Frontier orbital insights into the stability and activity of zero-valent single-atom catalysts

doi:10.1016/S1872-2067(26)65217-5

Abstract

Abstract:

The stability of single-atom catalysts (SACs) has been a major concern for their practical applications. The orbital-level understanding of the nature of metal-support interaction is of essential importance, but has been rarely reported. Here, frontier molecular orbital (FMO) theory is employed to investigate the stabilization mechanism of a nearly zero-valent Pd₁ catalyst supported on boron-doped g-C₃N₄ (Pd₁/BCN). We demonstrate that the exceptional stability originates from enhanced frontier orbital coupling under a staggered energy-level alignment between the Pd₁ atom and the support. Boron doping effectively modulates the support's band structure, enhancing both the charge transfer from the highest occupied molecular orbital of Pd₁ atom to the support's lowest unoccupied state and the electron back-donation from the support's highest occupied state to the lowest unoccupied molecular orbital of Pd₁. This balanced dual coupling minimizes net charge transfer, thereby stabilizing Pd₁ atoms in a nearly zero-valent state. The FMO theory further consistently rationalizes the superior H₂ activation kinetics and thermodynamics on electron-enriched Pd₁/BCN, establishing it as a valuable framework for the rational design of SACs with optimized activity and stability.

Key words: Single-atom catalysts, Metal-support interaction, Frontier orbital theory, Stability, Hydrogenation reactions

Yuxing Xu, Yin Li, Hengwei Wang, Botao Teng, Junling Lu. Frontier orbital insights into the stability and activity of zero-valent single-atom catalysts[J]. Chinese Journal of Catalysis, 2027, 92: 123-129.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65217-5

https://www.cjcatal.com/EN/Y2027/V92/I1/123

Figures/Tables 3

Fig. 1. Optimized structure of g-C3N4 (a) and its calculated band structure (left panel) and DOS (right panel) (b). (c) The top view of HOS and LUS of g-C3N4, with an isosurface value of 0.025 e-/Bohr3. Optimized structure of BCN (d) and its calculated band structure (left panel) and DOS (right panel) (e). (f) The top view of the HOS and LUS of BCN, with an isosurface value of 0.025 e-/Bohr3.

Fig. 2. (a) Adsorption energies of Pd1 in Pd1/g-C3N4 and Pd1/BCN. The insets show the top view of the Pd1/g-C3N4 and Pd1/BCN structures. (b) Side view of charge density differences and Bader charges of the Pd1 atom in Pd1/g-C3N4 (top) and Pd1/BCN (bottom). The yellow and cyan areas indicate the accumulation and depletion of electrons, respectively, with an isosurface value of 0.003 e-/Bohr3. The balls in blue, grey, pink and dark cyan represent N, C, B and Pd, respectively. (c) Schematic illustration of frontier orbital alignment for freestanding Pd1, N1 in g-C3N4 as well as N1 and B in BCN. (d) The PDOS analysis illustrates the frontier orbital coupling between the HOMO of Pd1 and the LUMO of N1 in g-C3N4 and BCN, respectively. (e) The PDOS analysis reveals distinct frontier orbital coupling between the LUMO of Pd1 and the HOMO of the N1 in g-C3N4 and BCN, respectively.

Fig. 3. Calculated H2 dissociation paths on Pd1/g-C3N4 (a) and Pd1/BCN (b). The insets show H2 molecule adsorbed on Pd1/g-C3N4 and Pd1/BCN, respectively. The balls in white, blue, grey, pink and dark cyan represent H, N, C, B and Pd, respectively. PDOS analysis of frontier orbital coupling between H2 LUMO and Pd1 HOMO for Pd1/g-C3N4 (c) as well as between H2 LUMO and Pd1 HOMO for Pd1/BCN (d). PDOS analysis of frontier orbital coupling between H atom and Pd1/g-C3N4 (e) as well as between H atom and Pd1/BCN (f).

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