Decomposition Of Dimethyl Methylphosphonate Research Articles

Understanding the Decomposition of Dimethyl Methyl Phosphonate on Metal-Modified TiO2(110) Surfaces Using Ensembles of Product Configurations.

The decomposition of dimethyl methyl phosphonate (DMMP), a simulant for the nerve agent sarin, was investigated on Cu4/TiO2(110) and K/Cu4/TiO2(110) surfaces using a combination of near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory calculations (DFT). Mass-selected Cu4 clusters and potassium (K) atoms were deposited onto TiO2(110) as a metal catalyst and alkali promoter to improve the reactivity and recyclability of the TiO2 surface after exposure to DMMP. Surface reaction products resulting from decomposition of DMMP were probed by NAP-XPS measurements of phosphorus (P) 2p and carbon 1s core-level spectra. The Cu4/TiO2(110) surface is found to be very active for DMMP decomposition with highly reduced P-species observed even at room temperature (RT). The codeposition of K atoms and Cu4 clusters further improves the reactivity with no intact DMMP detectable. Temperature-dependent measurements show that the presence of K atoms promotes the removal of residual P-species at temperatures > 600 K. Detailed DFT calculations were performed to determine the surface structures and energetically accessible pathways for DMMP decomposition on Cu4/TiO2(110) and K/Cu4/TiO2(110) surfaces. The calculations show that DMMP and P-containing reaction products preferentially bind to the TiO2 surface, while the molecular fragments, i.e., methoxy and methyl, bind to both the Cu4 clusters and TiO2. The Cu4 clusters make the P-O, O-C, and P-C bond cleavages of DMMP markedly more exothermic. The Cu4 clusters are highly fluxional with atomic structures that depend on the configuration of fragments bound to them. Finally, the manifold of P 2p chemical shifts calculated for a large number of energetically favorable configurations of decomposition products is in good agreement with the observed XPS spectra and provides an alternative way of interpreting incompletely resolved core-level spectra using an ensemble of observed structures.

Effects of the ZrO2 Crystalline Phase and Morphology on the Thermocatalytic Decomposition of Dimethyl Methylphosphonate.

Thermocatalytic decomposition is an efficient purification technology that is potentially applicable to degrading chemical warfare agents and industrial toxic gases. In particular, ZrO2 has attracted attention as a catalyst for the thermocatalytic decomposition of dimethyl methylphosphonate (DMMP), which is a simulant of the nerve gas sarin. However, the influence of the crystal phase and morphology on the catalytic performance of ZrO2 requires further exploration. In this study, monoclinic- and tetragonal-phase ZrO2 (m- and t-ZrO2, respectively) with nanoparticle, flower-like shape and hollow microsphere morphologies were prepared via hydrothermal and solvothermal methods, and their thermocatalytic decomposition of DMMP was systematically investigated. For a given morphology, m-ZrO2 performed better than t-ZrO2. For a given crystalline phase, the morphology of hollow microspheres resulted in the longest protection time. The exhaust gases generated by the thermocatalytic decomposition of DMMP mainly comprised H2, CO2, H2O and CH3OH, and the by-products were phosphorus oxide species. Thus, the deactivation of ZrO2 was attributed to the deposition of these phosphorous oxide species on the catalyst surface. These results are expected to help guide the development of catalysts for the safe disposal of chemical warfare agents.

Pyrolysis and kinetic study of dimethyl methylphosphonate (DMMP) by synchrotron photoionization mass spectrometry

Pyrolysis experiments of dimethyl methylphosphonate (DMMP) were carried out in a jet stirred reactor (JSR) coupled to synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) at 1 atm, from 900 to 1200 K, to quantitatively measure the mole fraction profiles of DMMP and its pyrolysis products. Furthermore, theoretical calculations were carried out. Geometry optimization and vibrational frequency analysis were conducted for DMMP unimolecular and isomerization reactions at the MN15/6-311+G(2df,2p) level of theory, and kinetic calculations were performed using the kinetic code of MESS. The results show that DMMP mainly undergoes isomerization channels to form its isomers before decomposing into pyrolysis products. This is different from the DMMP decomposition channels adopted in the literature models. The kinetic model of DMMP in the literature was modified and improved by adding newly calculated reactions and their rate constants and updating the rate constants of unimolecular reactions for DMMP as well based on computations. Some rate tuning of reactions by 5 or 10 factors has been tried in model development to better describe the experimental measurements. Finally, the model developed by this work showed much better prediction of DMMP consumption and major species production than the prediction by literature models. In addition, the updated model was validated against various previous experimental data (CO mole fraction distributions in the shock tube, the flame speed and species mole fraction distributions in the premixed flame), and the satisfactory validation results indicate the reliability of the DMMP model that was improved in this work. This preliminary work laid a foundation to further study the combustion properties and to develop the kinetic model of organophosphorus compounds.

Thermocatalytic Decomposition of Dimethyl Methylphosphonate Based on CeO2 Catalysts with Different Morphologies

The catalytic performances of the catalysts and decomposition mechanisms of dimethyl methylphosphonate (DMMP), a commonly used nerve agent simulant, are well understood based on previous studies. However, the effects of the morphology of the catalyst on DMMP decomposition performance and mechanisms remain unexplored. Thus, in this work, experimental studies were conducted on the thermocatalytic decomposition of DMMP on CeO2 nanomaterials with different morphologies, e.g., irregular nanoparticles, nanorods, and nanocubes. From the performance evaluation, CeO2 nanorods exhibited higher DMMP thermocatalytic decomposition performance as compared to irregular nanoparticles and nanocubes. The primary reaction pathways were the same on all three morphologies of materials, according to in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study, whereas side reaction paths showed variable behaviors. According to the catalytic reaction mechanism study, the surface lattice oxygen played a vital role in the thermocatalytic decomposition of DMMP and the accumulation of phosphates, carbonates, and formates were the main factors for deactivation of the catalyst. The behavior of CeO2 catalyst with different morphologies in the thermocatalytic decomposition of DMMP was revealed in this work, and this will be useful for the future design of high-performing catalysts for the efficient degradation of chemical toxicant.

Catalytic Oxidative Decomposition of Dimethyl Methyl Phosphonate over CuO/CeO2 Catalysts Prepared Using a Secondary Alkaline Hydrothermal Method

Bimetallic synergism plays an important role in lattice-doped catalysts. Therefore, lattice-doped bimetallic CuO/CeO2 catalysts were prepared by secondary alkaline hydrothermal reaction. During this process, the CeO2 nanomaterials were partially dissolved and recrystallized; thus, Cu ions were doped into the CeO2 lattice. The physical and chemical properties of CeO2, CuO/CeO2, and CuO were investigated. H2 temperature-programmed reduction characterization showed that the oxidation activity of CuO/CeO2 was significantly improved. X-ray photoelectron spectroscopy results showed that electron transfer occurred between Ce and Cu in the CuO/CeO2 catalyst. Additionally, Raman characterization confirmed the strong interaction between Cu and Ce. After CuO was loaded, the thermal catalytic decomposition performance of the catalyst was significantly improved with respect to the sarin simulant dimethyl methyl phosphonate (DMMP); with an increase in the Cu/Ce ratio, the performance first strengthened and then weakened. Additionally, the reaction tail gas and catalyst surface products were analyzed using mass spectrometry and ion chromatography, and the changes in the surface products during the thermal catalytic decomposition of DMMP were characterized at different temperatures using in situ diffuse reflectance infrared Fourier transform spectroscopy. Finally, the catalytic reaction pathways of DMMP on CeO2, CuO/CeO2, and CuO were inferred. The study results not only demonstrate an effective catalyst for the removal of nerve agent but also a feasible preparation method for lattice-doped bimetallic catalysts in the field of environmental protection.

Experimental and theoretical study on the suppression effect of water mist containing dimethyl methylphosphonate (DMMP) on hydrogen jet flame

This work investigates the suppression effect of water mist containing dimethyl methylphosphonate (DMMP) on H2 jet flame. The flame appearances are analyzed and the flame temperature is recorded by a high-speed infrared camera. Results show that the suppression effect of water mist containing DMMP is better than that of pure water mist. To better understand the suppression effect of water mist containing DMMP, the burning velocity, heat production and free radicals are analyzed. Results indicate that suppressant could scavenge lots of free radicals to reduce the burning velocity in a wide range of equivalence ratios. Moreover, the influence of DMMP on lean CH4 and H2 flames is compared. Different with that of lean CH4 flame, the combustion parameters of lean H2 flame decline with DMMP addition. There is no combustion enhancement effect of DMMP on lean H2 flame. Because of the higher combustion intensity of lean H2 flame, the hydrocarbon in DMMP has little impact on the combustion. Furthermore, the reaction path of DMMP decomposition is analyzed. Results demonstrate that the rates of most phosphorus reactions in H2 flame are larger than that in CH4 flame. This work could provide foundation for improving the safety of hydrogen energy application.

Understanding Dimethyl Methylphosphonate Adsorption and Decomposition on Mesoporous CeO2.

The increased risk of chemical warfare agent usage around the world has intensified the search for high-surface-area materials that can strongly adsorb and actively decompose chemical warfare agents. Dimethyl methylphosphonate (DMMP) is a widely used simulant molecule in laboratory studies for the investigation of the adsorption and decomposition behavior of sarin (GB) gas. In this paper, we explore how DMMP interacts with the as-synthesized mesoporous CeO2. Our mass spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy measurements indicate that DMMP can dissociate on mesoporous CeO2 at room temperature. Two DMMP dissociation pathways are observed. Based on our characterization of the as-synthesized material, we built the pristine and hydroxylated (110) and (111) CeO2 surfaces and simulated the DMMP interaction on these surfaces with density functional theory modeling. Our calculations reveal an extremely low activation energy barrier for DMMP dissociation on the (111) pristine CeO2 surface, which very likely leads to the high activity of mesoporous CeO2 for DMMP decomposition at room temperature. The two reaction pathways are possibly due to the DMMP dissociation on the pristine and hydroxylated CeO2 surfaces. The significantly higher activation energy barrier for DMMP to decompose on the hydroxylated CeO2 surface implies that such a reaction on the hydroxylated CeO2 surface may occur at higher temperatures or proceed after the pristine CeO2 surfaces are saturated.

Adsorption and Decomposition of Dimethyl Methylphosphonate on Size-Selected Zirconium Oxide Trimer Clusters

Adsorption and Decomposition of Dimethyl Methylphosphonate on Size-Selected Zirconium Oxide Trimer Clusters

Suppression mechanism of ultrafine water mist containing phosphorus compounds in methane/coal dust explosions

The effect of ultrafine water mist with phosphorus-containing compounds (PCCs) on the flame in CH4/coal dust explosion is experimentally and numerically investigated. In this research, dimethyl methylphosphonate (DMMP) and phytic acid (PA) are selected as additives. The thermal stability of the mixture of coal and additives, and the products of mixture pyrolysis in the gas phase are analyzed by STA-FTIR and STA-GC-TCD. The results show that water mist can act as a thermal barrier and effectively lower flame temperature. DMMP water mist can significantly slow down the flame speed and cut off the flame. PCC additives can boost the heat absorption ability of water mist. Compared to PA, DMMP can efficiently lower the concentration of toxic (CO) and combustible (CH4 and H2) gases in CH4/coal dust hybrid explosions. The chemical suppression mechanism of DMMP water mist is further investigated. The kinetic model indicates that the main suppression reactions of lean CH4/coal flame are HOPO2 + H = PO2 + H2O and PO2 + H + M = HOPO. Gas-phase species with P in higher oxidation states (+5, +3) produced by the decomposition of DMMP play an essential role in suppressing a lean flame.

Thermal Decomposition of Dimethyl Methylphosphonate on Size-Selected Clusters: A Comparative Study between Copper Metal and Cupric Oxide Clusters

Room temperature decomposition and thermal decomposition of dimethyl methylphosphonate (DMMP), a chemical warfare agent (CWA) simulant, on size-selected copper clusters have been studied via combined X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD). Cu100 and (CuO)80, which have the same nominal masses, were chosen to present a direct comparison between the reactivity of metallic copper and that of cupric oxide with DMMP. Room temperature XPS results have shown that most of the DMMP molecules decompose completely and reductively into atomic phosphorus on Cu100, while almost all the DMMP molecules are only dissociatively adsorbed on (CuO)80 as methyl methylphosphonate (MMP). XPS and TPD have been carried out to analyze the thermal decomposition of adsorbed DMMP by identifying the surface species after annealing to certain temperatures and the gaseous products evolved during linear temperature ramps, respectively. Methanol, formaldehyde, and methane are the three most significant gaseous products for DMMP decomposition on both Cu100 and (CuO)80. Methanol and formaldehyde, which evolve in the low temperature region, are believed to originate from surface methoxy species. Methanol, formaldehyde, and methane evolved in the high temperature region are related to further decomposition of the phosphorus-containing surface species. A set of methanol-probed TPD experiments have also been carried out, which suggest that methane evolution originates from the methyl group within DMMP instead of the surface methoxy species.

Kinetics of Dimethyl Methylphosphonate Adsorption and Decomposition on Zirconium Hydroxide Using Variable Temperature In Situ Attenuated Total Reflection Infrared Spectroscopy.

The decomposition mechanisms of dimethyl methylphosphonate (DMMP), a widely used simulant for organophosphorus chemical warfare agents (CWAs), are relatively well understood from previous studies. However, there still lacks a quantitative description of DMMP decomposition kinetics under ambient conditions that is relevant for sequestration applications. We investigated adsorption and decomposition kinetics of DMMP on amorphous zirconium hydroxide (ZH) using variable-temperature in situ attenuated total reflection (ATR) infrared spectroscopy. We demonstrate that quantifying DMMP decomposition kinetics using conventional methods, where the integrated absorbance of P-O vibrational modes is monitored, can be inaccurate because these spectra are also convoluted with C-O vibrational modes from transient surface methoxy species that are not proportional to DMMP decomposition due to methanol desorption. Here, we propose to use the ρ(PCH3) modes as an alternative way to track DMMP adsorption and decomposition reactions. On the basis of density functional theory (DFT) simulations and comparisons to relatively unreactive monoclinic zirconia (m-ZrO2), we assign the deconvoluted components of the ρ(PCH3) region and use it to monitor decomposition products over time at various temperatures. Because the PCH3 group is present in many toxic organophosphorus compounds, tracking the PCH3 bands in time-dependent IR spectra is useful for measuring surface kinetics of CWAs and their simulants on various decontamination materials.

Conformal Nanoscale Zirconium Hydroxide Films for Decomposing Chemical Warfare Agents

Amorphous zirconium hydroxide (ZH) has attracted recent attention for its high decomposition reactivity with chemical warfare agents (CWA). Conformal, 50 nm thick amorphous ZH films were produced on arbitrarily shaped metallic substrates by cathodic electrodeposition from ZrOCl2 in aqueous solution, with nanoscale control of the film thickness. The films had a root-mean-square (rms) roughness of ∼6–8 nm, ∼2.4 nm nanoscale pores, and a high specific surface area of 132 m2 g–1. These rapidly grown, cost-effective, and scalable films may be more suitable for some in situ decontamination needs than post-event application of powders prepared by conventional wet-synthesis methods. The morphology and chemical properties of the electrodeposited films were characterized with scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis mass spectrometry (TGA-MS), and nitrogen-sorption porosimetry. The decomposition activity of ZH toward dimethyl methylphosphonate (DMMP), a CWA simulant, was probed with gas chromatography–mass spectrometry (GC-MS) and in situ attenuated total reflection infrared spectroscopy (ATR) by monitoring the evolution of gas-phase methanol and the coverage of surface-bound methoxy and phosphonate species during and after DMMP dosing. We compared the chemical activity of electrochemically synthesized ZH (EZ), commercial ZH (CZ) and ZrO2 nanopowders, and calcined EZ at 100–500 °C. The ATR, XPS, and XRD results indicate that calcination to 500 °C decreased DMMP decomposition due to the loss of hydroxyls and conversion to crystalline ZrO2 and that EZ and CZ had virtually identical surface reactions. This study provides a framework for characterizing the evolution of complex reactions during the transition from amorphous-to-crystalline material.

Room temperature decomposition of dimethyl methylphosphonate on cuprous oxide yields atomic phosphorus

Organophosphorus compounds have a wide range of reactivity depending on the coordination and oxidation state of the P atom. Due to their toxicity, certain organophosphonates are used as pesticides, herbicides, and, notoriously, as chemical nerve agents. The organophosphonate decomposition mechanism depends strongly on the substrate material, which motivates careful analysis of a range of potential materials for decontamination and sensing applications. Here, we present a study of the decomposition of dimethyl methylphosphonate (DMMP), a simulant molecule for the nerve agent sarin, on polycrystalline cuprous oxide surfaces (Cu2O). We use ambient pressure X-ray photoelectron spectroscopy (APXPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to monitor the pressure-dependent surface chemistry during exposure to DMMP vapor. At room temperature, we observe extensive degradation of DMMP, which includes the formation of reduced P products on the sample surface. We identify five unique P-containing species in the P 2p APXPS spectra, including atomic P and a surface-bound phosphinate [OPH(OCH3)OCu]. We propose a DMMP decomposition pathway whereby accumulation of this phosphinate species leads to an autocatalytic reaction on the Cu2O surface which yields reduced P species. After DMMP exposure, heating the Cu2O sample to 265 °C leads to complete removal of all carbonaceous species and accumulation of a phosphate layer with stoichiometry similar to P2O5. These results introduce a new mechanism of room-temperature DMMP decomposition on metal oxides, which could be leveraged for the design of tailored metal oxide materials for catalyzing organophosphonate decomposition.

Adsorption and decomposition of dimethyl methylphosphonate (DMMP) on expanded graphite/metal oxides

Composites based on expanded graphite (EG) and metal oxides (MOs) were prepared by an explosive combustion and blending method. A metal oxide (Ag2O, CuO or ZnO)-containing phase was employed as a component with reactive functionality, which was supported on EG as a component with adsorptive functionality. The physical properties of the EG/MO composites were examined using SEM and FTIR spectroscopy, the results of which indicated that the MOs were incorporated in the EG matrix after impregnation. Solid state magic angle spinning (MAS) 1H, 31P and cross polarization (CP) MAS 13C NMR studies of the EG/MO composites were performed after adsorption of dimethyl methylphosphonate (DMMP). The FTIR and NMR data showed that the initial uptake occurred through both molecular and reactive adsorption. Molecular adsorption occurred by van der Waals interaction of M(Zn, Cu, Ag)⋯OP and hydrogen-bond formation to isolated hydroxyl groups. Reactive chemisorption appeared to occur through interaction with both Lewis acid sites and active oxygen species present on the MO surface. The FTIR and NMR results exhibited a trend of reactivity towards DMMP in the order Ag2O > ZnO > CuO, which indicated stronger interaction between the Lewis acid sites and the phosphoryl O atom of DMMP for Ag2O as compared with ZnO and CuO, with concomitant formation of surface-coordinated DMMP and bridge-bonded OPO phosphorus oxide species.

Adsorption and decomposition of dimethyl methylphosphonate on size-selected (MoO3)3 clusters.

The adsorption and decomposition of dimethyl methylphosphonate (DMMP), a chemical warfare agent (CWA) simulant, on size-selected molybdenum oxide trimer clusters, i.e. (MoO3)3, was studied both experimentally and theoretically. X-ray photoelectron spectroscopy (XPS), temperature programmed reaction (TPR), and density functional theory (DFT)-based simulations were utilized in this study. The XPS and TPR results showed both, desorption of intact DMMP, and decomposition of DMMP through the elimination of methanol at elevated temperatures on (MoO3)3 clusters. Theoretical investigation of DMMP on (MoO3)3 clusters suggested that, in addition to pure (MoO3)3 clusters, reduced molybdenum oxide clusters and hydroxylated molybdenum oxide clusters also play an important role in decomposing DMMP via a "reverse Mars-van Krevelen mechanism". The present study, which focused on oxide clusters, underlines the importance of surface defects, e.g., the oxygen vacancies and surface hydroxyls, in determining the reaction pathway of DMMP, in agreement with previous studies on thin films. In addition, the structural fluxionality and the Lewis acidity of molybdenum oxide clusters, i.e. (MoO3)3, may make them good candidates for adsorption and decomposition of chemical warfare agents with similar structures to DMMP.

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

Zirconium hydroxide (Zr(OH)4) 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)4 has been attributed to a combination of diverse surface hydroxyl species and defects; however, atmospheric components (e.g., CO2, H2O, etc.) and trace contaminants can form adsorbates with potentially detrimental impact to the chemical reactivity of Zr(OH)4. Here, we report the hydrolysis of a CWA simulant, dimethyl methylphosphonate (DMMP) on Zr(OH)4 determined by gas chromatography-mass spectrometry and in situ attenuated total reflectance Fourier transform infrared spectroscopy under ambient conditions. DMMP dosing on Zr(OH)4 formed methyl methylphosphonate and methoxy degradation products on free bridging and terminal hydroxyl sites of Zr(OH)4 under all evaluated environmental conditions. CO2 dosing on Zr(OH)4 formed adsorbed (bi)carbonates and interfacial carbonate complexes with relative stability dependent on CO2 and H2O partial pressures. High concentrations of CO2 reduced DMMP decomposition kinetics by occupying Zr(OH)4 active sites with carbonaceous adsorbates. Elevated humidity promoted hydrolysis of adsorbed DMMP on Zr(OH)4 to produce methanol and regenerated free hydroxyl species. Hydrolysis of DMMP by Zr(OH)4 occurred under all conditions evaluated, demonstrating promise for chemical decontamination under diverse, real-world conditions.

Spectroscopic and Computational Investigation of Room-Temperature Decomposition of a Chemical Warfare Agent Simulant on Polycrystalline Cupric Oxide

Certain organophosphorus molecules are infamous due to their use as highly toxic nerve agents. The filtration materials currently in common use for protection against chemical warfare agents were designed before organophosphorus compounds were used as chemical weapons. A better understanding of the surface chemistry between simulant molecules and the individual filtration-material components is a critical precursor to the development of more effective materials for filtration, destruction, decontamination, and/or sensing of nerve agents. Here, we report on the surface adsorption and reactions of a sarin simulant molecule, dimethyl methylphosphonate (DMMP), with cupric oxide surfaces. In situ ambient pressure X-ray photoelectron and infrared spectroscopies are coupled with density functional calculations to propose mechanisms for DMMP decomposition on CuO. We find extensive room temperature decomposition of DMMP on CuO, with the majority of decomposition fragments bound to the CuO surface. We observe breaking of PO–CH3, P–OCH3, and P–CH3 bonds at room temperature. On the basis of these results, we identify specific DMMP decomposition mechanisms not seen on other metal oxides. Participation of lattice oxygen in the decomposition mechanism leads to significant changes in chemical and electronic surface environment, which are manifest in the spectroscopic and computational data. This study establishes a computational baseline for the study of highly toxic organophosphorous compounds on metal oxide surfaces.

Atomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decomposition

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs8[Nb6O19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb6O19]8− polyanion, its Cs+ counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general base (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs8[Nb6O19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M)MPA) product to the polyanions, which ultimately inhibits catalytic turnover.

Probing Phosphorus Nitride (P≡N) and Other Elusive Species Formed upon Pyrolysis of Dimethyl Phosphoramidate.

The thermal behavior of organophosphorus compounds is intricate and poorly understood but crucial for understanding gas-phase flame inhibition, syntheses of thermally active phosphorus-based reactive precursors, catalytic combustion, incineration of toxic nerve gases, and astrochemistry. In this work, the pyrolysis of dimethyl phosphoramidate was investigated using photoion photoelectron coincidence spectroscopy in combination with vacuum ultraviolet synchrotron radiation. This technique enables isomer-selective detection of reactive intermediates, which are crucial in the understanding of the decomposition process. Combined with quantum chemical calculations, the experimental results permit the formulation of a comprehensive pyrolysis reaction pathway for dimethyl phosphoramidate, consisting of several reactive phosphorus species on four possible decomposition pathways. Compared to the decomposition of dimethyl methyl phosphonate, which leads exclusively to the formation of PO radicals, substitution of the methyl with an amino group most notably yields phosphorus nitride (P≡N). This mostly favored reaction pathway involves the subsequent loss of methanol and formaldehyde to yield three PONH2 tautomers, which eliminate water to generate P≡N. The thermally induced production of PN species and its possible role in flame inhibition has not previously been reported. In addition, the adiabatic ionization energy of O=P(OCH3 )2 NH2 was determined to be 9.79±0.02 eV.

Adsorption and decomposition of dimethyl methylphosphonate on pristine and mono-vacancy defected graphene: A first principles study

Here we report the adsorption and decomposition behavior of dimethyl methyl-phosphonate (DMMP) on pristine and defected graphene using the first principles theory. The primary objective of this study is to highlight the importance of a vacancy defect on the adsorption mechanism of a molecule. In order to account for the weak forces involved between the molecule and graphene, we have used dispersion corrected total energy calculations along with generalized gradient approximation scheme for the exchange correlation energy. Among various possible configurations, the most stable geometry shows oxygen atom of the DMMP molecule favors to be close to the surface plane and bind with one of the unsaturated carbon atoms at the defect site. The molecule-substrate interaction energy is stronger for defected graphene than pristine graphene. The decomposition of the DMMP molecule at the vacancy site of the defected graphene has been investigated. For the dissociative adsorption, it is seen that the CH bond of the DMMP breaks and H atom is transferred to one of the low-coordinated C-atoms at the vicinity of the defect, forming new CH bond. In addition, the CC bond formation between graphene and DMMP occurs. Finally, the nature of bonding and electronic structure at the interface was interpreted through site projected electronic density of states analysis.