Nitrogen Dissociation Research Articles

Hydrogen behavior in Ti surface nitridation: Hydrogen as an active component catalyzes the nitridation reaction

Typically, H2 is introduced into the nitriding atmosphere to enhance the efficiency of metal surface nitridation. However, the role of hydrogen as an active species in catalyzing the reaction is still uncertain. Here, we present the nitridation mechanism of pure titanium(Ti) surface (hexagonal, α phase) with and without H atoms(H) based on first-principles calculations of surface nitrogen adsorption, dissociation and penetration. First, the adsorption characteristics of N atoms(N) and N2 molecules(N2) and the system energy indicate that FCC and HCP are favorable adsorption sites. In contrast, the adsorption stability of N on H-containing surfaces shows higher trend. Second, the minimum energy path (MEP) study results based on the climb image nudged elastic band (CI-NEB) method show that H increases the efficiency of dissociation and penetration processes. A linear relationship exists between hydrogen concentration and the N penetration energy barrier. In addition, electronic structure calculations theoretically support H regulation of surface nitridation efficiency. The nearby H reduces the energy barrier for the dissociation of N2 and the penetration of N by enhancing the interaction between N and surrounding Ti. This study provides theoretical support and new insights into the microscopic mechanism of H regulating the nitridation reaction of the Ti surface.

Promoting the hydrogen spillover via dual active sites synergistically for efficient photo-driven nitrogen fixation

Photocatalytic ammonia synthesis is heralded as the most promising field that will certainly gain increasing attention as a sustainable strategy for low-carbon NH3 production and H2 storage. However, one great challenge is to design ideal catalysts, which can provide the energetic active sites for nitrogen activation and hydrogen dissociation at the same time. In this study, we report that efficient photo-driven ammonia synthesis can be realized by synergetic effect of abundant Mo (V) species and Pt under ambient conditions. More specifically, the optimized Pt-loaded MoO3-x photocatalyst has attained the superior NH3 production rates of 3456 μg·g−1·h−1 under visible light irradiation (≥400 nm). As evidenced experimentally and theoretically, the enhanced photocatalytic performance can be ascribed to dual-active sites, where the loaded Pt co-catalyst can boost hydrogen spillover from Pt to MoO3-x induced by OV due to the low barrier of H* migration between hydrogen activation sites (Pt-O bridge) and nitrogen activation sites (low-valence Mo species), further increasing the number of Mo (V) active sites. And Mo (V) species adjacent oxygen vacancy with outstanding electron-donating capability and strong nitrogen chemisorption played a crucial role in facilitating nitrogen dissociation. Therefore, synergizing abundant Mo (V) species and loaded-Pt can optimize the photo-driven nitrogen reduction and hydrogen oxidation. This work provides a new idea for the rational design of efficient photo-driven ammonia synthesis.

Electron transfer from yttrium hydride to Mo-carbonitride boosts low-temperature ammonia synthesis

Ammonia is pivotal to various chemical industries, which is produced using the Haber-Bosch process. This process requires harsh conditions (e.g., 20.0 MPa and (500–600)°C) to generate ammonia and thus, is an energy intensive process. The growing consensus is to mild the conditions for ammonia generation. Herein, we demonstrate the use of hydride to increase the activity of molybdenum carbonitride (MCN). YH@MCN (95:5, w/w) generates ammonia at a rate of 448μmolg−1h−1 at 255 °C and 0.1 MPa. To address the stability issue of hydride, we incorporate iron. The experiment demonstrates two-fold rates for such catalyst, comparing MCN alone. The activation energy (19.73kJmol-1) for YFeH@MCN is considerably low, owing to the electron transfer from YH to MCN that facilitates nitrogen dissociation. Hence, the use of distinct sites for easy dissociation of nitrogen molecules, and the synergy between them, results in an activity that exceeds of conventional molybdenum and iron-based catalysts, and is comparable to ruthenium-based catalysts. Our results illustrate the potential of using synergistic multiple active sites in catalysts, and introduce a design concept for ammonia synthesis catalysts, using readily available elements.

Vacuum ammonia stripping from liquid digestate: Effects of pH, alkalinity, temperature, negative pressure and process optimization

High ammonia-nitrogen digestate has become a key bottleneck limiting the anaerobic digestion of organic solid waste. Vacuum ammonia stripping can simultaneously remove and recover ammonia nitrogen, which has attracted a lot of attention in recent years. To investigate the parameter effects on the efficiency and mass transfer, five combination conditions (53 °C 15 kPa, 60 °C 20 kPa, 65 °C 25 kPa, 72 °C 35 kPa, and 81 °C 50 kPa) were conducted for ammonia stripping of sludge digestate. The results showed that 80% of ammonia nitrogen was stripped in 45 min for all experimental groups, but the ammonia transfer coefficient varied under different conditions, which increased with the rising of boiling point temperature, and reached the maximum value (39.0 mm/hr) at 81 °C 50 kPa. The ammonia nitrogen removal efficiency was more than 80% for 30 min vacuum stripping after adjusting the initial pH to above 9.5, and adjustment of the initial alkalinity also affects the pH value of liquid digestate. It was found that pH and alkalinity are the key factors influencing the ammonia nitrogen dissociation and removal efficiency, while temperature and vacuum mainly affect the ammonia nitrogen mass transfer and removal velocity. In terms of the mechanism of vacuum ammonia stripping, it underwent alkalinity destruction, pH enhancement, ammonia nitrogen dissociation, and free ammonia removal. In this study, two-stage experiments of alkalinity destruction and ammonia removal were also carried out, which showed that the two-stage configuration was beneficial for ammonia removal. It provides a theoretical basis and practical technology for the vacuum ammonia stripping from liquid digestate of organic solid waste.

Donor‐Site‐Acceptor Covalent Organic Frameworks Enable Spontaneous Nitrogen Dissociation for Boosted Photoelectrochemical Ammonia Synthesis

AbstractPhotoelectrochemical (PEC) technology offers new opportunities for pushing the renewable energy‐driven ammonia synthesis toward a practical level, while still facing unsatisfactory efficiency due to the obstacle of dissociating inert nitrogen triple‐bonds. Herein, a novel donor‐site‐acceptor system is constructed in covalent organic frameworks to tackle this challenge for highly efficient PEC ammonia synthesis. Highly active boron site is elaborately embedded between the donor and acceptor units, which can be effectively activated with continuous electron flow upon photoexcitation. With the assistance of solar irradiation, the stubborn nitrogen dissociation is successfully changed from a passive endothermic reaction to a spontaneous exothermic process, completely eliminating the energy barrier of the rate‐determining step and facilitating the overall reaction kinetics. The proof‐of‐concept system achieved an excellent PEC NRR performance with a remarkable Faradaic efficiency of 91.6%, reaching the target set by the U.S. Department of Energy (90%).

Quantum hardware calculations of the activation and dissociation of nitrogen on iron clusters and surfaces.

Catalytic processes are the cornerstone of chemical industry, and catalytic conversion of nitrogen to ammonia remains one of the largest industrial processes implemented. Rational design of catalysts and catalytic reactions largely depends on approximate computational chemistry methods, such as density functional theory, which, however, suffer from limited accuracy, especially for strongly-correlated materials. Rigorous ab initio methods which account for static and dynamic electron correlation, while arbitrarily accurate for small systems, are generally too expensive to be applied to modelling of catalytic cycles, due to prohibitive time and space computational complexity with respect to the size of the active space. Recent advances in quantum computing give hope for enabling access to accurate ab initio methods at scale. Herein, we present a prototype hybrid quantum-classical workflow for modeling chemical reactions on surfaces, applied to proof-of-concept models of activation and dissociation of nitrogen on small Fe clusters and a single-layer (221) iron surface. First, we determined the structures of species present in the catalytic cycle at DFT level and studied their electronic structure using CASSCF. We show that it is possible to decouple the half-filled Fe-3d band from the Fe-N and N-N bond orbitals, thereby reducing the active space significantly. Subsequently, we translated the CASSCF wavefunctions into corresponding qubit quantum states, using the Adaptive Variational Quantum Eigensolver, and estimated their energies using a state vector simulator, H1-1E quantum emulator and (for selected systems) H1-1 quantum computer. We demonstrated that if a sufficiently small active orbital space is chosen, ground state energies obtained with classical methods and with the quantum computer are in reasonable agreement. We argue that once quantum computing methods are scaled up so that larger active spaces are accessible, they can offer a tremendous practical advantage to the computational catalysis community.

Managing the Scaling Relationship for Plasma-Activated Electrolysis Toward Nitrogen Fixation

To substitute fossil feedstock, storing renewable electricity in chemical bonds has become one of the tremendous and attractive approaches. This approach enables the transformation of base molecules (i.e., H2O, N2, CO2) into energy or chemical-rich molecules. The energy stored in the nitrogen-based compound is a critical biogeochemical cycle in nature due to its essential nutrient for living organisms in the forms of ammonia, nitrates, urea, amino acids, and DNA/RNA nucleotides as well as the high atmospheric volume of 78%. Artificial nitrogen fixation via a catalytic approach powered by sustainable renewables (e.g. wind, solar) provides an alternative as well as promising route to resource the value-added chemicals.N2 is a nonreactive base molecule due to its non-polarity and a strong triple bond between the atoms. Subsequently, even with an active catalyst, a substantial amount of energy is needed to activate N2 [1]. This Account covers our group’s recent advances in solid oxide electrolysis cells (SOECs) for providing reacting species on catalysts in a controllable manner while a radio frequency (RF) plasma is used to increase the reactivity of nitrogen [2,3]. Using oxygen ion or proton conducting SOECs we can produce either ammonia or nitric oxide (via reacting with plasma-activated N2) by suppressing oxygen or hydrogen evolution, respectively. The spatial separation of nitrogen dissociation and catalytic formation of the target molecules provides true independent parameters to optimize the electrocatalytic reactions. In both cases, the concentration of products is orders of magnitude higher than equilibrium (in the absence of plasma) while very high selectivity to nitrogen fixation is observed.To date most of the studies have focused on the material axis, however, recent theoretical studies have revealed that large-scale N2 fixation necessitates the rational design of the reactor, catalyst selectivity, reaction kinetics, and fluid dynamics and thus it keeps the processes far from the optimum performance. In this contribution, we investigate several aspects including flow dynamics, nature of the catalyst, activation energy of the catalytic process, catalyst surface-to-volume ratio, catalyst selectivity, and residence time of plasma-activated nitrogen to reach the catalyst surface, toward solving the aforementioned limitations.

A study on adsorption, dissociation, penetration, and diffusion of nitrogen on and in α-Ti via First-principles calculations

A comprehensive description of the entire process of N2 molecules on Ti surface and in Ti bulk as well as the underlying nitridation mechanism were explored via first-principles calculations. The reaction process was divided into four steps and the mechanism for the determined reaction path was analyzed. Utilizing the methodology of the climbing image nudged elastic band (CI-NEB), we investigated the diffusion energy barrier at each step of the reaction path, and determined the minimum energy path (MEP) for the complete reaction path. The calculated adsorption energies of N atoms and N2 molecules show that they are most stable at the HCP site on the α-Ti (0001) surface. Charge transfer provided theoretical support for N2 dissociation. We calculated the diffusion energy barrier of the N atom by migrating from the HCP site to the octahedral (O) site, which the N atom prefers to occupy. The diffusion coefficient is highest when the diffusion channel travels from one O site to the next layer of the O site via the next H site, it takes the most energy to complete, compared to those other steps. Lastly, we determined the rate-determining steps of the reaction pathway for the entire nitridation process. This study provides valuable insight into the fundamental mechanisms governing the nitridation process of N2 molecules in titanium alloys. This study sheds light on the nitridation mechanism for N2 molecules in titanium alloys.

Numerical study of nitrogen oxides chemistry during plasma assisted combustion in a sequential combustor

Plasma Assisted Combustion (PAC) is a promising technology to enhance the combustion of lean mixtures prone to instabilities and flame blow-off. Although many PAC experiments demonstrated combustion enhancement, several studies report an increase in NOx emissions. The aim of this study is to determine the kinetic pathways leading to NOx formation in the second stage of a sequential combustor assisted by Nanosecond Repetitively Pulsed Discharges (NRPDs). For this purpose, Large Eddy Simulation (LES) associated with an accurate description of the combustion/NOx chemistry and a phenomenological model of the plasma kinetics is used. Detailed kinetics 0-Dimensional reactors complement the study. First, the LES setup is validated by comparison with experiments. Then, the NOx chemistry is analyzed. For the conditions of operation studied, it is shown that the production of atomic nitrogen in the plasma by direct electron impact on nitrogen molecules increases the formation of NO. Then, the NO molecules are transported through the turbulent flame without being strongly affected. This study illustrates the need to limit the diatomic nitrogen dissociation process in order to mitigate harmful emissions. More generally, the very good agreement with experimental measurements demonstrates the capability of LES combined with accurate models to predict the NRPD effects on both turbulent combustion and NOx emissions.

Nitrogen Reduction Reaction to Ammonia on Transition Metal Carbide Catalysts.

The development of a low-cost, energy-efficient, and environmentally friendly alternative to the currently utilized Haber-Bosch process to produce ammonia is of great importance. Ammonia is an essential chemical used in fertilizers and a promising high-density fuel source. The nitrogen reduction reaction (NRR) has been explored intensively as a potential avenue for ammonia production using water as proton source, but to this day a catalyst capable of producing this chemical at high Faradaic efficiency (FE) and commercial yield and rates has not been reported. Here, we investigate the activity of transition metal carbide (TMC) surfaces in the (100) facets of the rocksalt (RS) structure as potential catalysts for the NRR. In this study, we use density functional theory (DFT) to model reaction pathways, estimate stability, assess kinetic barriers, and compare adsorbate energies to determine the overall performance of each TMC surface. For pristine TMC surfaces (with no defects) we find that none of the studied TMCs possess both exergonic adsorption of nitrogen and the capability to selectively protonate nitrogen to form ammonia in the desired aqueous solution. ZrC, however, is shown to be a potential catalyst if used in a non-aqueous electrolyte. To circumvent the endergonic adsorption of nitrogen onto the surface, a carbon vacancy was introduced. This provides a well-defined high coordination active site on the surface. In the presence of a vacancy VC, NbC, and WC showed efficient nitrogen adsorption, selectivity towards ammonia, and a low overpotential (OP). NbC did, however, display an unfeasible kinetic barrier to nitrogen dissociation for ambient-condition purposes, and thus it is suggested for high tempearture/pressure ammonia synthesis. Both WC and VC in their RS (100) structure are promising materials for experimental investigations in aqueous electrolytes, and ZrC could potentially be interesting for non-aqueous electrolytic systems.

Chemical evolution in nitrogen shocked beyond the molecular stability limit.

Evolution of nitrogen under shock compression up to 100GPa is revisited via molecular dynamics simulations using a machine-learned interatomic potential. The model is shown to be capable of recovering the structure, dynamics, speciation, and kinetics in hot compressed liquid nitrogen predicted by first-principles molecular dynamics, as well as the measured principal shock Hugoniot and double shock experimental data, albeit without shock cooling. Our results indicate that a purely molecular dissociation description of nitrogen chemistry under shock compression provides an incomplete picture and that short oligomers form in non-negligible quantities. This suggests that classical models representing the shock dissociation of nitrogen as a transition to an atomic fluid need to be revised to include reversible polymerization effects.

Stochastic determination of thermal reaction rate coefficients for air plasmas.

This work deals with the stochastic inference of gas-phase chemical reaction rates in high temperature air flows from plasma wind tunnel experimental data. First, a Bayesian approach is developed to include not only measurements but also additional information related to how the experiment is performed. To cope with the resulting computationally demanding likelihood, we use the Morris screening method to find the reactions that influence the solution to the stochastic inverse problem from a mechanism comprising 21 different reactions for an air mixture with seven species: O2, N2, NO, NO+, O, N, e-. A set of six reactions, mainly involving nitrogen dissociation and exchange, are the ones identified to impact the solution the most. As such, they are assumed to be uncertain and estimated along with the boundary conditions of the experiment and the catalytic recombination parameters of the materials involved in the testing. The remaining 15 reactions are set to their nominal values. The posterior distribution is then propagated through the proposed boundary layer model to produce the posterior predictive distributions of the temperature and mass fraction profiles along the boundary layer stagnation line. It is identified that NO concentrations have the largest increase in uncertainty levels compared to cases where the inference problem is carried out for fixed chemical model parameter values. This allows us to inform a new experimental campaign targeting the reduction of uncertainties affecting the chemical models.

High temperature and pressure Gladstone–Dale coefficient measurements in air behind reflected shock waves

Understanding the optical properties of air is essential for the validation and characterization of plasmas and hypersonic flows. Beyond 6000 K, the dissociation of nitrogen and oxygen molecules, along with other reactions, alters the equilibrium composition of air, causing a temperature and pressure dependence in the Gladstone–Dale coefficient. Due to measurement complexities, there is currently very little experimental data to validate model predictions under these conditions. In this work, a unique quadrature fringe imaging interferometer technique is applied to high temperature and pressure measurements of air in the Sandia free-piston high enthalpy shock tube. The diagnostic method combines a narrowband and broadband source to capture large, nearly-discrete changes in the index of refraction by calibrating to interference pattern changes. For the experiments, the reflected shock front is used to generate temperatures between 6000 and 7800 K at pressures up to 300 psi (20 bars). Results behind the shock front exhibit complex flow bifurcation and tail shock feature before equilibrium conditions are reached. Measurements in these flows show close agreement with theoretical predictions of the nonconstant Gladstone–Dale coefficient at high temperatures and high pressures, providing new validation data for chemical equilibrium gas models.

Boosting ammonia synthesis over molybdenum nitride through nickel‐mediated nitrogen activation and hydrogen transfer

AbstractSynergistic optimization of nitrogen dissociation and hydrogen transfer might be an efficient strategy to develop a highly efficient ammonia synthesis catalyst. Herein, the Ni‐modified molybdenum nitride is used as the catalyst of ammonia synthesis. The presence of the highly dispersed Ni metal results in enhancement of nitrogen vacancy, causing the acceleration of the exchange and reaction of the lattice N species with the nitrogen species from the gaseous phase. In addition, the presence of Ni species facilitates the hydrogen transfer and spillover, as well as easy hydrogen release. As a result, the optimized molybdenum nitride catalyst with 0.1 wt% Ni shows a 2.5‐times higher catalytic activity than that of the catalyst without Ni species at 400°C owing to the coupling of nitrogen activation and hydrogen transfer effects. This general approach could inspire the rational design of other metal catalysts for ammonia synthesis.

MXene-supported transition metal single-atom catalysts for nitrogen dissociation

Industrial ammonia production follows the Haber-Bosch process, whose rate-limiting step is the dissociation of the nitrogen molecule (N2), hence requiring suitable catalysts to break its triple bond. MXenes, a class of two-dimensional transition metal carbides and nitrides, have been proposed as very efficient catalysts for N2 dissociation. Here, by employing density functional theory-based calculations, we assess whether the deposition of one atom of a transition metal element (TM) on the Ti2C MXene surface further improves the catalytic potential of the MXene, serving as a single-atom catalyst. The results show that, for 21 of the 30 TMs considered, N2 can exothermically bind to the TM adatom, this bonding being favourable with respect to adsorption on the pristine Ti2C MXene surface for TMs of groups 3 to 6 of the Periodic Table. All the 21 TMs that successfully bind to N2 effectively reduce the N2 dissociation energy barrier when compared to the bulk Ti2C MXene by 18 to 84 %. Our results strongly indicate that doping the Ti2C MXene with atoms of transition metal elements significantly reduces the energy required to break the triple bond in N2, which may impact the nitrogen-to-ammonia process.

Effects of Field Strength and Silver Nanowire Size on Plasmon-Enhanced N2 Dissociation.

Dissociation of the nitrogen molecule via plasmon-enhanced catalysis using noble metal nanoparticles has been investigated both experimentally and computationally in recent years. However, the mechanism of plasmon-enhanced nitrogen dissociation is still not very clear. In this work, we apply theoretical approaches to examine the dissociation of a nitrogen molecule on atomically thin Agn nanowires (n = 6, 8, 10, 12) and a Ag19+ nanorod. Ehrenfest dynamics provides information about the motion of nuclei during the dynamics process and real-time TDDFT calculations show the electronic transitions and population of electrons over the first 10 s of fs time scale. The activation and dissociation of nitrogen are typically enhanced when the electric field strength increases. However, the enhancement is not always monotonic with field strength. As the length of the Ag wire increases, nitrogen is typically easier to dissociate and thus requires lower field strengths, even though the plasmon frequency is lower. The Ag19+ nanorod leads to faster dissociation of N2 than the atomically thin nanowires. Overall, our detailed study yields insights into the mechanisms involved in plasmon-enhanced N2 dissociation, as well as provides information about factors that can be used to improve adsorbate activation.

Objective molecular dynamics investigation of dissociation and recombination kinetics in high-temperature nitrogen

In this study, we propose the use of the novel approach of objective molecular dynamics (OMD) simulating far-from-equilibrium gas dynamics problems with chemical reactions. The OMD method has an exact relation to models in continuum mechanics and can be used to improve those models. We provide a detailed molecular dynamics investigation of chemically reacting nitrogen gas in a space-homogeneous adiabatic reactor. The analysis is based on a first-principles derived reactive ReaxFF potential energy surface, which captures the relevant processes of rovibrational relaxation, dissociation, and exchange as well as recombination in a gas evolving under non-equilibrium conditions. We examine the evolution of the internal mode population distribution of all the molecules as well as the rovibrational probability distribution of the pre-collision dissociating and post-collision recombined N2 molecules to investigate the microscopic selectivity of various reactive processes. Subsequently, we make comparisons with results obtained by means of an alternative modeling approach called direct molecular simulation. The current work illustrates the application of the method of OMD to study the compression and expansion kinetics of dissociation-recombination nitrogen mixture relevant to normal shock wave and nozzle expansion.

Experimental Justification of the Influence of S and Ni on Crystallization of Low-Nitrogen Diamonds in a Melt of Fe at High Pressure

Based on analysis of the results of the synthesis and growth of diamonds in metal-sulfide melts at a high pressure, the cause of the crystallization of low-nitrogen diamond crystals is substantiated. The introduction of sulfur into an iron melt leads to a decrease in the solubility of nitrogen, which, in turn, leads to a decrease in the content of nitrogen atoms in the melt and the probability of their capture by growing diamond crystals in the form of a structural impurity. The addition of nickel reduces the melting point of the growth system, increases the amount of melt, and, accordingly, facilitates the dissociation of molecular nitrogen into separate atoms, which are captured as a structural impurity by diamonds during their growth.

First-Principles Study of Nitrogen Adsorption and Dissociation on ZrMnFe(110) Surface.

The adsorption, dissociation and penetration processes of N2 on the surface of ZrMnFe(110) were investigated using the first-principles calculation method in this paper. The results indicate that the vacancy Hollow 1 composed of 4Zr1Fe on the surface of ZrMnFe(110) is the best adsorption site for the N2 molecule and N atom, and the adsorption energies are 10.215 eV and 6.057 eV, respectively. Electron structure analysis indicates that the N2 molecule and N atoms adsorbed mainly interact with Zr atoms on the surface. The transition state calculation shows that the maximum energy barriers to be overcome for the N2 molecule and N atom on the ZrMnFe(110) surface were 1.129 eV and 0.766 eV, respectively. This study provides fundamental insight into the nitriding mechanism of nitrogen molecules in ZrMnFe.

EXPERIMENTAL JUSTIFICATION OF THE INFLUENCE OF S AND Ni ON CRYSTALLIZATION OF LOW-NITROGEN DIAMONDS IN A MELT OF Fe AT HIGH PRESSURE

Based on the analysis of the results on the synthesis and growth of diamonds in metal-sulfide melts at high pressure, the reason for the crystallization of low-nitrogen diamond crystals is substantiated. The introduction of sulfur into the iron melt leads to a decrease in the solubility of nitrogen, which, in turn, leads to a decrease in the content of nitrogen atoms in the melt and the probability of their capture by growing diamond crystals in the form of a structural impurity. The addition of nickel lowers the melting point of the growth system, increases the amount of melt, and, accordingly, promotes the dissociation of molecular nitrogen into individual atoms, which are captured by diamonds during growth as a structural impurity.