直接甲醇燃料电池阳极催化剂的失活机制及应对策略

doi:10.16085/j.issn.1000-6613.2023-0936

摘要/Abstract

摘要：

甲醇氧化电催化剂是决定直接甲醇燃料电池（direct methanol fuel cells，DMFC）性能与成本的关键。目前，铂基催化剂是最有前途的高效甲醇氧化电催化剂，但在反应过程中存在活性位的迁移、团聚与浸出、中毒以及载体的腐蚀与坍塌等原因引起的失活问题，阻碍了其进一步商业化发展。如何提高直接甲醇燃料电池阳极催化剂的稳定性是一个亟待解决的难题。本文首先总结了甲醇的电氧化原理和催化反应机理，详细综述了阳极催化剂的失活机制以及抑制改善其失活方面所取得的研究进展。最后对该领域未来的发展方向进行了展望，并指出利用限域作用限制活性金属的迁移和聚集，构建多元合金，设计增强复合型载体，将理论研究和原位表征技术相结合，是今后开发更高效、稳定阳极催化剂的重点研究方向。

关键词: 直接甲醇燃料电池, 阳极催化剂, 失活机制, 金属粒子的迁移、团聚与浸出, 载体腐蚀与坍塌

Abstract:

Among many factors determining the performance and cost of direct methanol fuel cells(DMFC), methanol oxidation electrocatalyst is the most crucial one. At present, platinum-based catalysts are considered to be the most promising and efficient for methanol oxidation reaction. However, during the reaction process, there are deactivation problems caused by the agglomeration and leaching of active sites, poor anti-CO toxicity, and the corrosion and collapse of the support, which hinder the commercialization of DMFC. How to improve the stability of anode catalyst for DMFC is an urgent problem to be solved. Firstly, the principle and catalytic mechanism of methanol electrooxidation are summarized in this review. Then, the deactivation mechanisms of anode catalysts were reviewed in detail, and the effective methods to solve the deactivation issues were discussed. Finally, it was pointed out that using the confinement to restrict metal migration and aggregation, the construction of multi-alloy, the design of composite support, and combining the theoretical research with the insitu characterization technique, which were the main research directions of the development of higher and more stable anode catalysts in the future.

Key words: direct methanol fuel cell, anode catalyst, inactivation mechanism, migration agglomeration and leaching of metal particles, support corrosion and collapse

中图分类号:

O643

郭鹏, 李红伟, 李贵贤, 季东, 王东亮, 赵新红. 直接甲醇燃料电池阳极催化剂的失活机制及应对策略[J]. 化工进展, 2024, 43(7): 3812-3823.

GUO Peng, LI Hongwei, LI Guixian, JI Dong, WANG Dongliang, ZHAO Xinhong. Mechanisms and coping strategies on deactivation of anode catalysts for direct methanol fuel cells[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3812-3823.

图/表 10

参考文献 77

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催化剂	制备方法	测试条件	稳定性
Ce改性的Pt NPs/C^[28]	乙二醇化学还原法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	-0.2V下放电1000s后保持79.2%的初始活性
PtCo₃@CNTs^[13]	g-C₃N₄辅助热合成法	0.5mol/L H₂SO₄ + 0.5mol/L CH₃OH	1500圈加速老化后保持87.3%的初始活性
Pd-P@Pt-Ni^[33]	化学还原法	0.5mol/L H₂SO₄ + 0.5mol/L CH₃OH	500圈循环后ECSA降低2%
Pd₉₃Pt₇^[34]	一锅法	0.1mol/L NaOH + 0.5mol/LCH₃OH	500圈循环后保持86.5%的初始活性
Pt/TiO₂-Nb-HSS^[35]	硬模板法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	80℃循环200圈活性未发生明显下降
Pt-Au HNU^[37]	种晶生长法	0.1mol/L HClO₄ + 0.5mol/L CH₃OH	3000圈加速老化后ECSA降低25%
PtCo CNCs^[38]	水热合成法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	0.6V下放电8000s保持约25%的初始活性
PtSn/ATO^[39]	化学还原法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	500圈加速老化后活性降低15%
Pt₃Co/CNTs-M^[40]	化学还原法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	500圈循环后质量比活性下降20.9%
PtRuCu^[41]	电化学置换法	0.1mol/L HClO₄ + 0.5mol/LCH₃OH	800圈循环后质量比活性下降27%
Pt₁₇Pd₁₆Ru₂₂Te₄₅^[36]	牺牲模板法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	1000圈加速老化后质量比活性下降2.75%

催化剂	制备方法	测试条件	稳定性
Ce改性的Pt NPs/C^[28]	乙二醇化学还原法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	-0.2V下放电1000s后保持79.2%的初始活性
PtCo₃@CNTs^[13]	g-C₃N₄辅助热合成法	0.5mol/L H₂SO₄ + 0.5mol/L CH₃OH	1500圈加速老化后保持87.3%的初始活性
Pd-P@Pt-Ni^[33]	化学还原法	0.5mol/L H₂SO₄ + 0.5mol/L CH₃OH	500圈循环后ECSA降低2%
Pd₉₃Pt₇^[34]	一锅法	0.1mol/L NaOH + 0.5mol/LCH₃OH	500圈循环后保持86.5%的初始活性
Pt/TiO₂-Nb-HSS^[35]	硬模板法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	80℃循环200圈活性未发生明显下降
Pt-Au HNU^[37]	种晶生长法	0.1mol/L HClO₄ + 0.5mol/L CH₃OH	3000圈加速老化后ECSA降低25%
PtCo CNCs^[38]	水热合成法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	0.6V下放电8000s保持约25%的初始活性
PtSn/ATO^[39]	化学还原法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	500圈加速老化后活性降低15%
Pt₃Co/CNTs-M^[40]	化学还原法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	500圈循环后质量比活性下降20.9%
PtRuCu^[41]	电化学置换法	0.1mol/L HClO₄ + 0.5mol/LCH₃OH	800圈循环后质量比活性下降27%
Pt₁₇Pd₁₆Ru₂₂Te₄₅^[36]	牺牲模板法	0.5mol/L H₂SO₄ + 1mol/L CH₃OH	1000圈加速老化后质量比活性下降2.75%

催化剂	制备方法	测试条件	抗中毒性
Pt₃Rh^[50]	化学还原法	0.5mol/L H₂SO₄+0.5mol/L CH₃OH	I_f/I_b=2.61
Au₃Ag NFs^[51]	一锅法	0.5mol/L KOH+2mol/L CH₃OH	I_f/I_b=2.5
Pt₁Ag₃ DSNCs^[52]	水热法	0.5mol/L H₂SO₄+0.5mol/L CH₃OH	I_f/I_b=1.28
Pt/SiC^[53]	化学还原法	0.5mol/L KOH+0.5mol/L CH₃OH	I_f/I_b=1.48

催化剂	制备方法	测试条件	抗中毒性
Pt₃Rh^[50]	化学还原法	0.5mol/L H₂SO₄+0.5mol/L CH₃OH	I_f/I_b=2.61
Au₃Ag NFs^[51]	一锅法	0.5mol/L KOH+2mol/L CH₃OH	I_f/I_b=2.5
Pt₁Ag₃ DSNCs^[52]	水热法	0.5mol/L H₂SO₄+0.5mol/L CH₃OH	I_f/I_b=1.28
Pt/SiC^[53]	化学还原法	0.5mol/L KOH+0.5mol/L CH₃OH	I_f/I_b=1.48

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