AuFe₃@Pd/γ-Fe₂O₃ Nanosheets as an In Situ Regenerable and Highly Efficient Hydrogenation Catalyst.

Abstract

Heterogenous Pd catalysts play a pivotal role in the chemical industry; however, it is plagued by S^2- or other strong adsorbates inducing surface poisoning long term. Herein, we report the development of AuFe₃@Pd/γ-Fe₂O₃ nanosheets (NSs) as an <i>in situ</i> regenerable and highly active hydrogenation catalyst. Upon poisoning, the Pd monolayer sites could be fully and oxidatively regenerated under ambient conditions, which is initiated by •OH radicals from surface defect/Fe_Tetra vacancy-rich γ-Fe₂O₃ NSs via the Fenton-like pathway. Both experimental and theoretical analyses demonstrate that for the electronic and geometric effect, the 2-3 nm AuFe₃ intermetallic nanocluster core promotes the adsorption of reactant onto Pd sites; in addition, it lowers Pd's affinity for •OH radicals to enhance their stability during oxidative regeneration. When packed into a quartz sand fixed-bed catalyst column, the AuFe₃@Pd/γ-Fe₂O₃ NSs are highly active in hydrogenating the carbon-halogen bond, which comprises a crucial step for the removal of micropollutants in drinking water and recovery of resources from heavily polluted wastewater, and withstand ten rounds of regeneration. By maximizing the use of ultrathin metal oxide NSs and intermetallic nanocluster and monolayer Pd, the current study demonstrates a comprehensive strategy for developing sustainable Pd catalysts for liquid catalysis.