Synthesis of Cu‐BTC Metal‐Organic Framework by Ultrasonic Wave‐Assisted Ball Milling with Enhanced Congo Red Removal Property

Abstract

Cu‐BTC (BTC=1,3,5‐benzenetricarboxylate) metal‐organic framework (MOF) with truncated octahedral morphology was synthesized by ultrasonic wave‐assisted ball milling at room temperature and atmospheric pressure. It was characterized by X‐ray powder diffraction (XRD), thermo‐gravimetric analysis (TGA), nitrogen adsorption and scanning electron microscopy (SEM). The parameters such as synthetic method, reaction time and raw material molar ratio (H3BTC: Cu2+) were studied to tune the growth of Cu‐BTC crystals. Adsorption of Congo red (CR) on Cu‐BTC was studied in respect of adsorption kinetics, isotherm and thermodynamics. Pseudo‐second‐order kinetics and Langmuir adsorption isotherm model were matched well with the adsorption process. The maximum adsorption capacity (Qm) was 884.96 mg/g, attributed to the interfacial effect in (100) facets. Thermodynamic parameters confirmed that the adsorption was a spontaneous and endothermic process, and entropy effect was the driving force for adsorption process.

Synthesis of Metal Organic Frameworks by Ball-Milling

“…In addition, long-term ball milling may also cause the MOF structure to collapse, lose its periodic structure, and become amorphous [84,85], which is difficult to achieve in a solution phase reaction. The ball milling method can also make it more convenient to combine MOFs and other materials to form binary or even multiple composite materials [18,[86][87][88][89][90][91][92][93], such as GO/MOFs composites [94][95][96][97][98][99] Cu-BTC with truncated octahedral shape, and showed significantly reduction of reaction time and effectively improvement of yield [78].…”

“…They have successfully used this method to synthesize a few of MOFs, such as Fe(III)-BTC [65][66][67], Co-BTC [68,69], Cu-BTC [69], Cu-BDC [69], and Co-BDC [69] and explored their application for adsorptive removal of organic dyes from aqueous solutions. This group also developed an ultrasonic wave-assisted ball milling technology to successfully synthesize Cu-BTC with truncated octahedral shape, and showed significantly reduction of reaction time and effectively improvement of yield [78].…”

Metal-organic Framework-based Materials: Synthesis, Stability and Applications in Food Safety and Preservation

“…[73,170] Advantages of mechanochemical reaction are solvent-free condition, [170] reduced reaction time, [171] and potential scale-up to industrial level. [172,173] One of the mechanochemical method, i.e., ball milling was successfully applied in MOF synthesis, [174][175][176] where metal oxides were usually employed as an initial reactant instead of metal ion salts, e.g., zinc oxide was utilized to produce zinc nitrate. [177,178] An early research performed a liquid-assisted grinding via the ball milling method to synthesize homo-and hetero-rare-earth MOFs from trivalent metal carbonates and benzene-1,3,5-tricarboxylic acid in small amount of DMF or water within only 20 min.…”

Improve the Conductivity of CuBTC by in‐situ Reduction to Core‐Shell CuTCNQ@CuBTC

“…As the conversion took place at the outer shell of CuBTC octahedron, the inner core remained. Cu-BTC is a famous MOF with excellent BET surface area, [1,8] so the porous structure of the inner core should remain after the redox reaction. To explore the porosity of the composite materials, isothermal nitrogen adsorption-desorption experiments were carried out (Figure 4).…”

“…[1] Since their emergence, MOFs have attracted intensive attention as functional materials in hydrogen storage, [2][3] molecular recognition, [4] gas adsorption and separation, [5] selective catalyst, [6] and so on. For example, CuBTC and CuBTC-derived composite materials are widely applied in the adsorption and removal of poluttant, [7][8] and Cu-based organic reaction catalysts. [9][10][11] Recently, MOFs and their derivatives are investigated as active materials for electrochemical applications such as batteries, [12] supercapacitors, [13] and electrocatalysts.…”