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通过低温热解稀释钯镍合金以增强电催化氢氧化反应

Dilute Pd-Ni Alloy through Low-temperature Pyrolysis for Enhanced Electrocatalytic Hydrogen Oxidation.

作者信息

Yuan Yi, Wu Xue-Qian, Yin Xi, Ruan Heng-Yu, Wu Ya-Pan, Li Shuang, Hai Guangtong, Zhang Gaixia, Sun Shuhui, Li Dong-Sheng

机构信息

College of Materials and Chemical Engineering, Key Laboratory of Inorganic Nonmetallic Crystalline and Energy Conversion Materials, China Three Gorges University, Yichang, 443002, P. R. China.

College of Electrical Engineering & New Energy, China Three Gorges University, Yichang, 443002, P. R. China.

出版信息

Angew Chem Int Ed Engl. 2024 Dec 20;63(52):e202412680. doi: 10.1002/anie.202412680. Epub 2024 Oct 24.

Abstract

Designing highly active and cost-effective electrocatalysts for the alkaline hydrogen oxidation reaction (HOR) is critical for advancing anion-exchange membrane fuel cells (AEMFCs). While dilute metal alloys have demonstrated substantial potential in enhancing alkaline HOR performance, there has been limited exploration in terms of rational design, controllable synthesis, and mechanism study. Herein, we developed a series of dilute Pd-Ni alloys, denoted as x% Pd-Ni, based on a trace-Pd decorated Ni-based coordination polymer through a facile low-temperature pyrolysis approach. The x% Pd-Ni alloys exhibit efficient electrocatalytic activity for HOR in alkaline media. Notably, the optimal 0.5 % Pd-Ni catalyst demonstrates high intrinsic activity with an exchange current density of 0.055 mA cm, surpassing that of many other alkaline HOR catalysts. The mechanism study reveals that the strong synergy between Pd single atoms (SAs)/Pd dimer and Ni substrate can modulate the binding strength of proton (H)/hydroxyl (OH), thereby significantly reducing the activation energy barrier of a decisive reaction step. This work offers new insights into designing advanced dilute metal or single-atom-alloys (SAAs) for alkaline HOR and potentially other energy conversion processes.

摘要

设计用于碱性氢氧化反应(HOR)的高活性且具有成本效益的电催化剂对于推进阴离子交换膜燃料电池(AEMFC)至关重要。虽然稀金属合金在提高碱性HOR性能方面已显示出巨大潜力,但在合理设计、可控合成和机理研究方面的探索却很有限。在此,我们通过一种简便的低温热解方法,基于微量钯修饰的镍基配位聚合物开发了一系列稀钯 - 镍合金,记为x% Pd - Ni。x% Pd - Ni合金在碱性介质中对HOR表现出高效的电催化活性。值得注意的是,最优的0.5% Pd - Ni催化剂具有高本征活性,交换电流密度为0.055 mA cm,超过了许多其他碱性HOR催化剂。机理研究表明,钯单原子(SAs)/钯二聚体与镍基底之间的强协同作用可以调节质子(H)/羟基(OH)的结合强度,从而显著降低关键反应步骤的活化能垒。这项工作为设计用于碱性HOR以及潜在的其他能量转换过程的先进稀金属或单原子合金(SAA)提供了新的见解。

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