OH Density Research Articles

The effect of difference in chemical composition between cellulose and lignin on carbon based solid acids applied for cellulose hydrolysis

Carbon based solid acids (CSAs) were prepared from cellulose and lignin at different carbonization temperatures and applied to hydrolysis of cellulose, which is of great significance for the multiple utilization of biomass. The structure and performance of cellulose based solid acids (CCSAs) and lignin based solid acids (LCSAs) were investigated by TG-DTG, XRD, FT-IR, XPS, elemental analysis, titration methods, etc. And immersion enthalpy was introduced into estimating the hydrophilicity of CSAs. The results show that the optimum carbonization temperature varies for raw material, and the optimum carbonization temperatures of cellulose and lignin are 683 and 653 K respectively. The adsorption capacities of CCSAs and LCSAs may not only be related to phenolic OH density, but may also relate to alkyl side chains and aromatic frameworks. Compared with LCSAs, the CCSAs possess higher immersion enthalpy, indicating that the CCSAs are more easily accessible to substrate, which contributes to hydrolysis. The hydrolysis activities of CCSAs are always higher than those of LCSAs, which may be due to a higher –SO3H groups densities and better accessibility between substrate and acid sites for CCSAs. These are determined by a big difference in the chemical composition between cellulose and lignin.

Laser induced fluorescence in nanosecond repetitively pulsed discharges for CO2 conversion

A CO2 nanosecond repetitively pulsed discharge (NRP) is a harsh environment for laser induced fluorescence (LIF) diagnostics. The difficulties arise from it being a strongly collisional system in which the gas composition, pressure and temperature, have quick and strong variations. The relevant diagnostic problems are described and illustrated through the application of LIF to the measurement of the OH radical in three different discharge configurations, with gas mixtures containing CO2 + H2O. These range from a dielectric barrier NRP with He buffer gas, a less hostile case in which absolute OH density measurement is possible, to an NRP in CO2+H2O, where the full set of drawbacks is at work. In the last case, the OH density measurement is not possible with laser pulses and detector time resolution in the ns time scale. Nevertheless, it is shown that with a proper knowledge of the collisional rate constants involved in the LIF process, a collisional energy transfer-LIF methodology is still applicable to deduce the gas composition from the analysis of LIF spectra.

Electron-impact vibrational excitation of the hydroxyl radical in the nighttime upper atmosphere

Chemical processes produce vibrationally excited hydroxyl (OH) in a layer centred at an altitude of about 87 km in the Earth's atmosphere. Observations of this layer are used to deduce temperatures in the mesosphere and to observe the passage of atmospheric gravity waves. Due to the low densities and energies at night of electrons at the relevant altitude, it is not expected that electron-impact excitation of OH would be significant. However, there are unexplained characteristics of OH densities and radiative emissions that might be explained by electron impact. These are measurements of higher than expected densities of OH above 90 km and of emissions at higher energies that cannot be explained by the chemical production processes. This study simulates the role of electron impact in these processes, using theoretical cross sections for electron-impact excitation of OH. The simulations show that electron impact, even in a substantial aurora, cannot fully explain these phenomena. However, in the process of this investigation, apparent inconsistencies in the theoretical cross sections and reaction rates were found, indicating that measurements of electron-impact excitation of OH are needed to resolve these problems and scale the theoretical predictions to allow more accurate simulations.

Investigation of Antibacterial 1,8-Cineole-Derived Thin Films Formed via Plasma-Enhanced Chemical Vapor Deposition.

The need for low-fouling coatings for biomedical devices has prompted considerable interest in antibacterial compounds from natural and sustainable sources, such as essential oils. Herein, a tea tree oil-based precursor, 1,8-cineole, is used to fabricate antimicrobial films (denoted ppCin) by plasma-enhanced chemical vapor deposition. Film properties were comprehensively characterized using a variety of surface and bulk analytical tools, and the plasma gas phase is assessed using optical emission spectroscopy, which can be correlated to ppCin film properties. Notably, film wettability increases linearly with plasma pressure, yielding water contact angles ranging from ∼50° to ∼90°. X-ray photoelectron spectroscopy reveals less oxygen is incorporated at higher pressures, likely arising from the lower density of OH(g) species. Further, we utilized H2O(v) plasma surface modification of the ppCin films to improve wettability and find this results in a substantial increase in surface oxygen content. To elucidate the role of film wettability and antibacterial properties, both as-deposited and H2O(v) plasma-modified films were exposed to Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus using glass slides and hydrocarbon films deposited from 1,7-octadiene as positive controls. Overall, bacteria attach to a similar extent on all films, including controls, yet only essential oil-based films significantly prevent biofilm formation (4-7% coverage compared to ∼40% for controls).

What makes a good descriptor for heterogeneous ice nucleation on OH-patterned surfaces

Freezing of water is arguably one of the most common phase transitions on Earth and almost always happens heterogeneously. Despite its importance, we lack a fundamental understanding of what makes substrates efficient ice nucleators. Here we address this by computing the ice nucleation (IN) ability of numerous model hydroxylated substrates with diverse surface hydroxyl (OH) group arrangements. Overall, for the substrates considered, we find that neither the symmetry of the OH patterns nor the similarity between a substrate and ice correlate well with the IN ability. Instead, we find that the OH density and the substrate-water interaction strength are useful descriptors of a material's IN ability. This insight allows the rationalization of ice nucleation ability across a wide range of materials, and can aid the search and design of novel potent ice nucleators in the future.

Emission considering self-absorption of OH to simultaneously obtain the OH density and gas temperature: validation, non-equilibrium effects and limitations

The measurement of absolute densities of ubiquitous OH radicals and gas temperatures in water containing plasmas has recently drawn a lot of attention. In this paper, we extend the self-absorption model introduced in Du et al 2016 Plasma Sources Sci. Technol. 25 04LT02 with a description of the excited state by a superposition of two Boltzmann distributions to take the non-thermal rotational distribution of the excited state into account. This technique is applied to a diffuse He + H2O RF discharge and it is shown that in addition to the determination of the ground state OH density and rotational temperature, the properties of the excited state OH(A) can also be simultaneously determined. A model of the steady-state distribution of the hot and cold group density of OH(A) is able to describe the dependence of the rotational population distributions of the excited state as a function of the water concentration. The method is also applied to a filamentary Ar + H2O DBD. While the non-homogeneous nature of the DBD leads to complications, the production of OH(A) by multiple production mechanisms leading to a complex nascent rotational population distribution causes the fitting procedure of the emission spectrum (with self-absorption) to break down.

Resolving the mesospheric nighttime 4.3 µm emission puzzle: comparison of the CO<sub>2</sub>(<i>ν</i><sub>3</sub>) and OH(<i>ν</i>) emission models

Abstract. In the 1970s, the mechanism of vibrational energy transfer from chemically produced OH(ν) in the nighttime mesosphere to the CO2(ν3) vibration, OH(ν) ⇒ N2(ν) ⇒ CO2(ν3), was proposed. In later studies it was shown that this "direct" mechanism for simulated nighttime 4.3 µm emissions of the mesosphere is not sufficient to explain space observations. In order to better simulate these observations, an additional enhancement is needed that would be equivalent to the production of 2.8–3 N2(1) molecules instead of one N2(1) molecule in each quenching reaction of OH(ν) + N2(0). Recently a new "indirect" channel of the OH(ν) energy transfer to N2(ν) vibrations, OH(ν) ⇒ O(1D) ⇒ N2(ν), was suggested and then confirmed in a laboratory experiment, where its rate for OH(ν = 9) + O(3P) was measured. We studied in detail the impact of the "direct" and "indirect" mechanisms on CO2(ν3) and OH(ν) vibrational level populations and emissions. We also compared our calculations with (a) the SABER/TIMED nighttime 4.3 µm CO2 and OH 1.6 and 2.0 µm limb radiances of the mesosphere–lower thermosphere (MLT) and (b) with ground- and space-based observations of OH(ν) densities in the nighttime mesosphere. We found that the new "indirect" channel provides a strong enhancement of the 4.3 µm CO2 emission, which is comparable to that obtained with the "direct" mechanism alone but assuming an efficiency that is 3 times higher. The model based on the "indirect" channel also produces OH(ν) density distributions which are in good agreement with both SABER limb OH emission observations and ground and space measurements. This is, however, not true for the model which relies on the "direct" mechanism alone. This discrepancy is caused by the lack of an efficient redistribution of the OH(ν) energy from higher vibrational levels emitting at 2.0 µm to lower levels emitting at 1.6 µm. In contrast, the new indirect mechanism efficiently removes at least five quanta in each OH(ν ≥ 5) + O(3P) collision and provides the OH(ν) distributions which agree with both SABER limb OH emission observations and ground- and space-based OH(ν) density measurements. This analysis suggests that the important mechanism of the OH(ν) vibrational energy relaxation in the nighttime MLT, which was missing in the emission models of this atmospheric layer, has been finally identified.

Catalytic ozonation for low-temperature NOX (x = 1, 2) removal with [rad]OH radicals over Cu doped Ce0.90Co0.10O2 − δ catalysts and mechanism analysis

A series of Ce0.90Co0.10O2−δ and Ce0.90−xCuxCo0.10O2−δ (x=0.03, 0.07 and 0.10) catalysts synthesized by an alkaline hydrothermal method were utilized as ozonation catalysts for the NOX (x=1, 2) removal at low temperatures. A novel catalyst-duct separation apparatus for denitrification by catalytic ozonation was developed by our group. Ce0.83Cu0.07Co0.10O2−δ exhibits the highest catalytic activity (91.5% removal at 120°C), whereas Ce0.80Cu0.10Co0.10O2−δ presents the lowest (74.1% removal at 120°C). Only NO3− is detected in the tail solutions. The catalytic performance presents a positive relationship with the corresponding OH concentration. OH radical can be “transferred” from catalyst surface to the duct, prolonging activation time through its own reproduction reaction. The surface –OH activation, not the surface –OH density determines the OH concentration in the present method. Ce0.83Cu0.07Co0.10O2−δ contains a large number of high-activation bridging –OH, whereas the bridging –OH is absent in Ce0.80Cu0.10Co0.10O2−δ. Therefore, Ce0.83Cu0.07Co0.10O2−δ shows much higher activation for promoting the formation of OH than Ce0.80Cu0.10Co0.10O2−δ.

Absolutely calibrated mass spectrometry measurement of reactive and stable plasma chemistry products in the effluent of a He/H2O atmospheric plasma

Mass spectrometry has been used to analyse the effluent of a micro-scaled atmospheric plasma jet operated in helium with a controlled concentration of water vapour. Absolute densities of H2O2 and OH have been measured as function of water vapour concentration and distance from the jet nozzle. The trend for both species densities are correlated and after an initial increase, the densities of H2O2 and OH saturate around 5000 ppm to 6000 ppm of water admixture. The largest densities for H2O2 ( ) and OH ( ) were measured at 7980 ppm water admixture and 2 mm distance from the jet. Densities of HO2 ( ) and O2 ( ) have been measured as well, although no trend could be observed. The direct electron impact ionisation cross-section of H2O2 at 70 eV electron energy was experimentally determined to be . The measured densities and profiles have been compared to a 2D axially symmetric fluid model of species transport and recombination reactions. The effluent reaction chemistry is dominated by the hydroxyl radical, where the hydrogen atoms seem to play an important role as well. The analysis of neutral plasma chemistry products have been complemented by measurements of qualitative ion signals.

Simulation of spatio-temporal variation of OH radical density in atmospheric-pressure streamer discharge

The spatio-temporal variation of OH radical density in an atmospheric-pressure plasma discharge is investigated via two-dimensional numerical simulation. The behaviours of OH are characterized in four regions in the inter-electrode gap, namely the ‘Hot anode’, ‘Secondary streamer’, ‘Primary streamer’, and ‘Near-cathode’ regions. In these regions, temporal variations of averaged reduced electric field, electron density, and gas temperature differ and they affect the temporal variation of OH density. In all regions, a relatively large amount of OH is produced by the dissociation reactions of H2O with electronically excited nitrogen molecules and oxygen atom rather than the direct electron-impact dissociation reactions. In the Hot anode and Secondary streamer regions, the instantaneous density of OH just after the discharge is high. However, the subsequent OH decay rates differ in these regions owing to the difference in gas temperatures. The reaction mechanism is discussed by dividing the effect of the diffusion-convection term and chemical reaction term in the continuous equation for OH radical density.

Spatial distributions of O, N, NO, OH and vacuum ultraviolet light along gas flow direction in an AC-excited atmospheric pressure Ar plasma jet generated in open air

Ground-state O (3Pj) and N (4Sº) atoms, nitric oxide (NO) and hydroxyl (OH) radicals, and vacuum ultraviolet (VUV) radiation emitted from an AC-excited Ar atmospheric pressure plasma jet (APPJ) operated in open air were measured using VUV absorption spectroscopy, laser induced fluorescence spectroscopy and optical emission spectroscopy, respectively. The O (3Pj) density decreased with increasing distance from the plasma head, and the decrease rate in the edge region of the plasma jet around 8 mm distance was especially high. On the other hand, the N (4Sº) atom density was almost constant up to approximately 10 mm and increased with the distance over 12 mm. The relative NO density increased with the distance up to 10 mm and then became saturated, although the OH density was significantly reduced from the plasma jet exit of the head, and could be observed in the plasma jet only up to the distance of 5 mm. Emissions due to N, H and O atoms were observed in the VUV region and the emission intensity for N atoms (wavelength: 174.3 nm) decreased exponentially with increasing the distance. The results obtained with the Ar APPJ operated in open air conditions indicate the generation of many different reactive oxygen and nitrogen species by gas-phase reactions, and the composition of the reactive species is strongly dependent on the distance from the plasma head. These results are very useful for clarifying the kinetics of reactive species in APPJs and their application in various technological fields.

Effect of water vapor on plasma morphology, OH and H2O2 production in He and Ar atmospheric pressure dielectric barrier discharges

Although atmospheric pressure dielectric barrier discharges (DBDs) have a long history, the effects of water vapor on the discharge morphology and kinetics have not been studied intensively. We report a simultaneous investigation of discharge morphology, OH and H2O2 production in Ar and He DBDs operated at different water vapor concentrations and powers. The combined study allows us to assess the impact of the discharge morphology and power on the concentration dependence of the OH and H2O2 production. The morphology of the discharge is investigated by ICCD images and current–voltage waveforms. These diagnostics are complemented by broadband absorption and a colorimetric method to measure the gas temperature and the OH and H2O2 concentrations. The number of filaments in Ar DBD increases with increasing water concentration and power. The surface discharge part of the micro-discharge also reduces with increasing water concentration most likely due to a change in surface conductivity of the dielectric with changing water concentration. The OH density in the case of Ar is approximately double the OH density in He for similar power and water admixture. In contrast to the root square dependence of the OH density on the water concentration in He similar to diffuse RF discharges, the OH density in Ar increases for small water concentrations followed by a saturation and reduces for higher water concentrations. This dependence of OH density on water concentration is found to correlate with changes in discharge morphology. An analytical balance of the production and destruction mechanism of H2O2 is shown to be able to reproduce the ratio of the measured OH and H2O2 density for realistic values of electron densities.

Model polymer etching and surface modification by a time modulated RF plasma jet: role of atomic oxygen and water vapor

The surface interaction of a well-characterized time modulated radio frequency (RF) plasma jet with polystyrene, poly(methyl methacrylate) and poly(vinyl alcohol) as model polymers is investigated. The RF plasma jet shows fast polymer etching but mild chemical modification with a characteristic carbonate ester and NO formation on the etched surface. By varying the plasma treatment conditions including feed gas composition, environment gaseous composition, and treatment distance, we find that short lived species, especially atomic O for Ar/1% O2 and 1% air plasma and OH for Ar/1% H2O plasma, play an essential role for polymer etching. For O2 containing plasma, we find that atomic O initiates polymer etching and the etching depth mirrors the measured decay of O atoms in the gas phase as the nozzle-surface distance increases. The etching reaction probability of an O atom ranging from 10−4 to 10−3 is consistent with low pressure plasma research. We also find that adding O2 and H2O simultaneously into Ar feed gas quenches polymer etching compared to adding them separately which suggests the reduction of O and OH density in Ar/O2/H2O plasma.

OH radical production in an atmospheric pressure surface micro-discharge array

The generation of OH radicals from an array of surface micro-discharges working in atmospheric pressure He/Ar/H2O mixtures is investigated. The absolute OH density and its temporal-and-spatial dynamics are detected by UV broadband absorption spectroscopy (UV-BAS) and laser-induced fluorescence (LIF) spectroscopy. The measured absolute density of OH(X) state is about 1021 m−3 in Ar/H2O mixture reaching a peak at 0.05% of H2O. In the case of He/H2O mixtures however, the peaking at ~1019 m−3 is approximately two orders of magnitude lower and decreases monotonously with increasing H2O content. From a control standpoint, the ratio of the Ar/He mixture may be adjusted to tune the OH density over two orders of magnitude and to modulate the H2O content dependence of the OH density. The capability of modulating the OH radical production over a large density range is of practical interest for many applications such as atmospheric chemistry and biochemistry. With the array of atmospheric micro-discharges sustained over a large electrode area, a uniform distribution of its OH density can be achieved in a plane parallel to the electrodes thus enabling spatially controlled surface treatment of large samples.

Time-delayed transition of normal-to-abnormal glow in pin-to-water discharge

Time-delayed transition of normal-to-abnormal glow was investigated in discharge between spoke-like pins and ultrapure water by applying AC-driven power at a frequency of 14.3 kHz at atmospheric pressure. The normal-to-abnormal transition can be recognized from the slope changes of current density, gas temperature, electrode temperature, and OH density. The slope changes took place in tens of minutes rather than just after discharge, in other words, the transition was delayed. The time-delay of the transition was caused by the interaction between the plasma and water. The plasma affected water properties, and then the water affected plasma properties.

Is it possible to deduce the ground state OH density from relative optical emission intensities of the OH(A2Σ+-X2Πi) transition in atmospheric pressure non-equilibrium plasmas?—An analysis of self-absorption

The measurement of absolute densities of reactive species and radicals such as OH is of growing interest for many plasma applications. In this paper, we extend the use of a self-absorption model for atomic emission spectroscopy to molecular emission spectroscopy. The proposed analysis of self-absorbed molecular emission spectra is a simple and inexpensive method to determine OH(X) densities and rotational temperatures compared to laser induced fluorescence. We compare the recorded absolute OH density in a non-equilibrium diffuse atmospheric-pressure RF glow discharge by this method with broadband UV absorption considering a number of rotational lines with J′ ⩽ 6.5, the detection limit of the line integrated OH(X) density with this method is of the order of 2 × 1019 m−2. The accuracy of the density is sensitive to the rotational temperature of the OH(A) state and the non-equilibrium rotational population distribution.

Absolute OH and O radical densities in effluent of a He/H2O micro-scaled atmospheric pressure plasma jet

The effluent of a micro-scaled atmospheric pressure plasma jet (μ-APPJ) operated in helium with admixtures of water vapor ( ppm) has been analyzed by means of cavity ring-down laser absorption spectroscopy and molecular beam mass spectrometry to measure hydroxyl (OH) radical densities, and by two-photon absorption laser-induced fluorescence spectroscopy to measure atomic oxygen (O) densities. Additionally, the performance of the bubbler as a source of water vapor in the helium feed gas has been carefully characterized and calibrated. The largest OH and O densities in the effluent of and , respectively, have been measured at around 6000 ppm. The highest selectivity is reached around 1500 ppm, where the OH density is at ∼63% of its maximum value and is 14 times larger than the O density. The measured density profiles and distance variations are compared to the results of a 2D axially symmetric fluid model of species transport and reaction kinetics in the plasma effluent. It is shown that the main loss of OH radicals in the effluent is their mutual reaction. In the case of O, reactions with other species than OH also have to be considered to explain the density decay in the effluent. The results presented here provide additional information for understanding the plasma-chemical processes in non-equilibrium atmospheric pressure plasmas. They also open the way to applying μ-APPJ with He/H2O as a selective source of OH radicals.

The impact of energetic electron precipitation on mesospheric hydroxyl during a year of solar minimum

AbstractIn 2008 a sequence of geomagnetic storms occurred triggered by high‐speed solar wind streams from coronal holes. Improved estimates of precipitating fluxes of energetic electrons are derived from measurements on board the NOAA/POES 18 satellite using a new analysis technique. These fluxes are used to quantify the direct impact of energetic electron precipitation (EEP) during solar minimum on middle atmospheric hydroxyl (OH) measured from the Aura satellite. During winter, localized longitudinal density enhancements in the OH are observed over northern Russia and North America at corrected geomagnetic latitudes poleward of 55°. Although the northern Russia OH enhancement is closely associated with increased EEP at these longitudes, the strength and location of the North America enhancement appear to be unrelated to EEP. This OH density enhancement is likely due to vertical motion induced by atmospheric wave dynamics that transports air rich in atomic oxygen and atomic hydrogen downward into the middle atmosphere, where it plays a role in the formation of OH. In the Southern Hemisphere, localized enhancements of the OH density over West Antarctica can be explained by a combination of enhanced EEP due to the local minimum in Earth's magnetic field strength and atmospheric dynamics. Our findings suggest that even during solar minimum, there is substantial EEP‐driven OH production. However, to quantify this effect, a detailed knowledge of where and when the precipitation occurs is required in the context of the background atmospheric dynamics.

Cold and intense OH radical beam sources.

We present the design and performance of two supersonic radical beam sources: a conventional pinhole-discharge source and a dielectric barrier discharge (DBD) source, both based on the Nijmegen pulsed valve. Both designs have been characterized by discharging water molecules seeded in the rare gases Ar, Kr, or Xe. The resulting OH radicals have been detected by laser-induced fluorescence. The measured OH densities are (3.0 ± 0.6) × 10(11) cm(-3) and (1.0 ± 0.5) × 10(11) cm(-3) for the pinhole-discharge and DBD sources, respectively. The beam profiles for both radical sources show a relative longitudinal velocity spread of about 10%. The absolute rotational ground state population of the OH beam generated from the pinhole-discharge source has been determined to be more than 98%. The DBD source even produces a rotationally colder OH beam with a population of the ground state exceeding 99%. For the DBD source, addition of O2 molecules to the gas mixture increases the OH beam density by a factor of about 2.5, improves the DBD valve stability, and allows to tune the mean velocity of the radical beam.

Effects of metastable species in helium and argon atmospheric pressure plasma jets (APPJs) on inactivation of periodontopathogenic bacteria

The helium and argon have been widely used as discharge gases in atmospheric pressure plasma jets (APPJs) for bacteria inactivation. The APPJs show apparent different in bullet propagation speed and bacteria inactivation rate apparently vary with discharge gas species. This work shows that these two distinctive features of APPJs can be linked through one factor, the metastable energy level. The effects of helium and argon metastable species on APPJ discharge mechanism for reactive oxygen nitrogen species (RONS) generation in APPJs are investigated by experiments and numerical estimation. The discharge mechanism is investigated by using the bullet velocity from the electric field which is obtained with laser induced fluorescence (LIF) measurement. The measured electric field also applied on the estimation of RONS generation, as electron energy source term in numerical particle reaction. The estimated RONS number is verified by comparing NO and OH densities to the inactivation rate of periodontitis bacteria. The characteristic time for bacteria inactivation of the helium-APPJ was found to be 1.63 min., which is significantly less than that of the argon-APPJ, 12.1 min. In argon-APPJ, the argon metastable preserve the energy due to the lack of the Penning ionization. Thus the surface temperature increase is significantly higher than helium-APPJ case. It implies that the metastable energy plays important role in both of APPJ bullet propagation and bacteria inactivation mechanism.