Exceptional Anisotropic Noncovalent Interactions in Ultrathin Nanorods: The Terminal σ-Hole

Nanomaterial is the Holy Grail of material science, which has been widely applied in the fields of energy, environment, chemistry, and biomedicine. Its catalytic merits were usually ascribed to the advantages of size effect, strain effect, and covalent effect. Noncovalent interactions are critical in the catalysis processes but often overlooked. Herein, different from the traditional understandings, we discover for the first time and give systematic insights into a unique noncovalent terminal σ-hole phenomenon in the 3d-metal-based nanorods, which should be one of the key origins of nanomaterial activity. As a proof-of-concept, pure metal and alloyed core-shell nanoclusters/nanorods composed of the two most important 3d metals (Co and Ni) growing from 0.5 to 2.5 nm are investigated. Unlike nanoclusters, the σ-hole only appears at the terminal sites of nanorods and the magnitude of the terminal σ-hole generally enhances with the growing processes. Further investigations show that this terminal σ-hole is closely related to the important physicochemical properties of nanorods. For example, the work function along the axis of the terminal σ-hole is smaller than other directions, contributing to the facile electronic transport along the axis of the terminal σ-hole. Most importantly, we find that the d-orbital center of the atoms around the terminal σ-hole shifts closer to the Fermi level as compared with other atoms, which can endow the terminal sites in nanorods with the higher chemical adsorption capability. We believe that this work will provide critical guidance for the rational design of nanomaterials in many potential applications.