Interfacial charge transfer via SMSI in heterostructured Pd/Bi2O3: A paradigm for sustainable electrochemical biomass upcycling

doi:10.1016/S1872-2067(26)65201-1

Abstract

Abstract:

The electrochemical oxidation of ethylene glycol (EG) to glycolic acid (GA) represents a promising route for valorizing plastic waste and biomass-derived feedstocks while co-producing hydrogen. However, existing catalysts are limited by low selectivity, rapid deactivation, and high overpotentials. Herein, we report a 0D/2D heterostructured catalyst, Pd-NCs/Bi₂O₃-NSs, in which Pd nanocrystals are uniformly anchored on ultrathin Bi₂O₃ nanosheets. Spectroscopic studies and density functional theory calculations reveal that the strong Pd-O-Bi interfacial interactions induce charge transfer from Bi₂O₃ to Pd, generating electron-rich Pd sites with a downshifted d-band center. Together with the effect of oxophilic Bi₂O₃, this optimizes reaction energetics and suppresses intermediate poisoning. As a result, the catalyst delivers 5.81 A mg_Pd^-1 mass activity, 92.1% Faradaic efficiency for GA, and excellent durability. Techno-economic and life-cycle analyses further confirm its cost competitiveness and environmental benefits.

Key words: Strong metal-support interaction, Ethylene glycol electrooxidation, Biomass valorization, Polyethylene terephthalate upcycling, Heterostructured catalysts

Han-Yue Yang, Jia-Jia Wen, Xue Xiao, Yu Chen. Interfacial charge transfer via SMSI in heterostructured Pd/Bi₂O₃: A paradigm for sustainable electrochemical biomass upcycling[J]. Chinese Journal of Catalysis, 2026, 91: 304-314.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65201-1

https://www.cjcatal.com/EN/Y2026/V91/I12/304

Figures/Tables 6

Scheme 1. Formation and SMSI of Pd nanoclusters anchored on ultrathin Bi2O3 nanosheets via Galvanic Replacement.

Fig. 1. (a) TEM image of Bi NSs. TEM image (b), HAADF-STEM image (c), AFM image (d), HR-TEM (e), lattice strain measured from GPA (f), and STEM-EDX elemental mapping images (g) of Pd-NCs/Bi2O3-NSs.

Fig. 2. (a) XRD pattern of Pd-NCs/Bi2O3-NSs. (b) Pd 3d XPS spectra of Pd-NCs/Bi2O3-NSs and Pd NCs. (c) Bi 4f XPS spectra of Pd-NCs/Bi2O3-NSs and Bi2O3 NSs. (d) WT-EXAFS spectra of Pd foil, Pd-NCs/Bi2O3-NSs, and PdO. (e) FT-EXAFS spectra of Pd foil, Pd-NCs/Bi2O3-NSs, and PdO. (f) FT-EXAFS spectra of Bi foil, Pd-NCs/Bi2O3-NSs and Bi2O3. (g) PDOS (d-band) of Pd and Pd-NCs/Bi2O3-NSs. (h) WT-EXAFS spectra of Bi foil, Pd-NCs/Bi2O3-NSs and Bi2O3. (i) COHP curve of the Pd bond in the Pd. (j) COHP curve of the Pd-Bi bond in the Pd-NCs/Bi2O3-NS.

Fig. 3. (a) CV curves of Pd-NCs/Bi2O3-NSs and Pd NCs in 1 mol L-1 KOH + 1 mol L-1 EG. (b) Corresponding Tafel slopes. Nyquist plots (c) and Arrhenius plots (d) of Pd-NCs/Bi2O3-NSs and Pd NCs. (e) FEGA of EGOR by Pd-NCs/Bi2O3-NSs and Pd NCs at different potentials. Data are presented as mean ± SD. Error bars (SD) represent the standard deviation of three separate measurements. (f) Comparison of the EGOR performance between this work and that of reported catalysts.

Fig. 4. (a) Open circuit potentials (OCPs) of Pd-NCs/Bi2O3-NSs in 1 mol L-1 KOH solution before and after 1 mol L-1 EG was added, and 1 mol L-1 KOH before and after 1 mol L-1 GA was added. (b) Corresponding Bode phase plots of Pd-NCs/Bi2O3-NSs electrode at varied potentials in 1 mol L-1 KOH with 1 mol L-1 EG. (c) In-situ Raman spectra of Pd-NCs/Bi2O3-NSs. (d) In-situ electrochemical FTIR spectra of EGOR catalyzed by Pd-NCs/Bi2O3-NSs. Calculated adsorption energies of EG* and OH* (e), and GA* and CO* (f), on the surfaces of Pd and Pd-NCs/Bi2O3-NSs. (g) Reaction Gibbs free energy of EGOR on Pd and Pd-NCs/Bi2O3-NSs.

Fig. 5. (a) The flow cell setup for paired HER (-) || EG oxidation (+) of Pt mesh and Pd-NCs/Bi2O3-NSs. (b) LSV curves for water splitting and EG electrolysis in the flow cell reactor. (c) Faradaic efficiency as function of current density for EG oxidation. (d) Sankey diagram for the mass flow of PET upcycling. (e) Subdivided the cost of the process. (f,g) LCOP for processing PET as function of current density, electrolysis energy, and faradic efficiency. (h) GWP of the conventional path and the system to produce GA powered by renewable power and thermal power.

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Interfacial charge transfer via SMSI in heterostructured Pd/Bi₂O₃: A paradigm for sustainable electrochemical biomass upcycling

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