一种用于PEM水电解制氢的高效负载型锰铱掺杂型催化剂

doi:10.12096/j.2096-4528.pgt.22184

摘要/Abstract

摘要：

质子交换膜(proton exchange membrane，PEM)水电解制氢是一种绿色、可持续的氢能制备方法，开发用于阳极析氧反应(oxygen evolution reaction，OER)的、高效经济的电催化剂是实现其大规模商业化应用的关键。通过两步合成法，合成了由不同锰基氧化物作载体的氧化铱催化剂IrO _x /Mn₈O₁₀Cl₃、IrO _x /β-MnO₂和IrO _x /α-MnO₂，铱的质量分数为55%左右。与现有商业IrO₂和其他含贵金属的电催化剂相比，合成的氧化铱/锰基氧化物催化剂具有更低的过电位和更高的电流密度。IrO _x /β-MnO₂在电流密度为10 mA/cm²时过电位仅为228 mV，IrO _x /Mn₈O₁₀Cl₃在1.53 V电压下比质量活度达到916.7 A/g_Ir，析氧反应活性的提升归功于催化剂表面丰富的羟基氧缺陷和Ir^III物种，丰富的结晶-非晶界面为反应提供了大量活性位点。所提的氧化铱/锰基氧化物为高效经济的酸性OER催化剂的开发提供了新思路。

关键词: 质子交换膜水电解, 析氧反应, 锰基氧化物载体, 氧化铱催化剂

Abstract:

Proton exchange membrane (PEM) water electrolysis is a green and sustainable method of hydrogen production. The development of efficient and economical electrocatalysts for anodic oxygen evolution reaction (OER) is the key to its large-scale commercialization. Iridium oxide catalysts supported by different manganese based oxide carriers (IrO _x /Mn₈O₁₀Cl₃, IrO _x /β-MnO₂ and IrO _x /α-MnO₂) were prepared by two-step synthesis method, and the content of iridium is about 55%. Compared with the commercial IrO₂ and other noble metal containing electrocatalysts, the synthesized catalysts have lower overpotential and higher current density. The overpotential of IrO _x /β-MnO₂ is only 228 mV at the current density of 10 mA/cm². The specific mass activity of IrO _x /Mn₈O₁₀Cl₃ reaches 916.7 A/g_Ir at 1.53V. The enhancement of OER activity is attributed to the abundant hydroxyl oxygen defects and Ir^III species on the catalyst surface. The rich crystalline-amorphous interface provides a large number of active sites for the reaction. The iridium oxide/manganese based oxide catalysts reported in this paper provide new insights for the development of efficient and economical catalysts for acidic OER.

Key words: proton exchange membrane water electrolysis, oxygen evolution reaction, manganese based oxide carriers, iridium oxide catalysts

中图分类号:

TK 91

张舒涵, 马晓锋, 张芮琳, 朱燕群, 何勇, 王智化. 一种用于PEM水电解制氢的高效负载型锰铱掺杂型催化剂[J]. 发电技术, 2023, 44(3): 340-349.

Shuhan ZHANG, Xiaofeng MA, Ruilin ZHANG, Yanqun ZHU, Yong HE, Zhihua WANG. An Efficient Mn-Ir Doped Supported Catalyst for PEM Water Electrolysis[J]. Power Generation Technology, 2023, 44(3): 340-349.

图/表 8

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催化剂	电解液	10 mA/cm²时过电位/mV	Tafel斜率/(mV/dec)	参考文献
IrO₂@α-MnO₂	0.1 mol/L HClO₄	275	59	[32]
(Mn_0.8Ir_0.2)O₂	0.5 mol/L H₂SO₄	240	46	[31]
(Ir_0.3Mn_0.7)O₂	0.1 mol/L H₂SO₄	383	49	[30]
IrO₂-RuO₂@Ru	0.5 mol/L H₂SO₄	281	53.1	[34]
Ir_0.7Co_0.3O _x	0.5 mol/L H₂SO₄	320	40	[35]
IrO₂/Ti	0.1 mol/L HClO₄	250	50.4	[24]
Li-IrO _x	0.5 mol/L H₂SO₄	300	39	[22]
Mn_7.5O₁₀Br₃	0.5 mol/L H₂SO₄	295	68	[29]
IrO _x /α-MnO₂	0.5 mol/L H₂SO₄	245	64	本文
IrO _x /β-MnO₂	0.5 mol/L H₂SO₄	228	46	本文
IrO _x /Mn₈O₁₀Cl₃	0.5 mol/L H₂SO₄	230	45	本文

催化剂	电解液	10 mA/cm²时过电位/mV	Tafel斜率/(mV/dec)	参考文献
IrO₂@α-MnO₂	0.1 mol/L HClO₄	275	59	[32]
(Mn_0.8Ir_0.2)O₂	0.5 mol/L H₂SO₄	240	46	[31]
(Ir_0.3Mn_0.7)O₂	0.1 mol/L H₂SO₄	383	49	[30]
IrO₂-RuO₂@Ru	0.5 mol/L H₂SO₄	281	53.1	[34]
Ir_0.7Co_0.3O _x	0.5 mol/L H₂SO₄	320	40	[35]
IrO₂/Ti	0.1 mol/L HClO₄	250	50.4	[24]
Li-IrO _x	0.5 mol/L H₂SO₄	300	39	[22]
Mn_7.5O₁₀Br₃	0.5 mol/L H₂SO₄	295	68	[29]
IrO _x /α-MnO₂	0.5 mol/L H₂SO₄	245	64	本文
IrO _x /β-MnO₂	0.5 mol/L H₂SO₄	228	46	本文
IrO _x /Mn₈O₁₀Cl₃	0.5 mol/L H₂SO₄	230	45	本文

催化剂	Ir原子分数/%	Mn原子分数/%	Cl原子分数/%	O原子分数/%	Ir质量分数/%
IrO _x /Mn₈O₁₀Cl₃	14.40	21.40	7.49	56.71	54.10
IrO _x /β-MnO₂	14.19	20.98	—	64.83	55.47
IrO _x /α-MnO₂	12.45	21.00	—	66.55	51.89

催化剂	Ir原子分数/%	Mn原子分数/%	Cl原子分数/%	O原子分数/%	Ir质量分数/%
IrO _x /Mn₈O₁₀Cl₃	14.40	21.40	7.49	56.71	54.10
IrO _x /β-MnO₂	14.19	20.98	—	64.83	55.47
IrO _x /α-MnO₂	12.45	21.00	—	66.55	51.89

催化剂	O_metal-O		O_OH		O_H2O		Ir^III相对面积/%
催化剂	结合能/eV	相对面积/%	结合能/eV	相对面积/%	结合能/eV	相对面积/%	Ir^III相对面积/%
IrO _x /Mn₈O₁₀Cl₃	530.00	27.97	531.42	46.46	532.62	25.57	28.92
IrO _x /β-MnO₂	530.20	29.62	531.50	45.52	532.60	24.86	27.89
IrO _x /α-MnO₂	529.92	33.39	531.45	42.60	532.62	24.01	26.44