氧空位增强PdNi/HfO2催化剂在乙二醇电催化氧化中的活性

doi:10.6023/A25020055

摘要/Abstract

为了进一步提升直接乙二醇燃料电池的性能, 开发高效的乙二醇氧化反应(EGOR)电催化剂至关重要. 尽管PdNi合金纳米晶表现出优异的EGOR活性, 但其性能仍难以满足燃料电池的实际应用需求. 基于此, 本研究提出通过构建氧空位(O_v)来增强PdNi合金电催化活性的创新策略. 在氧化铪(HfO₂)材料合成过程中引入镍(Ni)掺杂, 成功诱导HfO₂从晶相向非晶相转变, 并在其内部形成高浓度氧空位. 以此作为载体, 负载PdNi合金纳米晶, 即制备得到PdNi/HfO₂-O_v催化剂. 在碱性体系电化学EGOR中, PdNi/HfO₂-O_v催化剂质量活性达到10.28 , 较无氧空位的PdNi/HfO₂及商用钯碳(Pd/C)催化剂分别提升2.2倍与7.56倍. X射线光电子能谱(XPS)研究发现氧空位的引入能够调控Pd的电子结构, 产生电子效应进而提升PdNi活性. 通过Ni掺杂, 同时调控HfO₂载体晶型和氧空位缺陷, 并通过氧空位调控Pd合金电子结构和本征活性的研究思路, 为直接乙二醇燃料电池阳极催化剂设计提供了新策略.

关键词: 直接乙二醇燃料电池, 乙二醇氧化, PdNi合金, 氧空位, HfO₂

To further enhance the performance of direct ethylene glycol fuel cells, the development of highly efficient electrocatalysts for the ethylene glycol oxidation reaction (EGOR) is crucial. Although PdNi alloy nanocrystals exhibit excellent EGOR activity, their performance still falls short of the practical application requirements for fuel cells. Based on this, this study proposes an innovative strategy to enhance the electrocatalytic activity of PdNi alloys by introducing oxygen vacancies (O_v). By doping Ni into HfO₂, the transformation of HfO₂ from monoclinic to amorphous phases is induced, promoting the formation of high concentrations of oxygen vacancies within HfO₂ and thereby regulating the electronic structure and catalytic activity of the supported PdNi alloy. It was found that at lower Ni doping levels, a monoclinic carrier Ni/c-HfO₂ is obtained; at medium Ni doping levels, an amorphous carrier Ni/HfO₂-O_v rich in oxygen vacancies is obtained; and at high Ni doping levels, an amorphous Ni/HfO₂ without oxygen vacancies is obtained. This indicates that Ni doping can simultaneously regulate both the crystal structure and oxygen vacancy concentration of HfO₂. Further introduction of a Pd^2＋precursor onto the surface of the HfO₂ carrier followed by simple solution reduction prepares the PdNi alloy-supported catalyst. The study revealed that in a 1 mol/L KOH＋1 mol/L ethylene glycol (EG) electrolyte solution, PdNi/HfO₂-O_v exhibits excellent performance for EGOR with the lowest onset potential (0.3 V), the smallest charge transfer resistance (3.28 Ω), and mass activity (MA) and specific activity (SA) reaching 10.28 and 38.6 mA•cm^－2, respectively. Compared to PdNi/HfO₂ without oxygen vacancies and commercial Pd/C catalysts, the EGOR performance is significantly improved. X-ray photoelectron spectroscopy (XPS) analysis revealed that the introduction of oxygen vacancies facilitates charge transfer from Pd to the HfO₂ carrier, thereby optimizing the electronic structure of Pd and accelerating the reaction kinetics. The research approach of regulating both the crystal structure and oxygen vacancy defects of the HfO₂ carrier through Ni doping, and further regulating the electronic structure and intrinsic activity of the Pd alloy through oxygen vacancies, provides a new strategy for designing anode catalysts for direct ethylene glycol fuel cells.

Key words: direct ethylene glycol fuel cell, ethylene glycol oxidation, palladium-nickel alloy, oxygen vacancy, HfO₂

引用此文

张娜娜, 李静. 氧空位增强PdNi/HfO₂催化剂在乙二醇电催化氧化中的活性[J]. 化学学报, 2025, 83(7): 709-715.

Nana Zhang, Jing Li. Oxygen Vacancies Enhance the Activity of PdNi/HfO₂ Catalysts for Ethylene Glycol Electrocatalytic Oxidation[J]. Acta Chimica Sinica, 2025, 83(7): 709-715.

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图/表 6

图1. 催化剂的制备路线

Figure 1. Preparation route of the catalyst

图2. (a) XRD图谱; (b) PdNi/HfO2-Ov的TEM图像; (c) HRTEM图像; (d~f) EDS元素映射图像(Hf: 红色, Ni: 黄色, Pd: 绿色)

Figure 2. (a) XRD pattern; (b) TEM image of PdNi/HfO2-Ov; (c) HRTEM image; (d~f) EDS elemental mapping (Hf: red, Ni: yellow, Pd: green)

图3. 三组催化剂的EPR信号峰(a); PdNi/HfO2-Ov、PdNi/HfO2的XPS图谱(b) Pd 3d (c) Hf 4f (d) Ni 2p

Figure 3. (a) EPR spectra of PdNi/HfO2-Ov, PdNi/HfO2 and PdNi/c-HfO2; The high resolution XPS spectra of Pd 3d (b), Hf 4f (c), Ni 2p (d) for PdNi/HfO2-Ov and PdNi/HfO2

c[Ni(acac)₂]/(mmol•L^－1)	中间产物	产品	w(Ni) (by ICP-OES)/%	w(Pd) (by ICP-OES)/%	结构	氧空位
0.26	Ni/HfO₂	PdNi/HfO₂	6.4	5.1	无定形	无
0.13	Ni/HfO₂-O_v	PdNi/HfO₂-O_v	3.2	5	无定形	有
0.08	Ni/c-HfO₂	PdNi/c-HfO₂	1.9	3	单斜晶系	无

表1. 三组催化剂的结构参数

Table 1. The structural parameters of the three catalyst groups

图4. PdNi/HfO2-Ov、PdNi/HfO2、Pd/C催化剂电化学活性测试结果. (a) CV曲线(1 mol/L KOH, 扫描速率: 50 mV/s); (b)催化剂在1.0~0.5 V vs. RHE电位范围内的CV曲线; (c) ECSA值; (d) CV曲线(1 mol/L KOH＋1 mol/L EG, 扫描速率: 50 mV/s); (e)催化剂在0~0.7 V vs. RHE电位范围内的CV曲线; (f) If/Ib值; (g)质量活性和比活性; (h)本工作的PdNi/HfO2-Ov催化剂与文献报道的质量活性对比

Figure 4. The electrochemical activity test results for the PdNi/HfO2-Ov, PdNi/HfO2, and Pd/C catalysts: (a) CV curves (1 mol/L KOH, scan rate: 50 mV/s); (b) CV curves of the catalyst within the potential range of 1.0~0.5 V vs. RHE; (c) ECSA values; (d) CV curves (1 mol/L KOH＋1 mol/L EG, scan rate: 50 mV/s); (e) CV curves of the catalyst within the potential range of 0~0.7 V vs. RHE; (f) If/Ib values; (g) mass activity and specific activity; (h) comparison of the mass activity of the PdNi/HfO2-Ov catalyst in this work with those reported in the literature

图5. PdNi/HfO2-Ov、PdNi/HfO2、Pd/C催化剂电化学稳定性测试结果. (a) 100次CV循环后材料的稳定性; (b) 0.7 V vs. RHE下记录的计时电流测试曲线, 溶液为1 mol/L KOH＋1 mol/L EG; (c)稳定性测试后电流保留百分比和质量活性保留值; (d) EIS研究

Figure 5. The electrochemical stability test results for the PdNi/HfO2-Ov, PdNi/HfO2, and Pd/C catalysts: (a) stability of the materials after 100 cycles of cyclic voltammetry (CV); (b) Chronoamperometric curves recorded at 0.7 V vs. RHE in a solution of 1 mol/L KOH＋1 mol/L EG; (c) percentage of current retention and mass activity retention values after stability testing; (d) Electrochemical impedance spectroscopy (EIS) study

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氧空位增强PdNi/HfO₂催化剂在乙二醇电催化氧化中的活性

Oxygen Vacancies Enhance the Activity of PdNi/HfO₂ Catalysts for Ethylene Glycol Electrocatalytic Oxidation

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