Platinum-based heterogeneous catalysts are critical to many important commercial chemical processes, but their efficiency is extremely low on a per metal atom basis, because only the surface active-site atoms are used. Catalysts with single-atom dispersions are thus highly desirable to maximize atom efficiency, but making them is challenging. Here we report the synthesis of a single-atom catalyst that consists of only isolated single Pt atoms anchored to the surfaces of iron oxide nanocrystallites. This single-atom catalyst has extremely high atom efficiency and shows excellent stability and high activity for both CO oxidation and preferential oxidation of CO in H2. Density functional theory calculations show that the high catalytic activity correlates with the partially vacant 5d orbitals of the positively charged, high-valent Pt atoms, which help to reduce both the CO adsorption energy and the activation barriers for CO oxidation.

Surface-supported isolated atoms in single-atom catalysts (SACs) are usually stabilized by diverse defects. The fabrication of high-metal-loading and thermally stable SACs remains a formidable challenge due to the difficulty of creating high densities of underpinning stable defects. Here we report that isolated Pt atoms can be stabilized through a strong covalent metal-support interaction (CMSI) that is not associated with support defects, yielding a high-loading and thermally stable SAC by trapping either the already deposited Pt atoms or the PtO2 units vaporized from nanoparticles during high-temperature calcination. Experimental and computational modeling studies reveal that iron oxide reducibility is crucial to anchor isolated Pt atoms. The resulting high concentrations of single atoms enable specific activities far exceeding those of conventional nanoparticle catalysts. This non defect-stabilization strategy can be extended to non-reducible supports by simply doping with iron oxide, thus paving a new way for constructing high-loading SACs for diverse industrially important catalytic reactions.

Metal atoms dispersed on the oxide supports constitute a large category of single-atom catalysts. In this review, oxide supported single-atom catalysts are discussed about their synthetic procedures, characterizations, and reaction mechanism in thermocatalysis, such as water–gas shift reaction, selective oxidation/hydrogenation, and coupling reactions. Some typical oxide materials, including ferric oxide, cerium oxide, titanium dioxide, aluminum oxide, and so on, are intentionally mentioned for the unique roles as supports in anchoring metal atoms and taking part in the catalytic reactions. The interactions between metal atoms and oxide supports are summarized to give a picture on how to stabilize the atomic metal centers, and rationally tune the geometric structures and electronic states of single atoms. Furthermore, several directions in fabricating single-atom catalysts with improved performance are proposed on the basis of state-of-the-art understanding in metal-oxide interactions.