The crucial role of orbital interaction mode between catalysts and intermediates in electrocatalytic β-O-4 bond cleavage for lignin valorization

Electroreduction of lignin into value-added chemicals offers an effective route for its high-value utilization. However, how the electronic states of catalytic sites govern lignin conversion efficiency and product yield remains poorly understood. Here, we use Pt and a Pd@Pt heterostructure as model catalysts to systematically investigate catalyst-intermediate interactions and their influence on lignin electroreduction. In the Pd@Pt heterostructure, electron transfer from Pd to Pt reconstructs the Pt 5d states and shifts the catalyst-intermediate interaction from a strong Pt 5dxz-O 2py interaction on pure Pt with C 6 H 5 OH/C 6 H 5 COCH 3 to a weaker Pt 5d xy/yz -O 2p x interaction on Pd@Pt. This reduced orbital overlap significantly lowers the activation barrier of the rate-determining step, thereby enhancing lignin reduction activity. These findings highlight the critical role of orbital interaction modes in regulating catalyst activity and provide mechanistic insight for the rational design of advanced electrocatalysts for lignin reduction.