To validate the theoretical findings, Au/Ni-N-O-C was synthesized following the procedure outlined in Fig. . Initially, a Ni-doped IRMOF-3 was prepared by a twostep method, leveraging a pore confinement effect. This prepared Ni-doped IRMOF-3 retained the original crystallinity, functional groups, and morphology of IRMOF-3, as confirmed through X-ray diffraction patterns (XRD), Fourier-transform infrared (FTIR) and field emission scanning electron microscope (FE-SEM) analyses (Supplementary Figs. ). Subsequently, the Ni-N-O-C catalyst was obtained via simple pyrolysis under an Ar atmosphere, which then acted as a substrate for the growth of Au precursors. For comparison, an N-O-C catalyst was produced without Ni single atoms using a similar pyrolysis method. By introducing Au precursors with Following pyrolysis, the crystal structures of N-O-C and Ni-N-O-C substrates were analyzed using XRD (Supplementary Fig. ). Notably, these samples displayed distinct similarities in their diffraction patterns, exhibiting two broad peaks around 24° and 44°. These peaks corresponded to the (002) and (100) diffraction planes for and graphite (G) bands of graphitic carbon. The ID/IG band intensity ratio (1.1) in both samples was consistent, indicating a similar number of defects in both structures. The presence of rich structural defects stemmed from vaporized ZnO4 clusters. In the cases of the Au0. samples from the same MOFs precursors. In Fig. and Supplementary Fig. ). In the inset of Fig. , the pre-edge feature peak at approximately 8330 eV is assigned to the 1s → 3d transition of the central Ni atoms. This transition is typically forbidden in centrosymmetric point groups. In comparison to the weak peak observed in planar complexes NiPc, exhibiting a high D4h centrosymmetry, there is an increase in peak intensity observed in Ni-N-O-C and Au0.5/Ni-N-O-C, which is due to p-d mixing in non-centrosymmetric geometries. Regarding the 1s → 4pz transition near 8336 eV, NiPc showed a distinct transition characteristic of square-planar MN4 moieties. Therefore, the spectra obtained on the Ni-N-O-C sample are fitted assuming the presence of Ni1N3O1 sites, consistent with the preceding analyses, which is expected to bring desirable catalytic performance.