Efficient electrocatalytic oxidation of glycerol toward formic acid over well-defined nickel nanoclusters capped by ligands

doi:10.1016/S1872-2067(25)64779-6

Abstract

Abstract:

The electrocatalytic oxidation of glycerol toward formic acid is one of the most promising pathways for transformation and utilization of glycerol. Herein, a series of well-defined Ni_n(SR)₂_n nanoclusters (n = 4, 5, 6; denoted as Ni NCs) were prepared for the electrocatalytic glycerol oxidation toward formic acid, in which Ni₆-PET-50CV afforded the most excellent electrocatalytic performance with a high formic acid selectivity of 93% and a high glycerol conversion of 86%. This was attributed to the lowest charge transfer impedance and the most rapid reaction kinetics. Combined electrochemical measurements and X-ray absorption fine structure measurements revealed that the structures of Ni NCs remained intact after CV scanning pretreatment and electrocatalysis via forming the Ni-O bond. Additionally, the kinetic studies and in-situ Fourier transformed infrared suggested a sequential oxidation mechanism, in which the main reaction steps of glycerol → glyceraldehyde → glyceric acid were very rapid to produce a high selectivity of formic acid even though the low glycerol conversion. This work presents an opportunity to study Ni NCs for the efficient electrocatalytic oxidation of biomass-derived polyhydroxyl platform molecules to produce value-added carboxylic acids.

Key words: Nickel nanocluster, Well-defined structure, Electrocatalysis, Glycerol oxidation, Formic acid

Dan Yang, Xiang Cui, Zhou Xu, Qian Yan, Yating Wu, Chunmei Zhou, Yihu Dai, Xiaoyue Wan, Yuguang Jin, Leonid M. Kustov, Yanhui Yang. Efficient electrocatalytic oxidation of glycerol toward formic acid over well-defined nickel nanoclusters capped by ligands[J]. Chinese Journal of Catalysis, 2025, 76: 185-197.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64779-6

https://www.cjcatal.com/EN/Y2025/V76/I9/185

Figures/Tables 9

Fig. 1. (a) Crystal structures of Ni4, Ni5, and Ni6, all hydrogen atoms are omitted for clarity. (b) MALDI mass spectra of Ni NCs. (c) UV-vis spectra of Ni NCs. Ni K-edge XANES spectra (d) and FT-EXAFS spectra (e) for Ni6-PET NCs after 0, 20, 50 CV pretreatment at 0.7-2.3 V vs. RHE in 0.1 mol L-1 KOH. Ni foil and NiO are showed for comparison. Color labels: green = Ni; yellow = S; grey = C.

Fig. 2. Electrocatalytic performance of GLY oxidation over the Nix NCs. (a) The LSV curves of Ni6-PET NCs pretreated by different scanning segments in 0.1 mol L-1 KOH with 0.01 mol L-1 GLY. (b) Catalytic performance of different Ni6-PET NCs at 1.40 V vs. RHE. (c) LSV curves of Ni4-PET, Ni5-PETand Ni6-PET NCs pretreated by scanning 50 segments CV curves in 0.1 mol L-1 KOH solution with and without 0.01 mol L-1 GLY. (d) Catalytic performance of pretreated Nix-50CV NCs under different applied potentials, others mainly included small amounts of GLYC, LA and GLYO.

Fig. 3. (a) Schematic diagram of Ni6 structure with different organic ligands. (b) UV-vis spectra of Ni6-PET, Ni6-C4, and Ni6-C8 NCs. (c) LSV curves of Ni6-PET, Ni6-C4, and Ni6-C8 NCs pretreated by scanning 50 segments CV curves in 0.1 mol L-1 KOH solution with and without 0.01 mol L-1 GLY. (d) Catalytic performance of pretreated Nix-50CV NCs at 1.50 V vs. RHE, 40 °C for 8 h, others mainly included small amounts of GLYC, LA and GLYO.

Fig. 4. (a,c) Capacitive current densities of Nix-PET-nCV NCs in GLY oxidation as a function of scan rate. (b,d) ECSA normalized LSV curves of Nix-PET-nCV NCs.

Fig. 5. Structural evolutions of the Ni6-PET NCs pretreated by different CV scanning segments. (a) In-situ ATR-IR spectra of ligand changes; (b) UV-vis spectra; (c) Ni 2p; (d) S 2p XPS spectra.

Fig. 6. In-situ XANES spectra (a) and EXAFS spectra (b) for the Ni6-PET NCs after 50CV, 150CV and 350CV pretreatment. Time-resolved in-situ XANES spectra (c) and EXAFS spectra (d) for the Ni6-PET-50CV catalyzing GLY oxidation.

Fig. 7. Nyquist plots of Ni6-PET pretreated by different CV scanning segments (a), Ni4, Ni5, and Ni6 NCs pretreated by 50 scanning segments (b), different ligand capped Ni6 NCs pretreated by 50 scanning segments at an applied bias voltage (c). (d) Nyquist plots of Ni6-PET-50CV NCs at the applied potentials.

Fig. 8. In-situ ATR FT-IR spectra of Ni6-PET-0CV (a), Ni6-PET-20CV (b), Ni6-PET-50CV (c), and Ni6-PET-100CV (d) catalyzing the GLY electrooxidation

Fig. 9. The Tafel plots for GLY oxidation of Ni6-PET-nCV (a) and Ni NCs (b) with different sizes and ligands. (c) Kinetic profiles of Ni4-PET, Ni5-PET and Ni6-PET catalysts in GLY oxidation. Selectivity-conversion correlation of GLY oxidation over (d) Ni4-PET, (e) Ni4-PET, and (f) Ni6-PET catalysts. Reaction condition: 1.45 V vs. RHE, 25 °C, Ni NCs catalysts were pretreated by the 50 CV scanning.

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