Atomic Sulfur Passivation Improves the Photoelectrochemical Performance of ZnSe Nanorods

• Main Authors: Fei Huang, Jiajia Ning, Wei Xiong, Ting Shen, Yanling Zhao, Jianjun Tian, Ruiqin Zhang, Andrey L. Rogach
• Format: Article
• Language: English
• Published: MDPI AG 2020-05-01
• Series: Nanomaterials
• Subjects: photoelectrochemical cell; heavy metal-free photocatalyst; ZnSe nanorods; atomic sulfur passivation; ZnS monolayer
• Online Access: https://www.mdpi.com/2079-4991/10/6/1081

We introduced atomic sulfur passivation to tune the surface sites of heavy metal-free ZnSe nanorods, with a Zn²⁺-rich termination surface, which are initially capped with organic ligands and under-coordinated with Se. The S²⁻ ions from a sodium sulfide solution were used to partially substitute a 3-mercaptopropionic acid ligand, and to combine with under-coordinated Zn termination atoms to form a ZnS monolayer on the ZnSe surface. This treatment removed the surface traps from the ZnSe nanorods, and passivated defects formed during the previous ligand exchange process, without sacrificing the efficient hole transfer. As a result, without using any co-catalysts, the atomic sulfur passivation increased the photocurrent density of TiO₂/ZnSe photoanodes from 273 to 325 μA/cm². Notably, without using any sacrificial agents, the photocurrent density for sulfur-passivated TiO₂/ZnSe nanorod-based photoanodes remained at almost 100% of its initial value after 300 s of continuous operation, while for the post-deposited ZnS passivation layer, or those based on ZnSe/ZnS core–shell nanorods, it declined by 28% and 25%, respectively. This work highlights the advantages of the proper passivation of II-VI semiconductor nanocrystals as an efficient approach to tackle the efficient charge transfer and stability of photoelectrochemical cells based thereon.