Advanced bi-functional CoPi co-catalyst-decorated g-C3N4 nanosheets coupled with ZnO nanorod arrays as integrated photoanodes

In this work, a CoPi-decorated type II heterojunction composed of one-dimensional (1D) ZnO nanorod arrays (NRAs) coated with two-dimensional (2D) carbon nitride (g-C3N4) was successfully prepared and used as photoanode. CoPi has been speculated to be a mixture of amorphous compound and two cobalt-based compounds: Co3(PO3)6·14H2O and Co(H2PO2)2·6H2O. The advanced bi-functional CoPi acts like a shelter, effectively inhibiting the photocorrosion of CNNS/ZnO NRAs and providing a faster hole transfer channel. Synergistic effects at the interface of the heterojunction efficiently improve the separation of charge carriers from photoexcited g-C3N4 nanosheets to the ZnO nanorods. Photocurrent density is also greatly enhanced by loading CoPi on CNNS/ZnO NRAs heterojunction. The maximum photocurrent density (2.45 mA cm-2 at 1.23 V vs. RHE) generated from CoPi(10)-CNNS(600)/ZnO nanorods is about 10.2 times greater than that of pristine ZnO nanorods (0.24 mA cm-2 at 1.23 V vs. RHE) and 2.5 times higher than that of CNNS(800)/ZnO (0.95 mA cm-2 at 1.23 V vs. RHE). The further increase of photoelectrocatalytic performance may be attributed to CoPi relieving the charge accumulation at the semiconductor/electrolyte, which decreases the electron-hole recombination rate.