Pd基阳极催化剂在直接乙醇燃料电池中的应用研究进展

doi:10.16553/j.cnki.issn1000-985x.2026.0029

摘要/Abstract

摘要： 在“双碳”背景下，直接乙醇燃料电池（DEFCs）因高效、低污染而被广泛关注。DEFCs在能量转换过程中严重依赖催化剂的效能，其阳极催化剂易因中间产物累积、吸附而失活，合理的结构设计可大幅度提高催化材料的催化活性，实现催化材料的高效利用。基于此，本文从Pd基阳极催化剂构建策略出发，明确将当前DEFCs 中的阳极催化剂设计理念归为3类，即基于材料结构的形貌调控设计、基于活性位点的电子态调变设计与基于载体与界面工程的协同优化设计，并系统对比了酸性与碱性介质中Pd基催化剂的性能差异与设计策略。同时，结合其在乙醇氧化中展现出的优异催化性能，进一步剖析了中毒中间体的控制，并将其可归纳为3个阶段：1）C—C键断裂路径调控——中毒前体消除；2）d带中心调控——中毒物种吸附弱化；3）OH_ads供应强化——氧化去除加速。此外，本文将催化剂稳定性作为核心科学问题，系统梳理了Pd基催化剂的主要失活机制（Pd溶解、Ostwald熟化、载体腐蚀、中间体强吸附等）及相应的设计对策。针对当前Pd基阳极催化剂的研究，应在重点解决催化剂稳定性瓶颈的基础上，加快机器学习辅助设计步伐，结合原位表征技术来进行催化机制探索与解析，进一步从组分、结构、载体等多个维度进行协同优化，逐步攻克高效稳定Pd基催化剂的宏量和可控构筑。

关键词: 直接乙醇燃料电池（DEFCs）; 乙醇氧化; Pd基; 阳极催化剂; 稳定性; 失活机制

Abstract: Under the context of “dual carbon” goals （carbon peaking and carbon neutrality），direct ethanol fuel cells （DEFCs） have been extensively investigated owing to their high efficiency and low pollution emissions. The energy conversion process of DEFCs is heavily dependent upon the efficacy of catalysts，whereas the anode catalysts are prone to deactivation caused by the accumulation and adsorption of reaction intermediates. The catalytic activity of materials can be substantially enhanced and the efficient utilization of catalysts can be achieved through rational structural design. Based on this perspective，starting from the construction strategies of Pd-based anode catalysts，the current design concepts for anode catalysts in DEFCs are explicitly categorized into three classes of morphology engineering based on material structures，electronic state modulation based on active sites，and synergistic optimization based on support and interface engineering. The Pd-based catalyst performance and design strategies in alkaline are systematically compared. Meanwhile，combined with the superior catalytic performance demonstrated in ethanol oxidation，the control mechanisms of poisoning intermediates are further analyzed as follows： 1） C—C bond cleavage pathway regulation—poisoning precursor elimination； 2） d-band center modulation—the weakening of adsorption of poisoning species； 3） enhanced supply of adsorbed hydroxyl species （OH_ads）—accelerated oxidative removal. Furthermore，catalyst stability is addressed as a central scientific issue，with a systematic review of the major deactivation mechanisms of Pd-based catalysts （Pd dissolution，Ostwald ripening，support corrosion，and strong adsorption of intermediates） and corresponding design countermeasures. Regarding current research on Pd-based anode catalysts，priority should be given to solve the stability bottleneck of catalysts while considering catalyst stability. Combined with in-situ characterization techniques，the exploration and interpretation of catalytic mechanisms should be conducted，followed by synergistic optimization from multiple dimensions including composition，structure，and support materials，thereby gradually overcoming the challenges in scalable and controllable construction of highly efficient and stable Pd-based catalysts.

Key words: direct ethanol fuel cell （DEFC）; ethanol oxidation; Pd-based; anode catalyst; stability; deactivation mechanism

中图分类号:

TM911.4

梁茵茵, 南旭, 韦邦帜, 吴治超, 刘飞, 张琴, 王盾. Pd基阳极催化剂在直接乙醇燃料电池中的应用研究进展[J]. 人工晶体学报, 2026, 55(6): 830-842.

LIANG Yinyin, NAN Xu, WEI Bangzhi, WU Zhichao, LIU Fei, ZHANG Qin, WANG Dun. Research Progress on Application of Pd-Based Anode Catalysts in Direct Ethanol Fuel Cells[J]. Journal of Synthetic Crystals, 2026, 55(6): 830-842.

图/表 3

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Catalyst	Solution	ECSA/ （m²·g^-1）	Specific activity/（mA·cm^-2）	Mass activity/ （mA·mg_Pd^-1）	Stability	Reference
Pd/ZnO/MDC_（800）	1 mol/L KOH+1 mol/L CH₃CH₂OH	36.37		1 838.30	Near 300 mA·mg_Pd^-1 after 10 h	［10］
PdAuCu NPs-0.5	1 mol/L KOH+1 mol/L CH₃CH₂OH	217.49		22 997	2 000 mA·mg_Pd^-1 after 3 600 s	［21］
In₃Pd₂	1 mol/L KOH+1 mol/L CH₃CH₂OH	76.51		2 820	675.8 mA·mg_Pd^-1 after 2 100 s	［22］
In₃Pd₅	1 mol/L KOH+1 mol/L CH₃CH₂OH	73.28		1 980	NA	［22］
PdCuIn NPs	1 mol/L KOH+1 mol/L CH₃CH₂OH	250		15 540	220 mA·mg_Pd^-1 after 3 600 s	［23］
PdAg-0.1PVP/C	1 mol/L KOH+1 mol/L CH₃CH₂OH	60.1	19.1	9 745	736 mA·mg_Pd^-1 after 1 000 s	［50］
PdAu@N10.69C	1 mol/L KOH+1 mol/L CH₃CH₂OH	72.55	13.2	9 700	4.1 A·mg_Pd^-1 after 6 000 s	［59］
PdPt@s-EPS	1 mol/L KOH+1 mol/L CH₃CH₂OH	291.0	3.89	1 130	2.87 times of Pt/C after 20 000 s	［60］
Au@Pd NDs	1 mol/L KOH+1 mol/L CH₃CH₂OH	228.72		1 746.0	144.6 mA·mg_Pd^-1 after 3 600 s	［65］
PdCuB@N-G	1 mol/L KOH+1 mol/L CH₃CH₂OH	~83		5 830	3.62 A·mg_Pd^-1 after 5 000 cycles	［68］
Pd/Hy-1	0.5 mol/L KOH+0.5 mol/L CH₃CH₂OH	17.62		425		［63］
Pd₂Cu/Ni₂P-C	1 mol/L KOH+1 mol/L CH₃CH₂OH	108.68	3.656 7	3 974.08	45 mA·mg_Pd^-1 after 1 000 s	［64］
0D-2D PdPt NCs	0.5 mol/L KOH+1 mol/L CH₃CH₂OH	44	17.81	7 840	Near 2 000 mA·mg_Pd^-1 after 3 600 s	［47］
Pd-Cu/gC₃N₄	0.5 mol/L KOH+1 mol/L CH₃CH₂OH	54	4.54			［69］
Pd₉₀Cu₁₀B/GN	1 mol/L KOH+1 mol/L CH₃CH₂OH	112.00		975	65.4% of the highest current density after 1 000 cycles	［70］

Catalyst	Solution	ECSA/ （m²·g^-1）	Specific activity/（mA·cm^-2）	Mass activity/ （mA·mg_Pd^-1）	Stability	Reference
Pd/ZnO/MDC_（800）	1 mol/L KOH+1 mol/L CH₃CH₂OH	36.37		1 838.30	Near 300 mA·mg_Pd^-1 after 10 h	［10］
PdAuCu NPs-0.5	1 mol/L KOH+1 mol/L CH₃CH₂OH	217.49		22 997	2 000 mA·mg_Pd^-1 after 3 600 s	［21］
In₃Pd₂	1 mol/L KOH+1 mol/L CH₃CH₂OH	76.51		2 820	675.8 mA·mg_Pd^-1 after 2 100 s	［22］
In₃Pd₅	1 mol/L KOH+1 mol/L CH₃CH₂OH	73.28		1 980	NA	［22］
PdCuIn NPs	1 mol/L KOH+1 mol/L CH₃CH₂OH	250		15 540	220 mA·mg_Pd^-1 after 3 600 s	［23］
PdAg-0.1PVP/C	1 mol/L KOH+1 mol/L CH₃CH₂OH	60.1	19.1	9 745	736 mA·mg_Pd^-1 after 1 000 s	［50］
PdAu@N10.69C	1 mol/L KOH+1 mol/L CH₃CH₂OH	72.55	13.2	9 700	4.1 A·mg_Pd^-1 after 6 000 s	［59］
PdPt@s-EPS	1 mol/L KOH+1 mol/L CH₃CH₂OH	291.0	3.89	1 130	2.87 times of Pt/C after 20 000 s	［60］
Au@Pd NDs	1 mol/L KOH+1 mol/L CH₃CH₂OH	228.72		1 746.0	144.6 mA·mg_Pd^-1 after 3 600 s	［65］
PdCuB@N-G	1 mol/L KOH+1 mol/L CH₃CH₂OH	~83		5 830	3.62 A·mg_Pd^-1 after 5 000 cycles	［68］
Pd/Hy-1	0.5 mol/L KOH+0.5 mol/L CH₃CH₂OH	17.62		425		［63］
Pd₂Cu/Ni₂P-C	1 mol/L KOH+1 mol/L CH₃CH₂OH	108.68	3.656 7	3 974.08	45 mA·mg_Pd^-1 after 1 000 s	［64］
0D-2D PdPt NCs	0.5 mol/L KOH+1 mol/L CH₃CH₂OH	44	17.81	7 840	Near 2 000 mA·mg_Pd^-1 after 3 600 s	［47］
Pd-Cu/gC₃N₄	0.5 mol/L KOH+1 mol/L CH₃CH₂OH	54	4.54			［69］
Pd₉₀Cu₁₀B/GN	1 mol/L KOH+1 mol/L CH₃CH₂OH	112.00		975	65.4% of the highest current density after 1 000 cycles	［70］