Modification of acidity of Mo-Fe/HZSM-5 zeolite via argon plasma treatment

The NH₃-TPD characterization was conducted to confirm that the acidity of Mo-Fe/HZSM-5 zeolite could be selectively modified via the glow discharge plasma treatment. The plasma catalyst treatment could totally change the distribution of aromatic products with higher methane conversion compared to the untreated catalyst. Some polycyclic aromatics such as anthracene, pyrene and phenanthrene were also produced over the plasma treated catalyst, in addition to benzene, toluene and naphthalene, which were normally obtained over the untreated catalyst.     

Al-MCM-41 supported palladium catalyst for methane combustion: Effect of the preparation methodologies

This work aimed at elucidating the beneficial effect of plasma treatment on the catalytic performance of palladium (Pd) catalysts in methane combustion with the ordered mesoporous molecular sieve Al-MCM-41 as the model support. The plasma treated Pd/Al-MCM-41 catalyst exhibited a higher initial activity and a better stability in comparison with the untreated counterpart catalyst. To clarify the plasma effect, the catalysts were characterized by N₂ sorption analysis, X-ray diffraction (XRD), temperature-programmed desorption of ammonia (NH₃-TPD), pyridine adsorption-infrared spectroscopy (Py-IR), high resolution-transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (CH₄-TPR) experiments. The results obtained confirmed that palladium oxide (PdO) was the active phase. Plasma treatment enhanced the acidity of catalyst and improved the dispersion of PdO particles, which lead to a higher initial activity. The better stability for plasma treated Pd-based catalyst was proved to be closely related to the stronger interaction between palladium oxide and the molecular sieve support. In addition, the sintering of PdO particles over the plasma treated catalyst was not significant during the stability test. These findings may provide useful guidelines for further catalyst design for methane combustion.     

Enhancement of catalytic activity of Au/TiO2 by thermal and plasma treatment

A significant enhancement in the catalytic activity of Au/TiO₂ in CO oxidation and preferential oxidation reaction by creating the active sites on the catalyst surface by thermal treatment as well as by producing small gold particles by plasma treatment has been studied. Au/TiO₂ catalyst (Au (1 wt%) supported on TiO₂) was prepared by conventional deposition-precipitation method with NaOH (DP NaOH) followed by washing, drying and calcination in air at 400 °C for 4 h. Thermal treatment of Au/TiO₂ was carried out at 550 °C under 0.05 mTorr. A small amount of Au/TiO₂ catalyst was taken from the untreated and thermally treated Au/TiO₂ and both kinds of catalysts were treated with plasma sputtering at room temperature. The activity of the catalysts has been examined in the reaction of CO oxidation and preferential oxidation (PROX) at 25–250 °C. Thermally treated Au/TiO₂ showed better catalytic activity as compared to the untreated catalyst. There is also an additional enhancement in the catalytic activity due to plasma sputtering on the both kinds of catalysts. Thermally treated Au/TiO₂ followed by plasma sputtering Au/TiO₂ showed higher conversion rates for CO oxidation reaction compared with untreated, thermally treated and plasma sputtered Au/TiO₂ catalysts. It may be concluded that the enhancement of catalytic activity of thermally treated Au/TiO₂ followed by plasma sputtering is owing to the generation of active sites such as oxygen vacancies/defects in TiO₂ support using thermal treatment as well as by producing small gold particles using plasma treatment.     

The effect of plasma pre-treatment of carbon used as a Pt catalyst support for methanol electrooxidation

Vulcan XC-72 carbon black for use as a catalyst support was treated in three different plasma atmospheres, H₂, Ar and O₂. The results showed that the microstructure and surface functional groups were significantly changed after plasma treatment. Pt/C catalysts were prepared by chemical reduction of H₂PtCl₆ with HCHO and those with untreated and plasma treated carbon black supports were characterized and tested for methanol electrooxidation. TEM showed that the platinum nanoparticles on H₂ and Ar plasma treated carbon were uniform and well distributed. Those on untreated carbon were uniform in most regions but coalesced in others. On O₂ plasma treated carbon agglomeration of the platinum nanoparticles was significant. XRD showed that the catalysts were composed of face-centered cubic Pt nanoparticles and XPS showed that they were metallic with no oxides present. Cyclic voltammetry and chronoamperometry were used to study methanol electrooxidation on the Pt/C catalysts in a solution of 0.5 M H₂SO₄ + 0.5 M CH₃OH, and showed that the catalytic activity those using H₂ and Ar plasma treated carbon was higher than for the untreated one. Catalysts supported by O₂ plasma treated carbon showed no catalytic activity. The treatment atmosphere of carbon therefore had a large effect on the catalyst performance, with the H₂ plasma being the best.     

Post‐Plasma Catalysis for Methane Partial Oxidation to Methanol: Role of the Copper‐Promoted Iron Oxide Catalyst

Methane‐air partial oxidation to methanol over a ceramic‐supported Fe₂O₃‐CuO catalyst was investigated in a post‐plasma catalytic reactor at ambient conditions. The multicomponent catalyst exerted a better catalytic performance than the monocomponent Fe₂O₃ catalyst. Characterization of the catalysts by XPS showed that incorporation of the CuO additive to a Fe₂O₃‐based catalyst resulted in an increase of lattice oxygen in the surface of the catalyst which facilitated selective methane oxidation. Hydrogen temperature‐programmed reduction revealed that addition of the CuO promoter could improve the reduction performance of the catalyst. Moreover, this catalyst showed excellent stability and resistance against carbon deposition in the extended reactions while maintaining catalytic activity. A post‐plasma catalytic mechanism is proposed with three main pathways to methanol synthesis.     

介质阻挡放电技术再生Pd/AC催化剂的机理探讨

利用介质阻挡放电对失活钯炭催化剂(Pd/AC)进行再生,并通过催化臭氧氧化硝基苯反应评价再生后催化剂的活性。运用扫描电镜(SEM)、比表面积测定(BET)、热重分析(TG)等测定手段对Pd/AC进行表征;并对放电过程进行臭氧产量测定和等离子体发射光谱诊断,分析了Pd/AC催化剂再生的机理。结果表明,催化剂经放电处理30 min后再生率为95%;利用在最优条件下再生的Pd/AC进行催化臭氧氧化反应,硝基苯的降解率为87%;再生过程中臭氧贡献率仅为25.6%,表明放电过程中产生的强氧化性自由基是促使催化剂再生的主要因素。     

A Facile and Effective Method for the Distribution of Mo/HZSM-5 Catalyst Active Centers

Post-steaming treatment of Mo/HZSM-5 catalysts results in more molybdenum species migrating into and residing in the HZSM-5 zeolite channels. This is confirmed by XRF and XPS measurements. ¹H MAS NMR and ²⁹Si MAS NMR also demonstrate that the number of free Brönsted acid sites decreases in the Mo/HZSM-5 catalysts that underwent post-steaming treatment, compared to untreated Mo/HZSM-5 catalysts. As a result, the deactivation rate constant (k _d) on the Mo/HZSM-5 catalyst after post-steaming treatment for 0.5h is much smaller, and the catalyst therefore shows remarkable stability in the probe reaction of methane dehydro-aromatization. The results suggest that a more beneficial bi-functional balance between active Mo species for methane activation and acid sites for the following aromatization is developed over those Mo/HZSM-5 catalysts that have experienced post-steaming treatment for 0.5h, in comparison with the untreated Mo/HZSM-5 catalysts.     

Synthesis and Characterization of Dealuminated Ultra-Stable Zeolite Y Supported Cesium Salt of Phosphotungstic Acid for the Esterification of Acrylic Acid with Butanol

Wastewater containing 10–20 wt% of acrylic acid (AA) is released from petrochemical industries during the manufacture of AA, acrylic ester, water-soluble resin and flocculants. This untreated wastewater could have detrimental effects on the environment due to its high chemical oxygen demand. Heterogeneously catalyzed esterification of this wastewater with alcohol in a reactive distillation column (RDC) could be a promising treatment method to recover AA from the wastewater. Considering the importance of a water-resistant catalyst in this method, this work has synthesized and tested a potential catalyst, cesium salt of phosphotungstic acid (Cs_xH_3-xPW) supported on dealuminated ultra-stable zeolite Y (DUSY), for the esterification of AA with 1-butanol (BuOH). The catalysts were synthesized through impregnation using various solvents, DUSY with different compositions of silicon (Si) to aluminium (Al), compositions of cesium (Cs) and precursor loadings. The 30%(Cs_1.5(IWI)H_1.5PW_IWI)_DEE/DUSY₆₀ was the best catalyst, giving reasonably high yield and low leaching. The BA yield obtained was 9.53% at 80°C, stirring speed of 500 rpm, catalyst loading of 10 wt% and M_AA:BuOH of 1:3 for 4 h.     

CO Adsorbed Infrared Spectroscopy Study of Ni/Al2O3 Catalyst for CO2 Reforming of Methane

CO adsorbed infrared spectroscopy study was conducted in this work in order to better understand the significantly improved anti-coke performance of Ni/Al₂O₃ catalyst obtained via argon glow discharge plasma treatment. The present study revealed a significant decrease of linear to bridge (L/B) adsorbed CO for glow discharge plasma treated Ni/Al₂O₃, compared to that for untreated Ni/Al₂O₃, indicating an enhancement of close packed plane concentration. This structure change leads to lower methane turnover frequency (TOF) and better balance of carbon formation-gasification, resulting in better anti-coke property of Ni/Al₂O₃ for CO₂ reforming of methane.     

Hydrogen Production through Catalytic Water Splitting Using Liquid-Phase Plasma over Bismuth Ferrite Catalyst

This study examined the H₂ production characteristics from a decomposition reaction using liquid-phase plasma with a bismuth ferrite catalyst. The catalyst was prepared using a sol–gel reaction method. The physicochemical and optical properties of bismuth ferrite were analyzed. H₂ production was carried out from a distilled water and aqueous methanol solution by direct irradiation via liquid-phase plasma. The catalyst absorbed visible-light over 610 nm. The measured bandgap of the bismuth ferrite was approximately 2.0 eV. The liquid-phase plasma emitted UV and visible-light simultaneously according to optical emission spectrometry. Bismuth ferrite induced a higher H₂ production rate than the TiO₂ photocatalyst because it responds to both UV and visible light generated from the liquid-phase plasma.     

Complementary effect of plasma–catalysis hybrid system on methane complete oxidation over non-PGM catalysts

Methane complete oxidation reaction was carried out in a non-thermal plasma (dielectric barrier discharge) quartz tube reactor where both plasma and catalyst were combined into one in-plasma catalysis system. In plasma only condition, the CO selectivity was maintained at high value (~ 50%) until the temperature reached about 200 °C. In the presence of both plasma and catalyst, however, methane was oxidized even at room temperature mostly to CO₂ with low CO selectivity over certain non-PGM catalyst like Co₁Ni₁O_x. Hence, methane complete oxidation reaction proceeded at much lower temperature similar to PGM catalyst such as Pd/Al₂O₃, while maintaining low CO selectivity.     

介质阻挡放电等离子体处理载体对CO甲烷化Ni/SiO2催化剂性能的改进

以经介质阻挡放电等离子体处理的SiO₂为载体,用浸渍法制备了Ni/SiO₂催化剂,并进行了CO甲烷化反应评价。与载体未经处理的常规Ni/SiO₂催化剂相比,载体经处理的催化剂在400℃下的CO与H₂转化率均提高了约6%,且在经700℃烧结6 h后,活性仍高于常规催化剂。XRD、TEM和H₂-TPR结果表明,载体经处理的催化剂,Ni颗粒粒径更小、粒径分布更集中,Ni与SiO₂之间的相互作用更强,证明等离子体处理使SiO₂更有利于促进Ni的分散。     

Effects of ceria in CO2 reforming of methane over Ni/calcium hydroxyapatite

In CO₂ reforming of methane over a calcium hydroxyapatite-supported nickel catalyst, the carbon deposition occurred more severely with increase of the methane partial pressure and at temperatures below about 1,000 K. The effects of ceria that was added as a promoter to the nickel catalyst were investigated. It was observed that the ceria not only enhanced the catalyst stability but also increased the activity, and this is considered owing to the oxygen storage capacity of ceria. The TGA analysis demonstrated that the ceria promoted the removal of the deposited carbon. The optimum Ce/Ni mole ratio was ca. 0.3/2.5. The deposited carbon could easily be removed by oxygen treatment at 1,023 K and the catalytic activity could be restored.     

The removal of encapsulated catalyst particles from carbon nanotubes using molten salts

A novel method, using molten salts, is described for the removal of encapsulated nickel catalyst particles from multi-walled carbon nanotubes. The multi-walled carbon nanotubes, synthesised by the decomposition of methane and hydrogen over a NiO/SiO₂ aerogel catalyst, were treated in a LiCl-KCl eutectic molten salt and subsequently by hydrochloric acid to remove the nickel catalyst particles. The influence of the molten salt treatment on the microstructure of the carbon nanotubes was investigated by XRD, SEM and TEM analyses. The molten salt treatment promoted uncapping of the carbon capsules and the formation of strip-shaped carbon fragments. It was found that the hydrochloric acid treatment could then remove the nickel particles from the broken carbon capsules which was not possible prior to the molten salt treatment. The stability of carbon nanotubes in the molten salt is closely related to their ordered structure.     

Electrical contacts to nitrogen incorporated nanocrystalline diamond films

The effect of surface plasma treatment on the nature of the electrical contact to the nitrogen incorporated nanocrystalline diamond (n-NCD) films is reported. Nitrogen incorporated NCD films were grown in a microwave plasma enhanced chemical vapor deposition (MPECVD) reactor using CH₄ (1%)/N₂ (20%)/Ar (79%) gas chemistry. Raman spectra of the films showed features at ∼ 1140 cm^− 1, 1350 cm^− 1(D-band) and 1560 cm^− 1(G-band) respectively with changes in the bonding configuration of G-band after the plasma treatment. Electrical contacts to both untreated and surface plasma treated films are formed by sputtering and patterning Ti/Au metal electrodes. Ohmic nature of these contacts on the untreated films has changed to non-ohmic type after the hydrogen plasma treatment. The linear current–voltage characteristics could not be obtained even after annealing the contacts. The nature of the electrical contacts to these films depends on the surface conditions and the presence of defects and sp² carbon.     

Preparation of Ni/MgO catalyst for CO2 reforming of methane by dielectric-barrier discharge plasma

A novel plasma-treated Ni/MgO catalyst was prepared by treating coprecipitated NiCO₃–MgCO₃ with dielectric-barrier discharge plasma. The results by XRD, TEM and N₂ adsorption analyses showed that the plasma-prepared Ni/MgO catalyst possessed smaller particle size, enhanced nickel dispersion, and higher specific surface area than a conventionally reduced Ni/MgO catalyst. The plasma-prepared Ni/MgO catalyst also exhibited better catalytic activity for carbon dioxide reforming of methane. More than 20% higher conversions of methane and carbon dioxide were obtained than those over the conventional Ni/MgO catalyst at 700 °C and a space velocity of 96,000 mL/(h?g_cat).     

Plasma-Assisted Diesel Oxidation Catalyst on Bench Scale: Focus on Light-off Temperature and NOx Behavior

The effect of a non-thermal plasma reactor over a commercial Diesel oxidation catalyst (DOC) was investigated. Studies have been focused on the gas treatment efficiency together with lowering light-off temperature when a DOC catalyst was connected downstream to plasma reactor in test bench scale. Experiments have been conducted using multi-DBDs (dielectric barrier discharge) reactor in planar configuration driven by a HV AC generator (11 kV–15 kHz). The specific input energy was set to 57 and 85 J/L. Experiments were performed in gas composition simulating Diesel exhaust. Commercial DOC, monolith-supported Pt–Pd/Al₂O₃, was used at gas hourly space velocities of about 55,000 and 82,000 h^?1. CO and hydrocarbons light-off curves were determined for DOC, plasma, and plasma-DOC systems by temperature programmed surface reaction from 80 to 400 °C. Particular attention has been paid to the gas temperature between the plasma reactor and the DOC. Results show that the plasma-catalyst system provides the lowest light-off temperatures for CO and HCs. Under conditions of this study, light-off temperature improvement by about 57 °C was obtained and the plasma reactor totally oxidized NO to NO₂ at low temperature.     

Comparison of fibroblast and nerve cells response on plasma treated poly (L‐lactide) surface

Plasma technique can easily be used to introduce desired functional groups or chains onto the surface of materials, and so it has a special application to improve the cell affinity of polymers surfaces. The purpose of this study is to elucidate the interaction between the cells and the surface of crystalline poly (L ‐lactide) (PLLA) samples, which were modified using a low‐temperature plasma treatment apparatus. The plasma treatments were carried out in the carbon dioxide (CO₂) gas. The results showed that the contact angle of the samples, which was plasma treated in CO₂ gas, decreased compared with that of the untreated samples. The hydrophilicity increased because of the introduction of oxygen‐containing functional groups onto the PLLA surfaces according to the spectroscopy for chemical analysis. High quantities of ? C? O groups, such as hydroxyl and carboxyl could be in corporate into the surface of PLLA. The surface wettability, topography, and chemistry of treated PLLA samples were characterized by contact angle measurement, scanning electron microscope (SEM), and ATR‐FTIR spectroscopy. The origin and plasma‐treated samples were used to investigate the interaction of two different types of cells namely, B65 glial nervous, and L929 fibroblast cells. The nervous cell response on the PLLA plasma treated in the CO₂ gas were significantly superior to that of the L929 fibroblast cells and untreated one. The surface modification technique used in this study may be applicable to tissue engineering for the improvement of nerve tissue compatibility of polymer and scaffold‐type substrates. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Ar plasma treatment on ZnO–SnO2 heterojunction nanofibers and its enhancement mechanism of hydrogen gas sensing

In this study, ZnO–SnO₂ heterojunction nanofibers were fabricated using electrospinning and treated by Ar plasma. The post treatment demonstrated the ability to regulate adsorbed oxygen of nanofibers and thus affecting the gas sensing performance. The results revealed that the gas sensing performances increased with the increase of plasma treatment time at first, then showed a downward trend. The setting for the best H₂ gas performance was 20 min of plasma treatment, under which the response of the sample was 80% higher and the response time was two thirds shorter than those of the untreated sample. The explanation can be that appropriate plasma treatment can increase the oxygen vacancy on the surface of heterojunction nanofibers as well as the resistance modulation range in the air; however, excessive plasma treatment can result in the reduction of the resistance modulation range in the air by reducing the metal oxide to metal.     

Plasma-catalysis destruction of aromatics for environmental clean-up: Effect of temperature and configuration

A non-thermal, atmospheric pressure, packed-bed plasma reactor has been used to study the effect of temperature on the plasma-catalytic destruction of toluene and benzene in air using two catalyst positions. TiO₂ and γ-Al₂O₃ supports, and Ag (0.5 wt.%) impregnated catalysts of both supports, were used to determine their effects. The reactor (in the one-stage configuration) or the downstream catalyst (in the two-stage arrangement) could be heated to 600 °C and the destruction efficiencies for toluene and benzene were determined. Plasma catalysis is more effective at destroying benzene and toluene than both conventional thermal-catalysis and plasma alone. Toluene is destroyed much more efficiently than benzene, regardless of the temperature of the system and the reactor configuration. A one-stage, plasma-catalysis configuration is found to be more effective at destroying both toluene and benzene than a two-stage configuration. Plasma catalysis offers no advantage over thermal catalysis for destroying both pollutants in the two-stage configuration.