Bifunctional Electrocatalysts of Mn-doped Co3O4 for Oxygen Reduction and Oxygen Evolution Reactions in Alkaline Medium

doi:10.6023/A24050152

Abstract

Rechargeable zinc-air batteries (ZABs) have been extensively studied due to their high energy and power density, high safety and cost-effectiveness, which are considered to be one of the most promising clean power sources in the field of energy storage. Nevertheless, its practical application has been hampered by the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) during the discharge and charge processes, respectively. It is well known that Pt and IrO₂ are currently considered to be the most efficient ORR and OER catalysts. However, the high cost of precious metal catalysts has hindered their large-scale application. Herein, a series of spinel catalysts (Mn_x-Co₃O₄, x=0, 0.5, 1, 1.5) are prepared by co-precipitation method to achieve bifunctional oxygen electrocatalysis in alkaline media. Meanwhile, the potential of these transition metal oxide catalytic materials as bifunctional catalysts in replacing precious metals has been further explored. The results show that Mn-Co₃O₄ has excellent ORR performance (onset potential of 0.85 V, half-wave potential of 0.69 V), and significantly enhanced OER performance (overpotential of 0.57 V, the electron transfer resistance of 26.14 Ω), thereby leading to excellent bifunctional property. Furthermore, density functional theory (DFT) calculations demonstrate that Mn and Co sites can serve as potential active sites for ORR and OER respectively, exhibiting significant synergistic effects in electrocatalytic processes. The characterization results further confirm that the doping of manganese in the catalyst preparation process increases the specific surface area and oxygen vacancies of the catalyst, adjusts the surface chemistry and electronic state of the catalyst, and thus improves the ORR and OER performance of the catalyst. In addition, the Mn-Co₃O₄ catalyst delivers high cycle life of up to 40 h in liquid rechargeable zinc air batteries. In summary, this work demonstrates that manganese-cobalt bimetallic synergistic catalysis is a promising strategy to enhance the electrocatalytic activity of ORR and OER.

Key words: oxygen reduction reaction, oxygen evolution reaction, spinel oxide, oxygen vacancy, catalytic performance

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Ziyi Shui, Sile Yu, Wei Lu, Liuyun Xu, Qingye Liu, Wei Zhao, Yilun Liu. Bifunctional Electrocatalysts of Mn-doped Co₃O₄ for Oxygen Reduction and Oxygen Evolution Reactions in Alkaline Medium[J]. Acta Chimica Sinica, 2024, 82(10): 1039-1049.

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Fig. & Tab. 12

Figure 1. SEM images of (a) Co3O4, (b) Mn0.5-Co3O4, (c) Mn-Co3O4 and (d) Mn1.5-Co3O4 catalysts and (e) XRD patterns

Figure 2. N2 adsorption-desorption isotherm of (a) Co3O4, (b) Mn0.5-Co3O4, (c) Mn-Co3O4 and (g) Mn1.5-Co3O4 catalysts and pore distribution plot of (d) Co3O4, (e) Mn0.5-Co3O4, (f) Mn-Co3O4 and (h) Mn1.5-Co3O4 catalysts

Figure 3. (a) X-ray photoelectron spectroscopy (XPS) analysis of the Mnx-Co3O4 (x=0, 0.5, 1, 1.5) catalyst: survey spectra, (b, d) high-resolution Co 2p spectra of Mnx-Co3O4 (x=0, 0.5, 1, 1.5) catalyst, (c) Mn 2p spectra and (e) O1s spectra

样品	元素	XPS结果				EDS结果
样品	元素	原子比(%)	Mn/Co	原子比(%)	Mn/Co	原子比(%)	Mn/Co
Co₃O₄	Mn	0	0	0	0	0	0
Co₃O₄	Co	8.64	0	69.65	0	46.55	0
Mn_0.5-Co₃O₄	Mn	3.28	0.53	25.93	0.49	18.60	0.51
Mn_0.5-Co₃O₄	Co	6.21	0.53	51.99	0.49	36.14	0.51
Mn-Co₃O₄	Mn	4.51	0.82	36.31	0.77	25.4	0.83
Mn-Co₃O₄	Co	5.48	0.82	46.80	0.77	30.5	0.83
Mn_1.5-Co₃O₄	Mn	5.12	1.21	44.94	1.19	30.07	1.21
Mn_1.5-Co₃O₄	Co	4.23	1.21	37.55	1.19	24.84	1.21

Table 1. The elemental content of Mnx-Co3O4 (x=0, 0.5, 1, 1.5) obtained from XPS, ICP-OES, and EDS

	O_ads/O_latt	Mn³⁺/Mn⁴⁺	Co²⁺/Co³⁺	Co³⁺/Mn³⁺
Co₃O₄	0.68	—	0.88
Mn_0.5-Co₃O₄	0.98	1.37	0.94	1.13
Mn-Co₃O₄	1.76	1.98	1.25	0.91
Mn_1.5-Co₃O₄	0.90	2.23	1.18	0.32

Table 2. XPS of oxygen, cobalt and manganese contents for Mnx-Co3O4 (x=0, 0.5, 1, 1.5)

Figure 4. EPR spectra of Mnx-Co3O4 (x=0, 0.5, 1, 1.5) catalyst

Figure 5. Linear sweep voltammograms (LSV) and Koutecky-Levich plots of (a) Co3O4, (b) Mn0.5-Co3O4, (c) Mn-Co3O4 and (d) Mn1.5-Co3O4 at different rotation speed of rotating disk electrode; (e) the Koutecky-Levich plot of the four catalysts at 0.4 V and (f) electron transfer number and kinetic current density plot for Mnx-Co3O4 (x=0, 0.5, 1, 1.5)

Figure 6. (a) ORR Linear sweep voltammetry (LSV) curves and (b) corresponding Tafel plots and Tafel slope value table (inset) of catalysts of Mnx-Co3O4 (x=0, 0.5, 1, 1.5) in 0.1 mol?L?1 KOH, (c) OER Linear sweep voltammetry (LSV) curves and (d) corresponding Tafel plots of catalysts of Mnx-Co3O4 (x=0, 0.5, 1, 1.5) and (e) electrochemical impedance spectroscopy from 1 to 100 000 Hz under 5 mV voltage amplitude

		Co₃O₄	Mn_0.5-Co₃O₄	Mn-Co₃O₄	Mn_1.5-Co₃O₄
ORR	起始电位/V	0.75	0.83	0.85	0.78
	半波电位/V	0.65	0.66	0.69	0.58
	Tafel斜率/ (mV•dec⁻¹)	134.4	132.9	103.7	197.9
	电子转移数	3.15	3.36	3.57	3.29
OER	E_j₌₁₀/V	1.791	1.789	1.781	1.805
	相应过电位/ mV	0.561	0.559	0.551	0.575
	Tafel斜率/ (mV•dec⁻¹)	91.3	99.2	88.1	98.3

Table 3. ORR and OER performances of Mnx-Co3O4 (x=0, 0.5, 1, 1.5)

Figure 7. (a) ORR stability and (b) OER stability obtained by chronoamperometry techniques

Figure 8. The free energy diagram of ORR and OER mechanism on Mn-Co3O4 model at (a, b) Mn site and (c, d) Co site, and Co3O4 model at (e, f) Co site

Figure 9. (a) Open circuit voltage, (b) charge-discharge polarization curve and (c) its corresponding discharge power density curve, (d) constant current charge-discharge cycle data of rechargeable zinc air batteries (ZABs)

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Mn掺杂Co₃O₄双功能电催化剂在碱性介质下氧还原和析氧反应中的应用

Bifunctional Electrocatalysts of Mn-doped Co₃O₄ for Oxygen Reduction and Oxygen Evolution Reactions in Alkaline Medium

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Mn掺杂Co3O4双功能电催化剂在碱性介质下氧还原和析氧反应中的应用