Assembly of thiacalix[4]arene-supported high-nuclearity Cd24 cluster with enhanced photocatalytic activity

Cheng Shi; Min Zhang; Xinxin Hang; Yanfeng Bi; Liangliang Huang; Kun Zhou; Zhenhe Xu; Zhiping Zheng

doi:10.1039/C8NR03474E

Assembly of thiacalix[4]arene-supported high-nuclearity Cd₂₄ cluster with enhanced photocatalytic activity†

Cheng Shi,‡^a Min Zhang,‡^a Xinxin Hang,^a Yanfeng Bi,

*^a Liangliang Huang,^a Kun Zhou,

^a Zhenhe Xu

*^b and Zhiping Zheng*^ac

Author affiliations

* Corresponding authors

^a College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun 113001, P. R. China
E-mail: biyanfeng@lnpu.edu.cn

^b The Key Laboratory of Inorganic Molecule-Based Chemistry of Liaoning Province, College of Applied Chemistry, Shenyang University of Chemical Technology, Shenyang 110142, P. R. China
E-mail: xuzh@syuct.edu.cn

^c University of Arizona, Department of Chemistry, Tucson, AZ 85721, USA
E-mail: zhiping@email.arizona.edu

Abstract

A high-nuclearity nanoscale Cd₂₄ cluster has been hydrothermally synthesized by assembly of Cd₄-TC4A (H₄TC4A = p-tert-butylthiacalix[4]arene) second building units (SBUs) and in situ generated peroxy(mono)phosphate PO₅³⁻ groups and peroxyphenoxide groups of TC4A. The cluster was structurally characterized by single crystal X-ray diffractions. Photocatalytic studies revealed that the highest nuclearity Cd,S-co-rich Cd₂₄ cluster exhibits enhanced photocatalytic water splitting activities compared to the sandwich Cd₄(TC4A)₂ (Cd₄) cluster under the same conditions in the absence of a co-catalyst. The nanostructure of Cd₂₄ incorporated both peroxyphosphate and peroxyphenoxide groups, which increased the metal coordination numbers to give more labile Cd–O/S bonds and is believed to be the key feature that enables the significant photocatalytic water splitting activities.

This article is part of the themed collection: 2018 Nanoscale HOT Article Collection

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Article information

DOI: https://doi.org/10.1039/C8NR03474E
Article type: Paper
Submitted: 27 Eph 2018
Accepted: 10 Jul 2018
First published: 13 Jul 2018

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Nanoscale, 2018,10, 14448-14454

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Assembly of thiacalix[4]arene-supported high-nuclearity Cd₂₄ cluster with enhanced photocatalytic activity

C. Shi, M. Zhang, X. Hang, Y. Bi, L. Huang, K. Zhou, Z. Xu and Z. Zheng, Nanoscale, 2018, 10, 14448 DOI: 10.1039/C8NR03474E

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