Computational study on graphdiyne supported PdxCuy clusters as potential catalysts for formic acid dehydrogenation.

Designing low-cost and efficient catalysts for formic acid dehydrogenation (FAD) is crucial to facilitate the practical applications of formic acid as a hydrogen carrier. Using density functional theory calculations, we designed nine graphdiyne-supported Pd/Cu single-, double-, and triple-atom catalysts, investigating their stability and formic acid dehydrogenation performance. The results indicate that as the number of active metal sites increases, the catalytic activity for formic acid dehydrogenation improves, i.e., M 3 @GDY > M 2 @GDY > M 1 @GDY (M = Pd/Cu). Moreover, a synergistic effect between Pd and Cu atoms is observed in Pd x Cu 3-x @GDY, where the activity sequence of triple-atom catalysts was Pd 1 Cu 2 @GDY > Pd 2 Cu 1 @GDY > Pd 3 @GDY > Cu 3 @GDY. Particularly, Pd 1 Cu 2 @GDY exhibits superior FAD catalytic activity and hydrogen selectivity, presenting a potential novel formic acid dehydrogenation catalyst. Electronic structure analysis indicates that the band center difference Δε (Δε = ε d - ε p) serves as an assessment descriptor for formic acid dehydrogenation activity. Microkinetic analysis further confirms the performance of TACs predicted by DFT results, and shows that all TACs have good H 2 selectivity even at a high temperature. [Display omitted] • A series of Pd x Cu y @GDY catalysts for formic acid dehydrogenation were designed. • Pd 1 Cu 2 @GDY shows best activity and H 2 selectivity among all catalysts. • Band center difference is a good descriptor of the catalytic activity. [ABSTRACT FROM AUTHOR]