Graphynes (GYs) are carbon allotropes with single-atom thickness that feature layered 2D structure assembled by carbon atoms with sp - and sp - hybridization form. Various functional theories have predicted GYs to have natural band gap with Dirac cones structure, presumably originating from inhomogeneous π-bonding between those carbon atoms with different hybridization and overlap of the carbon 2p orbitals. Among all the GYs, graphdiyne (GDY) was the first reported to be prepared practically and, hence, attracted the attention of many researchers toward this new planar, layered material, as well as other GYs. Several approaches have been reported to be able to modify the band gap of GDY, containing invoking strain, boron/nitrogen doping, nanoribbon architectures, hydrogenation, and so on. GDY has been well-prepared in many different morphologies, like nanowires, nanotube arrays, nanowalls, nanosheets, ordered stripe arrays, and 3D framwork. The fascinating structure and electronic properties of GDY make it a potential candidate carbon material with many applications. It has recently revealed the practicality of GDY as catalyst; in rechargeable batteries, solar cells, electronic devices, magnetism, detector, biomedicine, and therapy; and for gas separation as well as water purification.

Organic electrodes are potential alternatives to current inorganic electrode materials for lithium ion and sodium ion batteries powering portable and wearable electronics, in terms of their mechanical flexibility, function tunability and low cost. However, the low capacity, poor rate performance and rapid capacity degradation impede their practical application. Here, we concentrate on the molecular design for improved conductivity and capacity, and favorable bulk ion transport. Through an in situ cross-coupling reaction of triethynylbenzene on copper foil, the carbon-rich frame hydrogen substituted graphdiyne film is fabricated. The organic film can act as free-standing flexible electrode for both lithium ion and sodium ion batteries, and large reversible capacities of 1050 mAh g−1 for lithium ion batteries and 650 mAh g−1 for sodium ion batteries are achieved. The electrode also shows a superior rate and cycle performances owing to the extended π-conjugated system, and the hierarchical pore bulk with large surface area.