Dissociation Of N2 Research Articles

Technical characteristics of a DC plasma jet with Ar/N2 and O2/N2 gaseous mixtures

In this paper, the optical emission spectroscopy technique is used to examine the physical properties and technical characteristics of the plasma discharge in a fabricated DC plasma jet. The background gas is nitrogen molecular gas which is mixed with argon and oxygen gases at various percentages. The emission spectra are analyzed and, the plasma density, rotational, vibrational and excitation temperatures are obtained for the formed plasma discharges with Ar/N2 and O2/N2 mixtures. Moreover, the NO and OH lines from NOγ(A2Σ+→X2Πr), (A2Σ,v=0→X2Π,v′=0) excitation transitions are observed. It is shown that, at the higher argon and oxygen percentages in both the Ar/N2 and O2/N2 gaseous mixture, the emission intensities of argon ions and oxygen atoms are increased. In addition, at the higher Ar and O2 contributions in both the gaseous mixtures, while the rotational, vibrational and excitation temperatures are higher, they are decreased at the O2/N2 gaseous mixture. Moreover, the plasma electron density reduces for O2/N2 and increases for Ar/N2 gaseous mixture. On the other hand, for both the mixtures, the plasma density, rotational, vibrational and excitation temperatures are increased at the higher DC power source currents. Furthermore, it is seen that the N2 dissociation rate increases at the higher DC currents and Ar and O2 percentages in both the mixtures. However, N2 dissociation rate in the formed plasma jet with Ar/N2 gaseous mixture is higher.

Mechanisms of Rh-Catalyzed Oxyaminofluorination and Oxyaminotrifluoromethylthiolation of Diazocarbonyl Compounds with Electrophilic Reagents.

Density functional theory calculations were performed to study the detailed reaction mechanisms of rhodium-catalyzed oxyaminofluorination and oxyaminotrifluoromethylthiolation of diazocarbonyl compounds with electrophilic N-F and N-SCF3-based reagents. The calculations show that the operating mechanisms for the two reactions are identical. The catalytic cycle starts with N2 dissociation to provide a rhodium-carbene intermediate, followed by nucleophilic attack of tetrahydrofuran on the carbene and a rhodium coordination change generating a rhodium-enolate intermediate. Subsequent electrophilic attack introduces the fluorine or the SCF3 moiety, and it is followed by nucleophilic attack of the remaining amino group to yield the final product.

N2 dissociation and kinetics of N(4S) atoms in nitrogen DC glow discharge

N2 dissociation in pure nitrogen plasma has a long history of research. It seems to be a complex process which comprises many reactions involving various electronic and vibrational nitrogen states whose contributions can vary depending on conditions. In this paper, we studied N2 dissociation in the stationary N2 discharge both experimentally and theoretically. We used a DC glow discharge in a quartz tube in pure N2 at moderate pressures (5–50 Torr). The degree of dissociation, atomic nitrogen loss rate and gas temperature were measured by applying optical emission spectroscopy (OES) and as a result an ‘effective’ rate constant for nitrogen dissociation was obtained across a wide range of the reduced field E/N. The analysis of N2 dissociation was carried out using a specially developed 1D radial self-consistent model which takes into account the spatial inhomogeneities of species concentrations, E/N, electron energy distribution function, Tgas etc, together with fairly complete plasma-chemical kinetics and all the cross-sections known to date for electron kinetics. The model was successfully validated through the experimental results obtained for electric field, gas temperature and N atom density. Comprehensive analysis of closely coupled processes in nitrogen plasmas—gas heating, VDF formation and N2 dissociation—was carried out. Simulations reproduced the experimental data on well and allowed us to evaluate the different contributions of the various dissociation channels considered. It was shown that the nitrogen dissociation mechanism in the stationary N2 discharge is provided by direct electron impact via the excitation of the pre-dissociative states from the vibrationally excited nitrogen molecules N2(X, υ). The upper limit for the rate constant of the processes N2(A) + N2(14 ⩽ υ ⩽ 19) → N + N + N2 was estimated to be 5 · 10−14 cm3 s−1.

Refining Defect States in W18O49 by Mo Doping: A Strategy for Tuning N2 Activation towards Solar-Driven Nitrogen Fixation.

Photocatalysis may provide an intriguing approach to nitrogen fixation, which relies on the transfer of photoexcited electrons to the ultrastable N≡N bond. Upon N2 chemisorption at active sites (e.g., surface defects), the N2 molecules have yet to receive energetic electrons toward efficient activation and dissociation, often forming a bottleneck. Herein, we report that the bottleneck can be well tackled by refining the defect states in photocatalysts via doping. As a proof of concept, W18O49 ultrathin nanowires are employed as a model material for subtle Mo doping, in which the coordinatively unsaturated (CUS) metal atoms with oxygen defects serve as the sites for N2 chemisorption and electron transfer. The doped low-valence Mo species play multiple roles in facilitating N2 activation and dissociation by refining the defect states of W18O49: (1) polarizing the chemisorbed N2 molecules and facilitating the electron transfer from CUS sites to N2 adsorbates, which enables the N≡N bond to be more feasible for dissociation through proton coupling; (2) elevating defect-band center toward the Fermi level, which preserves the energy of photoexcited electrons for N2 reduction. As a result, the 1 mol % Mo-doped W18O49 sample achieves an ammonia production rate of 195.5 μmol gcat-1 h-1, 7-fold higher than that of pristine W18O49. In pure water, the catalyst demonstrates an apparent quantum efficiency of 0.33% at 400 nm and a solar-to-ammonia efficiency of 0.028% under simulated AM 1.5 G light irradiation. This work provides fresh insights into the design of photocatalyst lattice for N2 fixation and reaffirms the versatility of subtle electronic structure modulation in tuning catalytic activity.

Collision induced dissociation cross-section for high energy N2-O2 collisions

Cross-sections for O2 and N2 dissociation on N2O2 CASSCF-CASPT2 PES are calculated and reported for high energy collisions (up to 30 eV). An earlier reported weighted data fitting scheme for enumerating the entire cross-section database is modified and extended for the N2O2 system. The cross-section database is suitable for studying reactions in hypersonic flows especially with high degree of non-equilibrium. Additionally, the relevance on NO formation as a result of N2-O2 collision is explored.

Control of nitrogen activation ability by Co-Mo bimetallic nanoparticle catalysts prepared via sodium naphthalenide-reduction

Co-Mo bimetallic nanoparticles (NPs) with various compositions were prepared on a CeO2 support (Co-Mo/CeO2) by sodium naphthalenide driven reduction. The Co-Mo/CeO2 catalyst exhibits much higher activity for ammonia synthesis than monometallic catalysts such as Co/CeO2 and Mo/CeO2, and the optimum activity is obtained at Co:Mo = 4:6. X-ray absorption fine structure (XAFS) analyses reveal that Co3Mo3N NPs are formed after ammonia synthesis reaction. Nitrogen temperature programmed desorption (N2-TPD) measurements indicate that the Co-Mo/CeO2 catalyst possesses a large number of nitrogen adsorption sites with an intermediate nitrogen adsorption energy between that of Co and Mo. Furthermore, nitrogen vacancy sites, which are active sites for N2 dissociation, are more easily formed on the Co-Mo/CeO2 catalyst than on bulk-type Co3Mo3N. As a consequence, the turnover frequency of the Co-Mo/CeO2 catalyst is much higher than that of bulk-type Co3Mo3N and is comparable to that of the efficient Ru/CeO2 catalyst.

Mechanisms of Rh-Catalyzed Oxyfluorination and Oxytrifluoromethylation of Diazocarbonyl Compounds with Hypervalent Fluoroiodine

The reaction mechanisms of rhodium-catalyzed geminal oxyfluorination and oxytrifluoromethylation of diazocarbonyl compounds with fluoro-benziodoxole and Togni reagents are investigated by means of density functional theory calculations. It is shown that the two reactions follow very similar mechanisms, involving N2 dissociation to form a Rh–carbene intermediate, alcohol insertion and proton transfer resulting in a stable Rh–enol intermediate, and concerted proton transfer/electrophilic addition of the hypervalent iodine reagent to the enol. Isomerization of the hypervalent iodine takes then place before a ligand coupling affords the final product. The role of the dirhodium catalyst in facilitating the various steps of the reaction is discussed. The presented mechanisms are consistent with available experimental information, and the obtained insights allow for extension to other reactions involving hypervalent iodine reagents.

Advancing Ammonia Synthesis through Plasma-Assisted Catalysis

Plasmas can enhance the selectivity, activity, and product yields for many chemical reactions. In the presence of a catalyst, synergy between the catalyst and the plasma exists to assist in the activation of reactants to promote the chemical transformation. We have been particularly interested in the use of non-thermal plasmas for the catalytic production of ammonia from nitrogen/hydrogen gas mixtures. The industrial Haber-Bosch process for ammonia synthesis from nitrogen and hydrogen is carried out at high pressures (100-200 bar) and temperatures (400-500 °C). N2 dissociation is the fundamental barrier for this reaction, and plasma-catalysis has been suggested as viable way to activate N2 under ambient conditions. We have demonstrated that is possible to produce ammonia at atmospheric pressure and temperatures between 100 - 200 °C by coupling the catalyst with a non-thermal plasma. It is speculated that the plasma assists in activating the source gas by generating reactive species, such as vibrationally or electronically excited N2*, ions, and radicals, which interact on the catalyst surface to produce ammonia. In this presentation, we will discuss our experimental results from varying the gas composition, bulk gas temperature, plasma input power, and reactor space velocity and how these conditions influence the catalyst-plasma interactions using a variety of catalysts (Fe/Al2O3, Ru/Al2O3, Pt/Al2O3, Ni/Al2O3, and Co/Al2O3).

Computational Design of Active Site Structures with Improved Transition-State Scaling for Ammonia Synthesis

The Haber–Bosch process for the reduction of atmospheric nitrogen to ammonia is one of the most optimized heterogeneous catalytic reactions, but there are aspects of the industrial process that remain less than ideal. It has been shown that the activity of metal catalysts is limited by a Bronsted–Evans–Polanyi (BEP) scaling relationship between the reaction and transition-state energies for N2 dissociation, leading to a negligible production rate at ambient conditions and a modest rate under harsh conditions. In this study, we use density functional theory (DFT) calculations in conjunction with mean-field microkinetic modeling to study the rate of NH3 synthesis on model active sites that require the singly coordinated dissociative adsorption of N atoms onto transition metal atoms. Our results demonstrate that this ”on-top” binding of nitrogen exhibits significantly improved scaling behavior, which can be rationalized in terms of transition-state geometries and leads to considerably higher predicted activi...

The magic of triads

Ammonia synthesis is an energy-intensive process due to the high activation barrier for N2 dissociation, which is the rate-determining step on conventional catalysts. Now, a ternary intermetallic catalyst is reported to be capable of catalysing this reaction through an alternative pathway.

Vibrational energy transfer and dissociation in O2-N2 collisions at hyperthermal temperatures.

Simulation of vibrational energy transfer and dissociation in O2-N2 collisions is conducted using the quasi-classical trajectory method on an ab initio potential energy surface. Vibrationally resolved rate coefficients are obtained in a high-temperature region between 8000 and 20 000 K by means of the cost-efficient classical trajectory propagation method. A system of master equations is constructed using the new dataset in order to simulate thermal and chemical nonequilibrium observed in shock flows. The O2 relaxation time derived from a solution of the master equations is in good agreement with the Millikan and White correlation at lower temperatures with an increasing discrepancy toward the translational temperature of 20 000 K. At the same time, the N2 master equation relaxation time is similar to that derived under the assumption of a two-state system. The effect of vibrational-vibrational energy transfer appears to be crucial for N2 relaxation and dissociation. Thermal equilibrium and quasi-steady state dissociation rate coefficients in O2-N2 heat bath are reported.

Storm-time variations of atomic nitrogen 149.3 nm emission

Net radiances of atomic nitrogen emission line (N-149.3 nm) from the thermosphere are extracted from the FUV spectra observed by TIMED/GUVI on dayside at sunlit latitudes. During geomagnetic storms, the N-149.3 nm intensity is clearly enhanced in the locations where O/N2 depletion and nitric oxide (NO) enhancement are observed. The N-149.3 nm intensity is linearly and tightly correlated with N2 LBHS (140–150 nm) radiance with a fixed LBHS/149.3 nm ratio of ∼4.5, suggesting that dissociation of N2 is the dominant source of the N-149.3 nm emission. In the regions without storm disturbances, the N-149.3 nm intensities are closely correlated with solar EUV flux.

Ternary intermetallic LaCoSi as a catalyst for N2 activation

Activating high-energy multiple bonds using earth-abundant metals is one of the most significant challenges in catalysis. Here, we show that LaCoSi—a ternary intermetallic compound—is an efficient and stable catalyst for N2 activation to produce NH3. The ammonia synthesis is significantly promoted by shifting the reaction bottleneck from the sluggish N2 dissociation to NH x formation, which few catalysts have achieved. Theoretical calculations reveal that the negatively charged cobalt mediates electron transfer from lanthanum to the adsorbed N2, which further reduces the activation barrier of N2 dissociation. Most importantly, the specific LaCoSi geometric configuration stabilizes the N2 adsorption with a strong exothermic effect, which dramatically decreases the apparent energy barrier of N2 activation. Consequently, LaCoSi shows a superior activity (1,250 μmol g−1 h−1), with a 60-fold increase over the activity of supported cobalt catalysts under mild reaction conditions (400 °C, 0.1 MPa). Ammonia synthesis is an energy-intensive process due to the high activation barrier for N2 dissociation. Here, Hosono and co-workers show that the intermetallic compound LaCoSi can lower the energy requirement for N2 activation and shift the rate-determining step of the process to NH x formation under mild conditions.

Activation of Dinitrogen with a Superalkali Species, Li3 F2.

The capability of the superalkali Li3 F2 to activate dinitrogen (N2 ) is presented. The (Li3 F2 )nN2 clusters (n=1-6) were investigated first at the MP2/6-311+G(3d2f,2df,2p)//B3LYP/6-311G(2d,d,p) level of theory. Clusters up to n=4 were also optimized through the CBS-QB3 composite model. The complete dissociation of N2 was confirmed through visualized molecular orbitals and bond order calculation. The N-N bond is weakened by the addition of Li3 F2 superalkali units. The enthalpy of atomization ΔatH0∘ and formation (ΔfH0∘ ), charge flows (Δq), binding energies, and the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital are calculated to help explain the N2 activation.

Adaptive coarse graining method for energy transfer and dissociation kinetics of polyatomic species.

A novel reduced-order method is presented for modeling reacting flows characterized by strong non-equilibrium of the internal energy level distribution of chemical species in the gas. The approach seeks for a reduced-order representation of the distribution function by grouping individual energy states into macroscopic bins, and then reconstructing state population using the maximum entropy principle. This work introduces an adaptive grouping methodology to identify and lump together groups of states that are likely to equilibrate faster with respect to each other. To this aim, two algorithms have been considered: the modified island algorithm and the spectral clustering method. Both methods require a measure of dissimilarity between internal energy states. This is achieved by defining "metrics" based on the strength of the elementary rate coefficients included in the state-specific kinetic mechanism. Penalty terms are used to avoid grouping together states characterized by distinctively different energies. The two methods are used to investigate excitation and dissociation of N2 (Σg+1) molecules due to interaction with N(Su4) atoms in an ideal chemical reactor. The results are compared with a direct numerical simulation of the state-specific kinetics obtained by solving the master equations for the complete set of energy levels. It is found that adaptive grouping techniques outperform the more conventional uniform energy grouping algorithm by providing a more accurate description of the distribution function, mole fraction and energy profiles during non-equilibrium relaxation.

Temperature-dependent BN cluster formation dynamics from a boron cluster: Density-functional tight-binding molecular dynamics simulations

The time-evolution dynamics of a boron nitride (BN) cluster from an amorphous B cluster is simulated by quantum chemical molecular dynamics based on the density-functional tight-binding method. In the simulations, N atoms are sequentially supplied around the B cluster in conjunction with the arc-melting BN fullerene synthesis from B-rich compounds. The simulations are performed at 1000, 1500, 2000, 2500, and 3000K, and we run 30 trajectories for 200ps at each temperature. At low temperature (1000K), the BN clusters tend to form stuffed cage structures, characterized by internal BN branched units. As the temperature increases, the proportion of stuffed cage structures decreases, whereas that of cage-like structure increases. At intermediate temperatures (2000 and 2500K), most of the BN clusters develop into hollow structures, exhibiting a strong cage forming preference. At 3000K, the BN clusters tend to form sparse branched chain structures, without forming cage-like structures. Mobility analysis of the cluster atoms at all the temperatures reveals that the transition from a liquid-like state to a solid-like state occurs at 2000 and 2500K, whereas the cluster remains in a solid-like state at 1000K and a liquid-like state at 3000K. The N2 dissociation reactions from the BN cluster proceed through various N2 unit formation processes in the BN cluster. We describe details of the representative N2 unit formation processes classified by the bonding of the cluster N atoms.

Fluid simulation of species concentrations in capacitively coupled N2/Ar plasmas: Effect of gas proportion

A two-dimensional self-consistent fluid model and the experimental diagnostic are employed to investigate the dependencies of species concentrations on the gas proportion in the capacitive N2/Ar discharges operated at 60 MHz, 50 Pa, and 140 W. The results indicate that the N2/Ar proportion has a considerable impact on the species densities. As the N2 fraction increases, the electron density, as well as the Ar+ and Arm densities, decreases remarkably. On the contrary, the N2+ density is demonstrated to increase monotonically with the N2 fraction. Moreover, the N density is observed to increase significantly with the N2 fraction at the N2 fractions below 40%, beyond which it decreases slightly. The electrons are primarily generated via the electron impact ionization of the feed gases. The electron impact ionization of Ar essentially determines the Ar+ density. For the N2+ production, the charge transition process between the Ar+ ions and the feed gas N2 dominates at low N2 fraction, while the electron impact ionization of N2 plays the more important role at high N2 fraction. At any gas mixtures, more than 60% Arm atoms are generated through the radiative decay process from Ar(4p). The dissociation of the feed gas N2 by the excited Ar atoms and by the electrons is responsible for the N formation at low N2 fraction and high N2 fraction, respectively. To validate the simulation results, the floating double probe and the optical emission spectroscopy are employed to measure the total positive ion density and the emission intensity originating from Ar(4p) transitions, respectively. The results from the simulation show a qualitative agreement with that from the experiment, which indicates the reliable model.

Excited-State N2 Dissociation Pathway on Fe-Functionalized Au.

Localized surface plasmon resonances (LSPRs) offer the possibility of light-activated chemical catalysis on surfaces of strongly plasmonic metal nanoparticles. This technology relies on lower-barrier bond formation and/or dissociation routes made available through energy transfer following the eventual decay of LSPRs. The coupling between these decay processes and a chemical trajectory (nuclear motion, charge-transfer, intersystem crossing, etc.) dictates the availability of these alternative (possibly lower barrier) excited-state channels. The Haber-Bosch method of NH3 synthesis from N2 and H2 is notoriously energy intensive. This is due to the difficulty of N2 dissociation despite the overall reaction being thermodynamically favorable at ambient temperatures and pressures. LSPRs may provide means to improve the kinetics of N2 dissociation via induced resonance electronic excitation. In this work, we calculate, via embedded n-electron valence second-order perturbation theory within the density functional embedding theory, the excited-state potential energy surfaces for dissociation of N2 on an Fe-doped Au(111) surface. This metal alloy may take advantage simultaneously of the strong LSPR of Au and the catalytic activity of Fe toward N2 dissociation. We find the ground-state dissociation activation energy to be 4.74 eV/N2, with Fe as the active site on the surface. Consecutive resonance energy transfers (RETs) may be accessed due to the availability of many electronically excited states with intermediate energies arising from the metal surface that may couple to states induced by the Fe-dopant and the adsorbate molecule, and crossing between excited states may effectively lower the dissociation barrier to 1.33 eV. Our work illustrates that large energetic barriers, prohibitive toward chemical reaction, may be overcome through multiple RETs facilitating an otherwise difficult chemical process.

Role of exact exchange in thermally-assisted-occupation density functional theory: A proposal of new hybrid schemes.

We propose hybrid schemes incorporating exact exchange into thermally assisted-occupation-density functional theory (TAO-DFT) [J.-D. Chai, J. Chem. Phys. 136, 154104 (2012)] for an improved description of nonlocal exchange effects. With a few simple modifications, global and range-separated hybrid functionals in Kohn-Sham density functional theory (KS-DFT) can be combined seamlessly with TAO-DFT. In comparison with global hybrid functionals in KS-DFT, the resulting global hybrid functionals in TAO-DFT yield promising performance for systems with strong static correlation effects (e.g., the dissociation of H2 and N2, twisted ethylene, and electronic properties of linear acenes), while maintaining similar performance for systems without strong static correlation effects. Besides, a reasonably accurate description of noncovalent interactions can be efficiently achieved through the inclusion of dispersion corrections in hybrid TAO-DFT. Relative to semilocal density functionals in TAO-DFT, global hybrid functionals in TAO-DFT are generally superior in performance for a wide range of applications, such as thermochemistry, kinetics, reaction energies, and optimized geometries.

Properties of Alumina/Chromia Scales in N2-Containing Low Oxygen Activity Environment Investigated by Experiment and Theory

The FeCrAl alloy Kanthal APMT™ was exposed to N2–5%H2 at 900 °C. Trace oxygen in the gases supplied an oxygen activity which was sufficient to render alumina and chromia thermodynamically stable. The exposures revealed that the oxide scale was penetrated by nitrogen exclusively at chromia domains. Microscopic analyses of the oxide scale did not reveal micro-cracks that could serve as points-of-entry for nitrogen. Instead it is suggested that nitrogen is transported through a dense chromia layer. Density functional theory was employed to investigate decisive nitrogen surface chemistry and transport properties in chromia and alumina. The study was used to validate that the complex redox chemistry of Cr3+ as opposed to Al3+ is a sufficient discriminating factor between alumina and chromia, facilitating N2 dissociation and mobility of N in chromia.