Highly dispersed Pd-based pseudo-single atoms in zeolites for hydrogen generation and pollutant disposal

Abstract

Atomically dispersed metal catalysts with excellent activity and stability are highly desired in heterogeneous catalysis. Herein, we synthesized zeolite-encaged Pd-based pseudo-single atoms via a facile and energy-efficient ligand-protected direct H₂ reduction method. C_s-corrected scanning transmission electron microscopy, extended X-ray absorption, and pair distribution function measurements reveal that the metal species are close to atomic-level dispersion and completely confined within the intersectional channels of silicalite-1 (S-1) zeolite with the MFI framework. The Pd@S-1-H exhibits excellent activity and stability in methane combustion reactions with a complete combustion temperature of 390 °C, and no deactivation is observed even after 100 h on stream. The optimized bimetallic 0.8Pd0.2Ni(OH)₂@S-1-H catalyst exhibits an excellent H₂ generation rate from FA decomposition without any additives, affording a superhigh turnover frequency up to 9308 h^-1 at 333 K, which represents the top activity among all of the best heterogeneous catalysts under similar conditions. Significantly, zeolite-encaged metal catalysts are first used for Cr(vi) reduction coupled with formic acid (FA) dehydrogenation and show a superhigh turnover number of 2980 mol(Cr₂O₇^2-) mol(Pd)^-1 at 323 K, surpassing all of the previously reported catalysts. This work demonstrates that zeolite-encaged pseudo-single atom catalysts are promising in efficient hydrogen storage and pollutant disposal applications.