Morphology Regulation of UiO-66-2I Supporting Systematic Investigations of Shape-Dependent Catalytic Activity for Degradation of an Organophosphate Nerve Agent Simulant.

Phosphonate-based nerve agents, as a kind of deadly chemical warfare agent, are a persistent and evolving threat to humanity. Zirconium-based metal-organic frameworks (Zr-MOFs) are a kind of highly porous crystalline material that includes Zr-OH-Zr sites and imitates the active sites of the phosphotriesterase enzyme, representing significant potential for the adsorption and catalytic hydrolysis of phosphonate-based nerve agents. In this work, we present a new Zr-MOF, UiO-66-2I, which attaches two iodine atoms in the micropore of the MOF and exhibits excellent catalytic activity on the degradation of a nerve agent simulant, dimethyl 4-nitrophenyl phosphate (DMNP), as the result of the formation of halogen bonds between the phosphate ester bonds and iodine groups. Furthermore, various morphologies of UiO-66-2I, such as blocky-shaped nanoparticles (NPs), two-dimensional (2D) nanosheets, hexahedral NPs, stick-like NPs, colloidal microspheres, and colloidal NPs, have been obtained by adding acetic acid (AA), formic acid (FA), propionic acid (PA), valeric acid (VA), benzoic acid (BA), and trifluoroacetic acid (TFA) as modulators, respectively, and show different catalytic hydrolysis activities. Specifically, the catalytic activities follow the trend UiO-66-2I-FA (t1/2 = 1 min) > UiO-66-2I-AA-NP (t1/2 = 4 min) ≈ UiO-66-2I-VA (t1/2 = 4 min) > UiO-66-2I-BA (t1/2 = 5 min) > UiO-66-2I-PA (t1/2 = 15 min) > UiO-66-2I-TFA (t1/2 = 18 min). The experimental results show that the catalytic hydrolysis activity of Zr-MOF is regulated by the crystallinity, defect quantity, morphologies, and hydrophilicity of these samples, which synergistically affect the accessibility of catalytic sites and the diffusion of phosphate in the pores of Zr-MOFs.

Highly porous BiOBr@NU-1000 Z-scheme heterojunctions for synergistic efficient adsorption and photocatalytic degradation of tetracycline.

Designing an effective photoactive heterojunction having dual benefits towards photoenergy conversion and pollutant adsorption is regarded as an affordable, green method for eliminating tetracycline (TC) from wastewater. In this regard, a series of BiOBr@NU-1000 (BNU-X, X = 1, 2 and 3) heterojunction photocatalysts are constructed. BNU-X preserves the original skeleton structure of the parent NU-1000, and its high porosity and specific surface area enable superior TC adsorption. At the same time, BNU-X is an effective Z-scheme photocatalyst that improves light trapping, promotes photoelectron-hole separation, and shows excellent photocatalytic degradation efficiency towards TC with the value of the photodegradation kinetic rate constant k being 2.2 and 24.8 times those of NU-1000 and BiOBr, respectively. The significant increase in the photocatalytic activity is ascribed to the construction of an efficient Z-scheme photocatalyst, which promotes the formation of superoxide radicals (˙O2-) and singlet oxygen (1O2) as the main oxidative species in the oxidation system. This research has the advantage of possibilities for the development of porous Z-scheme photocatalysts based on photoactive MOF materials and inorganic semiconductors for the self-purification and photodegradation of organic contaminants.

Zirconium-based MOF nanocrystals confined on amphoteric halloysite nanotubes for promoting the catalytic hydrolysis of an organophosphorus nerve agent simulant.

Exploiting efficient and practical catalysts for hydrolyzing organophosphorus nerve agents is significant and highly desirable. Herein, a new class of self-detoxifying composites, namely, halloysite nanotubes@NU-912 (HNTs@NU-912), HNTs@NU-912-I and HNTs@UiO-66-NH2, is constructed by in situ synthesis of hexanuclear zirconium cluster-based metal-organic frameworks (Zr-MOFs) NU-912, NU-912-I and UiO-66-NH2, respectively, with HNTs, which are natural nanotubular materials consisting of Si-O-Si tetrahedral sheets on the outer surface and Al-OH octahedral sheets on the inner surface. The results show that crystalline Zr-MOFs uniformly cover the outer surface of HNTs and the particle size of Zr-MOFs is greatly reduced to less than 50 nm. Furthermore, HNTs@NU-912, HNTs@NU-912-I and HNTs@UiO-66-NH2 display much higher catalytic efficiency for the hydrolysis of dimethyl-4-nitrophenyl phosphate (DMNP) than the corresponding Zr-MOFs both in an aqueous N-ethylmorpholine (NEM) buffer solution and under ambient conditions. Specifically, HNTs@NU-912-I shows a turnover frequency (TOF) of 0.315 s-1 in aqueous buffer solution, placing it among the best Zr-MOF-based heterogeneous catalysts for the hydrolysis of DMNP. The composites show high stability, and more importantly, can replace the buffer solvent and control the pH to a certain degree by virtue of its acidic Si-O-Si sheets and alkaline Al-OH sheets. This work provides a certain reference for the subsequent development of personal protective equipment.