Fine-tuning catalytic selectivity by modulating catalyst-environment interactions: CO2 hydrogenation over Pd-based catalysts

Capturing catalytic behaviors under operational conditions is pivotal to gaining a mechanistic understanding and promoting the design of robust catalysts. The challenge lies in the difficulty of monitoring real-time surface dynamics driven by catalyst-environment interactions. Here, we introduce a framework based on density functional calculations and kinetic modeling. This framework significantly improves the accuracy of theoretical models’ descriptions of experimental observations by quantifying environmental impacts on surface phases and active sites. CO₂ hydrogenation over Pd-based catalysts is taken as a showcase. The observed selectivity variations of Pd and Pd-M bimetallic catalysts strongly correlate with hydrogen coverage maintained under typical CO₂ hydrogenation conditions. By reducing the amount of surface hydrogen, the selectivity tuned effectively from formic acid toward CO and methanol. This study not only deepens the comprehension of dynamics of active sites under active chemical conditions but also introduces an alternative opportunity for catalytic tuning by modulating catalyst-environment interactions.