Insights into the Spray Synthesis of UiO-66 and UiO-66-NH2 Metal–Organic Frameworks: Effect of Zirconium Precursors and Process Parameters

Abstract

UiO-66, a zirconium-based metal–organic framework, was synthesized using a one-step spray synthesis method to investigate the effects of preheating the precursor solution and Zr sources on crystallinity. Using ZrCl4 with water as a modulator requires preheating at 80 °C for 120 min or 120 °C for 30 min for the spray synthesis of UiO-66 to form secondary building units (SBUs). By contrast, the use of Zr(OnPr)4 with acetic acid (AcOH) as a modulator allowed the spray synthesis of UiO-66 and UiO-66-NH2 without preheating because of the rapid formation of SBUs with AcOH. The spray-synthesized UiO-66 using Zr(OnPr)4 exhibited a BET surface area of 1258 m2/g and a CO2 adsorption capacity of 3.43 mmol/g at 273 K and 1 bar, while UiO-66-NH2 exhibited a BET surface area of 1263 m2/g and a CO2 adsorption capacity of 6.11 mmol/g under the same conditions.