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

doi:10.6023/A25020055

Abstract

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

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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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Fig. & Tab. 6

Figure 1. Preparation route of the catalyst

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)

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

Table 1. The structural parameters of the three catalyst groups

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

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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氧空位增强PdNi/HfO2催化剂在乙二醇电催化氧化中的活性