Desorption Energy Distribution Research Articles

A Coupling Calculation Method of Desorption Energy Distribution Applied to CO2 Capture by Chemical Absorption

The pursuit of low-energy-consumption CO2 capture technology has promoted the renewal and iteration of absorbents for chemical absorption. In order to evaluate the regeneration energy consumption of absorbents and obtain the distribution of energy consumption, a coupling method combining rigorous energy balance and simple estimation is proposed in this study. The data regarding energy balance and material balance from process simulation are transformed into the model parameters required in the simple estimation model. Regenerative energy consumption and distribution are determined by the empirical estimation formula. Two CO2 capture processes of an MEA aqueous solution and MEA–n-propanol aqueous solution (phase-change absorbent) were used to verify the feasibility and applicability of the coupling method. The effects of n-propanol concentration, CO2 loading in the lean solution, and temperature on energy consumption were discussed. The results show that the energy consumption of 30 wt% MEA aqueous solution is the lowest at 3.92 GJ·t−1-CO2 when CO2 load in the lean solution is 0.2 mol CO2·mol−1-MEA, and the reaction heat Qrec, sensible heat Qsen, and latent heat Qlatent were 1.97 GJ·t−1-CO2, 1.09 GJ·t−1-CO2, and 0.86 GJ·t−1-CO2, respectively. The lowest energy consumption of the phase-change absorbent with CO2 loading of 0.35 mol CO2·mol−1-MEA in the lean solution is 2.32 GJ·t−1-CO2. Qrec, Qsen, and Qlatent were 1.9 GJ·t−1-CO2, 0.29 GJ·t−1-CO2, and 0.14 GJ·t−1-CO2, respectively. This study provides a simple and meaningful method for accurately assessing absorber performance and process improvement, which can accelerate the development of economically viable, absorption-based CO2 capture processes.

Cu doping and Ti3C2OH quantum dots co-modifications of Zn3In2S6 boosted photocatalytic reduction of CO2 to CO via accelerating carriers transfer and enhancing CO2 adsorption and activation

In this study, the Zn3In2S6 was modified by Cu doping and loading of Ti3C2OH quantum dots (QDs) by hydrothermal method for efficient and highly selective photoreduction of CO2. Various characterizations and tests demonstrated that the Cu0.05Zn2.95In2S6@Ti3C2OH QDs exhibited desired morphology, superior light utilization ability, and the most efficient carriers’ separation and transfer. This optimized material exhibited a CO yield of 51.848 μmol g-1 h-1, with selectivity up to 99%. This high CO yield was 22.3 and 3.48 times of those of the Zn3In2S6 and Cu0.05Zn2.95In2S6, respectively; demonstrating that synergistic effect of Cu-doping and Ti3C2OH QDs modification existed for enhancing CO2 reduction to CO. Results of CO2-TPD and in-situ FTIR showed that the Cu0.05Zn2.95In2S6@Ti3C2OH QDs possessed the greatest CO2 adsorption and activation ability. DFT (density functional theory) calculation revealed that greatest CO2 adsorption energy, CO desorption energy and charge density distribution were key factors for the Cu0.05Zn2.95In2S6@Ti3C2OH QDs to achieve efficient reduction of CO2. Possible CO2 reduction pathways and mechanism were proposed. This study could advance the development of photocatalysts for highly selective CO2 reduction to CO and enrich related mechanism insights.

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

ABSTRACTThe 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.

Thermal desorption of formamide and methylamine from graphite and amorphous water ice surfaces

AbstractThermal desorption experiments of Formamide (NH2CHO) and methylamine (CH3NH2) were performed in LERMA-Cergy laboratory to determine the values of the desorption energies of formamide and methylamine from analogues of interstellar dust grain surfaces, and to understand their interaction with water ice. We found that more than 95 % of solid NH2CHO diffuses through the np-ASW ice surface towards the graphitic substrate, and is released into the gas phase with a desorption energy distribution Edes = (7460 – 9380) K, measured with the best-fit pre-exponential factor A=1018 s-1. Whereas, the desorption energy distribution of methylamine from the np-ASW ice surface (Edes =3850-8420 K) is measured with the best-fit pre-exponential factor A=1012s-1. A fraction of solid methylamine, of about 0.15 monolayer diffuses through the water ice surface towards the HOPG substrate, and desorbs later, with higher binding energies (5050-8420 K), which exceed that of the crystalline water ice (Edes =4930 K), calculated with the same pre-exponential factor A=1012 s-1.

Measurements of Diffusion of Volatiles in Amorphous Solid Water: Application to Interstellar Medium Environments

Abstract The diffusion of atoms and molecules in ices covering dust grains in dense clouds in interstellar space is an important but poorly characterized step in the formation of complex molecules in space. Here we report the measurement of diffusion of simple molecules in amorphous solid water (ASW), an analog of interstellar ices, which are amorphous and made mostly of water molecules. The new approach that we used relies on measuring, in situ, the change in band strength and position of mid-infrared features of OH dangling bonds as molecules move through pores and channels of ASW. We obtained the Arrhenius pre-exponents and activation energies for diffusion of CO, O2, N2, CH4, and Ar in ASW. The diffusion energy barrier of H2 and D2 were also measured, but only upper limits were obtained. These values constitute the first comprehensive set of diffusion parameters of simple molecules on the pore surface of ASW and can be used in simulations of the chemical evolution of Interstellar Medium environments, thus replacing unsupported estimates. We also present a set of argon temperature programmed desorption experiments to determine the desorption energy distribution of argon on non-porous ASW.

Thermal desorption of formamide and methylamine from graphite and amorphous water ice surfaces

Context. Formamide (NH2CHO) and methylamine (CH3NH2) are known to be the most abundant amine-containing molecules in many astrophysical environments. The presence of these molecules in the gas phase may result from thermal desorption of interstellar ices. Aims. The aim of this work is to determine the values of the desorption energies of formamide and methylamine from analogues of interstellar dust grain surfaces and to understand their interaction with water ice. Methods. Temperature programmed desorption (TPD) experiments of formamide and methylamine ices were performed in the sub-monolayer and monolayer regimes on graphite (HOPG) and non-porous amorphous solid water (np-ASW) ice surfaces at temperatures 40–240 K. The desorption energy distributions of these two molecules were calculated from TPD measurements using a set of independent Polanyi–Wigner equations. Results. The maximum of the desorption of formamide from both graphite and ASW ice surfaces occurs at 176 K after the desorption of H2O molecules, whereas the desorption profile of methylamine depends strongly on the substrate. Solid methylamine starts to desorb below 100 K from the graphite surface. Its desorption from the water ice surface occurs after 120 K and stops during the water ice sublimation around 150 K. It continues to desorb from the graphite surface at temperatures higher than160 K. Conclusions. More than 95% of solid NH2CHO diffuses through the np-ASW ice surface towards the graphitic substrate and is released into the gas phase with a desorption energy distribution Edes = 7460–9380 K, which is measured with the best-fit pre-exponential factor A = 1018 s−1. However, the desorption energy distribution of methylamine from the np-ASW ice surface (Edes = 3850–8420 K) is measured with the best-fit pre-exponential factor A = 1012 s−1. A fraction of solid methylamine monolayer of roughly 0.15 diffuses through the water ice surface towards the HOPG substrate. This small amount of methylamine desorbs later with higher binding energies (5050–8420 K) that exceed that of the crystalline water ice (Edes = 4930 K), which is calculated with the same pre-exponential factor A = 1012 s−1. The best wetting ability of methylamine compared to H2O molecules makes CH3NH2 molecules a refractory species for low coverage. Other binding energies of astrophysical relevant molecules are gathered and compared, but we could not link the chemical functional groups (amino, methyl, hydroxyl, and carbonyl) with the binding energy properties. Implications of these high binding energies are discussed.

Thermal desorption of astrophysically relevant molecules from forsterite(010)

We present temperature programmed desorption (TPD) measurements of CO, CH4, O2 and CO2 from the forsterite(010) surface in the sub-monolayer and multilayer coverage regimes. In the case of CO, CH4 and O2, multilayer growth begins prior to saturation of the monolayer peak, resulting in two clearly distinguishable desorption peaks. On the other hand, a single peak for CO2 is observed which shifts from high temperature at low coverage to low temperature at high coverages, sharpening upon multilayer formation. The leading edges are aligned for all the molecules in the multilayer coverage regime indicating zero order desorption. We have extracted multilayer desorption energies for these molecules using an Arrhenius analysis. For sub-monolayer coverages, we observe an extended desorption tail to higher temperature. Inversion analysis has been used to extract the coverage dependent desorption energies in the sub-monolayer coverage regime, from which we obtain the desorption energy distribution. We found that owing to the presence of multiple adsorption energy sites on the crystalline surface the typical desorption energies of these small molecules are significantly larger than obtained in previous measurements for several other substrates. Therefore molecules bound to crystalline silicate surfaces may remain locked in the solid state for a longer period of time before desorption into the gas phase.

Comprehensive Study of Thermal Desorption of Grain-surface Species by Accretion Shocks around Protostars

Abstract We conducted numerical simulations of the dust heating in accretion shocks induced by the interaction between the infalling envelope and the Keplerian disk surrounding a protostar, in order to investigate the thermal desorption of molecules from the dust-grain surfaces. It is thought that the surfaces of the amorphous dust grains are inhomogeneous; various adsorption sites with different binding energies should therefore exist. We assumed that the desorption energy has a Gaussian distribution and investigated the effect of the desorption energy distribution on the desorption-efficiency evaluation. We calculated the desorption fractions of the grain-surface species for wide ranges of input parameters and summarized our results in a shock diagram. The resulting shock diagram suggests that the enhanced line emissions around protostars observed using the Atacama Large Millimeter Array cannot be explained by the thermal desorption in an accretion shock if typical interstellar dust-grain sizes ( ) and a single desorption energy are considered. On the other hand, if significantly smaller dust grains are the main grain-surface species carriers and the desorption energy has a Gaussian distribution, the origin of the enhanced line emission can be explained by the accretion shock heating scenario for all of the three protostars examined in this study: IRAS 04368+2557, IRAS 04365+2535, and IRAS 16293–2422. The small-grain-carrier supposition is quite reasonable when the dust grains have a power-law size distribution because the smaller grains primarily contribute to the dust-grain surface area.

Thermal desorption of ammonia from crystalline forsterite surfaces

The thermal desorption of ammonia (NH$_3$) from single crystal forsterite (010) has been investigated using temperature-programmed desorption. The effect of defects on the desorption process has been probed by the use of a rough cut forsterite surface prepared from the cleaved forsterite sample. Several approaches have been used to extract the desorption energy and pre-exponential factor describing the desorption kinetics. In the sub-monolayer coverage regime, the NH$_3$ desorption shows a broad distribution of desorption energies, indicating the presence of different adsorption sites, which results in an apparent coverage-dependent desorption energy. This distribution is sensitive to the surface roughness with the cut forsterite surface displaying a significantly broader distribution of desorption energies compared to the cleaved forsterite surface. The cut forsterite surface exhibits sites with desorption energies up to 62.5 kJ mol$^{-1} $ in comparison to a desorption energy of up to 58.0 kJ mol$^{-1} $ for the cleaved surface. Multilayer desorption is independent of the nature of the forsterite surface used, with a desorption energy of ($25.8\pm0.9$) kJ mol$^{-1} $. On astrophysically relevant heating time-scales, the presence of a coverage dependent desorption energy distribution results in a lengthening of the NH$_3$ desorption time-scale by $5.9\times 10^4$ yr compared to that expected for a single desorption energy. In addition, the presence of a larger number of high-energy adsorption sites on the rougher cut forsterite surface leads to a further lengthening of ca. 7000 yr.

Studies of modified carbon nanotubes by means of thermogravimetry Q-TG and sorptometry techniques

The paper presents the physicochemical (adsorption and porosity) properties of closed carbon nanotubes, opened through the action of an oxidizing acid and modified with metal ions of nickel, cobalt, and iron/cobalt. The carbon nanotubes were prepared via the oxidation process by means of 65 % nitric acid and/or nickel and cobalt nitrates dissolved with 65 % nitric acid. Using special thermogravimetry Q-TG and sorptometry methods physicochemical properties of pure and modified nanotube surfaces were investigated. A numerical and analytical procedure for the evaluation of heterogeneous properties (adsorption capacity, statistical number of adsorbed liquid layers, desorption energy distribution functions) on the basis of liquid thermodesorption Q-TG from the sample surfaces under the quasi-equilibrium conditions are presented. The calculations of the specific surface areas, pore size and volume, and fractal dimensions of carbon nanotubes were made from sorptometry data.

Application of a diffusion-desorption rate equation model in astrochemistry.

Desorption and diffusion are two of the most important processes on interstellar grain surfaces; knowledge of them is critical for the understanding of chemical reaction networks in the interstellar medium (ISM). However, a lack of information on desorption and diffusion is preventing further progress in astrochemistry. To obtain desorption energy distributions of molecules from the surfaces of ISM-related materials, one usually carries out adsorption-desorption temperature programmed desorption (TPD) experiments, and uses rate equation models to extract desorption energy distributions. However, the often-used rate equation models fail to adequately take into account diffusion processes and thus are only valid in situations where adsorption is strongly localized. As adsorption-desorption experiments show that adsorbate molecules tend to occupy deep adsorption sites before occupying shallow ones, a diffusion process must be involved. Thus, it is necessary to include a diffusion term in the model that takes into account the morphology of the surface as obtained from analyses of TPD experiments. We take the experimental data of CO desorption from the MgO(100) surface and of D2 desorption from amorphous solid water ice as examples to show how a diffusion-desorption rate equation model explains the redistribution of adsorbate molecules among different adsorption sites. We extract distributions of desorption energies and diffusion energy barriers from TPD profiles. These examples are contrasted with a system where adsorption is strongly localized--HD from an amorphous silicate surface. Suggestions for experimental investigations are provided.

Adsorption and thermodesorption characteristics of benzene in nanoporous metal organic framework MOF-5

This study has been prepared and characterized a highly nanoporous metal organic framework (MOF-5). The nitrogen adsorption isotherm, gravimetric adsorption and thermodesorption method that utilize a quartz spring balance are used to examine the unusual adsorption behavior. Especially, the hybrid Langmuir–Sips isotherm equation is employed to correlate the experimental isotherm data. Moreover, the unusual adsorption behavior in MOF-5 is discussed in relation to its isosteric enthalpy of adsorption, adsorption energy distribution and desorption energy distribution calculated from benzene adsorption and thermodesorption measurements.

Adsorption and Thermo Desorption Characteristics of Hydrocarbons on Single Walled Carbon Nanotubes

We investigated the heterogeneous adsorption and thermal desorption behaviors of acetone, n-hexane and trichloroethylene (TCE) on single walled carbon nanotubes (SWCNTs). Adsorption isotherms for selected molecules on SWCNTs were measured using a quartz spring balance at temperatures ranging from 303.15 to 323.15 K. Thermal gravimetric desorption experiments were also conducted at different heating rates (2-10 K/min) to obtain information about the interaction strength of hydrocarbons with SWCNTs surfaces. The adsorption isotherm data were analyzed successfully with the temperature dependent Toth equation. To obtain the adsorption and desorption energy distribution functions (AED/DED) for hydrocarbons and nitrogen, the integral equation with Fowler-Guggenheim isotherm (for AED) and first order desorption rate equation (for DED) were solved using the generalized nonlinear regularization method. It was found that Henry's constants, the isosteric heats of adsorption, and the pattern of energy distribution function were highly dependent on the polarizability.

Effect of MgO addition on the basicity of Ni/ZrO2 and on its catalytic activity in carbon dioxide reforming of methane

Abstract The effect of the MgO content on the basicity and on the catalytic performance of Ni/ZrO 2 –MgO catalysts for carbon dioxide reforming of methane was studied. MgO addition to the zirconia support by co-precipitation (5% MgO) had several effects: stabilized the zirconia tetragonal phase by increasing its thermal stability, increased the basicity of the support, and decreased the reducibility of Ni 2+ . The CO 2 desorption energy distribution functions calculated from the TPD-CO 2 profiles were centred at activation energies around 100–134 kJ mol −1 . Besides the effect due to the modification of the zirconia properties by MgO addition, the catalytic activity was also related to the reduction degree of nickel on Ni/ZrO 2 –MgO catalysts, while the catalyst stability was related to the basic properties of the supports.

Adsorption and porosity properties of carbon-covered alumina surfaces

Uniformly carbon-covered alumina (CCA) was prepared via the carbonisation of sucrose highly dispersed on the alumina surface. Using special thermogravimetry and sorptometry methods physicochemical properties of carbon-covered alumina surfaces were investigated. A numerical and analytical procedure for the evaluation of total heterogeneous properties (desorption energy distribution and pore-size distribution functions) on the basis of liquid thermodesorption from the sample surfaces under the quasi-equilibrium conditions are presented. The desorption energy distribution was derived from the mass loss Q-TG and the differential mass loss Q-DTG curves of thermodesorption of pre-adsorbed polar and apolar liquid films. For the first time, the evaluation of the fractal dimensions of carbon-covered alumina using the sorptometry, thermogravimetry and AFM data is presented.

Estimation of total heterogeneity properties of carbon nanotubes

Physico-chemical properties (adsorption capacity, desorption energy distribution and pore-size distribution functions) of nanomaterial surfaces from selected materials, based on sorptometric and liquid thermodesorption measurements under quasi-equilibrium conditions, are presented. The fractal dimensions of nanotubes using sorptometric and AFM data have been evaluated.

Studies of physico-chemical properties of mixed adsorbent in the zeolite/SiO2 system

The paper presents physico-chemical properties of mixed adsorbents in the clinoptylolite (mordenite)/SiO2 system containing 30, 50, 80 mass% zeolite. Adsorption capacity towards polar (water, butanol) and non-polar (n-octane) substances as well as total surface heterogeneity (energetic and geometrical) were determined. Desorption energy distribution functions as well as fractal dimensions were also determined and compared with the low-temperature nitrogen adsorption data. Irregular shapes of the curves q=f(Ed) as well as large values of volumetric fractal dimensions (Df~2.6) revealed heterogeneous properties of the zeolite/SiO2 system surfaces. Addition of zeolite increases total heterogeneity of the material.

Studies of surface properties of Na- and La-montmorillonites

This paper presents possible applications of thermal analysis, sorptometry and porosimetry to study physico-chemical properties of Na- and La-montmorillonite samples, especially for determination of total surface heterogeneity. The quasi-isothermal thermogravimetric (Q-TG) mass loss and its first derivative (Q-DTG) curves with respect to temperature and time obtained during programmed liquid thermodesorption under quasi-isothermal conditions have been used to study adsorbed layers and heterogeneous properties of the Na- and La-montmorillonites. Calculations of the desorption energy distribution functions by analytical procedure using mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption under quasi-isothermal conditions of polar and non-polar liquid vapours preadsorbed on a material surface are presented. Parameters relating to porosity of samples were determined by sorptometry, mercury porosimetry and atomic force microscopy (AFM). From nitrogen sorption isotherms from sorptometry and porosimetry methods, the fractal dimensions of montmorillonites have been calculated. Moreover, a new approach is proposed to calculate fractal dimensions of materials obtained from Q-TG curve; this is compared with values obtained by the above methods. The total heterogeneous properties (energy distribution function and pore-size distribution functions) of samples studied were estimated. The radius and pore volume of the tested samples calculated on the basis of thermogravimetry, sorptometry and porosimetry techniques were compared and good correlations obtained.

Liquid phase synthesis of ethyl- tert-butyl ether: The relationship between acid, adsorption and catalytic properties of zeolite catalysts

The role of acid centers of natural zeolites in synthesis of ethyl- tert-butyl ether (ETBE) was investigated. The method for calculation of desorption energy distribution from stepwise desorption experiment was proposed. The method allows to calculate continuous desorption energy distribution of surface sites using different probes (ammonia, ethanol, iso-butylene, etc.). The correlation between rate of ETBE synthesis and concentration of weak acid sites ( E N H 3 = 70 – 75 kJ mol −1) was found. It has been shown that during ETBE synthesis iso-butylene is activated mainly on medium and strong acid centers and forms one type of surface complex, while ethanol forms two types of adsorbed complexes. Low energy surface ethanol complexes ( E = 53–60 kJ mol −1) located on weak acid centers of zeolites were found to be active in ETBE synthesis. These complexes govern the catalytic activity of catalyst in ETBE synthesis.

Electron stimulated desorption of cesium atoms from germanium-covered tungsten

The electron stimulated desorption (ESD) yield and energy distributions for Cs atoms from cesium layers adsorbed on germanium-covered tungsten have been measured for different Ge film thicknesses, 0.25–4.75 ML (monolayer), as a function of electron energy and cesium coverage Θ. The measurements have been carried out using a time-of-flight method and surface ionization detector. In the majority of measurements Cs is adsorbed at 300 K. The appearance threshold for Cs atoms is about 30 eV, which correlates well with the Ge 3d ionization energy. As the electron energy increases the Cs atom ESD yield passes through a wide maximum at an electron energy of about 120 eV. In the Ge film thickness range from 0.5 to 2 ML, resonant Cs atom yield peaks are observed at electron energies of 50 and 80 eV that can be associated with W 5p and W 5s level excitations. As the cesium coverage increases the Cs atom yield passes through a smooth maximum at 1 ML coverage. The Cs atom ESD energy distributions are bell-shaped; they shift toward higher energies with increasing cesium coverage for thin germanium films and shift toward lower energies with increasing cesium coverage for thick germanium films. The energy distributions for ESD of Cs from a 1 ML Ge film exhibit a strong temperature dependence; at T = 160 K they consist of two bell-shaped curves: a narrow peak with a maximum at a kinetic energy of 0.35 eV and a wider peak with a maximum at a kinetic energy of 0.5 eV. The former is associated with W level excitations and the latter with a Ge 3d level excitation. These results can be interpreted in terms of the Auger stimulated desorption model.