Atomically Precise Zr-Oxo and Zr/Ti-Oxo Nanoclusters by Deep Eutectic-Solvothermal Synthesis

Citation: NARAYANAM Nagaraju, CHINTAKRINDA Kalpana, FANG Weihui, ZHANG Lei, ZHANG Jian. Atomically Precise Zr-Oxo and Zr/Ti-Oxo Nanoclusters by Deep Eutectic-Solvothermal Synthesis[J]. Acta Physico-Chimica Sinica, 2018, 34(7): 781-785. doi: 10.3866/PKU.WHXB201711131 shu

具有精准结构Zr-O及Zr/Ti-O纳米团簇的深共熔溶剂热合成

1.
中国科学院福建物质结构研究所结构化学重点实验室，福州 350002
2.
中国科学院大学，北京 100049

通讯作者: 张磊, LZhang@fjirsm.ac.cn

基金项目:
国家自然科学基金(21473202，21673238)和福建省自然科学基金(2017J06009)资助项目

国家自然科学基金 21673238

福建省自然科学基金 2017J06009

国家自然科学基金 21473202

摘要: 近年来，深共熔溶剂热作为一种绿色合成方法被广泛用于多种杂化功能材料的合成。在本研究中，这一合成方法被引入到多核Zr-和Zr/Ti-O纳米团簇的制备，成功获得被邻菲罗啉、苯酚等共轭配体修饰的Zr₆以及Ti₁₁Zr₄团簇。此方法将为具有精准结构信息的被较多发色团包覆的纳米团簇的合成开辟新的技术路线。此外，光催化分解水产氢实验结果表明，由于具有不同的簇核环境，这两种纳米团簇表现出不同的分散性及与之相关的产氢活性。因此，该研究也为探索金属氧簇材料的结构–性能关系以及结构设计原则提供了借鉴。

关键词:

纳米团簇
/ 钛
/ 锆
/ 深共熔溶剂热
/ 产氢

English

Atomically Precise Zr-Oxo and Zr/Ti-Oxo Nanoclusters by Deep Eutectic-Solvothermal Synthesis

1.
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, P. R. China
2.
International College, University of Chinese Academy of Sciences, 100049 Beijing, P. R. China

Corresponding author: ZHANG Lei, LZhang@fjirsm.ac.cn

Received Date: 17 October 2017
Accepted Date: 07 November 2017
Revised Date: 06 November 2017
Available Online: 15 July 2018
Fund Project:
The project was supported by the National Natural Science Foundation of China (21473202, 21673238) and Natural Science Foundation of Fujian Province, China (2017J06009)

Abstract: Atomically precise nanoclusters form an important class of functional materials that have recently attracted research interest for their unique properties and easily tunable surface functionalities. Core-shell nanomaterials with precise structural information can be produced to better understand the structure–property relationships for different applications. Polyoxo-titanium clusters (PTCs) are such a kind of nanomaterial for different functional applications in catalysis, photovoltaics, ceramics, etc. However, the high bandgap of semiconductive PTCs is the limiting factor in their practical solar application in the visible region of sunlight. The development of PTCs with different surface-bound ligands is an emerging area of research in the design and synthesis of core-shell nanoclusters with reduced bandgaps. It has been extensively reported that the polynuclear growth of PTCs requires molecular-level water supply in reactions. Moreover, it is important to identify more environment-friendly synthetic methods. Deep eutectic-solvothermal (DES) synthesis is an emerging green method for the synthesis of different crystalline materials. The hygroscopic nature of DES should enhance the provision of water during polynuclear growth of nanoclusters. Hence, we chose to synthesize different kinds of PTCs using DES as solvent. Two nanoclusters, Zr-oxo (PTC-65) and Zr/Ti-oxo (PTC-66) clusters having surface-bound 1, 10-phenanthroline (1, 10-phn) and phenol ligands, were successfully synthesized using this approach; 1, 10-phn was employed as the precursor in the synthetic reaction, and phenol was not employed directly in the chemical reaction, but was supplied from the DES solvent used in the reaction. In the presence of chromophoric ligands, 1, 10-phn and phenol are believed to enhance the light absorption properties of the resulting functional nanomaterials. Their crystal structure revealed that they form core-shell mimics with Zr-oxo and Ti/Zr-oxo core units having surface-bound shell ligands. Based on their different structural characteristics, photocatalytic hydrogen evolution studies were performed on these two functional materials using an aqueous solution of H₂O (50 mL)/triethanol amine (10 mL). Interestingly, PTC-65 formed a turbid solution, whereas PTC-66 formed a clear solution. The possible reasons for their different dispersion behaviors are widely discussed, with emphasis on their structure–property relationships. This study provides a potential tool for the homogenization of Ti-O materials to improve their photocatalytic activities. Moreover, the success of our work confirms that deep eutectic-solvothermal synthesis can be an effective method for cluster preparation. Many other interesting polynuclear complexes like polyoxometalates, chalcogenides, and noble-metal clusters could be obtained by this synthetic methodology.

Key words:

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

具有精准结构Zr-O及Zr/Ti-O纳米团簇的深共熔溶剂热合成

通讯作者: 张磊, LZhang@fjirsm.ac.cn

English

Atomically Precise Zr-Oxo and Zr/Ti-Oxo Nanoclusters by Deep Eutectic-Solvothermal Synthesis

Corresponding author: ZHANG Lei, LZhang@fjirsm.ac.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

具有精准结构Zr-O及Zr/Ti-O纳米团簇的深共熔溶剂热合成

通讯作者: 张磊, LZhang@fjirsm.ac.cn

English

Atomically Precise Zr-Oxo and Zr/Ti-Oxo Nanoclusters by Deep Eutectic-Solvothermal Synthesis

Corresponding author: ZHANG Lei, LZhang@fjirsm.ac.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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