Selective Electrochemical Regeneration of Aqueous Amine Solutions to Capture CO2 and to Convert H2S into Hydrogen and Solid Sulfur

Removing CO2 from natural gas or biogas in the presence of H2S is technically challenging and expensive as it often requires separation of both acid gases from the gas, typically using an aqueous amine solution, followed by separation of CO2 from H2S and conversion of H2S into solid S. In this work, the proof of concept of electrochemical, instead of thermal, regeneration of an aqueous amine solution is developed. This invention might be a very promising technology and has several advantages. It has H2S versus CO2 selectivity of 100%, can directly convert H2S into S and H2, and is economically competitive with CO2 desorption energy around 100 kJmol−1 and H2S conversion around 200 kJmol−1. If renewable energy is used for electrochemical regeneration, CO2 emissions due to the CO2 capture process can be significantly reduced.

Technical Note: Classical and statistical thermodynamic treatment of adsorption and desorption kinetics and rates

Adsorption and desorption represent the initial processes of the interaction of gas species with the condensed phase. It has important implications for evaluating heterogeneous (gas-to-solid) and multiphase chemical kinetics involved in catalysis, environmental interfaces, and, in particular, aerosol particles. When describing gas uptake, gas-to-particle partitioning, and the chemical transformation of aerosol particles the desorption lifetime is a crucial parameter to assess the underlying chemical kinetics such as surface reaction and surface-to-bulk transfer. The desorption lifetime, in turn, depends on the desorption free energy which is affected by the chosen adsorbate model and standard states. To assess the impact of those conditions on desorption energy and, thus, desorption lifetime, we provide a complete classical and statistical thermodynamic treatment of the adsorption and desorption process considering transition state theory for two typically applied adsorbate models, the 2D ideal gas and the 2D ideal lattice gas, the latter being equivalent to Langmuir adsorption. Both models apply to solid and liquid substrate surfaces. We derive the thermodynamic and microscopic relationships for adsorption and desorption equilibrium constants, adsorption and desorption rates, first-order adsorption and desorption rate coefficients, and the corresponding pre-exponential factors. Although, some of these derivations can be found in the literature, this study aims to bring all derivations into one place to facilitate the interpretation and analysis of desorption energies for their application in multiphase chemical kinetics. This exercise allows for a microscopic interpretation of the underlying processes including the surface accommodation coefficient and highlights the importance of the choice of adsorbate model and standard states when analyzing and interpreting adsorption and desorption processes. We demonstrate how the choice of adsorbate model choice affects equilibrium surface concentrations and coverages, desorption rates, and decay of the adsorbate species with time. In addition, we show how those results differ when applying a concentration- or activity-based description. Our treatment demonstrates that the pre-exponential factor can differ by orders of magnitude depending on the choice of adsorbate model with similar effects on the desorption lifetime, yielding significant uncertainties in the desorption energy. Furthermore, uncertainties in surface coverage and assumptions in standard surface coverage can lead to significant changes in desorption energies derived from measured desorption rates. Providing a comprehensive thermodynamic and microscopic representation aims to guide theoretical and experimental assessments of desorption energies and estimate potential uncertainties in applied desorption energies and corresponding desorption lifetimes important for improving our understanding of multiphase chemical kinetics.

Using Surface Science Techniques to Investigate the Interaction of Acetonitrile with Dust Grain Analogue Surfaces

Surface science methodologies, such as reflection-absorption infrared spectroscopy (RAIRS) and temperature programmed desorption (TPD), are ideally suited to studying the interaction of molecules with model astrophysical surfaces. Here we describe the use of RAIRS and TPD to investigate the adsorption, interactions and thermal processing of acetonitrile and water containing model ices grown under astrophysical conditions on a graphitic dust grain analogue surface. Experiments show that acetonitrile physisorbs on the graphitic surface at all exposures. At the lowest coverages, repulsions between the molecules lead to a decreasing desorption energy with increasing coverage. Analysis of TPD data gives monolayer desorption energies ranging from 28.8 - 39.2 kJ mol-1 and an average multilayer desorption energy of 43.8 kJ mol-1. When acetonitrile is adsorbed in the presence of water ice, the desorption energy of monolayer acetonitrile shows evidence of desorption with a wide range of energies. An estimate of the desorption energy of acetonitrile from CI shows that it is increased to ~37 kJ mol-1 at the lowest exposures of acetonitrile. Amorphous water ice also traps acetonitrile on the graphite surface past its natural desorption temperature, leading to volcano and co-desorption. RAIRS data show that the C≡N vibration shifts, indicative of an interaction between the acetonitrile and the water ice surface.

Stochastic on-lattice simulation of H2 formation on interstellar grains

We realized stochastic model evaluating efficency of recombination H2 in interstellar medium based on the approach of the continious-time random walk on two-dimentional lattice. This method allows to model inhomogeneous surfaces. We estimate recombination efficiensy as a function of model parameters. The influence of uncertainty of diffusion/desorption energy ratio on molecular hydrogen recombination was considered also.

Efficient hydrogenolysis of aryl ethers over Ce-MOF supported Pd NPs under mild conditions: mechanistic insight using density functional theoretical calculations

The significant Pd0 content and optimum bonding of the reactant & product (higher adsorption energy of benzyl phenyl ether and lower desorption energy for phenol) are responsible for the exceptional catalytic activity of Pd/Ce-MOF.

Desorption energy of soft particles from a fluid interface

The efficiency of soft particles to stabilize emulsions is examined by measuring their desorption free energy, i.e., the mechanical work required to detach the particle from a fluid interface.

Adsorption isotherms and nucleation of methane and ethane on an analog of Titan’s photochemical aerosols

In planetary atmospheres, adsorption of volatile molecules occurs on aerosols prior to nucleation and condensation. Therefore, the way adsorption occurs affects the subsequent steps of cloud formation. In the classical theory of heterogeneous nucleation, several physical quantities are needed for gas condensing on a substrate like aerosols, such as the desorption energies of the condensing gases on the substrate and the wetting parameters of the condensed phases on the substrate. For most planetary atmospheres, the values of such quantities are poorly known. In cloud models, these values are often approximately defined from more or less similar cases or simply fixed to reproduce macroscopic observable quantities such as cloud opacities. In this work, we used the results of a laboratory experiment in which methane and ethane adsorption isotherms on tholin, an analog of photochemical aerosols, are determined. This experiment also permits determination of the critical saturation ratio of nucleation. With this information we then retrieved the desorption energies of methane and ethane, which are the quantitative functions describing the adsorption isotherms and wetting parameters of these two condensates on tholin. We find that adsorption of methane on tholin is well explained by a Langmuir isotherm and a desorption energy ΔFo = 1.519 ± 0.0715 × 10−20 J. Adsorption of ethane tholin can be represented by a Brunauer-Emmett-Teller isotherm of type III. The desorption energy of ethane on tholin that we retrieved is ΔFo = 2.35 ± 0.03 × 10−20 J. We also determine that the wetting coefficients of methane and ethane on tholin are m = 0.994 ± 0.001 and m = 0.966 ± 0.007, respectively. Although these results are obtained from experiments representative of the Titan case, they are also of general value in cases of photochemical aerosols in other planetary atmospheres.

Synthesis of Intermetallic (Mg1−x,Alx)2Ca by Combinatorial Sputtering

The synthesis–composition–structure relationship in the Mg–Ca–Al system is studied using combinatorial magnetron sputtering. With increasing deposition temperature, a drastic decrease in Mg concentration is obtained. This behavior can be understood based on density functional theory calculations yielding a desorption energy of 1.9 eV/atom for Mg from a hexagonal Mg nanocluster which is far below the desorption energy of Mg from a Mg2Ca nanocluster (3.4 eV/atom) implying desorption of excess Mg during thin film growth at elevated temperatures. Correlative structural and chemical analysis of binary Mg–Ca thin films suggests the formation of hexagonal Mg2Ca (C14 Laves phase) in a wide Mg/Ca range from 1.7 to 2.2, expanding the to date reported stoichiometry range. Pronounced thermally-induced desorption of Mg is utilized to synthesize stoichiometric (Mg1−x,Alx)2Ca thin films by additional co-sputtering of elemental Al, exhibiting a higher desorption energy (6.7 eV/atom) compared to Mg (3.4 eV/atom) from Mg2Ca, which governs its preferred incorporation during synthesis. X-ray diffraction investigations along the chemical gradient suggest the formation of intermetallic C14 (Mg1–x,Alx)2Ca with a critical aluminum concentration of up to 23 at.%. The introduced synthesis strategy, based on the thermally-induced desorption of weakly bonded species, and the preferential incorporation of strongly bonded species, may also be useful for solubility studies of other phases within this ternary system as well as for other intermetallics with weakly bonded alloying constituents.

Desorption of N2, CO, CH4, and CO2 from interstellar carbonaceous dust analogues

ABSTRACT The interaction of volatile species with carbonaceous interstellar dust analogues is of relevance in the chemistry and physics of dense clouds in the interstellar medium. Two deposits of hydrogenated amorphous carbon (HAC), with different morphologies and aromatic versus aliphatic ratio in their structure, have been grown to model interstellar dust. The interaction of N2, CO, CH4, and CO2 with these two surfaces has been investigated using thermal programmed desorption (TPD). Desorption energy distributions were obtained by analysing TPD spectra for one monolayer coverage with the Polanyi–Wigner equation. The desorption energies found in this work for N2, CO, and CH4 are larger by 10–20 per cent than those reported in the literature for siliceous or amorphous solid water surfaces. Moreover, the experiments suggest that the interaction of the volatiles with the aromatic substructure of HAC is stronger than that with the aliphatic part. Desorption of CO2 from the HAC surfaces follows zero-order kinetics, reflecting the predominance of CO2–CO2 interactions. A model simulation of the heating of cold cloud cores shows that the volatiles considered in this work would desorb sequentially from carbonaceous dust surfaces with desorption times ranging from hundreds to tens of thousands of years, depending on the molecule and on the mass of the core.