过渡金属氧化物氧还原催化剂的研究进展

doi:10.13208/j.electrochem.180147

摘要/Abstract

摘要： 过渡金属氧化物（TMOs）是阴离子交换膜燃料电池最有前途的氧还原催化剂之一. 目前，TMOs的氧还原活性同铂基催化剂相比仍然有一定的差距，研究如何合成具有高催化活性的TMOs催化剂非常重要. 导电性和本征活性一直被认为是开发高性能TMOs催化剂的两个关键因素，本文着重总结与评述了近年来有关TMOs氧还原催化剂在导电性和本征活性方面的研究进展，尝试提出了未来提高TMOs氧还原催化活性的努力方向.

关键词: 过渡金属氧化物, 氧还原反应, 燃料电池

Abstract: Transition metal oxides (TMOs) based catalysts have become the most promising catalysts to be employed in anion exchange membrane fuel cell for the sluggish oxygen reduction reaction (ORR). However, their ORR activity is still far from that of the Pt-based catalysts. Therefore, it is important to develop high performance TMO based catalysts. Electrical conductivity and intrinsic activity have been regarded as the two keys to affect the ORR activity of the TMOs based catalysts. In this review, we focused on the recent progresses in the fundamental viewpoints on the electrical conductivity and intrinsic activity of the TMOs based ORR catalysts. Accordingly, the strategies to enhance the electrical conductivity and intrinsic activity are also summarized. The electrical conductivity could be reinforced in two ways. On the one hand, by coupling with the conductive materials, the external electrical conductivity of TMOs based catalysts could be elevated strongly. On the other hand, the intrinsic electrical conductivity of TMOs based catalysts could be enhanced by introducing oxygen vacancies or doping other cations or anions into TMOs. For the intrinsic activity of the TMOs based ORR catalysts, the crystal structure modulation for TMOs based catalysts is presented. Besides, the ORR descriptor of TMOs based catalysts, which is important for the future catalysts design, is also concluded in this review. And the conclusions and some future perspectives are also outlined. Although many strategies have been proposed to evaluate the electrical conductivity of TMOs based catalysts, there is still room for the further enhancement when the durability of TMOs based catalysts has been taken into consideration. And the ORR mechanism of TMOs based catalysts also should be further explored. Hence, there is a challenging but desired avenue for the development of the high performance TMOs based catalysts which are expected to be applied into anion exchange membrane fuel cell.

Key words: transition-metal-oxides, oxygen reduction reaction, fuel cell

中图分类号:

O646

王尧，魏子栋. 过渡金属氧化物氧还原催化剂的研究进展[J]. 电化学（中英文）, 2018, 24(5): 427-443.

WANG Yao, WEI Zi-dong. Recent Process in Transition-Metal-Oxide Based Catalysts for Oxygen Reduction Reaction[J]. Journal of Electrochemistry, 2018, 24(5): 427-443.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.180147

https://electrochem.xmu.edu.cn/CN/Y2018/V24/I5/427

参考文献

[1] Nie Y, Li L, Wei Z D. Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction[J]. Chemical Society Reviews, 2015, 44(8): 2168-2201.
[2] Ding W(丁炜), Zhang X(张雪), Li L(李莉), et al. Recent progress in heteroatoms doped carbon materials a catalyst for oxygen reduction reaction[J]. Journal of Electrochemistry(电化学), 2014, 20(5): 426-438.
[3] Xie X H（谢小红）, Wei Z D（魏子栋）. Enhancing stability of PEM fuel cell catalysts via support changing[J]. Journal of Electrochemistry(电化学), 2015, 21(3): 221-233.
[4] Zhang Y（张云）, Hu J S（胡劲松）, Jiang W J（江文杰）, et al. Boosting electrocatalytic activity of nitrogen-doped graphene/carbon nanotube composite for oxygen reduction reaction[J]. Journal of Electrochemistry(电化学), 2014, 20(5): 401-409.
[5] He W, Wang Y, Jiang C, et al. Structural effects of a carbon matrix in non-precious metal O₂-reduction electrocatalysts[J]. Chemical Society Reviews, 2016, 45(9): 2396-2409.
[6] Lim B, Jiang M, Camargo P H C, et al. Pd-Pt bimetallic nanodendrites with high activity for oxygen reduction[J]. Science, 2009, 324(5932): 1302-1305.
[7] Huang X Q, Zhao Z P, Cao L, et al. High-performance transition metal-doped Pt₃Ni octahedra for oxygen reduction reaction[J]. Science, 2015, 348(6240): 1230-1234.
[8] Nie Y, Chen S G, Ding W, et al. Pt/C trapped in activated graphitic carbon layers as a highly durable electrocatalyst for the oxygen reduction reaction[J]. Chemical Communications, 2014, 50(97): 15431-15434.
[9] Jiang W J, Gu L, Li L, et al. Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe₃C nanoparticles boost the activity of Fe-Nx[J]. Journal of the American Chemical Society, 2016, 138(10): 3570-3578.
[10] Wang Y, Nie Y, Ding W, et al. Unification of catalytic oxygen reduction and hydrogen evolution reactions: Highly dispersive Co nanoparticles encapsulated inside Co and nitrogen co-doped carbon[J]. Chemical Communications, 2015, 51(43): 8942-8945.
[11] Wang Y, Ding W, Chen S G, et al. Cobalt carbonate hydroxide/C: An efficient dual electrocatalyst for oxygen reduction/evolution reactions[J]. Chemical Communications, 2014, 50(98): 15529-15532.
[12] Wang Y, Chen W, Nie Y, et al. Construction of a porous nitrogen-doped carbon nanotube with open-ended channels to effectively utilize the active sites for excellent oxygen reduction reaction activity[J]. Chemical Communications, 2017, 53(83): 11426-11429.
[13] Wu R, Chen S G, Zhang Y L, et al. Controlled synthesis of hollow micro/meso-pore nitrogen-doped carbon with tunable wall thickness and specific surface area as efficient electrocatalysts for oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2016, 4(7): 2433-2437.
[14] Ding W, Li L, Xiong K, et al. Shape fixing via salt recrystallization: A morphology-controlled approach to convert nanostructured polymer to carbon nanomaterial as a highly active catalyst for oxygen reduction reaction[J]. Journal of the American Chemical Society, 2015, 137(16): 5414-5420.
[15] Zhang Y, Huang L B, Jiang W J, et al. Sodium chloride-assisted green synthesis of a 3D Fe-N-C hybrid as a highly active electrocatalyst for the oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2016, 4(20): 7781-7787.
[16] Li W, Ding W, Wu G P, et al. Cobalt modified two-dimensional polypyrrole synthesized in a flat nanoreactor for the catalysis of oxygen reduction[J]. Chemical Engineering Science, 2015, 135(S1): 45-51.
[17] Ding W, Wei Z D, Chen S G, et al. Space-confinement-induced synthesis of pyridinic-and pyrrolic-nitrogen-doped graphene for the catalysis of oxygen reduction[J]. Angewandte Chemie-International Edition, 2013, 52(45): 11755-11759
[18] He Y, Zhang J F, He G W, et al. Ultrathin Co₃O₄ nanofilm as an efficient bifunctional catalyst for oxygen evolution and reduction reaction in rechargeable zinc-air batteries[J]. Nanoscale, 2017, 9(25): 8623-8630.
[19] Liu L L, Guo H P, Hou Y Y, et al. A 3D hierarchical porous Co₃O₄ nanotube network as an efficient cathode for rechargeable lithium-oxygen batteries[J]. Journal of Materials Chemistry A, 2017, 5(28): 14673-14681.
[20] Ge X M, Sumboja A, Wuu D, et al. Oxygen reduction in alkaline media: From mechanisms to recent advances of catalysts[J]. ACS Catalysis, 2015, 5(8): 4643-4667.
[21] Setzler B P, Zhuang Z, Wittkopf J A, et al. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells[J]. Nature Nanotechnology, 2016, 11(12): 1020-1025.
[22] Li Q, Cao R, Cho J, et al. Nanocarbon electrocatalysts for oxygen reduction in alkaline media for advanced energy conversion and storage[J]. Advanced Energy Materials, 2014, 4(6): 1301415.
[23] Kumar K, Canaff C, Rousseau J, et al. Effect of the oxide-carbon heterointerface on the activity of Co₃O₄/NRGO nanocomposites toward ORR and OER[J]. The Journal of Physical Chemistry C, 2016, 120(15): 7949-7958.
[24] Cheng Y, Dou S, Veder J P, et al. Efficient and durable bifunctional oxygen catalysts based on NiFeO@MnO_x core-shell structures for rechargeable Zn-air batteries[J]. ACS Applied Materials & Interfaces, 2017, 9(9): 8121-8133.
[25] Guan C, Sumboja A, Wu H J, et al. Hollow Co₃O₄ nano-sphere embedded in carbon arrays for stable and flexible solid-state zinc-air batteries[J]. Advanced Materials, 2017, 29(44): 1704117.
[26] Zhang C, Antonietti M, Fellinger T P. Blood ties: Co₃O₄ decorated blood derived carbon as a superior bifunctional electrocatalyst[J]. Advanced Functional Materials, 2014, 24(48): 7655-7665.
[27] Wang X J, Li Y, Jin T, et al. Electrospun thin-walled CuCo₂O₄@C nanotubes as bifunctional oxygen electrocatalysts for rechargeable Zn-air batteries[J]. Nano Letters, 2017, 17(12): 7989-7994.
[28] Kim G P, Sun H H, Manthiram A. Design of a sectionalized MnO₂-Co₃O₄ electrode via selective electrodeposition of metal ions in hydrogel for enhanced electrocatalytic activity in metal-air batteries[J]. Nano Energy, 2016, 30: 130-137.
[29] Wu C, Zhang Y H, Dong D, et al. Co₉S₈ nanoparticles anchored on nitrogen and sulfur dual-doped carbon nano-sheets as highly efficient bifunctional electrocatalyst for oxygen evolution and reduction reactions[J]. Nanoscale, 2017, 9(34): 12432-12440.
[30] Sidik R A, Anderson A B. Co₉S₈ as a catalyst for electroreduction of O₂: Quantum chemistry predictions[J]. The Journal of Physical Chemistry B, 2006, 110(2): 936-941.
[31] Balamurugan J, Peera S G, Guo M, et al. A hierarchical 2D Ni-Mo-S nanosheet@nitrogen doped graphene hybrid as a Pt-free cathode for high-performance dyesensitized solar cells and fuel cells[J]. Journal of Materials Chemistry A, 2017, 5(34): 17896-17908.
[32] Falkowski J M, Concannon N M, Yan B, et al. Heazlewoodite, Ni₃S₂: A potent catalyst for oxygen reduction to water under benign conditions[J]. Journal of the American Chemical Society, 2015, 137(25): 7978-7981.
[33] Giordano C, Antonietti M. Synthesis of crystalline metal nitride and metal carbide nanostructures by sol-gel chemistry[J]. Nano Today, 2011, 6(4): 366-380.
[34] Huang H, Du C, Wu S, et al. Thermolytical entrapment of ultrasmall MoC nanoparticles into 3D frameworks of nitrogen-rich graphene for efficient oxygen reduction[J]. The Journal of Physical Chemistry C, 2016, 120(29): 15707-15713.
[35] Wang H, Wang W, Xu Y Y, et al. Ball-milling synthesis of Co₂P nanoparticles encapsulated in nitrogen doped hollow carbon rods as efficient electrocatalysts[J]. Journal of Materials Chemistry A, 2017, 5(33): 17563-17569.
[36] Lei M, Wang J, Li J R, et al. Emerging methanol-tolerant AlN nanowire oxygen reduction electrocatalyst for alkaline direct methanol fuel cell[J]. Scientific Reports, 2014, 4: 6013.
[37] Lee K J, Shin D Y, Byeon A, et al. Hierarchical cobalt-nitride and -oxide co-doped porous carbon nanostructures for highly efficient and durable bifunctional oxygen reaction electrocatalysts[J]. Nanoscale, 2017, 9(41): 15846-15855.
[38] Zhao D, Cui Z, Wang S, et al. VN hollow spheres assembled from porous nanosheets for high-performance lithium storage and the oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2016, 4(20): 7914-7923.
[39] Zeng S, Chen H, Wang H, et al. Crosslinked carbon nanotube aerogel films decorated with cobalt oxides for flexible rechargeable Zn-air batteries[J]. Small, 2017, 13(29): UNSP 1700518.
[40] Wang Z J, Li B, Ge X M, et al. Co@Co₃O₄@PPD core@ bishell nanoparticle-based composite as an efficient electrocatalyst for oxygen reduction reaction[J]. Small, 2016, 12(19): 2580-2587.
[41] Niu Y L, Huang X Q, Wu X S, et al. One-pot synthesis of Co/N-doped mesoporous graphene with embedded Co/CoO_x nanoparticles for efficient oxygen reduction reaction[J]. Nanoscale, 2017, 9(29): 10233-10239.
[42] An L, Yan H J, Chen X, et al. Catalytic performance and mechanism of N-CoTi@ CoTiO₃ catalysts for oxygen reduction reaction[J]. Nano Energy, 2016, 20: 134-143.
[43] Lambert T N, Vigil J A, White S E, et al. Understanding the effects of cationic dopants on α-MnO₂ oxygen reduction reaction electrocatalysis[J]. The Journal of Physical Chemistry C, 2017, 121(5): 2789-2797.
[44] He L W, Wang Y W, Wang F, et al. Influence of Cu²⁺ doping concentration on the catalytic activity of CuxCo_3-xO₄ for rechargeable Li-O₂ batteries[J]. Journal of Materials Chemistry A, 2017, 5(35): 18569-18576.
[45] Tompsett D A, Parker S C, Islam M S. Rutile (β-)MnO₂ surfaces and vacancy formation for high electrochemical and catalytic performance[J]. Journal of the American Chemical Society, 2014, 136(4): 1418-1426.
[46] Luo Z, Irtem E, [1] Nie Y, Li L, Wei Z D. Recent advancements in Pt and Pt-free catalysts for oxygen reduction reaction[J]. Chemical Society Reviews, 2015, 44(8): 2168-2201.
[2] Ding W(丁炜), Zhang X(张雪), Li L(李莉), et al. Recent progress in heteroatoms doped carbon materials a catalyst for oxygen reduction reaction[J]. Journal of Electrochemistry(电化学), 2014, 20(5): 426-438.
[3] Xie X H（谢小红）, Wei Z D（魏子栋）. Enhancing stability of PEM fuel cell catalysts via support changing[J]. Journal of Electrochemistry(电化学), 2015, 21(3): 221-233.
[4] Zhang Y（张云）, Hu J S（胡劲松）, Jiang W J（江文杰）, et al. Boosting electrocatalytic activity of nitrogen-doped graphene/carbon nanotube composite for oxygen reduction reaction[J]. Journal of Electrochemistry(电化学), 2014, 20(5): 401-409.
[5] He W, Wang Y, Jiang C, et al. Structural effects of a carbon matrix in non-precious metal O₂-reduction electrocatalysts[J]. Chemical Society Reviews, 2016, 45(9): 2396-2409.
[6] Lim B, Jiang M, Camargo P H C, et al. Pd-Pt bimetallic nanodendrites with high activity for oxygen reduction[J]. Science, 2009, 324(5932): 1302-1305.
[7] Huang X Q, Zhao Z P, Cao L, et al. High-performance transition metal-doped Pt₃Ni octahedra for oxygen reduction reaction[J]. Science, 2015, 348(6240): 1230-1234.
[8] Nie Y, Chen S G, Ding W, et al. Pt/C trapped in activated graphitic carbon layers as a highly durable electrocatalyst for the oxygen reduction reaction[J]. Chemical Communications, 2014, 50(97): 15431-15434.
[9] Jiang W J, Gu L, Li L, et al. Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe₃C nanoparticles boost the activity of Fe-Nx[J]. Journal of the American Chemical Society, 2016, 138(10): 3570-3578.
[10] Wang Y, Nie Y, Ding W, et al. Unification of catalytic oxygen reduction and hydrogen evolution reactions: Highly dispersive Co nanoparticles encapsulated inside Co and nitrogen co-doped carbon[J]. Chemical Communications, 2015, 51(43): 8942-8945.
[11] Wang Y, Ding W, Chen S G, et al. Cobalt carbonate hydroxide/C: An efficient dual electrocatalyst for oxygen reduction/evolution reactions[J]. Chemical Communications, 2014, 50(98): 15529-15532.
[12] Wang Y, Chen W, Nie Y, et al. Construction of a porous nitrogen-doped carbon nanotube with open-ended channels to effectively utilize the active sites for excellent oxygen reduction reaction activity[J]. Chemical Communications, 2017, 53(83): 11426-11429.
[13] Wu R, Chen S G, Zhang Y L, et al. Controlled synthesis of hollow micro/meso-pore nitrogen-doped carbon with tunable wall thickness and specific surface area as efficient electrocatalysts for oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2016, 4(7): 2433-2437.
[14] Ding W, Li L, Xiong K, et al. Shape fixing via salt recrystallization: A morphology-controlled approach to convert nanostructured polymer to carbon nanomaterial as a highly active catalyst for oxygen reduction reaction[J]. Journal of the American Chemical Society, 2015, 137(16): 5414-5420.
[15] Zhang Y, Huang L B, Jiang W J, et al. Sodium chloride-assisted green synthesis of a 3D Fe-N-C hybrid as a highly active electrocatalyst for the oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2016, 4(20): 7781-7787.
[16] Li W, Ding W, Wu G P, et al. Cobalt modified two-dimensional polypyrrole synthesized in a flat nanoreactor for the catalysis of oxygen reduction[J]. Chemical Engineering Science, 2015, 135(S1): 45-51.
[17] Ding W, Wei Z D, Chen S G, et al. Space-confinement-induced synthesis of pyridinic-and pyrrolic-nitrogen-doped graphene for the catalysis of oxygen reduction[J]. Angewandte Chemie-International Edition, 2013, 52(45): 11755-11759
[18] He Y, Zhang J F, He G W, et al. Ultrathin Co₃O₄ nanofilm as an efficient bifunctional catalyst for oxygen evolution and reduction reaction in rechargeable zinc-air batteries[J]. Nanoscale, 2017, 9(25): 8623-8630.
[19] Liu L L, Guo H P, Hou Y Y, et al. A 3D hierarchical porous Co₃O₄ nanotube network as an efficient cathode for rechargeable lithium-oxygen batteries[J]. Journal of Materials Chemistry A, 2017, 5(28): 14673-14681.
[20] Ge X M, Sumboja A, Wuu D, et al. Oxygen reduction in alkaline media: From mechanisms to recent advances of catalysts[J]. ACS Catalysis, 2015, 5(8): 4643-4667.
[21] Setzler B P, Zhuang Z, Wittkopf J A, et al. Activity targets for nanostructured platinum-group-metal-free catalysts in hydroxide exchange membrane fuel cells[J]. Nature Nanotechnology, 2016, 11(12): 1020-1025.
[22] Li Q, Cao R, Cho J, et al. Nanocarbon electrocatalysts for oxygen reduction in alkaline media for advanced energy conversion and storage[J]. Advanced Energy Materials, 2014, 4(6): 1301415.
[23] Kumar K, Canaff C, Rousseau J, et al. Effect of the oxide-carbon heterointerface on the activity of Co₃O₄/NRGO nanocomposites toward ORR and OER[J]. The Journal of Physical Chemistry C, 2016, 120(15): 7949-7958.
[24] Cheng Y, Dou S, Veder J P, et al. Efficient and durable bifunctional oxygen catalysts based on NiFeO@MnO_x core-shell structures for rechargeable Zn-air batteries[J]. ACS Applied Materials & Interfaces, 2017, 9(9): 8121-8133.
[25] Guan C, Sumboja A, Wu H J, et al. Hollow Co₃O₄ nano-sphere embedded in carbon arrays for stable and flexible solid-state zinc-air batteries[J]. Advanced Materials, 2017, 29(44): 1704117.
[26] Zhang C, Antonietti M, Fellinger T P. Blood ties: Co₃O₄ decorated blood derived carbon as a superior bifunctional electrocatalyst[J]. Advanced Functional Materials, 2014, 24(48): 7655-7665.
[27] Wang X J, Li Y, Jin T, et al. Electrospun thin-walled CuCo₂O₄@C nanotubes as bifunctional oxygen electrocatalysts for rechargeable Zn-air batteries[J]. Nano Letters, 2017, 17(12): 7989-7994.
[28] Kim G P, Sun H H, Manthiram A. Design of a sectionalized MnO₂-Co₃O₄ electrode via selective electrodeposition of metal ions in hydrogel for enhanced electrocatalytic activity in metal-air batteries[J]. Nano Energy, 2016, 30: 130-137.
[29] Wu C, Zhang Y H, Dong D, et al. Co9S8 nanoparticles anchored on nitrogen and sulfur dual-doped carbon nano-sheets as highly efficient bifunctional electrocatalyst for oxygen evolution and reduction reactions[J]. Nanoscale, 2017, 9(34): 12432-12440.
[30] Sidik R A, Anderson A B. Co₉S₈ as a catalyst for electroreduction of O₂: Quantum chemistry predictions[J]. The Journal of Physical Chemistry B, 2006, 110(2): 936-941.
[31] Balamurugan J, Peera S G, Guo M, et al. A hierarchical 2D Ni-Mo-S nanosheet@nitrogen doped graphene hybrid as a Pt-free cathode for high-performance dyesensitized solar cells and fuel cells[J]. Journal of Materials Chemistry A, 2017, 5(34): 17896-17908.
[32] Falkowski J M, Concannon N M, Yan B, et al. Heazlewoodite, Ni₃S₂: A potent catalyst for oxygen reduction to water under benign conditions[J]. Journal of the American Chemical Society, 2015, 137(25): 7978-7981.
[33] Giordano C, Antonietti M. Synthesis of crystalline metal nitride and metal carbide nanostructures by sol-gel chemistry[J]. Nano Today, 2011, 6(4): 366-380.
[34] Huang H, Du C, Wu S, et al. Thermolytical entrapment of ultrasmall MoC nanoparticles into 3D frameworks of nitrogen-rich graphene for efficient oxygen reduction[J]. The Journal of Physical Chemistry C, 2016, 120(29): 15707-15713.
[35] Wang H, Wang W, Xu Y Y, et al. Ball-milling synthesis of Co₂P nanoparticles encapsulated in nitrogen doped hollow carbon rods as efficient electrocatalysts[J]. Journal of Materials Chemistry A, 2017, 5(33): 17563-17569.
[36] Lei M, Wang J, Li J R, et al. Emerging methanol-tolerant AlN nanowire oxygen reduction electrocatalyst for alkaline direct methanol fuel cell[J]. Scientific Reports, 2014, 4: 6013.
[37] Lee K J, Shin D Y, Byeon A, et al. Hierarchical cobalt-nitride and -oxide co-doped porous carbon nanostructures for highly efficient and durable bifunctional oxygen reaction electrocatalysts[J]. Nanoscale, 2017, 9(41): 15846-15855.
[38] Zhao D, Cui Z, Wang S, et al. VN hollow spheres assembled from porous nanosheets for high-performance lithium storage and the oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2016, 4(20): 7914-7923.
[39] Zeng S, Chen H, Wang H, et al. Crosslinked carbon nanotube aerogel films decorated with cobalt oxides for flexible rechargeable Zn-air batteries[J]. Small, 2017, 13(29): UNSP 1700518.
[40] Wang Z J, Li B, Ge X M, et al. Co@Co₃O₄@PPD core@ bishell nanoparticle-based composite as an efficient electrocatalyst for oxygen reduction reaction[J]. Small, 2016, 12(19): 2580-2587.
[41] Niu Y L, Huang X Q, Wu X S, et al. One-pot synthesis of Co/N-doped mesoporous graphene with embedded Co/CoO_x nanoparticles for efficient oxygen reduction reaction[J]. Nanoscale, 2017, 9(29): 10233-10239.
[42] An L, Yan H J, Chen X, et al. Catalytic performance and mechanism of N-CoTi@ CoTiO₃ catalysts for oxygen reduction reaction[J]. Nano Energy, 2016, 20: 134-143.
[43] Lambert T N, Vigil J A, White S E, et al. Understanding the effects of cationic dopants on α-MnO2 oxygen reduction reaction electrocatalysis[J]. The Journal of Physical Chemistry C, 2017, 121(5): 2789-2797.
[44] He L W, Wang Y W, Wang F, et al. Influence of Cu²⁺ doping concentration on the catalytic activity of Cu_xCo_3-xO₄ for rechargeable Li-O₂ batteries[J]. Journal of Materials Chemistry A, 2017, 5(35): 18569-18576.
[45] Tompsett D A, Parker S C, Islam M S. Rutile (β-)MnO2 surfaces and vacancy formation for high electrochemical and catalytic performance[J]. Journal of the American Chemical Society, 2014, 136(4): 1418-1426.
[46] Luo Z, Irtem E, Ibaánñez M, et al. Mn₃O₄@CoMn₂O₄-Co_xO_y nanoparticles: Partial cation exchange synthesis and electrocatalytic properties toward the oxygen reduction and evolution reactions[J]. ACS Applied Materials & Interfaces, 2016, 8(27): 17435-17444.
[47] Lei K X, Han X P, Hu Y X, et al. Chemical etching of manganese oxides for electrocatalytic oxygen reduction reaction[J]. Chemical Communications, 2015, 51(58): 11599-11602.
[48] Zhu Y L, Zhou W, Yu J, et al. Enhancing electrocatalytic activity of perovskite oxides by tuning cation deficiency for oxygen reduction and evolution reactions[J]. Chemistry of Materials, 2016, 28(6): 1691-1697.
[49] Ma T Y, Zheng Y, Dai S, et al. Mesoporous MnCo₂O₄ with abundant oxygen vacancy defects as high-performance oxygen reduction catalysts[J]. Journal of Materials Chemistry A, 2014, 2(23): 8676-8682.
[50] Kan D, Orikasa Y, Nitta K, et al. Overpotential-induced introduction of oxygen vacancy in La_0.67Sr_0.33MnO₃ surface and its impact on oxygen reduction reaction catalytic activity in alkaline solution[J]. The Journal of Physical Chemistry C, 2016, 120(11): 6006-6010.
[51] Guo C X, Zheng Y, Ran J R, et al. Engineering high-
energy interfacial structures for high-performance oxygen-involving electrocatalysis[J]. Angewandte Chemie International Edition, 2017, 56(29): 8539-8543.
[52] Kuo C H, Mosa I M, Thanneeru S, et al. Facet-dependent catalytic activity of MnO electrocatalysts for oxygen reduction and oxygen evolution reactions[J]. Chemical Communications, 2015, 51(27): 5951-5954.
[53] Indra A, Menezes P W, Sahraie N R, et al. Unification of catalytic water oxidation and oxygen reduction reactions: Amorphous beat crystalline cobalt iron oxides[J]. Journal of the American Chemical Society, 2014, 136(50): 17530-17536.
[54] Tominaka S, Ishihara A, Nagai T, et al. Noncrystalline titanium oxide catalysts for electrochemical oxygen reduction reactions[J]. ACS Omega, 2017, 2(8): 5209-5214.
[55] Dong C, Liu Z W, Liu J Y, et al. Modest oxygen-defective amorphous manganese-based nanoparticle mullite with superior overall electrocatalytic performance for oxygen reduction reaction[J]. Small, 2017, 13(16). UNSP 1603903.
[56] Liang Y Y, Li Y G, Wang H L, et al. Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction[J]. Nature Materials, 2011, 10(10): 780-786.
[57] Liang Y Y, Wang H L , Zhou J G, et al. Covalent hybrid of spinel manganese-cobalt oxide and graphene as advanced oxygen reduction electrocatalysts[J]. Journal of the American Chemical Society, 2012, 134(7): 3517-3523.
[58] Liang Y Y, Wang H L, Diao P, et al. Oxygen reduction electrocatalyst based on strongly coupled cobalt oxide nanocrystals and carbon nanotubes[J]. Journal of the American Chemical Society, 2012, 134(38): 15849-15857.
[59] Wu G P, Wang J, Ding W, et al. A strategy to promote the electrocatalytic activity of spinels for oxygen reduction by structure reversal[J]. Angewandte Chemie International Edition, 2016, 55(4): 1340-1344.
[60] Zhan Y, Xu C H, Lu M H, et al. Mn and Co co-substituted Fe₃O₄ nanoparticles on nitrogen-doped reduced graph-
ene oxide for oxygen electrocatalysis in alkaline solution[J]. Journal of Materials Chemistry A, 2014, 2(38): 16217-16223.
[61] Tong X L, Xia X H, Guo C X, et al. Efficient oxygen reduction reaction using mesoporous Ni-doped Co₃O₄ nanowire array electrocatalysts[J]. Journal of Materials Chemistry A, 2015, 3(36): 18372-18379.
[62] Davis D J, Lambert T N, Vigil J A, et al. Role of Cu-ion doping in Cu-α-MnO₂ nanowire electrocatalysts for the oxygen reduction reaction[J]. The Journal of Physical Chemistry C, 2014, 118(31): 17342-17350.
[63] Song W Q, Ren Z, Chen S Y, et al. Ni-and Mn-promoted mesoporous Co₃O₄: A stable bifunctional catalyst with surface-structure-dependent activity for oxygen reduction reaction and oxygen evolution reaction[J]. ACS Applied Materials & Interfaces, 2016, 8(32): 20802-20813.
[64] Lyu Y Q, Chen C, Gao Y, et al. In situ preparation of Ca_0.5Mn_0.5O/C as a novel high-activity catalyst for the oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2016, 4(48): 19147-19153.
[65] Hua B, Sun Y F, Li M, et al. Stabilizing double perovskite for effective bifunctional oxygen electrocatalysis in alkaline conditions[J]. Chemistry of Materials, 2017, 29(15): 6228-6237.
[66] Si C H, Zhang Y L, Zhang C Q, et al. Mesoporous nanostructured spinel-type MFe₂O₄ (M= Co, Mn, Ni) oxides as efficient bi-functional electrocatalysts towards oxygen reduction and oxygen evolution[J]. Electrochimica Acta, 2017, 245: 829-838.
[67] Yu Y, Wang X F, Gao W Y, et al. Trivalent cerium-preponderant CeO₂/graphene sandwich-structured nanocomposite with greatly enhanced catalytic activity for the oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2017, 5(14): 6656-6663.
[68] He X B, Yin F X, Li Y H, et al. NiMnO₃/NiMn₂O₄ oxides synthesized via the aid of pollen: Ilmenite/spinel hybrid nanoparticles for highly efficient bifunctional oxygen electrocatalysis[J]. ACS Applied Materials & Interfaces, 2016, 8(40): 26740-26757.
[69] Liu J, Jiang L H, Zhang B S, et al. Controllable synthesis of cobalt monoxide nanoparticles and the size-dependent activity for oxygen reduction reaction[J]. ACS Catalysis, 2014, 4(9): 2998-3001.
[70] Wang C W, Zhao Z, Li X F, et al. Three-dimensional framework of graphene nanomeshes shell/Co₃O₄ synthesized as superior bifunctional electrocatalyst for zinc-air batteries[J]. ACS Applied Materials & Interfaces, 2017, 9(47): 41273-41283.
[71] Xu J X, Yu Q M, Wu C X, et al. Oxygen reduction electrocatalysts based on spatially confined cobalt monoxide nanocrystals on holey N-doped carbon nanowires: The enlarged interfacial area for performance improvement[J]. Journal of Materials Chemistry A, 2015, 3(43): 21647-21654.
[72] Chen R W, Yan J, Liu Y, et al. Three-dimensional nitrogen-doped graphene/MnO nanoparticle hybrids as a high-performance catalyst for oxygen reduction reaction[J]. The Journal of Physical Chemistry C, 2015, 119(15): 8032-8037.
[73] Du J, Chen C C, Cheng F Y, et al. Rapid synthesis and efficient electrocatalytic oxygen reduction/evolution reaction of CoMn₂O₄ nanodots supported on graphene[J]. Inorganic Chemistry, 2015, 54(11): 5467-5474.
[74] Tong X L, Chen S, Guo C X, et al. Mesoporous NiCo₂O₄ nanoplates on three-dimensional graphene foam as an efficient electrocatalyst for the oxygen reduction reaction[J]. ACS Applied Materials & Interfaces, 2016, 8(42): 28274-28282.
[75] Liu Z Q, Cheng H, Li N, et al. ZnCo₂O₄ quantum dots anchored on nitrogen-doped carbon nanotubes as reversible oxygen reduction/evolution electrocatalysts[J]. Advanced Materials, 2016, 28(19): 3777-3784.
[76] Cao S Y, Han N, Han J, et al. Mesoporous hybrid shells of carbonized polyaniline/Mn₂O₃ as non-precious efficient oxygen reduction reaction catalyst[J]. ACS Applied Materials & Interfaces, 2016, 8(9): 6040-6050.
[77] Cheng H, Li M L, Su C Y, et al. Cu-Co bimetallic oxide quantum dot decorated nitrogen-doped carbon nanotubes: A high-efficiency bifunctional oxygen electrode for Zn-air batteries[J]. Advanced Functional Materials, 2017, 27(30): 1701833.
[78] El-Nagar G A, Hassan M A, Fetyan A, et al. A promising N-doped carbon-metal oxide hybrid electrocatalyst derived from crustacean’s shells: Oxygen reduction and oxygen evolution[J]. Applied Catalysis B: Environmental, 2017, 214: 137-147.
[79] Jin S, Li C, Shrestha L K, et al. Simple fabrication of titanium dioxide/N-doped carbon hybrid material as non-precious metal electrocatalyst for the oxygen reduction reaction[J]. ACS Applied Materials & Interfaces, 2017, 9(22): 18782-18789.
[80] Singh S K, Kashyap V, Manna N, et al. Efficient and durable oxygen reduction electrocatalyst based on comn-alloy oxide nanoparticles supported over N-doped porous graphene[J]. ACS Catalysis, 2017, 7(10): 6700-6710.
[81] Bag S, Roy K, Gopinath C S, et al. Facile single-step synthesis of nitrogen-doped reduced graphene oxide-Mn₃O₄ hybrid functional material for the electrocatalytic reduction of oxygen[J]. ACS Applied Materials & Interfaces, 2014, 6(4): 2692-2699.
[82] Liu X, Liu W, Ko M, et al. Metal (Ni, Co)-metal oxides/graphene nanocomposites as multifunctional electrocatalysts[J]. Advanced Functional Materials, 2015, 25(36): 5799-5808.
[83] Liu X, Park M, Kim M G, et al. Integrating NiCo alloys with their oxides as efficient bifunctional cathode catalysts for rechargeable zinc-air batteries[J]. Angewandte Chemie International Edition, 2015, 54(33): 9654-9658.
[84] Xia W, Zou R Q, An L, et al. A metal-organic framework route to in situ encapsulation of Co@Co₃O₄@C core@bishell nanoparticles into a highly ordered porous carbon matrix for oxygen reduction[J]. Energy & Environmental Science, 2015, 8(2): 568-576.
[85] Wang J, Wu Z X, Han L L, et al. Supramolecular gel-assisted synthesis of double shelled Co@CoO@N-C/C nanoparticles with synergistic electrocatalytic activity for the oxygen reduction reaction[J]. Nanoscale, 2016, 8(8): 4681-4687.
[86] Fu G T, Yan X X, Chen Y F, et al. Boosting bifunctional oxygen electrocatalysis with 3D graphene aerogel-supported Ni/MnO particles[J]. Advanced Materials, 2018, 30(5): 1704609.
[87] Guo Z Y, Wang F M, Xia Y, et al. In situ encapsulation of core-shell-structured Co@Co₃O₄ into nitrogen-doped carbon polyhedra as a bifunctional catalyst for rechargeable Zn-air batteries[J]. Journal of Materials Chemistry A, 2018, 6(4): 1443-1453.
[88] Boppella R, Lee J E, Mota F M, et al. Composite hollow nanostructures composed of carbon-coated Ti3+ self-doped TiO₂-reduced graphene oxide as an efficient electrocatalyst for oxygen reduction[J]. Journal of Materials Chemistry A, 2017, 5(15): 7072-7080.
[89] Vigil J A, Lambert T N, Eldred K. Electrodeposited MnOx/PEDOT composite thin films for the oxygen reduction reaction[J]. ACS Applied Materials & Interfaces, 2015, 7(41): 22745-22750.
[90] Du J, Zhang T R, Cheng F Y, et al. Nonstoichiometric perovskite CaMnO₃-δ for oxygen electrocatalysis with high activity[J]. Inorganic Chemistry, 2014, 53(17): 9106-9114.
[91] Yu J, Chen G, Sunarso J, et al. Cobalt oxide and cobalt-graphitic carbon core-shell based catalysts with remarkably high oxygen reduction reaction activity[J]. Advanced Science, 2016, 3(9): 1600060.
[92] Cheng H, Xu K, Xing L L, et al. Manganous oxide nano-particles encapsulated in few-layer carbon as an efficient electrocatalyst for oxygen reduction in alkaline media[J]. Journal of Materials Chemistry A, 2016, 4(30): 11775-11781.
[93] Vigil J A, Lambert T N, Duay J, et al. Nanoscale carbon modified α-MnO₂ nanowires: Highly active and stable oxygen reduction electrocatalysts with low carbon content[J]. ACS Applied Materials & Interfaces, 2018, 10(2): 2040-2050.
[94] Chen D J, Wang J, Zhang Z B, et al. Boosting oxygen reduction/evolution reaction activities with layered perovskite catalysts[J]. Chemical Communications, 2016, 52(71): 10739-10742.
[95] Yan L T, Lin Y, Yu X, et al. La_0.8Sr_0.2MnO₃-based perovskite nanoparticles with the A-site deficiency as high performance bifunctional oxygen catalyst in alkaline solution[J]. ACS Applied Materials & Interfaces, 2017, 9(28): 23820-23827.
[96] Lyu Y Q, Ciucci F. Activating the bifunctionality of a perovskite oxide toward oxygen reduction and oxygen evolution reactions[J]. ACS Applied Materials & Interfaces, 2017, 9(41): 35829-35836.
[97] Ling T, Yan D Y, Jiao Y, et al. Engineering surface atomic structure of single-crystal cobalt (II) oxide nanorods for superior electrocatalysis[J]. Nature Communications, 2016, 7: 12876.
[98] Su Y H, Jiang H L, Zhu Y H, et al. Enriched graphitic N-doped carbon-supported Fe₃O₄ nanoparticles as efficient electrocatalysts for oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2014, 2(20): 7281-7287.
[99] Ren J T, Yuan G G, Weng C C, et al. Rationally designed Co₃O₄-C nanowire arrays on Ni foam derived from metal organic framework as reversible oxygen evolution electrodes with enhanced performance for Zn-air batteries[J]. ACS Sustainable Chemistry & Engineering, 2017, 6(1): 707-718.
[100] Bin D, Guo Z, Tamirat A G, et al. Crab-shell induced synthesis of ordered macroporous carbon nanofiber arrays coupled with MnCo₂O₄ nanoparticles as bifunctional oxygen catalysts for rechargeable Zn-air batteries[J]. Nanoscale, 2017, 9(31): 11148-11157.
[101] Retuerto M, Pereira A G, Pérez-Alonso F J, et al. Structural effects of LaNiO₃ as electrocatalyst for the oxygen reduction reaction[J]. Applied Catalysis B: Environmental, 2017, 203: 363-371.
[102] Ma T Y, Dai S, Jaroniec M, et al. Metal-organic framework derived hybrid Co₃O₄-carbon porous nanowire arrays as reversible oxygen evolution electrodes[J]. Journal of the American Chemical Society, 2014, 136(39): 13925-13931.
[103] Li T T, Xue B, Wang B W, et al. Tubular monolayer superlattices of hollow Mn₃O₄ nanocrystals and their oxygen reduction activity[J]. Journal of the American Chemical Society, 2017, 139(35): 12133-12136.
[104] Liu X X, Zang J B, Chen L, et al. A microwave-assisted synthesis of CoO@Co core-shell structures coupled with N-doped reduced graphene oxide used as a superior multi-functional electrocatalyst for hydrogen evolution, oxygen reduction and oxygen evolution reactions[J]. Journal of Materials Chemistry A, 2017, 5(12): 5865-5872.
[105] Ning R, Tian J, Asiri A M, et al. Spinel CuCo₂O₄ nano-particles supported on N-doped reduced graphene oxide: A highly active and stable hybrid electrocatalyst for the oxygen reduction reaction[J]. Langmuir, 2013, 29(43): 13146-13151.
[106] Zhao A Q, Masa J, Xia W, et al. Spinel Mn-Co oxide in N-doped carbon nanotubes as a bifunctional electrocatalyst synthesized by oxidative cutting[J]. Journal of the American Chemical Society, 2014, 136(21): 7551-7554.
[107] Vigil J A, Lambert T N, Kelly M, et al. Hybrid PEDOT/MnO_x nanostructured electrocatalysts for oxygen reduction[J]. Materials Chemistry Frontiers, 2017, 1(8): 1668-1675.
[108] Lee D G, Kim S H, Joo S H, et al. Polypyrrole-assisted oxygen electrocatalysis on perovskite oxides[J]. Energy & Environmental Science, 2017, 10(2): 523-527.
[109] Liu H C, Long W J, Song W W, et al. Tuning the electronic bandgap: An efficient way to improve the electrocatalytic activity of carbon-supported Co₃O₄ nano-crystals for oxygen reduction reactions[J]. Chemistry-A European Journal, 2017, 23(11): 2599-2609.
[110] Cheng F Y, Zhang T R, Zhang Y, et al. Enhancing electrocatalytic oxygen reduction on MnO₂ with vacancies[J]. Angewandte Chemie-International Edition, 2013, 125(9): 2534-2537.
[111] Zhang T R, Cheng F Y, Du J, et al. Efficiently enhancing oxygen reduction electrocatalytic activity of MnO₂ using facile hydrogenation[J]. Advanced Energy Materials, 2015, 5(1): 1400654.
[112] Jijil C P, Lokanathan M, Chithiravel S, et al. Nitrogen doping in oxygen-deficient Ca₂Fe₂O₅: A strategy for efficient oxygen reduction oxide catalysts[J]. ACS Applied Materials & Interfaces, 2016, 8(50): 34387-34395.
[113] Wei Z D, Huang W Z, Zhang S T, et al. Induced effect of Mn₃O₄ on formation of MnO₂ crystals favourable to catalysis of oxygen reduction[J]. Journal of Applied Electrochemistry, 2000, 30(10): 1133-1136.
[114] Wei Z D, Huang W Z, Zhang S T, et al. Carbon-based air electrodes carrying MnO₂ in zinc-air batteries[J]. Journal of Power Sources, 2000, 91(2): 83-85.
[115] Li L, Feng X H, Nie Y, et al. Insight into the effect of oxygen vacancy concentration on the catalytic performance of MnO₂[J]. ACS Catalysis, 2015, 5(8): 4825-4832.
[116] Wang J, Liu D F, Qi X Q, et al. Insight into the effect of CaMnO₃ support on the catalytic performance of platinum catalysts[J]. Chemical Engineering Science, 2015, 135(SI): 179-186.
[117] Zhan Y, Xu C H, Lu M H, et al. Mn and Co co-substituted Fe₃O₄ nanoparticles on nitrogen-doped reduced graphene oxide for oxygen electrocatalysis in alkaline solution[J]. Journal of Materials Chemistry A, 2014, 2(38): 16217-16223.
[118] Pei D N, Gong L, Zhang A Y, et al. Defective titanium dioxide single crystals exposed by high-energy{001} facets for efficient oxygen reduction[J]. Nature Communications, 2015, 6: 8696.
[119] Li C, Han X P, Cheng F Y, et al. Phase and composition controllable synthesis of cobalt manganese spinel nano-particles towards efficient oxygen electrocatalysis[J]. Nature Communications, 2015, 6: 7345.
[120] Zhu H, Zhang S, Huang Y X, et al. Monodisperse M_xFe_3-xO₄ (M= Fe, Cu, Co, Mn) nanoparticles and their electrocatalysis for oxygen reduction reaction[J]. Nano Letters, 2013, 13(6): 2947-2951.
[121] Lee D, Jacobs R, Jee Y, et al. Stretching epitaxial La_0.6Sr_0.4CoO_3-δ for fast oxygen reduction[J]. The Journal of Physical Chemistry C, 2017, 121(46): 25651-25658.
[122] Yiligum,Wang Z J, Xu W H, et al. Bridged-multi-octahedral cobalt oxide nanocrystals with a Co-terminated surface as an oxygen evolution and reduction electrocatalyst[J]. Journal of Materials Chemistry A, 2017, 5(16): 7416-7422.
[123] Li L, Wei Z D, Li L L, et al. Ab initio study of the first electron transfer of O₂ on MnO₂ surface[J]. Acta Chimica Sinica, 2006, 64(4): 287-294.
[124] Li L, Wei Z D, Chen S G, et al. A comparative DFT study of the catalytic activity of MnO₂ (211) and (2-2-1) surfaces for an oxygen reduction reaction[J]. Chemical Physics Letters, 2012, 539: 89-93.
[125] Han X P, He G W, He Y, et al. Engineering catalytic active sites on cobalt oxide surface for enhanced oxygen electrocatalysis[J]. Advanced Energy Materials, 2018, 8(10): 1702222.
[126] Xiao J W, Kuang Q, Yang S H, et al. Surface structure dependent electrocatalytic activity of Co₃O₄ anchored on graphene sheets toward oxygen reduction reaction[J]. Scientific Reports, 2013, 3: 2300.
[127] Zhang X F, Zhang Y, Huang H D, et al. Electrochemical fabrication of shape-controlled Cu₂O with spheres, octahedrons and truncated octahedrons and their electrocatalysis for ORR[J]. New Journal of Chemistry, 2018, 42(1): 458-464.
[128] Li Q, Xu P, Zhang B, et al. Structure-dependent electrocatalytic properties of Cu₂O nanocrystals for oxygen reduction reaction[J]. The Journal of Physical Chemistry C, 2013, 117(27): 13872-13878.
[129] Cheng F Y, Shen J A, Peng B, et al. Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts[J]. Nature Chemistry, 2011, 3(1): 79-84.
[130] Fabbri E, Mohamed R, Levecque P, et al. Composite electrode boosts the activity of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ perovskite and carbon toward oxygen reduction in alkaline media[J]. ACS Catalysis, 2014, 4(4): 1061-1070.
[131] Wang Y, Cheng H P. Oxygen reduction activity on perovskite oxide surfaces: A comparative first-principles study of LaMnO₃, LaFeO₃, and LaCrO₃[J]. The Journal of Physical Chemistry C, 2013, 117(5): 2106-2112.
[132] Gavin A L, Watson G W. Modelling oxygen defects in orthorhombic LaMnO₃ and its low index surfaces[J]. Physical Chemistry Chemical Physics, 2017, 19(36): 24636-24646.
[133] Zhou Y, Xi S B, Wang J X, et al. Revealing the dominant chemistry for oxygen reduction reaction on small oxide nanoparticles[J]. ACS Catalysis, 2017, 8(1): 673-677.
[134] Tang Q W, Jiang L H, Liu J, et al. Effect of surface manganese valence of manganese oxides on the activity of the oxygen reduction reaction in alkaline media[J]. ACS Catalysis, 2014, 4(2): 457-463.
[135] Hwang J, Rao R R, Giordano L, et al. Perovskites in catalysis and electrocatalysis[J]. Science, 2017, 358(6364): 751-756.
[136] Suntivich J, Gasteiger H A, Yabuuchi N, et al. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries[J]. Nature Chemistry, 2011, 3(7): 546-550.
[137] Wei C, Feng Z, Scherer G G, et al. Cations in octahedral sites: A descriptor for oxygen electrocatalysis on transition-metal spinels[J]. Advanced Materials, 2017, 29(23): 1606800.
[138] Zhao Q, Yan Z H, Chen C C, et al. Spinels: Controlled preparation, oxygen reduction/evolution reaction application, and beyond[J]. Chemical Reviews, 2017, 117(15): 10121-10211.
[139] Yang N(杨娜), Wang J(王俊), Wu G P(吴光平), et al. Density functional theoretical study on the effect of spinel structure reversal on the catalytic activity for oxygen reduction reaction[J]. Scientia Sinica(Chimica) (中国科学:化学), 2017, 47(7): 882-890.M, et al. Mn₃O₄@CoMn₂O₄-Co_xO_y nanoparticles: Partial cation exchange synthesis and electrocatalytic properties toward the oxygen reduction and evolution reactions[J]. ACS Applied Materials & Interfaces, 2016, 8(27): 17435-17444.