Diffusion Coefficients Of CO2 Research Articles

CO2 hydrate formation in superabsorbent hydrogels for carbon capture—A comparison of water-confined framework vs non-water framework

This study investigates the kinetics of CO2 hydrate formation in saturated hydrogel particles—water-confined frameworks—through both experimental and numerical methods, and compares the results with those obtained in silica gels, silicon-based frameworks. Three hydrogel materials with varying swelling ratios were synthesized via radical polymerization. An advanced shrinking core model was developed, incorporating factors of CO2 solubility, gas diffusion, gas–water reaction, capillary effects, and hydrogel functional groups. Results showed rapid CO2 hydrate growth within the first 100 min, with CO2 uptake reaching 78%–82% of the final amount by 600 min. The highest percent water conversion achieved was 96.6%. Simulations indicated a significant decrease in CO2 diffusion coefficient through the hydrate shell over time, especially in hydrogels with higher methacrylic acid content. Capillary effects diminished as the reaction proceeded, with final water consumption via capillaries accounting for 14.4%–26.7% of the total. Hydrogels with higher swelling ratios and higher agglomeration degree formed more porous hydrate shells, enhancing CO2 diffusion but resulting in lower overall CO2 uptake due to their lower water content. Comparisons with hydrophilic porous silica gel revealed that, although hydrogels initially posed greater mass transfer resistance, they ultimately exhibited superior CO2 absorption capacity and rate.

Molecular Insights into CO2 Diffusion Behavior in Crude Oil

CO2 flooding plays a significant part in enhancing oil recovery and is essential to achieving CCUS (Carbon Capture, Utilization, and Storage). This study aims to understand the fundamental theory of CO2 dissolving and diffusing into crude oil and how these processes vary under reasonable reservoir conditions. In this paper, we primarily use molecular dynamics simulation to construct a multi-component crude oil model with 17 hydrocarbons, which is on the basis of a component analysis of oil samples through laboratory experiments. Then, the CO2 dissolving capacity of the multi-component crude was quantitatively characterized and the impacts of external conditions—including temperature and pressure—on the motion of the CO2 dissolution and diffusion coefficients were systematically investigated. Finally, the swelling behavior of mixed CO2–crude oil was analyzed and the diffusion coefficients were predicted; furthermore, the levels of CO2 impacting the oil’s mobility were analyzed. Results showed that temperature stimulation intensified molecular thermal motion and increased the voids between the alkane molecules, promoting the rapid dissolution and diffusion of CO2. This caused the crude oil to swell and reduced its viscosity, further improving the mobility of the crude oil. As the pressure increased, the voids between the internal and external potential energy of the crude oil models became wider, facilitating the dissolution of CO2. However, when subjected to external compression, the CO2 molecules’ diffusing progress within the oil samples was significantly limited, even diverging to zero, which inhabited the improvement in oil mobility. This study provides some meaningful insights into the effect of CO2 on improving molecular-scale mobility, providing theoretical guidance for subsequent investigations into CO2–crude oil mixtures’ complicated and detailed behavior.

Using Active Learning to Rapidly Develop Machine Learned Diffusion Coefficients of CO2 Conversion Reagents in Metal–Organic Frameworks

Using Active Learning to Rapidly Develop Machine Learned Diffusion Coefficients of CO₂ Conversion Reagents in Metal–Organic Frameworks

Determination of the Diffusion Coefficients of Binary CH4 and C2H6 in a Supercritical CO2 Environment (500–2000 K and 100–1000 atm) by Molecular Dynamics Simulations

The self-diffusion coefficients of carbonaceous fuels in a supercritical CO2 environment provide transport information that can help us understand the Allam Cycle mechanism at a high pressure of 300 atm. The diffusion coefficients of pure CO2 and binary CO2/CH4 and CO2/C2H6 at high temperatures (500 K~2000 K) and high pressures (100 atm~1000 atm) are determined by molecular dynamics simulations in this study. Increasing the temperature leads to an increase in the diffusion coefficient, and increasing the pressure leads to a decrease in the diffusion coefficients for both methane and ethane. The diffusion coefficient of methane at 300 atm is approximately 0.012 cm2/s at 1000 K and 0.032 cm2/s at 1500 K. The diffusion coefficient of ethane at 300 atm is approximately 0.016 cm2/s at 1000 K and 0.045 cm2/s at 1500 K. The understanding of diffusion coefficients potentially leads to the reduction in fuel consumption and minimization of greenhouse gas emissions in the Allam Cycle.

Diffusion of Co and Ga in α-Ti

The diffusion of Co and Ga atoms in α-Ti has been studied using the projector augmented-wave method in combination with the transition state theory. The formation energies of the interstitial and substitutional defects and the corresponding migration and activation energies along two crystallographic directions within the interstitial and vacancy diffusion mechanisms have been calculated. It has been shown that the energetically preferred interstice for the incorporation of both impurities is crowdion. In the case of Co, the formation energy of this defect is only 0.7 eV higher than that of the substitutional defect, while for Ga this difference reaches 2.6 eV. Using the Landman method and the eight-frequency model, the diffusion coefficients of Co and Ga have been calculated within both interstitial and vacancy mechanisms. It has been shown that Co diffusion occurs faster through the interstitials, while Ga diffuses within the vacancy mechanism. The migration and activation energies as well as diffusion coefficients and their anisotropy obtained in these cases are consistent with experimental data.

Cationic Imidazolium-Urethane-Based Poly(Ionic Liquids) Membranes for Enhanced CO2/CH4 Separation: Synthesis, Characterization, and Performance Evaluation.

The escalating emissions of CO2 into the atmosphere require the urgent development of technologies aimed at mitigating environmental impacts. Among these, aqueous amine solutions and polymeric membranes, such as cellulose acetate and polyimide are commercial technologies requiring improvement or substitution to enhance the economic and energetic efficiency of CO2 separation processes. Ionic liquids and poly(ionic liquids) (PILs) are candidates to replace conventional CO2 separation technologies. PILs are a class of materials capable of combining the favorable gas affinity exhibited by ionic liquids (ILs) with the processability inherent in polymeric materials. In this context, the synthesis of the IL GLYMIM[Cl] was performed, followed by ion exchange processes to achieve GLYMIM variants with diverse counter anions (NTf2-, PF6-, and BF4). Subsequently, PIL membranes were fabricated from these tailored ILs and subjected to characterization, employing techniques such as SEC, FTIR, DSC, TGA, DMA, FEG-SEM, and CO2 sorption analysis using the pressure decay method. Furthermore, permeability and ideal selectivity assessments of CO2/CH4 mixture were performed to derive the diffusion and solubility coefficients for both CO2 and CH4. PIL membranes exhibited adequate thermal and mechanical properties. The PIL-BF4 demonstrated CO2 sorption capacities of 33.5 mg CO2/g at 1 bar and 104.8 mg CO2/g at 10 bar. Furthermore, the PIL-BF4 membrane exhibited permeability and ideal (CO2/CH4) selectivity values of 41 barrer and 44, respectively, surpassing those of a commercial cellulose acetate membrane as reported in the existing literature. This study underscores the potential of PIL-based membranes as promising candidates for enhanced CO2 capture technologies.

Competitive adsorption of CH4/CO2 in shale nanopores during static and displacement process

During the development of shale gas, various issues such as low individual well production, rapid decline, limited reservoir control, and low recovery rates have arisen. Enhancing shale gas reservoir recovery rates has consistently been a focal point and challenge within the industry. Therefore, this paper employs molecular dynamic (MD) simulation methods to study the adsorption and diffusion characteristics of CH4/CO2 at different temperatures and mixing ratios. It compares the effects of temperature and CH4/CO2 molar ratio changes on the selectivity coefficient, adsorption capacity, and diffusion coefficient of CH4/CO2. The paper also plots the displacement interface and the function of CH4/CO2 injection/residual amounts over time. Furthermore, it analyzes the adsorption capacity of molecules on the graphene surface, the migration capacity of molecules in the slit, and the displacement process of CH4 by CO2 on the nanoscale, revealing the microscopic mechanism of CH4/CO2 competitive adsorption and displacement. The research results indicate that the influence of temperature on the selectivity coefficient is not significant, with an average decrease of 3% for every 20 K rise in temperature. Pressure has a more pronounced effect on the selectivity coefficient, with values around 1.4 at low pressures and around 1.2 at high pressures. Elevating the mole fraction of CO2 in the binary gas mixture results in an increase in the total adsorption amount and an accelerated variation of adsorption amount with pressure. As the CH4 mole fraction rises, the diffusion coefficient of CH4 increases, while the diffusion coefficient of CO2 diminishes with an increasing CO2 mole fraction. Under identical conditions, CO2 exhibits a stronger adsorption capacity over CH4 in shale organic nanopores, resulting in a concave moon-shaped displacement interface in the model. The larger the pre-adsorption pressure of CO2, the more intense the movement of CO2 along the graphene surface, and the faster the diffusion speed of CO2 along the wall. In a displacement pore (the pore space used to provide the displacement location or site) with a diameter of 3 nm, at smaller pressure differentials (≤10 MPa), the residual amount of CH4 remains relatively stable without substantial alteration. However, at a pressure differential of 20 MPa, the residual amount of CH4 decreases rapidly, and the displacement efficiency significantly improves.

Single-file diffusion and its influence on membrane gas separation: A case study on UTSA-280

Gas permeation in metal-organic framework-based (MOF-based) membranes is often elucidated through the solution-diffusion model, where the adsorption and diffusion of gases play equally vital roles. This study draws attention to a unique phenomenon known as single-file diffusion (SFD) occurring within MOF membranes that possess ultramicropores with dimensions comparable to the gas molecules themselves. When SFD takes place, the separation performance becomes solely reliant on the adsorption quantities on the feed side of the membrane. As a proof of concept, we fabricated a UTSA-280 membrane and subjected it to testing using gas mixtures of CO2/N2 and CO2/CH4. Two crucial observations substantiate the occurrence of single-file diffusion. Firstly, in the gas mixtures, the diffusion coefficients of N2 or CH4 were observed to align closely with that of CO2, despite the intrinsic diffusion coefficients of CO2, N2, and CH4, as determined from single-gas permeation experiments, exhibiting differences. Secondly, the CO2 mole fractions within the adsorption phase closely mirrored those in the gas phase on the permeate side. Given the high adsorption selectivity of UTSA-280 for CO2, the UTSA-280 membrane delivers outstanding permeation selectivity for CO2/N2 (611) and CO2/CH4 (80.7). Our experimental findings are supported by mesoscale kinetic Monte Carlo simulations, which confirmed the relation between the CO2 compositions in the adsorption phase on the feed side and in the gas phase on the permeate side. Furthermore, density functional theory calculations revealed high energy barriers associated with CO2 surpassing its counterparts, rendering such processes unfavorable, thereby reinforcing our experimental findings regarding single-file diffusion.

Phase behavior of rubber and supercritical CO2: Operating parameters and swelling characteristics

AbstractThis study aims to compare the difference in the swelling process between styrene butadiene rubber (SBR) and natural rubber (NR) in ScCO2. A high‐pressure visual stainless‐steel autoclave was used to carry out swelling measurements based on the sample dimensions. The swelling rates for both rubbers followed a first‐order kinetic model. The diffusion coefficient for CO2 was determined from the change in the swelling degree with time. The shrinking process for the expanded rubber obeyed a second‐order kinetic model. A 2‐level full factorial experimental design was employed to discuss the influence of variables on rubber swelling and CO2 diffusion. Temperature and pressure were found to have a great influence on the equilibrium swelling degree, swelling rate and diffusion coefficient. For both SBR and NR, the maximum equilibrium swelling degrees were observed at 120°C and 20 MPa, yielding values of 1.18 and 1.16, respectively. The maximum diffusion coefficient reached approximately 3 × 10−9 m2 s−1 for both types of rubber at 120°C and 8 MPa. The crosslink density failed to affect these three responses, but the volume of expansion and the shrinkage rate were found to significantly decrease and increase, respectively, with increasing crosslink density. The motion of polymer segments forced by ScCO2 led to rearrangement of the material structure, which governed the nature of swelling, expansion, and shrinkage. Due to a lower number of entanglements and a weak electrostatic interaction exists between CO2 and the π‐system, SBR can absorb more CO2 and easily restructure than NR under the same conditions, resulting in higher equilibrium swelling degree, larger expansion and faster shrinkage than NR.Highlights Swelling of nature rubber and styrene‐butadiene rubber in ScCO2 is compared. Swelling degree is positively correlated with temperature and pressure. Diffusion coefficient increases with temperature but decreases with pressure. Swelling degree varies with rubber type, while CO2 diffusion dose not. Crosslink density significantly affects expansion and shrinkage of rubber.

Application of group method of data handling and gene expression programming to modeling molecular diffusivity of CO2 in heavy crudes

Successful enhancement of heavy oil and bitumen production using CO2-based enhanced oil recovery (EOR) techniques requires extensive knowledge about the diffusivity of CO2 in heavy crudes. In this work, two advanced correlative approaches, namely group method of data handling (GMDH) and gene expression programming (GEP), were utilized to establish simple-to-use mathematical correlations by applying a comprehensive dataset including 260 laboratory data of CO2 diffusion coefficient (DC) in heavy crudes and taking into account all the parameters affecting the accuracy of the models. Moreover, the response surface and contour plots were analyzed to obtain the desired response values and operating conditions. The GMDH correlation represented more reliable results with better statistical criteria including average absolute percentage error (AAPRE) values of 7.47%, 7.83%, and 7.54% for training, testing, and the total sets, respectively. Also, the results showed that the increase in pressure and/or temperature caused an increment in the amount of diffusivity of CO2 in heavy crudes; and the maximum amount of CO2 DC was obtained at the upper limit of these operational parameters. At a given temperature and pressure, it appears that the highest CO2 DC in heavy crudes was obtained when the CO2 mass fraction was less than 0.02. Furthermore, the Pearson and Spearman correlation coefficients were used to investigate linear and non-linear relationships between input variables and the responses of GMDH and GEP correlations. The mass fraction of CO2, temperature, pressure, and temperature_PVT had a direct relationship, and on the other hand, the viscosity and density of crudes had a reverse relationship with CO2 DC. Finally, the reliability of the data bank of CO2 DC in heavy crudes along with the high validity of GMDH and GEP correlations was verified by the leverage technique. Notably, no out-of-leverage data were identified, with only seven and five data points considered as suspected for GMDH and GEP models, respectively.

Diffusivity of CO2 in H2O: A Review of Experimental Studies and Molecular Simulations in the Bulk and in Confinement.

An in-depth review of the available experimental and molecular simulation studies of CO2 diffusion in H2O, which is a central property in important industrial and environmental processes, such as carbon capture and storage, enhanced oil recovery, and in the food industry is presented. The cases of both bulk and confined systems are covered. The experimental and molecular simulation data gathered are analyzed, and simple and computationally efficient correlations are devised. These correlations are applicable to conditions from 273 K and 0.1 MPa up to 473 K and 45 MPa. The available experimental data for diffusion coefficients of CO2 in brines are also collected, and their dependency on temperature, pressure, and salinity is examined in detail. Other engineering models and correlations reported in literature are also presented. The review of the simulation studies focuses on the force field combinations, the data for diffusivities at low and high pressures, finite-size effects, and the correlations developed based on the Molecular Dynamics data. Regarding the confined systems, we review the main methods to measure and compute the diffusivity of confined CO2 and discuss the main natural and artificial confining media (i.e., smectites, calcites, silica, MOFs, and carbon materials). Detailed discussion is provided regarding the driving force for diffusion of CO2 and H2O under confinement, and on the role of effects such as H2O adsorption on hydrophilic confining media on the diffusivity of CO2. Finally, an outlook of future research paths for advancing the field of CO2 diffusivity in H2O at the bulk phase and in confinement is laid out.

Determination of the Diffusion Coefficient in Electrodeposition Reactions by Electrochemical Impedance Spectroscopy: A Case Study of Cobalt in Molten LiCl-KCl Salt

Compared to direct current (DC) techniques, electrochemical impedance spectroscopy (EIS) allows for a more accurate determination of the diffusion coefficient of metal ions in electrodeposition reactions. However, its actual application has been less attempted due to the difficulty in determining complex parameters, such as the concentration of deposited species in the electrode matrix. Here, we introduce a simplified approach to facilitate the EIS application to electrodeposition reactions, using the Co(II)/Co(0) reaction in molten LiCl-KCl salt as a case study. The working electrode surface area was determined by the photography of the electrochemical cell taken in situ. The diffusion coefficients of Co(II) in the LiCl-KCl salt, determined by EIS, were found to be (3.56 ± 0.49) × 10−5 cm2/s and (1.61 ± 0.12) × 10−5 cm2/s for the tungsten and liquid bismuth electrodes, respectively. The possible reasons for the observed discrepancy in the diffusion coefficients of Co(II) obtained from the two different electrodes were discussed.

Enhanced oil recovery via dissolution of low molecular weight PDMS in CO2 during immiscible gas injection in matrix-fracture system

Oil recovery in natural fracture reservoirs can be improved by reducing the capillary force during the gravity drainage process in matrix-fracture system. In the current study, a modified gas was generated via dissolution of low molecular weight poly(dimethyl siloxane) (PDMS, average Mw 3780 g/mol, 10000 – 50000 ppm) in CO2 to enhance oil recovery at 50 °C or 70 °C and 3000 psi. Cloud point measurements indicated that PDMS dissolved in CO2 at pressures less than 3000 psi, which was below the minimum miscibility pressure (MMP) of ∼3600 psi at 70 °C determined with the vanishing interfacial technique. The solution density increased from 669.6 kg/m3 for pure CO2 to 780.3 kg/m3 for CO2/PDMS (50000 ppm) at 70 °C and 3000 psi, thereby reducing the density difference between the CO2-rich fluid and crude oil (ρo=865.2 kg/m3) in matrix-fracture system. Also, CO2-oil interfacial tension (IFT) was reduced from 65 to 15 dyn/cm via the dissolution of 50000 ppm PDMS in CO2. Therefore, it led to the CO2 diffusion coefficient increased in both reservoir-fluid saturated porous media and bulk oil scenarios 3–4 fold and 4–7 fold respectively in comparison to pure CO2 injection. These PDMS-induced changes reduced the capillary effects in gas-invaded zone, which consequently led to an increase in oil recovery of 25% points (from 31% to 56%) compared to pure CO2 injection in the case of capillary continuity during gravity drainage tests. For the field-scale, because the PDMS can dissolve in CO2 at pressures and temperatures which are commensurate with CO2 EOR, it is a promising CO2-philic chemical for increasing CO2 density and improving CO2 diffusion coefficient in gas invaded zone compared to conventional CO2 injection.

Calculating diffusion coefficients from molecular dynamics simulations for modelling foam processes of polypropylene: Investigating different process conditions and blowing agents

The choice of blowing agent is very important in foaming processes. In an earlier work the use of molecular dynamics simulations for the estimation of the diffusion coefficients of different blowing agents was discussed at elevated temperatures above the melting point. Therein it was shown that these simulations can give valuable information on blowing agent diffusion in polypropylene. The aim of the recent work is to expand this discussion to the simulation of different influences like pressure, blowing agent mixtures and blowing agents with higher molecular weight at temperatures above the melting point of PP. First a pressure range applied on the combined system of polymer and blowing agent, reasonable for the foam processing is discussed and their influence on the diffusion coefficients for CO2 in polypropylene is evaluated via MD simulations. The next step is the investigation of the influence of mixing a blowing agent with a co-blowing agent. The last part is the presentation of diffusion coefficients for different organic solvents, namely 2-propanol, acetone, ethyl acetate and butyl acetate which could be used as potential co-blowing agents. For both, the change in pressure and the mixing of blowing agents for the systems in question only small influences on the diffusion coefficients was discovered. The results of the diffusion coefficients for the different organic solvents are compared to each other and with former results, considered different molecular structure, size and polarities and are found to be reasonable.

Simulation study on the coupled heat and mass transfer of CO2 in a heavy oil-water liquid system based on an improved lattice Boltzmann (LB) method

This study investigates the heat and mass transfer when low-temperature CO2 diffuses in a heavy oil–water liquid system based on an improved Lattice Boltzmann (LB) method. First, we determine the CO2 diffusion coefficients in heavy oil and water and the heat transfer coefficients of heavy oil and water using the pressure drop (DP) method and the laser flash (LF) method, respectively. Then, a numerical model that couples the heat and mass transfer in the system is established based on the improved LB method. The effect of low-temperature CO2 on the temperature field of the system and the effect of changes in the temperature field on CO2 diffusion are investigated. Finally, we develop a micro-model reproducing the heat and mass transfer of CO2 in water and heavy oil-saturated porous media to validate the accuracy of the numerical model. The results demonstrate that the CO2 diffusion coefficients in heavy oil and water linearly increase with the temperature increases. The heat transfer coefficients of heavy oil and water are insensitive to the changes in temperature. The heat transfer process has a great impact on the mass transfer of CO2 in the liquid system. The CO2 diffusion velocity slows down as the system temperature decreases because of the heat transfer (from 400 K to 300 K), leading to a reduction percentage of 300 % in the CO2 front movement velocity. Compared to the scenarios neglecting heat transfer, CO2 diffusion distance and amount decrease by 38 % and 50 %, respectively because of the changes in the temperature field of the system.

Optimization of Flow-By CO2 Electrolyzers: Impact of Differential Pressure and Gas Diffusion Layer Composition

The electrochemical reduction of CO2 (eCO2R) into valuable chemicals offers a great ecological solution to lower anthropogenic CO2 in the atmosphere, since it can close the carbon cycle by utilizing renewable energy, resulting in a sustainable carbon recycling system. Consequently, it has gathered significant scientific interest over the past decade [1,2]. However, to make significant progress towards making the process industrially feasible, it would be beneficial to replace the typical anodic oxygen evolution reaction at the counter electrode with an economically more interesting one, like alkane dehydrogenation, while at the same time lowering cell potential and increasing energy efficiency. However, this requires the CO2 reduction to operate efficiently at elevated temperatures (up to 100°C) [3]. Unfortunately, little is known on the impact of elevated temperatures on the overall performance of CO2 electrolyzers and its components.In this research, we studied the effect of increasing the temperature on CO2 electrolyzers to ultimately enable selective and stable eCO2R to formic acid not only at room temperature. Heating the system leads to many changes (e.g. decreased electrolyte surface tension, decreased hydrophobicity of the gas diffusion layer (GDL), lower dissolved CO2 content and, increased CO2 diffusion coefficient), all affecting the performance of a conventional CO2 electrolyzer, consequently raising the need for re-evaluating many of its components and their configuration, considering they have been optimized for operation at ambient conditions. Specifically, we focused on the three-phase boundary, where the eCO2R reaction actually takes place. Logically, it is important that this boundary is at the exact location of the catalyst layer (CL), as the catalyst is the active species towards the desired reaction. To this end, GDLs are specifically designed to align this boundary to the right location through variations in hydrophobic additives, thickness, porosity, etc. However, we have found that all these efforts to perfect the GDL's properties can be forfeited if the differential pressure across it were to change as it shifts the three-phase boundary. A shift inwards the GDL will result in a flooded CL, lengthening the diffusion path of the gaseous CO2 in the electrolyte to the active sites of the CL resulting in increased hydrogen evolution. A shift outward the GDL will result in a CL that is not fully used, as such lowering the activity. Since the CL is a thin layer, it can be easily understood that the margin within which the boundary can shift without becoming catastrophic for the overall performance is very small, making it extremely critical to have precise control over its position. Changing the temperature of the system will affect the location of the boundary layer and by optimizing the differential pressure we can shift its location back to its optimal position and increase the performance of the CO2 electrolyzer.We investigated the influence of deliberately altering the differential pressure across a GDE in a flow-by electrolyzer with Bi2O3 nanoparticles for the eCO2R towards formate, at different temperatures. At higher temperatures (i.e. 85°C), flooding was a pronounced problem, which resulted in a rapid decrease of performance, and after 24 hours of electrolysis only a 40% faradaic efficiency towards formate (FEHCOOH) was maintained from the initial 70%. We discovered that by increasing the differential pressure, by elevating the backpressure at the gas side, we could limit flooding of the GDE. By mitigating the flooding, the system was able to maintain a better performance, i.e. FEHCOOH of 65% after 24 hours of electrolysis was maintained, which is a 1.6 factor increase (Figure). The present findings confirm that, without altering any of the more significant electrochemical aspects of the electrolyzer, it is possible to increase performance by solely varying the differential pressure over the GDE, showing the importance of also optimizing the operational conditions.Once the optimal differential pressure of the system was established, it was still necessary to investigate the GDE structure itself. Indeed, the GDE should be designed to appropriately mediate all transport processes necessary to achieve high eCO2R performance and further reduce flooding phenomena, by favourably affecting CO2 transport, local pH and water transport [4]. Therefore, the next step was to investigate and compare other commercially available GDLs. For this research we selected commercially available GDLs that are primarily used in high-temperature proton exchange fuel cells, since their required characteristics (hydrophobicity, thickness and pore structure) are similar to the needs of our system.By re-evaluating and optimizing these (operational) conditions, we are getting closer to making the electrochemical CO2 reduction efficient, also at elevated temperatures.[1] https://doi.org/10.1016/j.petlm.2016.11.003[2] https://doi.org/10.1016/j.joule.2017.09.003[3] https://doi.org/10.1002.celc.201900872[4] https://doi.org/10.1038/s41578-021-00356-2 Figure 1

Effect of metal ion intercalation on the gas diffusion confined in two-dimensional MXene nanosheets

Designing and regulating the metal ion adsorption sites is an effective strategy to improve the gas separation performance of porous materials. The diffusion behavior of gas molecules (H2, H2O, CO2, N2, CH4, SO2 and COS) confined in ion intercalated (Li+, Na+, K+, Rb+, Cs+, Mg2+ and Al3+) MXene nanoslits was studied by molecular dynamics method. The results showed that, due to the increase of steric hindrance after ion intercalation, the diffusion of gas molecules in confined nanoslits is subject to varying degrees of restriction. The diffusion coefficients of CO2, SO2 and COS, which interact strongly with metal ions, are significantly reduced, thus significantly improving the diffusion selectivity between these molecules and weakly interacting molecules (H2, N2 and CH4). In particular, Al3+, which has a high charge number and a small ionic radius, has a significant effect on improving the diffusion selectivity of mixed gases. The effect of metal ion intercalated MXene on the selectivity of the gas mixture is the result of the synergistic effect of adsorption and steric hindrance.

Insights into adsorption and diffusion of CO2, CH4 and their mixture in MIL-101(Cr) via molecular simulation

An in-depth comprehension of the adsorption and diffusion properties of CH4, CO2, and their mixture in MIL-101(Cr) is crucial for its application in the highly selective separation of CO2 and CH4 mixtures in biogas. Existing studies often overlook the influence of gas molecular radius and MIL-101 topological structure on adsorption and lack quantitative analysis of the primary and secondary adsorption sites of MIL-101. Additionally, there is a significant gap in research on the adsorption mechanism of gas mixtures. To address these gaps and to provide new knowledge, this study employs Monte Carlo and molecular dynamics simulations to evaluate various factors such as CH4 and CO2 adsorption isotherms, density distribution profiles, self-diffusion coefficients, radial distribution functions (RDF), and CO2/CH4 selectivity within MIL-101 metal-organic framework (MOF). The insightful and comprehensive atomic-level study reveals several unique and new findings, include 1) the RDF analysis shows that the C = C double bond of the benzene ring within MIL-101 primarily governs the adsorption of CH4, while the open metal center (Cr) exhibits significant adsorption effects on CO2; 2) the density distribution profile analysis indicates that CH4 molecules tend to localize in the larger and medium-sized cages, whereas CO2 molecules exhibit relatively uniform distribution. 3) evaluation of self-diffusivity coefficients and diffusion activation energies demonstrated that CH4 diffuses more easily than CO2, and in the CO2 and CH4 two-component gas, the existence of CH4 can further reduce the diffusion coefficient of CO2. This investigation provides a microscopic understanding of adsorption and diffusion phenomena within MIL-101, contributing to the overall comprehension of its behavior in gas separation applications.

Amino acid ionic liquids as efficient catalysts for CO2 capture: A combined static and dynamic approach

Amino acid ionic liquids (AAILs) have gained significant attention as green solvents that are biocompatible, biodegradable, and useful in various applications, including catalysts, absorbents, and solvents. This study investigates the detailed interactions of three amino acid anions (glycine [Gly]-, histidine [His]-, and arginine [Arg]-) with the cation 1-methoxylbutyl-3-methylimidazolium [MOBMIM]+ and their role in CO2 absorption using quantum mechanical calculations and molecular dynamics (MD) simulations. The Density Functional Theory (DFT) calculations elucidate the reaction mechanisms underlying CO2 absorption and cycloaddition, and facilitate a comparative analysis of the impact of different amino acids on these reactions, and the synergies between them. Notably, arginine displays superior CO2 absorption capacity in comparison to glycine and histidine. Additionally, the cycloaddition reaction with CO2 exhibits a lower energy barrier when arginine is involved. Insights from the MD simulations highlight the higher level of electrostatic interaction between [MOBMIM]+[Arg]- and CO2, relative to the other studied molecules. Moreover, the Lennard Jones interaction emerges as the dominant type of interaction in these systems. The diffusion coefficient for CO2 was highest when interacting with [MOBMIM]+[Gly]-, followed by [MOBMIM]+[Arg]-. Consequently, both MD and DFT investigations converge to suggest that [MOBMIM]+[Arg]- followed by [MOBMIM]+[Gly]- may serve as advantageous choices for CO2 fixation and cycloaddition. The findings from this study underscore the considerable potential of the investigated AAILs as materials conducive to CO2 capture and utilization, thus paving the way for the integration of CO2 capture into valuable chemical products.

Effect of Amino-Functionalized Polyhedral Oligomeric Silsesquioxanes on Structure-Property Relationships of Thermostable Hybrid Cyanate Ester Resin Based Nanocomposites.

Nanocomposites of cyanate ester resin (CER) filled with three different reactive amino-functionalized polyhedral oligomeric silsesquioxane (POSS) were synthesized and characterized. The addition of a small quantity (0.1 wt.%) of amino-POSS chemically grafted to the CER network led to the increasing thermal stability of the CER matrix by 12-15 °C, depending on the type of amino-POSS. A significant increase of the glass transition temperature, Tg (DSC data), and the temperature of α relaxation, Tα (DMTA data), by 45-55 °C of the CER matrix with loading of nanofillers was evidenced. CER/POSS films exhibited a higher storage modulus than that of neat CER in the temperature range investigated. It was evidenced that CER/aminopropylisobutyl (APIB)-POSS, CER/N-phenylaminopropyl (NPAP)-POSS, and CER/aminoethyl aminopropylisobutyl (AEAPIB)-POSS nanocomposites induced a more homogenous α relaxation phenomenon with higher Tα values and an enhanced nanocomposite elastic behavior. The value of the storage modulus, E', at 25 °C increased from 2.72 GPa for the pure CER matrix to 2.99-3.24 GPa for the nanocomposites with amino-functionalized POSS nanoparticles. Furthermore, CER/amino-POSS nanocomposites possessed a higher specific surface area, gas permeability (CO2, He), and diffusion coefficients (CO2) values than those for neat CER, due to an increasing free volume of the nanocomposites studied that is very important for their gas transport properties. Permeability grew by about 2 (He) and 3.5-4 times (CO2), respectively, and the diffusion coefficient of CO2 increased approximately twice for CER/amino-POSS nanocomposites in comparison with the neat CER network. The efficiency of amino-functionalized POSS in improving the thermal and transport properties of the CER/amino-POSS nanocomposites increased in a raw of reactive POSS containing one primary (APIB-POSS) < eight secondary (NPAP-POSS) < one secondary and one primary (AEAPIB-POSS) amino groups. APIB-POSS had the least strongly pronounced effect, since it could form covalent bonds with the CER network only by a reaction of one -NH2 group, while AEAPIB-POSS displayed the most highly marked effect, since it could easily be incorporated into the CER network via a reaction of -NH2 and -NH- groups with -O-C≡N groups from CER.