Formation of Black Silicon in a Process of Plasma Etching with Passivation in a SF6/O2 Gas Mixture.

This article discusses a method for forming black silicon using plasma etching at a sample temperature range from -20 °C to +20 °C in a mixture of oxygen and sulfur hexafluoride. The surface morphology of the resulting structures, the autocorrelation function of surface features, and reflectivity were studied depending on the process parameters-the composition of the plasma mixture, temperature and other discharge parameters (radical concentrations). The relationship between these parameters and the concentrations of oxygen and fluorine radicals in plasma is shown. A novel approach has been studied to reduce the reflectance using conformal bilayer dielectric coatings deposited by atomic layer deposition. The reflectivity of the resulting black silicon was studied in a wide spectral range from 400 to 900 nm. As a result of the research, technologies for creating black silicon on silicon wafers with a diameter of 200 mm have been proposed, and the structure formation process takes no more than 5 min. The resulting structures are an example of the self-formation of nanostructures due to anisotropic etching in a gas discharge plasma. This material has high mechanical, chemical and thermal stability and can be used as an antireflective coating, in structures requiring a developed surface-photovoltaics, supercapacitors, catalysts, and antibacterial surfaces.

Efficient degradation of polystyrene microplastic pollutants in soil by dielectric barrier discharge plasma.

In this study, the atmospheric dielectric barrier discharge (DBD) plasma was proposed for the degradation of polystyrene microplastics (PS-MPs) for the first time, due to its ability to generate reactive oxygen species (ROS). The local temperature in plasma was found to play a crucial role, as it enhanced the degradation reaction induced by ROS when it exceeded the melting temperature of PS-MPs. Factors including applied voltage, air flow rate, and PS-MPs concentration were investigated, and the degradation products were analyzed. High plasma energy and adequate supply of ROS were pivotal in promoting degradation. At 20.1 kV, the degradation efficiency of PS-MPs reached 98.7% after 60 min treatment, with gases (mainly COx, accounting for 96.4%) as the main degradation products. At a concentration of 1 wt%, the PS-MPs exhibited a remarkable conversion rate of 90.6% to COx, showcasing the degradation performance and oxidation degree of this technology. Finally, the degradation mechanism of PS-MPs combined with the detection results of ROS was suggested. This work demonstrates that DBD plasma is a promising strategy for PS-MPs degradation, with high energy efficiency (8.80 mg/kJ) and degradation performance (98.7% within 1 h), providing direct evidence for the rapid and comprehensive treatment of MP pollutants.

Application of traceable calibration for gaseous oxidized mercury in air.

BACKGROUND: The current speciation methods for mercury (Hg) measurements are fraught with considerable uncertainty, from sample collection to calibration. High reactivity of gaseous oxidized Hg (GOM) species and their ultra-trace level presence makes them difficult to sample and calibrate. Given that improper calibration may lead to measurement biases, reliable and metrologically traceable calibration methods are required for accurately quantifying GOM in air. In the present study, we applied the recently developed calibration method based on non-thermal plasma oxidation of elemental Hg, to a commercially available Hg air speciation system for actual environmental measurements of GOM for the first time. RESULTS: Hg species such as HgO, HgCl2, and HgBr2 were produced with trace amounts of reactant gases (oxygen and electrolytically produced chlorine and bromine) and the production was driven by plasma-assisted oxidation. The plasma oxidation efficiency of elemental Hg with oxygen was 98.5 ± 7.5 % (k = 2), while that for chlorine and bromine was 96.8 ± 6.9 % (k = 2) and 97.4 ± 9.6 % (k = 2), respectively. The calibration method was tested against the internal permeation (Hg0) source of the Tekran 2537B Hg analyzer on-field by loading HgO to different KCl-coated denuders using the plasma. GOM concentrations were measured using the Tekran speciation system. With internal calibration, concentrations were up to 9.1 % lower than those in plasma calibration, thereby emphasizing the importance of the calibration strategy. Measurement uncertainty (k = 2) further emphasizes this distinction. Internal calibration measurement uncertainty was 36.8 %, while plasma calibration boasted lower uncertainty at 13.8 %. SIGNIFICANCE: The non-thermal plasma calibration strategy, as a unique and discrete calibration method traceable to the NIST SRM 3133 for ambient air GOM measurements, provide a higher level of confidence in the accuracy of GOM measurements with several advantages over other methods. Calibrations at extreme low concentrations (<100 pg) are possible with this method relevant to ambient air GOM concentrations.

Unraveling Exclusive In-Plasma Initiated Oxidation Processes Occurring at Polymeric Surfaces upon O2 Admixtures to Medium Pressure Ar and N2 DBD Treatments.

Polymeric surfaces have been increasingly plasma-activated to adopt adequate chemistries, enabling their use in different applications. An unavoidable surface oxygen insertion upon exposure to non-oxygen-containing plasmas was always observed and mainly attributed to in-plasma oxidation stemming from O2 impurities in plasma reactors. Therefore, this work investigates exclusive in-plasma oxidation processes occurring on polyethylene surfaces by purposely admixing different O2 concentrations to medium-pressure Ar and N2 dielectric barrier discharges (base pressure: 10-7 kPa). Hence, distinctive optical emission spectroscopy and in-situ X-ray photoelectron spectroscopy (XPS) data were carefully correlated. Pure N2 discharge triggered an unprecedented surface incorporation of large nitrogen (29%) and low oxygen (3%) amounts. A steep rise in the O-content (10%) at the expense of nitrogen (15%) was detected upon the addition of 6.2 × 10-3% of O2 to the feed gas. When the added O2 exceeded 1%, the N content was completely quenched. Around 8% of surface oxygen was detected in Ar plasma due to high-energy Ar metastables creating more surface radicals that reacted with O2 impurities. When adding only 6.2 × 10-3% of O2 to Ar, the surface O content considerably increased to 12%. Overall, in-plasma oxidation caused by O2 impurities can strikingly change the surface chemistry of N2 and Ar plasma-treated polymers.

Luminal Surface Plasma Treatment of Closed Cylindrical Microchannels: A Tool toward the Creation of On-Chip Vascular Endothelium.

On-chip vascular microfluidic models provide a great tool to study aspects of cardiovascular diseases in vitro. To produce such models, polydimethylsiloxane (PDMS) has been the most widely used material. For biological applications, its hydrophobic surface has to be modified. The major approach has been plasma-based surface oxidation, which has been very challenging in the case of channels enclosed within a microfluidic chip. The preparation of the chip combined a 3D-printed mold with soft lithography and commonly available materials. We have introduced the high-frequency low-pressure air-plasma surface modification of seamless channels enclosed within a PDMS microfluidic chip. The plasma treatment modified the luminal surface more uniformly than in previous works. Such a setup enabled a higher degree of design freedom and a possibility of rapid prototyping. Further, plasma treatment in combination with collagen IV coating created a biomimetic surface for efficient adhesion of vascular endothelial cells as well as promoted long-term cell culture stability under flow. The cells within the channels were highly viable and showed physiological behavior, confirming the benefit of the presented surface modification.

Multifaceted Structurally Coloured Materials: Diffraction and Total Internal Reflection (TIR) from Nanoscale Surface Wrinkling.

We investigate the combined effects of surface diffraction and total internal reflection (TIR) in the design of 3-dimensional materials exhibiting distinct structural colour on various facets. We employ mechanical wrinkling to introduce surface diffraction gratings (from the nano to the micron scales) on one face of an elastomeric rectangular parallelepiped-shaped slab and explore the roles, in the perceived colours, of wrinkling pattern, wavelength, the directionality of incident light and observation angles. We propose a simple model that satisfactorily accounts for all experimental observations. Employing polydimethylsiloxane (PDMS), which readily swells in the presence of various liquids and gases, we demonstrate that such multifaceted colours can respond to their environment. By coupling a right angle triangular prism with a surface grating, we demonstrate the straightforward fabrication of a so-called GRISM (GRating + prISM). Finally, using a range of examples, we outline possibilities for a predictive material design using multi-axial wrinkling patterns and more complex polyhedra.

Speciation of Oxygen Functional Groups on the Carbon Support Controls the Electrocatalytic Activity of Cobalt Oxide Nanoparticles in the Oxygen Evolution Reaction.

The effective use of the active phase is the main goal of the optimization of supported catalysts. However, carbon supports do not interact strongly with metal oxides, thus, oxidative treatment is often used to enhance the number of anchoring sites for deposited particles. In this study, we set out to investigate whether the oxidation pretreatment of mesoporous carbon allows the depositing of a higher loading and a more dispersed cobalt active phase. We used graphitic ordered mesoporous carbon obtained by a hard-template method as active phase support. To obtain different surface concentrations and speciation of oxygen functional groups, we used a low-temperature oxygen plasma. The main methods used to characterize the studied materials were X-ray photoelectron spectroscopy, transmission electron microscopy, and electrocatalytic tests in the oxygen evolution reaction. We have found that the oxidative pretreatment of mesoporous carbon influences the speciation of the deposited cobalt oxide phase. Moreover, the activity of the electrocatalysts in oxygen evolution is positively correlated with the relative content of the COO-type groups and negatively correlated with the C═O-type groups on the carbon support. Furthermore, the high relative content of COO-type groups on the carbon support is correlated with the presence of well-dispersed Co3O4 nanoparticles. The results obtained indicate that to achieve a better dispersed and thus more catalytically active material, it is more important to control the speciation of the oxygen functional groups rather than to maximize their total concentration.

Dielectric barrier discharge plasma for the remediation of microplastic-contaminated soil from landfill.

The huge amount of plastic waste accumulated in landfills has caused serious microplastic (MP) pollution to the soil environment, which has become an urgent issue in recent years. It is challenging to deal with the non-biodegradable MP pollutants in actual soil from landfills. In this study, a coaxial dielectric barrier discharge (DBD) system was proposed to remediate actual MP-contaminated landfill soil due to its strong oxidation capacity. The influence of carrier gas type, applied voltage, and air flow rate was investigated, and the possible degradation pathways of MP pollutants were suggested. Results showed the landfill soil samples contained four common MP pollutants, including polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyvinyl chloride (PVC) with sizes ranging from 50 to 1500 µm. The MP pollutants in the soil were rapidly removed under the action of reactive oxygen species (ROS) generated by DBD plasma. Under the air flow rate of 1500 mL min-1, the maximum remediation efficiency represented by mass loss reached 96.5% after 30 min treatment. Compared with nitrogen, when air was used as the carrier gas, the remediation efficiency increased from 41.4% to 81.6%. The increased applied voltage from 17.5 to 24.1 kV could also promote the removal of MP contaminants. Sufficient air supply was conducive to thorough removal. However, when the air flow rate reached 1500 mL min-1 and continued to rise, the final remediation efficiency would be reduced due to the shortened residence time of ROS. The DBD plasma treatment proposed in this study showed high energy efficiency (19.03 mg kJ-1) and remediation performance (96.5%). The results are instructive for solving MP pollution in the soil environment.

Promotion of bone formation and antibacterial properties of titanium coated with porous Si/Ag-doped titanium dioxide.

Implant materials are mainly used to repair and replace defects in human hard tissue (bones and teeth). Titanium (Ti) and Ti alloys are widely used as implant materials because of their good mechanical properties and biocompatibilities, but they do not have the ability to induce new bone formation and have no antibacterial properties. Through surface modification, Ti and its alloys have certain osteogenic and antibacterial properties such that Ti implants can meet clinical needs and ensure integration between Ti implants and bone tissue, and this is currently an active research area. In this study, bioactive Si and Ag were introduced onto a Ti surface by plasma oxidation. The surface morphology, structure, elemental composition and valence, surface roughness, hydrophilicity and other physical and chemical properties of the coating were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), a profiler and a contact angle meter (CA). Adhesion and extensions of osteoblasts on the surface of the material were observed by scanning electron microscopy, and mineralization of osteoblasts on the surface of the material were observed by alizarin red staining. The antibacterial properties of the material were tested by culturing Staphylococcus aureus on the surface of the material. The osteogenic properties of Ti implants with porous Si/Ag TiO2 (TCP-SA) coatings were evaluated with in vivo experiments in rats. The results showed that Si and Ag were successfully introduced onto the Ti surface by plasma oxidation, and doping with Si and Ag did not change the surface morphology of the coating. The osteoblasts showed good adhesion and extension on the surfaces of Si/Ag coated samples, and the porous Si/Ag TiO2 coating promoted cell proliferation and mineralization. The bacterial experiments showed that the porous TiO2 coatings containing Si/Ag had certain antibacterial properties. The animal experiments showed that Si/Ag-coated Ti implants promoted integration between the implants and the surrounding bone. It was concluded that the porous Si/Ag TiO2 coating on the Ti surface had good osteogenic and antibacterial properties and provides an optimal strategy for improving the osteogenic and antibacterial properties of Ti implants.

Steep Subthreshold Swing and Enhanced Illumination Stability InGaZnO Thin-Film Transistor by Plasma Oxidation on Silicon Nitride Gate Dielectric.

In this paper, an InGaZnO thin-film transistor (TFT) based on plasma oxidation of silicon nitride (SiNx) gate dielectric with small subthreshold swing (SS) and enhanced stability under negative bias illumination stress (NBIS) have been investigated in detail. The mechanism of the high-performance InGaZnO TFT with plasma-oxidized SiNx gate dielectric was also explored. The X-ray photoelectron spectroscopy (XPS) results confirmed that an oxygen-rich layer formed on the surface of the SiNx layer and the amount of oxygen vacancy near the interface between SiNx and InGaZnO layer was suppressed via pre-implanted oxygen on SiNx gate dielectric before deposition of the InGaZnO channel layer. Moreover, the conductance method was employed to directly extract the density of the interface trap (Dit) in InGaZnO TFT to verify the reduction in oxygen vacancy after plasma oxidation. The proposed InGaZnO TFT with plasma oxidation exhibited a field-effect mobility of 16.46 cm2/V·s, threshold voltage (Vth) of -0.10 V, Ion/Ioff over 108, SS of 97 mV/decade, and Vth shift of -0.37 V after NBIS. The plasma oxidation on SiNx gate dielectric provides a novel approach for suppressing the interface trap for high-performance InGaZnO TFT.

Nanoscale-Precision Removal of Copper in Integrated Circuits Based on a Hybrid Process of Plasma Oxidation and Femtosecond Laser Ablation.

Copper (Cu) is the main interconnect conductor for integrated circuits (IC), and its processing quality is very important to device performance. Herein, a hybrid process of plasma oxidation and femtosecond laser (fs-laser) ablation was proposed for the nanoscale precision removal of Cu in integrated circuits. In this hybrid process, the surface layer of Cu was oxidized to the copper oxide by plasma oxidation, and then the fs-laser with a laser fluence lower than the Cu ablation threshold was used to remove the copper oxide without damaging the underlying Cu. Theoretically, the surface temperature evolutions of Cu and copper oxide under the femtosecond laser were studied by the two-temperature model, and it was revealed that the ablation threshold of copper oxide is much lower than that of Cu. The experimental results showed that the ablation threshold of copper oxide is lower than that of Cu, which is consistent with the theoretical analysis. Using the hybrid process, a surface roughness of 3 nm and a removal accuracy of 4 nm were obtained in the process of Cu film processing, which were better than those obtained by fs-laser ablation. This demonstrated that the hybrid process has good application potential in the field of copper micromachining.

Effect of surface modification of Ti-6Al-4V alloy by electron cyclotron resonance plasma oxidation.

Ti-6Al-4V alloy is used as biomaterials for dental and orthopedic implants because of their excellent biocompatibilities and mechanical properties. However, it is unclear that electron cyclotron resonance (ECR) plasma oxidation can create the oxide films on Ti-6Al-4V alloy surface, and this technique improves the ability of its osseointegration. The purpose of this study was to investigate the characteristics and calcification ability of the oxide films. X-ray diffraction (XRD) peaks of rutile phase were intensified with increasing the temperature. Scanning electron microscopy (SEM) images showed a crater-like structure, and bonding strengths between the substrate and oxide film reached a maximum at 400°C. Calcium phosphate (CaP) compounds after calcification process were identified as octacalcium phosphate (OCP) and precipitation amount was maximized at 400°C. The results suggested that the altered surface of Ti-6Al-4V alloy by ECR plasma oxidation might have the potential of accelerating the ability of its osseointegration through enhancement of OCP.

Electrochemical sensor using gold nanoparticles and plasma pretreated graphene based on the complexes of calcium and Troponin C to detect Ca2+ in meat.

A simple electrochemical sensor was developed to determine the concentration of Ca2+ in meat. Graphene was treated with oxygen plasma for 10 s and 30 s comparing with the pristine graphene. Through analyzing morphology and chemical composition, the graphene with the lowest defect density was chosen to mix with bovine serum albumin molecule-functionalized gold nanoparticles. It was interesting that only a few gold nanoparticles were trapped in the graphene with 10 s plasma treatment. Then, under the optimal condition measured, the limit of detection was detected as 3.9 × 10-8 M with a linear relationship from 5 × 10-8 to 3 × 10-4 M. Finally, the proposed electrochemical method was applied to detect Ca2+ in the pork sample with stability and reproducibility verified by parallel detections. Thus, the proposed method demonstrates its potential for effectively detecting Ca2+ in meat and prominently reduces time consumption on operations and pretreatments.

Combination of plasma oxidation process with microbial fuel cell for mineralizing methylene blue with high energy efficiency.

Plasma advanced oxidation process (PAOP) has great ability to break recalcitrant pollutants into small molecular compounds but suffers from poor performance and low energy efficiency for mineralizing dyeing pollutants. Combining advanced oxidation process with biodegradation process is an effective strategy to improve mineralization performance and reduce cost. In this study, a combined process using PAOP as pre-treatment followed by microbial fuel cell (MFC) treatment was investigated to mineralize methylene blue (MB). The PAOP could degrade MB by 97.7%, but only mineralize MB by 23.2% under the discharge power of 35 W for 10 min. Besides, BOD5/COD ratio of MB solution raised from 0.04 to 0.38 while inhibition on E. coli growth decreased from 85.5% to 28.3%. The following MFC process increased MB mineralization percentage to 63.0% with a maximum output power density of 519 mW m-2. The combined process achieved a mineralization energy consumption of 0.143 KWh gTOC-1 which was only 41.8% of that of PAOP. FT-IR, UV-vis and pH variation demonstrated that PAOP could break the aromatic and heterocyclic structures in MB molecule to form organic acids. Possible degradation pathways of MB were accordingly proposed based on LC-MS, GC-MS, and density functional theory calculation.

Non-thermal plasma oxidation of Cu(II)-EDTA and simultaneous Cu(II) elimination by chemical precipitation.

Cu2+ readily complexes with ethylenediaminetetraacetic acid (EDTA) to form a heavy metal complex (Cu-EDTA) that is typical in the effluents from mining and electroplating industries. It was difficult for the classical alkaline precipitation method to eliminate the heavy metal complex due to the strong bonding ability between Cu(II) and EDTA. Cu(II) release and removal performance after Cu-EDTA decomplexation in a non-thermal plasma oxidation system was carried out in this study. The removal process was characterized by chemical oxygen demand, total organic carbon, atomic force microscopy, and electroconductivity analysis. The toxicity effect of the treated Cu-EDTA solution was also tested by photobacterium bioassay. The experimental results showed that 80.2% of Cu was released and removed within 60 min of the non-thermal plasma treatment/alkaline precipitation. Relatively higher energy input, lower Cu-EDTA concentration, and acidic conditions were necessary to obtain greater Cu release and removal performance, and there existed an appropriate air flow rate for high-efficient Cu release and removal. O2-, OH, 1O2, and O3 were the main active substances leading to Cu2+ release. Its residual toxicity to P.phosphoreum sp.-T3 was significantly reduced after treatment.

Micrometric Wrinkled Patterns Spontaneously Formed on Hydrogel Thin Films via Argon Plasma Exposure.

The generation of microstructured patterns on the surface of a specific polymeric material could radically improve their performance in a particular application. Most of the interactions with the environment occur at the material interface; therefore, increasing the exposed active surface considerably improves their range of application. In this article, a simple and reliable protocol to form spontaneous wrinkled patterns using a hydrogel layer is reported. For this purpose, we took advantage of the doctor blade technique in order to generate homogenous films over solid substrates with controlled thickness and large coverage. The hydrogel wrinkle formation involves a prepolymerization step which produces oligomers leading to a solution with increased viscosity, enough for doctor blade deposition. Subsequently, the material was exposed to vacuum and plasma to trigger wrinkled pattern formation. Finally, a UV-polymerization treatment was applied to fix the undulations on top. Interestingly, the experimental parameters allowed us to finely tune the wrinkle characteristics (period, amplitude, and orientation). For this study, two main aspects were explored. The first one is related to the role of the substrate functionalization on the wrinkle formation. The second study correlates the deswelling time and its relationship with the dimensions and distribution of the wrinkle pattern. In the first batch, four different 3-(trimethoxysilyl)propyl methacrylate (TSM) concentrations were used to functionalize the substrate in order to enhance the adhesion between hydrogel film and the substrate. The wrinkles formed were characterized in terms of wrinkle amplitude, wavelength, pattern roughness, and surface Young modulus, by using AFM in imaging and force spectroscopy modes. Moreover, the chemical composition of the hydrogel film cross-section and the effect of the plasma treatment were analyzed with confocal Raman spectroscopy. These results demonstrated that an oxidized layer was formed on top of the hydrogel films due to the exposure to an argon plasma.

A DLC-Punch Array to Fabricate the Micro-Textured Aluminum Sheet for Boiling Heat Transfer Control.

A diamond-like carbon (DLC) film, coated on an SKD11 (alloy tool steel) substrate, was shaped by plasma oxidation to form an assembly of DLC macro-pillars and to be used as a DLC-punch array that is micro-embossed into aluminum sheets. First, the SKD11 steel die substrate was prepared and DLC-coated to have a film thickness of 10 µm. This DLC coating worked as a punch material. The two-dimensional micro-patterns were printed onto this DLC film by maskless lithography. The unprinted DLC films were selectively removed by plasma oxidation to leave the three-dimensional DLC-punch array on the SKD11 substrate. Each DLC punch had a head of 3.5 µm × 3.5 µm and a height of 8 µm. This DLC-punch array was fixed into the cassette die set for a micro-embossing process using a table-top servo-stamper. Furthermore, through numerically controlled micro-embossing, an alignment of rectangular punches was transcribed into a micro-cavity array in the aluminum sheet. The single micro-cavity had a bottom surface of 3.2 µm × 3.2 µm and an average depth of 7.5 µm. A heat-transfer experiment in boiling water was also performed to investigate the effect of micro-cavity texture on bubbling behavior and the boiling curve.

The Study on the Overall Plasma Electrolytic Oxidation for 6061-7075 Dissimilar Aluminum Alloy Welded Parts Based on the Dielectric Breakdown Theory.

Electrical connection of dissimilar metals will lead to galvanic corrosion. Therefore, overall surface treatment is necessary for the protection of dissimilar metal welded parts. However, serious unbalanced reactions may occur during overall surface treatment, which makes it difficult to prepare integral coating. In this paper, an overall ceramic coating was fabricated by plasma electrolytic oxidation to wrap the 6061-7075 welded part integrally. Moreover, the growth mechanism of the coating on different areas of the welded part was studied based on the dielectric breakdown theory. The reaction sequence of each area during the treatment was verified through specially designed dielectric breakdown tests. The results showed that the high impedance overall of ceramic coating can inhibit the galvanic corrosion of the 6061-7075 welded part effectively.

Binder-Free N- and O-Rich Carbon Nanofiber Anodes for Long Cycle Life K-Ion Batteries.

Carbon nanofibers produced by electrospinning of polyacrylonitrile polymer and subsequent carbonization were tested as freestanding potassium-ion anodes. The effect of oxygen functionalization on K-ion carbon anode performance was tested for the first time via plasma oxidation of prepared carbon nanofibers. The produced materials exhibited exceptional cycling stability through the amorphous carbon structuring and one-dimensional architecture accommodating significant material expansion upon K+ intercalation, resulting in a stable capacity of 170 mAh g-1 after 1900 cycles at 1C rate for N-rich carbon nanofibers. Excellent rate performance of 110 mAh g-1 at 10C rate, as compared to 230 mAh g-1 at C/10 rate, resulted from the K-ion surface storage mechanism and the increased K+ solid diffusion coefficient in carbon nanofibers as compared to graphite. Plasma oxidation treatment augmented surface storage of K+ by oxygen functionalities but increased material charge transfer resistance as compared to N-rich carbon fibers. Ex situ characterization revealed that the one-dimensional structure was maintained throughout cycling, despite the increase in graphitic interlattice spacing from 0.37 to 0.46 nm. The carbon nanofibers demonstrate great potential as an anode material for potassium-ion batteries with superior cycling stability and rate capability over previously reported carbon materials.

Removal of toluene by sequential adsorption-plasma oxidation: Mixed support and catalyst deactivation.

A sequential adsorption-plasma oxidation system was used to remove toluene from simulated dry air using γ-Al2O3, HZSM-5, a mixture of the two materials or their supported Mn-Ag catalyst as adsorbents under atmospheric pressure and room temperature. After 120min of plasma oxidation, γ-Al2O3 had a better carbon balance (∼75%) than HZSM-5, but the CO2 yield of γ-Al2O3 was only ∼50%; and there was some desorption of toluene when γ-Al2O3 was used. When a mixture of HZSM-5 and γ-Al2O3 with a mass ratio of 1/2 was used, the carbon balance was up to 90% and 82% of this was CO2. The adsorption performance and electric discharge characteristics of the mixed supports were tested in order to rationalize this high COx yield. After seven cycles of sequential adsorption-plasma oxidation, support and Mn-Ag catalyst deactivation occurred. The support and catalyst were characterized before and after deactivation by SEM, a BET method, XRD, XPS and GC-MS in order to probe the mechanism of their deactivation. 97.6% of the deactivated supports and 76% of the deactivated catalysts could be recovered by O2 temperature-programmed oxidation.