Photocatalytic Mechanism Control and Study of Carrier Dynamics in CdS@C₃N₅ Core–Shell Nanowires

Abstract

We present a potential solution to the problem of extraction of photogenerated holes from CdS nanocrystals and nanowires. The nanosheet form of C₃N₅ is a low-band-gap (<i>E</i>_g = 2.03 eV), azo-linked graphenic carbon nitride framework formed by the polymerization of melem hydrazine (MHP). C₃N₅ nanosheets were either wrapped around CdS nanorods (NRs) following the synthesis of pristine chalcogenide or intercalated among them by an <i>in situ</i> synthesis protocol to form two kinds of heterostructures, CdS-MHP and CdS-MHPINS, respectively. CdS-MHP improved the photocatalytic degradation rate of 4-nitrophenol by nearly an order of magnitude in comparison to bare CdS NRs. CdS-MHP also enhanced the sunlight-driven photocatalytic activity of bare CdS NWs for the decolorization of rhodamine B (RhB) by a remarkable 300% through the improved extraction and utilization of photogenerated holes due to surface passivation. More interestingly, CdS-MHP provided reaction pathway control over RhB degradation. In the absence of scavengers, CdS-MHP degraded RhB through the N-deethylation pathway. When either hole scavenger or electron scavenger was added to the RhB solution, the photocatalytic activity of CdS-MHP remained mostly unchanged, while the degradation mechanism shifted to the chromophore cleavage (cycloreversion) pathway. We investigated the optoelectronic properties of CdS-C₃N₅ heterojunctions using density functional theory (DFT) simulations, finite difference time domain (FDTD) simulations, time-resolved terahertz spectroscopy (TRTS), and photoconductivity measurements. TRTS indicated high carrier mobilities >450 cm² V^-1 s^-1 and carrier relaxation times >60 ps for CdS-MHP, while CdS-MHPINS exhibited much lower mobilities <150 cm² V^-1 s^-1 and short carrier relaxation times <20 ps. Hysteresis in the photoconductive <i>J-V</i> characteristics of CdS NWs disappeared in CdS-MHP, confirming surface passivation. Dispersion-corrected DFT simulations indicated a delocalized HOMO and a LUMO localized on C₃N₅ in CdS-MHP. C₃N₅, with its extended π-conjugation and low band gap, can function as a shuttle to extract carriers and excitons in nanostructured heterojunctions, and enhance performance in optoelectronic devices. Our results demonstrate how carrier dynamics in core-shell heterostructures can be manipulated to achieve control over the reaction mechanism in photocatalysis.