Rational Design of Three Dimensional Hollow Heterojunctions for Efficient Photocatalytic Hydrogen Evolution Applications.

The efficiency of photocatalytic hydrogen evolution is currently limited by poor light adsorption, rapid recombination of photogenerated carriers, and ineffective surface reaction rate. Although heterojunctions with innovative morphologies and structures can strengthen built-in electric fields and maximize the separation of photogenerated charges. However, how to rational design of novel multidimensional structures to simultaneously improve the above three bottleneck problems is still a research imperative. Herein, a unique Cu 2 O─S@graphene oxide (GO)@Zn 0.67 Cd 0.33 S Three dimensional (3D) hollow heterostructure is designed and synthesized, which greatly extends the carrier lifetime and effectively promotes the separation of photogenerated charges. The H 2 production rate reached 48.5 mmol g -1  h -1 under visible light after loading Ni 2+ on the heterojunction surface, which is 97 times higher than that of pure Zn 0.67 Cd 0.33 S nanospheres. Furthermore, the H 2 production rate can reach 77.3 mmol g -1  h -1 without cooling, verifying the effectiveness of the photothermal effect. Meanwhile, in situ characterization and density flooding theory calculations reveal the efficient charge transfer at the p-n 3D hollow heterojunction interface. This study not only reveals the detailed mechanism of photocatalytic hydrogen evolution in depth but also rationalizes the construction of superior 3D hollow heterojunctions, thus providing a universal strategy for the materials-by-design of high-performance heterojunctions.