Editorial Feature

Rapid Synthesis of Metal Organic Frameworks Using a Femtosecond Laser

Luminescent metal-organic frameworks (LMOFs) are a class of MOF materials that have received much research interest across various fields. However, conventional techniques employed to produce them find it difficult to overcome challenges associated hybrid-organic nature. Research published in the journal Optics Express puts forth a new femtosecond laser based technique to synthesize LMOFs. 

Rapid Synthesis of Metal Organic Frameworks Using a Femtosecond Laser

Image Credit: donatas1205/Shutterstock.com

MOFs are compounds containing metal ions coordinated to organic ligands, have well-controlled porosity, high surface area, and electrochemical properties. Their use covers various fields like biomedical sensing, light-emitting techologies, and catalysts.

MOFs are widely synthesized through solvothermal synthesis, traditionally done in a Teflon reactor with a convention oven technique. However, this technique is time-consuming.

These methods produce crystallized powders, which can be integrated into devices via patterning techniques; micro-contact printing, inkjet printing, and photolithography are typical examples. Patterning approaches are a complicated, multistep process, taking place under harsh conditions. Because of this, performance degradation of the final product is often observed. 

Here, researchers detail the usefulness of femtosecond laser-induced in-situ crystallization of Terbium (Tb)-based luminescent metal-organic framework, introducing this method into directly patterning MOFs for the first time.

The potential for femtosecond laser techniques in delivering the fast fabrication and integration of MOFs is evidenced. 

Methodology

The Tb(BTC)·G (BTC = 1,3,5-Benzenetricarboxylic acid and G = guest solvent) was generated by dissolving metal salt and an organic ligand into an appropriate solvent to form a precursor solution which was irradiated by multiple femtosecond laser pulses.

The technique puts chemical synthesis and device integration into a single step, reducing the creation time from hours to seconds or even milliseconds.

Chemicals like Terbium(III) nitrate hexahydrate, N, N-dimethylformamide, 1,3,5-Benzenetricarboxylic acid, N-Methyl pyrrolidone were mixed and heated to 60 °C under vigorous stirring for 5 minutes to prepare the precursor sample. The resultant mixture was filtered using a polytetrafluoroethylene membrane filter.

The experiments took place on a homemade direct writing system with a femtosecond laser (532nm wavelength, pulse duration 170fs). 

Tb(BTC)·G micro-disks were produced by moving the sample using a piezo XYZ stage while maintaining a stable laser beam.  

Morphological characterization of the Tb(BTC)·G micro-disk arrays was carried out with a high-resolution field-emission scanning electron microscope. The high-resolution transmission electron microscopy (HRTEM) images, selected area electron diffraction (SAED), energy dispersive spectrum (EDS), patterns, and elemental mapping analysis were also conducted and noted by a Titan G2 60-300 transmission electron microscope. 

The photoluminescence images were obtained with the help of a homemade wide-field fluorescence microscope. An ultraviolet-visible-near infrared spectrophotometer was used to register the absorption spectra of the NMP solution.

Results

In this study, a femtosecond laser was employed as the energy source to cause a highly confined photon synthesis reaction region, which triggered the in-situ crystallization of the MOF samples. Figure 1 illustrates the femtosecond in-situ laser-induced crystallization of Tb(BTC)·G.

Schematic of the femtosecond laser-induced in-situ crystallization of Tb(BTC)·G. (a) schematic of the laser writing process: I. the initial state of the precursor, II. high intensity and short exposure laser-induced dot arrays of polymerized NMP, III. low intensity and long exposure laser-induced dot arrays of Tb(BTC)·G; (b) absorption curve of the NMP solvent and the precursor; (c) chemical reaction of the NMP under high intense irradiation of the femtosecond laser; (d) SEM image of polymerized NMP; (e) SEM image of Tb(BTC)·G; (f) the molecular structure of the Tb(BTC)·G.

Figure 1. Schematic of the femtosecond laser-induced in-situ crystallization of Tb(BTC)·G. (a) schematic of the laser writing process: I. the initial state of the precursor, II. high intensity and short exposure laser-induced dot arrays of polymerized NMP, III. low intensity and long exposure laser-induced dot arrays of Tb(BTC)·G; (b) absorption curve of the NMP solvent and the precursor; (c) chemical reaction of the NMP under high intense irradiation of the femtosecond laser; (d) SEM image of polymerized NMP; (e) SEM image of Tb(BTC)·G; (f) the molecular structure of the Tb(BTC)·G. Image Credit: Liu, et al., 2021

Enabling in-situ crystallization of Tb(BTC)·G with the femtosecond laser requires a suitable solvent; it must be optically transparent to the exciting wavelength and dissolve the organic ligand and metal salt; possess a high boiling point.

The most widely used solvents are ethanol, water, N-methyl pyrrolidone (NMP), and N, N-dimethylformamide (DMF). 

Various Tb(BTC)·G microdisk arrays were produced on a glass substrate by the proposed technique (see Figure 2).

(a, b, c) SEM images of the Tb(BTC)·G dot arrays, (d) HRTEM of Tb(BTC)·G, (e) SAED patterns of Tb(BTC)·G, (f) EDS of Tb(BTC)·G, (g) elemental mapping analysis of Tb(BTC)·G.

Figure 2. (a, b, c) SEM images of the Tb(BTC)·G dot arrays, (d) HRTEM of Tb(BTC)·G, (e) SAED patterns of Tb(BTC)·G, (f) EDS of Tb(BTC)·G, (g) elemental mapping analysis of Tb(BTC)·G. Image Credit: Liu, et al., 2021

Various sizes of micro Tb(BTC)·G structures were produced by tuning the laser power and the exposure time. The influence of the laser exposure time on the size of Tb(BTC)·G was later analyzed. Figure 3a illustrates the SEM image of the Tb(BTC)·G dot.

(a) SEM image of Tb(BTC)·G dot arrays with different exposure times. (b) the diameter and height of Tb(BTC)·G change with different exposure times.

Figure 3. (a) SEM image of Tb(BTC)·G dot arrays with different exposure times. (b) the diameter and height of Tb(BTC)·G change with different exposure times. Image Credit: Liu, et al., 2021

Synthesis of metal organic frameworks can range between minutes to several days when traditional methods are used. In this research, a new approach utilizing femtosecond laser methods is proposed, which demonstrates a significantly reduced processing time. 

This reduced timeframe is thought to be attributed to the laser's fast energy injection, which is then absorbed by the precursor where it is converted to heat energy.  

In rare-earth MOFs, fluorescence is an attractive character. Rare earth MOFs combine rare earth metal ions and organic ligands which facilitates a broad range of photon emission phenomena like metal-based emission, linker-based luminescence, and other more complicated emissions.

The produced Tb(BTC)·G with a femtosecond laser shows excellent fluorescence properties (see Figure 4). 

(a) fluorescence image of the Tb(BTC)·G, (b) fluorescence spectrum of Tb(BTC)·G (red) and Tb ions in ethanol.

Figure 4. (a) fluorescence image of the Tb(BTC)·G, (b) fluorescence spectrum of Tb(BTC)·G (red) and Tb ions in ethanol. Image Credit: Liu, et al., 2021

Conclusion

The study demonstrated a femtosecond laser triggered in-situ crystallization of Tb-based metal-organic frameworks. Samples were produced at target positions within milliseconds, a significant improvement to conventional solvothermal processes. 

Researchers also found that by varying variables such as exposure time, the size of the Tb(BTC)·G samples could be changed. 

The strong fluorescence of the prepared Tb(BTC)·G indicates their potential in a range of optoelectronic applications, though future work will be required to deconstruct this fluorescence mechanism. 

The proposed approach offers a means to synthesize and integrate MOFs in a single step, enhancing the creation of miniature devices based on MOF materials.

Continue reading: A Guide to AFM Nanotips.

Journal Reference

Liu, Y., Chai, N., Wang, X., Luo, Z., Zhao, J., Xie, C., Gan, Z. (2021) Femtosecond laser induced in-situ crystallization of Tb-based luminescent metal organic framework. Optics Express, 29(24), pp. 39304–39311. Available online: https://doi.org/10.1364/OE.411315.

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Megan Craig

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Megan Craig

Megan graduated from The University of Manchester with a B.Sc. in Genetics, and decided to pursue an M.Sc. in Science and Health Communication due to her passion for learning about and sharing scientific innovations. During her time at AZoNetwork, Megan has interviewed key Thought Leaders across several scientific, medical and engineering sectors and attended prominent exhibitions worldwide.

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