Morphology-controlled synthesis of multi-metal-based spinel oxide nanocatalysts and their performance for oxygen reduction

Abstract

We present a one-pot colloidal synthesis method for producing monodisperse multi-metal (Co, Mn, and Fe) spinel nanocrystals (NCs), including nanocubes, nano-octahedra, and concave nanocubes. This study explores the mechanism of morphology control, showcasing the pivotal roles of metal precursors and capping ligands in determining the exposed crystal planes on the NC surface. The cubic spinel NCs, terminated with exclusive {100}-facets, demonstrate superior electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media compared to their octahedral and concave cubic counterparts. Specifically, at 0.85 V, (CoMn)Fe₂O₄ spinel oxide nanocubes achieve a high mass activity of 23.9 A/g and exhibit excellent stability, highlighting the promising ORR performance associated with {100}-facets of multi-metal spinel oxides over other low-index and high-index facets. Motivated by exploring the correlation between ORR performance and surface atom arrangement (active sites), surface element composition, as well as other factors, this study introduces a prospective approach for shapecontrolled synthesis of advanced spinel oxide NCs. It underscores the significance of catalyst shape control and suggests potential applications as nonprecious metal ORR electrocatalysts.

Keywords

alkaline media / morphology control / multi-metal spinel catalyst / nanocrystals / oxygen reduction

References

[1] Li C, Kwon S, Chen X, et al. Improving oxygen reduction performance of surface-layer-controlled Pt–Ni nano-octahedra via gaseous etching. Nano Lett. 2023;23(8):3476-3483.

[2] Li C, Selvam NCS, Fang J. Shape-controlled synthesis of platinum-based nanocrystals and their electrocatalytic applications in fuel cells. Nano-Micro Lett. 2023;15(1):83.

[3] Zhou M, Li C, Fang J. Noble-metal based random alloy and intermetallic nanocrystals: syntheses and applications. Chem Rev. 2021;121(2):736-795.

[4] Zhou M, Guo J, Zhao B, Li C, Zhang L, Fang J. Improvement of oxygen reduction performance in alkaline media by tuning phase structure of Pd–Bi nanocatalysts. J Am Chem Soc. 2021;143(38):15891-15897.

[5] Xie C, Niu Z, Kim D, Li M, Yang P. Surface and interface control in nanoparticle catalysis. Chem Rev. 2020;120(2):1184-1249.

[6] Zhang J, Yang H, Fang J, Zou S. Synthesis and oxygen reduction activity of shape-controlled Pt₃Ni nanopolyhedra. Nano Lett. 2010;10(2):638-644.

[7] Wei C, Feng Z, Scherer GG, Barber J, Yang S-H, Xu ZJ. Cations in octahedral sites: a descriptor for oxygen electrocatalysis on transition-metal spinels. Adv Mater. 2017;29(23):1606800.

[8] Angotzi MS, Musinu A, Mameli V, et al. Spinel ferrite core–shell nanostructures by a versatile solvothermal seed-mediated growth approach and study of their nanointerfaces. ACS Nano. 2017;11(8):7889-7900.

[9] Li C, Han X, Cheng F, Hu Y, Chen C, Chen J. Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis. Nat Commun. 2015;6(1):7345.

[10] Zhao A, Masa J, Xia W, et al. Spinel Mn–Co oxide in N-doped carbon nanotubes as a bifunctional electrocatalyst synthesized by oxidative cutting. J Am Chem Soc. 2014;136(21):7551-7554.

[11] Liang Y, Li Y, Wang H, et al. CO₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat Mater. 2011;10(10):780-786.

[12] Cheng F, Shen J, Peng B, Pan Y, Tao Z, Chen J. Rapid room-temperature synthesis of nanocrystalline spinels as oxygen reduction and evolution electrocatalysts. Nat Chem. 2011;3(1):79-84.

[13] Huang H, Huang A, Liu D, et al. Tailoring oxygen reduction reaction kinetics on perovskite oxides via oxygen vacancies for low-temperature and knittable zinc–air batteries. Adv Mater. 2023;35(36):2303109.

[14] Hao Y, Hung S-F, Zeng W-J, et al. Switching the oxygen evolution mechanism on atomically dispersed Ru for enhanced acidic reaction kinetics. J Am Chem Soc. 2023;145(43):23659-23669.

[15] Hao Y, Yu D, Zhu S, et al. Methanol upgrading coupled with hydrogen product at large current density promoted by strong interfacial interactions. Energy Environ Sci. 2023;16(3):1100-1110.

[16] Lin F, Li M, Zeng L, Luo M, Guo S. Intermetallic nanocrystals for fuel-cells-based electrocatalysis. Chem Rev. 2023;123(22):12507-12593.

[17] Bates JS, Johnson MR, Khamespanah F, Root TW, Stahl SS. Heterogeneous M-N-C catalysts for aerobic oxidation reactions: lessons from oxygen reduction electrocatalysts. Chem Rev. 2023;123(9):6233-6256.

[18] Wang Y, Su H, He Y, et al. Advanced electrocatalysts with single-metal-atom active sites. Chem Rev. 2020;120(21):12217-12314.

[19] Qin R, Liu K, Wu Q, Zheng N. Surface coordination chemistry of atomically dispersed metal catalysts. Chem Rev. 2020;120(21):11810-11899.

[20] Yang Y, Xiong Y, Holtz ME, et al. Octahedral spinel electrocatalysts for alkaline fuel cells. Proc Natl Acad Sci USA. 2019;116(49):24425-24432.

[21] Yang Y, Peng H, Xiong Y, et al. High-loading composition-tolerant Co-Mn spinel oxides with performance beyond 1 W/cm² in alkaline polymer electrolyte fuel cells. ACS Energy Lett. 2019;4(6):1251-1257.

[22] Xiong Y, Yang Y, Feng X, DiSalvo FJ, Abruña HD. A strategy for increasing the efficiency of the oxygen reduction reaction in Mn-doped cobalt ferrites. J Am Chem Soc. 2019;141(10):4412-4421.

[23] Zhou Y, Xi S, Wang J, et al. Revealing the dominant chemistry for oxygen reduction reaction on small oxide nanoparticles. ACS Catal. 2018;8(1):673-677.

[24] Wang Z, Huang J, Wang L, et al. Cation-tuning induced d-band center modulation on Co-based spinel oxide for oxygen reduction/evolution reaction. Angew Chem Int Ed. 2022;61(16):e202114696.

[25] Zhou M, Yoon D, Yang Y, et al. Enhanced oxygen reduction performance on {101} CoMN₂O₄ spinel facets. ACS Energy Lett. 2023;8(8):3631-3638.

[26] Zhou M, Wang H, Zhang L, et al. Facet impact of CuMN₂O₄ spinel nanocatalysts on enhancement of the oxygen reduction reaction in alkaline media. ACS Catal. 2022;12(21):13663-13670.

[27] Zhao Q, Yan Z, Chen C, Chen J. Spinels: controlled preparation, oxygen reduction/evolution reaction application, and beyond. Chem Rev. 2017;117(15):10121-10211.

[28] Wang L, Wang X, Luo J, et al. Core-shell-structured magnetic ternary nanocubes. J Am Chem Soc. 2010;132(50):17686-17689.

[29] Zeng H, Rice PM, Wang SX, Sun S. Shape-controlled synthesis and shape-induced texture of MnFe₂O₄ nanoparticles. J Am Chem Soc. 2004;126(37):11458-11459.

[30] Sun S, Zeng H, Robinson DB, et al. Monodisperse MFe₂O₄ (M = Fe, Co, Mn) nanoparticles. J Am Chem Soc. 2004;126(1):273-279.

[31] Wang Y, Yang Y, Jia S, et al. Synergistic Mn-Co catalyst outperforms Pt on high-rate oxygen reduction for alkaline polymer electrolyte fuel cells. Nat Commun. 2019;10(1):1506.

[32] Zhou Y, Sun S, Xi S, et al. Superexchange effects on oxygen reduction activity of edge-sharing [Co_xMN_1-xO₆] octahedra in spinel oxide. Adv Mater. 2018;30(11):1705407.

[33] Kim J, Ko W, Yoo JM, et al. Structural insights into multi-metal spinel oxide nanoparticles for boosting oxygen reduction electrocatalysis. Adv Mater. 2022;34(8):2107868.

[34] Choi S-I, Lee SR, Ma C, et al. Facile synthesis of rhodium icosahedra with controlled sizes up to 12 nm. ChemNanoMat 2016;2(1):61-66.

RIGHTS & PERMISSIONS

2024 The Author(s). Electron published by Harbin Institute of Technology and John Wiley & Sons Australia, Ltd.