Knudsen Cell Research Articles

Tailored Growth of Transition Metal Dichalcogenides' Monolayers by Chemical Vapor Deposition.

Here, results on the tailored growth of monolayers (MLs) of transition metal dichalcogenides (TMDs) are presented using chemical vapor deposition (CVD) techniques. To enable reproducible growth, the flow of chalcogen precursors is controlled by Knudsen cells providing an advantage in comparison to the commonly used open crucible techniques. It is demonstrated that TMD MLs can be grown by CVD on large scale with structural, and therefore electronic, photonic and optoelectronic properties similar to TMD MLs are obtained by exfoliating bulk crystals. It is shown that besides the growth of the "standard" TMD MLs also the growth of MLs that are not available by the exfoliation is possible including examples like lateral TMD1-TMD2 ML heterostructures and Janus TMDs. Moreover, the CVD technique enables the growth of TMD MLs on various 3D substrates on large scale and with high quality. The intrinsic properties of the grown MLs are analyzed by complementary microscopy and spectroscopy techniques down to the nanoscale with a particular focus on the influence of structural defects. Their functional properties are studied in devices including field-effect transistors, photodetectors, wave guides and excitonic diodes. Finally, an outlook of the developed methodology in both applied and fundamental research is given.

Aging of mineral dusts and proxies by uptake of methylglyoxal: A Knudsen cell study

This study investigates interactions between methylglyoxal (MGL) and 29 different samples, such as clays, proxies and natural dusts from the arid regions of the planet. Initial and quasi steady state uptake coefficients (ɣ0 and ɣqss) of MGL are determined using a Knudsen cell at concentration of 70 ppb, under dry conditions. Remarkably high ɣ0 values for MGL, ranging from 0.05 to 0.67, are determined, close to those of radical species, suggesting a high affinity for dusts. ɣ0 is evidenced to be linearly correlated with the Al/Si ratio of dust samples, indicating a specific initial affinity of MGL with aluminum surface sites. Ɣqss, determined after 40 minutes of exposure, ranges from 2.9 × 10-7 to 5.9 × 10-6. Ɣqss is linearly correlated with Ti/Si ratio, highlighting specific affinity of MGL with titanium. The impact of concentration on ɣqss is investigated on Gobi dust with MGL concentrations ranging from 0.1 ppt to 2.2 ppm. Ɣqss increases when MGL concentration decreases. Under typical dust storm conditions, MGL uptake competes with gas phase removal by OH radicals or photolysis. In addition, the maximum storage capacity of MGL by samples is determined at 2 ppm with Knudsen cell. MGL uptake does not exceed a compact monolayer on natural dust samples, whereas on some surrogates multilayer uptake is reached. Comparison of ɣ0 and ɣqss of glyoxal and MGL shows that MGL generally exhibits higher affinity with samples. The maximum number of molecules taken up by Gobi dust (Nmax) of MGL is compared with those for isoprene, isopropanol and acetic acid retrieved from literature. It points at the dependance of Nmax on chemical functionality of VOCs: oxygenated compounds exhibit higher interactions with dust. Data are available to increase the representativeness of modeling.

Thermodynamics and kinetics of evaporation and thermal decomposition of 1-ethyl- and 1-butyl-3-methylimidazolium methanesulfonate ionic liquids: Experimental and computational study

Knudsen cell mass spectrometry was used to study the evaporation of two ionic liquids, 1-ethyl-3-methylimidazolium methanesulfonate ([EtMIm][MS], MS = CH3SO3) and 1-butyl-3-methylimidazolium methanesulfonate ([BuMIm][MS]), accompanied by thermal decomposition (thermolysis). The independent occurrence of evaporation and thermolysis reactions made it possible to determine their thermodynamic and kinetic characteristics under identical experimental conditions. The saturated vapor pressures were measured and the standard enthalpies of vaporization of [EtMIm][MS](l) and [BuMIm][MS](l) were obtained. The standard thermodynamic functions of formation in the liquid and gaseous states at 298.15 K were estimated from the available experimental data and the results of quantum chemical calculations. The gaseous decomposition products of ionic liquids were identified and the pressures of the thermolysis products of [EtMIm][MS](l) were determined. According to the experimental data and quantum chemical calculations, the thermolysis of [EtMIm][MS](l) occurs through heterogeneous reactions far from the equilibrium state. The kinetics of the reactions is described in two ways. When the degree of sample conversion is used as a variable, the constant reaction rates at the initial stage of thermolysis correspond to a pseudo-zero order reaction with a monotonic increase in the degree of conversion. In the proposed alternative approach, the reaction rates are estimated from the fluxes of thermolysis products and are expressed in terms of ionic liquid concentration.

Thermal instability of 1-butyl-3-methylimidazolium chloride ionic liquid

The evaporation and thermal decomposition (thermolysis) of 1-butyl-3-methylimidazolium chloride ionic liquid, [BuMIm][Cl](l), were studied in the temperature range of 373–463 K by thermogravimetry–mass spectrometry (TG–MS) and Knudsen cell mass spectrometry (KCMS) methods. The saturated vapor pressures and the enthalpy of vaporization of [BuMIm][Cl](l) were determined within 373–398 K, where the thermolysis of this ionic liquid occurs via the SN2 mechanism at a low rate. With increasing temperature, the thermolysis becomes more extensive, which is accompanied by the C2-methylation of [BuMIm][Cl](l). The resulting ion pairs [BuMMIm+][Cl-] are thermally unstable and decomposed. A decrease in the vapor pressure of the ion pairs [BuMIm+][Cl-] at a constant temperature takes place due to side reactions, resulting in the suppression of the evaporation. Complex ionic compounds were found in the thermolysis/evaporation residues using atmospheric pressure chemical ionization (APCI) and matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) methods. The priority and possible pathways of reactions involving ion pairs and the thermolysis products were established by quantum chemical calculations.

Knudsen effusion mass spectrometry: Current and future approaches.

Knudsen effusion mass spectrometry (KEMS) has been a powerful tool in physical chemistry since 1954. There are many excellent reviews of the basic principles of KEMS in the literature. In this review, we focus on the current status and potential growth areas for this instrumental technique. We discuss (1) instrumentation, (2) measurement techniques, and (3) selected novel applications of the technique. Improved heating methods and temperature measurement allow for better control of the Knudsen cell effusive source. Accurate computer models of the effusive beam and its introduction to the ionizer allow optimization of such parameters as sensitivity and removal of background signals. Computer models of the ionizer allow for optimized sensitivity and resolution. Additionally, data acquisition systems specifically tailored to a KEMS system permit improved quantity and quality of data. KEMS is traditionally utilized for thermodynamic measurements of pure compounds and solutions. These measurements can now be strengthened using first principles and model-based computational thermochemistry. First principles can be used to calculate accurate Gibbs energy functions (gefs) for improving third law calculations. Calculated enthalpies of formation and dissociation energies from ab initio methods can be compared to those measured using KEMS. For model-based thermochemistry, solution parameters can be derived from measured thermochemical data on metallic and nonmetallic solutions. Beyond thermodynamic measurements, KEMS has been used for many specific applications. We select examples for discussion: measurements of phase changes, measurement/control of low-oxygen potential systems, thermochemistry of ultrahigh-temperature ceramics, geological applications, nuclear applications, applications to organic and organometallic compounds, and thermochemistry of functional room temperature materials, such as lithium ion batteries. We present an overview of the current status of KEMS and discuss ideas for improving KEMS instrumentation and measurements. We discuss selected KEMS studies to illustrate future directions of KEMS.

Unraveling Ammonia and Trimethylamine Uptake on Conductive Doped Polyaniline.

Polyaniline (PAni)-based sensors are a promising solution for ammonia (NH3) detection at the ppb level. However, the nature of the NH3-PAni interaction and underlying drivers remain unclear. This paper proposes to characterize the interaction between doped PAni (dPAni) sensing material and NH3 by using a Knudsen cell. First, to characterize the dPAni interface, the probe-gas method, i.e., titration of surface sites with a gas of specific properties, is deployed. The dPAni interface is found to be homogeneous with more than 96% of surface sites of acid nature or with hydroxyl functional groups. This result highlights that basic gases such as amines might act as interfering gases for NH3 detection by polyaniline-based sensors. Second, the adsorption isotherms of NH3 and trimethylamine (TMA) on dPAni are reported at ambient temperature conditions, 293 K. The uptake of NH3 and TMA on dPAni follows a Langmuir-type behavior. This approach allows for the first time to quantify the uptake of NH3 and TMA on gas-sensor materials and determine typical Langmuir adsorption parameters, i.e., the partitioning coefficient, KLang, and the maximum surface coverage, Nmax. The corresponding values obtained for NH3 and TMA are Klang (NH3) = 19.7 × 10-15 cm3 molecules-1 Nmax (NH3) = 11.6 × 1014 molecules cm-2, KLang (TMA) = 7.0 × 10-15 cm3 molecules-1 Nmax (TMA) = 5.0 × 1014 molecules cm-2. KLang and Nmax values of NH3 are higher than those of TMA, suggesting that NH3 is more efficiently taken up than TMA on dPAni. The results of this work suggest that strong hydrogen bonding drives the performance of a polyaniline-based gas sensor for NH3 and amines. In conclusion, the Knudsen cell approach allows reconsidering the fundamentals of NH3 interactions with dPAni and provides new insights on drivers to enhance sensing properties.

Enthalpy of Formation of Calcium and Magnesium Oxide Obtained by Knudsen Effusion Mass Spectrometry

Calcium and magnesium oxide are important components of metallurgical slag systems. However, the literature values for the standard enthalpy of formation ΔfH298∘\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\Delta }_{f}H}_{298}^{^\\circ }$$\\end{document} of both oxides exhibit large variations in some cases. Since ΔfH298∘\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\Delta }_{f}H}_{298}^{^\\circ }$$\\end{document} is crucial for the modeling and prediction of equilibrium states and, thus, also for process optimization; it was determined by Knudsen effusion mass spectrometry (KEMS). Pure CaO as well as MgO were investigated in an iridium Knudsen cell. For this purpose, the intensities of the main species present in the gas phase were recorded in a temperature range between 1825 K to 2125 K and 1675 K to 2075 K, respectively, and their partial pressures were obtained. It was observed that CaO and MgO evaporated congruently with the main species in the gas phase, Ca, Mg, O, and O2. The experimental vapor pressures of the gas species in the study of MgO are in good agreement with the calculated values using FactSageTM 7.3 and the FactPS database, while those for the evaporation of CaO show significant differences. These calculations are based on available thermodynamic information, including the Gibbs energy functions of CaO(s), Ca(g), MgO(s), Mg(g), O(g), and O2(g). After calculating the partial pressures and equilibrium constants of reactions, an average formation enthalpy of ΔfH298∘\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\Delta }_{f}H}_{298}^{^\\circ }$$\\end{document} = − 624.5 ± 3.5 kJ/mol for CaO(s) and ΔfH298∘\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\Delta }_{f}H}_{298}^{^\\circ }$$\\end{document} = − 598 ± 10 kJ/mol for MgO(s) based on the third law method of thermodynamics were obtained. The deviation of ΔfH298∘\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\\Delta }_{f}H}_{298}^{^\\circ }$$\\end{document} for MgO from the previous literature values can be attributed to the use of different ionization cross sections, temperature calibration, and variation of tabulated Gibbs energy functions.

Elucidating gas-surface interactions relevant to atmospheric particle growth using combined temperature programmed desorption and temperature-dependent uptake.

Understanding growth mechanisms for particles in air is fundamental to developing a predictive capability for their impacts on human health, visibility, and climate. In the case of highly viscous semi-solid or solid particles, the likelihood of impinging gases being taken up to grow the particle will be influenced by the initial uptake coefficient and by the residence time of the adsorbed gas on the surface. Here, a new approach that combines Knudsen cell capabilities for gas uptake measurements with temperature programmed desorption (TPD) for binding energy measurements of gases is described. The application of this unique capability to the uptake of organic gases on silica demonstrates its utility and the combination of thermodynamic and kinetic data that can be obtained. Lower limits to the initial net uptake coefficients at 170 K are (3.0 ± 0.6) × 10-3, (4.9 ± 0.6) × 10-3 and (4.3 ± 0.8) × 10-3 for benzene, 1-chloropentane, and methanol, respectively, and are reported here for the first time. The uptake data demonstrated that the ideal gas lattice model was appropriate, which informed the analysis of the TPD data. From the thermal desorption measurements, desorption energies of 34.6 ± 2.5, 45.8 ± 5.5, and 40.0 ± 5.6 kJ mol-1 (errors are 1σ) are obtained for benzene, 1-chloropentane, and methanol, respectively, and show good agreement with previously reported measurements. A multiphase kinetics model was applied to quantify uptake, desorption, and diffusion through the particle multilayers and hence extract desorption kinetics. Implications for uptake of organics on silica surfaces in the atmosphere and the utility of this system for determining relationships between residence times of organic gases and particle surfaces of varying composition are discussed in the context of developing quantitative predictions for growth of aerosol particles in air.

Vaporization processes and thermodynamic properties of the SrO-ZrO<sub>2 </sub> system at high temperatures

Vaporization processes and thermodynamic properties of the SrO-ZrO2 system in the concentration range from 10 to 90 mol% SrO were studied by high-temperature differential mass spectrometry. Evaporation of the studied samples were carried out from tungsten Knudsen effusion cell. Partial pressures of vapor species in the temperature range of 1975-2800 K were determined. The values of SrO and ZrO2 activities, as well as Gibbs energies and excess Gibbs energies in the composition range from 90 to 45 mol% SrO were obtained at the temperature of 1940 K and from 45 to 10 mol% SrO at the temperature of 2123 K. It is established that in the SrO-ZrO2 system minor negative deviations from ideal behavior are observed.

Distinct Temperature Trends in the Uptake of Gaseous n-Butylamine on Two Solid Diacids.

Uptake coefficients of n-butylamine (BA) on solid succinic (SA) and glutaric acids (GA) from 298 to 177 K were measured using a newly combined Knudsen cell temperature-programmed desorption apparatus. The uptake coefficients on SA increase monotonically from (1.9 ± 0.5) × 10-4 at 298 K to 0.14 ± 0.05 at 177 K (errors represent 2σ statistical errors, overall errors are estimated to be ±60%). This is consistent with a surface reaction mechanism to form solid aminium carboxylate. In contrast, the uptake coefficients on GA increase from 0.11 ± 0.04 at 298 K to 0.25 ± 0.04 at 248 K but then decrease to 0.030 ± 0.010 at 177 K. This unusual trend in temperature dependence of the uptake coefficient is due to formation of an ionic liquid (IL) layer upon the surface reaction of BA with GA, leading to a competition between the rate of desorption of BA and the rates of diffusion and reaction within the IL. Overall, the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB) satisfactorily reproduces these unique trends. This work provides mechanistic insight and predictive capability for the temperature-dependence of reactive uptake processes involving multiple phase changes upon surface reaction.

Evaporation and thermal decomposition of 1-ethyl-3-methylimidazolium chloride

The use of ionic liquids (IL) at elevated temperatures has revealed interest in the study of evaporation and thermal decomposition (thermolysis) processes that determine the thermal stability of IL. In this work the evaporation of 1-ethyl-3-methyl-imidazolium chloride ([EtMIm][Cl]), which is accompanied by the significant thermal decomposition, was studied by the Knudsen cell mass spectrometry. The composition of gas phase over [EtMIm][Cl] and its change in time were established in the temperature range of 403–449 K. The saturated vapor pressures, vaporization enthalpy and rate constants of thermolysis reactions were determined. The equilibrium and rate constants for gas-phase thermolysis reactions of [EtMIm][Cl] were calculated by the quantum chemical methods. Based on the results of experiments and calculations, the processes responsible for mass loss – thermolysis and evaporation – were quantitatively described.

Evaporation thermodynamics of 1‐butyl‐3‐methylimidazolium tetrafluoroborate ionic liquid

Thermodynamic properties of evaporation of 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMImBF4) ionic liquid (IL) were determined by Knudsen effusion mass spectrometry. Heating of this compound is accompanied by competing evaporation and decomposition. Interpretation of mass spectrum was carried out by the analysis of data obtained for different evaporation conditions: i) Knudsen cell with a small effusion orifice, ii) open Knudsen cell, and iii) open surface of IL. It was revealed that at non-equilibrium Langmuir conditions BMImBF4 IL evaporates congruently practically only in the form of neutral ion pairs (NIPs). In equilibrium conditions, decomposition products prevail in vapor with only about 7 % vapor fraction of NIPs. The main route of IL decomposition is the formation of substituted imidazole‐2‐ylidene (C8N2H14BF3) and hydrofluoric acid (HF). The mass spectrum of C8N2H14BF3 was obtained by the analysis of a distillate collected during evaporation in the Knudsen cell. The decomposition products, due to their high volatility, do not accumulate practically in the liquid phase and hence the activity of IL may be considered to be 1. This circumstance makes it possible to perform the thermodynamic calculations for the IL evaporation reaction. The temperature dependence of the NIPs’ vapor pressure, ln(p/Pa) = (–13.806 ± 0.252)∙103/T + (23.443 ± 0.519), was used to obtain the vaporization enthalpy, ΔvH°(298.15 K) = 138 ± 5 kJ·mol−1, by the methods of the second and third laws. The formation enthalpy of BMImBF4 NIPs, ΔfH°(298.15 K) = −1084 ± 15 kJ·mol−1, was found from combination of the vaporization enthalpy and the formation enthalpy of IL. The vapor composition over BMImBF4 under equilibrium conditions was computed. It was demonstrated that decomposition of IL is kinetically hindered so the studied system is characterized by a partial equilibrium.

Influence of the Deposition Rate and Substrate Temperature on the Morphology of Thermally Evaporated Ionic Liquids

The wetting behavior of ionic liquids (ILs) on the mesoscopic scale considerably impacts a wide range of scientific fields and technologies. Particularly under vacuum conditions, these materials exhibit unique characteristics. This work explores the effect of the deposition rate and substrate temperature on the nucleation, droplet formation, and droplet spreading of ILs films obtained by thermal evaporation. Four ILs were studied, encompassing an alkylimidazolium cation (CnC1im) and either bis(trifluoromethylsulfonyl)imide (NTf2) or the triflate (OTf) as the anion. Each IL sample was simultaneously deposited on surfaces of indium tin oxide (ITO) and silver (Ag). The mass flow rate was reproducibly controlled using a Knudsen cell as an evaporation source, and the film morphology (micro- and nanodroplets) was evaluated by scanning electron microscopy (SEM). The wettability of the substrates by the ILs was notably affected by changes in mass flow rate and substrate temperature. Specifically, the results indicated that an increase in the deposition rate and/or substrate temperature intensified the droplet coalescence of [C2C1im][NTf2] and [C2C1im][OTf] on ITO surfaces. Conversely, a smaller impact was observed on the Ag surface due to the strong adhesion between the ILs and the metallic film. Furthermore, modifying the deposition parameters resulted in a noticeable differentiation in the droplet morphology obtained for [C8C1im][NTf2] and [C8C1im][OTf]. Nevertheless, droplets from long-chain ILs deposited on ITO surfaces showed intensified coalescence, regardless of the deposition rate or substrate temperature.

Quantification of thermodynamic properties for vaporisation reactions above solid Ga2O3 and In2O3 by Knudsen Effusion Mass Spectrometry

Even though Ga2O3 and In2O3 are broadly used as semi-conductors, thermodynamic data for their vaporisation reactions exhibit a large spread. Therefore, the vaporisation behaviour of solid Ga2O3 and In2O3 was determined by means of Knudsen Effusion Mass Spectrometry (KEMS). Ga2O3 and In2O3 were studied in an iridium Knudsen cell and heated over a temperature range of 1200–1750 K in order to identify the species present in the vapour phase, and determine their partial pressures. We find that M2O (where M = Ga or In) is the most abundant gas species above the solid oxide, followed by M and MO, in accord with tabulated data. Following the calculation of partial pressures and equilibrium constants, we propose ΔfH298,3rdoGa2Og = −68966 ± 7442 Jmol-1 and ΔfH298,3rdoIn2Og = −22245 ± 964 Jmol-1 from the 3rd law method. Deviations in ΔfH298,3rdoi relative to literature KEMS measurements are generally within ∼2% relative, and can be ascribed to the use of different ionisation cross sections, Knudsen cell material, temperature calibrations, as well as tabulated Gibbs energy functions. However, comparison with ab initio studies suggests the data reported in this work is more accurate than in previous studies, given that the ΔfH298,3rdoInOg = 157744 ± 3681 Jmol-1 deviates by only ∼0.2% from the theoretical value.

Vaporization and the Thermodynamic Properties of the SrO–Al2O3–SiO2 System

Vaporization and thermodynamic properties of the SrO–Al2O3–SiO2 system are studied by high-temperature differential mass spectrometry in the concentration range from 90 to 10 mol % of SrO and the molar ratio of x(Al2O3)/x(SiO2) = 1.5. The samples are evaporated from Knudsen effusion cell made of tungsten. The partial pressures of the molecular forms of the vapor, the activities of the condensed phase components, the Gibbs energies, and the excess Gibbs energies are determined. It is established that the studied system is characterized by a slight negative deviation from the ideal behavior. For mullite (Al6Si2O13) the value of the standard enthalpy of formation is determined. The melting points of the synthesized samples are established by high-temperature microscopy.

Quantum chemical and experimental thermodynamic studies of HfO(g).

Hafnium dioxide vaporizes primarily to HfO(g) in a reducing environment. The thermochemistry of HfO(g) is calculated from quantum methods and measured via Knudsen effusion mass spectrometry. For the computations, all-electron and relativistic effective core potential calculations are used. The calculation of an accurate dissociation energy and an entire potential energy curve is reported. These calculations lead to ΔfH°(298) = 63.19 ± 10 kJ/mol, S°(298) = 235.52 J/mol K, and Cp(298-2500K) = (2.741 × 10-9)T3 - (9.853 × 10-6)T2 + (1.295 × 10-2)T + 2.761 × 10-1 J/mol K. Experimentally, HfO(g) is generated from the reaction of Hf(s) and HfO2(s) in a specially made Hf Knudsen cell. A third law treatment of the data leads to ΔfH°(298) of 58.4 ± 12.3 kJ/mol, in good agreement with the calculated value.

Nucleation, Coalescence, and Thin-Film Growth of Triflate-Based Ionic Liquids on ITO, Ag, and Au Surfaces

This study investigates the nucleation and growth of micro-/nanodroplets of triflate-based ionic liquids (ILs) fabricated by vapor deposition on different surfaces: indium tin oxide (ITO); silver (Ag); gold (Au). The ILs studied are constituted by the alkylimidazolium cation and the triflate anion—[CnC1im][OTF] series. One of the key issues that determine the potential applications of ILs is the wettability of surfaces. Herein, the wetting behavior was evaluated by changing the cation alkyl chain length (C2 to C10). A reproducible control of the deposition rate was conducted employing Knudsen cells, and the thin-film morphology was evaluated by high-resolution scanning electron microscopy (SEM). The study reported here for the [CnC1im][OTF] series agrees with recent data for the [CnC1im][NTf2] congeners, highlighting the higher wettability of the solid substrates to long-chain alkylimidazolium cations. Compared to [NTf2], the [OTF] series evidenced an even more pronounced wetting ability on Au and coalescence processes of droplets highly intense on ITO. Higher homogeneity and film cohesion were found for cationic groups associated with larger alkyl side chains. An island growth was observed on both Ag and ITO substrates independently of the cation alkyl chain length. The Ag surface promoted the formation of smaller-size droplets. A quantitative analysis of the number of microdroplets formed on Ag and ITO revealed a trend shift around [C6C1im][OTF], emphasizing the effect of the nanostructuration intensification due to the formation of nonpolar continuous domains.

Kinetics of Heterogeneous Reaction of H2O2 and SO2 on Coal Fly Ash: Temperature Effect and Their Synergistic Effects

Coal-derived fly ash is a major aerosol composition in the atmosphere and presents a major challenge in understanding the atmospheric environment. In this study, the heterogeneous uptake of hydrogen peroxide and sulfur dioxide on coal fly ash was investigated using a Knudsen cell reactor coupled with a quadrupole mass spectrometer. The uptake coefficients were measured as a function of the initial mixing ratio of H2O2 and SO2 from 10 to 60 ppbv, and the temperature dependence of the uptake coefficients was also carried out over a range from 253 to 313 K. The mixing ratio of H2O2 and SO2 showed little effect on the uptake coefficients for these heterogeneous processes. As a function of temperature, the initial uptake coefficients of H2O2 and SO2 on coal fly ash were (0.48–1.65) × 10−4 and (1.50–8.54) × 10−5, respectively, which decreased with an increase in temperature. The steady-state uptake coefficients of H2O2 on coal fly ash were in the range of 2.46 × 10−5 to 4.84 × 10−5, which increased with an increase in temperature. Furthermore, we examined the synergistic effects between SO2 and H2O2 in their reaction on coal fly ash and found the existence of gaseous H2O2 appeared to enhance the ability of SO2 uptake on coal fly ash. Therefore, this finding suggests that the oxidation of SO2 on the surface of coal fly ash by gaseous H2O2 would promote SO2 consumption and transformation.

Molecular beam epitaxy of PtSe2 using a co-deposition approach

The structural properties of co-deposited ultrathin PtSe2 films grown at low temperatures by molecular beam epitaxy on c-plane Al2O3 are studied. By simultaneously supplying a Se flux from a Knudsen cell and Pt atoms from an electron-beam evaporator, crystalline (001)-oriented PtSe2 films were formed between 200 °C and 300 °C. The long separation between substrate and electron beam evaporator of about 60 cm ensured minimal thermal load. At optimum deposition temperatures, a ten times or even higher supply rate of Se compared to Pt ensured that the pronounced volatility of the Se was compensated and the PtSe2 phase was formed and stabilized at the growth front. Postgrowth anneals under a Se flux was found to dramatically improve the crystalline quality of the films. Even before the postgrowth anneal in Se, the crystallinity of PtSe2 films grown with the co-deposition method was superior to films realized by thermal assisted conversion. Postgrowth annealed films showed Raman modes with narrower peaks and more than twice the intensity. Transmission electron microscopy investigations revealed that the deposited material transitioned to a two-dimensional layered structure only after the postgrowth anneal. PtSe2 growth was found to start as single layer islands that preferentially nucleated at atomic steps of the substrate and progressed in a layer-by-layer like fashion. A close to ideal wetting behavior resulted in coalesced PtSe2 films after depositing about 1.5 PtSe2 layers. Detailed Raman investigation of the observed PtSe2 layer breathing modes of films grown under optimized co-deposition conditions revealed an interlayer coupling force constant of 5.0–5.6 × 1019 N m−3.

The Composition of Saturated Vapor over 1-Butyl-3-methylimidazolium Tetrafluoroborate Ionic Liquid: A Multi-Technique Study of the Vaporization Process.

A multi-technique approach based on Knudsen effusion mass spectrometry, gas phase chromatography, mass spectrometry, NMR and IR spectroscopy, thermal analysis, and quantum-chemical calculations was used to study the evaporation of 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4). The saturated vapor over BMImBF4 was shown to have a complex composition which consisted of the neutral ion pairs (NIPs) [BMIm+][BF4−], imidazole-2-ylidene C8N2H14BF3, 1-methylimidazole C4N2H6, 1-butene C4H8, hydrogen fluoride HF, and boron trifluoride BF3. The vapor composition strongly depends on the evaporation conditions, shifting from congruent evaporation in the form of NIP under Langmuir conditions (open surface) to primary evaporation in the form of decomposition products under equilibrium conditions (Knudsen cell). Decomposition into imidazole-2-ylidene and HF is preferred. The vapor composition of BMImBF4 is temperature-depended as well: the fraction ratio of [BMIm+][BF4−] NIPs to decomposition products decreased by about a factor of three in the temperature range from 450 K to 510 K.