Electronic interactions between neighboring functionalized guest Sb single atoms and Pt clusters enhance CO tolerance

Platinum-based (Pt) catalysts are notoriously susceptible to deactivation in industrial chemical processes due to carbon monoxide (CO) poisoning. Overcoming this poisoning deactivation of Pt-based catalysts while enhancing their catalytic activity, selectivity, and durability remains a major challenge. Herein, we propose a strategy to enhance the CO tolerance of Pt clusters (Pt n ) by introducing neighboring functionalized guest single atoms (such as Fe, Co, Ni, Cu, Sb, and Bi). Among them, antimony (Sb) single atoms (SAs) exhibit significant performance enhancement, achieving 99% CO selectivity and 33.6% CO 2 conversion at 450 °C. Experimental results and density functional theory (DFT) calculations indicate the optimization arises from the electronic interaction between neighboring functionalized Sb SAs and Pt clusters, leading to optimal 5 d electron redistribution in Pt clusters compared to other functionalized guest single atoms. The redistribution of 5 d electrons weaken both the σ donation and π backdonation interactions, resulting in a weakened bond strength with CO and enhancing catalyst activity and selectivity. In situ environmental transmission electron microscopy (ETEM) further demonstrates the exception thermal stability of the catalyst, even under H 2 at 700 °C. Notably, the functionalized Sb SAs also improve CO tolerance in various heterogenous catalysts, including Co/CeO 2 , Ni/CeO 2 , Pt/Al 2 O 3 , and Pt/CeO 2 -C. This finding provides an effective approach to overcome the primary challenge of CO poisoning in Pt-based catalysts, making their broader applications in various industrial catalysts.