Green solvents assisted de-novo synthesis and defect-engineered UiO-66 for improved CO2 adsorption and kinetics- experimental and DFT approach

• A green solvent-assisted de-novo synthesis approach is applied to get highly tuned structural parameters and preserve extra open metal sites on MOF's surface. • Missing linker defects and engineering defects are created onto the UiO-66 structure using four different modulators. • An enhanced CO2 adsorption capacity and kinetic performance are achieved as a result of the combined de-novo synthesis and defect-engineered approach. • Pseudo-first-order and pseudo-second-order reaction rate constants suggests fast CO2 diffusion on defect-engineered structures. • Missing linker defects are created and CO2 computational adsorption performance of the defect-engineered UiO-66 is examined using density functional theory (DFT). The CO 2 concentration in the atmosphere is increasing at an alarming rate, which is causing distress to human society and the natural environment. Adsorption is one of the most widely used methods of removing CO 2 from flue gases, which reduces its adverse effects on our environment. For adsorption purposes, a facile green solvent-assisted de-novo synthesis approach was developed to construct a UiO-66′s structure to target CO 2 at low pressure due to the partial pressure of CO 2 in flue gases in the atmosphere (0.01⁓0.02 MPa). In the de-novo synthesis approach, a combination of various types of modulators and deep eutectic solvents (DES) are utilized to graft structural defects and induce quantitative and dispersive deep eutectic solvents onto the UiO-66 structure, respectively. The green solvent-assisted de-novo synthesis approach helped to tune all three structural parameters and preserve extra open metal sites (Lewis acid and Bronsted basis sites) with active NH 2 and OH groups for improved CO 2 adsorption and kinetics under flue gas conditions (CO 2 /N 2 =15/85 %). In comparison to the parent UiO-66, de-novo synthesized ChClProp x5 @UiO-66 showed increased CO 2 uptake (65.04 mg g -1 ) by 73 % at 0.15 bar and 25 °C, and the cyclic capacity remained almost similar over 10 consecutive cycles with an almost 94 % retention rate. After 3 times of regeneration at 105 °C under N 2 atmosphere, the sample reserved almost similar adsorption capacity and could be recycled without dropping CO 2 uptake. The strong and rapid interaction between guest CO 2 and de-novo synthesized UiO-66 was confirmed by pseudo-first-order and second-order kinetics with reaction rate constants of 0.00026 and 0.00259, respectively. Furthermore, through periodic Density Functional Theory (DFT) calculations, a variety of linker defects are engineered onto the UiO-66 structure to preserve more open metal sites. For each of the engineering defects, free energies, adsorption energies, and the interaction of CO 2 molecules on defect structures with bond length (Ɩ, Å) and bond angle (θ˚) are calculated for the most stable structures of UiO-66. Missing linker defects are engineered onto UiO-66 for enhanced adsorption and kinetics