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Title: Direct synthesis of all-inorganic heterostructured CdSe/CdS QDs in aqueous solution for improved photocatalytic hydrogen generation

Abstract

Here we present a facile aqueous approach to synthesize heterostructured CdSe/CdS QDs with all-inorganic chalcogenide S2- ligands under mild conditions. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and steady-state emission spectroscopy demonstrate that the heterostructured CdSe/CdS QDs with sulfur-rich surface composition are formed by heterogeneous nucleation of Cd2+ and S2- precursors on the CdSe QDs. After adsorption of small Ni(OH)(2) clusters over the surface in situ, the CdSe/CdS-Ni(OH)(2) photocatalyst enables H-2 production efficiently with an internal quantum yield of 52% under visible light irradiation at 455 nm, up to an 8-fold increase of activity to that of spherical CdSe QDs-Ni(OH)(2) under the same conditions. Femtosecond transient absorption spectroscopy, X-ray transient absorption (XTA) spectroscopy, steady-state and time-resolved emission spectroscopy show that the quasi-type-II band alignment in the CdSe/CdS heterostructure is responsible for the efficiency enhancement of light harvesting and surface/interfacial charge separation in solar energy conversion. The unprecedented results exemplify an easily accessible pattern of aqueous synthesis of all-inorganic heterostructured QDs for advanced photosynthetic H-2 evolution.

Authors:
; ; ORCiD logo; ; ; ; ; ; ; ORCiD logo; ; ; ; ; ORCiD logo; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Ministry of Science and Technology of the People's Republic of China; National Natural Science Foundation of China (NNSFC); USDOE Office of Science - Office of Basic Energy Sciences - Scientific User Facilities Division
OSTI Identifier:
1392521
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 21; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Li, Zhi-Jun, Fan, Xiang-Bing, Li, Xu-Bing, Li, Jia-Xin, Zhan, Fei, Tao, Ye, Zhang, Xiaoyi, Kong, Qing-Yu, Zhao, Ning-Jiu, Zhang, Jian-Ping, Ye, Chen, Gao, Yu-Ji, Wang, Xu-Zhe, Meng, Qing-Yuan, Feng, Ke, Chen, Bin, Tung, Chen-Ho, and Wu, Li-Zhu. Direct synthesis of all-inorganic heterostructured CdSe/CdS QDs in aqueous solution for improved photocatalytic hydrogen generation. United States: N. p., 2017. Web. doi:10.1039/c7ta01670k.
Li, Zhi-Jun, Fan, Xiang-Bing, Li, Xu-Bing, Li, Jia-Xin, Zhan, Fei, Tao, Ye, Zhang, Xiaoyi, Kong, Qing-Yu, Zhao, Ning-Jiu, Zhang, Jian-Ping, Ye, Chen, Gao, Yu-Ji, Wang, Xu-Zhe, Meng, Qing-Yuan, Feng, Ke, Chen, Bin, Tung, Chen-Ho, & Wu, Li-Zhu. Direct synthesis of all-inorganic heterostructured CdSe/CdS QDs in aqueous solution for improved photocatalytic hydrogen generation. United States. doi:10.1039/c7ta01670k.
Li, Zhi-Jun, Fan, Xiang-Bing, Li, Xu-Bing, Li, Jia-Xin, Zhan, Fei, Tao, Ye, Zhang, Xiaoyi, Kong, Qing-Yu, Zhao, Ning-Jiu, Zhang, Jian-Ping, Ye, Chen, Gao, Yu-Ji, Wang, Xu-Zhe, Meng, Qing-Yuan, Feng, Ke, Chen, Bin, Tung, Chen-Ho, and Wu, Li-Zhu. Sun . "Direct synthesis of all-inorganic heterostructured CdSe/CdS QDs in aqueous solution for improved photocatalytic hydrogen generation". United States. doi:10.1039/c7ta01670k.
@article{osti_1392521,
title = {Direct synthesis of all-inorganic heterostructured CdSe/CdS QDs in aqueous solution for improved photocatalytic hydrogen generation},
author = {Li, Zhi-Jun and Fan, Xiang-Bing and Li, Xu-Bing and Li, Jia-Xin and Zhan, Fei and Tao, Ye and Zhang, Xiaoyi and Kong, Qing-Yu and Zhao, Ning-Jiu and Zhang, Jian-Ping and Ye, Chen and Gao, Yu-Ji and Wang, Xu-Zhe and Meng, Qing-Yuan and Feng, Ke and Chen, Bin and Tung, Chen-Ho and Wu, Li-Zhu},
abstractNote = {Here we present a facile aqueous approach to synthesize heterostructured CdSe/CdS QDs with all-inorganic chalcogenide S2- ligands under mild conditions. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and steady-state emission spectroscopy demonstrate that the heterostructured CdSe/CdS QDs with sulfur-rich surface composition are formed by heterogeneous nucleation of Cd2+ and S2- precursors on the CdSe QDs. After adsorption of small Ni(OH)(2) clusters over the surface in situ, the CdSe/CdS-Ni(OH)(2) photocatalyst enables H-2 production efficiently with an internal quantum yield of 52% under visible light irradiation at 455 nm, up to an 8-fold increase of activity to that of spherical CdSe QDs-Ni(OH)(2) under the same conditions. Femtosecond transient absorption spectroscopy, X-ray transient absorption (XTA) spectroscopy, steady-state and time-resolved emission spectroscopy show that the quasi-type-II band alignment in the CdSe/CdS heterostructure is responsible for the efficiency enhancement of light harvesting and surface/interfacial charge separation in solar energy conversion. The unprecedented results exemplify an easily accessible pattern of aqueous synthesis of all-inorganic heterostructured QDs for advanced photosynthetic H-2 evolution.},
doi = {10.1039/c7ta01670k},
journal = {Journal of Materials Chemistry. A},
issn = {2050-7488},
number = 21,
volume = 5,
place = {United States},
year = {2017},
month = {1}
}

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