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

doi:10.6023/A24050152

摘要/Abstract

可充电锌空气电池(ZABs)由于其高能量和功率密度、高安全性和成本效益, 被认为是未来储能领域中最有前途的清洁电源之一. 然而, 其实际应用受到放电和充电过程中氧还原反应(ORR)和析氧反应(OER)动力学缓慢的阻碍. Pt和IrO₂是目前公认的高效ORR和OER催化剂, 但贵金属催化剂的高成本阻碍了它们商业化的步伐. 本工作通过共沉淀法制备了一系列尖晶石催化剂(Mn_x-Co₃O₄, x=0, 0.5, 1, 1.5), 以实现在碱性介质中高效催化ORR和OER的目的, 并进一步探索这些过渡金属氧化物催化材料作为双功能复合催化剂在取代贵金属方面的潜力. 实验结果显示: Mn-Co₃O₄具有优异的ORR性能(起始电位为0.85 V, 半波电位为0.69 V)和OER性能(过电位为0.57 V, 电子转移电阻为26.14 Ω). 此外, 密度泛函理论(DFT)计算表明, Mn和Co位点可以分别作为ORR和OER的潜在活性位点, 在电催化过程中具有显著的协同作用. 表征结果进一步证实锰的掺杂增加了催化剂的比表面积和氧空位, 调整了催化剂表面化学和电子状态, 从而提高了催化剂的ORR和OER性能. 另外, 该催化剂在液态可充电锌空气电池中显示出长达40 h的循环寿命. 总而言之, 本工作证明了锰钴双金属协同催化是提高ORR和OER选择性的一种有效策略.

关键词: 氧还原反应, 析氧反应, 尖晶石氧化物, 氧空位, 催化性能

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

引用此文

税子怡, 于思乐, 陆伟, 许留云, 刘庆叶, 赵炜, 刘益伦. 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[J]. 化学学报, 2024, 82(10): 1039-1049.

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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图/表 12

图1. (a) Co3O4, (b) Mn0.5-Co3O4, (c) Mn-Co3O4, (d) Mn1.5-Co3O4催化剂的SEM图像和(e) XRD图谱

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

图2. (a) Co3O4, (b) Mn0.5-Co3O4, (c) Mn-Co3O4和(g) Mn1.5-Co3O4催化剂的N2吸附-解吸等温线以及(d) Co3O4, (e) Mn0.5-Co3O4, (f) Mn-Co3O4和(h) Mn1.5-Co3O4催化剂的孔分布图

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

图3. (a) Mnx-Co3O4 (x=0, 0.5, 1, 1.5)催化剂的X射线光电子能谱; Mnx-Co3O4 (x=0, 0.5, 1, 1.5)催化剂的(b, d)高分辨率Co 2p光谱; (c) Mn 2p光谱和(e) O 1s光谱

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

表1. Mnx-Co3O4 (x=0, 0.5, 1, 1.5)的XPS、ICP-OES和EDS元素含量对比

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

表2. Mnx-Co3O4 (x=0, 0.5, 1, 1.5)从XPS获得的氧、钴和锰含量

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

图4. Mnx-Co3O4 (x=0, 0.5, 1, 1.5)催化剂的EPR图像

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

图5. 不同转速下(a) Co3O4、(b) Mn0.5-Co3O4、(c) Mn-Co3O4和(d) Mn1.5-Co3O4催化剂在旋转盘电极下线性扫描伏安图(LSV)和Koutecky-Levich图; (e) Mnx-Co3O4 (x=0, 0.5, 1, 1.5)催化剂在0.4 V下的Koutecky-Levich图以及(f)电子转移数和动能电流密度图

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)

图6. (a) Mnx-Co3O4 (x=0, 0.5, 1, 1.5)催化剂在0.1 mol?L?1 KOH中的ORR线性扫描伏安法(LSV)曲线和(b)相应的Tafel图; (c) Mnx-Co3O4 (x=0, 0.5, 1, 1.5)催化剂在0.1 mol?L?1 KOH中的OER线性扫描伏安法(LSV)曲线和(d)相应的Tafel图; (e) Mnx-Co3O4 (x=0, 0.5, 1, 1.5)催化剂在5 mV电压振幅下从1到100 000 Hz的电化学阻抗谱

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

表3. Mnx-Co3O4 (x=0, 0.5, 1, 1.5)催化剂ORR和OER性能汇总

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

图7. 通过计时安培法技术测试(a) ORR稳定性和(b) OER稳定性

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

图8. Mn-Co3O4模型上(a, b) Mn位点和(c, d) Co位点, 以及Co3O4模型上(e, f) Co位点在ORR和OER过程的自由能图

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

图9. (a)可充电锌空气电池的开路电压; (b)充放电极化曲线及(c)其相应的放电功率密度曲线; (d)恒流充放电循环数据

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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