CO2 Gas Adsorption Research Articles

Luminescence Changeable CO2-Storage Cylinder: Triple-Stranded Helical Eu(III)/Tb(III) Fluorinated MOFs with Amide Linkers.

Triple-stranded helical lanthanide MOFs with CO2 adsorption properties were investigated. Lanthanide MOFs ([Eu0.1Tb0.9(hfa)3(dpa)]n) are composed of lanthanide luminophores (Eu(III) and/or Tb(III) ions), fluorinated antenna ligands (hfa: hexafluoroacetylacetonate), and polyamide-type linker ligands (dpa: 4-(diphenylphosphoryl)-N-(4-(diphenylphosphoryl)phenyl)benzamide). The cylindrical structure was characterized by single-crystal X-ray analysis, thermogravimetric analysis, and gas adsorption measurements. The inner surfaces of the cylindrical channels were covered with the fluorine atoms of the hfa ligands. The emission intensity ratio (IEu/ITb) in [Eu0.1Tb0.9(hfa)3(dpa)]n is affected by the CO2 gas adsorption behavior. The change in IEu/ITb value was caused by the intermolecular interactions between the CO2 gas molecules and the fluorinated ligands, resulting in an electronic structural change of the lowest triplet excited state in the photosensitized hfa ligands.

Impact of gas adsorption of nitrogen, argon, methane, and CO2 on gas permeability in nanoporous rocks

Gas adsorption on the surface of nanoporous rocks is an important process that occurs in many applied scenarios such as shale gas production or CO2 enhanced gas recovery or storage. While there are few theoretical considerations on the effect of gas adsorption on permeability, a systematic laboratory investigation of the impact of gas adsorption on gas flow and permeability is still lacking. In this paper, permeability of four adsorptive gases, i.e., nitrogen, argon, methane, and carbon dioxide, was measured, along with helium permeability, for two nanoporous rock samples that have high and low total organic carbon (TOC) content, respectively. The measurements were conducted at a range of pore pressures from 150 to 1500 psi (1.03–10.34 MPa). Gas adsorption isotherms were also measured at the same conditions. A mathematical model that considers adsorption with specific boundary conditions for the experimental setup was used for data analysis. The results show that gas adsorption causes larger drop in pressure decay and greater retardation in pressure equilibrium. However, the reduction of permeability relative to helium (25%–46%) is similar for gases with different levels of adsorption, indicating the occurrence of single-layer adsorption for these gases. Comparison between the two samples further supports the concept of single-layer adsorption and signifies the impact of pore size on the permeability reduction due to adsorption. These new findings deepen the fundamental understanding and provide important clarification on the effect of gas adsorption on gas flow and permeability in nanoporous rocks.

Abnormal Gas Generation during First Discharge Process of Sodium Ion Battery.

In recent years, sodium-ion batteries (SIBs) have attracted a lot of attention and are considered an ideal alternative to lithium-ion batteries (LIBs). The hard carbon (HC) anode in SIBs presents a unique challenge for studying the formation process of the solid electrolyte interphase (SEI) during initial cycling, owing to its distinctive porous structure. This study employs a combination of ultrasonic scanning techniques and differential electrochemical mass spectrometry to conduct an in-depth analysis of the two-dimensional distribution and composition of gases during the formation process. The findings reveal distinct gas evolution behaviors in SIBs compared to LIBs during formation. Notably, significant gas evolution is observed during the discharge phase of the formation cycle in SIBs, with higher discharge rates leading to increased gas evolution rates. This phenomenon is likely attributed to the adsorption of CO2 gas by the abundant pores in HC, followed by desorption during discharge. Furthermore, the study demonstrates that the addition of 5A molecular sieves, which competitively adsorb gases, effectively reduces gas adsorption on the anode during formation, thereby significantly enhancing battery performance. This research elucidates the gas adsorption and desorption behavior at the battery interface, providing new insights into the SEI formation process in SIBs.

Abnormal Gas Generation during First Discharge Process of Sodium Ion Battery

AbstractIn recent years, sodium‐ion batteries (SIBs) have attracted a lot of attention and are considered an ideal alternative to lithium‐ion batteries (LIBs). The hard carbon (HC) anode in SIBs presents a unique challenge for studying the formation process of the solid electrolyte interphase (SEI) during initial cycling, owing to its distinctive porous structure. This study employs a combination of ultrasonic scanning techniques and differential electrochemical mass spectrometry to conduct an in‐depth analysis of the two‐dimensional distribution and composition of gases during the formation process. The findings reveal distinct gas evolution behaviors in SIBs compared to LIBs during formation. Notably, significant gas evolution is observed during the discharge phase of the formation cycle in SIBs, with higher discharge rates leading to increased gas evolution rates. This phenomenon is likely attributed to the adsorption of CO2 gas by the abundant pores in HC, followed by desorption during discharge. Furthermore, the study demonstrates that the addition of 5A molecular sieves, which competitively adsorb gases, effectively reduces gas adsorption on the anode during formation, thereby significantly enhancing battery performance. This research elucidates the gas adsorption and desorption behavior at the battery interface, providing new insights into the SEI formation process in SIBs.

Silica surface modification using cellulose as a renewable organosilane derived from coconut coir fiber for carbon capture

The properties of silica surface modification for carbon capture were studied, utilizing cellulose-amine as a modification agent derived from dissolved coconut coir fiber. To form bonds with NH2 functional groups through amination processes, cellulosic biomass waste is utilized, which is analogous to replacing alkoxy ligands. The dual-function mixture reagents dimethyl sulfoxide (DMSO) and ammonium hydroxide (NH4OH) were employed in the same system as the amine sources and solvents. Waterglass is used as a source of silica, and the modified particles are formed using a one-step consecutive sol-gel spray drying process used in a direct condensation route. Changes in the concentration of sodium lauryl sulfate (SLS) were examined to determine how they affected the essential parameters of the particles. The template is removed during particle formation without further physical or chemical processing. The particle morphology changed from donut-shaped to spherical after SLS application, as evidenced by the increase in SLS concentration. This also shows that the increase in the particle surface area is directly influenced by the increase in the formation of new pore structures with increasing SLS concentration. Through this mechanism, it is possible to extend the pore size distribution to the meso-macropore regime and initiate the formation of new mesopores. This has a direct impact on the capacity to absorb CO2 gas by increasing the cellulose-amine mass fraction that can be grafted to as high as 32.35 %wt. At an operating pressure of 6 bar, a maximum CO2 gas adsorption capacity of 5.32 mmol/g silica was attained by adding SLS 3 CMC to the silica particles. This value is 2.3 times higher than that obtained when using an aminosilane-based modification agent.

Dibenzodioxin-Based Polymers of Intrinsic Microporosity with Enhanced Transport Properties for Lithium Ions in Aqueous Media.

Boosting the transport and selectivity properties of membranes based on polymers of intrinsic microporosity (PIMs) toward one specific working analyte of interest is challenging. In this work, a novel family of PIM membranes, prepared by casting and exhibiting optima mechanical properties and high thermal stability, was synthesized from 4,4'-(2,2,2-trifluoro-1-phenylethane-1,1-diyl) bis(benzene-1,2-diol) and two tetrafluoro-nitrile derivatives. Gas permeability measurements evidenced a CO2/CH4 selectivity up to 170% relative to the reference polymer, PIM-1, in agreement with their calculated fractional free volume and the analysis of the textural properties by N2 and CO2 gas adsorption. Besides, the chemical modification by acid hydrolysis of the PIM membranes favored the permeability for lithium ions (LiCl 2M, 6 × 10-9 cm2·s-1) compared to other alkali metal analogs such as sodium (NaCl 2M, 7.38 × 10-10 cm2·s-1) and potassium (KCl 2M, 1.05 × 10-9 cm2·s-1). Moreover, the complete mitigation of the crossover of redox species with higher molecular sizes than the ions from alkali metal salts was confirmed by using in-line benchtop NMR methods. Additionally, the modified PIM membranes were measured in a symmetric electrochemical flow cell using an aqueous electrolyte by combining lithium ferro/ferricyanide redox compounds and lithium chloride. The electrochemical tests showed low polarization, high-rate capability, and capacity retention values of 99% when cycled at 10 mA·cm-2 for over 50 cycles. Based on these results, these polymers could be used as highly selective and conducting membranes in electrodialysis for lithium separation and lithium-based redox flow batteries and as a protective layer in high-energy density lithium metal batteries.

Comparison of upward and downward flow in high-pressure bulk CO2 gas adsorption on NaY zeolite fixed bed

Adsorption is an appealing technology for the removing of CO2 from natural gas because it can handle high CO2 concentrations at high pressures. The determination of mono-component breakthrough curves provides heat and mass transfer parameters to assess separation effectiveness that can be used for simulation of swing adsorption separation processes (PSA, TSA etc.). However, in lab-scale fixed-bed adsorption, it may be challenging to perform this assessment due to low flow conditions that are usually employed, affecting the flow regimedepending on the operation conditions. In this sense, this work aimed to evaluate the effect of flow regime configurations and difference in gases densities by means of residence time distribution (RTD) analysis in the PSA of CO2 in a NaY zeolite fixed bed , in order to to collect information that satisfy pipeline specifications in industrial applications. A high-pressure lab-scale apparatus was used with NaY particles of 0.7250 mm mean diameter, a 10.5 cm bed height , and a tubular column of 2.0 cm internal diameter. The upward and downward flows were conducted under 528.82 ± 4.59 NmL min−1 inlet mass flow rate, 51 bar, and 30 °C. The RTD analysis was performed to verify the flow regime, and mass transfer zone (MTZ) length was estimated. It was observed that downward flow conditions promoted higher concentration spread than upward flow. RTD analysis showed that downward flow is dominated by laminar convection while the upward flow is dominated by dispersion. MTZ length increased from 0.64 cm in upward flow to 5.81 cm in downward flow. Therefore, assessing CO2 flow conditions and, additionally, the difference in gases densities, are important steps that should be taken when dealing with fluid adsorption under high pressure because different densities between fluid components severely changed and affected flow regime and, consequently, separation effectiveness.

Exploitation of Pore Structure for Increased CO2 Selectivity in Type 3 Porous Liquids.

CO2 capture requires materials with high adsorption selectivity and an industrial ease of implementation. To address these needs, a new class of porous materials was recently developed that combines the fluidity of solvents with the porosity of solids. Type 3 porous liquids (PLs) composed of solvents and metal-organic frameworks (MOFs) offer a promising alternative to current liquid carbon capture methods due to the inherent tunability of the nanoporous MOFs. However, the effects of MOF structural features and solvent properties on CO2-MOF interactions within PLs are not well understood. Herein experimental and computational data of CO2 gas adsorption isotherms were used to elucidate both solvent and pore structure influences on ZIF-based PLs. The roles of the pore structure including solvent size exclusion, structural environment, and MOF porosity on PL CO2 uptake were examined. A comparison of the pore structure and pore aperture was performed using ZIF-8, ZIF-L, and amorphous-ZIF-8. Adsorption experiments here have verified our previously proposed solvent size design principle for ZIF-based PLs (1.8× ZIF pore aperture). Furthermore, the CO2 adsorption isotherms of the ZIF-based PLs indicated that judicious selection of the pore environment allows for an increase in CO2 selectivity greater than expected from the individual PL components or their combination. This nonlinear increase in the CO2 selectivity is an emergent behavior resulting from the complex mixture of components specific to the ZIF-L + 2'-hydroxyacetophenone-based PL.

The possibility of using the Zn (II) Butadiyne-linked porphyrin nanoring for detection and adsorption of AsH3, NO2, H2O, SO2, CS2, CO, and CO2 gases

The present research aims to study the probability of applying the Zn (II)-Butadiyne-linked porphyrin (ZBPN) nanoring for detection and adsorption of some of the most important air pollutants such as AsH3, NO2, H2O, SO2, CS2, CO, and CO2 gases by using the density functional theory (DFT) method. The key results of the thermodynamic calculations indicated that ZBPN nanoring is able to absorb SO2, AsH3, NO2, and H2O gases; while, it could not strongly adsorb CS2, CO, or CO2. Subsequent to the thermodynamic results, the changes of band gaps and the frontier molecular orbital (FMO) calculations show that ZBPN nanoring might release stronger signals in the presence of SO2 (σ = 1.64(1010) s), AsH3 (σ = 1.35(1010) s), and H2O (σ = 1.11(1010) s) single molecules compared to the other considered ones. Therefore, ZBPN could be used as a relatively good sensor for detection of SO2, AsH3, and H2O (compared to CS2, CO, CO2, and NO2 gases). Regarding the key findings of this research, it hopes that in the future, the results of the work be helpful for experimental synthesis of ZBPN nanoring for adsorption and sensing of the mentioned gases.

Multi-Scale Characterization of Pores and Fractures in Coals with Different Coal-Body Structures from the Jincheng Mine, Qinshui Basin, Northern China

The Qinshui Basin is located in the southeast of Shanxi Province, China. It is one of the most abundant coal resources from Permo-Carboniferous North China. It is rich in coal and coalbed methane resources. However, the accumulation of coalbed methane is complex and the enrichment law has not been fully understood because of the high heterogeneity of coal reservoirs in the Qinshui Basin. The examination of dissimilarities between tectonically deformed coals (TDCs) and primary coals at multiple scales holds paramount importance in advancing our understanding of the occurrence and flow patterns of coalbed methane, and in providing guidance for exploration efforts. In the present study, the samples from the Jincheng Mine, Qinshui Basin, were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), mercury intrusion porosimetry (MIP), CO2 gas adsorption and 3D X-ray micro-computed tomography. The results showed that the dominant minerals in coal were illite, kaolinite, and calcite, with minor amounts of quartz and ankerite. In comparison to primary coal, tectonism could increase the microfractures density of type A (the fracture of width ≥ 5 μm and length > 10 mm) in TDCs. In CO2 gas adsorption in mylonite coal, it was observed that the volume of micropores (<2 nm) was significantly reduced leading to a decrease in gas adsorption capacity. The result of Micro-CT scanning revealed that the minerals occurred as veins in primary coal, but as irregular aggregates in TDCs. Moreover, tectonism had a staged impact on fracture structure, which was initially closed in cataclastic coal and then formed into granulated coal during the tectonic evolution. The effects of tectonism on coal structure had an impact on the connectivity of micropores at the micrometer scale by the destruction of the pore throat structure, increasing the heterogeneity of the reservoir. These findings help to better understand the changes in TDC structure at different scales for developing effective strategies for coalbed methane exploration and production.

Crab shell-based hierarchical micro/meso-porous carbon as an efficient nano-adsorbent for CO2/CH4 separation: experiments and DFT modeling

In this study, we prepared a range of nanoporous carbon nano-adsorbents from crab shells (CSs) using KOH activation and evaluated their suitability for selective adsorption of CO2/CH4 gas mixtures. We employed various characterization techniques, including XRD, FT-IR, SEM, Raman, TGA, and BET analysis, to assess the properties of these nano-adsorbents. Our investigation includes the systematic study of various parameters, such as activation time, activation temperature, and the KOH to CS activating agent ratio. The nanoporous carbons were evaluated for their CO2 adsorption capabilities at 1–10 bar and 25 ℃ condition. The results demonstrated that the CS-2-2-900 sample, activated for 1 h at 900 ℃ with a 2:1 ratio of KOH to CS, exhibited the highest gas adsorption capacity, reaching 7.217 mmol/g at a pressure of 10 bar under room temperature conditions. Additionally, the synthesized CS-2-2-900 sample displayed excellent surface area (914.85 m2/g), a pore volume of 1.1 cm3/g, and an average pore diameter of 4.82 nm. Furthermore, we functionalized the CSs to enhance their selectivity for ammonia adsorption. Using the Myers and Pravnitz theory, we calculated that the FCS-2-2-900 sample exhibited the highest selectivity, reaching 18.99 at 25 ℃ under pressures of up to 10 bar. To gain a more comprehensive understanding of the interactions between the adsorbents and the adsorbed molecules, as well as to identify the active sites involved in the adsorption process, we employed density functional theory (DFT). Our DFT calculations revealed that pyrrolic nitrogen and carboxylic sites played a significant role in enhancing the separation of CO2 in binary mixtures. In summary, nanoporous carbons derived from crab shells outperformed those derived from other waste materials. These functionalized porous nanocarbons represent promising adsorbents for the selective adsorption of CO2 gas in CO2/CH4 mixtures due to their nitrogen content, high porosity, stability, and economic efficiency.

Lanthanide-based F-MOFs: Structure, hydrolytic stability, spectral and magnetic properties

A series of five novel lanthanide-based fluorinated metal-organic frameworks (Ln-F-MOFs) have been synthesized under solvothermal conditions by the reaction of 3,3′-bis(trifluoromethyl)-[1,1′-biphenyl]-4,4′-dicarboxylic acid (H2L) and lanthanide Ln(III) ions (Ln(III)La, Ce, Pr, Nd and Eu). Powder X-ray diffraction (PXRD) analysis revealed that all prepared complexes are isostructural. A single-crystal X-ray crystallographic study of one representative of the isostructural group, namely {[La2(L)3(DMF)2(H2O)2]}n showed, that compound crystallizes in a triclinic system with space group P-1. The lattice parameter values are a = 8.563(2) Å, b = 13.199(3) Å, c = 16.008(4) Å, α = 104.588(7) °, β = 92.904(7) ° and γ = 92.717(7) °, with two formula units in the unit cell. The overall structure is formed by 2D polymeric layers, which are arranged into a semi-3D supramolecular structure through hydrogen bonds and other intramolecular interactions. The study of the hydrophobic properties of the complexes showed that the complexes exhibit surface hydrophobicity with a “rose petal effect” and a contact angle of approximately 107°. However, the structures are not hydrolytically stable in the long term and the structure starts to delaminate after two days in water. This is a manifestation of the fact that the complexes do not form a 3D polymer network, it is made up of 2D layers connected only by weak non-bonding interactions. The photoluminescence properties of the Ln(III) complexes are determined by the characteristic 5d-4f or 4f-4f electron transitions for the individual lanthanide ions. The magnetic properties of Nd(III), Pr(III) and Eu(III) variants were studied. The magnetic properties of {[Pr2(L)3(DMF)2(H2O)2]}n are characterized by the presence of a low-lying quasi-doublet with 15.6 cm−1 energy splitting, whereas Eu(III) variant is nonmagnetic at low temperatures, but the magnetic 7F1 state is accessible by thermal excitation. For Nd(III) complex, the X-band EPR measurements were performed. Since 1D channels with dimensions of 4.90 × 7.23 Å2 are present within the structure, the adsorption of N2, CO2 and H2 gases was also studied.

Investigation of Ultramicroporous Structure of One-Dimensional Lepidocrocite Titanates Using Carbon Dioxide and Nitrogen Gases.

The novel material, one-dimensional lepidocrocite (1DL) titanate, is attracting industrial and scientific interest because of its applicability to a wide range of practical applications and its ease of synthesis and scale up of production. In this study, we investigated the CO2 adsorption capability and pore structures of 1DL freeze-dried and lithium chloride washed air-dried powders. The synthesized 1DL was characterized by X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. Using the constant-volume method, CO2 gas adsorption revealed that the 1DL exhibits type IV adsorption-desorption isotherms. The heats of adsorption obtained from the adsorption branches are lower than those obtained from the desorption branches. Brunauer-Emmett-Teller (BET) analysis, using N2 gas adsorption isotherms at 77 K showed that 1DL possesses 80.2 m2/g of BET specific surface area. Nonlocal density functional theory analysis indicated that two types of pores, meso-pores and ultramicro pores, exist in the 1DL freeze-dried powders. This work provides deep insights into the pore structures and CO2 adsorption mechanisms of 1DL powders.

Experimental study on pore structure evolution of thermally treated shales: implications for CO2 storage in underground thermally treated shale horizons

Extracting gas from unconventional shale reservoirs with low permeability is challenging. To overcome this, hydraulic fracturing (HF) is employed. Despite enhancing shale gas production, HF has drawbacks like groundwater pollution and induced earthquakes. Such issues highlight the need for ongoing exploration of novel shale gas extraction methods such as in situ heating through combustion or pyrolysis to mitigate operational and environmental concerns. In this study, thermally immature shales of contrasting organic richness from Rajmahal Basin of India were heated to different temperatures (pyrolysis at 350, 500 and 650 °C) to assess the temperature protocols necessary for hydrocarbon liberation and investigate the evolution of pore structural facets with implications for CO2 sequestration in underground thermally treated shale horizons. Our results from low-pressure N2 adsorption reveal reduced adsorption capacity in the shale splits treated at 350 and 500 ºC, which can be attributed to structural reworking of the organic matter within the samples leading to formation of complex pore structures that limits the access of nitrogen at low experimental temperatures. Consequently, for both the studied samples BET SSA decreased by ∼58% and 72% at 350 °C, and ∼67% and 68% at 500 °C, whereas average pore diameter increased by ∼45% and 91% at 350 °C, and ∼100% and 94% at 500 °C compared to their untreated counterparts. CO2 adsorption results, unlike N2, revealed a pronounced rise in micropore properties (surface area and volume) at 500 and 650 ºC (∼30%–35% and ∼41%–63%, respectively for both samples), contradicting the N2 adsorption outcomes. Scanning electron microscope (SEM) images complemented the findings, showing pore structures evolving from microcracks to collapsed pores with increasing thermal treatment. Analysis of the SEM images of both samples revealed a notable increase in average pore width (short axis): by ∼4 and 10 times at 350 °C, ∼5 and 12 times at 500 °C, and ∼10 and 28 times at 650 °C compared to the untreated samples. Rock-Eval analysis demonstrated the liberation of almost all pyrolyzable kerogen components in the shales heated to 650 °C. Additionally, the maximum micropore capacity, identified from CO2 gas adsorption analysis, indicated 650 °C as the ideal temperature for in situ conversion and CO2 sequestration. Nevertheless, project viability hinges on assessing other relevant aspects of shale gas development such as geomechanical stability and supercritical CO2 interactions in addition to thermal treatment.

DFT insights into the electronic properties and gas sensing performance of C19X (X = C, N, and Si) nanocages for the detection of CO2, CO, N2, and H2 gases

The development of carbon nanocage-based sensors for the detection of toxic and pollutant gases has attracted significant attention from researchers. In this computational study, the interactions of CO2, CO, N2, and H2 gases with the C19X nanocages (X = C, N, and Si) were evaluated using the M062X/6-31G(d) level of density functional theory (DFT) calculations. The results demonstrated a reduction in the energy gap (Egap) across all studied systems, especially pronounced in the C19N and C19Si nanocages, compared to the complexes with a higher priority of the C19Si nanocages. The gas molecules were found to have weak adsorption in all the C20 nanocage complexes, while the adsorption of CO gas was more pronounced in the C19N and C19Si nanocages compared to the other gases studied. A quantum theory of atoms in molecule (QTAIM) analysis was conducted to examine the interactions and their features, through which the physical interactions that contribute to the formation of the complexes were identified. Further electrical characterizations revealed that the C19Si nanocage has a high sensitivity for the detection of CO gas, making it a promising sensor material. In conclusion, the engineered C19N and C19Si nanocages demonstrated significant improvements over the original C20 nanocage in terms of adsorption capabilities for CO2, CO, N2, and H2 gases, making them promising candidates for sensor applications.

Thermomechanical coupling seepage in fractured shale under stimulation of supercritical carbon dioxide

As a waterless fracturing fluids for gas shale stimulation with low viscosity and strong diffusibility, supercritical CO2 is promising than the water by avoiding the clay hydration expansion and reducing reservoir damage. The permeability evolution influenced by the changes of the temperature and stress is the key to gas extraction in deep buried shale reservoirs. Thus, the study focuses on the coupling influence of effective stress, temperature, and CO2 adsorption expansion effects on the seepage characteristics of Silurian Longmaxi shale fractured by supercritical CO2. The results show that when the gas pressure is 1–3 MPa, the permeability decreases significantly with the increase in gas pressure, and the Klinkenberg effects plays a predominant role at this stage. When the gas pressure is 3–5 MPa, the permeability increases with the increase in gas pressure, and the influence of effective stress on permeability is dominant. The permeability decreases exponentially with the increase in effective stress. The permeability of shale after the adsorption of CO2 gas is significantly lower than that of before adsorption; the permeability decreases with the increase in temperature at 305.15 K–321.15 K, and with the increase in temperature, the permeability sensitivity to the temperature decreases. The permeability is closely related to supercritical CO2 injection pressure and volume stress; when the injection pressure of supercritical CO2 is constant, the permeability decreases with the increase in volume stress. The results can be used for the dynamic prediction of reservoir permeability and gas extraction in CO2-enhanced shale gas development.

Zeolite-coated 3D-printed gyroid scaffolds for carbon dioxide adsorption

3D-printed adsorbents are gaining increased attention owing to their potential in overcoming operational challenges faced by the conventionally structured counterparts. In this work, cylindrical scaffolds of triply periodic minimal surface (TPMS) configuration were synthesized using 3D-printing by stereolithography. This unique gyroid sheet TPMS network was selected as it offers a high surface-area-to-volume ratio. The surface of the scaffolds was modified by a silanization process followed by coating via grafting with zeolite 13X crystals toward CO2 adsorption application. A secondary zeolite coating step was also employed to enhance the zeolite 13X loading, resulting in zeolite loadings of 16 wt% and 23 wt% after the primary and secondary coatings, respectively. Following morphological and structural characterization, the CO2 adsorption performance of the 3D-printed materials was evaluated with respect to adsorption capacity, kinetics, selectivity, and heat of adsorption. Cyclic stability was also assessed over CO2 adsorption–desorption pressure swing adsorption cycles at 25 °C. Comparative analysis showed that the 3D-printed coated samples exhibited higher CO2/N2 selectivity and improved cyclic stability with a slightly lower CO2 adsorption capacity than the zeolite 13X powder. The heat of adsorption ranged from 18 to 41 kJ mol−1 for both the powder and the coated adsorbents, indicating physisorption. The gyroid lattice of the 3D-printed structures, featuring a densely arranged network of smooth, interconnected flow channels, facilitated molecular transport thus yielding higher CO2 adsorption kinetics than the powder. Indicatively, the primary and secondary coatings attained an equilibrium capacity of 4 mmol g−1 at 25 °C in 62 and 57 min, respectively, while the powder required 110 min at the same conditions. The 3D-printed materials exhibited also significantly higher CO2/N2 selectivity values of 569 and 115 at 50 mbar and 1 bar, respectively, for the primary coating sample, and 536 and 73 at 50 mbar and 1 bar, respectively, for the secondary coating one. The findings highlight the potential of 3D-printing to produce coated structured adsorbents with complex geometries for sustainable CO2 capture and gas adsorption processes.

Effective Prevention of Palladium Metal Particles Sintering by Histidine Stabilization on Silica Catalyst Support

AbstractA robust method for enhancing the dispersion and stabilization of small metal nanoparticles in heterogeneous catalysts is developed. It involves in situ complexation of palladium(II) by histidine, in water, prior to impregnation in fumed silica. TEM images show that the histidine facilitates dispersion of the Pd(II) into finer nanoscale particles (≈2 nm) uniformly distributed on the support, rather than the large clusters (≈5 nm) seen in the absence of histidine. After hydrogen reduction, assessments using CO chemisorption and propylene hydrogenation indicate that the coordinated histidine might obscure the active sites on the Pd particles. However, as histidine decomposes between 220 and 300 °C in air, these materials are treated at 225 °C in air for 48 h. Afterwards the Pd(II) particles remain the same size, but after hydrogen reduction, there is a 2.4‐fold increase in CO gas adsorption, indicative of an expanded Pd surface area. Furthermore, superior catalyst stability (activity >200 h) is observed during propylene hydrogenation at 250 °C. This is consistent with histidine use having generated widely spaced, uniformly small, Pd nanoparticles on the silica support which is expected to help prevent agglomeration (sintering) during catalysis. This is a convenient low‐cost strategy for reducing metal content, preventing sintering and optimizing catalyst performance.

Critical role of solvation on CC13 porous organic cages for design of porous liquids

Efficient carbon capture requires the design of new materials with high CO2 selectivity and gas adsorption capacity that can be incorporated into existing industrial processes. Porous liquids (PLs) are promising candidate materials that consist of a nanoporous host and a solvent forming a liquid with permanent porosity based on exclusion of the solvent from the interior of the nanoporous host. Stable PLs are based on solvent-nanoporous host interactions, which can be evaluated through molecular simulations. Here, time- and temperature-dependent density functional theory simulations were performed between four solvents, 2-bromophenol, 4-methylphenol, 2,4-dimethylphenol, and cyclohexanone and the CC13 porous organic cage (POC) as a prototypical PL composition. Overall, minimal reactions occurred in the PL including no changes in the POC structure. Additionally, POC-solvent coordination occurred through interactions of neighboring functional groups such as methyl/bromide and hydroxyl on the solvent molecules with the POC surface. Therefore, the location rather than the number of functional groups on the solvent molecule controls the POC-solvent interactions. Additionally, the POC pore window contracted or expanded up to 8% during solvation, which correlates with the experimental solubility and static solvent-POC binding, where solvents that caused less contraction of the POC pore window increased POC solubility. These results allow for the design of optimized POC-based PL compositions based on solvent-nanoporous host binding and variation in the pore window during solvation.

Efficient mesoporous cross-linkable hybrid poly Schiff-base based on polyimide as a promising molecular sieve for sustainable CO2 capturing and separation

ABSTRACT A cross-linked hybrid poly Schiff-base (PSB) was synthesized and characterized through spectroscopic, morphological, and structural approaches. The BET surface area (SBET) of the PSB is 20.33 m2/g, the pore volume (Vp) is 0.024 cm3/g, and the pore diameter (Dp) is 4.13 nm. The current study elucidates PSB’s strong chemical and thermal stability, as well as the remarkable capacity to adsorb CO2 with perfect selectivity. This property is accomplished by the synergistic interaction of the polymer’s physicochemical and structural features when exposed to CO2, N2 and CH4 molecules. This mesoporous polymer exhibits a CO2/N2 = 60 and CO2/CH4 = 10.5 selectivity, and can adsorb 3.22 mmol/g CO2 (at 298 K/1 bar). Furthermore, the isotherms of CO2 gas adsorption and desorption in the porous polymer are reversible. The use of PSB having effective imide, imine, and meta-hydroxyl functional groups in the adsorption and selectivity of CO2 gas produced excellent results, which make it a suitable candidate for CO2 storage and separation applications.