Kinetic Modeling Analysis of Ar Addition to Atmospheric Pressure N2-H2 Plasma for Plasma-Assisted Catalytic Synthesis of NH3.

Zero-dimensional kinetic modeling of atmospheric pressure Ar-N2-H2 nonthermal plasma was carried out to gain mechanistic insights into plasma-assisted catalytic synthesis of ammonia. Ar dilution is a common technique for tailoring plasma discharge properties and has been shown to enhance NH3 formation when added to N2-H2 plasma. The kinetic model was developed for a coaxial dielectric barrier discharge quartz wool-packed bed reactor operating at near room temperature using a kHz-frequency plasma source. With 30% Ar mixed in a 1:1 N2-H2 plasma at 760 Torr, we find that NH3 production is dominated by Eley-Rideal (E-R) surface reactions, which heavily involve surface NHx species derived from N and H radicals in the gas phase, while the influence of excited N2 molecules is negligible. This is contrary to the commonly proposed mechanism that excited N2 molecules created by Penning excitation of N2 by Ar(4s) and Ar(4p) play a significant role in assisting NH3 formation. Our model shows that the enhanced NH3 formation upon Ar dilution is unlikely due to the interactions between Ar and H species, as excited Ar atoms have a weak effect on H radical formation through H2 dissociation compared to electrons. We find that excited Ar atoms contribute to 28% of the N radical production in the gas phase via N2 dissociation, while the rest are dominated by electron-impact dissociation. Furthermore, Ar species play a negligible role in the product NH3 dissociation. N2 conversion sensitivity analyses were carried out for electron number density (ne) and reduced electric field (E/N), and contributions from Ar to gas-phase N radical production were quantified. The model can provide guidance on potential reasons for observing enhanced NH3 formation upon Ar dilution in N2-H2 plasma beyond changes in the discharge characteristics.

Particle-based mesoscopic model for phase separation in a binary fluid mixture.

A mesoscopic simulation model to study the phase separation in a binary fluid mixture in three dimensions (3D) is presented here by augmenting the existing particle-based multiparticle collision dynamics (MPCD) algorithm. The approach describes the nonideal equation of the fluid state by incorporating the excluded-volume interaction between the two components within the framework of stochastic collision, which depends on the local fluid composition and velocity. Calculating the nonideal contribution to the pressure both from simulation and analytics shows the model to be thermodynamically consistent. A phase diagram to explore the range of parameters that give rise to phase separation in the model is investigated. The interfacial width and phase growth obtained from the model agree with the literature for a wide range of temperatures and parameters.

Effect of Porous Catalyst Support on Plasma-Assisted Catalysis for Ammonia Synthesis.

We report on the effect of catalyst support particle porosity on the conversion of NH3 synthesis from N2 and H2 in a coaxial dielectric barrier discharge (DBD) plasma reactor. The discharge was created using an AC applied voltage with the reactor at room temperature and near atmospheric pressure (550 Torr). Two different particles of almost equal diameter (∼1.5 mm)─porous silica (SiO2) ceramic beads (average pore size: 8 nm) and smooth, nonporous soda lime glass beads─were compared in the DBD reactor. As the pore size in the SiO2 particles was smaller than the Debye length, penetration of the plasma into the pores of the particles was unlikely; however, reactive species generated in the plasma outside the particles could diffuse into the pores. The N2 conversion and energy yield of NH3 increased with applied voltage for both particle types, and these values were consistently higher when using the SiO2 beads. Discharge and plasma properties were estimated from Lissajous plots and using calculations with the BOLSIG+ software. The effect of these two different catalyst supports on the physical properties of the discharge was negligible. High resolution optical emission spectra revealed that the concentrations of N2+, atomic N, and atomic H (Hα, Hß) in the plasma discharge were lower with the porous SiO2 beads than with the glass beads at every applied voltage tested. This indicates that these active species participate in heterogeneous reactions at support particle surfaces and that the larger surface area presented by the porous particles led to higher rates of depletion of these intermediates and a higher rate of ammonia synthesis.

Engineered Nanoparticle-Protein Interactions Influence Protein Structural Integrity and Biological Significance.

Engineered nanoparticles (ENPs) are artificially synthesized particles with unique physicochemical properties. ENPs are being extensively used in several consumer items, elevating the probability of ENP exposure to biological systems. ENPs interact with various biomolecules like lipids, proteins, nucleic acids, where proteins are most susceptible. The ENP-protein interactions are mostly studied for corona formation and its effect on the bio-reactivity of ENPs, however, an in-depth understanding of subsequent interactive effects on proteins, such as alterations in their structure, conformation, free energy, and folding is still required. The present review focuses on ENP-protein interactions and the subsequent effects on protein structure and function followed by the therapeutic potential of ENPs for protein misfolding diseases.

Experimental observation of precursor solitons in a flowing complex plasma.

The excitation of precursor solitons ahead of a rapidly moving object in a fluid, a spectacular phenomenon in hydrodynamics that has often been observed ahead of moving ships, has surprisingly not been investigated in plasmas where the fluid model holds good for low frequency excitations such as ion acoustic waves. In this Rapid Communication we report an experimental observation of precursor solitons in a flowing dusty plasma. The nonlinear solitary dust acoustic waves (DAWs) are excited by a supersonic mass flow of the dust particles over an electrostatic potential hill. In a frame where the fluid is stationary and the hill is moving the solitons propagate in the upstream direction as precursors while wake structures consisting of linear DAWs are seen to propagate in the downstream region. A theoretical explanation of these excitations based on the forced Korteweg-deVries model equation is provided and their practical implications in situations involving a charged object moving in a plasma are discussed.