Plasma catalysis. A study of the influence of oxysulfur, SOx• species through the degradation of sulfonated dyes by non-thermal plasma.

This work studied the degradation reaction of sulfonated dyes, indigo carmine, phenol red, and their mixtures by non-thermal plasma (NTP). Interestingly, the degradation rate constant showed a faster process and lower activation energy (Ea) for the dye mixtures than for the degradation reaction of the individual dyes. This unexpected result opened up new opportunities for understanding plasma chemistry and the interaction between reactive species formed by the plasma and the target molecule. As no catalyst or chemical additive was added to the reactor, the decrease in Ea came from a self-synergistic effect (SSE), through the dye molecules fragmentation, which resulted in plasma catalysis. The hypothesis proposed in this work is that oxysulfur (SOx) species are formed by the desulfonation reaction of dyes. The sulfonic groups (SO3) present in the chemical structures of dyes can function as precursors for forming several SOx•- species. Studies based on oxygenated sulfonated species such as SO3•-, SO4•- and SO5•- have been widely applied in advanced oxidative and reductive processes due to their satisfactory efficiency and low cost. Among them, SO4•- is the key reactive species with the best performance in the degradation of pollutants due to its high oxidation potential (E° = 2.60 V). In addition, it is an alternative source of HO• in aqueous media, improving the oxidation reaction. In order to elucidate the SSE, the kinetic process was followed by UV-Vis analysis, and the reactive species, such as alkyl, hydroxyl, and oxy-sulfur radicals were identified by Electron Paramagnetic Resonance. The by-products of the NTP degradation reaction were analyzed by ultrafast liquid chromatography coupled with a mass spectrometer, and a fragmentation route was proposed.

Influence of non-thermal plasma reactor geometry and plasma gas on the inactivation of Escherichia coli in water.

The inactivation of bacteria Escherichia coli (E. coli) by non-thermal plasma (NTP) was investigated using argon, air and 1:1 mixture of air/Ar as plasma gas on five different reactors. The experiments were carried out in triplicate in each reactor, using 60 mL of distilled water pre-inoculated with E.coli. The physical-chemical analysis of pH, conductivity, nitrite, nitrate and temperature were performed soon after of 10 min of NTP treatment. The microbiological analysis of E. coli inactivation was performed using 100 µL samples withdrawn from the plasma reactor after 10 min and compared with the positive and negative control test results. The best performance were achieved whit the NTP reactors working with the upper electrode in the gas phase using 1:1 air/Ar and air as plasma gas. The results are linked with the E. coli inactivation due to membrane rupture by the NTP discharge followed by the attack of the reactive species produced in the solution. The E. coli inactivation was only partial using argon as plasma gas and the direct barrier discharge reactors showed partial inactivation even when air was used as plasma gas.

Reaction Mechanism of the Reduction of Ozone on Graphite.

The kinetics of the ozonation of graphite with different particle sizes (106 µm, G106; 6.20 µm, G6.2) was studied at several temperatures under a flow of O3 diluted in O2. The reaction was first-order with respect to graphite and to the consumption of ozone. X-ray photoelectron spectrum (XPS) showed that the reactions occurring in the solid under steady-state conditions maintain the original stoichiometry, as predicted by the postulated mechanism for SO2. The deoxygenation reaction occurred along with the ozonation reaction at 100 °C. The rate of oxygen elimination in the flow system has the same rate-determining kinetic barrier as ozone insertion. Ozonation and deoxygenation reactions are sequentially related. Ozonation occurs with the insertion of O3, forming a 1,2,3-trioxolane followed by an oxygen transfer that produces a peroxide valence tautomer in equilibrium with 1,3-dicarbonyl, [peroxide ↔ dicarbonyl], and an oxirene that eliminates atomic oxygen. The decarboxylation reaction was studied at 600 °C from the ozonated G106 (ΔG≠ = 83.60 ± 0.08 kcal·mol-1). Total decarboxylation at 600 °C matched the number of moles of CO2 removed and the oxygen content after ozonation, showing that the reduction of ozone on graphite was essentially a clean reduction with no secondary oxidations. When ozonized graphite was heated to 600 °C, only [peroxide ↔ dicarbonyl] species remained in the matrix. The peroxide tautomer isomerized to dioxirane and eliminated CO2 as a dioxicarbene. Total deoxygenation of decarboxylated graphite G106 was obtained by pyrolysis. There was residual oxygen that arose from the atomic oxygen eliminated from the oxirene, intercalated in graphite layers, and formed basal epoxy groups. Also, incoming O atoms reacted with the intercalated O atoms to produce O2 molecules. Thermal annealing deintercalated molecular oxygen (600-900 °C).

Degradation of indigo carmine in water induced by non-thermal plasma, ozone and hydrogen peroxide: A comparative study and by-product identification.

The non-thermal plasma (NTP) technique is an advanced oxidation technology (AOT) applied to the degradation of organic compounds in water. In this study, the degradation kinetics of indigo carmine was investigated systematically, applying N2-NTP, O2-NTP, ozonolysis and hydrogen peroxide and the results were compared. The transient species (OH, O and NO radicals) formed with the NTP discharge at the gas-liquid interface and their products (NO3-, NO2-, H2O2) stabilized by the water, were identified and quantified. These species contribute to the effects on the chemical characteristics of the water, such as a decrease in the pH and increase in the conductivity and redox potential. Additionally, the stabilization of the oxidative species was estimated from the degradation reactions induced by the post-discharge effect, which was significant in the case of N2-NTP, due to the presence of long-lived species, such as nitrite and nitrate. The kinetics study revealed first-order kinetics for IC color removal and the rate constant values followed the order: O2-NTP (3.0 × 10-1 min-1) > O3 (1.4 × 10-1 min-1) > N2-NTP (2.2 × 10-2 min-1) > H2O2 (negligible). Also the main by-products of N2-NTP, O2-NTP and ozonolysis degradation reaction were identified by ultra-fast liquid chromatography coupled with mass spectrometry. The route fragmentation showed the formation of indole intermediates, such as isatin, which is an important precursor in organic synthesis.

Photo-immobilization of proteins on carbons.

The photofunctionalization of three different carbons with two proteins was studied at room temperature. Water solutions of bovine serum albumin, BSA, and α-amylase, AA, were photolyzed at 21 °C in the presence of graphite microparticles (6.20 µm), MPG, graphene oxide, MPGO, and graphene oxide modified with SO2, mMPGO. The insertion of BSA on carbon matrixes occurred with a deoxygenation reaction, most likely due to a dehydration step of a water molecule. XPS, TOC and TGA, showed that the BSA photo-insertion on MPG was highly efficient with 34.9% of the weight of MPG after photolysis, with an initial concentration of 1 g∙L-1 of BSA. A high yield of AA photoinsertion on the carbons was also obtained. The calculated weight of AA inserted on MPG and MPGO after photolysis was 22.30% and 18.08%, respectively, with respect to the initial weight of carbon, when the initial concentration of AA was 60 mg∙L-1. AA immobilized on MPG was active while the enzyme on MPGO showed a smaller activity, within the experimental error. Although a certain extent of denaturalization of both proteins was observed during photolysis, the molecular weight and composition changed very little during the photolysis, which would produce mainly conformational changes and isomerization reactions.

Removal of methylene blue by adsorption on aluminosilicate waste: equilibrium, kinetic and thermodynamic parameters.

An aluminosilicate waste (AW) was investigated as adsorbent for methylene blue (MB) dye. AW was characterized by petrography, X-ray diffractometry, X-ray fluorescence, scanning electron microscopy, thermogravimetry and zeta potential measurements. It was found that AW contains kaolinite, and other minor components such as quartz, muscovite, smectite, siderite, pyrite and organic compounds. The chemical composition of AW is mainly SiO2 (49%) and Al2O3 (23%) and it has negative superficial charge above pH 1.73. Adsorption of MB dye was studied in a batch system under different conditions of initial dye concentration, contact time and temperature. The isothermal data from batch experiments were fitted to Langmuir and Freundlich equations, with a better fit shown by the Langmuir isotherm equation. Also, pseudo-first-order, pseudo-second-order and intraparticle diffusion models were considered to evaluate the rate parameters. The experimental data fitted the pseudo-first-order kinetic model best. Thermodynamic parameters were calculated, showing the adsorption to be an endothermic yet spontaneous process, with the activation energy of +37.8 kJ mol-1. The results indicate that AW adsorbs MB efficiently, and can be employed as a low-cost alternative in wastewater treatment for the removal of cationic dyes.

Treatment of methyl orange by nitrogen non-thermal plasma in a corona reactor: The role of reactive nitrogen species.

Methyl orange (MO) azo dye served as model organic pollutant to investigate the role of reactive nitrogen species (RNS) in non-thermal plasma (NTP) induced water treatments. The results of experiments in which MO aqueous solutions were directly exposed to N2-NTP are compared with those of control experiments in which MO was allowed to react with nitrite, nitrate and hydrogen peroxide, which are species formed in water exposed to N2-NTP. Treatment of MO was also performed in PAW, Plasma Activated Water, that is water previously exposed to N2-NTP. Both direct N2-NTP and N2-PAW treatments induced the rapid decay of MO. No appreciable reaction was instead observed when MO was treated with NO3(-) and H2O2 either under acidic or neutral pH. In contrast, in acidic solutions MO decayed rapidly when treated with NO2(-) and with a combination of NO2(-) and H2O2. Thorough product analysis was carried out by HPLC coupled with UV-vis and ESI-MS/MS detectors. In all experiments in which MO reaction was observed, the major primary product was a derivative nitro-substituted at the ortho position with respect to the N,N-dimethylamino group of MO. The reactions of RNS are discussed and a mechanism for the observed nitration products is proposed.

Photolysis of phenylalanine in the presence of oxidized carbon nanotubes.

Photolyses at 254 nm of phenylalanine (Phe) in aqueous solutions, were carried out in the presence of oxidized carbon nanotubes modified by the reaction with SO2 (mNTO). Kinetics of the photolyses were followed by UV spectrophotometry at 220 nm, and the products were characterized by HPLC, XPS, and (13)C-SSNMR. The ratio of the initial rates of photolysis in the presence and absence of mNTO, k*/ko*, showed a systematic decrease. The photolytic decay of Phe occurs with minor formation of tyrosine. The mass of nanotubes produced an exponential attenuation of the photolytic decomposition of Phe. Total carbon analyses (TCA) showed no inorganic carbon formation after the photolyses. The first-order rate constant of photofunctionalization of mNTO by the insertion of phenylalanine onto the nanotube matrix was calculated from TCA to be kin = 30.1 min(-1). Comparison of the XPS spectra of the mNTO before and after the photolysis, using the atom inventory technique, suggests the insertion of Phe along with the extrusion of a sulfide radical anion ((•)S(-)) which undergo subsequent oxidation to SO4(2-). The obtained results show the effects of mNTO on the photolysis of Phe and provide a new method of photofunctionalization of carbon materials, modified by the intermediates of the reduction of SO2, with an organic moiety.

Pyrite-enhanced methylene blue degradation in non-thermal plasma water treatment reactor.

In this study, methylene blue (MB) removal from an aqueous phase by electrical discharge non-thermal plasma (NTP) over water was investigated using three different feed gases: N(2), Ar, and O(2). The results showed that the dye removal rate was not strongly dependent on the feed gas when the electrical current was kept the same for all gases. The hydrogen peroxide generation in the water varied according to the feed gas (N(2)

Mechanisms of acid decomposition of dithiocarbamates. 5. Piperidyl dithiocarbamate and analogues.

In this work, the acid cleavage at 25 degrees C in 20% v/v aqueous ethanol of a series of analogues of piperidine dithiocarbamate X(C2H4)2NCS2(-) (X = CH2, CHCH3, NH, NCH3, S, O) was studied. The pH-rate profiles were obtained in the range of H(o)-5 and pH 5. They all presented a dumbell shaped curve with a plateau from which the pH-independent first-order rate constant k(o) (or the specific acid catalysis k(H)) was calculated, in addition to the acid dissociation constant of the free (pKa) and conjugate acid (pK(+)) species of the DTC. LFERs of the kinetically determined pKa and pK(+) versus pKN (pKa of parent amine) were used to characterize the reactive species and the structure of the transition state of the rate-determining step. For X = CH2, CH3CH the values of k(H) agree with those of alkDTCs in the strong base region of the Brønsted plot of log k(H) versus pKN where the transition state is close to a zwitterion formed by intramolecular water-catalyzed S-to-N proton transfer of the dithiocarbamic acid. However, when X = NH, CH 3N, O, S, the reactive species is the DTC anion, which is as reactive as an arylDTC, and similarly, the pK(+) values correspond to a parent amine that is about 3-4 pK units more basic. The solvent isotope effect indicated that the acid decomposition of these dithiocarbamate anions is specifically catalyzed by a Hydron anchimerically assisted by the heteroatom through a boat conformation.