Highly efficient electrocatalytic reductive cleavage of lignin model compounds over Ru@Bi/N-C: Interfacial and defect effects

doi:10.1016/S1872-2067(26)65005-X

Abstract

Abstract:

Understanding and regulating the substrate adsorption behavior and hydrogen species (H_spe) migration channels are crucial for achieving efficient lignin electrocatalytic hydrogenation (ECH). This effective Bi-Ru interface and adjacent N-defect sites were constructed on Ru@Bi/N-C catalyst, thereby controllably modulating the blocking and exposure of substrate adsorption sites while establishing ideal H_spe migration pathways. By introducing heteropolyacid (HPW) and hexafluoroisopropanol (HFIP) electrolyte, the conversion of 2-phenoxy-1-phenylethanol attained 93.64%, with Faraday efficiency (FE) of 91.92%. Moreover, the high hydrogenation deoxygenation efficiency (> 90%) was also obtained for phenolic monomers, demonstrating superior performance compared to most advanced electrocatalytic systems. Synchrotron radiation, in-situ Raman, and density functional theory calculations have demonstrated that the Bi-Ru interface obstructed the strong substrates adsorption on the Ru crystal surface, thereby facilitating the adsorption-activation and rapid desorption at N-defect sites. The blocking effect of Bi-Ru interface inhibited the hydrogen evolution reaction while promoting the spillover of adsorbed hydrogen (H_ads) to enable efficient ECH. Additionally, HPW mediated electron transfer could supply abundant H_ads, whereas polar HFIP promoted the protonation of substrate hydroxyl. This research developed a universal strategy for creating an exquisite catalytic network and establishing an optimized electrolyte microenvironment, providing significant insights for the development of highly efficient lignin ECH systems.

Key words: Lignin electrochemical hydrogenation, Interface effect, Hydrogen species migration channel, Adsorption modulation

Jingjing Shi, Yanju Lu, Kui Wang, Zupeng Chen, Junming Xu, Jianchun Jiang. Highly efficient electrocatalytic reductive cleavage of lignin model compounds over Ru@Bi/N-C: Interfacial and defect effects[J]. Chinese Journal of Catalysis, 2026, 84: 401-416.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65005-X

https://www.cjcatal.com/EN/Y2026/V84/I5/401

Figures/Tables 7

Fig. 1. (a) Schematic illustration of the value-added utilization of lignocellulosic biomass. The electrocatalytic processes of previously reported lignin dimers (b-1) and monophenolic (b-2). (c) The electrocatalytic strategy of Ru@Bi/N-C put forward in this work for dimer (upper) and monophenol (lower).

Fig. 2. (a) Schematic diagram of Ru@Bi/N-C preparation process. (b) XRD patterns of different catalysts. The representative TEM (c), HRTEM (d,e) images, the FFT derived image corresponding to the rectangular area (f,g), and the corresponding EDS elemental mappings of Ru@Bi/N-C (h?k,l).

Fig. 3. XANES spectra (a) and Fourier transformed EXAFS spectra (b) at Ru K-edge of RuO2, Ru foil, Ru/N-C and Ru@Bi/N-C. (c) Ru K-edge EXAFS (line) and curve fit (points) for Ru/N-C and Ru@Bi/N-C. (d) Wavelet transform of the Ru K-edge for the EXAFS spectra of RuO2 (d-1), Ru foil (d-2), Ru/N-C (d-3) and Ru@Bi/N-C (d-4). Ru 3d (e), Bi 4f (f), C 1s (g), and N 1s (h) XPS spectra of Ru@Bi/N-C. Raman (i) and EPR (j) spectra of N-C-900, Ru/N-C and Ru@Bi/N-C.

Fig. 4. (a) The conversion and FE of different catalysts. (b) The conversion and FE of Ru@Bi/N-C and Ru/N-C at different current densities. (c) The LSV curves of different catalysts. (d) The LSV curves of Ru@Bi1/N-C and Bi+Ru/N-C. (e) Tafel slopes of different catalysts. (f) The relationship between current density and scan rate on Ru@Bi/N-C and Ru/N-C. Bode plots of Ru/N-C (g) and Ru@Bi/N-C (h) without and with 2-phenoxy-1-phenylethanol. (i,j) The free energy diagrams of HER on Ru/N-C and Ru@Bi/N-C. (k) H2-TPD results of Ru/N-C and Ru@Bi/N-C. Reaction conditions: 50 mmol·L?1 substrate, 0.02 g catalyst, 0.1? mol·L?1 HFIP and 0.1 mol·L?1 HPW solution (15 mL), 20 ?mA·cm?2, 60? °C, 2 ?h, 300 ?rpm.

Fig. 5. In-situ Raman spectra of Ru@Bi/N-C (a) and Ru/N-C (b) at different times with applied current density of 20 mA·cm?2. (c) The adsorption model of 2-phenoxy-1-phenylethanol on Ru@Bi/N-C, Ru/N-C and N-C. The adsorption energies of 2-phenoxy-1-phenylethanol (d) and phenol (e) on Ru@Bi/N-C, Ru/N-C, and N-C. Schematic diagram of Hspe migration channel and substrate fracture paths on Ru/N-C (f) and Ru@Bi/N-C (g).

Fig. 6. (a) HPW electrolysis diagram. The LSV curves (b) and Tafel slopes (c) of Ru@Bi/N-C in different electrolyte. (d) The conversion and FE of Ru@Bi/N-C in different electrolyte. (e) The monomer yield of at Ru@Bi/N-C different current densities. (f) Possible reaction pathways for 2-phenoxy-1-phenylethanol.

Fig. 7. (a) The conversion and FE of Ru@Bi/N-C for 13 successive electrolysis cycles. Reaction conditions: substrate (50 mmol·L?1), 0.02 g catalyst, 0.1? mol·L?1 HFIP and 0.1 mol·L?1 HPW solution (15 mL), 20 ?mA·cm?2, 60? °C, 2 ?h, 300 ?rpm. The representative TEM (b), HRTEM (c) image, and the corresponding EDS elemental mappings (d?g) of the used Ru@Bi/N-C, respectively. (h) XRD pattern of the used Ru@Bi/N-C. XPS total (i) and Ru 3d (j) spectra of the used Ru@Bi/N-C. (k) The ECH of monophenolic model compounds with varying substituents. Reaction conditions: substrate (10 mmol·L?1), 0.02 g catalyst, 0.1? mol·L?1 HFIP and 0.1 mol·L?1 HPW solution (15 ?mL), 20 ?mA·cm?2, 60? °C, 4 ?h, 300 ?rpm.

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