Unveiling charge dynamics of Co3S4 nanowalls/CdS nanospheres n-n heterojunction for efficient photoelectrochemical Cr(VI) detoxification and N2 fixation

Abstract

Photoelectrochemical (PEC) conversion of solar energy is a sustainable and ecological approach as it offers green energy carriers, renewable fuels as well as environmental remediation. Herein, a polyaniline-coated anodized stainless-steel mesh (PANI-ASSM) was supported n-n heterojunction of CdS nanosphere (NSs)-Co3S4 nanowalls (NWs) by a simple step by step electrochemical deposition method. The PEC performance of the developed photoanode was then assessed toward Cr(VI) detoxification and N2 fixation. The PL, UV-Vis, electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent spectroscopy (IMPS), cyclic voltammetry (CV), transient photocurrent (TPC), chronopotentiometry, and Bode phase tests also proved the excellent PEC performance and significant stability of this catalyst. UV–vis, Urbach energy (UE), Mott-Schottky (M-S), and linear sweep voltammetry (LSV) results coupled to the Robert Mulliken method confirmed the formation of robust n-n CdS-NSs-Co3S4-NWs heterojunction with viable band edge potential for Cr(VI) detoxification and N2 fixation; while PANI only acted as a powerful bridge to transfer the photo-generated electrons to ASSM support. The possible mechanism was investigated by experimental and electrochemical analysis which suggested a 3-electron-coupled Cr(VI) and 6-electron-coupled N2 reduction pathway. Such a PEC exhibited considerable electrocatalytic performance due to effective electron-hole separation with an ammonia yield and Cr(VI) reduction of 12.33 µg/mol.h NH3 and 90.61%, respectively. This work presented a new paradigm for the illustrative design of promising photoanodes for renewable fuel production and detoxification performance.