Copper (Cu) nanoparticles (NPs) have received extensive interest owing to their advantageous properties compared with their bulk counterparts. Although the natural oxidation of Cu NPs can be alleviated by passivating the surfaces with additional moieties, obtaining non-oxidized bare Cu NPs in air remains challenging. Here we report that bare Cu NPs with surface excess electrons retain their non-oxidized state over several months in ambient air. Cu NPs grown on an electride support with excellent electron transfer ability are encapsulated by the surface-accumulated excess electrons, exhibiting an ultralow work function of ~3.2 eV. Atomic-scale structural and chemical analyses confirm the absence of Cu oxide moiety at the outermost surface of air-exposed bare Cu NPs. Theoretical energetics clarify that the surface-accumulated excess electrons suppress the oxygen adsorption and consequently prohibit the infiltration of oxygen into the Cu lattice, provoking the endothermic reaction for oxidation process. Our results will further stimulate the practical use of metal NPs in versatile applications.

We present an example of host–guest complexes of atomically precise noble metal nanoparticles with cucurbit[7]­uril (CB) in water, specifically concentrating on Ag29(LA)12 (where LA is α-lipoic acid), a well-known red luminescent silver cluster. Such host–guest interactions resulted in enhanced luminescence of about 1.25 times for the modified system, compared to the parent cluster. We extended our study to cyclodextrins (CDs), where about 1.5 times enhanced luminescence was estimated compared to the parent cluster. The formation of supramolecular complexes was confirmed using high-resolution electrospray ionization mass spectrometry (HRESI MS) and nuclear magnetic resonance spectroscopy. Molecular docking and density functional theory calculations supported our experimental results and showed that while CB formed inclusion complexes by encapsulation of one of the LA ligands of the cluster, CD formed supramolecular adducts by interaction with the cavity built by the ligands on the cluster surface. The complexation was favored by geometrical compatibility. Consequently, these superstructures are labeled as Ag29LA12∩CB n and Ag29LA12@CD n (n = 1–3), where ∩ and @ indicate the inclusion complex and supramolecular adduct, respectively. Solution-phase Ag29LA12@CD n complexes were employed to detect dopamine (10 nM). Luminescent Ag29LA12@CD n and Ag29LA12∩CB n complexes in water could be potential candidates for organic pollutant sensing and biomedical applications.

Metal nanoparticles (MeNPs) have been used in various industrial applications, owing to their unique physical and chemical properties different from the bulk counterparts. However, the natural oxidation of MeNPs is an imminent hindrance to their widespread applications despite much research efforts to prevent it. Here, a rational approach for non‐oxidized bare MeNPs in air, which requires no additional surface passivation treatment is reported. The direct synthetic route uses the [Gd2C]2+ · 2e− electride as an exceptional electron‐donating agent to reduce diverse metal precursors in alcoholic solvents. All synthesized bare Cu, Ag, and Sn nanoparticles are ultra‐stable in ambient air, exhibiting no trace of metal oxides even on their outermost atomic layer. This unique resistance to oxidation is ascribed to the accumulation of excess electrons on the surface of bare MeNPs, which originates from the spontaneous transfer of anionic electrons from the electride during the nanoparticle growth process. This approach provides not only a revolutionary scheme to obtain MeNPs with non‐passivated and non‐oxidized surfaces, but also fundamental knowledge about metal oxidation.

Engineering active sites of metal nanoparticle‐based heterogeneous catalysts is one of the most prerequisite approaches for the efficient production of chemicals, but the limited active sites and undesired oxidation on the metal nanoparticles still remain as key challenges. Here, it is reported that the negatively charged surface of copper nanoparticles on the 2D [Ca2N]+∙e− electride provides the unrestricted active sites for catalytic selective sulfenylation of indoles and azaindoles with diaryl disulfides. Substantial electron transfer from the electride support to copper nanoparticles via electronic metal–support interactions results in the accumulation of excess electrons at the surface of copper nanoparticles. Moreover, the surface‐accumulated excess electrons prohibit the oxidation of copper nanoparticle, thereby maintaining the metallic surface in a negatively charged state and activating both (aza)indoles and disulfides under mild conditions in the absence of any further additives. This study defines the role of excess electrons on the nanoparticle‐based heterogeneous catalyst that can be rationalized in versatile systems.