongping Shao,et al.  Influence of crystal structure on the electrochemical performance of A-site-deficient Sr1−sNb0.1Co0.9O3−δ perovskite cathodes , 2014 .

[41]  Chunming Xu,et al.  Highly active catalysts of gold nanoparticles supported on three-dimensionally ordered macroporous LaFeO3 for soot oxidation. , 2011, Angewandte Chemie.

[42]  Zhonghua Zhu,et al.  Calcium-doped lanthanum nickelate layered perovskite and nickel oxide nano-hybrid for highly efficient water oxidation , 2015 .

[43]  Y. Yoon,et al.  Anode catalysts for direct methanol fuel cells in acidic media: do we have any alternative for Pt or Pt-Ru? , 2014, Chemical reviews.

[44]  Ziyu Wu,et al.  Nonstoichiometric perovskite CaMnO(3-δ) for oxygen electrocatalysis with high activity. , 2014, Inorganic chemistry.

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

[46]  Piotr Zelenay,et al.  Nanostructured nonprecious metal catalysts for oxygen reduction reaction. , 2013, Accounts of chemical research.

[47]  P. Porta,et al.  AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 perovskites: structural and redox properties , 2001 .

[48]  N. Hebalkar,et al.  Shape evolution of perovskite LaFeO3 nanostructures: a systematic investigation of growth mechanism, properties and morphology dependent photocatalytic activities , 2013 .

[49]  G. K. Pradhan,et al.  Hydrated manganese(II) phosphate (Mn₃(PO₄)₂·3H₂O) as a water oxidation catalyst. , 2014, Journal of the American Chemical Society.

[50]  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.

[51]  Y. Shao-horn,et al.  Thickness-Dependent Photoelectrochemical Water Splitting on Ultrathin LaFeO3 Films Grown on Nb:SrTiO3. , 2015, The journal of physical chemistry letters.

[52]  W. Schuhmann,et al.  Mn(x)O(y)/NC and Co(x)O(y)/NC nanoparticles embedded in a nitrogen-doped carbon matrix for high-performance bifunctional oxygen electrodes. , 2014, Angewandte Chemie.

[53]  J. Goodenough,et al.  A Perovskite Oxide Optimized for Oxygen Evolution Catalysis from Molecular Orbital Principles , 2011, Science.

[54]  Daniel G. Nocera,et al.  In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+ , 2008, Science.