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.