Desorption Of Methanol Research Articles

Exploring complete catalytic cycle of methane oxidation to methanol on Cu2O2 stabilized within MIL-53(Al) framework: A combined DFT and microkinetic study

Although inspiration from copper-based natural enzymes has shown promise in improving catalyst design for methane-to-methanol (MTM) oxidation, high productivity, and selectivity under mild conditions remain a significant challenge. This study constructs the dinuclear copper (Cu2) species stabilized within the metal-organic framework (MOF), MIL-53(Al), containing Cu as efficient catalytic sites and explores the ability of different oxidants (O2, N2O, and H2O2) to oxidize Cu2 into the dicopper-oxo (Cu2O2) species using density functional theory (DFT) calculations. Our results indicate the kinetic and thermodynamic favorability of Cu2O2 species formation using O2 as an oxidant within the MIL-53(Al) framework. Furthermore, the thermal stability of Cu2O2/MIL-53(Al) has been verified via ab initio molecular dynamics (AIMD) calculations. The kinetics of the complete MTM oxidation cycle over Cu2O2/MIL-53(Al) have been studied using both DFT and microkinetic simulation methods. The present study predicts that the C-H activation on the Cu2O2/MIL-53(Al) has a low free energy barrier (0.77 eV) and that the high stability of CH3 and its very low free energy barrier in the C-O coupling step favors the methanol formation over the formaldehyde. More importantly, Cu2O2/MIL-53(Al) exhibits high methanol selectivity owing to the inhibition of CH3 dehydrogenation and low methanol desorption energy (0.21 eV). Microkinetic simulations confirm the methanol production under relatively mild reaction conditions (200–280 K and 1 bar). This work provides insights into the feasibility of selective MTM oxidation over this family of MOF under mild conditions.

Unveiling the Role of Water in Heterogeneous Photocatalysis of Methanol Conversion for Efficient Hydrogen Production.

Water molecules, which act as both solvent and reactant, play critical roles in photocatalytic reactions for methanol conversion. However, the influence of water on the adsorption of methanol and desorption of liquid products, which are two essential steps that control the performance in photocatalysis, has been well under-explored. Herein, we reveal the role of water in heterogeneous photocatalytic processes of methanol conversion on the platinized carbon nitride (Pt/C3N4) model photocatalyst. In situ spectroscopy techniques, isotope effects, and computational calculations demonstrate that water shows adverse effects on the adsorption of methanol molecules and desorption processes of methanol oxidation products on the surface of Pt/C3N4, significantly altering the reaction pathways in photocatalytic methanol conversion process. Guided by these discoveries, a photothermal-assisted photocatalytic system is designed to achieve a high solar-to-hydrogen (STH) conversion efficiency of 2.3 %, which is among the highest values reported. This work highlights the important roles of solvents in controlling the adsorption/desorption behaviours of liquid-phase heterogeneous catalysis.

Unveiling the Role of Water in Heterogeneous Photocatalysis of Methanol Conversion for Efficient Hydrogen Production

AbstractWater molecules, which act as both solvent and reactant, play critical roles in photocatalytic reactions for methanol conversion. However, the influence of water on the adsorption of methanol and desorption of liquid products, which are two essential steps that control the performance in photocatalysis, has been well under‐explored. Herein, we reveal the role of water in heterogeneous photocatalytic processes of methanol conversion on the platinized carbon nitride (Pt/C3N4) model photocatalyst. In situ spectroscopy techniques, isotope effects, and computational calculations demonstrate that water shows adverse effects on the adsorption of methanol molecules and desorption processes of methanol oxidation products on the surface of Pt/C3N4, significantly altering the reaction pathways in photocatalytic methanol conversion process. Guided by these discoveries, a photothermal‐assisted photocatalytic system is designed to achieve a high solar‐to‐hydrogen (STH) conversion efficiency of 2.3 %, which is among the highest values reported. This work highlights the important roles of solvents in controlling the adsorption/desorption behaviours of liquid‐phase heterogeneous catalysis.

Development of a reliable method for determination of N-nitrosamines in medicines using disposable pipette extraction and HPLC-MS analysis.

This study outlines the development and optimization of an analytical method using Disposable Pipette Extraction (DPX) followed by high performance liquid chromatography-mass spectrometry (HPLC-MS) analysis to determine NAs in medicines. HPLC-MS analysis utilized a reversed-phase and positive mode electrospray ion source. DPX parameters were optimized through univariate and multivariate analyses, including extraction phase, desorption solvent, sample pH, equilibrium time, and extraction/desorption cycles. The optimized conditions included a C18 extraction phase, methanol desorption solvent, pH at 7, an equilibrium time of 30 seconds, 2 extraction cycles, and 5 desorption cycles. Considering this method, it was possible to achieve a sample preparation step for the analysis of NAs in medicines using a minimal amount of extraction phase, sample, and desorption solvent. Furthermore, the total extraction procedure enables the extraction of NAs in around 4 minutes with NA recovery up to 98%. Analytical performance demonstrated precision and accuracy below 15% and a quantification limit of 1 ng mL-1, meeting validation requirements set by regulations worldwide. Thus, the DPX/HPLC-MS technique offers a faster and cost-effective method for analyzing NAs in medicines compared to traditional approaches. Besides, this method reduces solvent consumption and residue generation, enhancing environmental sustainability according to green chemistry principles.

Morphology effect of Pd/In2O3/CeO2 catalysts on methanol steam reforming for hydrogen production

Catalyst support morphology strongly influences its surface and structural properties, therefore, may have a significant impact on their reactivity in heterogeneous catalysis. Herein, the Pd/In2O3/CeO2-x (loaded with 1 wt% Pd and In2O3) catalysts with different morphologies of rods(r), cubes(c) and irregularity(w) shapes were prepared by hydrothermal method and impregnation method. At temperature of 275–425 °C, as-prepared catalysts were evaluated for hydrogen production from methanol steam reforming (MSR). The activity data showed the outstanding performance of the rod-shaped Pd/In2O3/CeO2 catalysts, exhibiting the complete conversion of methanol and particularly low CO (1.3%) at 375 °C. The structural properties and physicochemical of Pd/In2O3/CeO2-x with different morphologies were characterized by means of X-ray diffraction (XRD), high resolution transmission microscopy (HR-TEM), CO pulse chemisorption, X-ray photoelectron spectroscopy (XPS) and temperature programmed desorption of methanol (CH3OH-TPD). Activity data and catalyst characterization results correlated, and indicated that the excellent reactivity for the rod-shaped Pd/In2O3/CeO2 catalysts in MSR is ascribed to the large particle size of palladium nanoparticles and the abundant oxygen vacancies induced by the strong interaction between Pd, In and Ce. HR-TEM results revealed that rod-like CeO2 mainly expose (110) crystalline surface with high mobility of surface oxygen and possess the most abundant surface oxygen vacancies with the low formation energy, facilitating the formation of active species of Pd0 on catalyst surface, and promoting the activation and adsorption of methanol and water molecules. Furthermore, the rod-shaped Pd/In2O3/CeO2 catalysts showed excellent reactivity and stability in MSR for 30 h, demonstrating its potential of being used as catalysts in methanol steam reforming in PEMFC systems.

Insights into the interfacial structure of Cu/ZrO2 catalysts for methanol synthesis from CO2 hydrogenation: Effects of Cu-supported nano-ZrO2 inverse interface

The performance of Cu-based catalysts in the low temperature CO2 conversion to methanol highly correlates with interfacial structure. In this paper, the interfacial structure of Cu/ZrO2 catalysts is tuned by changing the molar ratio and precipitation sequence of Cu and Zr precursors in the oxalate precipitation method. Structural characterizations demonstrate that the interface structure gradually transforms from the conventional ZrO2-supported nano-Cu interface to the Cu-supported nano-ZrO2 inverse interface with the ascending Cu/Zr ratio. The space–time yield (STY) of methanol over 90 molCu% Cu/ZrO2 inverse catalyst is 518 gCH3OH/kgcat/h, which far exceeds that of the optimized 40 molCu% Cu/ZrO2 catalyst (351 gCH3OH/kgcat/h). The inverse catalyst also exhibits the best methanol selectivity and lowest apparent activation energy. The correlation of the exposed Cu surface area, Cu particle size, and CO2 adsorption capacity with STYmethanol reveal that there is an optimal coverage of fine ZrO2 particles and the Cu supported nano-ZrO2 inverse configuration is a more suitable structure for methanol synthesis from CO2. High-pressure in situ DRIFTS experiment shows that the adsorbed formate and methoxy intermediates over 90 molCu% Cu/ZrO2 inverse catalyst are more reactive for further hydrogenation. In addition, the inverse configuration is more favorable for the methanol desorption from surface. The enhanced hydrogenation ability and relatively weak oxygenates adsorption of Cu-supported nano-ZrO2 interface is probably the main reasons for the improved catalytic performances of inverse catalysts.

Electrochemical Oxidation of Methane to Methanol on Electrodeposited Transition Metal Oxides

Electrochemical partial oxidation of methane to methanol is a promising approach to the transformation of stranded methane resources into a high-value, easy-to-transport fuel or chemical. Transition metal oxides are potential electrocatalysts for this transformation. However, a comprehensive and systematic study of the dependence of methane activation rates and methanol selectivity on catalyst morphology and experimental operating parameters has not been realized. Here, we describe an electrochemical method for the deposition of a family of thin-film transition metal (oxy)hydroxides as catalysts for the partial oxidation of methane. CoOx, NiOx, MnOx, and CuOx are discovered to be active for the partial oxidation of methane to methanol. Taking CoOx as a prototypical methane partial oxidation electrocatalyst, we systematically study the dependence of activity and methanol selectivity on catalyst film thickness, overpotential, temperature, and electrochemical cell hydrodynamics. Optimal conditions of low catalyst film thickness, intermediate overpotentials, intermediate temperatures, and fast methanol transport are identified to favor methanol selectivity. Through a combination of control experiments and DFT calculations, we show that the oxidized form of the as-deposited (oxy)hydroxide catalyst films are active for the thermal oxidation of methane to methanol even without the application of bias potential, demonstrating that high valence transition metal oxides are intrinsically active for the activation and oxidation of methane to methanol at ambient temperatures. Calculations uncover that electrocatalytic oxidation enables reaching an optimum potential window in which methane activation forming methanol and methanol desorption are both thermodynamically favorable, methanol desorption being favored by competitive adsorption with hydroxide anion.

One-step synthesis of methanol and hydrogen from methane and water using non-thermal plasma and Cu-Mordenite catalyst

In this study, the copper-mordenite zeolite (Cu-MOR) and non-thermal plasma were used to produce methanol and hydrogen from methane and water at low temperature (120 °C) without CO2 formation. Energy efficiency for methanol and hydrogen were 68.8 mmol·kJ−1 and 562.3 mmol·kJ−1, respectively, and the selectivity of methanol in liquid products reached 86%. The reaction mechanism likely involves methane being excited to methyl (·CH3) and hydrogen radicals (·H) under DBD plasma conditions, which can then adsorb on the catalyst surface at the Cu2-(μ-O)2+ active sites, accompanied by water co-adsorption to facilitate formation and desorption of methanol. XPS analysis showed that with the prolongation of reaction time, Cu2-(μ-O)2+ was reduced to Cu+ and Cu(II) hydroxide, and the catalyst had carbon deposition, resulting in the decrease of catalytic activity. It is also worth noting that in an oxygen atmosphere, Cu2-(μ-O)2+ regenerates rapidly and eliminates catalyst carbon deposits. Trace oxygen was introduced into the reactor, and the reaction was carried out for 30 h, and the catalytic activity did not decrease.

Constraints on the non-thermal desorption of methanol in the cold core LDN 429-C

Context. Cold cores are one of the first steps of star formation, characterized by densities of a few 104–105 cm−3, low temperatures (15 K and below), and very low external UV radiation. In these dense environments, a rich chemistry takes place on the surfaces of dust grains. Understanding the physico-chemical processes at play in these environments is essential to tracing the origin of molecules that are predominantly formed via reactions on dust grain surfaces. Aims. We observed the cold core LDN 429-C (hereafter L429-C) with the NOEMA interferometer and the IRAM 30 m single dish telescope in order to obtain the gas-phase abundances of key species, including CO and CH3OH. Comparing the data for methanol to the methanol ice abundance previously observed with Spitzer allows us to put quantitative constraints on the efficiency of the non-thermal desorption of this species. Methods. With physical parameters determined from available Herschel data, we computed abundance maps of 11 detected molecules with a non-local thermal equilibrium (LTE) radiative transfer model. These observations allowed us to probe the molecular abundances as a function of density (ranging from a few 103 to a few 106 cm−3) and visual extinction (ranging from 7 to over 75), with the variation in temperature being restrained between 12 and 18 K. We then compared the observed abundances to the predictions of the Nautilus astrochemical model. Results. We find that all molecules have lower abundances at high densities and visual extinctions with respect to lower density regions, except for methanol, whose abundance remains around 4.5 × 10−10 with respect to H2. The CO abundance spreads over a factor of 10 (from an abundance of 10−4 with respect to H2 at low density to 1.8 × 10−5 at high density) while the CS, SO, and H2S abundances vary by several orders of magnitude. No conclusion can be drawn for CCS, HC3N, and CN because of the lack of detections at low densities. Comparing these observations with a grid of chemical models based on the local physical conditions, we were able to reproduce these observations, allowing only the parameter time to vary. Higher density regions require shorter times than lower density regions. This result can provide insights on the timescale of the dynamical evolution of this region. The increase in density up to a few 104 cm−3 may have taken approximately 105 yr, while the increase to 106 cm−3 occurs over a much shorter time span (104 yr). Comparing the observed gas-phase abundance of methanol with previous measurements of the methanol ice, we estimate a non-thermal desorption efficiency between 0.002 and 0.09%, increasing with density. The apparent increase in the desorption efficiency cannot be reproduced by our model unless the yield of cosmic-ray sputtering is altered due to the ice composition varying as a function of density.

Composites “lithium chloride/vermiculite” for adsorption thermal batteries: Giant acceleration of sorption dynamics

Adsorption thermal batteries have been proposed for storing heat from renewable and waste energy sources. Composites “salt in porous matrix” based on expanded vermiculite have extraordinary methanol sorption and heat storage capacities. However, their practical implementation is restricted by slow desorption, leading to low battery power. This paper aims to accelerate methanol desorption from a composite LiCl/vermiculite through its modification by an aluminum-oxygen containing additive. First, the dynamics of methanol sorption/desorption is studied for a pristine LiCl/vermiculite to reveal the factors braking sorption. Slow heterogeneous nucleation and sluggish growth of crystalline LiCl are shown to dramatically inhibit the methanol desorption from the pristine LiCl/vermiculite composite. To accelerate the nucleation, the vermiculite is modified by 2.5–8.9 wt% of aluminum-oxygen containing additive. Both pristine and modified sorbents are characterized by XRD, SEM, DSC, and BET techniques. The modification allows a giant acceleration of methanol desorption. The characteristic time corresponding to conversion 0.8 reduces by a factor of 2–12 as compared with the pristine composite. The dynamics acceleration affords fourfold increase in the specific power of the heat storage stage of adsorption thermal batteries employing the new composite. In a broader sense, the proposed approach could help accelerate the sorption of methanol, water, and ammonia on composites based on macroporous matrixes and could be advantageous for various adsorption applications.

Metal-Support Interaction-Promoted Photothermal Catalytic Methane Reforming into Liquid Fuels.

Clean and renewable photocatalytic technology for methane reforming into high-value liquid fuels, such as methanol, is a promising strategy for commercial industrial applications. However, poor charge separation, sluggish methane activation, and excessive oxidation collectively inhibit the production of methanol from photocatalytic methane reforming. Herein, we have developed enhanced metal-support interactions between a GaN nanowire photocatalyst and a Cu nanoparticle (CuNP) cocatalyst via p-doping in GaN. CuNP-loaded p-type GaN (Cu/p-GaN) with enhanced metal-support interaction has 3.5-fold higher activity (12.8 mmol g-1 h-1, higher than previous reports) for methanol production in photothermal catalytic methane reforming with oxygen as an oxidant and sunlight as the sole energy source than CuNP-loaded intrinsic GaN (Cu/i-GaN) or n-type GaN (Cu/n-GaN). In-situ IR measurements indicate that enhanced metal-support interaction significantly promotes activation of methane and formation of methanol. Combining with X-ray photoelectron spectroscopy (XPS), density functional theory (DFT) simulations demonstrate that this enhanced metal-support interaction in Cu/p-GaN greatly improves electron transfer from p-GaN photocatalysts to the 3d states of CuNP cocatalysts through the interface between them. Catalytic pathway simulations further reveal that the enhanced metal-support interaction in Cu/p-GaN also desirably decreases the reaction energy of rate-determining methanol desorption, which decreases the excessive oxidation of the produced methanol and accelerates the regeneration of surface catalytic sites. These studies and findings offer critical insights into the design and development of metal nanoparticle-loaded photocatalysts for photocatalysis-based methane reforming into methanol.

Identifying the crucial role of water and chloride for efficient mild oxidation of methane to methanol over a [Cu2(μ-O)]2+-ZSM-5 catalyst

Controllable methane oxidation to methanol is a challenging in catalysis, usually suffering from over-oxidation. We report that a single-metal [Cu2(μ-O)]2+-ZSM-5 catalyst can activate methane to methanol with superior high selectivity up to 91.3% in C1 oxygenates and 12.31 molmethanol kgcat-1h−1 by avoiding over-oxidation. Density functional theory (DFT) calculations combined with in situ FT-IR and EPR demonstrated that methanol forms via direct dissociation of strongly adsorbed *CH3OOH generated by *CH3 spontaneously reacting with H2O2 rather than OH. It was found that water plays a crucial role in enhancing methanol formation as other solvents ethanol and acetone show negligible activity. DFT calculations and TPD results confirmed that adsorbed H2O* facilitates active site regeneration and accelerate methanol desorption via H migration between H2O* and [Cu2(μ-OH)2]2+. In addition, the introduction of chloride is favorable for the formation of active [Cu2(μ-O)]2+ species owing to a decrease in binding energy between active sites and ZSM-5, and can promote methanol production by weakening the interaction between methanol and active sites by accepting electron from Cu.

Methane oxidation to methanol over copper-containing zeolite

Methane oxidation to methanol over copper-containing zeolite

Dynamics and Sorption Kinetics of Methanol Monomers and Clusters on Nopinone Surfaces

Organic–organic interactions play important roles in secondary organic aerosol formation, but the interactions are complex and poorly understood. Here, we use environmental molecular beam experiments combined with molecular dynamics simulations to investigate the interactions between methanol and nopinone, as atmospheric organic proxies. In the experiments, methanol monomers and clusters are sent to collide with three types of surfaces, i.e., graphite, thin nopinone coating on graphite, and nopinone multilayer surfaces, at temperatures between 140 and 230 K. Methanol monomers are efficiently scattered from the graphite surface, whereas the scattering is substantially suppressed from nopinone surfaces. The thermal desorption from the three surfaces is similar, suggesting that all the surfaces have weak or similar influences on methanol desorption. All trapped methanol molecules completely desorb within a short experimental time scale at temperatures of 180 K and above. At lower temperatures, the desorption rate decreases, and a long experimental time scale is used to resolve the desorption, where three desorption components are identified. The fast component is beyond the experimental detection limit. The intermediate component exhibits multistep desorption character and has an activation energy of Ea = 0.18 ± 0.03 eV, in good agreement with simulation results. The slow desorption component is related to diffusion processes due to the weak temperature dependence. The molecular dynamics results show that upon collisions the methanol clusters shatter, and the shattered fragments quickly diffuse and recombine to clusters. Desorption involves a series of processes, including detaching from clusters and desorbing as monomers. At lower temperatures, methanol forms compact cluster structures while at higher temperatures, the methanol molecules form layered structures on the nopinone surface, which are visible in the simulation. Also, the simulation is used to study the liquid–liquid interaction, where the methanol clusters completely dissolve in liquid nopinone, showing ideal organic–organic mixing.

Harnessing of Diluted Methane Emissions by Direct Partial Oxidation of Methane to Methanol over Cu/Mordenite.

The upgrading of diluted methane emissions into valuable products can be accomplished at low temperatures (200 °C) by the direct partial oxidation of methanol over copper-exchanged zeolite catalysts. The reaction has been studied in a continuous fixed-bed reactor loaded with a Cu–mordenite catalyst, according to a three-step cyclic process: adsorption of methane, desorption of methanol, and reactivation of the catalyst. The purpose of the work is the use of methane emissions as feedstocks, which is challenging due to their low methane concentration and the presence of oxygen. Methane concentration had a marked influence on methane adsorption and methanol production (decreased from 164 μmol/g Cu for pure methane to 19 μmol/g Cu for 5% methane). The presence of oxygen, even in low concentrations (2.5%), reduced methane adsorption drastically. However, methanol production was only affected slightly (average decrease of 9%), concluding that methane adsorbed on the active centers yielding methanol is not influenced by oxygen.

Complex organic molecules in protoplanetary disks: X-ray photodesorption from methanol-containing ices

Context.Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object that irradiate interstellar ices in the disk, followed by the ejection of molecules in the gas phase, are a possible route to explain the abundances observed in the cold regions. This process, known as X-ray photodesorption, needs to be quantified for methanol-containing ices. This Paper I focuses on the case of X-ray photodesorption from pure methanol ices.Aims.We aim at experimentally measuring X-ray photodesorption yields (in molecule desorbed per incident photon, displayed as molecule/photon for more simplicity) of methanol and its photo-products from pure CH3OH ices, and to shed light on the mechanisms responsible for the desorption process.Methods.We irradiated methanol ices at 15 K with X-rays in the 525–570 eV range from the SEXTANTS beam line of the SOLEIL synchrotron facility. The release of species in the gas phase was monitored by quadrupole mass spectrometry, and photodesorption yields were derived.Results.Under our experimental conditions, the CH3OH X-ray photodesorption yield from pure methanol ice is ~10−2molecule/photon at 564 eV. Photo-products such as CH4, H2CO, H2O, CO2, and CO also desorb at increasing efficiency. X-ray photodesorption of larger COMs, which can be attributed to either ethanol, dimethyl ether, and/or formic acid, is also detected. The physical mechanisms at play are discussed and must likely involve the thermalization of Auger electrons in the ice, thus indicating that its composition plays an important role. Finally, we provide desorption yields applicable to protoplanetary disk environments for astrochemical models.Conclusions.The X-rays are shown to be a potential candidate to explain gas-phase abundances of methanol in disks. However, more relevant desorption yields derived from experiments on mixed ices are mandatory to properly support the role played by X-rays in nonthermal desorption of methanol (see Paper II).

Methanol degradation mechanisms and permeability phenomena in novolac epoxy and polyurethane coatings

On a global scale, methanol is one of the most important feedstocks and is used widely as solvent and co-solvent. However, due to the polar nature and associated ability to conduct current, the small molecule can take part in galvanic corrosion of metal storage tanks and degrade the barrier properties of protective coatings. In the present work, we investigated the degradation of two novolac epoxy coatings and a polyurethane (PU) coating exposed to methanol with the aim of quantifying the various degradation paths. Absorption and desorption rates were measured and the thermomechanical properties followed by dynamic mechanical analysis. For evaluation of the coating barrier properties (i.e., breakthrough time and steady state permeation rates of methanol), permeation cells were applied. During methanol absorption, simultaneous leaching of certain coating ingredients and bonding of methanol to the binder matrix via hydrogen bonds was evidenced. In terms of classification, the bonding of methanol took place by two types of mechanisms. In Type I, the methanol molecule forms a single hydrogen bond to the coating network, thereby acting as a plasticizer, which decreases the coating storage modulus and glass transition temperature. For Type II bonding of methanol, on the other hand, two hydrogen bonds to the coating network form per molecule, resulting in so-called physical crosslinking. The Type I mechanism boosted segmental mobility and contributed to the leaching of the plasticizer benzyl alcohol from the novolac epoxy coatings and residual solvents (i.e., naphtha and xylene) from the PU coating. Following the methanol desorption, and attributed to an increased effective crosslinking density from Type II bound methanol, the novolac epoxy and PU coatings exhibited significant increases in the glass transition temperatures. In addition, for the three coatings, a gradual decline in the permeability rate of methanol was observed over time. These enhanced (and unexpected) barrier properties result from a combination of effects ascribed to Type II bound methanol and the leaching process.

Acidity as Descriptor for Methanol Desorption in B-, Ga- and Ti-MFI Zeotypes

The isomorphous substitution of Si with metals other than Al in zeotype frameworks allows for tuning the acidity of the zeotype and, therefore, to tailor the catalyst’s properties as a function of the desired catalytic reaction. In this study, B, Ga, and Ti are incorporated in the MFI framework of silicalite samples and the following series of increasing acidity is observed: Ti-silicalite < B-silicalite < Ga-silicalite. It is also observed that the lower the acidity of the sample, the easier the methanol desorption from the zeotype surface. In the target reaction, namely the direct conversion of methane to methanol, methanol extraction is affected by the zeotype acidity. Therefore, the results shown in this study contribute to a more enriched knowledge of this reaction.

Highly selective recovery of medium chain carboxylates from co-fermented organic wastes using anion exchange with CO2-expanded methanol desorption

Contribution to the International Chain Elongation Conference 2020 | ICEC 2020. An abstract can be found in the right column.

Distribution of methanol and cyclopropenylidene around starless cores

Context. The spatial distribution of molecules around starless cores is a powerful tool for studying the physics and chemistry governing the earliest stages of star formation. Aims. Our aim is to study the chemical differentiation in starless cores to determine the influence of large-scale effects on the spatial distribution of molecules within the cores. Furthermore, we want to put observational constraints on the mechanisms responsible in starless cores for the desorption of methanol from the surface of dust grains where it is efficiently produced. Methods. We mapped methanol, CH3OH, and cyclopropenylidene, c-C3H2, with the IRAM 30 m telescope in the 3 mm band towards six starless cores embedded in different environments, and in different evolutionary stages. Furthermore, we searched for correlations among physical properties of the cores and the methanol distribution. Results. From our maps we can infer that the chemical segregation between CH3OH and c-C3H2 is driven by uneven illumination from the interstellar radiation field (ISRF). The side of the core that is more illuminated has more C atoms in the gas-phase and the formation of carbon-chain molecules like c-C3H2 is enhanced. Instead, on the side that is less exposed to the ISRF the C atoms are mostly locked in carbon monoxide, CO, the precursor of methanol. Conclusions. We conclude that large-scale effects have a direct impact on the chemical segregation that we can observe at core scale. However, the non-thermal mechanisms responsible for the desorption of methanol in starless cores do not show any dependency on the H2 column density at the methanol peak.