Atomically dispersed M-N-C has been considered an effective catalyst for various electrochemical reactions such as oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which faces the challenge of increasing metal load while simultaneously maintaining catalytic performance. Herein, we put forward a strategy for boosting catalytic performances of a single Cu atom coordinated with three N atoms (CuN₃) for both ORR and OER by increasing the density of connected CuN₃ moieties. Our calculations first show that a single CuN₃ moiety exhibiting no catalytic performance for ORR and OER can be activated by increasing the density of metal centers, which weakens the binding affinity to *OH due to the lowered d-band center of the metal atoms. These findings stimulate the further theoretical design of a two-dimensional compound of C₃N₃Cu with a high concentration of homogeneously distributed CuN₃ moieties serving as bifunctional active sites, which demonstrates efficient catalytic performance for both ORR and OER as reflected by the overpotentials of 0.71 and 0.43 V, respectively. This work opens a new avenue for designing effective single-atom catalysts with potential applications as energy storage and conversion devices possessing high density of metal centers independent of the doping strategy and defect engineering, which deserves experimental investigation in the future.

Montmorillonite clay was modified by pillaring with AlMn oxides in different Al/Mn ratios and intercalation of two kinds of N-containing polymers (i.e., chitosan (CS) and polyvinyl pyrrolidinone (PVP)) chains. The modified pillared montmorillonite clay (PM) showed a rich two-dimensional layered porous structure with tunable parameters, such as large interlayer spacing, high specific area, and large porous volume. They were then used as supports for Pd nanoparticles. As applied in coupling reactions of aryl halides with terminal alkynes, Pd@CS/AlMn-PM showed better comprehensive catalytic performance than Pd@PVP/AlMn-PM. This was mainly attributed to its higher specific area, stronger chelation to Pd species, and better solvent resistance.

In this study, a combination of the porous carbon (PCN), montmorillonite (MMT), and TiO₂ was synthesized into a composite immobilized Pd metal catalyst (TiO₂-MMT/PCN@Pd) with effective synergism improvements in catalytic performance. The successful TiO₂-pillaring modification for MMT, derivation of carbon from the biopolymer of chitosan, and immobilization of Pd species for the prepared TiO₂-MMT/PCN@Pd⁰ nanocomposites were confirmed using a combined characterization with X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N₂ adsorption–desorption isotherms, high-resolution transition electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. It was shown that the combination of PCN, MMT, and TiO₂ as a composite support for the stabilization of the Pd catalysts could synergistically improve the adsorption and catalytic properties. The resultant TiO₂-MMT₈₀/PCN₂₀@Pd⁰ showed a high surface area of 108.9 m²/g. Furthermore, it exhibited moderate to excellent activity (59–99% yield) and high stability (recyclable 19 times) in the liquid–solid catalytic reactions, such as the Sonogashira reactions of aryl halides (I, Br) with terminal alkynes in organic solutions. The positron annihilation lifetime spectroscopy (PALS) characterization sensitively detected the development of sub-nanoscale microdefects in the catalyst after long-term recycling service. This study provided direct evidence for the formation of some larger-sized microdefects during sequential recycling, which would act as leaching channels for loaded molecules, including active Pd species.