Modulating active sites via Mn-doping in NiCo LDH for energy-saving paired electrosynthesis of H2O2 and formate

doi:10.1016/S1872-2067(26)65137-6

Abstract

Abstract:

Electrochemical H₂O₂ synthesis via the two-electron oxygen reduction reaction (2e^- ORR) offers a green alternative to the energy-intensive anthraquinone process, but its practical viability is hindered by the sluggish and low-value oxygen evolution reaction (OER) at the anode. Here, we present an energy-saving paired electrolysis strategy that replaces anodic OER with methanol oxidation reaction (MOR) using a ternary Mn-doped NiCo layered double hydroxide (Ni_0.50Co_0.30Mn_0.20 LDH) catalyst in situ grown on nickel foam (NF) by a one-step hydrothermal method. The optimized catalyst achieves a low MOR potential of 1.32 V_RHE at 10 mA cm^-2 and a formate Faradaic efficiency of 92.9%, outperforming its undoped counterpart (Ni_0.61Co_0.39 LDH, 1.37 V_RHE and 83.3%). In-situ Raman spectroscopy and density functional theory calculations reveal that Mn doping lowers the energy barrier for the Ni²⁺/Ni³⁺ redox transition, facilitating the generation of catalytically active Ni³⁺ species. When coupled with graphitized hydroxyl-functionalized multi-walled carbon nanotubes coated on carbon paper (CNTs@CP) as the 2e^- ORR cathode in a two-electrode electrolyzer, at the operation condition of 50 mA cm^-2, the 2e^- ORR||MOR system delivers a cell voltage reduction of 254 mV, enabling a 10.3% decrease in energy consumption for H₂O₂ production, compared with the conventional 2e^- ORR||OER system. Moreover, the simultaneous generation of value-added formate at the anode yields a 97.9% increase in net economic benefit. This work establishes a generalizable paired electrolysis paradigm for the decentralized, energy-efficient, and economically viable co-production of H₂O₂ and high-value chemicals.

Key words: Hydrogen peroxide electrosynthesis, Methanol oxidation reaction, Coupled electrolysis, Low energy

Jiayu Zhang, Kun Wang, Jinglu Yu, Kaiyang Xu, Lu Yang, Jiali Rao, Shuqin Song, Yi Wang. Modulating active sites via Mn-doping in NiCo LDH for energy-saving paired electrosynthesis of H₂O₂ and formate[J]. Chinese Journal of Catalysis, 2026, 88: 307-321.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65137-6

https://www.cjcatal.com/EN/Y2026/V88/I9/307

Figures/Tables 7

Fig. 1. Schematic illustration of the conventional anthraquinone process (a), the conventional electrochemical system for H2O2 synthesis (b), and the coupled electrochemical system for co-producing H2O2 and formate in this work (c).

Fig. 2. (a) Synthesis process of Ni0.61Co0.39 LDH and Mn-NiCo LDH. (b) XRD patterns of Ni0.61Co0.39 LDH and Mn-NiCo LDH powders. (c-e) XPS spectra of Ni0.50Co0.30Mn0.20 LDH for Ni 2p (c), Co 2p (d) and Mn 2p (e). (f) SEM image of Ni0.50Co0.30Mn0.20 LDH. (g) HR-TEM image of Ni0.50Co0.30Mn0.20 LDH. (h) HAADF-STEM image and corresponding elemental mappings of Ni0.50Co0.30Mn0.20 LDH.

Fig. 3. (a) LSV curves of Ni0.61Co0.39 LDH and Mn-NiCo LDH series in 1.0 mol L-1 KOH + 1.0 mol L-1 CH3OH. (b) EIS of Ni0.61Co0.39 LDH and Mn-NiCo LDH series in 1.0 mol L-1 KOH + 1.0 mol L-1 CH3OH. (c,d) LSV curves and Tafel plots of Ni0.61Co0.39 LDH and Ni0.50Co0.30Mn0.20 LDH in 1.0 mol L-1 KOH with and without 1.0 mol L-1 CH3OH. (e) Cdl of Ni0.61Co0.39 LDH and Ni0.50Co0.30Mn0.20 LDH in 1.0 mol L-1 KOH. (f) Constant current measurement of Ni0.61Co0.39 LDH and Ni0.50Co0.30Mn0.20 LDH in 1.0 mol L-1 KOH + 1.0 mol L-1 CH3OH. (g) FE of formate for Ni0.61Co0.39 LDH and Ni0.50Co0.30Mn0.20 LDH with different cumulative times at 100 mA cm-2. (h) Comparison of MOR activities of various catalysts in 1.0 mol L-1 KOH + 1.0 mol L-1 CH3OH.

Fig. 4. (a) Schematic illustration of in-situ Raman spectroscopy setup. (b,c) 2D in-situ Raman spectra of Ni0.61Co0.39 LDH and Ni0.50Co0.30Mn0.20 LDH at different potentials in 1.0 mol L-1 KOH. (d,e) Corresponding in-situ Raman spectra for both catalysts at various potentials in 1.0 mol L-1 KOH. (f, g) In-situ Raman spectra for both catalysts at various potentials in 1.0 mol L-1 KOH + 1.0 mol L-1 CH3OH. (h) Multi-potential step curves of Ni0.50Co0.30Mn0.20 LDH in 1.0 mol L-1 KOH with or without 1.0 mol L-1 CH3OH.

Fig. 5. (a) Schematic illustration of the Ni2+ to Ni3+ transformation coupled with CH3OH adsorption at Ni sites, where Ni: gray, Co: blue, Mn: purple, O: red, H: white, C: brown. (b) Gibbs free energy diagram for the catalytic MOR process on Ni0.61Co0.39 LDH and Ni0.50Co0.30Mn0.20 LDH, respectively. (c) PDOS of Ni-3d electrons calculated for Ni0.61Co0.39 LDH and Ni0.50Co0.30Mn0.20 LDH. (d) Differential charge density plot of CH3OH adsorbed on Ni0.50Co0.30Mn0.20 LDH, blue and yellow represent electron depletion and accumulation.

Fig. 6. (a) Schematic illustration of the two-electrode 2e- ORR||MOR system. (b) LSV curves of 2e- ORR||MOR and conventional 2e- ORR||OER electrolyzers. (c) H2O2 production rate. (d) Faradaic efficiency of H2O2. (e) Energy consumption per mol of H2O2 produced. (f) Formate production rate in the 2e- ORR||MOR system. (g) Faradaic efficiency of formate. (h) Comparison of hourly net economic benefit between the 2e- ORR||MOR and 2e- ORR||OER systems.

Fig. 7. (a) Schematic illustration of the 2e- ORR||MOR electrolysis system in the flow cell. (b) Schematic illustration of the flow-cell device for the 2e- ORR||MOR electrolysis system. (c) LSV curves of 2e- ORR||MOR and conventional 2e- ORR||OER electrolysis in the flow cell. (d) Comparison of cell voltage and current density between this work and previous H2O2 electrosynthesis systems. (e) Stability test of the 2e- ORR||MOR electrolysis system in the flow cell.

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Modulating active sites via Mn-doping in NiCo LDH for energy-saving paired electrosynthesis of H₂O₂ and formate

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