Dual-site CuS-Co9S8 heterojunctions for efficient and selective glycerol electrooxidation

doi:10.1016/S1872-2067(26)65032-2

Abstract

Abstract:

Electrocatalytic oxidation of surplus glycerol from biodiesel production is fundamentally limited by the competitive adsorption of glycerol and OH^- ions on catalyst surfaces. To overcome this challenge, a CuS-Co₉S₈ heterojunction was fabricated via a two-step hydrothermal sulfidation method. This catalyst features spatially and functionally decoupled active sites, in which CuS domains preferentially adsorbs glycerol and Co₉S₈ promotes OH^- activation, thereby balancing surface reactant concentrations and suppressing oxygen evolution side reactions. In-situ Raman spectroscopy and theoretical calculations reveal that interfacial electron redistribution stabilizes high-valent cobalt species and enables dual-site cooperative reactivity. The resulting electrode delivers an industrially relevant current density of 200 mA cm^-2 at a low potential of 1.24 V (vs. RHE) with a Faradaic efficiency of 94.8% for formate at 1.5 V. In a flow-type membrane electrode assembly, stable operation over 100 h at 200 mA cm^-2 is achieved, yielding a formate production rate of ’86.1 kg m^-2. Techno-economic analysis indicates a net profit potential of ’$775 per ton of glycerol processed. This study establishes a general dual-site design principle for overcoming adsorption competition in polyol electrooxidation, offering a scalable pathway for efficient biomass valorization.

Key words: Electrocatalytic glycerol oxidation, Heterojunction, Sulfurization, Co-adsorption, Biomass valorization

Yuwei Li, Yuxin He, Zongyao Guo, Jingyi Zhang, Yizhi Wu, Mingkun Jiang, Shiyu Chen, Dan Wu. Dual-site CuS-Co₉S₈ heterojunctions for efficient and selective glycerol electrooxidation[J]. Chinese Journal of Catalysis, 2026, 85: 272-285.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65032-2

https://www.cjcatal.com/EN/Y2026/V85/I6/272

Figures/Tables 8

Fig. 1. (a) Schematic illustration of the CuS-Co9S8/NF electrode preparation process. XRD pattern (b), SEM images (c-e), STEM-EDS elemental mappings (f), TEM images (g,h), and Mott-Schottky plots (i) of the CuS-Co9S8/NF electrode.

Fig. 2. FTIR spectrum (a) and Raman spectra (b) of CuS-Co9S8/NF. XPS spectra of Co 2p for CuS-Co9S8/NF and Co9S8/NF (c), Cu 2p for CuS-Co9S8/NF and CuS/NF (d). (e) Cu LMM Auger spectra for CuS-Co9S8/NF and CuS/NF. (f) XPS spectra of S 2p for CuS-Co9S8/NF, CuS/NF, and Co9S8/NF.

Fig. 3. Electrochemical GOR performance of different electrodes. LSV curves (a), potentials at different current densities (b), comparison of catalyst performance (c, d), Tafel plots (e), Cdl fitting plots (f), and FEs (g) of formic acid for CuS/NF, Co9S8/NF, and CuS-Co9S8/NF electrodes in 1 mol L-1 KOH + 0.1 mol L-1 glycerol. Stability test at 1.5 V with FEs of GOR products (h) and glycerol conversion and formic acid yield (i) for the CuS-Co9S8/NF electrode.

Fig. 4. (a) CV curves of CuS-Co9S8/NF in 1 mol L-1 KOH and 1 mol L-1 KOH + 0.1 mol L-1 glycerol electrolytes. (b) DPV curves of CuS-Co9S8/NF and Co9S8/NF in 1 mol L-1 KOH. (c,d) Multi-step potential tests on CuS-Co9S8/NF. FEs of oxidation products in 1 mol L-1 KOH + 0.1 mol L-1 glyceraldehyde (e), 1 mol L-1 KOH + 0.1 mol L-1 glycolic acid (f), and 1 mol L-1 KOH + 0.1 mol L-1 glycerol (g) at 1.45 V under different pH values. (h) Proposed GOR pathway over the CuS-Co9S8/NF electrode. In-situ Raman spectra measured at different anodic potentials in 1 mol L-1 KOH (i) and 1 mol L-1 KOH + 0.1 mol L-1 glycerol (j) on CuS-Co9S8/NF.

Fig. 5. In-situ Bode plots of CuS-Co9S8/NF (a), CuS /NF (b), and Co9S8/NF (c) electrodes under different potentials in 1 mol L-1 KOH + 0.1 glycerol. (d) Equivalent circuit model representing interfacial processes during GOR. (e) Potential-dependent Rct. (f) Inductive impedance in the mid-frequency region. (g) OCP responses of the three electrodes in 1 mol L-1 KOH before (left) and after (right) 0.1 mol L-1 glycerol injection.

Fig. 6. LSV curves of Co9S8 (a), CuS (b), and CuS-Co9S8 (c) in 0.1 mol L-1 glycerol with different KOH concentrations (Inset: GOR current density at 1.4 V as a function of cKOH. LSV curves of Co9S8 (d), CuS (f), and CuS-Co9S8 (g) in 1 mol L-1 KOH with different glycerol concentrations (Inset: GOR current density at 1.4 V as a function of cglycerol. Apparent redox rate constants (Ks) in 1 mol L-1 KOH with (g) and without (h) 0.1 mol L-1 glycerol.

Fig. 7. Adsorption energies of glycerol (a) and OH- (b) on Co9S8/NF, CuS/NF, and CuS-Co9S8/NF. (c) DOS profiles of three electrodes.

Fig. 8. (a) Schematic illustration of the MEA device. (b) LSV curves comparing OER‖HER and GOR‖HER configurations using CuS-Co9S8/NF as the anode. (c) Stability test of the GOR‖HER electrolyzer at 200 mA cm-2. (d) FEs and yield of formate as a function of time. (e,f) TEA of the proposed electro-upcycling strategy for glycerol valorization.

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Dual-site CuS-Co₉S₈ heterojunctions for efficient and selective glycerol electrooxidation

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