直接甲酸燃料电池（DFAFCs）是一种电化学能源转换装置，其能将甲酸的化学能直接转化为电能。因具备高效、清洁、便携等诸多优势，DFAFCs受到广泛关注。然而，在DFAFCs的运行过程中，阳极的甲酸电催化氧化反应（FAOR）动力学速率较慢，所以阳极往往需要催化剂来降低反应势垒。目前，常用的FAOR电催化剂为Pd，但Pd的高昂价格与地壳中的稀缺性使得DFAFCs的成本大幅上升。因此，开发一种高活性且成本较低的Pd基催化剂，对降低DFAFCs成本并提升其性能具有重要意义。

要实现这一目标，需要关注两个关键点：提高电催化剂的本征活性以及增加活性位点的数量。引入价格相对低廉的第二组元金属，与Pd形成合金，这样不仅能降低Pd基催化剂的成本，还能调节其结构，优化表面吸附能，从而增强其本征活性。此外，通过调控电催化剂的形貌，如构建一维纳米结构，可以扩大其比表面积，提高原子利用率，构建轴向电子传输通道，从而暴露更多活性位点，进一步提升电催化剂的性能。

本研究基于柯肯达尔效应（Kirkendall效应），采用Cu纳米线作为模板，通过电偶置换反应将Pd纳米颗粒沉积在Cu纳米线（Cu NW）上，利用不同原子间的扩散速率差异，成功合成了PdCu纳米管（PdCu NT）。通过对合成条件的优化，深入探讨了PdCu NT的生长机理，合成过程中，Pd原子向Cu原子发生相向扩散运动，Cu的扩散速率小于Pd的扩散速率，使Cu线内部形成空位缺陷，空位缺陷逐渐聚集，形成空心结构，同时，Pd与Cu发生置换扩散，逐渐形成PdCu合金纳米管壁。本文采用系统的物性表征和电化学分析手段，对其组分、结构、形貌以及FAOR电催化性能进行了全面的表征和评估。建立了结构与电催化剂性能之间的联系，明确了PdCu NT电催化剂中的“构效关系”，具体研究结果如下：

1.以Cu NW为模板，采用电偶置换法将Pd纳米粒子还原并沉积在Cu NW的表面，Cu NW的Cu原子和Pd纳米颗粒中的Pd原子由于电极电势的差异，发生置换扩散，逐步实现合金化，由于扩散速率的差异，产生Kirkendall效应，Pd原子向内扩散的速率小于Cu原子向外扩散的速率，使得Cu纳米线内部出现空心结构，形成了一维中空合金结构的PdCu NT。

2.PdCu NT中通过Cu的引入，有效分散了Pd纳米粒子，同时调节了Pd的几何结构和电子结构，同时，一维中空结构有效暴露更多活性位点，提高了该催化剂的电化学活性面积，相较于其他形貌的PdCu合金电催化剂，PdCu NT的电

 

化学活性面积最高（PdCu NT:71.31 cm² mg^-1_Pd）。

3.通过调节制备时间，合成一系列PdCu NT，并对其进行物相表征，发现调节反应时间可以有效调控合成的纳米管的管壁厚度和内径尺寸，随着制备时间的增长，管壁厚度和内径逐渐增大，反应6 h时，PdCu NT 6h的内径占纳米管直径的比例最高（41 %），Pd和Cu的分布更加均匀。具有一维中空结构的PdCu合金，构建了长程的物质传输通路和电子传递通道，增强了合金的电子传输和物质传递能力。引入的Cu对Pd的“第三体效应”，有效隔离了Pd表面对CO的吸附位点，同时调节了Pd的电子结构，优化了Pd的吸附能，此外，Cu作为亲氧组分，使催化剂表面吸附更多的含氧基团（OH_ads），在反应过程中与Pd形成双功能机理，从而增强催化剂的催化活性和抗中毒能力。PdCu NT 6h具有最高的本征活性（11.86 mA cm^-2）和质量比活性（909.2 mA mg^-1Pd），分别为商用Pd/C本征活性（2.3 mA cm^-2）的5.2倍和质量比活性（264.2 mA mg^-1Pd）的3.4倍。PdCu NT 6h同样具有最佳的抗CO中毒能力和相对良好的稳定性。本研究为设计和制备双金属空心纳米管FAOR电催化剂提供了实验基础和理论依据。

Direct formic acid fuel cells (DFAFCs) are electrochemical energy conversion devices that can directly convert the chemical energy of formic acid into electrical energy. Due to their many advantages such as high efficiency, cleanliness, and portability, DFAFCs have received widespread attention. However, during the operation of DFAFCs, the kinetic rate of formic acid oxidation reaction (FAOR) at the anode is slow, so the anode often requires a catalyst to reduce the reaction barrier. At present, the Pd-based material is one of the commonly used FAOR electrocatalysts, but the high price of Pd and its scarcity in the Earth's crust have significantly increased the cost of DFAFCs. Therefore, developing a highly active and low-cost Pd based catalyst is of great significance for reducing the cost and improving the performance of DFAFCs.

To achieve this goal, two key points need to be focused on: improving the intrinsic activity of the electrocatalyst and increasing the number of active sites. Introducing a relatively inexpensive second component metal to form an alloy with Pd not only reduces the cost of Pd based catalysts, but also adjusts their structure, optimizes surface adsorption energy, and enhances their intrinsic activity. In addition, by regulating the morphology of electrocatalysts, such as constructing one-dimensional nanostructures, their specific surface area can be expanded, atomic utilization can be improved, axial electron transport channels can be constructed, thereby exposing more active sites and further enhancing the performance of electrocatalysts.

This dissertation is based on the Kirkendall effect, using Cu nanowires as templates, and depositing Pd nanoparticles on Cu nanowires (Cu NW) through galvanic displacement reaction. By utilizing the difference in diffusion rates between different atoms, PdCu nanotubes (PdCu NT) were successfully synthesized. By optimizing the synthesis conditions, the growth mechanism of PdCu NT was deeply explored. During the synthesis process, the Pd atomic nucleus and Cu atoms undergo opposite diffusion movement, and the diffusion rate of Cu is lower than that of Pd, resulting in the formation of vacancy defects inside the Cu wire. The vacancy defects gradually aggregate, forming a hollow structure. At the same time, Pd and Cu undergo displacement diffusion, gradually forming PdCu alloy nanotube walls. This article adopts systematic physical characterization and electrochemical analysis methods to

 

comprehensively characterize and evaluate its composition, structure, morphology, and FAOR electrocatalytic performance. The relationship between structure and electrocatalyst performance has been established, and the "structure-activity relationship" in PdCu NT electrocatalysts has been clarified. The specific research results are as follows:

1. Using Cu NW as a template, Pd nanoparticles were reduced and deposited on the surface of Cu NW by electrochemical displacement method. Due to the difference in electrode potential, Cu atoms in Cu NW and Pd atoms in Pd nanoparticles underwent displacement diffusion, gradually achieving alloying. Due to the difference in diffusion rate, Kirkendall effect was generated, where the rate of inward diffusion of Pd atoms was lower than the rate of outward diffusion of Cu atoms, resulting in the formation of hollow structures inside Cu nanowires and the formation of one-dimensional hollow alloy structured PdCu NT.

2.By introducing Cu into PdCu NT, Pd nanoparticles are effectively dispersed, and the geometric and electronic structures of Pd are adjusted. At the same time, the one-dimensional hollow structure effectively exposes more active sites, increasing the electrochemical active area of the catalyst. Compared with other morphologies of PdCu alloy electrocatalysts, PdCu NT has the highest electrochemical active area (PdCu NT: 71.31 cm2 mg^-1_Pd).

3. By adjusting the preparation time, a series of PdCu NTs were synthesized and phase characterized. It was found that adjusting the reaction time could effectively control the wall thickness and inner diameter size of the synthesized nanotubes. As the preparation time increased, the wall thickness and inner diameter gradually increased. At 6 hours of reaction, the proportion of the inner diameter of PdCu NT at 6 hours to the nanotube diameter was the highest (41%), and the distribution of Pd and Cu was more uniform. The PdCu alloy with a one-dimensional hollow structure has constructed long-range material and electron transfer pathways, enhancing the alloy's electronic and material transfer capabilities. The introduced Cu exhibits a "third body effect" on Pd, effectively isolating the adsorption sites of CO on the Pd surface, while regulating the electronic structure of Pd and optimizing its adsorption energy. In addition, Cu acts as an oxygen friendly component, allowing the catalyst surface to adsorb more oxygen-containing groups (OH_ads), forming a dual functional mechanism with Pd during the reaction process, thereby enhancing the catalytic activity and anti

 

poisoning ability of the catalyst. PdCu NT exhibited the highest intrinsic activity (11.86 mA cm^-2) and mass specific activity (909.2 mA mg^-1_Pd) at 6h, which were 5.2 times higher than the intrinsic activity (2.3 mA cm^-2) and 3.4 times higher than the mass specific activity (264.2 mA mg^-1_Pd) of commercial Pd/C, respectively. PdCu NT also exhibits the best resistance to CO poisoning and relatively good stability after 6 hours. This study provides experimental and theoretical basis for the design and preparation of bimetallic hollow nanotube FAOR electrocatalysts.

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