Acid-Base Bifunctional Metal-Organic Frameworks: Green Synthesis and Application in One-Pot Glucose to 5-HMF Conversion

NANO ◽  
2018 ◽  
Vol 13 (11) ◽  
pp. 1850132 ◽  
Author(s):  
Yunlei Zhang ◽  
Pei Jin ◽  
Minjia Meng ◽  
Lin Gao ◽  
Meng Liu ◽  
...  

The direct synthesis of metal-organic frameworks (MOFs) with acidic and basic active sites is challenging due to the introduction of functional groups by post-functionalization method often jeopardize the framework integrity. Herein, we report the direct synthesis of acid-base bi-functional MOFs with tuning acid-base strength. Employing modulated hydrothermal (MHT) approach, microporous MOFs named UiO-66-NH2 was prepared. Through the ring-opening reaction of 1,3-propanesultone with amino group, UiO-66-NH2-SO3H-type catalysts can be obtained. The synthesized catalysts were well characterized and their catalytic performances were evaluated in one-pot glucose to 5-HMF conversion. Results revealed the acid-base bi-functional catalyst possessed high activity and excellent stability. This work provides a general and economically viable approach for the large-scale synthesis of acid-base bi-functional MOFs for their potential use in catalysis field.

2020 ◽  
Vol 10 (2) ◽  
pp. 315-322 ◽  
Author(s):  
Yanjing Hu ◽  
Jian Zhang ◽  
Hang Huo ◽  
Zhe Wang ◽  
Xianzhu Xu ◽  
...  

Bimetallic MIL-101(Al/Fe)–NH2 exhibits enhanced acid–base bifunctional catalytic activity due to its synergistic mechanism and hierarchical pore system.


Catalysts ◽  
2020 ◽  
Vol 10 (3) ◽  
pp. 309 ◽  
Author(s):  
Mingming Zheng ◽  
Yanxiang Wang ◽  
Pingyun Feng

A family of heterometallic metal-organic frameworks (MOFs) (CPM200s) harmoniously coexisting as Lewis acids and base (azo) sites were prepared. Seven CPM200s were employed as multifunctional heterogeneous cascade catalysts for the one-pot deacetalization-Knoevenagel reaction in a solvent-free system. Benefiting from the cooperation between Lewis acids from the open metal sites and base sites from the ligands, the CPM200s showed high activity and selectivity for the tandem reaction. The heterometallic 3D porous framework reported here not only offers a combination of two opposite active sites in the same framework of materials but also increases mass transfer of the substrate, thus maximizing the efficiency and substrate selectivity of the bifunctional catalysts. The CPM200s showed the highest turnover frequency (TOF), outperforming that of the reported MOFs in tandem with the deacetalization-Knoevenagel reaction. A strong correlation between the TOF and charge-to-radius ratio (z/r) of metal ions in the CPM200s was observed for the first time. The bifunctional CPM200s catalysts can be reused five times without significant loss of activity.


2021 ◽  
Author(s):  
Bahareh ameri ◽  
Akbar Mohammadi Zardkhoshoui ◽  
Saied Saeed Hosseiny Davarani

Metal-organic frameworks (MOFs) derived nanoarchitectures have special features, such as high surface area (SA), abundant active sites, exclusive porous networks, and remarkable supercapacitive performance when compared to traditional nanoarchitectures. Herein,...


Crystals ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 15
Author(s):  
Cheng-An Tao ◽  
Jian-Fang Wang

Metal-organic frameworks (MOFs) have been used in adsorption, separation, catalysis, sensing, photo/electro/magnetics, and biomedical fields because of their unique periodic pore structure and excellent properties and have become a hot research topic in recent years. Ball milling is a method of small pollution, short time-consumption, and large-scale synthesis of MOFs. In recent years, many important advances have been made. In this paper, the influencing factors of MOFs synthesized by grinding were reviewed systematically from four aspects: auxiliary additives, metal sources, organic linkers, and reaction specific conditions (such as frequency, reaction time, and mass ratio of ball and raw materials). The prospect for the future development of the synthesis of MOFs by grinding was proposed.


CrystEngComm ◽  
2021 ◽  
Author(s):  
Qing Luo ◽  
Zhen Ding ◽  
Huamin Sun ◽  
Zhen Cheng ◽  
Naien SHI ◽  
...  

Ultrathin two-dimensional (2D) metal-organic framework (MOF) nanosheets are prosperous advanced materials due to their particularly thin thickness and exposed active sites. The difficulty in the controlled synthesis of 2D MOF...


Sensors ◽  
2021 ◽  
Vol 21 (5) ◽  
pp. 1679
Author(s):  
Roberta Puglisi ◽  
Anna L. Pellegrino ◽  
Roberto Fiorenza ◽  
Salvatore Scirè ◽  
Graziella Malandrino

Gadolinium metal-organic frameworks (Gd-MOFs) and Eu-doped Gd-MOFs have been synthesized through a one-pot green approach using commercially available reagents. The 1,4-benzenedicarboxylic acid (H2-BDC) and 2,6-naphthalenedicarboxylic acid (H2-NDC) were chosen as ditopic organic linkers to build the 3D structure of the network. The Gd-MOFs were characterized using powder X-ray diffraction (XRD), FT-IR spectroscopy, field emission scanning electron microscopy (FE-SEM) and N2 adsorption–desorption analysis. The Gd-MOF structures were attributed comparing the XRD patterns, supported by the FT-IR spectra, with data reported in the literature for Ln-MOFs of similar lanthanide ionic radius. FE-SEM characterization points to the effect of the duration of the synthesis to a more crystalline and organized structure, with grain dimensions increasing upon increasing reaction time. The total surface area of the MOFs has been determined from the application of the Brunauer–Emmett–Teller method. The study allowed us to correlate the processing conditions and ditopic linker dimension to the network surface area. Both Gd-MOF and Eu-doped Gd-MOF have been tested for sensing of the inorganic ions such as Fe3+ and Cr2O72−.


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