Evaluating the Stability of Active Manganese Sites During Electrochemical Reactions by Cyclic Voltammetry

Abstract

Manganese oxides are a promising class of electrocatalysts for renewable energy devices, such as fuel cells. Mn(III) ions with e _g electron filling of − 1 are the active sites for manganese-based electrocatalysts. However, Mn(III) sites may be disproportionated during electrochemical reactions, thus reducing the number of Mn(III) active sites and decreasing the catalytic activity of manganese oxides. In this work, we developed a facile cyclic voltammetry method to monitor the evolution of Mn(III) sites on a series of manganese oxides under “working” conditions. We proposed a descriptor S _Mn(III) to describe the stability of Mn(III). Our simulated and experimental results show that the higher is S _Mn(III), the higher the active Mn(III) density, and the higher the electrocatalytic activity of the manganese oxide electrocatalyst.

Keywords

Manganese oxides / Mn(III) sites / Cyclic voltammetry

References

[1] Chung HT, Cullen DA, Higgins D, et al. Direct atomic-level insight into the active sites of a high-performance PGM-free ORR catalyst. Science, 2017, 357(6350): 479-484.

[2] Zhou Y, Guan XF, Zhou H, et al. Strongly correlated perovskite fuel cells. Nature, 2016, 534(7606): 231-234.

[3] Li YJ, Cui L, Da PF, et al. Multiscale structural engineering of Ni-doped CoO nanosheets for zinc-air batteries with high power density. Adv Mater, 2018, 30(46): e1804653.

[4] Mu C, Mao J, Guo JX, et al. Rational design of spinel cobalt vanadate oxide Co₂VO₄ for superior electrocatalysis. Adv Mater, 2020, 32(10): e1907168.

[5] Ren SS, Duan XD, Liang S, et al. Bifunctional electrocatalysts for Zn-air batteries: recent developments and future perspectives. J Mater Chem A, 2020, 8(13): 6144-6182.

[6] Yamaguchi A, Inuzuka R, Takashima T, et al. Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH. Nat Commun, 2014, 5: 4256.

[7] Shi HH, Liang HF, Ming FW, et al. Efficient overall water-splitting electrocatalysis using lepidocrocite VOOH hollow nanospheres. Angew Chem Int Ed Engl, 2017, 56(2): 573-577.

[8] Wang XT, Ouyang T, Wang L, et al. Redox-inert Fe^{3 +} ions in octahedral sites of Co-Fe spinel oxides with enhanced oxygen catalytic activity for rechargeable zinc-air batteries. Angew Chem Int Ed Engl, 2019, 58(38): 13291-13296.

[9] Lu XF, Chen Y, Wang SB, et al. Interfacing manganese oxide and cobalt in porous graphitic carbon polyhedrons boosts oxygen electrocatalysis for Zn-air batteries. Adv Mater, 2019, 31(39): e1902339.

[10] Zheng XL, Zhang B, De Luna P, 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(2): 149-154.

[11] Risch M, Stoerzinger KA, Han BH, et al. Redox processes of manganese oxide in catalyzing oxygen evolution and reduction: an in situ soft X-ray absorption spectroscopy study. J Phys Chem C, 2017, 121(33): 17682-17692.

[12] Rabe M, Toparli C, Chen YH, et al. Alkaline manganese electrochemistry studied by in situ and operando spectroscopic methods—metal dissolution, oxide formation and oxygen evolution. Phys Chem Chem Phys, 2019, 21(20): 10457-10469.

[13] Geiger S, Kasian O, Ledendecker M, et al. The stability number as a metric for electrocatalyst stability benchmarking. Nat Catal, 2018, 1(7): 508-515.

[14] Parra-Puerto A, Ng KL, Fahy K, et al. Supported transition metal phosphides: activity survey for HER, ORR, OER, and corrosion resistance in acid and alkaline electrolytes. ACS Catal, 2019, 9(12): 11515-11529.

[15] Speck FD, Santori PG, Jaouen F, et al. Mechanisms of manganese oxide electrocatalysts degradation during oxygen reduction and oxygen evolution reactions. J Phys Chem C, 2019, 123(41): 25267-25277.

[16] Kuai CG, Xu ZR, Xi C, et al. Phase segregation reversibility in mixed-metal hydroxide water oxidation catalysts. Nat Catal, 2020, 3(9): 743-753.

[17] Su HY, Gorlin Y, Man IC, et al. Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis. Phys Chem Chem Phys, 2012, 14(40): 14010-14022.

[18] Xiong Y, Yang Y, Feng XR, et al. 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.

[19] Ryabova AS, Napolskiy FS, Poux T, et al. Rationalizing the influence of the Mn(IV)/Mn(III) Red-Ox transition on the electrocatalytic activity of manganese oxides in the oxygen reduction reaction. Electrochim Acta, 2016, 187: 161-172.

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

[21] Zhou Y, Sun S, Xi S, et al. Superexchange effects on oxygen reduction activity of edge-sharing [Co _xMn_{1− x}O₆] octahedra in spinel oxide. Adv Mater, 2018, 30(11): 1705407.

[22] Stoerzinger KA, Risch M, Han BH, et al. Recent insights into manganese oxides in catalyzing oxygen reduction kinetics. ACS Catal, 2015, 5(10): 6021-6031.

[23] Tang QW, Jiang LH, Liu J, et al. Effect of surface manganese valence of manganese oxides on the activity of the oxygen reduction reaction in alkaline media. ACS Catal, 2014, 4(2): 457-463.

[24] Suntivich J, May KJ, Gasteiger HA, et al. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science, 2011, 334(6061): 1383-1385.

[25] Suntivich J, Gasteiger HA, Yabuuchi N, et al. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries. Nat Chem, 2011, 3(7): 546-550.

[26] Wei C, Feng Z, Scherer GG, et al. Cations in octahedral sites: a descriptor for oxygen electrocatalysis on transition-metal spinels. Adv Mater, 2017, 29(23): 1606800.

[27] Hwang J, Rao RR, Giordano L, et al. Perovskites in catalysis and electrocatalysis. Science, 2017, 358(6364): 751-756.

[28] Yaghoobnejad AH, Manthiram A Proton-induced disproportionation of Jahn–Teller-active transition-metal ions in oxides due to electronically driven lattice instability. J Am Chem Soc, 2020, 142(50): 21122-21130.

[29] Gibson A, Johannessen B, Beyad Y, et al. Dynamic electrodeposition of manganese dioxide: temporal variation in the electrodeposition mechanism. J Electrochem Soc, 2016, 163(5): H305-H312.

[30] Yang Y, Wang Y, Xiong Y, et al. In situ X-ray absorption spectroscopy of a synergistic Co-Mn oxide catalyst for the oxygen reduction reaction. J Am Chem Soc, 2019, 141(4): 1463-1466.

[31] Trześniewski BJ, Diaz-Morales O, Vermaas DA, et al. In situ observation of active oxygen species in Fe-containing Ni-based oxygen evolution catalysts: the effect of pH on electrochemical activity. J Am Chem Soc, 2015, 137(48): 15112-15121.

[32] Jin K, Seo H, Hayashi T, et al. Mechanistic investigation of water oxidation catalyzed by uniform, assembled MnO nanoparticles. J Am Chem Soc, 2017, 139(6): 2277-2285.

[33] Takashima T, Yamaguchi A, Hashimoto K, et al. In situ UV-Vis absorption spectra of intermediate species for oxygen-evolution reaction on the surface of MnO₂ in neutral and alkaline media. Electrochemistry, 2014, 82(5): 325-327.

[34] Takashima T, Hashimoto K, Nakamura R Mechanisms of pH-dependent activity for water oxidation to molecular oxygen by MnO₂ electrocatalysts. J Am Chem Soc, 2012, 134(3): 1519-1527.

[35] Nikitina VA, Kurilovich AA, Bonnefont A, et al. ORR on simple manganese oxides: molecular-level factors determining reaction mechanisms and electrocatalytic activity. J Electrochem Soc, 2018, 165(15): J3199-J3208.