Crystal engineering of porous coordination networks to enable separation of C2 hydrocarbons

Crystal engineering, the field of chemistry that studies the design, properties, and applications of crystals, is exemplified by the emergence over the past thirty years of porous coordination networks (PCNs), including metal-organic frameworks (MOFs) and hybrid coordination networks (HCNs). PCNs have now come of age thanks to their amenability to design from first principles and how this in turn can result in new materials with task-specific features. Herein, we focus upon how control over the pore chemistry and pore size of PCNs has been leveraged to create a new generation of physisorbents for efficient purification of light hydrocarbons (LHs). The impetus for this research comes from the need to address LH purification processes based upon cryogenic separation, distillation, chemisorption or solvent extraction, each of which is energy intensive. Adsorptive separation by physisorbents (in general) and PCNs (in particular) can offer two advantages over these existing approaches: improved energy efficiency; lower plant size/cost. Unfortunately, most existing physisorbents suffer from low uptake and/or poor sorbate selectivity and are therefore unsuitable for trace separations of LHs including the high volume C2 LHs (C2Hx, x = 2, 4, 6). This situation is rapidly changing thanks to PCN sorbents that have set new performance benchmarks for several C2 separations. Herein, we review and analyse PCN sorbents with respect to the supramolecular chemistry of sorbent-sorbate binding and detail the crystal engineering approaches that have enabled the exquisite control over pore size and pore chemistry that affords highly selective binding sites. Whereas the structure-function relationships that have emerged offer important design principles, several development roadblocks remain to be overcom

Pillar modularity in fsc topology hybrid ultramicroporous materials based upon tetra(4-pyridyl)benzene

.Hybrid ultramicroporous materials (HUMs) are porous coordination networks composed of combinations of organic and inorganic linker ligands with a pore diameter of 10 for 1:99 C2H2/C2H4 and >5 for 1:1 C2H2/CO2. The approach taken, systematic variation of pillars with retention of structure, enables differences in selectivity to be attributed directly to the choice of the inorganic pillar. This study introduces fsc topology HUMs as a modular platform that is amenable to fine-tuning of structure and properties</p

The Effect of pendent groups upon flexibility in coordination networks with square lattice topology

Gas or vapor-induced phase transformations in flexible coordination networks (CNs) offer the potential to exceed the performance of their rigid counterparts for separation and storage applications. However, whereas ligand modification has been used to alter the properties of such stimulus-responsive materials, they remain understudied compared with their rigid counterparts. Here, we report that a family of Zn2+ CNs with square lattice (sql) topology, differing only through the substituents attached to a linker, exhibit variable flexibility. Structural and CO2 sorption studies on the sql networks, [Zn(5-Ria)(bphy)]n, ia = isophthalic acid, bphy = 1,2-bis(pyridin-4-yl)hydrazine, R = −CH3, −OCH3, −C(CH3)3, -N-N-Ph, and -N-N-Ph(CH3)2, 2−6, respectively, revealed that the substituent moieties influenced both structural and gas sorption properties. Whereas 2−3 exhibited rigidity, 4, 5, and 6 exhibited reversible transformation from small pore to large pore phases. Overall, the insight into the profound effect of pendent moieties of linkers upon phase transformations in this family of layered CNs should be transferable to other CN classes.</p

Water vapour induced structural flexibility in a square lattice coordination network

Herein, we introduce a new square lattice topology coordination network, sql-(1,3-bib)(ndc)-Ni, with three types of connection and detail its gas and vapour induced phase transformations. Exposure to humidity resulted in an S-shaped isotherm profile, suggesting potential utility of such materials as desiccants.</p

Dinuclear copper sulfate-based square lattice topology network with high alkyne selectivity

ABSTRACT: Porous coordination networks (PCNs) sustained by inorganic anions that serve as linker ligands can offer high selectivity toward specific gases or vapors in gas mixtures. Such inorganic anions are best exemplified by electron-rich fluorinated anions, e.g., SiF6 2−, TiF6 2−, and NbOF5 2−, although sulfate anions have recently been highlighted as inexpensive and earth-friendly alternatives. Herein, we report the use of a rare copper sulfate dimer molecular building block to generate two square lattice, sql, coordination networks which can be prepared via solvent layering or slurrying, CuSO4(1,4-bib)1.5, 1, (1,4-bib = 1,4-bisimidazole benzene) and CuSO4(1,4-bin)1.5, 2, (1,4-bin = 1,4-bisimidazole naphthalene). Variable-temperature SCXRD and PXRD experiments revealed that both sql networks underwent reversible structural transformations due to linker rotations or internetwork displacements. Gas sorption studies conducted upon the narrow-pore phase of CuSO4(1,4-bin)1.5, 2np, found a high calculated 1:99 selectivity for C2H2 over C2H4 (33.01) and CO2 (15.18), as well as strong breakthrough performance. Across-the-board, C3H4 selectivity vs C3H6, CO2, and C3H8 was also observed. Sulfate-based PCNs, although still understudied, appear increasingly likely to offer utility in gas and vapor separations.</p

Advances in adsorptive separation of benzene and cyclohexane by metal-organic framework adsorbents

The chemical industry represents ca. 7% of the global GDP and 40% of its immense energy footprint stems from the separation/purification processes of commodity chemicals, particularly downstream processing of hydrocarbons. Of critical importance is the separation of C6 cyclic hydrocarbons benzene (C6H6) and cyclohexane (C6H12). Supplanting thermally driven distillation protocols such as azeotropic and extractive distillation methods by recyclable adsorbents, such as metal-organic framework (MOF) physisorbents, holds great promise for the reduction of this energy footprint. Whilst MOFs have come of age as physisorbents, they have been studied as benzene or cyclohexane selective adsorbents only rarely. Thanks to their amenability to crystal engineering, intensive research efforts have enabled metal-organic chemists to offer tunable coordination nanospaces in MOF sorbents in an adsorbate-specific manner, including aromatic benzene or aliphatic cyclohexane molecules. Despite the ever-expanding library of MOFs that often features families or isoreticular platforms of high surface-area materials with electron-rich or electron-deficient local pore environments, this research topic is underexplored and represents a niche area with a high upside potential. This review captures the progress made in MOF adsorbents to accomplish adsorption selectivity guided separation of the foregoing pair of C6 azeotropic hydrocarbons, which is crucial to the production of high-grade cyclohexane and benzene -important feedstock chemicals for further conversion into more useable commodity products, or as liquid organic hydrogen carriers. We also critically interrogate these examples to understand key structural and compositional approaches in order to efficiently design MOFs to extract benchmark selectivities and consequent high separation performances. </p

Highly selective p‑Xylene separation from mixtures of C8 aromatics by a nonporous molecular apohost

High and increasing production of separation of C8 aromatic isomers demands the development of purification methods that are efficient, scalable, and inexpensive, especially for p-xylene, PX, the largest volume C8 commodity. Herein, we report that 4-(1H-1,2,4-triazol-1-yl)-phenyl-1H-benzo[de]isoquinoline-1,3(2H)-dione (TPBD), a molecular compound that can be prepared and scaled up via solid-state synthesis, exhibits exceptional PX selectivity over each of the other C8 isomers, o-xylene (OX), m-xylene (MX), and ethylbenzene (EB). The apohost or α form of TPBD was found to exhibit conformational polymorphism in the solid state enabled by rotation of its triazole and benzene rings. TPBD-αI and TPBD-αII are nonporous polymorphs that transformed to the same PX inclusion compound, TPBD-PX, upon contact with liquid PX. TPBD enabled highly selective capture of PX, as established by competitive slurry experiments involving various molar ratios in binary, ternary, and quaternary mixtures of C8 aromatics. Binary selectivity values for PX as determined by 1 H NMR spectroscopy and gas chromatography ranged from 22.4 to 108.4, setting new benchmarks for both PX/MX (70.3) and PX/EB (59.9) selectivity as well as close to benchmark selectivity for PX/OX (108.4). To our knowledge, TPBD is the first material of any class to exhibit such high across-the-board PX selectivity from quaternary mixtures of C8 aromatics under ambient conditions. Crystallographic and computational studies provide structural insight into the PX binding site in TPBD-PX, whereas thermal stability and capture kinetics were determined by variable-temperature powder X-ray diffraction and slurry tests, respectively. That TPBD offers benchmark PX selectivity and facile recyclability makes it a prototypal molecular compound for PX purification or capture under ambient condition</p

A robust molecular porous material for C2H2/CO2 separation

A molecular porous material, MPM-2, comprised of cationic [Ni2(AlF6) (pzH)8(H2O)2] and anionic [Ni2Al2F11(pzH)8(H2O)2] complexes that generate a charge-assisted hydrogen-bonded network with pcu topology is reported. The packing in MPM-2 is sustained by multiple interionic hydrogen bonding interactions that afford ultramicroporous channels between dense layers of anionic units. MPM-2 is found to exhibit excellent stability in water (>1 year). Unlike most hydrogen-bonded organic frameworks which typically show poor  stability in organic solvents, MPM-2 exhibited excellent stability with respect to various organic solvents for at least two days. MPM-2 is found to be permanently porous with gas sorption isotherms at 298 K revealing a strong affinity for C2H2 over CO2 thanks to a high (ΔQst)AC [Qst (C2H2) − Qst (CO2)] of 13.7 kJ mol−1 at low coverage. Dynamic column breakthrough experiments on MPM-2 demonstrated the separation of C2H2 from a 1:1 C2H2/CO2 mixture at 298 K with effluent CO2 purity of 99.995% and C2H2 purity of >95% after temperature-programmed desorption. C-H···F interactions between C2H2 molecules and F atoms of AlF6 3− are found to enable high selectivity toward C2H2, as determined by density functional theory simulations.</p

Metal cation substitution can tune CO2, H2O and CH4 switching pressure in transiently porous coordination networks

Compared to rigid physisorbents, switching coordination networks that reversibly transform between closed (non-porous) and open (porous) phases offer promise for gas/vapour storage and separation owing to their improved working capacity and desirable thermal management properties. We recently introduced a coordination network, X-dmp-1-Co, which exhibits switching enabled by transient porosity. The resulting “open” phases are generated at threshold pressures even though they are conventionally non-porous. Herein, we report that X-dmp-1-Co is the parent member of a family of transiently porous coordination networks [X-dmp-1-M] (M = Co, Zn and Cd) and that each exhibits transient porosity but switching events occur at different threshold pressures for CO2 (0.8, 2.1 and 15 mbar, for Co, Zn and Cd, respectively, at 195 K), H2O (10, 70 and 75% RH, for Co, Zn and Cd, respectively, at 300 K) and CH4 (</p

Crystal engineering of two light and pressure responsive physisorbents

An emerging strategy in the design of efficient gas storage technologies is the development of stimuliresponsive physisorbents which undergo transformations in response to a particular stimulus, such as pressure, heat or light. Herein, we report two isostructural light modulated adsorbents (LMAs) containing bis-3-thienylcyclopentene (BTCP), LMA-1 [Cd(BTCP)(DPT)2] (DPT=2,5-diphenylbenzene-1,4-dicarboxylate) and LMA-2 [Cd(BTCP)(FDPT)2] (FDPT=5-fluoro-2,diphenylbenzene-1,4-dicarboxylate). Both LMAs undergo pressure induced switching transformations from non-porous to porous via adsorption of N2, CO2 and C2H2. LMA-1 exhibited multi-step adsorption while LMA-2 showed a single-step adsorption isotherm. The light responsive nature of the BTPC ligand in both frameworks was exploited with irradiation of LMA-1 resulting in a 55% maximum reduction of CO2 uptake at 298 K. This study reports the first example of a switching sorbent (closed to open) that can be further modulated by light.</p