Highly efficient visible-light-assisted photocatalytic hydrogen generation from water splitting catalyzed by Zn0.5Cd0.5S/Ni2P heterostructures

Abstract

Development of heterostructured photocatalysts which can facilitate spatial separation of photo-generated charge carriers is crucial for achieving improved photocatalytic H2 production. Consequently, herein, we report the synthesis of Zn0.5Cd0.5S/Ni2P heterojunction photocatalysts with varying amount of Ni2P, 0.5 (S1), 1 (S2), 3 (S3), 5 (S4) and 10wt% (S5) for the efficient visible-light-assisted H2 generation by water splitting. The heterostructures were characterized thoroughly by PXRD, FE-SEM, EDS, HR-TEM and XPS studies. FE-SEM and HR-TEM analyses of the samples unveiled the presence of Zn0.5Cd0.5S microspheres composed of smaller nanocrystals with the surface of the microspheres covered with Ni2P nanosheets and the intimate contact between the Zn0.5Cd0.5S and the Ni2P. Further, visiblelight- assisted photocatalytic investigation of the samples showed excellent water splitting activity of the heterostructure, Zn0.5Cd0.5S/1wt%Ni2P (S2) with very high H2 generation rate of 21.19 mmol h 1g 1 and the AQY of 21.16% at 450 nm with turnover number (TON) and turnover frequency (TOF) of 251,516 and 62,879 h 1 respectively. Interestingly, H2 generation activity of S2 was found to be about four times higher than that of pure Zn0.5Cd0.5S (5.0 mmol h 1g 1) and about 240 times higher than that of CdS/1wt%Ni2P. The enhanced H2 generation activity of S2 has been attributed to efficient spatial separation of photogenerated charge carriers and the presence of highly reactive Ni2P sites on the surface of Zn0.5Cd0.5S microspheres. A possible mechanism for the enhanced photocatalytic H2 generation activity of Zn0.5Cd0.5S/1wt%Ni2P (S2) has been proposed and is further supported by photoluminescence and photocurrent measurements. Furthermore, the catalyst, S2 can be recycled for several cycles without significant loss of catalytic activity and photostability. Remarkably, the H2 generation activity of S2 was found to be even higher than the reported examples of ZnxCd1-xS doped with noble metal cocatalysts. Hence, the present study highlights the importance of Zn0.5Cd0.5S/Ni2P heterostructures based on non-noble metal co-catalyst for efficient visible-light-driven H2 production from water splitting.