Bifunctional hydrogen production and storage on 0D-1D heterojunction of Cd₀.₅Zn₀.₅S@Halloysites

Development of efficient solar‐driven hydrogen (H₂) evolution and H₂ storage materials is challenging. Sulfide nanocatalysts show large potential for H₂ production, but suffer from the drawbacks of inefficient charge separation, serious photocorrosion, and easy agglomeration. Herein, a 0D–1D satellite‐core ethylenediaminetetraacetic acid (EDTA)‐bridged Cd_0.5Zn_0.5S@halloysite nanotubes tertiary structure is designed via facile in situ assembly, which settles all the above‐mentioned issues and achieves exceptional and stable photocatalytic H₂ evolution and storage. Significantly, EDTA grafted on halloysites as the hole (h⁺) traps steers the photogenerated h⁺ and electrons (e−) from Cd_0.5Zn_0.5S separately to halloysites and outer surface Pt sites, achieving efficient directional separation between h+ and e− and inhibiting the h⁺‐dominated photocorrosion occurring on Cd_0.5Zn_0.5S. Benefiting from these advantages, the hierarchy shows an unprecedented photocatalytic H₂ evolution rate of 25.67 mmol g⁻¹ h⁻¹ with a recording apparent quantum efficiency of 32.29% at λ = 420 nm, which is seven‐fold that of Cd_0.5Zn_0.5S. Meanwhile, an H₂ adsorption capacity of 0.042% is achieved with the room temperature of 25°C and pressure of 2.65 MPa. This work provides a new perspective into designing hierarchical structure for H₂ evolution, and proposes an integration concept for H₂ evolution and storage.