A unique coordination-driven route for the precise nanoassembly of metal sulfides on metal–organic frameworks,Nanoscale Horizons

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A unique coordination-driven route for the precise nanoassembly of metal sulfides on metal–organic frameworks
Nanoscale Horizons ( IF 8.0 ) Pub Date : 2020-01-24 , DOI: 10.1039/c9nh00769e
Xiang-Yu Lin _{1,

2,

3,

4,

5} , Yue-Hua Li _{1,

2,

3,

4,

5} , Ming-Yu Qi _{1,

2,

3,

4,

5} , Zi-Rong Tang _{2,

3,

4,

5,

6} , Hai-Long Jiang _{7,

8,

9,

10,

11} , Yi-Jun Xu _{1,

2,

3,

4,

5}

Affiliation

Incorporating different materials, such as metal sulfides, with metal–organic frameworks (MOFs) to develop MOF-based multifunctional composites with enhanced performance is an important area of research. However, the intrinsically high interfacial energy barrier significantly restricts the heterogeneous nucleation and nanoassembly of metal sulfides onto MOFs during the wet chemistry synthesis process. Herein, taking advantage of the natural tailorability of MOFs, the precise and controllable growth of metal sulfide nanoparticles (NPs) (CdS, ZnS, CuS and Ag₂S) at the coordinatively unsaturated metal sites (CUSs) of MOFs to form MOF@metal sulfide composites under mild conditions is achieved via a cysteamine-assisted coordination-driven route. During the process, the molecular linker of cysteamine, possessing one amino group for chelating with the CUSs of the MOF and one thiol group as a docking site to anchor metal ions, plays a prominent role in enhancing interfacial interactions between the MOF and metal ions. The subsequent S²⁻ anion exchange process leads to intimate surface-attached nucleation and epitaxial growth of metal sulfide NPs on the surface of the MOF. The as-formed composites exhibit enhanced charge separation and transfer capability, and thus boost photocatalytic performance. This general and simple approach provides a new avenue for the design of MOF–metal sulfide hybrids.

中文翻译：

独特的配位驱动途径，可在金属-有机骨架上精确地纳米组装金属硫化物

将不同的材料（例如金属硫化物）与金属有机骨架（MOF）结合使用，以开发具有增强性能的基于MOF的多功能复合材料是一个重要的研究领域。但是，本质上较高的界面能垒显着限制了湿化学合成过程中金属硫化物在MOF上的异质成核和纳米组装。在此，利用MOF的天然适应性，在MOF的配位不饱和金属位点（CUSs）上金属硫化物纳米颗粒（NPs）（CdS，ZnS，CuS和Ag ₂ S）的精确可控生长，形成MOF @ metal硫化物在温和条件下的合成是通过半胱胺辅助的协调驱动途径。在此过程中，半胱胺的分子接头具有一个与MOF的CUS螯合的氨基和一个巯基作为固定金属离子的对接位点，在增强MOF与金属离子之间的界面相互作用中起着重要作用。随后的S ^2-阴离子交换过程导致MOF表面上紧密的表面附着形核和金属硫化物NP的外延生长。如此形成的复合物表现出增强的电荷分离和转移能力，因此提高了光催化性能。这种通用而简单的方法为MOF-金属硫化物杂化物的设计提供了新途径。

更新日期：2020-01-24

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