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.

Dry reforming of methane (DRM) is an attractive route to utilize CO2 as a chemical feedstock with which to convert CH4 into valuable syngas and simultaneously mitigate both greenhouse gases. Ni-based DRM catalysts are promising due to their high activity and low cost, but suffer from poor stability due to coke formation which has hindered their commercialization. Herein, we report that atomically dispersed Ni single atoms, stabilized by interaction with Ce-doped hydroxyapatite, are highly active and coke-resistant catalytic sites for DRM. Experimental and computational studies reveal that isolated Ni atoms are intrinsically coke-resistant due to their unique ability to only activate the first C-H bond in CH4, thus avoiding methane deep decomposition into carbon. This discovery offers new opportunities to develop large-scale DRM processes using earth abundant catalysts.

Strong metal-support interaction (SMSI) has gained great attention in the field of heterogeneous catalysis. However, whether single-atom catalysts can exhibit SMSI remains unknown. Here, we demonstrate that SMSI can occur on TiO 2-supported Pt single atoms but at a much higher reduction temperature than that for Pt nanoparticles (NPs). Pt single atoms involved in SMSI are not covered by the TiO 2 support nor do they sink into its subsurface. The suppression of CO adsorption on Pt single atoms stems from coordination saturation (18-electron rule) rather than the physical coverage of Pt atoms by the support. Based on the new finding it is revealed that single atoms are the true active sites in the hydrogenation of 3-nitrostyrene, while Pt NPs barely contribute to the activity since the NP sites are selectively encapsulated. The findings in this work provide a new approach to study the active sites by tuning SMSI.

Single-atom catalysts (SACs) have demonstrated superior catalytic performance in numerous heterogeneous reactions. However, producing thermally stable SACs, especially in a simple and scalable way, remains a formidable challenge. Here, we report the synthesis of Ru SACs from commercial RuO 2 powders by physical mixing of sub-micron RuO 2 aggregates with a MgAl 1.2 Fe 0.8 O 4 spinel. Atomically dispersed Ru is confirmed by aberration-corrected scanning transmission electron microscopy and X-ray absorption spectroscopy. Detailed studies reveal that the dispersion process does not arise from a gas atom trapping mechanism, but rather from anti-Ostwald ripening promoted by a strong covalent metalsupport interaction. This synthetic strategy is simple and amenable to the large-scale manufacture of thermally stable SACs for industrial applications.

Unique interfacial properties within heterostructures play vital roles in enhancing hydrogen evolution reaction (HER) electrocatalysis. On the basis of the MoO2-Ni heterostructure, we hereby propose an upraised atomic orbital promoted catalytic mechanism for accelerating the HER kinetics. A controllable gradient-pyrolysis approach is adopted on molybdates to integrate Ni with MoO2, possessing numerous phase-separation-induced intimate interfaces. In situ characterizations demonstrate the formation process of MoO2-Ni interfaces and excellent compositional stability under alkaline conditions. The optimized MoO2-Ni catalyst delivers remarkable Pt-like HER activity and good stability with 50 h operation in 1 M KOH. An enhancement of 3 orders of magnitude on the exchange current density is achieved for MoO2-Ni in comparison to the simplex MoO2. Further experimental and theoretical analyses verify the existence of a concentrated surface charge at MoO2-Ni interfaces. Meanwhile, with the incorporation of Ni into MoO2, the most active sites dramatically change from Mo to O atoms at MoO2-Ni interfaces. The Ni contact upraises the O 2p orbital in MoO2, thus strengthening the hydrogen adsorption for enhanced HER kinetics.