Synthesis and characterization of ZnBTC-based MOFs: effect of solvents and salt published by Ural Federal University eISSN 2411-1414 chimicatechnoacta.ru ARTICLE 2023, vol. 10(1), No. 202310105 DOI: 10.15826/chimtech.2023.10.1.05 1 of 7 Synthesis and characterization of ZnBTC-based MOFs: effect of solvents and salts Maria V. Timofeeva * , Andrey N. Yankin School of Physics and Engineering, ITMO University, St. Petersburg 197101, Russia * Corresponding author: maria.timofeeva@metalab.ifmo.ru This paper belongs to the MOSM2022 Special Issue. Abstract In this work, we studied the optimization of synthetic approaches to cre- ating structurally modified metal-organic frameworks under various syn- thesis conditions. We investigated the influence of the various solvents and zinc salts on the structural characteristics of the metal-organic frame- work based on benzene-1,3,5-tricarboxylic acid (H3BTC). The results indi- cate that the variation of the types of both solvent and salt is a parameter affecting the crystallinity, phase purity, and morphology of the metal-or- ganic framework. This was confirmed by comprehensive structural char- acterization (SEM, EDX, PXRD). Keywords metal-organic frameworks solvothermal synthesis trimesic acid MOF synthesis Received: 11.11.22 Revised: 13.12.22 Accepted: 13.12.22 Available online: 22.12.22 Key findings ● The synthesis method for obtaining ZnBTC. ● New morphology of ZnBTC not previously described in the literature was obtained. ● It was found that the type of solvents and the type of salts used in the synthesis of the ZnBTC affect the morphology of the compounds. © 2022, the Authors. This article is published in open access under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/). 1. Introduction Materials have always played an important role in the devel- opment of humanity. The past 20 years have been marked by major achievements in the theoretical and applied materials science, which continues to develop rapidly. The main direc- tions of modern materials science are as follows: a) polyfunc- tionality – giving the material the maximum number of dif- ferent useful properties; b) the use of nano-sized materials; c) creation of smart materials capable of changing their char- acteristics under the effect of various external factors (light, temperature, electromagnetic field, etc.). Currently, various materials have been intensively stud- ied in materials science, such as inorganic nanoparticles [1– 3], molecular crystals [4–6], COF (covalent organic frame- work) [7, 8]. Applications for these materials include elec- tronics [9], cancer treatment [10], catalysis [11], etc. Porous materials attract special attention in materials science. Porous materials are solids with voids filled with air or other gases. Porous materials can be ordered (crys- talline, with a regular pore system) and disordered (irreg- ular pores system). Inorganic materials often have a highly ordered structure, whilst plastics, for example, are amor- phous or partially ordered. Amorphous materials have certain advantages: they are inexpensive and easy to process. Their disadvantage is the uncertainty of the structure (due to the difficulties in X-ray diffraction analysis). Their synthesis is most often unpre- dictable; they exist in the form of several modifications and have low mechanical strength. More interesting are the highly ordered materials, the structure of which can be studied by X-ray diffraction methods. These are, for example, crystalline zeolites [12, 13]. They have a regular structure, are strong, and possess the ion exchange capability. Their main applications are is molecular sieves and catalysts [14–16]. The development of a new class of highly ordered hybrid structures – metal- organic frameworks – is the next stage in the development of zeolite-like materials. Metal-organic framework (MOF) are a class of crystal- line porous coordination compounds with a 1-, 2-, 3-dimen- sional structure consisting of metal ions or clusters linked by organic linkers [17–21]. Different functionality, adjustable porosity, mechanical strength and thermal stability can be http://chimicatechnoacta.ru/ https://doi.org/10.15826/chimtech.2023.10.1.05 mailto:maria.timofeeva@metalab.ifmo.ru http://creativecommons.org/licenses/by/4.0/ https://orcid.org/0000-0002-8156-5411 https://orcid.org/0000-0003-4221-5619 https://crossmark.crossref.org/dialog/?doi=https://doi.org/10.15826/chimtech.2023.10.1.05&domain=pdf&date_stamp=2022-12-22 Chimica Techno Acta 2023, vol. 10(1), No. 202310105 ARTICLE 2 of 7 DOI: 10.15826/chimtech.2023.10.1.05 imparted to the framework by changing its constituent parts [22]. Due to these properties MOF appear as promising ma- terials that can be used for the adsorption/storage and sepa- ration of gases, in catalysis, biomedicine, and also for the cre- ation of sensor devices [23–26]. Of particular interest is the further modification of the structure of MOFs, including their intracrystalline space, to create new properties or optimize existing structural/chemical characteristics [27,28]. However, there are just a few studies that demonstrate the conditions for the MOFs synthesis effect on the struc- ture and properties of the framework. The comprehensive understanding of the framework’s synthesis and formation and its effect on the final structure are still missing [29–31]. Among the ligands for the synthesis of MOFs, trimesic acid has a leading position. Thus, the most famous and one of the first MOFs, HKUST-1, is based on trimesic acid and copper salt [32, 33]. Trimesic acid and its derivatives are available and ecofriendly substances that can be used as intermediate pharmaceutical products and as drug deliv- ery agents as parts of MOF [34, 35]. There are many pub- lications on MOFs based on Ni [36], Fe [37], Co [38, 39] and other metals [40], where trimesic acid played the role of a ligand [41–43]. Basically, these publications investi- gated the possible applications MOF: catalysis [44–46], medicine [47, 48], adsorption [49–51], sensors [52–53]. However, to the best of our knowledge, there is no re- search on the development of a synthesis strategy and de- sign of BTC-based MOFs. Nowadays, there are different methods for MOFs pro- duction: solvothermal (synthesis under high pressure, in a boiling solvent), microwave (synthesis by radiation of a microwave explosion), sonochemical (synthesis under the action of ultrasound), microfluidic (control of liquid flows at micro- and nanoscales), mechanochemical, electro- chemical and slow evaporation method (does not require any traces, electricity or mechanical action). Conse- quently, there is often a discrepancy in the structural data between different reports on the same MOF, which usually arises from using different methods and parameters of synthesis. ZnBTC is a well-known MOF in which infinite zinc chains are connected by organic ligand into a three-dimen- sional microporous framework [54]. Despite only one syn- thesis method, there are various ZnBTC morphologies known, which can be explained by different conditions of the solvothermal reaction. Among existing morphologies, nonuniform rod-like [55], large crumps with irregular shapes [56], and spherical nanoparticle [57, 58] structures of ZnBTC can be distinguished. It is important to mention that all known methods for the synthesis of ZnBTC take place at high temperatures ( >120 °C). Here we report the optimization of the MOFs synthesis based on zinc salt and trimesic acid. We studied the critical role of the solvent type variation on the morphology and crystallinity of the synthesized MOF based on zinc salt. We report the soft synthesis conditions (80 °C temperature). In this regard, the following adjustments to the synthesis technique were attempted: a) variation of the solvent mix- ture; b) precursor (zinc salt type) variation. 2. Experimental All the chemical reagents were obtained from commercial sources and used without further purification unless other- wise specified: Zn(NO3)2·6H2O (Sigma-Aldrich, ≥98.0%), ZnSO4·7H2O (Sigma-Aldrich, ≥98.0%), Zn(CH3CO2)2·2H2O (Sigma-Aldrich, ≥98.0%), 1,3,5-benzenetricarboxylic acid (Sigma-Aldrich, Trimesic acid (H3BTC), 95%), dimethylfor- mamide (ACS reagent, ≥99.8%), ethanol (ACS reagent, ≥99,5%), 1,4-dioxane (Dioxane, ACS reagent, ≥99,5%), eth- anol (EtOH, ACS reagent, ≥ 99,5%), toluene (Tol, ACS rea- gent, ≥99,5%), chlorobenzene (PhCl, ACS reagent, ≥99,5%), and dimethyl sulfoxide (DMSO, ACS reagent, ≥99,5%) were used in all syntheses. The chemical composition and homogeneity of obtained compounds were controlled with a scanning electron micro- scope (SEM, Quanta 200, FEI, Netherlands) with an accel- erating voltage of 10 kV. Dry samples were coated with a gold thin film and imaged with SEM. Diffraction patterns of the samples were recorded on a Shimadzu 7000-maxima X-ray diffractometer with a 2 kW characteristic Cu Kα (Kα1 λ = 1.54059 Å, angular range 2θ = 5° – 80°) X-ray radiation source and a Bragg-Brentano goniometer geometry. The angular resolution during the anal- ysis was 0.05 degree at a scanning speed of 1 degree/min. Energy-dispersive elemental analysis was performed using SEM SUPRA 55 VP at an accelerating voltage of 10 kV. Before imaging, samples were coated with gold. 2.1. General synthesis of ZnBTC Fifteen different ZnBTC samples were each prepared as fol- lows. Two precursors, a zinc salt and 1,3,5-benzenetricar- boxylic acid, were taken in the quantities listed in Table 1 and dissolved under ultrasound in a mixture of three sol- vents, 1 ml each (see Table 1). After that, the solution mix- ture was hermetically sealed with a lid with a rubber sep- tum in a 4 ml vial to exclude the interaction with the exter- nal environment and create excess pressure in the vial. The solution mixture was heated up to 80 °C and kept for 48 h, after which the reaction mixture was cooled down to room temperature. The formed powder was separated from the mother liquid by filtration, and then it was repeatedly washed 5 times with the same mixture of solvents as the one used for its synthesis (see Table 1). The washed powder was dried in the air. 3. Results and Discussion The synthesis of MOFs was performed under solvothermal reaction conditions (Scheme 1). Along with the study of the synthesis conditions effect on ZnBTC structure, we analyzed the solvent composition https://doi.org/10.15826/chimtech.2023.10.1.05 Chimica Techno Acta 2023, vol. 10(1), No. 202310105 ARTICLE 3 of 7 DOI: 10.15826/chimtech.2023.10.1.05 (polarity of the mixed aqueous-organic solvent) and the counterion in the Zn salt composition. The MOF synthesis process can be affected by the reac- tion medium due to the polarity of the solvent used. To ex- plore this aspect, several ZnBTC were prepared by sol- vothermal reactions of the Zn2+ ion with the H3BTC ligand in various solvent systems DMF/H2O/Dioxane, DMF/H2O/EtOH, DMF/H2O/Toluene, DMF/H2O/PhCl, DMF/H2O/DMSO, respectively (Table 1). It is known that the medium polarity (the solvent nature) has a great influence on the course of a chemical reaction. The polarity of the medium during the synthesis of ZnBTC-1– 15 was calculated according to the literature data. The sol- vent mixture of DMSO/DMF/H2O had the highest polarity (corresponds to samples ZnBTC-5, ZnBTC-10, ZnBTC-15), whilst the solvents mixture of Toluene/DMF/H2O (corresponds to samples ZnBTC-3, ZnBTC-8, ZnBTC-13) was the least polar of the solvent mixtures presented in Table 2. In the SEM images (Figure 1a–e), all obtained compounds of ZnBTC-1–5 are mainly needle-shaped agglomerates of crystals in the form of "blowball". This form of ZnBTC crys- tals was obtained for the first time. According to the litera- ture, ZnBTC is usually characterized by a single rectangular crystal [55–58]. However, SEM failed to detect a fragment with a rectangular topology. Compounds of ZnBTC-3 and ZnBTC-4 (Figure 1c and d), synthesized in the solvent mix- tures DMF/H2O/Tol and DMF/H2O/PhCl, respectively, did not assemble into a whole "blowball". Such small differences in the crystalline form of the compounds at the same temperature, synthesis time and type of salt could be explained by use of the different types of synthesis medium. The qualitative and quantitative com- position of the compounds was analyzed by energy disper- sive X-ray (EDX) spectroscopy (Figure 2a–e). The SEM images of compounds ZnBTC-6–10 can also be described as needle-shaped crystals (Figure 3a–e), but their «blowball» shape is less pronounced than that of substances ZnBTC-1–5. The morphologies of ZnBTC-1 and ZnBTC-6 are different. The synthesis parameters differed only in the type of salt (Zn(NO3)2·2H2O and ZnSO4·7H2O), and the solvent medium was the same (Diox- ane/DMF/H2O). Therefore, it can be assumed that the type of salt (counterion) affects the growth of crystals. This as- sumption is confirmed by the third ZnBTC-MOF series. ZnBTC-11–15, obtained by the interaction of H3BTC and Zn(CH3COO2)2·2H2O, did not form the "blowball" crystal- line agglomerates (Figure 4a–e). All compounds ZnBTC- 11–15 are crystalline powders. The nature of the crystalline phase was studied using PXRD analysis [64]. All diffraction patterns of ZnBTC-1–15 (Figure 1f, 3f and 4f) show an intense diffraction peak at 2θ = 10°, which corresponds to the literature data [65], confirming the formation of ZnBTC. The diffraction pat- terns show no background noise over the entire 2θ range. This confirms the presence of a crystalline phase in the studied compositions. Scheme 1 General synthesis of ZnBTC. Table 2 Polarity of solvents mixture. Solvent mixture Polarity Dioxane/DMF/H2O 21.4 EtOH/DMF/H2O 21.8 Toluene/DMF/H2O 19 PhCl/DMF/H2O 19.3 DMSO/DMF/H2O 23.8 Table 1 Optimization of the synthesis of ZnBTC (Ligand: H3BTC). Sample No. Zn salt Mixture of solvents (1 ml each) Ligand/Salt quantities (mmol) 1 Zn(NO3)2·6H2O Dioxane/DMF/H2O 0.067/0.036 2 Zn(NO3)2·6H2O EtOH/DMF/H2O 0.067/0.036 3 Zn(NO3)2·6H2O Toluene/DMF/H2O 0.067/0.036 4 Zn(NO3)2·6H2O PhCl/DMF/H2O 0.067/0.036 5 Zn(NO3)2·6H2O DMSO/DMF/H2O 0.067/0.036 6 ZnSO4·7H2O Dioxane/DMF/H2O 0.070/0.035 7 ZnSO4·7H2O EtOH/DMF/H2O 0.070/0.035 8 ZnSO4·7H2O ZnSO4·7H2O Toluene/DMF/H2O 0.070/0.035 9 ZnSO4·7H2O ZnSO4·7H2O PhCl/DMF/H2O 0.070/0.035 10 ZnSO4·7H2O ZnSO4·7H2O DMSO/DMF/H2O 0.070/0.035 11 Zn(CH3CO2)2·2H2O Dioxane/DMF/H2O 0.091/0.046 12 Zn(CH3CO2)2·2H2O EtOH/DMF/H2O 0.091/0.046 13 Zn(CH3CO2)2·2H2O Toluene/DMF/H2O 0.091/0.046 14 Zn(CH3CO2)2·2H2O PhCl/DMF/H2O 0.091/0.046 15 Zn(CH3CO2)2·2H2O DMSO/DMF/H2O 0.091/0.046 https://doi.org/10.15826/chimtech.2023.10.1.05 Chimica Techno Acta 2023, vol. 10(1), No. 202310105 ARTICLE 4 of 7 DOI: 10.15826/chimtech.2023.10.1.05 Figure 1 SEM images of ZnBTC-1–5 (a–e, respectively), compara- tive diffraction pattern of samples ZnBTC-1–5 (f). Figure 2 EDX of ZnBTC-1–15 (a–0, respectively). The appearance of sharp reflections in PXRD patterns indicates a good degree of crystallinity of the synthesized products. The presence of reflections in the region of small angles confirms that the synthesized samples are MOFs. The positions of the main diffraction peaks of all substances ZnBTC-1–15, namely, 10°, 15–20°, 25–30° and 35–40° 2θ (Theta) are identical, which indicates that they possess the same crystal structure. Figure 3 SEM images of ZnBTC-6–10 (a–e, respectively), compar- ative diffraction pattern of samples ZnBTC-6–10 (f). Figure 4 SEM images of ZnBTC-11–15 (a–e, respectively), compar- ative diffraction pattern of samples ZnBTC-11–15 (f). But compounds ZnBTC-1–5 also have a diffraction peak at 52° 2θ (Theta) in their PXRD patterns and, in addition, the intensities of the main diffraction peaks of samples ZnBTC- 1–5 are greater than those of the other samples. It can be as- sumed that this is due to the increased crystallinity of the samples ZnBTC-1–5 and the effect of Zn(NO3)2·6H2O on the f) https://doi.org/10.15826/chimtech.2023.10.1.05 Chimica Techno Acta 2023, vol. 10(1), No. 202310105 ARTICLE 5 of 7 DOI: 10.15826/chimtech.2023.10.1.05 crystal growth during synthesis. The diffraction patterns of samples ZnBTC-5 and ZnBTC-10 synthesized in DMSO have additional reflections. It can be assumed that ZnBTC-5 is characterized by a crystal structure different from that of the other ZnBTC. Comparative analysis of powder diffraction patterns of ZnBTC-1–15 showed that the replacement of the counterion in the composition of the precursor does not affect the ele- mental composition of MOF and is not included in the struc- ture of the final MOF (Figure 1–4), but the crystallinity and morphology of obtained structures are strongly dependent on the type of salt (Zn(NO3)2·6H2O facilitates the formation of more crystalline materials, while Zn(CH3CO2)2·2H2O – of more amorphous, and zinc acetate does not form into "blowball" during the solvothermal synthesis). The reason for this could be that Zn(NO3)2·6H2O and ZnSO4·7H2O are more acidic (pH<7) than Zn(CH3CO2)2·2H2O (pH = 7). Polarity of the solvent also affects the crystallinity and structure of the obtained compounds. The mixture of DMSO/DMF/H2O solvents that has the highest polarity among the other ones (Table 2) yields an additional diffrac- tion peak in the region of 10–15° 2θ (Theta) in the PXRD pattern of the synthesized ZnBTC. 4. Limitations We obtained a new morphology of ZnBTC; therefore, we needed to confirm its structure by single-crystal X-ray crys- tallography. However, the particles of ZnBTC were agglom- erates. The possible solution of this challenge is a recrystal- lization of a synthesized compound to obtain a single crystal. 5. Conclusions The results of the study show that the type of solvent and salt does not affect the elemental composition and crystal- linity of a ZnBTC-based MOF. However, these critical pa- rameters affect the morphology of the MOF. According to the SEM images, ZnBTC crystals in the form of "blowball" were obtained for the first time. Such sample surface can potentially be used for the sorption of organic molecules. ● Supplementary materials No supplementary materials are available. ● Funding This work was supported by the Russian Science Foundation (grant no. 22-23-00738), https://www.rscf.ru/en. ● Acknowledgments This research would not have been possible without the help of the following organizations: – Saint Petersburg State Institute of Technology; – the Faculty of Physics of ITMO; ● Author contributions Conceptualization: M.V.T., A.N.Y. Data curation: M.V.T. Formal Analysis: M.V.T. Funding acquisition: M.V.T. Investigation: M.V.T., A.N.Y. Methodology: M.V.T. Project administration: M.V.T. Resources: M.V.T. Software: M.V.T. Supervision: M.V.T. Validation: M.V.T. Visualization: M.V.T. Writing – original draft: M.V.T., A.N.Y. Writing – review & editing: M.V.T. ● Conflict of interest The authors declare no conflict of interest. ● Additional information Author IDs: Maria V. 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