Archetype Mesoporous UiO-66(Zr) Enabled by the Salt-Oil Synergetic Mechanism

Despite that prototype hierarchically mesoporous UiO-66-(Zr) (HMUiO-66-(Zr)) integrates coupled micropores and mesopores within a single crystal, there are few, if any, reports on the direct construction of such a material with exceptional chemical and thermal stability. Herein, a salt-oil synergetic mechanism was proposed to rationalize the soft-template-directed assembly of prototype HMUiO-66-(Zr) under mild conditions. The salts significantly lowered the crystallization temperature of UiO-66-(Zr) in the aqueous phase, while the oil phase enhanced the stability of the soft-template aggregate at elevated temperatures, making the assembly environment of crystal and template phases gradually compatible. The synergy between salts and the oil phase enabled precise control over mesopore sizes and texture of HMMOFs as salting-out and salting-in ions influenced emulsion swelling and resulted in a different mesopore structure. Based on the tunable mesopores and excellent stability of HMUiO-66-(Zr), a versatile platform was obtained for the loading of various enzymes and specific recognition toward their metabolic substrates. By matching the mesopore size to accommodate dehydrogenases and NAD⁺, various probes were designed for detecting biomarkers of diabetic acidosis, including β-hydroxybutyrate, glucose, l-lactate, and d-lactate. These probes were integrated into a sensing array, which enabled the simultaneous detection and correlation analysis of these biomarkers, effectively distinguishing different types of diabetic acidosis.