An Fe-embedded C2N monolayer as a promising single-atom catalyst for CO oxidation by O2 has been investigated based on first-principles calculations. It is found that the single Fe atom can be strongly trapped in the cavity of the C2N monolayer with a large adsorption energy of 4.55 eV and a high diffusion barrier of at least 3.00 eV to leave the cavity, indicating that Fe should exist in the isolated single-atom form. Due to the localized metal 3d orbitals near the Fermi level, the embedded Fe single-atom catalyst has a high chemical activity for the adsorption of CO and O2 molecules. CO oxidation by O2 on the catalyst would proceed via a two-step mechanism. The first step of the CO oxidation reaction has been studied via the Langmuir-Hinshelwood and Eley-Rideal mechanisms with energy barriers of 0.46 and 0.65 eV, respectively. The second step of the CO oxidation reaction follows the Eley-Rideal mechanism with a much smaller energy barrier of 0.24 eV. For both the steps, the CO2 molecules produced are weakly adsorbed on the substrates, suggesting that the proposed catalyst will not be poisoned by the generated CO2. Our results indicate that the Fe-embedded C2N monolayer is a promising single-atom catalyst for CO oxidation by O2 at low temperatures.

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First-principles calculations were performed to investigate the effect of Pd concentration and oxygen vacancies on the stability of Pd at LaFeO3 surfaces. We found a much stronger tendency of Pd to segregate by taking the aggregation of Pd at LaFe1-xPdxO3-y surfaces into consideration, resulting in a pair of Pd-Pd around a vacancy. Moreover, we predicted that one oxygen-vacancy-containing FeO2-terminated surfaces would be stable at high temperatures by comparing the stability of LaFe1-xPdxO3-y surfaces, which further supports our previous conclusion that a Pd-containing perovskite catalyst should be calcined at 1,073 K or higher temperatures in air to enhance the segregation of Pd in the vicinity of surfaces to rapidly transform the Pd catalyst from oxidized to reduced states on the perovskite support.

Using ab initio density functional theory calculations, we have investigated the influence of Mo, V and Pd on the H-induced grain boundary embrittlement in Fe. We find that, in the high impurity concentration systems, all of the three alloying elements facilitate H embrittlement at the Σ3 (111) [Formula: see text] grain boundary in Fe. The calculated binary effects of the H-X (X = Mo, V, Pd) couples are 0.063, 0.074 and 0.040 eV, respectively. On the other hand, in the large unit cell with low impurity concentration, both Mo and V can facilitate H embrittlement, and the binary effects of pairs are 0.152 and 0.164 eV, respectively. While Pd reduces the H embrittlement on the cohesion of the Fe grain boundary with the binary effect of - 0.1 eV. The H-X (X = Mo, V, Pd) interactions are interpreted by electronic structure analyses.