N2 Uptake Research Articles

Host-Guest Interactions Facilitated by Chalcogen Bonding within Selenadiazole Functionalised Porphyrin Nanotubes.

The structural rigidity of tetrakis(4-pyridyl)porphyrin (TPyP) has been utilised to prepare a robust novel porous coordination polymer of composition Cd2(TPyP)(sez)2 (TPyP=5,10,15,20-tetra(4-pyridyl)porphyrin, sez=1,2,5-benzoselenadiazole-5-carboxylate). The coordination polymer may be described as a hexagonal porphyrin nanotube (PNT) and has the potential to bind guest molecules through chalcogen bonding. Single crystal X-ray diffraction (SCXRD) data indicate an internal pore diameter ~9 Å which represents ~35 % of the crystal volume. Immersion of the PNTs in solvents such as DMSO and CS2 result in the incorporation of these molecules within the nanotubes with chalcogen bonding between host and guest. The crystallographic guest-inclusion investigations are complemented by solid-state 77Se, 13C, 113Cd and 2H NMR studies which provide insights into dynamic behaviour. The porosity of the crystals was further explored using gas adsorption experiments, indicating the reversible uptake of CO2, CH4, H2 and N2. Structure-function relationships are clearly established from complementary crystallographic, NMR and adsorption investigations.

Assessing the combined impacts of microplastics and nickel oxide nanomaterials on soybean growth and nitrogen fixation potential

The excessive presence of polystyrene microplastic (PS-MPx) and nickel oxide nanomaterials (NiO-NPs) in agriculture ecosystem have gained serious attention about their effect on the legume root-nodule symbiosis and biological nitrogen fixation (BNF). However, the impact of these contaminants on the root-nodule symbiosis and biological N2-fixation have been largely overlooked. The current findings highlighted that NiO-NMs at 50 mg kg−1 improved nodule formation and N2-fixation potential, leading to enhanced N2 uptake by both roots and shoots, resulting in increased plant growth and development. While single exposure of PS-MPx (500 mg kg−1) significantly reduced the photosynthetic pigment (8–14 %), phytohormones (9–25 %), nodules biomass (24 %), N2-related enzymes (12–17 %) that ultimately affected the N2-fixation potential. Besides, co-exposure of MPx and NiO at 100 mg kg−1 altered the nodule morphology. Additionally, single and co-exposure of MPx and NiO-NMs at 100 mg kg−1 reduced the relative abundance of Proteobacteria, Gemmatimonadota, Actinobacteria, Firmicutes, and Bacteroidetes is associated with N2-cycling and N2-fixation potential. The findings of this study will contribute to understanding the potential risks posed by MPx and NiO-NMs to leguminous crops in the soil environment and provide scientific insights into the soybean N2-fixation potential.

Finding high-performance MOFs for effective SF6/N2 separation through high-throughput computational screening and machine learning

Abstract Given the rapidly expanding pool of synthesized and hypothetical metal–organic frameworks (MOFs), testing every single material for SF6/N2 separation by iterative experimental methods or computationally demanding molecular simulations is not practical. In this study, we integrated high-throughput computational screening and machine learning (ML) approaches to evaluate SF6/N2 mixture adsorption and separation performances of over 25 000 different types of synthesized and hypothetical MOFs (hypoMOFs), representing the largest set of structures studied for SF6/N2 separation to date. SF6/N2 mixture adsorption data that we produced for synthesized MOFs using molecular simulations were utilized to develop ML models to accurately and quickly predict SF6 and N2 uptakes, SF6/N2 selectivities, SF6 working capacities, adsorbent performance scores, and regenerabilities of both synthesized and hypoMOFs. Results showed the MOF space that we studied exhibits very high SF6/N2 selectivities in the range of 1.8–4204 at 1 bar in addition to high SF6 working capacities between 0.04–5.68 mol kg−1 at an adsorption pressure of 1 bar and desorption pressure of 0.1 bar at room temperature. The top-performing MOF adsorbents for SF6/N2 mixture separation were identified to have Zn, Cu, Ni metals; terphenyl, pyridine, naphthalene linkers; and medium pore sizes. Our comprehensive computational approach offers a highly efficient alternative to brute-force computer simulations by enabling the rapid assessment of the MOF adsorbents for SF6/N2 separation and provides molecular insights into the key structural features of the most promising adsorbents.

Porous Bimetallic Ti-MOFs for Photocatalytic Oxidation of Amines in Air.

A family of microporous titanium-containing metal-organic frameworks (denoted as M2Ti-CPCDC, M = Mn, Co, Ni) has been synthesized by using a bimetallic [M2Ti(μ3-O)(COO)6] cluster and a tritopic carbazole-based organic ligand H3CPCDC. M2Ti-CPCDC are stable and display permanent porosity for N2 and CO2 uptake, ranking among the most porous titanium-based metal-organic frameworks. M2Ti-CPCDC crystals exhibit n-type semiconductor behavior. Further catalytic studies demonstrate that all M2Ti-CPCDC materials are applicable for triggering photo-oxidative reactions of amines in air. More specifically, amines with electron-donating groups afford the aldehydes as the main products, while amines bearing electron-withdrawing groups give rise to imines as the main product. Among them, Mn2Ti-CPCDC exhibit the best photocatalytic activity, with conversion of benzylamine up to 99% and selectivity of 99%. Mn2Ti-CPCDC could be recycled in at least three runs while retaining crystallinity and catalytic activity. The reaction mechanism indicates that photoinduced hole (h+), superoxide radical anion (O2·-), and singlet oxygen (1O2) are the main active species involved in the photo-oxidation process.

Linkage engineering of covalent-organic frameworks for CO2 capture

The growing concern over climate change due to the continuous increase in CO2 concentration calls for efficient ways for carbon capture. Covalent-organic frameworks (COFs), as a new type of porous materials, are considered ideal platforms for carbon capture due to their high surface area and porosity, while their intrinsic CO2 uptake is relatively low owing to the lack of functionalities. Herein, we report a linkage engineering strategy to develop more efficient CO2 adsorbents through the conversion of imine-bonded COFs to amide-bonded COFs. After conversion, the CO2 uptake capacity is increased significantly from ∼ 55 mg/g to ∼ 235 mg/g, while the N2 uptake capacity remains almost unchanged, and breakthrough experiments show that the CO2/N2 separation performance is greatly improved. Monte Carlo simulations and density-functional theory calculations show that the interaction between the carbonyl group in the amide segment and the CO2 molecule is the key to the improved performance. Overall, this work provides an efficient and facile strategy for the structural design of COFs for carbon capture applications.

Crystal-Defect-Induced Longer Lifetime of Excited States in a Metal-Organic Framework Photocatalyst to Enhance Visible-Light-Mediated CO2 Reduction.

We report the structural defects in Zr-metal-organic framework (MOFs) for achieving highly efficient CO2 reduction under visible light irradiation. A series of defective Zr-MOF-X (X = 160, 240, 320, or 400) are synthesized by acid-regulated defect engineering. Compared to pristine defect-free Zr-MOF (NNU-28), N2 uptake increases for Zr-MOF-X synthesized with the HAc modulator, producing a larger pore space and Brunauer-Emmett-Teller surface area. The pore size distribution demonstrates that defective Zr-MOF-X exhibits mesoporous structures. Electrochemistry tests show that defective Zr-MOF-X possesses a more negative reduction potential and a higher photocurrent responsive signal than that of pristine NNU-28. Consequently, the defective samples exhibit a significantly higher efficiency in the photoreduction of CO2 to formate. Transient absorption spectroscopies manifest that structural defects modulate the excited-state behivior of Zr-MOF-X and improve the photogenerated charge separation of Zr-MOF-X. Furthermore, electron paramagnetic resonance and in-suit X-ray photoelectron spectroscopy provide additional evidence of the high photocatalytic performance exhibited by defective Zr-MOF-X. Results demonstrate that structural defects in Zr-MOF-X also improve the charge transfer, producing abundant Zr(III) catalytically active sites, exhibiting a slower decay process than defect-free Zr-MOF. The long-lifetime Zr(III) species in defective Zr-MOF-X are fully exposed to a high-concentration CO2 atmosphere, thereby enhancing the photocatalytic efficiency of CO2 reduction.

PACMAN: A Robust Partial Atomic Charge Predicter for Nanoporous Materials Based on Crystal Graph Convolution Networks.

We report a fast and easy method (PACMAN) to assign partial atomic charges on metal-organic framework (MOF) and covalent-organic framework (COF) crystal structures based on graph convolution networks (GCNs) trained on >1.8 million high-fidelity partial atomic charge data obtained from the Quantum Metal-Organic Framework (QMOF) database. The developed model shows outstanding performance, achieving a mean absolute error (MAE) of 0.0055 e (test set performance) while maintaining consistency with DDEC6, Bader, and CM5 charges across diverse chemistry and topologies of MOFs and COFs. We find that the new method accurately assigns partial atomic charges for ion-containing nanoporous materials, which has not been possible in previous machine learning (ML) models. Grand canonical Monte Carlo (GCMC) simulation results for CO2 and N2 uptakes and the Widom particle insertion calculation for Henry's law constant of water results based on PACMAN and the original DDEC6 charges show excellent agreements compared to other ML models reported in the literature. The runtime analysis of the new method demonstrates that the partial atomic charges of MOF and COF structures with up to 500 atoms can be obtained in less than 10 s. An easy-to-use web interface has been developed to facilitate the adoption of the developed model.

Synthesis, characterization, hysteretic two-step CO2 adsorption, and fluorescence properties of two isoreticular mixed-ligand pillared-layer frameworks

Two isostructural and isomorphrous metal–organic frameworks (MOFs), namely [Zn2(Brtpt)2 (bpBTD)]n (1) and {[Zn2 (ntpt)2 (bpBTD)]∙solvent}n (2), where bpBTD = bis(pyridin-4-yl)benzothiadiazole, H2Brtpt = 2-bromoterephthalic acid, H2ntpt = 2-nitroterephthalic acid, with thermal stability of 355 °C for 1 and 265 °C for 2 were hydro (solvo)thermally synthesized in DMF/H2O media at 100 °C. Single-crystal X-ray diffraction analysis revealed that 1 and 2 both possess 2-fold interpenetrating pillared-layer frameworks showing pcu net topology with the point symbol of 41,263. The sufficient extra-framework void spaces are approximately 30.1 % for 1 and 32.0 % for 2 with open channels along the b axis, where the window sizes are ca. 5.51 × 3.15 Å2 in edge for the former and ca. 5.47 × 3.44 Å2 and 3.12 × 3.44 Å2 in edge for the latter. Gas adsorption isotherms revealed that thermally activated 1 and 2 both hardly adsorb N2 with very low N2 uptakes at 77 K. Comparably, the CO2 adsorption isotherms of thermally activated 1 and 2 both revealed gate-opening (two-step) sorption behaviors with an apparent hysteretic adsorption–desorption process, where the maximum uptakes are 135.4 and 171.5 cm3 g−1 STP for 1 and 2, respectively, at 195 K and P/P0 = 1. Photoluminescence studies showed that 1 and 2 both emitted bpBTD-dominated ligand-centered emissions, being as cyan and pearl aqua color fluorescence centered at λem = 467 and 495 nm, respectively, in solid-state and as cyan color fluorescence centered at λem = 455 and 458 nm, respectively, in H2O suspensions.

Nitrogen Fixation at the Mid‐Atlantic Bight Shelfbreak and Transport of Newly Fixed Nitrogen to the Slope Sea

AbstractContinental shelves contribute a large fraction of the ocean's new nitrogen (N) via N2 fixation; yet, we know little about how physical processes at the ocean's margins shape diazotroph biogeography and activity. Here, we test the hypothesis that frontal mixing favors N2 fixation at the Mid‐Atlantic Bight shelfbreak. Using the 15N2 bubble release method, we measured N2 fixation rates on repeat cross‐frontal transects in July 2019. N2 fixation rates in shelf waters (median = 5.42 nmol N L−1 d−1) were higher than offshore (2.48 nmol N L−1 d−1) but did not significantly differ front frontal waters (8.42 nmol N L−1 d−1). However, specific N2 uptake rates, indicative of the relative contribution of diazotroph‐derived N to particulate N turnover, were significantly higher in frontal waters, suggesting that diazotroph‐derived N is of greater importance in supporting productivity there. This study furthered captured an ephemeral shelf‐water streamer, which resulted from the impingement of a warm core ring on the shelf. The streamer transported shelf‐water diazotrophs (including UCYN‐A and Richelia spp., as assessed by qPCR) offshore with sustained high N2 fixation rates. This feature injected >50 metric tons d−1 of newly fixed N to the Slope Sea—a rate equivalent to ∼4% of the total N flux estimated for the entire Mid‐Atlantic Bight. As intrusions of Gulf Stream meanders and eddies onto the shelf are increasing in frequency due to climate change, episodic lateral fluxes of new N into the Slope Sea may become increasingly important to regional budgets and ecosystem productivity.

From abandoned mines to carbon sinks: Assessing the CO2 storage capacity of Austrian low-rank coal deposits

This study represents the first assessment of CO2 storage potential in Austrian coal seams. Coal samples were taken from Fohnsdorf and Leoben abandoned coal mines, with particular emphasis on the Fohnsdorf coal since Leoben coal reserves were largely mined during previous coal production. Several methods were used to compare coal characteristics, including Rock-Eval pyrolysis (RE), organic petrography, and low-pressure N2 and CO2 sorption measurements. Both Fohnsdorf and Leoben coal samples show low sulfur and ash yields, as well as correspondingly high total organic carbon (TOC) contents. The pyrolysis Tmax and vitrinite reflectance values agree with a low coal rank for both sites. According to the N2 adsorption measurements at 77 K, low-lying mire coals from Fohnsdorf show a higher BET-specific surface area (BET-SSA) and BJH pore volume compared to raised-mire coals from Leoben. However, sapropelic shales and high-ash coals from Leoben show the highest BET-SSA and BJH pore volumes of all investigated samples and considerably exceed the N2 adsorption volumes of pure coals from both locations (N2 uptake up to 16 cm3/g; avg. for all samples 5.4 cm3/g). In contrast, the mean adsorbed CO2 uptake measured at 273 K and ∼ 1 bar followed the order of Fohnsdorf low-lying mire coals > Leoben raised-mire coals > Leoben sapropelic coals and shales, ranging at ∼0.8 mmol/g, ∼0.7 mmol/g, and ∼ 0.2 mmol/g, respectively. This shows that BET-SSA and BJH equations did not allow for adequate estimation of CO2 adsorption capacity trends in the investigated sample set. Furthermore, based on the existence of a hysteresis loop between CO2 adsorption and desorption branches for all investigated samples, the occurrence of weak chemisorption phenomena during CO2 adsorption is indicated. This effect helps to increase CO2 uptake and storage safety since the chemisorption process is not fully reversible upon pressure decrease. Ultimately, the theoretical CO2 sequestration potential of the remaining unmined Fohnsdorf coal reserves was estimated at 4.65 million tons, with an additional potential for enhanced coal bed methane production due to the gas-rich nature of Fohnsdorf coals with an estimated 1.2 billion m3 of CH4 in place.

Shaping of MIL-53-Al and MIL-101 MOF for CO2/CH4, CO2/N2 and CH4/N2 separation

Metal-organic frameworks (MOF) are promising materials for gas storage and separation. The formulation and shaping of MOFs in mechanically stable bead forms is an essential requirement for their practical application as an adsorbent for gas and liquid mixture separations. In this work, MIL-53-Al and MIL-101 MOF beads are synthesized using sodium alginate as a binder, and calcium chloride as a gelling agent. The synthesized MIL-53-Al and MIL-101 MOF beads are characterized by powder X-ray diffraction (PXRD), BET surface area, porosity analysis from N2 uptake data at 77 K, FTIR, TGA, and scanning electron microscopy (SEM). The isothermal equilibrium adsorption uptake of CH4 and N2 gases is measured up to 10 bar pressure while the CO2 equilibrium uptake is measured up to 1 bar at 298 and 313 K respectively. The isotherm data of all adsorbates are fitted in Dual Site Langmuir (DSL) isotherm equations. The adsorption selectivity for CH4/N2, CO2/CH4, and CO2/N2 binary systems are predicted using the Ideal Adsorbed Solution Theory (IAST) method. The dynamic column breakthrough experiments are carried out on MIL-53-Al beads for CH4/N2 (30:70 and 50:50 v/v), CO2/CH4 (45:55 v/v) and CO2/N2 (15: 85 v/v) feed mixtures. The IAST selectivity and breakthrough time obtained under the same superficial velocity, pressure, and temperature conditions follow the order CO2/N2 > CO2 /CH4 > CH4/N2. The MIL-53-Al beads show higher CH4/N2, CO2/CH4, and CO2/N2 selectivity for the targeted mixtures than MIL-101 beads.

Enhancement effect of Li addition on nitriding reaction and combustion of Al-Li alloy in N2

For aluminum-based alloy particles, the addition of alloying element lithium (Li) with the properties of a high chemical activity and a low melting/boiling point can significantly improve the thermo-reactive properties of aluminum (Al) particles. To further reveal the combustion mechanism, this paper presents the nitriding reaction and combustion characteristics of Al-Li alloy in nitrogen (N2) through thermogravimetric analysis and differential scanning calorimetry (TG-DSC) analysis at a low heating rate and laser-induced ignition experiments at a high heating rate, considering the influences of two kinds of Li contents (1.0 wt% @ Al-1.0Li and 2.5 wt% @ Al-2.5Li) on these characteristics and making a comparison to the counterpart Al. Al-Li alloy powders as-prepared by gas atomization method showed the texture of the Li-rich eutectic phase compounds on the surface by scanning electron microscope (SEM) characterization. The TG-DSC results demonstrated that the thermal nitriding reaction of Al-Li alloy in N2 was significantly faster than that of pure Al. The nitriding reaction temperature decreased from 853 °C for pure Al to 245 °C for Al-2.5Li alloy with a reduction of 71 %. The final weight gain of Al-2.5Li alloy was almost three times higher than that of pure Al in N2. The SEM photograph of intermediate nitriding products revealed that the cracks and loose “island” structures in the Li-rich zone on the Al-Li surface were the key to preventing the formation of a “passivation effect” into Al and promoting N2 uptake during melting. In addition, Li also acts as a catalytic carrier and “oxygen absorber” to enhance the Al-N reaction. The combustion of single Al-Li alloy microparticles induced by laser showed two stages: preheating and rapid nitriding. Al-Li alloy particles were ignited more rapidly and showed typical gas-phase / surface combustion modes different from pure Al. According to these findings, the combustion mechanism was proposed to help guide the development of Al-based solid propellants containing Li and the synthesis of AlN/Al composites in nitrogen-rich environments.

Water-Stable Microporous Bipyrazole-Based Framework for Efficient Separation of MTO Products.

Recently, methanol-to-olefins (MTO) technology has been widely used. The development of new adsorbents to separate MTO products and obtain high-purity ethylene (C2H4) and propylene (C3H6) has become an urgent task. Herein, an exceptionally highly water-stable metal-organic framework (MOF), [Cu3(OH)2(Me2BPZ)2]·(solvent)x (1) (H2Me2BPZ = 3,3'-dimethyl-1H,1'H-4,4'-bipyrazole) with hexagonal pores, has been elaborately designed and constructed. After being soaked in water for 7 days, it still maintains its structure, and the uptake of N2 at 77 K is unchanged. The adsorption capacity of C3H6 can reach 138 cm3 g-1, while the uptake of C2H4 is only 52 cm3 g-1 at 298 K and 1 bar. The dynamic breakthrough experiments show that the mixture of C3H6/C2H4 (50/50, v/v) can be efficiently separated in one step. High-purity C2H4 and C3H6 can be obtained through an adsorption and desorption cycle and the yields of C2H4 (purity ≥ 99.95%) and C3H6 (purity ≥ 99%) are 84 and 48 L kg-1, respectively. Surprisingly, when the flow rate is increased, the separation performance has no obvious change. Additionally, humidity has no effect on the separation performance. Finally, theoretical simulations indicate that there are stronger interactions between the C3H6 molecule and the framework, which are beneficial to capturing C3H6 over C2H4.

Synergistic Nitrogen Binding Sites in a Metal‐Organic Framework for Efficient N2/O2 Separation

AbstractPorous materials with d3 electronic configuration open metal sites have been proved to be effective adsorbents for N2 capture and N2/O2 separation. However, the reported materials remain challenging to address the trade‐off between adsorption capacity and selectivity. Herein, we report a robust MOF, MIL‐102Cr, that features two binding sites, can synergistically afford strong interactions for N2 capture. The synergistic adsorption site exhibits a benchmark Qst of 45.0 kJ mol−1 for N2 among the Cr‐based MOFs, a record‐high volumetric N2 uptake (31.38 cm3 cm−3), and highest N2/O2 selectivity (13.11) at 298 K and 1.0 bar. Breakthrough experiments reveal that MIL‐102Cr can efficiently capture N2 from a 79/21 N2/O2 mixture, providing a record 99.99 % pure O2 productivity of 0.75 mmol g−1. In situ infrared spectroscopy and computational modelling studies revealed that a synergistic adsorption effect by open Cr(III) and fluorine sites was accountable for the strong interactions between the MOF and N2.

Synergistic Nitrogen Binding Sites in a Metal-Organic Framework for Efficient N2 /O2 Separation.

Porous materials with d3 electronic configuration open metal sites have been proved to be effective adsorbents for N2 capture and N2 /O2 separation. However, the reported materials remain challenging to address the trade-off between adsorption capacity and selectivity. Herein, we report a robust MOF, MIL-102Cr, that features two binding sites, can synergistically afford strong interactions for N2 capture. The synergistic adsorption site exhibits a benchmark Qst of 45.0 kJ mol-1 for N2 among the Cr-based MOFs, a record-high volumetric N2 uptake (31.38 cm3 cm-3 ), and highest N2 /O2 selectivity (13.11) at 298 K and 1.0 bar. Breakthrough experiments reveal that MIL-102Cr can efficiently capture N2 from a 79/21 N2 /O2 mixture, providing a record 99.99 % pure O2 productivity of 0.75 mmol g-1 . In situ infrared spectroscopy and computational modelling studies revealed that a synergistic adsorption effect by open Cr(III) and fluorine sites was accountable for the strong interactions between the MOF and N2 .

Cardiorespiratory adaptations in small cetaceans and marine mammals.

The dive response, or the 'master switch of life', is probably the most studied physiological trait in marine mammals and is thought to conserve the available O2 for the heart and brain. Although generally thought to be an autonomic reflex, several studies indicate that the cardiovascular changes during diving are anticipatory and can be conditioned. The respiratory adaptations, where the aquatic breathing pattern resembles intermittent breathing in land mammals, with expiratory flow exceeding 160litres s-1 has been measured in cetaceans, and where exposure to extreme pressures results in alveolar collapse (atelectasis) and recruitment upon ascent. Cardiorespiratory coupling, where breathing results in changes in heart rate, has been proposed to improve gas exchange. Cardiorespiratory coupling has also been reported in marine mammals, and in the bottlenose dolphin, where it alters both heart rate and stroke volume. When accounting for this respiratory dependence on cardiac function, several studies have reported an absence of a diving-related bradycardia except during dives that exceed the duration that is fuelled by aerobic metabolism. This review summarizes what is known about the respiratory physiology in marine mammals, with a special focus on cetaceans. The cardiorespiratory coupling is reviewed, and the selective gas exchange hypothesis is summarized, which provides a testable mechanism for how breath-hold diving vertebrates may actively prevent uptake of N2 during routine dives, and how stress results in failure of this mechanism, which results in diving-related gas emboli.

Solvent-Directed Construction of a Nanoporous Metal-Organic Framework with Potential in Selective Adsorption and Separation of Gas Mixtures Studied by Grand Canonical Monte Carlo Simulations.

In this report, a microporous metal-organic framework of [Ca(TDC)(DMA)]n (1) and a two-dimensional coordination polymer of [Ca(TDC)(DMF)2 ]n (2), (TDC2- =Thiophene-2,5-dicarboxylate, DMA=N, N'-dimethylacetamide and DMF=N, N'-dimethylformamide) based on Ca(II) were designed by the effect of solvent, and X-ray analysis was performed for the single crystals of 1 and 2. Then, compound 1 was synthesized in three different methods and identified with a set of analyses. Compared to other adsorbents, MOFs are widely used in the field of adsorption and separation of various gases due to a series of distinctive features such as diverse and adjustable structures pores with different dimensions, high porosity and surface area with regular distribution of active sites. Therefore, the ability of 1 to uptake single gases (CH4 , CO2 , C2 H2 , H2, and N2 ) and separation of several binary mixtures of gases (CO2 /CH4 , CO2 /N2 , CO2 /H2 and CO2 /C2 H2 ), were investigated using Grand Canonical Monte Carlo simulations. Volumetric and gravimetric adsorption isotherms in various operating conditions, the isosteric heat of adsorption (qst ), the chemical potential for each thermodynamic state, and snapshots during the simulation process were reported in all cases. The results obtained from the adsorption simulation indicate that compound 1 has a high capacity for uptake of H2 (16 mmol g-1 ) and N2 (12.5 mmol g-1 ), CO2 (6.6 mmol g-1 ), C2 H2 (5 mmol g-1 ) and CH4 (1.5 mmol g-1 ) gases at 1 bar. It also performs well in separating CO2 in binary mixtures, which can be attributed to the presence of open metal sites in nodes of 1 and their electrostatic tendency to interact with CO2 containing the higher quadrupole dipole moment compared to other components of the mixture.

CO2 Adsorption Behavior of Nanosized CHA Zeolites Synthesized in the Presence of Barium or Calcium Cations

AbstractAlkaline‐earth metal cations impact the rate of crystallization and the adsorption of N2 and CO2 on nanosized chabazite zeolites. In this study, either calcium or barium is added to precursor mixtures containing alkali‐metal cations (Na+, K+, Cs+) to prepare chabazite (labeled Ca‐CHA and Ba‐CHA), and are compared to a reference sample (Ref‐CHA) synthesized using exclusively Na+, K+, and Cs+. Partial substitution of the Na+ and the pore‐blocking Cs+ extra‐framework cations is observed for Ca‐CHA depending on the molar ratio of K2O used in the synthesis, while a change to the amount of Na+ cations only is observed for Ba‐CHA. The type of alkaline‐earth metal cation affects the crystallization rate; slower in the presence of Ca2+ (10 h to full crystallinity) and similar rates in the presence of Ba2+ (4 h to full crystallinity); the crystallite size and morphology remained similar. The presence of Ca2+ or Ba2+ extra‐framework cations leads to N2 uptake values of 290 and 169 mmol g−1 (−196 °C, 100 kPa), respectively, while at low CO2 pressure (<1 kPa, 25 °C), the physisorbed CO2 capacity for Ref‐CHA, Ca‐CHA, and Ba‐CHA zeolites is 0.63, 0.66, and 0.59 mmol g−1, respectively. Interestingly, an opposite effect is observed for the amount of chemisorbed CO2 species.

The controlled microfluidic formation of stable mixed phase HCP/FCC-UiO-67(Zr)-benzoic acid through modification of water concentration

This work reports the synthesis of a mixed crystal phase mesoporous metal–organic framework (MOF) through a new synthesis route. The Hexagonal Centred Planar/Face Centred Cubic mixed phase UiO-67(Zr) product was microfluidically synthesised using benzoic acid as the acid modulator. This phase ratio can be altered through changing the concentration of water present in the reaction solution. This product shows increased mesoporosity and uptake of N2 at 77 K and 1 bar of 1083 cm3/g, as compared to 615 cm3/g for the product made via the traditional batch approach. This leads to an increase working capacity due to the change in isotherm type, from type I to type IV, with the uptake occurring more gradually overall as pressure increases. An increased working capacity allows for a greater range of control for the volume of N2 stored in/released from the material. This product has only been successful in microfluidic conditions, highlighting the potential importance of this method for future synthesis of this MOF.

A Novel Hydrogen-Bonded Organic Framework Constructed by Triptycene-2,3,6,7,14, 15-Hexacarboxylic Acid

Abstract Triptycene-2,3,6,7,14,15-hexacarboxylic acid (4) was synthesized via a new and efficient route. A single-component, porous hydrogen-bonded organic framework (TrpHOF) was constructed by recrystallization of 4. Although TrpHOF shows almost no N2 uptake, not even at 1 atm and 77 K, the maximum CO2 adsorption at 1 atm and 273 K is 8.2 cm3/g, showing a type-I isotherm, which is characteristic of microporous materials.