Electrocatalytic Upgrading of Lignin‐Derived Bio‐Oil Based on Surface‐Engineered PtNiB Nanostructure

Abstract The development of robust electrocatalysts for electrocatalytic hydrogenation (ECH) of guaiacol and related lignin model monomers is necessary for the stabilization or upgrading of bio‐oil. Additionally, the efficiency of biomass conversion to bio‐oil products remains below the minimum requirements for its implementation at scale. Herein, a PtNiB/CMK‐3 catalyst with pronounced ECH performance in the conversion of guaiacol and related model lignin monomers to bio‐oil under optimally mild conditions, through a modulation strategy that modified the electronic structure of PtNi via boron alloying, is prepared. Notably, the optimized PtNiB/CMK‐3 exhibited an inspiring high faradaic efficiency of 86.2%, which is significantly higher (13.7 times) than that of the PtNi/CMK‐3 without B‐doping (6.3%). Experimental results and theoretical calculations showed that the B‐doping optimized the PtNiB alloy surface electron structure, simultaneously promoting substrate and intermediate adsorption and the ECH process. In addition, the uniform dispersion of PtNiB nanoparticles embedded within the mesoporous channels of CMK‐3 ensures an enhanced utilization efficiency, leading to improvements in stability and bio‐oil product generation. The lab‐scale ECH experiment of guaiacol also certified the scale‐up potential. This work opens a promising avenue to the rational design of advanced and highly efficient electrocatalysts for biomass upgrading.