3D porous sulfur-graphdiyne with splendid electrocatalytic and energy storage application

The blooming emergence of graphdiyne featuring embellished sp-hybridized carbons has been highly alluring for electrocatalysis and ion storage. Here, a porous 3D material sulfur-graphdiyne (3D-SGDY) is theoretically designed comprising butadiyne chains and sulfur as a heteroatom, owing a stable cubic skeleton and an atypical tuneable indirect bandgap. Compared to sp²-bonded carbon materials, the existence of sp-bonded carbon in 3D-SGDY tuned the direction of organic reactions leading to a single carbon product with numerous storage sites for the metal ions. Anchoring a single Cu atom in 3D-SGDY, we realize the unique Cu–C (3D-SGDY) chemical bonds exhibiting unconventional selectivity for CO₂ reduction. The Cu–C bond in 3D-SGDY predominantly forms the *OCHO intermediates in lieu of *COOH and provides an active charge deportation channel during the reduction process of CO₂ into CH₄ product. Additionally, the porous structure reveals its astounding potential as an anode material by facilitating rapid transportation with a very low diffusion barrier of 0.06 eV and an ultrahigh capacity of 1826.4 mAhg⁻¹ for Ca-ions. This work not only provides the 3D prototype of GDY but also administers the atomic level selectivity for CO₂RR and high-performance Ca-ion batteries.