酸性电解水过程中氧析出反应的机理及铱基催化剂的研究进展

doi:10.19894/j.issn.1000-0518.210336

摘要/Abstract

摘要：

可持续能源的迅速发展，使绿色清洁的氢能源成为热点。质子交换膜（PEM）水电解是一项很有前途的技术，可高效生产高纯度氢气。IrO₂作为质子交换膜（PEM）水电解槽阳极氧析出反应（OER）的商用电催化剂，既能在强酸性、高强度腐蚀条件下保持稳定，又表现出优异的催化性能。然而，由于Ir的稀缺性和昂贵的价格，提高Ir基催化剂的OER活性，开发低Ir催化剂就显得至关重要。对其反应机理的认知是当前的研究热点之一，也是设计优异的OER催化剂的关键所在。因此，首先从OER机理出发，对目前被广泛认可的吸附物逸出机理（AEM）和晶格氧逸出机理（LOER）两种反应机理进行了研究。随后，根据所提出的这两种机理，介绍了OER催化剂设计的基本准则，即调控Ir基催化剂的电子结构，改善反应中间物种在催化活性位点上的吸附能，从而提高OER催化活性。并从催化剂的结构设计、形貌控制、载体材料3个方面简单概述了最近OER催化剂的研究进展。最后，在已有研究的基础上，提出了目前OER催化剂面临的困难与挑战，这为以后相关的研究指明了方向。

关键词: 质子交换膜电解水技术, 氧析出反应, Ir基催化剂, 吸附物逸出机理, 晶格氧逸出机理

Abstract:

The rapid development of sustainable energy has made green and clean hydrogen energy a hot spot. Proton exchange membrane （PEM） water electrolysis is a promising technology that can efficiently produce high-purity hydrogen. IrO₂， the-state-of-the-art electrocatalyst for the oxygen evolution reaction （OER）， can not only overcome the high corrosion conditions in acidic media， but also exhibit superior catalytic performance. However， due to the scarcity and high price of Ir， it is crucial to develop low-Ir catalysts and improve the OER activity. The study of its reaction mechanism is one of the current research hotspots， and it is also the key to the design of excellent OER catalysts. The conventional adsorbate evolution mechanism （AEM） and lattice oxygen evolution reaction mechanism （LOER） are introduced. Subsequently， based on the two proposed mechanisms， the basic design principles of OER catalysts are introduced， namely， regulating the electronic structure of Ir-based catalysts， improving the adsorption energy of reaction intermediate species on the catalytic active sites， thereby increasing the catalytic activity of OER. It also briefly summarizes the recent research progress of OER catalysts from the three aspects of catalyst structure design， morphology control， and support materials， and the recent research progress of OER catalysts is briefly summarized. Moreover， several unresolved problems are put forward on the basis of the existing OER catalysts， which points out the direction for further research.

Key words: Proton exchange membrane water electrolysis technology, Oxygen evolution reaction, Ir-based catalysts, Adsorbate evolution mechanism, Lattice oxygen evolution mechanism

中图分类号:

O643

王雪, 王意波, 王显, 祝建兵, 葛君杰, 刘长鹏, 邢巍. 酸性电解水过程中氧析出反应的机理及铱基催化剂的研究进展[J]. 应用化学, 2022, 39(4): 616-628.

Xue WANG, Yi-Bo WANG, Xian WANG, Jian-Bing ZHU, Jun-Jie GE, Chang-Peng LIU, Wei XING. Research Progress of Mechanism of Acidic Oxygen Evolution Reaction and Development of Ir⁃based Catalysts[J]. Chinese Journal of Applied Chemistry, 2022, 39(4): 616-628.

图/表 1

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催化剂 Catalyst	电解质 Electrolyte	电极 Electrode	负载量 Mass loading/（mg·cm^-2）	过电势 Overpotential/mV	Tafel斜率 Tafel slope/（mV·dec^-1）
F（10%）?IrO₂^［63］	1 mol/L H₂SO₄	Ti箔 Ti foils	0.3	≈250	64
Ce_0.2?IrO₂@NPC^［26］	0.5 mol/L H₂SO₄	碳纸 Carbon paper （CP）	0.4	224	55.9
Ir₄Co₂Ni₂O₁₃^［29］	0.1 mol/L HClO₄	Ti板 Ti plates	0.2	285	53
IrCoNi^［28］	0.1 mol/L HClO₄	玻碳电极 Glassy carbon electrode （GCE）	0.01 mg_Ir	303	53.8
Li?IrSe₂^［64］	0.5 mol/L H₂SO₄	碳纤维纸 Carbon fiber paper （CFP）	0.25	220	-
SrCo_0.9Ir_0.1O_3-δ^［65］	0.1 mol/L HClO₄	玻碳电极 Glassy carbon electrode （GCE）	0.25	270	-
（Mn_0.7Ir₀₃）O₂：F^［66］	1 mol/L H₂SO₄	薄膜电极 Thin film electrodes	0.3	120	67
Mn?IrO₂^［67］	0.1 mol/L H₂SO₄	Ti箔 Ti foils	-	350	74

催化剂 Catalyst	电解质 Electrolyte	电极 Electrode	负载量 Mass loading/（mg·cm^-2）	过电势 Overpotential/mV	Tafel斜率 Tafel slope/（mV·dec^-1）
F（10%）?IrO₂^［63］	1 mol/L H₂SO₄	Ti箔 Ti foils	0.3	≈250	64
Ce_0.2?IrO₂@NPC^［26］	0.5 mol/L H₂SO₄	碳纸 Carbon paper （CP）	0.4	224	55.9
Ir₄Co₂Ni₂O₁₃^［29］	0.1 mol/L HClO₄	Ti板 Ti plates	0.2	285	53
IrCoNi^［28］	0.1 mol/L HClO₄	玻碳电极 Glassy carbon electrode （GCE）	0.01 mg_Ir	303	53.8
Li?IrSe₂^［64］	0.5 mol/L H₂SO₄	碳纤维纸 Carbon fiber paper （CFP）	0.25	220	-
SrCo_0.9Ir_0.1O_3-δ^［65］	0.1 mol/L HClO₄	玻碳电极 Glassy carbon electrode （GCE）	0.25	270	-
（Mn_0.7Ir₀₃）O₂：F^［66］	1 mol/L H₂SO₄	薄膜电极 Thin film electrodes	0.3	120	67
Mn?IrO₂^［67］	0.1 mol/L H₂SO₄	Ti箔 Ti foils	-	350	74

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