The development of photocatalysts with efficient charge separation and transferring is essential for efficient photocatalytic H₂ generation. Here, we have constructed Sn²⁺ and Sn⁴⁺ double-doped ZnIn₂S₄ (Sn²⁺/Sn⁴⁺-ZnIn₂S₄) catalyst by using a one-step solvothermal method. Sn⁴⁺ replaces the Zn ion and creates an additional energy state near the Fermi level, which act as electron accepters. The receptor states boost the metallic conductive properties of ZnIn₂S₄ and reduce the recombination of photo-induced electrons and holes. The Sn²⁺ combines with edge S atoms of ZnIn₂S₄ due to the large ionic radius, which modulates the band gap structure. Both experimental results and theoretical calculations show that the Sn²⁺and Sn⁴⁺ ion double doping increases charge density and narrows the bandgap for light capture. Therefore, the Sn²⁺/Sn⁴⁺-ZnIn₂S₄ catalyst shows an excellent catalytic activity for hydrogen production (2.48 mmol·g⁻¹·h⁻¹), and it is 35.4 times that of the original ZnIn₂S₄ (0.07 mmol⋅g⁻¹⋅h⁻¹). This work opens a promising path for developing highly efficient photocatalysts for solar photocatalytic H₂ generation.

Graphical Abstract

中文翻译：

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通过 Sn(II)/Sn(IV) 共掺杂调节 ZnIn2S4 上的电子转移以实现高效光催化制氢

开发具有高效电荷分离和转移的光催化剂对于高效光催化H ₂生成至关重要。在此，我们采用一步溶剂热法构建了Sn ²⁺和Sn ⁴⁺双掺杂ZnIn ₂ S ₄ (Sn ²⁺ /Sn ⁴⁺ -ZnIn ₂ S _{4 )催化剂。}Sn ⁴⁺取代了 Zn 离子并在费米能级附近产生了一个额外的能态，充当电子受体。受体态提高了 ZnIn ₂ S _{4的金属导电性能}并减少光致电子和空穴的复合。由于较大的离子半径， Sn ²⁺与ZnIn ₂ S ₄的边缘S原子结合，从而调节了带隙结构。实验结果和理论计算都表明，Sn ²⁺和Sn ⁴⁺离子双掺杂增加了电荷密度并缩小了光捕获的带隙。因此，Sn ²⁺ /Sn ⁴⁺ -ZnIn ₂ S ₄催化剂表现出优异的制氢催化活性（2.48 mmol·g ^-1 ·h ^-1），是原始ZnIn ₂ S的35.4倍。₄ (0.07 mmol·g ^-1 ⋅h ^-1 )。_{这项工作为开发用于太阳能光催化H 2}生成的高效光催化剂开辟了一条有希望的道路。

图形概要