物理化学学报 >> 2018, Vol. 34 >> Issue (7): 781-785.doi: 10.3866/PKU.WHXB201711131

所属专题: 原子水平上精确控制纳米簇和纳米粒子

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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

NARAYANAM Nagaraju1,2,CHINTAKRINDA Kalpana1,方伟慧1,张磊1,*(),张健1   

  1. 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
  • 收稿日期:2017-10-17 发布日期:2018-03-26
  • 通讯作者: 张磊 E-mail:LZhang@fjirsm.ac.cn
  • 基金资助:
    国家自然科学基金(21473202);国家自然科学基金(21673238);福建省自然科学基金(2017J06009)

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

Nagaraju NARAYANAM1,2,Kalpana CHINTAKRINDA1,Weihui FANG1,Lei ZHANG1,*(),Jian ZHANG1   

  1. 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
  • Received:2017-10-17 Published:2018-03-26
  • Contact: Lei ZHANG E-mail:LZhang@fjirsm.ac.cn
  • Supported by:
    the National Natural Science Foundation of China(21473202);the National Natural Science Foundation of China(21673238);Natural Science Foundation of Fujian Province, China(2017J06009)

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

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: Nanocluster, Titanium, Zirconium, Deep-eutectic solvothermal, H2 evolution

MSC2000: 

  • O641