Environmental Effects on Zirconium Hydroxide Nanoparticles and Chemical Warfare Agent Decomposition: Implications of Atmospheric Water and Carbon Dioxide

Abstract

Zirconium hydroxide (Zr(OH)) has excellent sorption properties and wide-ranging reactivity toward numerous types of chemical warfare agents (CWAs) and toxic industrial chemicals. Under pristine laboratory conditions, the effectiveness of Zr(OH) has been attributed to a combination of diverse surface hydroxyl species and defects; however, atmospheric components (e.g., CO, HO, etc.) and trace contaminants can form adsorbates with potentially detrimental impact to the chemical reactivity of Zr(OH). Here, we report the hydrolysis of a CWA simulant, dimethyl methylphosphonate (DMMP) on Zr(OH) determined by gas chromatography-mass spectrometry and in situ attenuated total reflectance Fourier transform infrared spectroscopy under ambient conditions. DMMP dosing on Zr(OH) formed methyl methylphosphonate and methoxy degradation products on free bridging and terminal hydroxyl sites of Zr(OH) under all evaluated environmental conditions. CO dosing on Zr(OH) formed adsorbed (bi)carbonates and interfacial carbonate complexes with relative stability dependent on CO and HO partial pressures. High concentrations of CO reduced DMMP decomposition kinetics by occupying Zr(OH) active sites with carbonaceous adsorbates. Elevated humidity promoted hydrolysis of adsorbed DMMP on Zr(OH) to produce methanol and regenerated free hydroxyl species. Hydrolysis of DMMP by Zr(OH) occurred under all conditions evaluated, demonstrating promise for chemical decontamination under diverse, real-world conditions.

Synthesis, plasmonic properties, and CWA simulant decontamination activity of first row early transition metal nitride powders and nanomaterials

“…9. We believe this S-S coupling is potentially taking place in the inlet of the GC instrument which is kept at 275 °C, as the hydrolysis reaction of organophosphate is consistent with previous reports which conducted analysis on similar materials [30,35,36]. The disulfide byproduct is present for both TiN and TiN-Al 2 O 3 materials and is consistent with the preferential reaction route for the decontamination of the organophosphate nerve agent VX with other hydrolytic agents [29][30][31][32][33][34].…”

Zr(OH)4/GO Nanocomposite for the Degradation of Nerve Agent Soman (GD) in High-Humidity Environments

“…Metal-organic frameworks (MOFs) [ 10 ], metal oxides (hydroxides) [ 11 , 12 ], and composite materials [ 12 ] have attracted significant attention as potential materials [ 13 , 14 , 15 , 16 ]. Zirconium hydroxide (Zr(OH) 4 ), which has various surface hydroxyl species and defect sites, is considered as one of the most prominent materials because of its superior sorptive property and wide range of reactivity toward nerve agents [ 17 , 18 , 19 , 20 , 21 , 22 ]. However, many existing researches on Zr(OH) 4 studied its effects on simulants, rather than real CWAs [ 17 , 20 , 21 , 22 , 23 , 24 ].…”

Degradation of chemical warfare agents over cotton fabric functionalized with UiO-66-NH2

“…5,6 Recent reports reveal that CWAs can be efficiently decomposed over metal-containing materials such as metal nanoparticles, metal oxides, and inorganic-organic complexes. [7][8][9][10] For instance, Zr(OH) 4 is believed to efficiently catalyze the decomposition of CWAs [11][12][13] and toxic industrial chemicals. 14,15 Furthermore, the adsorption-based removal of CWAs can be realized using a large number of catalytically active porous materials such as porous organic polymers, zeolites, 16 polyoxometalates, [17][18][19] and metal-organic frameworks (MOFs).…”