*3.2. Synthesis*

#### 3.2.1. **UiO66** MOF Nano-Catalyst Synthesis

#### Synthesis of UiO-66\_14 nm (1) and UiO-66-NH2\_14 nm (4)

All **UiO-66** MOF materials with 14 (**1**), 200 (**2**), and 540 (**3**) nm and **UiO-66-NH2** MOF materials in 14 nm (**4**) were prepared and activated according to previously reported procedure by Morris et al. [31] with slight modifications. The 1,4-benzenedicarboxylic acid (500 mg, 3.0 mmol) was dissolved in 10 mL of N,N-dimethylformamide (DMF). In a separate vial, zirconyl chloride octahydrate (270 mg, 0.83 mmol) was dissolved in 30 mL of DMF. The two solutions were mixed together in a 100 mL Erlenmeyer flask and acetic acid (3 mL) was added to the reaction mixture. The solution was mixed well to obtain a homogeneous solution. The homogeneous solution was separated into seven 15 mL glass vials, with approximately 6 mL in each vial. The solution vials were heated at 90 ◦C for 18 h to yield **UiO-66** with an average size of 14 nm (**UiO-66\_14nm** (**1**). The MOF nanoparticles were purified by centrifugation (10,000 rpm, 30 min) followed by a solvent exchange (3× DMF and 3× H2O) over a 24 h period. Similar procedure was followed for **UiO-66-NH2\_14nm** (**4**) for MOF synthesis and purification. 2-amino-1-4-benzenedicarboxylic acid was used in this reaction instead of 1,4-benzenedicarboxylic acid, but the remaining materials were the same as for **UiO-66\_14nm** (**1**). To confirm the formation of product, the crystallinity and particle size of all the synthesized MOF materials were analyzed by powder X-ray di ffraction (PXRD) as well as TEM and SEM EDX-elemental mapping. The analysis data obtained were verified against the reported results.

#### Synthesis of UiO-66\_200 nm (2) and UiO-66\_540 nm (3)

The same synthetic conditions mentioned earlier were used, but the volume of acetic acid was changed from 3 to 21 and 35 mL for **UiO-66\_200** (**2**) and **UiO-66\_540 nm** (**3**), respectively [31]. Based on the methodology used in this paper, increasing the amount of acetic acid in the MOF synthesis procedure results in larger crystals.

#### 3.2.2. Synthesis of Paraoxon-Ethyl

Paraoxon-ethyl was prepared by following the synthesis method reported by Tamilselvi et al. [32]. Diethyl chlorophosphate (0.860 mL, 5 mmol), p-nitrophenol (0.696 g, 5 mmol), and triethylamine (0.7 mL) were mixed in diethyl ether (20 mL). After stirring the reaction mixture for 12 h at room temperature, the reaction mixture was poured into water and the compound was extracted from the aqueous layer with diethyl ether. The combined organic fractions were evaporated to dryness to produce a yellow oil, which was subjected to reverse-phase flash chromatography to obtain pure paraoxon. The formation of paraoxon-ethyl and purity were verified by analyzing with 1H and 31P NMR spectroscopy and comparing the data to reported results.
