Lignin valorization toward value-added chemicals and fuels via electrocatalysis: A perspective

doi:10.1016/S1872-2067(21)63839-1

Abstract

Abstract:

Developing efficient approaches for lignin upgrading is of interest for the industrial production of chemicals and fuels from renewable biomass. Electrocatalytic lignin upgrading powered by renewable electricity operating under gentle conditions (at or near ambient pressures and temperatures) enables a decentralized production of chemicals and fuels. Herein, we will cover the structures of lignin and review the recent advances in the electrocatalytic lignin upgrade, the electrocatalytic depolymerization of lignin, and the electrocatalytic upgrading of lignin monomers to value-added chemicals and fuels. Finally, we provide insights into the main challenges and future perspectives of this field.

Key words: Electrochemistry, Electrocatalysis, Lignin, Valorization, Lignin monomer

Chenxin Yang, Henan Chen, Tao Peng, Baiyao Liang, Yun Zhang, Wei Zhao. Lignin valorization toward value-added chemicals and fuels via electrocatalysis: A perspective[J]. Chinese Journal of Catalysis, 2021, 42(11): 1831-1842.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63839-1

https://www.cjcatal.com/EN/Y2021/V42/I11/1831

Figures/Tables 13

Fig. 1. Illustration of lignin to chemicals and fuels.

Fig. 2. Typical lignin structure and linkage.

Table 1 Content of lignin units in the typical natural plants [20,21].

Monolignol	H/%	G/%	S/%
Softwood (Conifer wood)	0-5	90-100	0-1
Hardwood (Broadleaf wood)	Trace	25-50	46-75
Grass	5-33	25-80	20-54

Table 2 Possible reaction mechanisms of electro-hydrogenation and electro-oxidation [36,41-47].

Typical reaction	Process	Acid aqueous electrolyte	Basic aqueous electrolyte
Electro-hydrogenation	*H formation	H⁺+ e^- + * → *H	H₂O + e^- + * → *H + OH^-
	lignin-based substrate reaction	R + * → R R + H → RH RH → + RH
	H₂ generation	H⁺+ e^- + H → + H₂ H + H → * + H₂	H₂O + e^- + H → + H₂ + OH^- H + H → * + H₂
Electro-oxidation	*O formation	H₂O + * → OH + e^- + H⁺ OH → *O + e^- + H⁺	OH^- + * → OH + e^- OH + OH^- → *O + e^- + H₂O
	lignin-based substrate reaction	R + * → R R + O → RO RO → + RO
	O₂ generation	O + H₂O → OOH + e^- + H⁺ OOH → + O₂ + e^- + H⁺	O + HO^- → OOH + e^- OOH + OH^-→ + O₂ + e^- + H₂O

Fig. 3. (a,b) Two typical electrochemical reaction cells for electrocatalytic lignin valorization.

Fig. 4. Mass spectra of various lignin monomers from lignin (a) phenol of 94 g·mol-1, (b) guaiacol of 124 g·mol-1, (c) 4-propyl-guaiacol of 166 g·mol-1, and (d) 4-propylsyringol of 196 g·mol-1, showing their molecular mass and fragments.

Fig. 5. 1H NMR spectrum of phenol and cyclohexene (in CDCl3). Reprinted with permission from Ref. [57]. Copyright (2015) The Royal Society of Chemistry.

Fig. 6. Main types of reaction precursors (a) and several typical electrolytes (b) for electrochemical lignin depolymerization.

Fig. 7. Potential reaction mechanism of lignin downgrading in a thio-assisted electrolytic system. Reprinted with permission from Ref. [67]. Copyright (2021) The Royal Society of Chemistry.

Fig. 8. (a) Vanillin production rates (produced from electro-oxidation lignin depolymerization) versus cell voltages. (b) Lignin depolymerization to vanillin via electro-oxidation at the NiOOH interface. (c) Proposed mechanism for electro-oxidation lignin depolymerization in a t-BuOOH-assisted electrolytic system. (a) Reprinted with permission from Ref. [83]. Copyright (2020) The Electrochemical Society; (b) Reprinted with permission from Ref. [82]. Copyright (2018) John Wiley & Sons; (c) Reprinted with permission from Ref. [90]. Copyright (2021) American Chemical Society.

Fig. 9. Possible reaction pathways of electro-hydrogenation of phenol (a), guaiacol (b), and benzaldehyde (c). (a) Reprinted with permission from Ref. [96]. Copyright (2015) Elsevier; (b) Reprinted with permission from Ref. [94]. Copyright (2019) John Wiley&Sons; (c) Reprinted with permission from Ref. [97]. Copyright (2019) American Chemical Society.

Fig. 10. (a) Electro-hydrogenation for phenol during “suspension” operation; Electro-hydrogenation of guaiacol in a separated cell via (b) Raney-Nickel and (c) PtNiB/CMK-3 catalyst; (d) Reaction rate of electro-hydrogenation of benzaldehyde to benzyl alcohol versus the computed binding energies of benzaldehyde. (a) Reprinted with permission from Ref. [96]. Copyright (2015) Elsevier. (b) Reprinted with permission from Ref. [53]. Copyright (2015) Royal Society of Chemistry. (c) Reprinted with permission from Ref. [33]. Copyright (2019) John Wiley & Sons. (d) Reprinted with permission from Ref. [97]. Copyright (2019) American Chemical Society.

Fig. 11. Electro-oxidation of lignin derivatives to carboxylates in a separated cell. Reprinted with permission from Ref. [95]. Copyright (2021) John Wiley&Sons.

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