CO2 Clusters Research Articles

Rotational spectra of ten new fluoroethylene/CO2 clusters, (C2H3F)x(CO2)y: Application of data-centered methods to the assignment of spectra in complex mixtures

Chirped-pulse Fourier-transform microwave (CP-FTMW) spectroscopy has been used to measure the spectra of ten previously unobserved fluoroethylene (FE)/CO2 clusters, (FE)x(CO2)y, with x from 1 to 4 and y from 0 to 4. Multiple spectra were recorded with varying concentrations of CO2 in the sample, and at least 400,000 free induction decays averaged per data set. This allowed implementation of data-centered approaches, using intensity variation, to identify subsets of transitions belonging to the same cluster species or those of similar composition, simplifying the assignment process for the complex mixture of clusters present. All spectra were fitted to Watson A-reduction Hamiltonians, including quartic distortion constants, with very few species requiring higher order distortion constants for satisfactory fits to be obtained. Computational data at MP2/6-311++G(2d,2p) and ωB97X-D/6-31+G(d,p) levels suggested FE:CO2 ratios and likely structural arrangements of each cluster based on comparisons with experimental rotational constants.

Micro-scale experimental investigations of CO2-WAG injection and Ostwald ripening analysis in carbonate rocks with different pore structures

Carbonate reservoirs are rich in hydrocarbon resources. However, carbonate reservoirs usually have strong pore structure heterogeneity, and thus it is necessary to understand the effect of heterogeneity on pore-scale fluid distributions during CO2 enhanced oil recover (CO2-EOR) process. We thus conducted water-alternating-gas (CO2-WAG) injection in the three carbonate samples with strong to weak heterogeneity. The 15 sets of images showed that the fractured-vuggy carbonate with the strongest heterogeneity had the highest additional oil recovery. CO2-WAG injection significantly changed the residual oil distribution, and further oil production can be achieved by increasing the number of CO2-WAG cycles. For CO2 geological storage, with the increase of carbonate heterogeneity, CO2 capillary-trapping capacity decreased, CO2 dissolution trapping potentiality decreased, but the stability of CO2 capillary trapping enhanced. These key parameters related to CO2 storage were described through the saturation of trapped gas, the types of trapped gas, and the surface area-volume relationship of CO2 clusters. For example, the higher amount of network gas is detrimental to the stability of CO2 capillary trapping because the network gas is easily displaced when the hydrodynamic force is enhanced. The specific surface area of CO2 cluster determines dissolution dynamics, and a higher specific surface area is beneficial for CO2 dissolution. Another interesting phenomenon - Ostwald ripening, is related to long-term CO2 transport. The CO2 concentration gradient in aquifer generates a vertically upward diffusive flux, causing CO2 remobilization. By calculating the height of the transition zone and the time to reach gravity-capillary pressure equilibrium, we found that as carbonate heterogeneity increased, the height of transition zone (the area where CO2 is trapped by capillary pressure) increased, while equilibrium time shortened. By comparing the results of previous gas-water two-phase flow experiments, we believe that the relationship between CO2 storage characteristics and carbonate heterogeneity summarized in this paper are universally applicable.

The pulmonary neuroepithelial body-vagal sensory nerve axis is altered in a mouse model of bronchopulmonary dysplasia (BPD)

Breathing control problems, like apnea of prematurity, are a common complication in preterm infants with bronchopulmonary dysplasia (BPD), but the underlying factors remain incompletely understood. A subpopulation of pulmonary vagal afferent nerve fibers (Calb1+) innervate CO2 and O2 sensitive clusters of lung neuroendocrine cells (neuroepithelial bodies (NEBs)) located along conducting airways. Calb1+ fibers provide direct sensory input to the brainstem that putatively limit tidal volume. NEBs are hyperplastic in BPD infants and may increase activity of inhibitory Calb1+ vagal fibers. Herein, we sought to determine if the NEB-Calb1 lung-brainstem axis is altered in association with breathing control in BPD. BPD in mice was established by exposure to chronic neonatal (postnatal day (P) 0-14) hyperoxia (Hx; 70% O2; n=20) or normoxia (Nx; n=17). Consistent with human BPD, Hx caused alveolar simplification supported by a reduction in alveolar density and alveoli (p<0.05; separate t-tests) in P22 H&E-stained lung sections (n=5-7/group). Like human infants at risk for BPD, Hx mice adapted to increased dead space (caused by reduction in alveoli) by hyperventilating (p<0.05; generalized linear modeling accounting for fat free mass and heat production, measured by NMR and respirometry; n=10-24/group). This was facilitated by an increase in tidal volume that was significantly reduced at P14 but increased at P17 and P21 (n=19-28) (Tukey’s post-hoc: p<0.05). NEBs and associated innervation (vagal and dorsal root ganglia) were next assessed in subsets of mice. First, IT instillation of WGA-594 lectin into subsets of mice (n=9 mice/18 ganglia per group) and subsequent quantification of 594+ neurons per vagal ganglia revealed fewer neurons (p=0.07; t-test) in Hx mice (110.8 ± 6.9 vs 95.2 ± 4.9). Second, CGRP+ innervation to NEBs is reduced in Hx mice (Quantification of CGRP+ nerve fibers only: 17740.4 +/- 4126 vs 10474.6 +/- 2140 +CGRP pixels; p=0.12 n=5-7/group). Third, there was greater frequency of NEBs per unit airway (p<0.05; 0.306 ± 0.03 vs 0.401 ± 0.03) with a tendency for larger NEBs (p=0.06; 9.14 ± 0.7 vs 11.93 ± 1.3) indicating NEB hyperplasia. Together, these data indicate individual NEB innervation is reduced in BPD but that total NEB innervation may remain unchanged. If this is true for Calb1+ vagal fibers remain untested. To functionally assess Calb1-vagal fibers we activated, with DCZ, the excitatory synthetic Gq-DREAD receptor (DTR) expressed in Calb1cre mice via microinjection of AAV-Cre-Gq-mCherry into the left vagal ganglia. DCZ but not vehicle caused a major increase in peak inspiratory flow during acute hypoxic challenges compared to vehicle treated mice (Pre-DMSO, Post-DMSO, Pre-DCZ = ~1ml/sec vs 4ml/sec post-DCZ; p<0.05, n=4/group). Collection of vagal ganglia confirms DTR expression but spillover of DTR is present. Repeating these studies with diluted AAV-Cre-Gq in control and BPD mice are ongoing. Together, our data verify that hyperoxia induced BPD in mice causes a similar reduction in alveoli and compensation to increased dead space by hyperventilation as observed in human BPD. Additionally, BPD structurally alters the NEB-vagal axis but whether these changes are functionally significant to nCOB is being addressed with ongoing studies. AHA 20CDA35310121, Advancing Healthier Wisconsin Endowment. This is the full abstract presented at the American Physiology Summit 2024 meeting and is only available in HTML format. There are no additional versions or additional content available for this abstract. Physiology was not involved in the peer review process.

Simulation of CO2 dissolution reactions in saline aquifers using lattice Boltzmann method

CO2 dissolution reactions in saline aquifers during geologic carbon sequestration (GCS) involve multiple physicochemical processes and pose a challenge for both experimental and numerical techniques to capture reactive transport features and complex porous structures. Benefited from advanced models in the lattice Boltzmann (LB) community, namely, multiphase flow LB model and multicomponent transport LB model with chemical reactions, dynamics of CO2-water interfaces, concentration evolution of ions, and heterogeneous and homogeneous reactions could be readily captured by the proposed LB model to characterize CO2 dissolution reactions applicable to far-field applications. This LB model can not only emphasize CO2 dissolution processes at the scale of a few pores but also elaborate on the corresponding controlling mechanisms in porous media during GCS in saline aquifers. LB simulations herein indicate that both diffusion coefficient and reactive interfacial length may change the total concentration gradient at the CO2-water interface to further affect CO2 dissolution reactions. It is also confirmed that CO2 dissolution is a non-equilibrium process, which could not be neglected in reservoir-scale simulations. The effect of reactive interfacial length on CO2 dissolution is negligible due to a narrower range of contact angles in saline aquifers. Influenced by the structural complexity of porous media, the dissolution of CO2 clusters shows a strong heterogeneous characteristic evaluated by the pore size distribution. The evolution of pH in homogeneous reactions is estimated via mass action equations. Besides, the effects of partial pressure, formation temperature, and salinity, as three key factors in the practical application, are thoroughly probed. The high pressure is conducive for sequestration because of its greater sequestration efficiency, but the temperature has both positive and negative impacts on CO2 dissolution trapping and should be carefully evaluated in a certain saline aquifer before the operation. High ion strength would decrease the efficiency of dissolution trapping to some extent.

Pore-scale flow simulation of CO2 sequestration in deep shale based on thermal-hydro-mechanical coupled model

The technology of sequestering CO2 in deep shale has shown great potential due to the low permeability of shale and the high adsorption of CO2 by organic-rich characteristics. Deep shale is characterized by high temperature and high pressure with a significant hydro-mechanical coupling effect. The Darcy–Brinkman–Stokes method was integrated with heat transfer equations to simulate thermal-hydro-mechanical coupled single-phase steady-state flow, combined with multiphase flow equations to simulate hydro-mechanical coupled transient flow under high-temperature conditions. This study aims to reveal the effect of temperature difference between CO2 and reservoir, Reynolds number, and formation pressure on the flow process of CO2 geological storage in deep shale based on the constructed real core structure consisting of organic pore, organic matter, and inorganic matter. The results indicate that low-temperature CO2 is conducive to giving full play to the role of convection heat transfer, improving the CO2 saturation and the swept volume of organic pores. The Reynolds number has a negligible impact on the transition of convective and conduction heat transfer. At higher Reynolds numbers, CO2 flows extensively and deeply, and CO2 clusters occupy a higher proportion in organic pores. At higher confining pressures, the Nusselt number is higher and convective heat transfer is more dominant. Shallower reservoirs are favorable conditions for adsorption trapping, as their cores are subjected to slightly lower confining pressure, resulting in higher CO2 saturation in the organic matter and higher sweep efficiency of organic pores. Our main finding is that low-temperature CO2, a higher Reynolds number, and shallower buried depth favor carbon sequestration.

CO2-brine mass transfer patterns and interface dynamics under geological storage conditions

CO2 geological storage is a promising carbon negative technology with important application prospects. Dissolution trapping is a reliable method throughout the life cycle of a storage project, because it plays a significant role in minimizing risks. A comprehensive understanding of its mechanism is challenging due to the complex mass transfer process controlled by numerous physical and chemical factors, which needs to be clarified at different scales but still significantly limited in current research. Investigating CO2-brine interfacial mass transfer in real rock cores during imbibition provides valuable insights into the behavior of CO2 in geological formations. This study conducted a series of pore-scale CO2-brine interfacial mass transfer experiments during imbibition in three rock cores using an X-ray micro-computed tomography machine. The dissolution patterns and interface dynamics during the dissolving processes were discussed systematically. The results indicate that the overall slice-averaged and per-cluster mass transfer coefficient between CO2 and brine is in the order of 10−8 m/s, but its specific value depends on the dissolution patterns and bubble sizes. Various dissolution patterns were found in different rock cores. A core-length dissolution finger was formed in the Berea core, causing higher per-cluster mass transfer coefficients around the finger, while lower coefficients elsewhere in the dissolution experiments. The interfacial mass transfer process, coupled with gravity instability, induced remobilization of isolated CO2 bubbles at a much lower capillary number than the critical capillary number. The remobilization of CO2 bubbles can even occur at single-pore scale. CO2 remobilization also created a phenomenon similar to intermittent pathway flow. Interface dynamics of CO2 dissolving processes were revealed for the first time, giving rise to non-uniform dissolutions in CO2 singlets, ganglia, and clusters, respectively.

Heterocycles for direct air capture and MOFs prepared from CO2 utilization

Direct air capture via heterocycles and various flexible MOFs prepared from CO2, heterocycles, and Zn clusters.

Two diverse 3D 6-connected Cd(II)/Co(II) MOFs based on binuclear clusters as fluorescence sensors for detection of Fe3+, Cr2O72− and nitrobenzene

Two novel three-dimensional (3D) Cd(II)/Co(II) metal-organic frameworks (MOFs), [Cd2(seb)2(bbmb)(H2O)2]n (1) and {[Co2(seb)2(bbmb)2(H2O)]·0·5H2O}n (2), were synthesized under hydrothermal conditions based on sebacic acid (H2seb) and 4,4′-Bis(benzimidazol-1-ylmethyl) biphenyl (bbmb) ligands. Their crystal structures were structurally characterized by single-crystal X-ray diffraction. MOFs 1 and 2 both show a 3D framework based on binuclear Cd2 or Co2 clusters, respectively. In 1, the Cd2 clusters are linked by seb2- into a 2D corrugated layer. These layers are further connected by bbmb to generate a 3D structure with 6-connected (44·610·8) mab topology. In 2, the Co2 clusters form a 1D chain through the bbmb ligands, the chains are linked by seb2− into a 3D framework with 6-connected (48·54·63) bsn topology. Fluorescence sensing experiments show that 1 and 2 have good ability for detection of Fe3+, Cr2O72− and nitrobenzene (NB) with low detection limits as 5.83μM, 1.36μM and 2.70 × 10−7M for 1 and 6.19μM, 1.40μM and 2.90 × 10−7M for 2, respectively. Furthermore, the sensing mechanism was also investigated in detail by various detection means and theoretical calculations.

Pore-scale numerical simulation of supercritical CO2-brine two-phase flow based on VOF method

CO2 capture and storage technology is favorable for the reduction of CO2 emissions. In recent years, a great number of research achievements have been obtained on CO2 geological storage from nano scale to oil/gas reservoir scale, but most studies only focus on the flow behaviors in single-dimension porous media. Besides, the physical experiment method is influenced by many uncertain factors and consumes a lot of time and cost. In order to deeply understand the flow behaviors in the process of CO2 geological storage in microscopic view and increase the volume of CO2 geological storage, this paper established 2D and 3D models by using VOF (Volume of Fluid) method which can track the dynamic change of two-phase interface, to numerically simulate supercritical CO2-brine two-phase flow. Then, the distribution characteristics of CO2 clusters and the variation laws of CO2 saturation under different wettability, capillary number and viscosity ratio conditions were compared, and the intrinsic mechanisms of CO2 storage at pore scale were revealed. And the following research results were obtained. First, with the increase of rock wettability to CO2, the sweep range of CO2 enlarged, and the disconnection frequency of CO2 clusters deceased, and thus the volume of CO2 storage increased. Second, with the increase of capillary number, the displacement mode transformed from capillary fingering to stable displacement, and thus the volume of CO2 storage increased. Third, as the viscosity of injected supercritical CO2 gradually approached that of brine, the flow resistance between two-phase fluids decreased, promoting the "lubricating effect". As a result, the flow capacity of CO2 phase was improved, and thus the volume of CO2 storage was increased. Fourth, the influence degrees of wettability, capillary number and viscosity ratio on CO2 saturation were different in multi-dimensional porous media models. In conclusion, the CO2-brine two-phase flow simulation based on VOF method revealed the flow mechanisms in the process of CO2 geological storage at pore scale, which is of guiding significance to the development of CCUS technology and provides theoretical guidance and technical support for the study of CO2 geological storage in a larger scale.

Temperature-dependent rearrangement of gas molecules in ultramicroporous materials for tunable adsorption of CO2 and C2H2

The interactions between adsorbed gas molecules within porous metal-organic frameworks are crucial to gas selectivity but remain poorly explored. Here, we report the modulation of packing geometries of CO2 and C2H2 clusters within the ultramicroporous CUK-1 material as a function of temperature. In-situ synchrotron X-ray diffraction reveals a unique temperature-dependent reversal of CO2 and C2H2 adsorption affinities on CUK-1, which is validated by gas sorption and dynamic breakthrough experiments, affording high-purity C2H2 (99.95%) from the equimolar mixture of C2H2/CO2 via a one-step purification process. At low temperatures (<253 K), CUK-1 preferentially adsorbs CO2 with both high selectivity (>10) and capacity (170 cm3 g−1) owing to the formation of CO2 tetramers that simultaneously maximize the guest-guest and host-guest interactions. At room temperature, conventionally selective adsorption of C2H2 is observed. The selectivity reversal, structural robustness, and facile regeneration of CUK-1 suggest its potential for producing high-purity C2H2 by temperature-swing sorption.

The NEB-P2ry1 lung-brainstem axis and the control of breathing in a mouse model of bronchopulmonary dysplasia

Breathing control problems, like apnea of prematurity, are a common complication in preterm infants with bronchopulmonary dysplasia (BPD), but the underlying factors remain incompletely understood. A subpopulation of pulmonary vagal afferent nerve fibers (P2ry1+) innervate CO2 and O2 sensitive clusters of lung neuroendocrine cells (neuroepithelial bodies (NEBs)) located along conducting airways. P2ry1 fibers provide direct sensory input to the brainstem and inhibit breathing upon stimulation. NEBs are hyperplastic in BPD infants and may increase activity of inhibitory P2ry1 vagal fibers. Herein, we sought to determine if the NEB-P2ry1 lung-brainstem axis is altered in association with breathing control in BPD. BPD in mice was induced by exposure to chronic neonatal (postnatal day (P) 0-14) hyperoxia (Hx; 70% O2; n=20) or normoxia (Nx; n=17). Consistent with human BPD, Hx caused alveolar simplification supported by a reduction in alveolar density (p&lt;0.05) and alveoli (p&lt;0.05) in P22 H&amp;E-stained lung sections. Hx mice spent more time apneic at P14 and P17 (p&lt;0.05) in room air and acute hypoxia. Overall (main effect), room air minute ventilation (VE) was reduced in HX mice (p&lt;0.05). Further, VE was reduced during acute hypoxia at P14 and P17 (not P21) with an overall reduction of breathing in Hx mice (p&lt;0.05). From a subset of mice (n=4-5/group) VCO2, VO2, and heat production at rest were greater in P21 Hx mice during room air, suggesting the Hx mice were hypoventilating. Immunofluorescent staining of CGRP (hallmark NEB marker), Ki67 (proliferation), and SEZ6L2 (new NEB cell-membrane marker) in Hx and Nx lungs were imaged and analyzed by a blinded investigator. Consistent with clinical findings, Hx mice had hyperplastic NEBs (8.6 ± 0.45 vs 10.7 ± 1.3 cells/NEB; p&lt;0.05) while only 2 of 143 NEBs expressed Ki67, suggesting no proliferation at P22. CGRP co-localized with SEZ6L2 in both Nx and Hx lungs. A subset of mice received intratracheal delivery of 1ug SEZ6L2-Saporin toxin to lesion NEBs and assess their function. 4 days after SEZ-Saporin treatment breathing frequency was elevated by 11% ± 5% in room air and by 7% ± 5% during acute hypoxia but not in PBS-treated, adult mice (n=3/group) suggesting NEBs have a mild inhibitory influence under normal conditions. Lastly, wireless optogenetic stimulation of P2ry1 vagal fibers in unanesthetized adult control mice (n=3) increased room air breathing by 20% ± 1% and drive to breathe by 36% ± 19% compared to pre-stim breathing. Together, our data demonstrate that hyperoxia-induced BPD alters the control of breathing which may in part be mediated via a unique lung-brainstem axis comprised of hyperplastic NEBs causing greater inhibition of excitatory P2ry1 vagal fibers. The NEB-P2ry1 axis may serve as a novel target for improving breathing in BPD. GCM: Advancing Healthier Wisconsin REAC Award, AHA 20CDA35310121; MRH: HL122358; JLG: DK133121, HL134850, and HL084207; JLS: DK133121 This is the full abstract presented at the American Physiology Summit 2023 meeting and is only available in HTML format. There are no additional versions or additional content available for this abstract. Physiology was not involved in the peer review process.

In-Situ Imaging of CO2 Trapping and Oil Recovery in Three-Phase Systems: Dependence on Pore Geometry and Wettability

SummaryCarbon dioxide (CO2) injection into reservoirs can be combined with enhanced oil recovery. Pore geometry and wettability are critical factors in CO2 trapping and oil recovery. However, their relationship has not been tackled and the influence of wettability is always controversial. To elucidate this intrinsic link, we prepared simple models using glass beads and angular grains, changed wettability by aging, and imaged the three-phase displacement process at high resolution. The results showed that the oil flow occurred through the ways of direct drainage and double imbibition, which is caused by the trapped CO2 under immiscible conditions. More residual CO2 was trapped in the angular grain sample and the water-wet sample, and more residual oil was trapped in the angular grain sample and the oil-wet sample. Under water-wet conditions, CO2 was easier to be trapped as the state of gas-in-oil-in-water or gas-in-water. While under oil-wet conditions, more CO2 was directly surrounded by oil and more small-size residual oil dispersed near the throats. The statistics of the residual clusters showed that the capillary-trapping capacity Ctrap of the angular grain sample was high (12.97% &amp;gt; 8.69%), but the oil recovery R2 was low (89.89% &amp;lt; 93.85%). The altered wettability (water-wet to oil-wet) increased the number of isolated CO2 clusters and the proportion of oil and CO2 in the smaller pores while decreasing the Ctrap (8.93% &amp;lt; 10.34%) and R2 (84.48% &amp;lt; 91.04%). The dissolution trapping and capillary trapping were maximized in the angular grain sample due to the increased surface-to-volume ratio of CO2 clusters and higher capillary force. The effect of wettability on dissolution trapping was slight, but the residual CO2 saturation was higher under water-wet conditions, thus the water-wet media were more conducive to CO2 trapping. We suggested that reservoirs with strong heterogeneity should be selected as CO2 storage sites, and the wettability of oil-wet rocks should be changed by using tertiary oil recovery technology to enhance CO2 storage efficiency and oil recovery. Our study provided direct evidence of the influence of pore geometry and wettability on residual CO2 and oil distribution, and clarified that complex pore geometry and water-wet systems were more conducive to CO2 trapping under immiscible conditions.

Investigation of supercritical CO2 mass transfer in porous media using X-ray micro-computed tomography

Understanding the mass transfer of CO2 into formation brine both qualitatively and quantitatively is important for improving the security of geologic carbon sequestration. In this study, quasi-dynamic X-ray micro-computed tomographic (MCT) imaging was used to track the time-evolution of supercritical CO2 (scCO2) clusters in a sandstone throughout brine injection. A cluster-matching workflow enabled the identification of depletion, merging, and snap-off of the scCO2 clusters, and subsequently the mass transfer coefficient of individual scCO2 clusters was found to range between 3.0×10−5 and 3.5×10−4 mm/s. The macroscopic average mass transfer coefficient was estimated as 1.4×10−4 mm/s. For application to geologic carbon sequestration, these values give an indication of the range of mass transfer coefficients that may be expected for similar state and flow conditions. With the macroscopic average mass transfer coefficient evaluated, we back-calculated the in-situ CO2 concentration field for brine, which provides quantitative insight of the distribution of dissolved CO2 in the sample. Despite slow injection rate (Ca = 10−7), mobilization of small scCO2 clusters was also observed, and was attributed to the combined effect of incomplete dissolution of snapped-off clusters and the reduction in the fluid–fluid interfacial tension (IFT) due to the high local CO2 concentration in brine accompanying scCO2 dissolution. This highlights the coupling of dissolution and mobilization processes and demonstrates the need to understand these interlinked dynamics to improve CO2 storage in geological formations.

Differentially expressed genes against Colletotrichum lindemuthiamum in a bean genotype carrying the Co-2 gene revealed by RNA-sequencing analysis.

Anthracnose is responsible for large yield losses in common bean crops. RNA-sequencing was used to investigate the differentially expressed genes (DEGs) in response to race 38 of Colletotrichum lindemuthianum in two near-isogenic lines (A25 and A4804) that differ in the presence of a resistance gene located in the cluster Co-2. Their responses were analyzed at different hours after inoculation (0, 24, and 48) and within and between genotypes. In all, 2,850 DEGs were detected, with 2,373 assigned to at least one functional GO term. Enriched GO terms in the resistant genotype were mainly related to functions as a response to stimulus, hormone signaling, cellular component organization, phosphorylation activities, and transcriptional regulation. The region containing the Co-2 cluster was delimited at the end of chromosome Pv11 (46.65–48.65 Mb) through a comparison with the SNP genotypes, obtained using ‘Genotyping by Sequencing,’ among seven resistant lines harboring the Co-2 gene and the susceptible line A25. The delimited region contained 23 DEGs, including 8 typical R genes, that showed higher expression levels in the resistant genotype and non-changes in the susceptible genotype after inoculation. Six R genes encoding protein kinases and an LRR domain formed a cluster in a core region between 46.98 and 47.04 Mb. The alignment of the raw transcriptome reads in the core region revealed structural changes that were used to design four potential breeder-friendly DNA markers, and it revealed some alignments with the intergenic regions, suggesting the presence of genes in addition to those annotated in the reference genome.

Mineralization mechanism of carbon dioxide with illite interlayer cations using molecular dynamics simulation and experiments

Clay minerals can be identified as a prospective target for long-term CO2 sequestration due to their accessible interlayer cations and periodic sheet structure. Understanding the reactive motion of mineral and fluids has dual advantages of resources and environment. To clarify the storage mechanism, an alternative strategy for CO2 mineralization was investigated through molecular dynamics (MD) simulation and scCO2H2Oillite experiments. The MD simulation predicts the protonation of non-bridging oxygen (NBO) at the illite surface in the first picoseconds, resulting in HCO3- ion formations via the bonding between CO2 molecules and hydroxyl group dissociated from H2O molecules. Surface protonation leads to interlayer K+ cations hopping to the illite/fluids interface since the middle stage, mainly after 1 ns of the reaction. The leached K+ cations bond with the HCO3- ions and later interact with the hydroxyl groups, forming K2CO3 molecules at the interface. In accordance with the experimental results, the K+ cations’ concentration in the filtrates progressively increases throughout the reaction. Results of SEM-EDS, Raman and XPS measurements find that free CO2 clusters in contact with the leached interlayer cations can be converted into carbonate species through the mineralization reaction, precipitating at the surface and thus inducing interlayer swelling. These observations reveal that the clay-related mineralization is estimated to undergo an accumulated process, accessibly enhancing the amount of captured CO2. This is a new report that demonstrates the mechanism of CO2 mineralization in clay minerals, presenting a potential solution for CO2 sequestration enhancement. Insights into K+ cations leaching and mineralization kinetics and their underlying mechanisms during the scCO2H2Oillite reaction is a matter of generalization in clay minerals for CO2 storage.

The origin of enhanced {{{{{{{{rm{O}}}}}}}}}_{2}^{+} production from photoionized CO2 clusters

CO2-rich planetary atmospheres are continuously exposed to ionising radiation driving major photochemical processes. In the Martian atmosphere, CO2 clusters are predicted to exist at high altitudes motivating a deeper understanding of their photochemistry. In this joint experimental-theoretical study, we investigate the photoreactions of CO2 clusters (≤2 nm) induced by soft X-ray ionisation. We observe dramatically enhanced production of {{{{{{{{rm{O}}}}}}}}}_{2}^{+} from photoionized CO2 clusters compared to the case of the isolated molecule and identify two relevant reactions. Using quantum chemistry calculations and multi-coincidence mass spectrometry, we pinpoint the origin of this enhancement: A size-dependent structural transition of the clusters from a covalently bonded arrangement to a weakly bonded polyhedral geometry that activates an exothermic reaction producing {{{{{{{{rm{O}}}}}}}}}_{2}^{+}. Our results unambiguously demonstrate that the photochemistry of small clusters/particles will likely have a strong influence on the ion balance in atmospheres.

Shells in CO2 clusters.

Abundance spectra of (CO2)N clusters up to N ≈ 500 acquired under a wide range of adiabatic expansion conditions are analyzed within the evaporative ensemble framework. The analysis reveals that the cluster stability functions display a strikingly universal pattern for all expansion conditions. These patterns reflect the inherent properties of individual clusters. From this analysis the size-dependent cluster binding energies are determined, shell and subshell closing sizes are identified, and cuboctahedral packing ordering for sizes above N ≈ 130 is confirmed. It is demonstrated that a few percent variation in the dissociation energies translates into significant abundance variations, especially for the larger clusters.

Atomic perspective revealing for combustion evolution of nitromethane/nano-aluminum hydride composite

Adding aluminum hydride (AlH3) into energetic materials (EMs) can improve their combustion and energy performance effectively. However, the potential mechanism of AlH3 on EMs is still unclear. Based on the ReaxFF-lg method, the thermal decomposition of nitromethane/nano-aluminum hydride (NM/nano-AlH3) composites were studied. The addition of AlH3 reduces the energy barrier and increases the energy release during the decomposition of NM, accelerates the decomposition of NM. The main way of AlH3 oxidation involves the capture of O atoms from NM. The results show that AlH3 content and passivated layer affect the oxidation and hydrogen release of AlH3. The explosion of small particle size AlH3 leads to rapid oxidation and hydrogen release. The oxidation of large particle size AlH3 is dominated by the inward and outward diffusion of O and Al atoms. The products of NM/nano-AlH3 composites are H2O, CO2, N2 gases, and Al clusters. This work is expected to guide the application of AlH3 in EMs.

Molecular Dynamics Study on CO2 Storage in Water-Filled Kerogen Nanopores in Shale Reservoirs: Effects of Kerogen Maturity and Pore Size.

CO2 sequestration in shale reservoirs is an economically viable option to alleviate carbon emission. Kerogen, a major component in the organic matter in shale, is associated with a large number of nanopores, which might be filled with water. However, the CO2 storage mechanism and capacity in water-filled kerogen nanopores are poorly understood. Therefore, in this work, we use molecular dynamics simulation to study the effects of kerogen maturity and pore size on CO2 storage mechanism and capacity in water-filled kerogen nanopores. Type II kerogen with different degrees of maturity (II-A, II-B, II-C, and II-D) is chosen, and three pore sizes (1, 2, and 4 nm) are designed. The results show that CO2 storage mechanisms are different in the 1 nm pore and the larger ones. In 1 nm kerogen pores, water is completely displaced by CO2 due to the strong interactions between kerogen and CO2 as well as among CO2. CO2 storage capacity in 1 nm pores can be up to 1.5 times its bulk phase in a given volume. On the other hand, in 2 and 4 nm pores, while CO2 is dissolved in the middle of the pore (away from the kerogen surface), in the vicinity of the kerogen surface, CO2 can form nano-sized clusters. These CO2 clusters would enhance the overall CO2 storage capacity in the nanopores, while the enhancement becomes less significant as pore size increases. Kerogen maturity has minor influences on CO2 storage capacity. Type II-A (immature) kerogen has the lowest storage capacity because of its high heteroatom surface density, which can form hydrogen bonds with water and reduce the available CO2 storage space. The other three kerogens are comparable in terms of CO2 storage capacity. This work should shed some light on CO2 storage evaluation in shale reservoirs.

MgO Cluster Models for Capture CO2 Molecule

The density functional theory (DFT) method was used to study the adsorption of acidic CO2 molecule on the oxide clusters (MgO)n , (n = 2, 4, 6, 8, 9 and 12). Basis sets, 6–311 G, 6–311G (d) and 6–311G (2d) were employed in order to test the effect on adsorption structures and binding energies. Both and adsorption sites have been considered. Our previous calculation DFT energies have been achieved for the (MgO)n, (CaO)n, (n = 1–4, 6, 8, 9, and 12 clusters), [WJERT, 2019, Vol.5, Issue 1, 328-341]. The present work investigates the adsorption properties (e.g., adsorption energies, geometries and HOMO and LUMO molecular orbitals) of a single CO2 molecule. The results show that the CO2 molecule / (MgO)n clusters prefer to adsorb as [Mg surf – with one acidic sites, while the interaction with surface basic sites, carbonate species consequently may occur. The HOMO and LUMO interaction between CO2 and MgO cluster models were also studied. Furthermore, such nanostructures systems can be potential candidates for practical applications of capturing CO2 from hot exhaust gases.