Ni1−xCoxSe2C/ZnIn2S4 Hybrid Nanocages with Strong 2D/2D Hetero‐Interface Interaction Enable Efficient H2‐Releasing Photocatalysis

Abstract Designing a semiconductor‐based heterostructure photocatalyst for achieving the efficient separation of photogenerated electron‐hole pairs is highly important for enhancing H 2 releasing photocatalysis. Here, a new class of Ni 1− x Co x Se 2 –C/ZnIn 2 S 4 hierarchical nanocages with abundant and compact ZnIn 2 S 4 nanosheets/Ni 1− x Co x Se 2  C nanosheets 2D/2D hetero–interfaces, is designed and synthesized. The constructed heterostructure photocatalyst exposes rich hetero‐junctions, supplying the broad and short transfer paths for charge carriers. The close contacts of these two kinds of nanosheets induce a strong interaction between ZnIn 2 S 4 and Ni 1− x Co x Se 2 C, improving the separation and transfer of photo‐generated electron‐hole pairs. As a consequence, the distinctive Ni 1− x Co x Se 2 C/ZnIn 2 S 4 hierarchical nanocages without using additional noble‐metal cocatalysts, display remarkable H 2 ‐relaesing photocatalytic activity with a rate of 5.10 mmol g −1 h −1 under visible light irradiation, which is 6.2 and 30 times higher than those of fresh ZnIn 2 S 4 nanosheets and bare Ni 1− x Co x Se 2 C nanocages, respectively. Spectroscopic characterizations and theory calculations reveal that the strong interaction between ZnIn 2 S 4 and Ni 1− x Co x Se 2 C 2D/2D hetero‐interfaces can powerfully promote the separation of photo‐generated charge carriers and the electrons transfer from ZnIn 2 S 4 to Ni 1− x Co x Se 2 C.