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

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 Cα–Cβ 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 Ed upon P‐doping leads to an increase in the antibonding level, which facilitates the Cα–Cβ 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. P‐doping‐induced lattice growth of CoMoO4 increases crystal defects and causes the D‐band center to migrate higher to obtain the appropriate adsorption energy and significantly lower overpotential, therefore this system performs well in lignin oxidation breakage and furfural reduction.