Textiles capable of capture and detoxification toxic chemicals, such as chemical-warfare agents (CWAs), are high interest. Some metal-organic frameworks (MOFs) exhibit superior reactivity toward CWAs. However, it remains a challenge to integrate powder MOFs into engineered materials like textiles, while retaining functionalities crystallinity, adsorptivity, reactivity. Here, we present simple method electrospinning UiO-66-NH2, zirconium MOF, with polyvinylidene fluoride (PVDF). The...

TiO(2)-supported gold nanoparticles exhibit surprising catalytic activity for oxidation reactions compared to noble bulk which is inactive. The localized at the perimeter of Au where atoms are atomically adjacent TiO(2) support. At these dual-catalytic sites an oxygen molecule efficiently activated through chemical bonding both and Ti(4+) sites. A significant inhibition by a factor 22 in CO reaction rate observed 120 K when preoxidized, caused oxygen-induced positive charge produced on...

A fullerene-based photosensitizer is incorporated postsynthetically into a Zr6 -based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to overall generation of from material under UV irradiation. generated by MOF/fullerene shown oxidize sulfur mustard selectively less toxic bis(2-chloroethyl)sulfoxide with half-life only 11 min.

The extended interface between Cu nanoparticles and TiO₂ aerogel supports stabilizes against oxidation enough to preserve its plasmonic behavior, even after exposure air.

We report experimental as well theoretical evidence that suggests Au–CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared density functional theory calculations point migration. STM surface at pressures in range from 10–8 10–4 Torr (dosage up 106 langmuir) indicates Au atom extraction dislocation herringbone...

For the first time, an increasing number of defects were introduced to metal-organic framework UiO-66-NH2 in attempt understand structure-activity trade-offs associated with toxic chemical removal. It was found that optimum exists moderate for chemicals react linker, whereas those require hydrolysis at secondary building unit performed better when more introduced. The insights obtained through this work highlight ability dial-in appropriate material formulations, even within same parent...

Zirconium hydroxide (Zr(OH)4) has excellent sorption properties and wide-ranging reactivity toward numerous types of chemical warfare agents (CWAs) toxic industrial chemicals. Under pristine laboratory conditions, the effectiveness Zr(OH)4 been attributed to a combination diverse surface hydroxyl species defects; however, atmospheric components (e.g., CO2, H2O, etc.) trace contaminants can form adsorbates with potentially detrimental impact Zr(OH)4. Here, we report hydrolysis CWA simulant,...

Infrared (IR) studies of Au/TiO2 catalyst particles indicate that charge transfer from van der Waals-bound donor or acceptor molecules on TiO2 to Au occurs via transport carriers in the semiconductor support. The ΔνCO is shown be proportional polarizability support fully covered with molecules, producing a frequency shift νCO. Charge through associated population electron trap sites bandgap and can independently followed by changes photoluminescence intensity shifts broad IR absorbance...

Nerve agents are among the most toxic substances known to man. Recent events in Syria, Malaysia, and UK illustrate that threat of these is real actual. The timely detection identification nerve great importance facilitate decontamination or medical countermeasures. In this work, an effective sensitive system, based on metal–organic framework (MOF) NU-1000, was developed for disclosure V-agents, a class very persistent, highly toxic, difficult detect. NU-1000 zirconium-based MOF can hydrolyze...

Multifunctional composites that couple high-capacity adsorbents with catalytic nanoparticles (NPs) offer a promising route toward the degradation of organophosphorus pollutants or chemical warfare agents (CWAs). We mesoporous TiO2 aerogels plasmonic Cu (Cu/TiO2) and characterize CWA sarin under both dark illuminated conditions. Cu/TiO2 combine high rates, which are facilitated by hydrolytically active sites at Cu||TiO2 interface, photoenhanced courtesy semiconducting surface plasmon...

The oxidative-dehydrogenation of carboxylic acids to selectively produce unsaturated at the second and third carbons regardless alkyl chain length was found occur on a Au/TiO2 catalyst. Using transmission infrared spectroscopy (IR) density functional theory (DFT), acrylate (H2C═CHCOO) crotonate (CH3CH═CHCOO) were observed form from propionic acid (H3CCH2COOH) butyric (H3CCH2CH2COOH), respectively, catalyst with ∼3 nm diameter Au particles TiO2 400 K. Desorption experiments also show gas...

The increased risk of chemical warfare agent usage around the world has intensified search for high-surface-area materials that can strongly adsorb and actively decompose agents. Dimethyl methylphosphonate (DMMP) is a widely used simulant molecule in laboratory studies investigation adsorption decomposition behavior sarin (GB) gas. In this paper, we explore how DMMP interacts with as-synthesized mesoporous CeO2. Our mass spectroscopy situ diffuse reflectance infrared Fourier transform...

Here we report molecular level details regarding the adsorption of sarin (GB) gas in a prototypical zirconium-based metal–organic framework (MOF, UiO-66). By combining predictive modeling and experimental spectroscopic techniques, unambiguously identify several unique bindings sites within MOF, using P═O stretch frequency GB as probe. Remarkable agreement between predicted IR spectrum is demonstrated. As previously hypothesized, undercoordinated Lewis acid metal site most favorable binding...

Mesoporous copper–titanium dioxide (Cu/TiO2) composite aerogels with <5-nm-diameter copper (Cu) nanoparticles hydrolyze the chemical warfare (CW) simulant dimethyl methylphosphonate (DMMP) under aerobic and anaerobic conditions. After Cu/TiO2 is exposed to DMMP in an situ diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) reaction chamber, hydrolysis products (i.e., methoxy groups) are bound surface, while no intact observed. In contrast, degradation not observed our DRIFTS...

Despite a recent dramatically increased risk of using chemical warfare agents in attacks and assassinations, fundamental interactions toxic chemicals with other materials are poorly understood, micromechanisms their degradation yet to be established. This represents an outstanding challenge both science practical applications combat against weapons. One the most versatile multifunctional oxides, TiO2, has been suggested as promising material quickly adsorb effectively destroy toxins. In this...

The partial oxidation of model C2–C4 (acetic, propionic, and butyric) carboxylic acids on Au/TiO2 catalysts consisting Au particles ∼3 nm in size was investigated using transmission infrared spectroscopy density functional theory. All three readily undergo oxidative dehydrogenation Au/TiO2. Propionic butyric acid dehydrogenate at the C2–C3 positions, whereas acetic dehydrogenates C1–C2 position. resulting acrylate crotonate intermediates are subsequently oxidized to form β-keto that...

Surface adsorption and activation of propene, to catalytically produce propene oxide, is the first step in industrially important gas-phase epoxidation reaction. Motivated by significant practical importance this reaction, site-specific on nanoparticulate titania-supported Au (Au/TiO2) has been systematically characterized through Fourier transform infrared (FTIR) spectroscopy density functional theoretical (DFT) calculations. The spectra, recorded during uptake at low surface temperatures,...

Electrical impedance spectroscopy, in conjunction with the metal-organic framework (MOF) UiO-66-NH2, is used to detect trace levels of explosive simulant 2,6-dinitrotoluene. The combination porosity and functionality MOF provides an effective dielectric structure, resulting changes magnitude phase angle. promising data indicate that MOFs may be low-cost, robust detection devices.

Operando conditions, such as the presence of H2O, can dramatically alter reaction pathways molecular interactions on a surface. Here, we determine how water affects decomposition chemistry SO2(g) dry and wet Zr(OH)4 powder, material being transitioned for battlefield chemical sequestration decomposition. Diffuse reflectance infrared Fourier transform spectroscopy X-ray photoelectron reveal that SO2 products differ significantly. Sulfites (sulfates) dominate (wet) surfaces. Kinetic analysis...

The promising reactive sorbent zirconium hydroxide (ZH) was challenged with common environmental contaminants (CO2, SO2, and NO2) to determine the impact on chemical warfare agent decomposition. Several adsorbates rapidly formed ZH surface through available hydroxyl species coordinatively unsaturated sites. decontamination effectiveness determined using a suite of instrumentation including in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) monitor sarin (GB)...

The kinetics and mechanism of reactions between gas-phase ozone surface-bound C60 have been investigated by monitoring changes to reflection–absorption infrared spectra within a well-characterized film during exposure controlled flux pure ozone. These ultrahigh vacuum studies provide direct spectroscopic evidence for the formation decomposition primary ozonide C60. spectral assignments this highly unstable intermediate verified using electronic structure calculations. Theory experiment...

Inexpensive strategies for efficient decontamination of hazardous chemicals are required. In this study, the effect visible light (λ &gt; 400 nm) on decomposition 2-chloroethyl ethyl sulfide (2-CEES, a sulfur mustard (HD) simulant) Au/TiO2 photocatalyst under anaerobic and aerobic conditions has been investigated in situ by diffuse reflectance infrared Fourier –transformed spectroscopy (DRIFTS). Under conditions, 2-CEES partially desorbs from surface likely due to photothermal effect,...