Carbon bowl-confined subnanometric palladium-gold clusters for formic acid dehydrogenation and hexavalent chromium reduction

Abstract

Formic acid (FA), a high-value product of CO2 hydrogenation and biomass conversion, is considered a promising liquid organic hydrogen carrier for its high hydrogen content, easy accessibility, and relative stability. The development of an efficient heterogeneous catalyst toward FA dehydrogenation and Cr(VI) reduction by FA is needed to boost its sluggish kinetics but still remains a challenge. Herein, uniformly dispersed subnanometric PdAu alloy clusters (i.e., 0.9 nm) were successfully prepared and confined by amine-functionalized carbon bowls (ACB). By virtue of the tiny size and abundant active sites of PdAu clusters, the promotional effect of surface amine groups, and electronic interaction between subnanometric PdAu clusters and support, this as-prepared PdAu/ACB catalyst exhibits superior catalytic property for additive-free FA dehydrogenation (turnover frequency, 10597 h−1 at 323 K) and Cr(VI) reduction (rate constant, 0.47 min−1 at 298 K) under mild conditions, higher than most of the catalysts reported so far. This study offers insight into the design of efficient and durable catalysts for various catalytic applications in energy and environment.