氧化锰电催化析氧反应及其电极界面特性

doi:10.11949/0438-1157.20210441

摘要/Abstract

摘要：

析氧半反应是速控步骤。氧化锰（MnO_x）具有多价态，可形成多个子步骤降低活化能。二氧化钛（TiO₂）是抗氧化性半导体。考察两种氧化锰催化剂析氧性能，即滑动弧等离子体合成MnO_x（pM）和商业化（cM），与商业化TiO₂ （cT）比较。通过理想极化电极系统（IPE）解析，表达电极界面特性，揭示三相界面与活性的关联。结果表明：对两种MnO_x 催化剂，pM比cM性能更优。碱性环境中，前者起始电位低180 mV，Tafel斜率近半。酸性中，均表现阶跃式极化，析氧性能相近。cM比cT催化剂析氧性能更优，起始电位低420 mV。溶液电阻R_s与活性变化趋势一致。对相同催化剂，考察I/C、担量、单双层结构，电容压降占比f_Cd与活性一致。对不同催化剂，考察cM， cT或pM， cM，f_Cd与活性不一致，这与多价态锰参与非法拉第过程有关。

关键词: 氧化锰, 二氧化钛, 滑动弧等离子体, 析氧反应, 电极-溶液界面

Abstract:

Oxygen evolution reaction (OER) is the rate-determining step for water electrolysis. Manganese oxides (MnO_x) possess five valence states, hence with multiple steps to reduce the activation energy, and semiconductor titanium dioxide (TiO₂) exhibits corrosion resistance. Here we demonstrate OER performance over three catalysts, of MnO_x synthesized by gliding arc plasma (pM) and commercial MnO_x (cM), and commercial TiO₂ (cT). Of non- Faradiac process, using ideal polarized electrode (IPE), it expresses the electrode-solution interface, hence reveals the association between triple phase boundary (TPB) and activity. It suggests that, the MnO_xof pM shows better activity than cM. In alkali, the former has 180 mV lower potential vs RHE, and nearly half Tafel slope. In acid, both the MnO_x catalysts show step-current polarization with similar activity. Moreover, cM shows higher activity than cT, e.g., 420 mV lower potential. The revealed solution resistance, R_s is consistent with activity. For the same catalyst, the fraction in voltage drop of capacitance f_Cd, is also in accordance with the activity in terms of ionomer to catalyst ratio (I/C), loading and single/double layer(s). However, for the varied catalysts, e.g., cM versus cT, or pM versus cM, the f_Cd is inconsistent with the activity, which might result from involving the non-Faradiac process of MnO_x.

Key words: MnO_x, TiO₂, gliding arc plasma, oxygen evolution reaction, electrode-solution interface

中图分类号:

O 646

朱晓兵, 李佳佳, 李怡宁, 杨洪月, 李小松, 刘景林. 氧化锰电催化析氧反应及其电极界面特性[J]. 化工学报, 2021, 72(S1): 398-405.

ZHU Xiaobing, LI Jiajia, LI Yining, YANG Hongyue, LI Xiaosong, LIU Jinglin. Oxygen evolution reaction over manganese oxides and the electrode-solution interface[J]. CIESC Journal, 2021, 72(S1): 398-405.

图/表 7

图1 氧化锰MnOx (pM, cM)电极[I/C=1, 231 μg/cm2, 双层，pM催化剂t0,x，is=(0.659 s, 63.8 μA)，cM催化剂(2.749 s, 65.6 μA)，电解液为1 mol/L KOH]

Fig.1 Oxygen evolution over MnOx (pM, cM)[I/C=1, 231 μg/cm2, with double layer coating, 1 mol/L KOH, t0,x, is =(0.659 s, 63.8 μA) for pM, (2.749 s, 65.6 μA) for cM]

图2 氧化锰MnOx (pM, cM)电极[I/C=4, 693 μg/cm2, 双层，pM催化剂t0,x，is=(7.97 s, 4.86 μA), cM催化剂(6.72 s, 32.7 μA)]

Fig.2 Oxygen evolution over MnOx (pM, cM) [I/C=4, 693 μg/cm2, with double layer coating, t0,x, is =(7.97 s, 4.86 μA) for pM, (6.72 s, 32.7 μA) for cM]

图3 氧化锰和氧化钛(cM, cT)电极[单层，I/C=0.2，231 μg/cm2, t0,x，is=(8.84 s, 13.5 μA), cM催化剂；I/C=0.3，693 μgcat/cm2, (2.02 s, 1.5 μA), cT催化剂, cT扫速50 mV/s]

Fig.3 Oxygen evolution over MnOx (cM), TiO2 (cT)[I/C=0.2, 231 μg/cm2, I/C=0.3, 693 μgcat/cm2 with single layer coating, with t0,x，is=(8.84 s, 13.5 μA) for cM, (2.02 s, 1.5 μA) for cT, respectively. The scan rate for cT is 50 mV/s]

图4 不同I/C的氧化锰(pM)电极[I/C=1, 2, 4, 231 μg/cm2, 双层，t0,x，is=(8.4 s, 1.86 μA), I/C=1；(9.8 s, 1.26 μA), I/C=2；(7.37 s,3.29 μA), I/C=4]

Fig.4 Oxygen evolution over MnOx (pM) at various I/C=1, 2, 4, loading of 231 μg/cm2, with double layer coating, with t0,x, is =(8.4 s, 1.86 μA) for I/C=1, (9.8s, 1.26 μA) for I/C=2, (7.37 s, 3.29 μA) for I/C=4

图5 不同担量的氧化锰(pM)电极[231, 693 μg/cm2, I/C=4, 双层: t0,x，is=(7.37 s, 3.29 μA), 231 μg/cm2; t0,x，is=(7.97 s, 4.86 μA), 693 μg/cm2。曲线2数据同图2曲线1]

Fig.5 Oxygen evolution over MnOx (pM) at various loadings=231, 693 μg/cm2, at I/C=4, with double layer coating, t0,x, is =(7.37 s, 3.29 μA) for 231 μg/cm2, (7.97 s, 4.86 μA) for 693 μg/cm2; Curve 2, the same as curve 1 in Fig.2

图6 不同层结构的氧化锰(cM)电极[单层、双层，I/C=0.2, 231 μg/cm2: t0,x，is=(8.84 s, 13.5 μA),单层；t0,x，is=(7.43 s, 58.2 μA), 双层；曲线1同图3曲线2]

Fig.6 Oxygen evolution over MnOx (cM) withsingle layer or double layer coating, at I/C=0.2, 231 μg/cm2, t0,x, is =(8.84 s, 13.5 μA) for single layer, (7.43 s, 58.2 μA) for double layer; Curve 1, the same as curve 2 in Fig. 3

表1 氧化锰MnOx（pM， cM）电极参数［图1（a）］

Table 1 Electrode parameters of MnOx （pM， cM）（sourced from Fig.1（a））

Catalyst

Onset potential /V

b^①/

(mV/dec)

Starting Tafel (E, i)^②/(V, mA)

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