3D-Printed Hierarchical Nanostructured N-Co2NiO4 NF Electrode for Efficient Concurrent Electrocatalytic Production of Hydrogen and Formate

Zhaojing Han; Hanwen Tao; Gang Wang; Chuanting Fan; Jie Zhang; Zhiyong Tang

doi:10.1002/smll.202407349

3D-Printed Hierarchical Nanostructured N-Co₂NiO₄ NF Electrode for Efficient Concurrent Electrocatalytic Production of Hydrogen and Formate

Small. 2025 Jan;21(3):e2407349. doi: 10.1002/smll.202407349. Epub 2024 Dec 9.

Authors

Zhaojing Han^{1

2}, Hanwen Tao^{1

2}, Gang Wang^{1

2}, Chuanting Fan^{1

2}, Jie Zhang^{1

2}, Zhiyong Tang^{1

2

3

4}

Affiliations

¹ Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, 201210, P. R. China.
² School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
³ School of Chemistry and Material Science, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
⁴ Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Engineering Research Center of Carbon Neutrality, College of Chemistry and Materials Science, Anhui Normal University, Wuhu, 241000, P. R. China.

PMID: 39654346
DOI: 10.1002/smll.202407349

Abstract

Replacing the oxygen evolution reaction with the alternative glycerol electro-oxidation reaction (GER) provides a promising strategy to enhance the efficiency of hydrogen production via water electrolysis while co-generating high-value chemicals. However, obtaining low-cost and efficient GER electrocatalysts remains a big challenge. Herein, a self-supported N-doped Co₂NiO₄ nanoflakes (N-Co₂NiO₄ NF) is proposed for efficient electrocatalytic oxidation of glycerol to formate. The synergistic effect induced by the interaction of the layered Co₂NiO₄ nanostructures on the 3D-printed Nickel-Yttria-stabilized zirconia (Ni-YSZ) substrate and the amorphous nitrogen-doping promotes the anodic GER. The N-Co₂NiO₄ NF exhibits low potentials of 1.07 and 1.18 V (vs. RHE) for GER to drive 10 and 50 mA cm^-2, respectively. The constituted two-electrode electrolyzer (N-Co₂NiO₄ NF//NiS-Co-NiP) displays excellent activity that only requires ultralow cell voltages of 1.24 and 1.55 V to afford 10 and 200 mA cm^-2, respectively, with a high FE (97%) for formate production and an excellent durability (120 h). This study provides a versatile approach for manufacturing high-performance Ni-based electrocatalyst for GER, paving the way for the energy-saving and environmentally-friendly co-production of value-added chemicals and hydrogen.

Keywords: alkaline water electrolysis; electrocatalyst; glycerol electro‐oxidation; hydrogen production; nitrogen‐doping.

Abstract

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