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The development of an efficient and low-cost electrocatalyst for the oxygen evolution reaction (OER) via an eco-efficient route is a desirable, although challenging, outcome for overall water splitting. Herein, an iron-rich La0.6Sr0.4Co0.2Fe0.8O2.9 (LSCF28) perovskite with an open porous topographic structure was developed as an electrocatalyst by a straightforward molten-salt synthesis approach. It was found that porosity correlates with both the iron content and the molten-salt approach. Benefiting from the large surface area, high activity of the porous internal surface, and the optimal electronic configuration of redox sites, this inexpensive material exhibits high performance with a large mass activity of 40.8 A·g–1 at a low overpotential of 0.345 V in 0.1 M KOH, surpassing the state-of-the-art precious metal IrO2 catalyst and other well-known perovskites, such as Ba0.5Sr0.5Co0.8Fe0.2O3 and SrCoO2.7. Our work illustrates that the molten-salt method is an effective route to generate porous structures in perovskite oxides, which is important for energy conversion and storage devices.
Chu, S.; Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 2012, 488, 294-303.
Cook, T. R.; Dogutan, D. K.; Reece, S. Y.; Surendranath, Y.; Teets, T. S.; Nocera, D. G. Solar energy supply and storage for the legacy and nonlegacy worlds. Chem. Rev. 2010, 110, 6474-6502.
Montoya, J. H.; Seitz, L. C.; Chakthranont, P.; Vojvodic, A.; Jaramillo, T. F.; NØrskov, J. K. Materials for solar fuels and chemicals. Nat. Mater. 2017, 16, 70-81.
Koper, M. T. M. Hydrogen electrocatalysis: A basic solution. Nat. Chem. 2013, 5, 255-256.
Gasteiger, H. A.; Marković, N. M. Just a dream—or future reality? Science. 2009, 324, 48-49.
Gorlin, Y.; Jaramillo, T. F. A bifunctional nonprecious metal catalyst for oxygen reduction and water oxidation. J. Am. Chem. Soc. 2010, 132, 13612-13614.
Seh, Z. W.; Kibsgaard, J.; Dickens, C. F.; Chorkendorff, I.; NØrskov, J. K.; Jaramillo, T. F. Combining theory and experiment in electrocatalysis: Insights into materials design. Science 2017, 355, eaad4998.
Gong, M.; Wang, D. -Y.; Chen, C. -C.; Hwang, B. -J.; Dai, H. J. A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction. Nano Res. 2016, 9, 28-46.
Chen, D. J.; Chen, C.; Baiyee, Z. M.; Shao, Z. P.; Ciucci, F. Nonstoichiometric oxides as low-cost and highly-efficient oxygen reduction/evolution catalysts for low-temperature electrochemical devices. Chem. Rev. 2015, 115, 9869-9921.
Bao, J.; Zhang, X. D.; Fan, B.; Zhang, J. J.; Zhou, M.; Yang, W. L.; Hu, X.; Wang, H.; Pan, B. C.; Xie, Y. Ultrathin spinel-structured nanosheets rich in oxygen deficiencies for enhanced electrocatalytic water oxidation. Angew. Chem. 2015, 127, 7507-7512.
Nai, J. W.; Yin, H. J.; You, T. T.; Zheng, L. R.; Zhang, J.; Wang, P. X.; Jin, Z.; Tian, Y.; Liu, J. Z.; Tang, Z. Y. et al. Efficient electrocatalytic water oxidation by using amorphous Ni-Co double hydroxides nanocages. Adv. Energy Mater. 2015, 5, 1401880.
Correa-Baena, J. P.; Saliba, M.; Buonassisi, T.; Grätzel, M.; Abate, A.; Tress, W.; Hagfeldt, A. Promises and challenges of perovskite solar cells. Science 2017, 358, 739-744.
Fabbri, E.; Nachtegaal, M.; Binninger, T.; Cheng, X.; Kim, B. J.; Durst, J.; Bozza, F.; Graule, T.; Schäublin, R.; Wiles, L. et al. Dynamic surface self-reconstruction is the key of highly active perovskite nano-electrocatalysts for water splitting. Nat. Mater. 2017, 16, 925-931.
Royer, S.; Duprez, D.; Can, F.; Courtois, X.; Batiot-Dupeyrat, C.; Laassiri, S.; Alamdari, H. Perovskites as substitutes of noble metals for heterogeneous catalysis: Dream or reality. Chem. Rev. 2014, 114, 10292-10368.
Zhu, Y. L.; Zhou, W.; Yu, J.; Chen, Y. B.; Liu, M. L.; Shao, Z. P. Enhancing electrocatalytic activity of perovskite oxides by tuning cation deficiency for oxygen reduction and evolution reactions. Chem. Mater. 2016, 28, 1691-1697.
Yan, Z. H.; Sun, H. M.; Chen, X.; Fu, X. R.; Chen, C. C.; Cheng, F. Y.; Chen, J. Rapid low-temperature synthesis of perovskite/carbon nanocomposites as superior electrocatalysts for oxygen reduction in Zn-air batteries. Nano Res. , in press, DOI: 10.1007/s12274-017-1869-8.
Zhu, Y. L.; Zhou, W.; Shao, Z. P. Perovskite/carbon composites: Applications in oxygen electrocatalysis. Small. 2017, 13, 1603793.
Suntivich, J.; May, K. J.; Gasteiger, H. A.; Goodenough, J. B.; Shao-Horn, Y. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 2011, 334, 1383-1385.
Suntivich, J.; Gasteiger, H. A.; Yabuuchi, N.; Nakanishi, H.; Goodenough, J. B.; Shao-Horn, Y. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries. Nat. Chem. 2011, 3, 546-550.
Zhu, Y. L.; Zhou, W.; Zhong, Y. J.; Bu, Y. F.; Chen, X. Y.; Zhong, Q.; Liu, M. L.; Shao, Z. P. A perovskite nanorod as bifunctional electrocatalyst for overall water splitting. Adv. Energy Mater. 2017, 7, 1602122.
Mefford, J. T.; Rong, X.; Abakumov, A. M.; Hardin, W. G.; Dai, S.; Kolpak, A. M.; Johnston, K. P.; Stevenson, K. J. Water electrolysis on La1-xSrxCoO3−δ perovskite electrocatalysts. Nat. Commun. 2016, 7, 11053.
Zhou, S. M.; Miao, X. B.; Zhao, X.; Ma, C.; Qiu, Y. H.; Hu, Z. P.; Zhao, J. Y.; Shi, L.; Zeng, J. Engineering electrocatalytic activity in nanosized perovskite cobaltite through surface spin-state transition. Nat. Commun. 2016, 7, 11510.
Chen, G.; Zhou, W.; Guan, D. Q.; Sunarso, J.; Zhu, Y. P.; Hu, X. F.; Zhang, W.; Shao, Z. P. Two orders of magnitude enhancement in oxygen evolution reactivity on amorphous Ba0.5Sr0.5Co0.8Fe0.2O3-δ nanofilms with tunable oxidation state. Sci. Adv. 2017, 3, e1603206.
Zhu, Y. L.; Zhou, W.; Sunarso, J.; Zhong, Y. J.; Shao, Z. P. Phosphorus-doped perovskite oxide as highly efficient water oxidation electrocatalyst in alkaline solution. Adv. Funct. Mater. 2016, 26, 5862-5872.
Grimaud, A.; May, K. J.; Carlton, C. E.; Lee, Y. -L.; Risch, M.; Hong, W. T.; Zhou, J.; Shao-Horn, Y. Double perovskites as a family of highly active catalysts for oxygen evolution in alkaline solution. Nat. Commun. 2013, 4, 2439.
Yagi, S.; Yamada, I.; Tsukasaki, H.; Seno, A.; Murakami, M.; Fujii, H.; Chen, H.; Umezawa, N.; Abe, H.; Nishiyama, N.; Mori, S. Covalency-reinforced oxygen evolution reaction catalyst. Nat. Commun. 2015, 6, 8249.
Shao, Z. P.; Zhou, W.; Zhu, Z. H. Advanced synthesis of materials for intermediate-temperature solid oxide fuel cells. Progress in Mater. Sci. 2012, 57, 804-874.
Zhu, Y. L.; Zhou, W.; Chen, Z. -G.; Chen, Y. B.; Su, C.; Tadé, M. O.; Shao, Z. P. SrNb0.1Co0.7Fe0.2O3−δ perovskite as a next-generation electrocatalyst for oxygen evolution in alkaline solution. Angew. Chem., Int. Ed. 2015, 54, 3897-3901.
Lee, J. J.; Oh, M. Y.; Nahm, K. S. Effect of ball milling on electrocatalytic activity of perovskite La0.6Sr0.4CoO3-δ applied for lithium air battery. J. Electrochem. Soc. 2016, 163, A244-A250.
Hashimoto, S. -I.; Fukuda, Y.; Kuhn, M.; Sato, K.; Yashiro, K.; Mizusaki, J. Thermal and chemical lattice expansibility of La0.6Sr0.4Co1−yFeyO3−δ (y = 0.2, 0.4, 0.6 and 0.8). Solid State Ionics 2011, 186, 37-43.
Heel, A.; Holtappels, P.; Hug, P.; Graule, T. Flame spray synthesis of nanoscale La0.6Sr0.4Co0.2Fe0.8O3−δ and Ba0.5Sr0.5Co0.8Fe0.2O3−δ as cathode materials for intermediate temperature solid oxide fuel cells. Fuel Cells. 2010, 10, 419-432.
Dieterle, L.; Bockstaller, P.; Gerthsen, D.; Hayd, J.; Ivers-Tiffée, E.; Guntow, U. Microstructure of nanoscaled La0.6Sr0.4CoO3-δ cathodes for intermediate-temperature solid oxide fuel cells. Adv. Energy Mater. 2011, 1, 249-258.
Morán-Ruiz, A.; Vidal, K.; Larrañaga, A.; Arriortua, M. I. Chemical compatibility and electrical contact of LaNi0.6Co0.4O3−δ (LNC) between Crofer22APU interconnect and La0.6Sr0.4FeO3 (LSF) cathode for IT-SOFC. Fuel Cells 2013, 13, 398-403.
Natile, M. M.; Poletto, F.; Galenda, A.; Glisenti, A.; Montini, T.; De Rogatis, L.; Fornasiero, P. La0.6Sr0.4Co1-yFeyO3−δ perovskites: Influence of the Co/Fe atomic ratio on properties and catalytic activity toward alcohol steam-reforming. Chem. Mater. 2008, 20, 2314-2327.
Shannon, R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. Section A 1976, 32, 751-767.
Wang, Y. C.; Zhou, T.; Jiang, K.; Da, P. M.; Peng, Z.; Tang, J.; Kong, B.; Cai, W. -B.; Yang, Z. Q.; Zheng, G. F. Reduced mesoporous Co3O4 nanowires as efficient water oxidation electrocatalysts and supercapacitor electrodes. Adv. Energy Mater. 2014, 4, 1400696.
Kruk, M.; Jaroniec, M.; Ko, C. H.; Ryoo, R. Characterization of the porous structure of SBA-15. Chem. Mater. 2000, 12, 1961-1968.
Liu, X. F.; Antonietti, M. Moderating black powder chemistry for the synthesis of doped and highly porous graphene nanoplatelets and their use in electrocatalysis. Adv. Mater. 2013, 25, 6284-6290.
Mao, Y. B.; Banerjee, S.; Wong, S. S. Large-scale synthesis of single-crystalline perovskite nanostructures. J. Am. Chem. Soc. 2003, 125, 15718-15719.
Kang, J. S.; Lee, H. J.; Kim, G.; Kim, D. H.; Dabrowski, B.; Kolesnik, S.; Lee, H.; Kim, J. Y.; Min, B. I. Electronic structure of the cubic perovskite SrMn1−xFexO3 investigated by X-ray spectroscopies. Phys. Rev. B 2008, 78, 154434.
Lin, H. J.; Chin, Y. Y.; Hu, Z.; Shu, G. J.; Chou, F. C.; Ohta, H.; Yoshimura, K.; Hebert, S.; Maignan, A.; Tanaka, A. et al. Local orbital occupation and energy levels of Co in NaxCoO2: A soft X-ray absorption study. Phy. Rev. B 2010, 81, 115138.
Zhang, B.; Zheng, X. L.; Voznyy, O.; Comin, R.; Bajdich, M.; Garcia-Melchor, M.; Han, L. L.; Xu, J. X.; Liu, M.; Zheng, L. R. et al. Homogeneously dispersed multimetal oxygen-evolving catalysts. Science 2016, 352, 333-337.
Hong, W. T.; Stoerzinger, K. A.; Lee, Y. -L.; Giordano, L.; Grimaud, A.; Johnson, A. M.; Hwang, J.; Crumlin, E. J.; Yang, W.; Shao-Horn, Y. Charge-transfer-energy-dependent oxygen evolution reaction mechanisms for perovskite oxides. Energy Environ. Sci. 2017, 10, 2190-2200.
Luo, K.; Roberts, M. R.; Hao, R.; Guerrini, N.; Pickup, D. M.; Liu, Y. S.; Edström, K.; Guo, J.; Chadwick, A. V.; Duda, L. C. et al. Charge-compensation in 3D-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen. Nat. Chem. 2016, 8, 684-691.
Zhang, H.; Liu, J. Y.; Zhao, G. Q.; Gao, Y. J.; Tyliszczak, T.; Glans, P. A.; Guo, J. H.; Ma, D.; Sun, X. H.; Zhong, J. Probing the interfacial interaction in layered-carbon-stabilized iron oxide nanostructures: A soft X-ray spectroscopic study. ACS Appl. Mater. Interfaces 2015, 7, 7863-7868.
Zheng, X. L.; Zhang, B.; De Luna, P.; Liang, Y. F.; Comin, R.; Voznyy, O.; Han, L. L.; de Arquer, F. P. G.; Liu, M.; Dinh, C. T. et al. Theory-driven design of high-valence metal sites for water oxidation confirmed using in situ soft X-ray absorption. Nat. Chem. 2018, 10, 149-154.
Wilson, S. A.; Kroll, T.; Decreau, R. A.; Hocking, R. K.; Lundberg, M.; Hedman, B.; Hodgson, K. O.; Solomon, E. I. Iron L-edge X-ray absorption spectroscopy of oxy-picket fence porphyrin: Experimental insight into Fe-O2 bonding. J. Am. Chem. Soc. 2013, 135, 1124-1136.
Mizokawa, T.; Wakisaka, Y.; Sudayama, T.; Iwai, C.; Miyoshi, K.; Takeuchi, J.; Wadati, H.; Hawthorn, D. G.; Regier, T. Z.; Sawatzky, G. A. Role of oxygen holes in LixCoO2 revealed by soft X-ray spectroscopy. Phy. Rev. Let. 2013, 111, 056404.
Chen, J. -M.; Chin, Y. -Y.; Valldor, M.; Hu, Z. W.; Lee, J. -M.; Haw, S. -C.; Hiraoka, N.; Ishii, H.; Pao, C. -W.; Tsuei, K. -D. et al. A complete high-to-low spin state transition of trivalent cobalt ion in octahedral symmetry in SrCo0.5Ru0.5O3−δ. J. Am. Chem. Soc. 2014, 136, 1514-1519.
Xu, L.; Jiang, Q. Q.; Xiao, Z. H.; Li, X. Y.; Huo, J.; Wang, S. Y.; Dai, L. M. Plasma-engraved Co3O4 nanosheets with oxygen vacancies and high surface area for the oxygen evolution reaction. Angew. Chem. 2016, 128, 5363-5367.