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

Abstract 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 Cu2O─S@graphene oxide (GO)@Zn0.67Cd0.33S Three dimensional (3D) hollow heterostructure is designed and synthesized, which greatly extends the carrier lifetime and effectively promotes the separation of photogenerated charges. The H2 production rate reached 48.5 mmol g−1 h−1 under visible light after loading Ni2+ on the heterojunction surface, which is 97 times higher than that of pure Zn0.67Cd0.33S nanospheres. Furthermore, the H2 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.

S1, S2] The lattice constants of Cu2OxS1-x are estimated: Therefore, the diffraction peak at 42.6 o is belong to Cu2OxS1-x.The formula for calculating the average value of τ is as follows:      Cu2O-S@GO@Zn0.

Figure S4 .
Figure S4.EDX spectrum of A) Cu2O, B) Cu2O-S and C) Cu2O-S/2 from SEM pictures in figure S3 (the illustrated table shows the corresponding elemental content).

Figure S14 .
Figure S14.Comparison of photocatalytic H2 evolution activities of Cu2O-S@GO@ZCS-Ni(OH)2 composites with different theoretical contents of GO.

Figure S15 .
Figure S15.A brief summary of relevant types of catalysts in recent years.

Figure S19 .
Figure S19.The most stable Ni doping sites on the surface of the Cu2O-S/Zn0.67Cd0.33S

Figure S20 .
Figure S20.The optimized configurations of H atoms adsorption on the surfaces of Cu2O-S/Zn0.67Cd0.33Sheterojunction.The black values are the total energies with respect to figure A.

Figure S21 .
Figure S21.The optimized configurations of H atoms adsorption on the surfaces of Cu2O-S/Zn0.67Cd0.33S-Niheterojunction.The black values are the total energies with respect to Figure A.

Figure S24 .
Figure S24.The optimizied configurations of S doped on the interface of Cu2O/Zn0.67Cd0.33Sheterojunction.The black values are the total energies with respect to figure A.

Figure S27 .
Figure S27.AES for Cu LMM of the 7% CSGZCS-4.5Nibefore and after the reaction.

Table S2
Kinetic parameters of PL decay for ZCS, CSZCS, COGZCS and CSGZCS

Table S3
A brief summary table of the relevant types of catalysts mentioned above in recent years.