暖等离子体合成过渡金属掺杂氧化锰析氧电催化剂

doi:10.15541/jim20230542

无机材料学报 ›› 2024, Vol. 39 ›› Issue (7): 835-844.DOI: 10.15541/jim20230542

暖等离子体合成过渡金属掺杂氧化锰析氧电催化剂

李家琪¹(), 李小松¹, 李煊赫¹, 朱晓兵¹^,²(), 朱爱民¹

1.大连理工大学等离子体物理化学实验室, 大连 116024
2.大连理工大学氢能与环境催化中心, 大连 116024

收稿日期:2023-11-24 修回日期:2024-02-06 出版日期:2024-02-26 网络出版日期:2024-02-26
通讯作者: 朱晓兵, 副教授. E-mail: xzhu@dlut.edu.cn
作者简介:李家琪(1999-), 女, 硕士研究生. E-mail: lijiaqi621@mail.dlut.edu.cn
基金资助:
国家自然科学基金(22278052)

Transition Metal-doped Manganese Oxide: Synthesis by Warm Plasma and Electrocatalytic Performance for Oxygen Evolution Reaction

LI Jiaqi¹(), LI Xiaosong¹, LI Xuanhe¹, ZHU Xiaobing¹^,²(), ZHU Aimin¹

1. Laboratory of Plasma Physical Chemistry, Dalian University of Technology, Dalian 116024, China
2. Center for Hydrogen Energy and Environmental Catalysis, Dalian University of Technology, Dalian 116024, China

Received:2023-11-24 Revised:2024-02-06 Published:2024-02-26 Online:2024-02-26
Contact: ZHU Xiaobing, associate professor. E-mail: xzhu@dlut.edu.cn
About author:LI Jiaqi (1999-), female, Master candidate. E-mail: lijiaqi621@mail.dlut.edu.cn
Supported by:
National Natural Science Foundation of China(22278052)

摘要/Abstract

摘要：

可再生能源发电与质子交换膜水电解结合产生“绿色氢”对能源安全具有战略意义, 其速控步骤是析氧反应。从稳定性、活性和成本角度考虑, 本研究采用滑动弧暖等离子体一步合成了氧化锰(MnO_x)及过渡金属掺杂(Fe-MnO_x, Co-MnO_x, Ni-MnO_x)的析氧电催化剂, 并对其晶体结构、形貌尺寸、元素组成和表面价态进行了表征。氧化锰主要由晶相Mn₂O₃和无定形Mn₃O₄组成。与之相比, 掺杂的氧化锰尽管晶相组成基本不变, 但其粒径明显变小、比表面积增大; 掺杂Co促使氧化锰的表面电子增多。氧化锰基催化剂在酸性电解液的循环伏安测试中表现出独特的电流阶跃现象(低电势Ⅰ-Ⅱ区: 1.4~1.8~2.4 V; 高电势Ⅲ区: 2.4~2.7 V)。该电流阶跃过程与Bulter-Volmer简化方程的电极动力学参照曲线相吻合, 属于多价态锰参与的电催化反应。低电势区Fe-MnO_x的电化学活性最优, 而高电势区Co-MnO_x表现最优。Co-MnO_x的起始电位比MnO_x低160 mV, 且在恒电位电解中其末端电流密度是MnO_x的3倍。与其活性趋势一致, Fe-MnO_x、Co-MnO_x分别在低电势区、高电势区更具稳定性。本研究通过掺杂过渡金属优化氧化锰的颗粒尺寸、比表面积和电子结构, 显著提高了催化剂析氧反应活性及稳定性。

关键词: MnO_x, 过渡金属掺杂, 电流阶跃, 析氧反应, 滑动弧暖等离子体

Abstract:

By using renewable electricity proton exchange membrane (PEM), water electrolysis can produce “green hydrogen” of which the rate-determining step is oxygen evolution reaction. Considering the problems of stability, activity and cost, manganese oxides (MnO_x) doped with transition metals as a kind of electrocatalysts (Fe-MnO_x, Co-MnO_x, and Ni-MnO_x) were directly synthesized in one-step by gliding arc warm plasma. Complementary characterizations of the crystal structure, morphology, element composition, and surface valence state on this kind of synthetic catalysts were conducted. The results show that MnO_x mostly consists of crystalline Mn₂O₃ and amorphous Mn₃O₄. Although the transition metal doped catalysts possess the very approximate crystalline compositions to MnO_x, they showed a remarkable decrease in particle size and an increase in specific surface area are achieved. Introducing Co to form Co-MnO_x can increase surface density of electrons as compared to pure MnO_x. We further reveal a unique current step of MnO_x-based catalysts in acidic medium which appears in three consecutive potential regions (low I: 1.4-1.8 V, low II: 1.8-2.4 V, and high III: 2.4-2.7 V) under cyclic voltammetry (CV) measurements. This current step process is quite consistent with the electrode dynamics curve (as reference) which is reduced by a simplified version of Bulter-Volmer equation, during which the electrocatalytic behavior involves manganese at multi-valence states. At low potential regions Fe-MnO_x achieves the highest activity among all catalysts, while at high potential region only Co-MnO_x achieves. Furthermore, Co-MnO_x onset potential is 160 mV lower than that of pure MnO_x, and three times of the ending current density of pure MnO_x during bulk electrolysis under potentiostat. Consistent with the trend in activity, at low potential regions Fe-MnO_x is the most stable, while at high potential region Co-MnO_x is. Consequently, the significant increase in oxygen evolution reaction activity and stability of manganese oxides doped with transition metals is attributed to transition metal doping, which obviously optimizes the particle size, specific surface area, and electronic structure of MnO_x.

Key words: MnO_x, transition metal doping, current step, oxygen evolution reaction, gliding arc warm plasma

中图分类号:

O643

李家琪, 李小松, 李煊赫, 朱晓兵, 朱爱民. 暖等离子体合成过渡金属掺杂氧化锰析氧电催化剂[J]. 无机材料学报, 2024, 39(7): 835-844.

LI Jiaqi, LI Xiaosong, LI Xuanhe, ZHU Xiaobing, ZHU Aimin. Transition Metal-doped Manganese Oxide: Synthesis by Warm Plasma and Electrocatalytic Performance for Oxygen Evolution Reaction[J]. Journal of Inorganic Materials, 2024, 39(7): 835-844.

图/表 16

表1 采用ICP-OES, BET, XRD, TEM表征MnOx, Ni-MnOx, Co-MnOx和Fe-MnOx催化剂的物理化学参数

Table 1 Physicochemical parameters of MnOx, Ni-MnOx, Co-MnOx, and Fe-MnOx catalysts by ICP-OES, BET, XRD, and TEM

Catalyst	Doping element content/% (in atomic)	S_BET/ (m²∙g^-1)	D_XRD / nm	D_TEM / nm
MnO_x	-	35.7	32.7	37.9
Ni-MnO_x	1.23	57.5	27.4	37.5
Co-MnO_x	1.41	51.1	26.9	20.1
Fe-MnO_x	1.22	54.8	28.1	19.1

图S1 滑动弧暖等离子体合成的氧化锰基催化剂的形貌照片

Fig. S1 Pictures of catalysts synthesized by warm plasma (of gliding arc) (a) MnOx; (b) Ni-MnOx; (c) Co-MnOx; (d) Fe-MnOx

图1 MnOx, Ni-MnOx, Co-MnOx和Fe-MnOx催化剂的XRD谱图

Fig. 1 XRD patterns of MnOx, Ni-MnOx, Co-MnOx, and Fe-MnOx catalysts Colorful figure is available on website

图2 (a, e)MnOx, (b, f)Ni-MnOx, (c, g)Co-MnOx和(d, h)Fe-MnOx催化剂的(a~d)TEM和(e~h)HRTEM照片((a~d)中的插图为相应的颗粒粒径分布直方图)

Fig. 2 (a-d) TEM and (e-h) HRTEM images of (a, e) MnOx, (b, f) Ni-MnOx, (c, g) Co-MnOx, and (d, h) Fe-MnOx catalysts with insets in (a-d) showing corresponding histograms of particle size distributions

图S2 氧化锰基催化剂的元素能谱分布(EDX)图

Fig. S2 EDX elemental mappings of MnOx-based catalysts (a) MnOx; (b) Ni-MnOx; (c) Co-MnOx; (d) Fe-MnOx

图3 MnOx, Ni-MnOx, Co-MnOx和Fe-MnOx催化剂的(a)Mn2p和(b)O1s XPS谱图

Fig. 3 (a) Mn2p and (b) O1s XPS spectra of MnOx, Ni-MnOx, Co-MnOx and Fe-MnOx catalysts

图S3 Ni-MnOx催化剂的(a)Ni2p, Co-MnOx催化剂的(b)Co2p和Fe-MnOx催化剂的(c)Fe2p XPS谱图

Fig. S3 XPS spectra of (a) Ni2p for Ni-MnOx, (b) Co2p for Co-MnOx and (c) Fe2p for Fe-MnOx catalysts

图4 MnOx, Ni-MnOx, Co-MnOx和Fe-MnOx催化剂的循环伏安曲线

Fig. 4 Cyclic voltammetric curves of MnOx, Ni-MnOx, Co-MnOx, and Fe-MnOx catalysts Colorful figure is available on website

图5 滑动弧暖等离子体合成MnOx催化剂在截止电压为(a)1.5, (b)1.7, (c)1.9, (d)2.3, (e)2.6 V的CV曲线, (f)CV的测试和拟合曲线

Fig. 5 Cyclic voltammetric curves of MnOx catalysts synthesized by gliding arc warm plasma at ending potentials of (a) 1.5, (b) 1.7, (c) 1.9, (d) 2.3, and (e) 2.6 V, and (f) the comparison between the measured CV curve and the fitting curve educed by Bulter-Volmer equation (simple version) Colorful figures are available on website

图S4 滑动弧暖等离子体合成MnOx催化剂在不同截止电压(a)1.3, (b)1.4, (c)1.6, (d)1.8, (e)2.0, (f)2.1, (g)2.2, (h)2.4和(i)2.5 V的循环伏安图

Fig. S4 Cyclic voltammetry of MnOx catalyst synthesized by gliding arc warm plasma at ending potentials of (a) 1.3, (b) 1.4, (c) 1.6, (d) 1.8, (e) 2.0, (f) 2.1, (g) 2.2, (h) 2.4, and (i) 2.5V

图6 MnOx、Ni-MnOx、Co-MnOx和Fe-MnOx催化剂的(a)lgj-E曲线和(b)类Tafel斜率图

Fig. 6 (a) lgj-E curves and (b) Tafel-type plots of MnOx, Ni-MnOx, Co-MnOx, and Fe-MnOx catalysts The data is derivative from Fig. 4; Colorful figures are available on website

表S1 MnOx, Ni-MnOx, Co-MnOx和Fe-MnOx催化剂的电化学性能(源自图6)

Table S1 Electrochemical performances for MnOx, Ni-MnOx, Co-MnOx, and Fe-MnOx catalysts from Fig. 6

Catalyst	Potential/V	Slope/ (mV∙dec^-1)	Starting Tafel (E, i)/(V, mA)
MnO_x	1.27-1.75^I	153	(1.33, 0.02)
	1.75-2.42^II	359	(1.82, 0.64)
	2.42-2.65^III	893	(2.55, 1.86)
Ni-MnO_x	1.27-1.74^I	186	(1.33, 0.51)
	1.74-2.42^II	356	(1.82, 0.71)
	2.42-2.65^III	879	(2.52, 1.98)
Co-MnO_x	1.27-1.74^I	131	(1.31, 0.18)
	1.74-2.26^II	423	(1.82, 0.80)
	2.26-2.65^III	806	(2.44, 2.41)
Fe-MnO_x	1.25-1.74^I	144	(1.30, 0.04)
	1.74-2.36^II	363	(1.82, 1.03)
	2.36-2.65^III	874	(2.50, 2.52)

图S5 三维多孔电极中Co-MnOx催化剂与文献[S1-S5]报道的二维薄膜电极中氧化锰基催化剂在酸性条件下的析氧反应起始电位比较

Fig. S5 Comparison of onset potentials on Co-MnOx catalyst in this work with manganese oxides based electrocatalysts in literatures[S1-S5]

图7 MnOx, Ni-MnOx, Co-MnOx和Fe-MnOx催化剂的电化学阻抗谱图(插图为所测全部频率谱图)

Fig. 7 Electrochemical impedance spectra of MnOx, Ni-MnOx, Co-MnOx, and Fe-MnOx catalysts with insert showing full-range frequency measurement

图8 MnOx, Ni-MnOx, Co-MnOx和Fe-MnOx催化剂在(a, d)1.5, (b, e) 1.9和(c, f) 2.5 V电压下的(a~c)电流密度-时间(j-t)的稳定性实验, 以及(d~f)电流衰减率与上述稳定性实验的末端电流密度的关系

Fig. 8 (a-c) Current density-time (j-t) dependence of stability tests, and (d-f) relationship between current decay rate and ending current density on MnOx, Ni-MnOx, Co-MnOx, and Fe-MnOx catalysts at (a, d) 1.5, (b, e) 1.9 and (c, f) 2.5 V Colorful figures are available on website

图9 电流阶跃特征的双电层解释示意图

Fig. 9 Schematic double layer (of Helmholtz plane) for the featured current step Bottom left: A potentiostat that linearly loads voltage to double layer (at left side); Right: A double layer that consists of two sides of solid (MnOx catalyst) and solution

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暖等离子体合成过渡金属掺杂氧化锰析氧电催化剂

Transition Metal-doped Manganese Oxide: Synthesis by Warm Plasma and Electrocatalytic Performance for Oxygen Evolution Reaction

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