Cooperative Carbon Dioxide Capture in Diamine-Appended Magnesium-Olsalazine Frameworks.

Diamine-appended Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks have emerged as promising candidates for carbon capture owing to their exceptional CO2 selectivities, high separation capacities, and step-shaped adsorption profiles, which arise from a unique cooperative adsorption mechanism resulting in the formation of ammonium carbamate chains. Materials appended with primary,secondary-diamines featuring bulky substituents, in particular, exhibit excellent stabilities and CO2 adsorption properties. However, these frameworks display double-step adsorption behavior arising from steric repulsion between ammonium carbamates, which ultimately results in increased regeneration energies. Herein, we report frameworks of the type diamine-Mg2(olz) (olz4- = (E)-5,5'-(diazene-1,2-diyl)bis(2-oxidobenzoate)) that feature diverse diamines with bulky substituents and display desirable single-step CO2 adsorption across a wide range of pressures and temperatures. Analysis of CO2 adsorption data reveals that the basicity of the pore-dwelling amine─in addition to its steric bulk─is an important factor influencing adsorption step pressure; furthermore, the amine steric bulk is found to be inversely correlated with the degree of cooperativity in CO2 uptake. One material, ee-2-Mg2(olz) (ee-2 = N,N-diethylethylenediamine), adsorbs >90% of the CO2 from a simulated coal flue stream and exhibits exceptional thermal and oxidative stability over the course of extensive adsorption/desorption cycling, placing it among top-performing adsorbents to date for CO2 capture from a coal flue gas. Spectroscopic characterization and van der Waals-corrected density functional theory calculations indicate that diamine-Mg2(olz) materials capture CO2 via the formation of ammonium carbamate chains. These results point more broadly to the opportunity for fundamentally advancing materials in this class through judicious design.

A cooperative adsorbent for the switch-like capture of carbon dioxide from crude natural gas.

Natural gas constitutes a growing share of global primary energy due to its abundant supply and lower CO2 emission intensity compared to coal. For many natural gas reserves, CO2 contamination must be removed at the wellhead to meet pipeline specifications. Here, we demonstrate the potential of the diamine-appended metal-organic framework ee-2-Mg2(dobpdc) (ee-2 = N,N-diethylethylenediamine; dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) as a next-generation CO2 capture material for high-pressure natural gas purification. Owing to a cooperative adsorption mechanism involving formation of ammonium carbamate chains, ee-2-Mg2(dobpdc) can be readily regenerated with a minimal change in temperature or pressure and maintains its CO2 capacity in the presence of water. Moreover, breakthrough experiments reveal that water enhances the CO2 capture performance of ee-2-Mg2(dobpdc) by eliminating "slip" of CO2 before full breakthrough. Spectroscopic characterization and multicomponent adsorption isobars suggest that the enhanced performance under humid conditions arises from preferential stabilization of the CO2-inserted phase in the presence of water. The favorable performance of ee-2-Mg2(dobpdc) is further demonstrated through comparison with a benchmark material for this separation, zeolite 13X, as well as extended pressure cycling. Overall, these results support continued development of ee-2-Mg2(dobpdc) as a promising adsorbent for natural gas purification.

Evaluation of the Stability of Diamine-Appended Mg2(dobpdc) Frameworks to Sulfur Dioxide.

Diamine-appended Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) metal-organic frameworks are a promising class of CO2 adsorbents, although their stability to SO2─a trace component of industrially relevant exhaust streams─remains largely untested. Here, we investigate the impact of SO2 on the stability and CO2 capture performance of dmpn-Mg2(dobpdc) (dmpn = 2,2-dimethyl-1,3-propanediamine), a candidate material for carbon capture from coal flue gas. Using SO2 breakthrough experiments and CO2 isobar measurements, we find that the material retains 91% of its CO2 capacity after saturation with a wet simulated flue gas containing representative levels of CO2 and SO2, highlighting the robustness of this framework to SO2 under realistic CO2 capture conditions. Initial SO2 cycling experiments suggest dmpn-Mg2(dobpdc) may achieve a stable operating capacity in the presence of SO2 after initial passivation. Evaluation of several other diamine-Mg2(dobpdc) variants reveals that those with primary,primary (1°,1°) diamines, including dmpn-Mg2(dobpdc), are more robust to humid SO2 than those featuring primary,secondary (1°,2°) or primary,tertiary (1°,3°) diamines. Based on the solid-state 15N NMR spectra and density functional theory calculations, we find that under humid conditions, SO2 reacts with the metal-bound primary amine in 1°,2° and 1°,3° diamine-appended Mg2(dobpdc) to form a metal-bound bisulfite species that is charge balanced by a primary ammonium cation, thereby facilitating material degradation. In contrast, humid SO2 reacts with the free end of 1°,1° diamines to form ammonium bisulfite, leaving the metal-diamine bond intact. This structure-property relationship can be used to guide further optimization of these materials for CO2 capture applications.

Overcoming Metastable CO2 Adsorption in a Bulky Diamine-Appended Metal-Organic Framework.

Carbon capture at fossil fuel-fired power plants is a critical strategy to mitigate anthropogenic contributions to global warming, but widespread deployment of this technology is hindered by a lack of energy-efficient materials that can be optimized for CO2 capture from a specific flue gas. As a result of their tunable, step-shaped CO2 adsorption profiles, diamine-functionalized metal-organic frameworks (MOFs) of the form diamine-Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are among the most promising materials for carbon capture applications. Here, we present a detailed investigation of dmen-Mg2(dobpdc) (dmen = 1,2-diamino-2-methylpropane), one of only two MOFs with an adsorption step near the optimal pressure for CO2 capture from coal flue gas. While prior characterization suggested that this material only adsorbs CO2 to half capacity (0.5 CO2 per diamine) at 1 bar, we show that the half-capacity state is actually a metastable intermediate. Under appropriate conditions, the MOF adsorbs CO2 to full capacity, but conversion from the half-capacity structure happens on a very slow time scale, rendering it inaccessible in traditional adsorption measurements. Data from solid-state magic angle spinning nuclear magnetic resonance spectroscopy, coupled with van der Waals-corrected density functional theory, indicate that ammonium carbamate chains formed at half capacity and full capacity adopt opposing configurations, and the need to convert between these states likely dictates the sluggish post-half-capacity uptake. By use of the more symmetric parent framework Mg2(pc-dobpdc) (pc-dobpdc4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate), the metastable trap can be avoided and the full CO2 capacity of dmen-Mg2(pc-dobpdc) accessed under conditions relevant for carbon capture from coal-fired power plants.

Hysteresis curves reveal the microscopic origin of cooperative CO2 adsorption in diamine-appended metal-organic frameworks.

Diamine-appended metal-organic frameworks (MOFs) of the form Mg2(dobpdc)(diamine)2 adsorb CO2 in a cooperative fashion, exhibiting an abrupt change in CO2 occupancy with pressure or temperature. This change is accompanied by hysteresis. While hysteresis is suggestive of a first-order phase transition, we show that hysteretic temperature-occupancy curves associated with this material are qualitatively unlike the curves seen in the presence of a phase transition; they are instead consistent with CO2 chain polymerization, within one-dimensional channels in the MOF, in the absence of a phase transition. Our simulations of a microscopic model reproduce this dynamics, providing a physical understanding of cooperative adsorption in this industrially important class of materials.

Porous materials for carbon dioxide separations.

Global investment in counteracting climate change has galvanized increasing interest in carbon capture and sequestration (CCS) as a versatile emissions mitigation technology. As decarbonization efforts accelerate, CCS can target the emissions of large point-source emitters, such as coal- or natural gas-fired power plants, while also supporting the production of renewable or low-carbon fuels. Furthermore, CCS can enable decarbonization of difficult-to-abate industrial processes and can support net CO2 removal from the atmosphere through bioenergy coupled with CCS or direct air capture. Here we review the development of porous materials as next-generation sorbents for CO2 capture applications. We focus on stream- and sector-specific challenges while highlighting case studies within the context of the rapidly shifting energy landscape. We conclude with a discussion of key needs from the materials community to expand deployment of carbon capture technologies.

Cooperative carbon capture and steam regeneration with tetraamine-appended metal-organic frameworks.

Natural gas has become the dominant source of electricity in the United States, and technologies capable of efficiently removing carbon dioxide (CO2) from the flue emissions of natural gas-fired power plants could reduce their carbon intensity. However, given the low partial pressure of CO2 in the flue stream, separation of CO2 is particularly challenging. Taking inspiration from the crystal structures of diamine-appended metal-organic frameworks exhibiting two-step cooperative CO2 adsorption, we report a family of robust tetraamine-functionalized frameworks that retain cooperativity, leading to the potential for exceptional efficiency in capturing CO2 under the extreme conditions relevant to natural gas flue emissions. The ordered, multimetal coordination of the tetraamines imparts the materials with extraordinary stability to adsorption-desorption cycling with simulated humid flue gas and enables regeneration using low-temperature steam in lieu of costly pressure or temperature swings.

Kinetics of cooperative CO2 adsorption in diamine-appended variants of the metal-organic framework Mg2(dobpdc).

Carbon capture and sequestration is a key element of global initiatives to minimize anthropogenic greenhouse gas emissions. Although many investigations of new candidate CO2 capture materials focus on equilibrium adsorption properties, it is also critical to consider adsorption/desorption kinetics when evaluating adsorbent performance. Diamine-appended variants of the metal-organic framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising materials for CO2 capture because of their cooperative chemisorption mechanism and associated step-shaped equilibrium isotherms, which enable large working capacities to be accessed with small temperature swings. However, the adsorption/desorption kinetics of these unique materials remain understudied. More generally, despite the necessity of kinetics characterization to advance adsorbents toward commercial separations, detailed kinetic studies of metal-organic framework-based gas separations remain rare. Here, we systematically investigate the CO2 adsorption kinetics of diamine-appended Mg2(dobpdc) variants using a thermogravimetric analysis (TGA) assay. In particular, we examine the effects of diamine structure, temperature, and partial pressure on CO2 adsorption and desorption kinetics. Importantly, most diamine-appended Mg2(dobpdc) variants exhibit an induction period prior to reaching the maximum rate of CO2 adsorption, which we attribute to their unique cooperative chemisorption mechanism. In addition, these materials exhibit inverse Arrhenius behavior, displaying faster adsorption kinetics and shorter induction periods at lower temperatures. Using the Avrami model for nucleation and growth kinetics, we determine rate constants for CO2 adsorption and quantitatively compare rate constants among different diamine-appended variants. Overall, these results provide guidelines for optimizing adsorbent design to facilitate CO2 capture from diverse target streams and highlight kinetic phenomena relevant for other materials in which cooperative chemisorption mechanisms are operative.

Cooperative Carbon Dioxide Adsorption in Alcoholamine- and Alkoxyalkylamine-Functionalized Metal-Organic Frameworks.

A series of structurally diverse alcoholamine- and alkoxyalkylamine-functionalized variants of the metal-organic framework Mg2 (dobpdc) are shown to adsorb CO2 selectively via cooperative chain-forming mechanisms. Solid-state NMR spectra and optimized structures obtained from van der Waals-corrected density functional theory calculations indicate that the adsorption profiles can be attributed to the formation of carbamic acid or ammonium carbamate chains that are stabilized by hydrogen bonding interactions within the framework pores. These findings significantly expand the scope of chemical functionalities that can be utilized to design cooperative CO2 adsorbents, providing further means of optimizing these powerful materials for energy-efficient CO2 separations.

Amine Dynamics in Diamine-Appended Mg2(dobpdc) Metal-Organic Frameworks.

Variable-temperature 15N solid-state NMR spectroscopy is used to uncover the dynamics of three diamines appended to the metal-organic framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), an important family of CO2 capture materials. The results imply both bound and free amine nitrogen environments exist when diamines are coordinated to the framework open Mg2+ sites. There are rapid exchanges between two nitrogen environments for all three diamines, the rates and energetics of which are quantified by 15N solid-state NMR data and corroborated by density functional theory calculations and molecular dynamics simulations. The activation energy for the exchange provides a measure of the metal-amine bond strength. The unexpected negative correlation between the metal-amine bond strength and CO2 adsorption step pressure reveals that metal-amine bond strength is not the only important factor in determining the CO2 adsorption properties of diamine-appended Mg2(dobpdc) metal-organic frameworks.

Correction: Enhancement of CO2 binding and mechanical properties upon diamine functionalization of M2(dobpdc) metal-organic frameworks.

[This corrects the article DOI: 10.1039/C7SC05217K.].

Water Enables Efficient CO2 Capture from Natural Gas Flue Emissions in an Oxidation-Resistant Diamine-Appended Metal-Organic Framework.

Supported by increasingly available reserves, natural gas is achieving greater adoption as a cleaner-burning alternative to coal in the power sector. As a result, carbon capture and sequestration from natural gas-fired power plants is an attractive strategy to mitigate global anthropogenic CO2 emissions. However, the separation of CO2 from other components in the flue streams of gas-fired power plants is particularly challenging due to the low CO2 partial pressure (∼40 mbar), which necessitates that candidate separation materials bind CO2 strongly at low partial pressures (≤4 mbar) to capture ≥90% of the emitted CO2. High partial pressures of O2 (120 mbar) and water (80 mbar) in these flue streams have also presented significant barriers to the deployment of new technologies for CO2 capture from gas-fired power plants. Here, we demonstrate that functionalization of the metal-organic framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) with the cyclic diamine 2-(aminomethyl)piperidine (2-ampd) produces an adsorbent that is capable of ≥90% CO2 capture from a humid natural gas flue emission stream, as confirmed by breakthrough measurements. This material captures CO2 by a cooperative mechanism that enables access to a large CO2 cycling capacity with a small temperature swing (2.4 mmol CO2/g with ΔT = 100 °C). Significantly, multicomponent adsorption experiments, infrared spectroscopy, magic angle spinning solid-state NMR spectroscopy, and van der Waals-corrected density functional theory studies suggest that water enhances CO2 capture in 2-ampd-Mg2(dobpdc) through hydrogen-bonding interactions with the carbamate groups of the ammonium carbamate chains formed upon CO2 adsorption, thereby increasing the thermodynamic driving force for CO2 binding. In light of the exceptional thermal and oxidative stability of 2-ampd-Mg2(dobpdc), its high CO2 adsorption capacity, and its high CO2 capture rate from a simulated natural gas flue emission stream, this material is one of the most promising adsorbents to date for this important separation.

Challenges and opportunities for adsorption-based CO2 capture from natural gas combined cycle emissions.

In recent years, the power sector has shown a growing reliance on natural gas, a cleaner-burning fuel than coal that emits approximately half as much CO2 per kWh of energy produced. This rapid growth in the consumption of natural gas has led to increased CO2 emissions from gas-fired power plants. To limit the contribution of fossil fuel combustion to atmospheric CO2 levels, carbon capture and sequestration has been proposed as a potential emission mitigation strategy. However, despite extensive exploration of solid adsorbents for CO2 capture, few studies have examined the performance of adsorbents in post-combustion capture processes specific to natural gas flue emissions. In this perspective, we emphasize the importance of considering gas-fired power plants alongside coal-fired plants in future analyses of carbon capture materials. We address specific challenges and opportunities related to adsorptive carbon capture from the emissions of gas-fired plants and discuss several promising candidate materials. Finally, we suggest experiments to determine the viability of new CO2 capture materials for this separation. This broadening in the scope of current carbon capture research is urgently needed to accelerate the deployment of transformational carbon capture technologies.

Elucidating CO2 Chemisorption in Diamine-Appended Metal-Organic Frameworks.

The widespread deployment of carbon capture and sequestration as a climate change mitigation strategy could be facilitated by the development of more energy-efficient adsorbents. Diamine-appended metal-organic frameworks of the type diamine-M2(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) have shown promise for carbon-capture applications, although questions remain regarding the molecular mechanisms of CO2 uptake in these materials. Here we leverage the crystallinity and tunability of this class of frameworks to perform a comprehensive study of CO2 chemisorption. Using multinuclear nuclear magnetic resonance (NMR) spectroscopy experiments and van-der-Waals-corrected density functional theory (DFT) calculations for 13 diamine-M2(dobpdc) variants, we demonstrate that the canonical CO2 chemisorption products, ammonium carbamate chains and carbamic acid pairs, can be readily distinguished and that ammonium carbamate chain formation dominates for diamine-Mg2(dobpdc) materials. In addition, we elucidate a new chemisorption mechanism in the material dmpn-Mg2(dobpdc) (dmpn = 2,2-dimethyl-1,3-diaminopropane), which involves the formation of a 1:1 mixture of ammonium carbamate and carbamic acid and accounts for the unusual adsorption properties of this material. Finally, we show that the presence of water plays an important role in directing the mechanisms for CO2 uptake in diamine-M2(dobpdc) materials. Overall, our combined NMR and DFT approach enables a thorough depiction and understanding of CO2 adsorption within diamine-M2(dobpdc) compounds, which may aid similar studies in other amine-functionalized adsorbents in the future.

Cooperative adsorption of carbon disulfide in diamine-appended metal-organic frameworks.

Over one million tons of CS2 are produced annually, and emissions of this volatile and toxic liquid, known to generate acid rain, remain poorly controlled. As such, materials capable of reversibly capturing this commodity chemical in an energy-efficient manner are of interest. Recently, we detailed diamine-appended metal-organic frameworks capable of selectively capturing CO2 through a cooperative insertion mechanism that promotes efficient adsorption-desorption cycling. We therefore sought to explore the ability of these materials to capture CS2 through a similar mechanism. Employing crystallography, spectroscopy, and gas adsorption analysis, we demonstrate that CS2 is indeed cooperatively adsorbed in N,N-dimethylethylenediamine-appended M2(dobpdc) (M = Mg, Mn, Zn; dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate), via the formation of electrostatically paired ammonium dithiocarbamate chains. In the weakly thiophilic Mg congener, chemisorption is cleanly reversible with mild thermal input. This work demonstrates that the cooperative insertion mechanism can be generalized to other high-impact target molecules.

Enhancement of CO2 binding and mechanical properties upon diamine functionalization of M2(dobpdc) metal-organic frameworks.

The family of diamine-appended metal-organic frameworks exemplified by compounds of the type mmen-M2(dobpdc) (mmen = N,N'-dimethylethylenediamine; M = Mg, Mn, Fe, Co, Zn; dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are adsorbents with significant potential for carbon capture, due to their high working capacities and strong selectivity for CO2 that stem from a cooperative adsorption mechanism. Herein, we use first-principles density functional theory (DFT) calculations to quantitatively investigate the role of mmen ligands in dictating the framework properties. Our van der Waals-corrected DFT calculations indicate that electrostatic interactions between ammonium carbamate units significantly enhance the CO2 binding strength relative to the unfunctionalized frameworks. Additionally, our computed energetics show that mmen-M2(dobpdc) materials can selectively adsorb CO2 under humid conditions, in agreement with experimental observations. The calculations further predict an increase of 112% and 124% in the orientationally-averaged Young's modulus E and shear modulus G, respectively, for mmen-Zn2(dobpdc) compared to Zn2(dobpdc), revealing a dramatic enhancement of mechanical properties associated with diamine functionalization. Taken together, our calculations demonstrate how functionalization with mmen ligands can enhance framework gas adsorption and mechanical properties.

Near-Perfect CO2/CH4 Selectivity Achieved through Reversible Guest Templating in the Flexible Metal-Organic Framework Co(bdp).

Metal-organic frameworks are among the most promising materials for industrial gas separations, including the removal of carbon dioxide from natural gas, although substantial improvements in adsorption selectivity are still sought. Herein, we use equilibrium adsorption experiments to demonstrate that the flexible metal-organic framework Co(bdp) (bdp2- = 1,4-benzenedipyrazolate) exhibits a large CO2 adsorption capacity and approaches complete exclusion of CH4 under 50:50 mixtures of the two gases, leading to outstanding CO2/CH4 selectivity under these conditions. In situ powder X-ray diffraction data indicate that this selectivity arises from reversible guest templating, in which the framework expands to form a CO2 clathrate and then collapses to the nontemplated phase upon desorption. Under an atmosphere dominated by CH4, Co(bdp) adsorbs minor amounts of CH4 along with CO2, highlighting the importance of studying all relevant pressure and composition ranges via multicomponent measurements when examining mixed-gas selectivity in structurally flexible materials. Altogether, these results show that Co(bdp) may be a promising CO2/CH4 separation material and provide insights for the further study of flexible adsorbents for gas separations.

Overcoming double-step CO2 adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg2(dobpdc).

Alkyldiamine-functionalized variants of the metal-organic framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising for CO2 capture applications owing to their unique step-shaped CO2 adsorption profiles resulting from the cooperative formation of ammonium carbamate chains. Primary,secondary (1°,2°) alkylethylenediamine-appended variants are of particular interest because of their low CO2 step pressures (≤1 mbar at 40 °C), minimal adsorption/desorption hysteresis, and high thermal stability. Herein, we demonstrate that further increasing the size of the alkyl group on the secondary amine affords enhanced stability against diamine volatilization, but also leads to surprising two-step CO2 adsorption/desorption profiles. This two-step behavior likely results from steric interactions between ammonium carbamate chains induced by the asymmetrical hexagonal pores of Mg2(dobpdc) and leads to decreased CO2 working capacities and increased water co-adsorption under humid conditions. To minimize these unfavorable steric interactions, we targeted diamine-appended variants of the isoreticularly expanded framework Mg2(dotpdc) (dotpdc4- = 4,4''-dioxido-[1,1':4',1''-terphenyl]-3,3''-dicarboxylate), reported here for the first time, and the previously reported isomeric framework Mg-IRMOF-74-II or Mg2(pc-dobpdc) (pc-dobpdc4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate, pc = para-carboxylate), which, in contrast to Mg2(dobpdc), possesses uniformally hexagonal pores. By minimizing the steric interactions between ammonium carbamate chains, these frameworks enable a single CO2 adsorption/desorption step in all cases, as well as decreased water co-adsorption and increased stability to diamine loss. Functionalization of Mg2(pc-dobpdc) with large diamines such as N-(n-heptyl)ethylenediamine results in optimal adsorption behavior, highlighting the advantage of tuning both the pore shape and the diamine size for the development of new adsorbents for carbon capture applications.

Unexpected Diffusion Anisotropy of Carbon Dioxide in the Metal-Organic Framework Zn2(dobpdc).

Metal-organic frameworks are promising materials for energy-efficient gas separations, but little is known about the diffusion of adsorbates in materials featuring one-dimensional porosity at the nanoscale. An understanding of the interplay between framework structure and gas diffusion is crucial for the practical application of these materials as adsorbents or in mixed-matrix membranes, since the rate of gas diffusion within the adsorbent pores impacts the required size (and therefore cost) of the adsorbent column or membrane. Here, we investigate the diffusion of CO2 within the pores of Zn2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) using pulsed field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) simulations. The residual chemical shift anisotropy for pore-confined CO2 allows PFG NMR measurements of self-diffusion in different crystallographic directions, and our analysis of the entire NMR line shape as a function of the applied field gradient provides a precise determination of the self-diffusion coefficients. In addition to observing CO2 diffusion through the channels parallel to the crystallographic c axis (self-diffusion coefficient D∥ = (5.8 ± 0.1) × 10-9 m2 s-1 at a pressure of 625 mbar CO2), we unexpectedly find that CO2 is also able to diffuse between the hexagonal channels in the crystallographic ab plane (D⊥ = (1.9 ± 0.2) × 10-10 m2 s-1), despite the walls of these channels appearing impermeable by single-crystal X-ray crystallography and flexible lattice MD simulations. Observation of such unexpected diffusion in the ab plane suggests the presence of defects that enable effective multidimensional CO2 transport in a metal-organic framework with nominally one-dimensional porosity.

Enantioselective Recognition of Ammonium Carbamates in a Chiral Metal-Organic Framework.

Chiral metal-organic frameworks have attracted interest for enantioselective separations and catalysis because of their high crystallinity and pores with tunable shapes, sizes, and chemical environments. Chiral frameworks of the type M2(dobpdc) (M = Mg, Mn, Fe, Co, Ni, Zn; dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) seem particularly promising for potential applications because of their excellent stability, high internal surface areas, and strongly polarizing open metal coordination sites within the channels, but to date these materials have been isolated only in racemic form. Here, we demonstrate that when appended with the chiral diamine trans-1,2-diaminocyclohexane (dach), Mg2(dobpdc) adsorbs carbon dioxide cooperatively to form ammonium carbamate chains, and the thermodynamics of CO2 capture are strongly influenced by enantioselective interactions within the chiral pores of the framework. We further show that it is possible to access both enantiomers of Mg2(dobpdc) with high enantiopurity (≥90%) via framework synthesis in the presence of varying quantities of d-panthenol, an inexpensive chiral induction agent. Investigation of dach-M2(dobpdc) samples following CO2 adsorption-using single-crystal and powder X-ray diffraction, solid-state nuclear magnetic resonance spectroscopy, and density functional theory calculations-revealed that the ammonium carbamate chains interact extensively with each other and with the chiral M2(dobpdc) pore walls. Subtle differences in the non-covalent interactions accessible in each diastereomeric phase dramatically impact the thermodynamics of CO2 adsorption.