燃料电池金属有机框架质子膜材料研究展望

doi:10.3969/j.issn.2097-0706.2022.08.011

摘要/Abstract

摘要：

质子交换膜燃料电池（PEMFC）是清洁高效的能源转换装置。质子交换膜作为重要的组件之一,会选择性地允许质子转移,但其昂贵的制作成本及较差的高温稳定性限制了在宽温范围的应用。金属有机框架（MOF）材料合成方法简单、结构稳定、比表面积高,广泛应用于催化和吸附等领域。近年来,研究人员发现某些MOF材料在一定温度、湿度范围内拥有优异的质子传导性能,且合成价格低廉,可作为潜在的质子交换膜替代材料。从有机配体（羧酸盐、膦酸盐、磺酸盐等）和客体分子（咪唑、铵根离子等）两部分叙述MOF材料的合成,每种MOF材料的化学稳定性、质子导电性能及其导电机理等方面的研究进展,并指出该类导电材料的发展前景和未来面临的挑战及可实施策略。

关键词: 金属有机框架, 燃料电池, 质子传导, 有机配体, 客体分子, 稳定性

Abstract:

A proton exchange membrane fuel cell（PEMFC） is a clean and efficient energy conversion device. Proton exchange membrane,as an important component of a PEMFC, can selectively permit the transfer of protons. However, high cost and poor stability against high temperature of proton exchange membranes restrict their practical applications in wide temperature range. Metal organic framework （MOF） materials are widely applied in catalytic and adsorption fields due to their facile synthesis, robust structures and high specific surface areas. In recent years, it has been revealed that a few MOF materials with high proton conductivity and low cost are deemed as potential alternatives for proton exchange membranes. Herein, the synthesis, chemical stability, proton conductivity and mechanism of MOF materials are discussed based on organic ligands （carboxylate, phosphonate, sulfonate, etc.） and guest molecules （imidazole, ammonium ion, etc.）. The development prospect, future challenges and feasible strategies of the conductive MOF materials are also proposed.

Key words: metal organic frameworks, fuel cell, proton conduction, organic ligand, guest molecule, stability

中图分类号:

TK01:TM911

张靖, 刘宇宙, 贺贝贝, 赵凌. 燃料电池金属有机框架质子膜材料研究展望[J]. 综合智慧能源, 2022, 44(8): 97-106.

ZHANG Jing, LIU Yuzhou, HE Beibei, ZHAO Ling. Reviews on proton membrane materials for metal-organic frameworks in fuel cells[J]. Integrated Intelligent Energy, 2022, 44(8): 97-106.

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有机配体	金属有机框架	结构	质子电导率/(S·cm^-1)	参考文献
草酸盐/甲酸盐	[Fe(ox)(H₂O)₂]	1D	1.30×10^-6(25 ℃,40%~95%RH)	[43]
	[La₂(ox)₃(H₂O)₆]·4H₂O	2D	3.35×10^-7(95 ℃,100%RH)	[44]
	[Er₂(ox)₃(H₂O)₆]·12H₂O	3D	1.76 ×10^-9(90 ℃,100%RH)	[44]
	LaCr(ox)₃·10H₂O	1D	1.00×10^-6(25 ℃,40%~95%RH)	[45]
	LaCo(ox)₃·10H₂O	1D	1.00×10^-5(25 ℃,40%~95%RH)	[45]
	LaRu(ox)₃·10H₂O	2D	3.00×10^-8(25 ℃,40%~95%RH)	[45]
	LaLa(ox)₃·10H₂O	2D	3.00×10^-8(25 ℃,40%~95%RH)	[45]
	LaCo(ox)₃·10H₂O	2D	1.00×10^-10(25 ℃,40%~95%RH)	[45]
	MOF-801	3D	1.88×10^-3(25 ℃,98%RH)	[46]
芳香羧酸酯	Zr₆O₄(OH)₆(p-BDC)₅	3D	6.93×10^-3(65 ℃,95%RH)	[47]
	Mg(p-BDC)(PyOH)	3D	8.30×10^-6(90 ℃,90%RH)	[48]
	[[Zn(2-MBIm)(o-BDC)(H₂O)]·2H₂O]_n	1D	1.00×10^-5(25 ℃,100%RH)	[49]
	[Cu(H₄L)(DMF)₄]_n	1D	3.46×10^-3(95 ℃,95%RH)	[50]
咪唑类	[Cu(p-IPhHIDC)]_n	2D	1.15×10^-3(100 ℃,98%RH)	[51]
咪唑类	{Na[Cd(MIDC)]}_n	3D	1.04×10^-3(100 ℃,98%RH)	[52]
磷酸盐	[Li₃(HPA)(H₂O)₄]·H₂O	1D	1.10×10^-4(24 ℃,98%RH)	[53]
	Na₂(HHPA)(H₂O)₄	3D	5.60×10^-3(24 ℃,98%RH)	[53]
	K₂(HHPA)(H₂O)₂	3D	1.30×10^-3(24 ℃,98%RH)	[53]
	Cs(H₂HPA)	3D	3.50×10^-5(24 ℃,98%RH)	[53]
	[Ca₂(H₃PiPhtA)₂(H₂PiPhtA)(H₂O)₂]·5H₂O	3D	5.70×10^-4(24 ℃,98%RH)	[54]
	MgH₆ODTMP·6H₂O	3D	1.60×10^-3(19 ℃,100%RH)	[55]
	Zr₂(PO₄)H₅(L)₂·2H₂O	2D	1.00×10^-3(140 ℃,95%RH)	[56]
磺酸盐	BUT-8	3D	1.27×10^-1(80 ℃,100%RH)	[57]
磺酸盐	UiO-66-SO₃H	—	3.40×10^-1(80 ℃,98%RH)	[58]

有机配体	金属有机框架	结构	质子电导率/(S·cm^-1)	参考文献
NH₄⁺	(NH₄)₄[MnCr₂(ox)₆]·4H₂O	2D	1.10×10^-3(40 ℃,96%RH)	[74]
NH₄⁺	NH₄Br@HKUST-1	3D	8.99×10^-4(25 ℃,99%RH)	[75]
咪唑类	Al(OH)(1,4-ndc)	3D	2.20×10^-5(25 ℃,99%RH)	[76]
	Im@(NENU-3)	3D	1.82×10^-2(70 ℃,90%RH)	[77]
	Im-Cu@(NENU-3a)	3D	3.16×10^-4(70 ℃,90%RH)	[77]
	Im@Fe-MOF	3D	4.23×10^-3(60 ℃,98%RH)	[78]