Jun 2019, Volume 13 Issue 2

Cover illustration

  • (Rusen Zhou, Renwu Zhou, Xianhui Zhang, Kateryna Bazaka, Kostya (Ken) Ostrikov, pp. 340-349)
    Electrifying chemical industry for cleaner future
    Plasma technology is one of the most promising innovations to electrify the chemical engineering field with applications varying from pollution abatement to energy conversion. New engineering solutions are poised to arise based on synergistic plasma effects. In this issue, Zhou et al. demonstrate that synergizing a [Detail] ...

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    Erik C. Neyts
    Michael Bonitz, Alexey Filinov, Jan-Willem Abraham, Karsten Balzer, Hanno Kählert, Eckhard Pehlke, Franz X. Bronold, Matthias Pamperin, Markus Becker, Dettlef Loffhagen, Holger Fehske

    Solids facing a plasma are a common situation in many astrophysical systems and laboratory setups. Moreover, many plasma technology applications rely on the control of the plasma-surface interaction, i.e., of the particle, momentum and energy fluxes across the plasma-solid interface. However, presently often a fundamental understanding of them is missing, so most technological applications are being developed via trial and error. The reason is that the physical processes at the interface of a low-temperature plasma and a solid are extremely complex, involving a large number of elementary processes in the plasma, in the solid as well as fluxes across the interface. An accurate theoretical treatment of these processes is very difficult due to the vastly different system properties on both sides of the interface: Quantum versus classical behavior of electrons in the solid and plasma, respectively; as well as the dramatically differing electron densities, length and time scales. Moreover, often the system is far from equilibrium. In the majority of plasma simulations surface processes are either neglected or treated via phenomenological parameters such as sticking coefficients, sputter rates or secondary electron emission coefficients. However, those parameters are known only in some cases and with very limited accuracy. Similarly, while surface physics simulations have often studied the impact of single ions or neutrals, so far, the influence of a plasma medium and correlations between successive impacts have not been taken into account. Such an approach, necessarily neglects the mutual influences between plasma and solid surface and cannot have predictive power.

    In this paper we discuss in some detail the physical processes of the plasma-solid interface which brings us to the necessity of coupled plasma-solid simulations. We briefly summarize relevant theoretical methods from solid state and surface physics that are suitable to contribute to such an approach and identify four methods. The first are mesoscopic simulations such as kinetic Monte Carlo and molecular dynamics that are able to treat complex processes on large scales but neglect electronic effects. The second are quantum kinetic methods based on the quantum Boltzmann equation that give access to a more accurate treatment of surface processes using simplifying models for the solid. The third approach are ab initio simulations of surface process that are based on density functional theory (DFT) and time-dependent DFT. The fourths are nonequilibrium Green functions that able to treat correlation effects in the material and at the interface. The price for the increased quality is a dramatic increase of computational effort and a restriction to short time and length scales. We conclude that, presently, none of the four methods is capable of providing a complete picture of the processes at the interface. Instead, each of them provides complementary information, and we discuss possible combinations.

    Anna Khlyustova, Cédric Labay, Zdenko Machala, Maria-Pau Ginebra, Cristina Canal

    Reactive oxygen and nitrogen species (RONS) are among the key factors in plasma medicine. They are generated by atmospheric plasmas in biological fluids, living tissues and in a variety of liquids. This ability of plasmas to create a delicate mix of RONS in liquids has been used to design remote or indirect treatments for oncological therapy by treating biological fluids by plasmas and putting them in contact with the tumour. Documented effects include selective cancer cell toxicity, even though the exact mechanisms involved are still under investigation. However, the “right” dose for suitable therapeutical activity is crucial and still under debate. The wide variety of plasma sources hampers comparisons. This review focuses on atmospheric pressure plasma jets as the most studied plasma devices in plasma medicine and compiles the conditions employed to generate RONS in relevant liquids and the concentration ranges obtained. The concentrations of H2O2, NO2, NO3 and short-lived oxygen species are compared critically to provide a useful overview for the reader.

    Annemie Bogaerts, Maksudbek Yusupov, Jamoliddin Razzokov, Jonas Van der Paal

    Plasma is gaining increasing interest for cancer treatment, but the underlying mechanisms are not yet fully understood. Using computer simulations at the molecular level, we try to gain better insight in how plasma-generated reactive oxygen and nitrogen species (RONS) can penetrate through the cell membrane. Specifically, we compare the permeability of various (hydrophilic and hydrophobic) RONS across both oxidized and non-oxidized cell membranes. We also study pore formation, and how it is hampered by higher concentrations of cholesterol in the cell membrane, and we illustrate the much higher permeability of H2O2 through aquaporin channels. Both mechanisms may explain the selective cytotoxic effect of plasma towards cancer cells. Finally, we also discuss the synergistic effect of plasma-induced oxidation and electric fields towards pore formation.

    J. Christopher Whitehead

    The issues of describing and understanding the changes in performance that result when a catalyst is placed into plasma are discussed. The different chemical and physical interactions that result and how their combination might produce beneficial results for the plasma-catalytic processing of different gas streams are outlined with particular emphasis being placed on the different range of spatial and temporal scales that must be considered both in experiment and modelling. The focus is on non-thermal plasma where the lack of thermal equilibrium creates a range of temperature scales that must be considered. This contributes in part to a wide range of inhomogeneity in different properties such as species concentrations and electric fields that must be determined experimentally by in situ methods and be incorporated into modelling. It is concluded that plasma-catalysis is best regarded as conventional catalysis perturbed by the presence of a discharge, which modifies its operating conditions, properties and outcomes often in a very localised way. The sometimes used description “plasma-activated catalysis” is an apt one.

    Leila Ouni, Ali Ramazani, Saeid Taghavi Fardood

    The scarcity of water, mainly in arid and semi-arid areas of the world is exerting exceptional pressure on sources and necessitates offering satisfactory water for human and different uses. Water recycle/reuse has confirmed to be successful and promising in reliable water delivery. For that reason, attention is being paid to the effective treatment of alternative resources of water (other than fresh water) which includes seawater, storm water, wastewater (e.g., dealt with sewage water), and industrial wastewater. Carbon nanotubes (CNTs) are called the technology of 21st century. Nowadays CNTs have been widely used for adsorption of heavy metals from water/wastewater due to their unique physical and chemical properties. This paper reviews some recent progress (from 2013 to 2018) in the application of CNTs for the adsorption of heavy metals in order to remove toxic pollutants from contaminated water. CNTs are expected to be a promising adsorbent in the future because of its high adsorption potential in comparison to many traditional adsorbents.

    Anandarup Goswami, Manoj B. Gawande

    The field of 2-dimensional (2D) materials has witnessed a sharp growth since its inception and can majorly be attributed to the substantial technical and scientific developments, leading to significant improvements in their syntheses, characterization and applications. In the list of 2D materials, the relatively newer addition is phosphorene, which ideally consists of a single layer of black phosphorous. Keeping in mind the past, and ongoing research activities, this short account offers a brief overview of the present status and the associated challenges in the field of phosphorene-related research, with special emphasis on their syntheses, properties, applications and future opportunities.

    Di Lu, Ran Tao, Zheng Wang

    Carbon-based materials have been extensively applied in photodynamic therapy owing to the unique optical characteristics, good biocompatibility and tunable systematic toxicity. This mini-review mainly focuses on the recent application of carbon-based materials including graphene, carbon nanotube, fullerene, corannulene, carbon dot and mesoporous carbon nanoparticle. The carbon-based materials can perform not only as photosensitizers, but also effective carriers for photosensitizers in photodynamic therapy, and its combined treatment.

    Pascal Brault, William Chamorro-Coral, Sotheara Chuon, Amaël Caillard, Jean-Marc Bauchire, Stève Baranton, Christophe Coutanceau, Erik Neyts

    Molecular dynamics simulations are carried out for describing growth of Pd and PdO nanoclusters using the ReaxFF force field. The resulting nanocluster structures are successfully compared to those of nanoclusters experimentally grown in a gas aggregation source. The PdO structure is quasi-crystalline as revealed by high resolution transmission microscope analysis for experimental PdO nanoclusters. The role of the nanocluster temperature in the molecular dynamics simulated growth is highlighted.

    Ana Mora-Boza, Francisco J. Aparicio, María Alcaire, Carmen López-Santos, Juan P. Espinós, Daniel Torres-Lagares, Ana Borrás, Angel Barranco

    Novel antibacterial materials for implants and medical instruments are essential to develop practical strategies to stop the spread of healthcare associated infections. This study presents the synthesis of multifunctional antibacterial nanocoatings on polydimethylsiloxane (PDMS) by remote plasma assisted deposition of sublimated chlorhexidine powders at low pressure and room temperature. The obtained materials present effective antibacterial activity against Escherichia coli K12, either by contact killing and antibacterial adhesion or by biocide agents release depending on the synthetic parameters. In addition, these multifunctional coatings allow the endure hydrophilization of the hydrophobic PDMS surface, thereby improving their biocompatibility. Importantly, cell-viability tests conducted on these materials also prove their non-cytotoxicity, opening a way for the integration of this type of functional plasma films in biomedical devices.

    Rusen Zhou, Renwu Zhou, Xianhui Zhang, Kateryna Bazaka, Kostya (Ken) Ostrikov

    Continuous processes which allow for large amount of wastewater to be treated to meet drainage standards while reducing treatment time and energy consumption are urgently needed. In this study, a dielectric barrier discharge plasma water bed system was designed and then coupled with granular activated carbon (GAC) adsorption to rapidly remove acid fuchsine (AF) with high efficiency. Effects of feeding gases, treatment time and initial concentration of AF on removal efficiency were investigated. Results showed that compared to the N2 and air plasmas treatments, O2 plasma processing was most effective for AF degradation due to the strong oxidation ability of generated activated species, especially the OH radicals. The addition of GAC significantly enhanced the removal efficiency of AF in aqueous solution and shorten the required time by 50%. The effect was attributed to the ability of porous carbon to trap and concentrate the dye, increasing the time dye molecules were exposed to the plasma discharge zone, and to enhance the production of OH radicals on/in GAC to boost the degradation of dyes by plasma as well as in situ regenerate the exhausted GAC. The study offers a new opportunity for continuous effective remediation of wastewater contaminated with organic dyes using plasma technologies.

    Xiuqi Fang, Carles Corbella, Denis B. Zolotukhin, Michael Keidar

    Graphene platelet networks (GPNs) were deposited onto silicon substrates by means of anodic arc discharge ignited between two graphite electrodes. Substrate temperature and pressure of helium atmosphere were optimized for the production of the carbon nanomaterials. The samples were modified or destroyed with different methods to mimic typical environments responsible of severe surface degradation. The emulated conditions were performed by four surface treatments, namely thermal oxidation, substrate overheating, exposition to glow discharge, and metal coating due to arc plasma. In the next step, the samples were regenerated on the same substrates with identical deposition technique. Damaging and re-growth of GPN samples were systematically characterized by scanning electron microscopy and Raman spectroscopy. The full regeneration of the structural and morphological properties of the samples has proven that this healing method by arc plasma is adequate for restoring the functionality of 2D nanostructures exposed to harsh environments.

    Mahmoud Trad, Alexandre Nominé, Natalie Tarasenka, Jaafar Ghanbaja, Cédric Noël, Malek Tabbal, Thierry Belmonte

    The synthesis of CdO, Ag2O (5 nm) and Ag (~20‒30 nm) nano-objects is achieved simultaneously by nanosecond-pulsed discharges in liquid nitrogen between one cadmium electrode and one silver electrode. Oxidation occurs when liquid nitrogen is fully evaporated and nanoparticles are in contact with the air. No alloy is formed, whatever the conditions, even though both elements are present simultaneously, as showed by time-resolved optical emission spectroscopy. This lack of reactivity between elements is attributed to the high pressure within the discharge that keeps each metallic vapor around the electrode it comes from. Each element exhibits a specific behavior. Cubic Cd particles, formed at 4 kV, get elongated with filamentary tips when the applied voltage reaches 7 and 10 kV. Cd wires are formed by assembly in liquid nitrogen of Cd nanoparticles driven by dipole assembly, and not by dielectrophoresis. On the contrary, silver spherical particles get assembled into 2D dendritic structures. The anisotropic growth of these structures is assumed to be due to the existence of pressure gradients.

    Long Cheng, Ruirui Zhang, Hongke Wu, Xinghai Liu, Tianming Xu

    A series of novel 6-(tert-butyl)-8-fluoro-2,3-dimethylquinoline carbonate derivatives were designed and synthesized. Bioassay results showed that some of them exhibited good activity against Pyricularia oryzae (P. oryzae). It was found that the compound 5q (benzyl (6-(tert-butyl)-8-fluoro-2,3-dimethylquinolin-4-yl) carbonate) possessed good activity against P. oryzae whatever protective activity (10 mg·L1) or curative activity (25 mg·L1), which was better than that of control tebufloquin. In addition, the frontier molecular orbit results revealed that the compound held higher activity against P. oryzae when the total energy was low and the ClogP was high, which may provide useful information for further design novel fungicides.

    Miao Zhao, Shufei Li, Qinghong Zhou, Dianming Zhou, Ning He, Zhiyong Qian

    Microbial pesticides can prevent and control diseases and pests of crops, and has become one of the important measures to ensure food and environmental safety. However, the potential harm of microbial pesticides to humans and animals is a serious concern at home and abroad. In this paper, we have investigated the infectivity and pathogenicity of a representative of viral microbial pesticides, helicoverpa armigera nuclear polyhedrosis virus (HaNPV), by specific and highly sensitive polymerase chain reaction technology. The results show that HaNPV can be gradually cleared in a short time after getting into blood of experimental rats, and does not infect other tissues or organs of animals; also indicate that the test subjects are not infectious to experimental rats after intravenous injection of HaNPV. Our method has good specificity and repeatability, and could provide an important reference for establishment of infectivity and pathogenicity detection methods for viral microbial pesticides in future.

    Longli Bo, Shaoyuan Sun

    A novel Cu-Mn-Ce/cordierite honeycomb catalyst was prepared by an incipient wetness method and the catalyst was characterized. The active ingredients were present as various spinel species of Cu, Mn and Ce oxides with different valences and they were unevenly dispersed over the surface of the catalyst. The catalytic oxidation of gaseous toluene was primarily investigated using a fixed bed reactor under microwave heating in the continuous flow mode. Under the optimal conditions of 6.7 wt-% loading of the active component, a bed temperature of 200°C, a flow rate of 0.12 m3·h−1 and an initial concentration of toluene of 1000 mg·m−3, the removal and mineralization efficiencies of toluene were 98% and 70%, respectively. Thus the use of the microwave effectively improved the oxidation of toluene and this is attributed to dipole polarization and hotspot effects. After four consecutive cycles (a total of 1980 min), the Cu-Mn-Ce/cordierite catalyst still exhibited excellent catalytic activity and structural stability, and the toluene removal was higher than 90%. This work demonstrates the possibility of treating volatile organic compounds in exhaust gases by microwave-assisted catalytic oxidation.

    Fan Shu, Meng Wang, Jinbo Pang, Ping Yu

    A free-standing superhydrophobic film is prepared by sequentially dip-coating a commercially available filter paper with nano SiO2 suspension, epoxy emulsion, and octyltrimethoxysilane solution. A surface with micro- or nano-roughness is formed because SiO2 nanoparticles are uniformly and firmly adhered on the backbone of the filter paper by the cured epoxy resin. Furthermore, the surface energy is significantly reduced because of introducing octytrimethoxysilane. Such a surface structure makes the prepared film a superhydrophobic material. Due to its free-standing nature, this superhydrophobic film can be used to remove water from turbine oil by filtration. The efficiency of water removal is high (up to 94.1%), and the filtration process is driven solely by gravity without extra energy consumption. Because of the facile fabrication process and the high efficiency of water removal, this free-standing superhydrophobic film may find application in power industry.

    Meibo He, Zhuang Liu, Tong Li, Chen Chen, Baicang Liu, John C. Crittenden

    Thin-film composite (TFC) nanofiltration (NF) membranes were fabricated via the interfacial polymerization of piperazine (PIP) and 1,3,5-benzenetricarbonyl trichloride on polysulfone (PSf) support membranes blended with K+-responsive poly(N-isopropylacryamide-co-acryloylamidobenzo-15-crown-5) (P(NIPAM-co-AAB15C5)). Membranes were characterized by attenuated total reflection Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscope, scanning electron microscope, contact angle, and filtration tests. The results showed that: (1) Under K+-free conditions, the blended P(NIPAM-co-AAB15C5)/PSf supports had porous and hydrophilic surfaces, thereby producing NF membranes with smooth surfaces and low MgSO4 rejections; (2) With K+ in the PIP solution, the surface roughness and water permeability of the resultant NF membrane were increased due to the K+-induced transition of low-content P(NIPAM-co-AAB15C5) from hydrophilic to hydrophobic; (3) After a curing treatment at 95 °C, the improved NF membrane achieved an even higher pure water permeability of 10.97 L·m−2·h−1·bar−1 under 200 psi. Overall, this study provides a novel method to improve the performance of NF membranes and helps understand the influence of supports on TFC membranes.

    Xuantao Wu, Jie Wang

    Catalytic steam gasification of fine coal char particles was carried out using a self-made laboratory reactor to determine the intrinsic kinetics and external diffusion under varying pressures (0.1–0.5 MPa) and superficial gas flow velocities (GFVs) of 13.8– 68.8 cm∙s−1. In order to estimate the in-situ gas release rate at a low GFV, the transported effect of effluent gas on the temporal gasification rate pattern was simulated by the Fluent computation and verified experimentally. The external mass transfer coefficients (kmam) and the effectiveness factors were determined at lower GFVs, based on the intrinsic gasification rate obtained at a high GFV of 55.0 cm∙s–1. The kmam was found to be almost invariable in a wider carbon conversion of 0.2–0.7. The variations of kmam at a median carbon conversion with GFV, temperature and pressure were found to follow a modified Chilton-Colburn correlation: Sh=0.311Re2.83Sc13(PP0)2.07 (0.04<Re<0.19), where P is total pressure and P0 is atmospheric pressure. An intrinsic kinetics/external diffusion integrating model could well describe the gasification rate as a function of GFV, temperature and pressure over a whole gasification process.