Abstract: In this work, we use density functional theory calculations to study the combined effect of external electric fields, surface morphology, and surface charge on CO2 activation over Cu(111), Cu(211), Cu(110), and Cu(001) surfaces. We observe that the binding energy of the CO2 molecule on Cu surfaces increases significantly upon increasing the applied electric field strength. In addition, rougher surfaces respond more effectively to the presence of the external electric field toward facilitating the formation of a carbonate-like CO2 structure and the transformation of the most stable adsorption mode from physisorption to chemisorption. The presence of surface charges further strengthens the electric field effect and consequently causes an improved bending of the CO2 molecule and C−O bond length elongation. On the other hand, a net charge in the absence of an externally applied electric field shows only a marginal effect on CO2 binding. The chemisorbed CO2 is more stable and further activated when the effects of an external electric field, rough surface, and surface charge are combined. These results can help to elucidate the underlying factors that control CO2 activation in heterogeneous and plasma catalysis, as well as in electrochemical processes.

Abstract: We developed a novel in situ (i.e. inside plasma and during operation) IR dielectric barrier discharge cell allowing investigation of plasma catalysis in transmission mode, atmospheric pressure, flow conditions (WHSV similar to 0-50 000 mL g(-1) h(-1)), at relevant discharge voltages (similar to 0-50 kV) and frequencies (similar to 0-5 kHz). We applied it to study the IR-active surface species formed on a SiO2 support and on a 3 wt% Ru/SiO2 catalyst, which can help to reveal the important surface reaction mechanisms during the plasma-catalytic dry reforming of methane (DRM). Moreover, we present a technique for the challenging task of estimating the temperature of a catalyst sample in a plasma-catalytic system in situ and during plasma operation. We found that during the reaction, water is immediately formed at the SiO2 surface, and physisorbed formic acid is formed with a delay. As Ru/SiO2 is subject to greater plasma-induced heating than SiO2 (with a surface temperature increase in the range of 70-120 degrees C, with peaks up to 150 degrees C), we observe lower amounts of physisorbed water on Ru/SiO2, and less physisorbed formic acid formation. Importantly, the formation of surface species on the catalyst sample in our plasma-catalytic setup, as well as the observed conversions and selectivities in plasma conditions, can not be explained by plasma-induced heating of the catalyst surface, but must be attributed to other plasma effects, such as the adsorption of plasma-generated radicals and molecules, or the occurrence of Eley-Rideal reactions.

Abstract: We discuss the synthesis of carbon nanotubes (CNTs) and graphene by catalytic chemical vapour deposition (CCVD) and plasma-enhanced CVD (PECVD), summarising the state-of-the-art understanding of mechanisms controlling their growth rate, chiral angle, number of layers (walls), diameter, length and quality (defects), before presenting a new model for 2D nucleation of a graphene sheet from amorphous carbon on a nickel surface. Although many groups have modelled this process using a variety of techniques, we ask whether there are any complementary ideas emerging from the different proposed growth mechanisms, and whether different modelling techniques can give the same answers for a given mechanism. Subsequently, by comparing the results of tight-binding, semi-empirical molecular orbital theory and reactive bond order force field calculations, we demonstrate that graphene on crystalline Ni(111) is thermodynamically stable with respect to the corresponding amorphous metal and carbon structures. Finally, we show in principle how a complementary heterogeneous nucleation step may play a key role in the transformation from amorphous carbon to graphene on the metal surface. We conclude that achieving the conditions under which this complementary crystallisation process can occur may be a promising method to gain better control over the growth processes of both graphene from flat metal surfaces and CNTs from catalyst nanoparticles.

Abstract: Atomic, layer deposition,(ALD of ruthenium using two ruthenium precursors, i.e., Ru(C5H5)(2) (RuCp2) and Ru(C5H5)(C4H4N) (RuCpPy), is studied using density functional theory. By investigating the reaction mechanisms On bare ruthenium surfaces, i.e., (001), (101), and (100), and H-terminated surfaces, an atomistic insight in the Ru ALD is provided. The calculated results show that on the Ru surfaces both RuCp2 and RuCpPy an undergo dehydrogenation and ligand dissociation reactions. RuCpPy is more reactive than RuCp2. By forming a, strong, bond between N of Py and Ru of the surface, RuCpPy can easily chemisorb on the surfaces. The reactions of RuCp2,On the Surfaces are less favorable the adsorption is not strong enough This could be a,factor contributing to the higher growth-per-cycle of Ru using RuCpPy, as observed experimentally. By Studying, the adsorption on H-terminated Ru surfaces, We showed that H Can prevent the adsorption of the precursors, thus inhibiting the growth of Ru. Our calculations indicate that the H content on the surface can have an impact on the growth-per-cycle. Finally, our simulations also demonstrate large impacts of the surface structure on the reaction mechanisms. Of the three surfaces, the (100) surface, which is the less stable and has a zigzag surface structure, is also the most reactive one.

Abstract: Surface charging is an often overlooked factor in many plasma-surface interactions and in particular in plasma catalysis. In this study, we investigate the effect of excess electrons induced by a plasma on the adsorption properties of CO2 on titania-supported Cu-5 and Ni-5 clusters using spin-polarized and dispersion-corrected density functional theory calculations. The effect of excess electrons on the adsorption of Ni and Cu pentamers as well as on CO2 adsorption on a pristine anatase TiO2(101) slab is studied. Our results indicate that adding plasma-induced excess electrons to the system leads to further stabilization of the bent CO2 structure. Also, dissociation of CO2 on charged clusters is energetically more favorable than on neutral clusters. We hypothesize that surface charge is a plausible cause for the synergistic effects sometimes observed in plasma catalysis.

Abstract: Grain boundaries between 60 degrees rotated and twinned crystals constitute the dominant type of extended line defects in two-dimensional transition metal dichalcogenides (2D MX2) when grown on a single crystalline template through van der Waals epitaxy. The two most common 60 degrees grain boundaries in MX2 layers, i.e., beta- and gamma-boundaries, introduce distinct distortion and strain into the 2D lattice. They impart a localized tensile or compressive strain on the subsequent layer, respectively, due to van der Waals coupling in bilayer MX2 as determined by combining atomic resolution electron microscopy, geometric phase analysis, and density functional theory. Based on these observations, an alternate route to strain engineering through controlling intrinsic van der Waals forces in homobilayer MX2 is proposed. In contrast to the commonly used external means, this approach enables the localized application of strain to tune the electronic properties of the 2D semiconducting channel in ultra-scaled nanoelectronic applications.

Abstract: Ammonia is one of the most produced chemicals, mainly synthesized from fossil fuels for fertilizer applications. Furthermore, ammonia may be one of the energy carriers of the future, when it is produced from renewable electricity. This has spurred research on alternative technologies for green ammonia production. Research on plasma-driven ammonia synthesis has recently gained traction in academic literature. In the current review, we summarize the literature on plasma-driven ammonia synthesis. We distinguish between mechanisms for ammonia synthesis in the presence of a plasma, with and without a catalyst, for different plasma conditions. Strategies for catalyst design are discussed, as well as the current understanding regarding the potential plasma-catalyst synergies as function of the plasma conditions and their implications on energy efficiency. Finally, we discuss the limitations in currently reported models and experiments, as an outlook for research opportunities for further unravelling the complexities of plasma-catalytic ammonia synthesis, in order to bridge the gap between the currently reported models and experimental results.

Abstract: Optimization of catalytic materials for a given application is greatly constrained by linear scaling relations. Recently, however, it has been demonstrated that it is possible to reversibly modulate the chemisorption of molecules on nanomaterials by charging (i.e., injection or removal of electrons) and hence reversibly and selectively modify catalytic activity beyond structure−activity correlations. The fundamental physical relation between the properties of the material, the charging process, and the chemisorption energy, however, remains unclear, and a systematic exploration and optimization of charge-switchable sorbent materials is not yet possible. Using hybrid DFT calculations of CO2 chemisorption on hexagonal boron nitride nanosheets with several types of defects and dopants, we here reveal the existence of fundamental correlations between the electron affinity of a material and charge-induced chemisorption, show how defect engineering can be used to modulate the strength and efficiency of the adsorption process, and demonstrate that excess electrons stabilize many topological defects. We then show how these insights could be exploited in the development of new electrocatalytic materials and the synthesis of doped nanomaterials. Moreover, we demonstrate that calculated chemical properties of charged materials are highly sensitive to the employed computational methodology because of the self-interaction error, which underlines the theoretical challenge posed by such systems.

Abstract: The combination of catalysis and nonthermal plasma holds promise for enabling difficult chemical conversions. The possible synergy between both depends strongly on the nature of the reactive plasma species and the catalyst material. In this paper, we show how vibrationally excited species and plasma-generated radicals interact with transition metal catalysts and how changing the catalyst material can improve the conversion rates and product selectivity. We developed a microkinetic model to investigate the impact of vibrational excitations and plasma-generated radicals on the nonoxidative coupling of methane over transition metal surfaces. We predict a significant increase in ethylene formation for vibrationally excited methane. Plasma-generated radicals have a stronger impact on the turnover frequencies with high selectivity toward ethylene on noble catalysts and mixed selectivity on non-noble catalysts. In general, we show how the optimal catalyst material depends on the desired products as well as the plasma conditions.

Abstract: Molecular dynamics simulations are used to investigate the effect of an AFM tip when indenting graphene nano bubbles filled by a noble gas (i.e. He, Ne and Ar) up to the breaking point. The failure points resemble those of viral shells as described by the Foppl-von Karman (FvK) dimensionless number defined in the context of elasticity theory of thin shells. At room temperature, He gas inside the bubbles is found to be in the liquid state while Ne and Ar atoms are in the solid state although the pressure inside the nano bubble is below the melting pressure of the bulk. The trapped gases are under higher hydrostatic pressure at low temperatures than at room temperature.

Abstract: Molecular dynamics (MD) simulations were performed to provide atomic scale insight in the initial interaction between hydroxyl radicals (OH) and peptide systems in solution. These OH radicals are representative reactive oxygen species produced by cold atmospheric plasmas. The use of plasma for biomedical applications is gaining increasing interest, but the fundamental mechanisms behind the plasma modifications still remain largely elusive. This study helps to gain more insight in the underlying mechanisms of plasma medicine but is also more generally applicable to peptide oxidation, of interest for other applications. Combining both reactive and nonreactive MD simulations, we are able to elucidate the reactivity of the amino acids inside the peptide systems and their effect on their structure up to 1 μs. Additionally, experiments were performed, treating the simulated peptides with a plasma jet. The computational results presented here correlate well with the obtained experimental data and highlight the importance of the chemical environment for the reactivity of the individual amino acids, so that specific amino acids are attacked in higher numbers than expected. Furthermore, the long time scale simulations suggest that a single oxidation has an effect on the 3D conformation due to an increase in hydrophilicity and intra- and intermolecular interactions.

Abstract: We report on multi-level atomistic simulations for the interaction of reactive oxygen species (ROS) with the head groups of the phospholipid bilayer, and the subsequent effect of head group and lipid tail oxidation on the structural and dynamic properties of the cell membrane. Our simulations are validated by experiments using a cold atmospheric plasma as external ROS source. We found that plasma treatment leads to a slight initial rise in membrane rigidity, followed by a strong and persistent increase in fluidity, indicating a drop in lipid order. The latter is also revealed by our simulations. This study is important for cancer treatment by therapies producing (extracellular) ROS, such as plasma treatment. These ROS will interact with the cell membrane, first oxidizing the head groups, followed by the lipid tails. A drop in lipid order might allow them to penetrate into the cell interior (e.g., through pores created due to oxidation of the lipid tails) and cause intracellular oxidative damage, eventually leading to cell death. This work in general elucidates the underlying mechanisms of ROS interaction with the cell membrane at the atomic level.