Covalent Triazine Framework Encapsulated Ultrafine PdAu Alloy Nanoclusters as Additive-Free Catalysts for Efficient Hydrogen Production from Formic Acid

Dehydrogenation of formic acid (FA) represents a promising route for clean hydrogen production, the economic viability of which, however, is largely hindered by the catalyst inefficiency. Here, ultrafine Au–Pd bimetallic nanoclusters (NCs) confined within the cavities of bipyridyl covalent triazine frameworks (CTFs) are constructed via a metal-nitrogen coordination reduction strategy, which is enabled by the chelation between bidentate nitrogen sites of the bipyridine ligands and metal ion precursors. The resulting CTF-confined PdAu NCs exhibit a high initial turnover frequency up to 12,368 h –1 (333 K) toward the dehydrogenation of FA without any additives. The experimental and theoretical studies disclose that the pyridinic nitrogen sites of CTF not only facilitate the formation of monodisperse small-sized metal NCs via the anchoring and the pore confinement effect but also serve as a proton buffer which can store excess protons and thus suppress the recombination of adsorbed formate and hydrogen on the PdAu alloy surface. These findings would have significant implications for designing high-performance hydrogen production catalysts.