Simultaneous Oxidative Cleavage of Lignin and Reduction of Furfural via Efficient Electrocatalysis by P-Doped CoMoO4

Abstract

Electrochemical oxidative lignin cleavage and coupled 2-furaldehyde reduction provide a promising approach for producing high-value added products. However, developing efficient bifunctional electrocatalysts with noble-metal-like activity still remains a challenge. Here, an efficient electrochemical strategy is reported for the selective oxidative cleavage of C_α -C_β bonds in lignin into aromatic monomers by tailoring the electronic structure through P-doped CoMoO₄ spinels (99% conversion, highest monomer selectivity of 56%). Additionally, the conversion and selectivity of 2-furaldehyde reduction to 2-methyl furan reach 87% and 73%, respectively. In situ Fourier transform infrared and density functional theory analysis reveal that an upward shift of the E_d upon P-doping leads to an increase in the antibonding level, which facilitates the C_α -C_β adsorption of the lignin model compounds, thereby enhancing the bifunctional electrocatalytic activity of the active site. This work explores the potential of a spinel as a bifunctional electrocatalyst for the oxidative cracking of lignin and the reductive conversion of small organic molecules to high-value added chemicals via P-anion modulation.

Keywords: biomass valorization; electrocatalysis; furfural reduction; lignin oxidation; spinel.