ABSTRACT
Noble gas xenon (Xe) is an excellent anesthetic gas, but its rarity, high cost and constrained production prohibits wide use in medicine. Here, we have developed a closed-circuit anesthetic Xe recovery and reusage process with highly effective CO2-specific adsorbent CUPMOF-5 that is promising to solve the anesthetic Xe supply problem. CUPMOF-5 possesses spacious cage cavities interconnected in four directions by confinement throat apertures of ~3.4â Å, which makes it an ideal molecular sieving of CO2 from Xe, O2, N2 with the benchmark selectivity and high uptake capacity of CO2. In situ single-crystal X-ray diffraction (SCXRD) and computational simulation solidly revealed the vital sieving role of the confined throat and the sorbent-sorbate induced-fit strengthening binding interaction to CO2. CUPMOF-5 can remove 5 % CO2 even from actual moist exhaled anesthetic gases, and achieves the highest Xe recovery rate (99.8 %) so far, as verified by breakthrough experiments. This endows CUPMOF-5 great potential for the on-line CO2 removal and Xe recovery from anesthetic closed-circuits.
ABSTRACT
Stimuli-responsive physisorbents that undergo reversible structural transformations induced by external stimuli (e.g. light, guests, or heat) offer the promise of utility in gas storage and separation. Whereas reports on guest or light-responsive sorbents have increased in recent years, we are unaware of reports on sorbents that exhibit both light and guest-induced structural transformations. Herein, we report that the square lattice, sql, topology coordination network Zn(fba)(bis) â 2DMF (sql-5,6-Zn-α, 5=trans-4,4'-bis(1-imidazolyl)stilbene=bis, 6=2,2-bis(4-carboxyphenyl)hexafluoropropane=H2fba) underwent single-crystal-to-single-crystal transformation (SCSC) upon activation, affording nonporous sql-5,6-Zn-ß. Parallel alignment at 3.23â Å of olefinic moieties on adjacent bis ligands in sql-5,6-Zn-α enabled SCSC [2+2] photocycloaddition upon exposure to UV light (365â nm) or sunlight. sql-5,6-Zn-α thereby transformed to mot-5,6-Zn-α, which was subsequently activated to the narrow pore phase mot-5,6-Zn-ß. sql-5,6-Zn-ß and mot-5,6-Zn-ß both exhibited S-shaped adsorption isotherms characteristic of guest-induced structural changes when exposed to CO2 at 195â K (type-F-IV and typeâ F-I, respectively). Cycling experiments conducted upon sql-5,6-Zn-ß reduced particle size after cycle 1 and induced transformation into a rare example of a shape memory coordination network, sql-5,6-Zn-γ. Insight into this smorgasbord of SCSC phase changes was gained from in situ PXRD, single crystal XRD and 1H NMR spectroscopy experiments.
ABSTRACT
A 44.610.8 topology hybrid ultramicroporous material (HUM), {[Cu1.5F(SiF6)(L)2.5]·G}n, (L = 4,4'-bisimidazolylbiphenyl, G = guest molecules), 1, formed by cross-linking interpenetrated 3D four-connected CdSO4-type nets with hexafluorosilicate anions is synthesized and evaluated in the context of gas sorption and separation herein. 1 is the first HUM functionalized with two different types of fluorinated sites (SiF6 2- and F- anions) lining along the pore surface. The optimal pore size (≈5 Å) combining mixed and high-density electronegative fluorinated sites enable 1 to preferentially adsorb C2H2 over CO2 and C2H4 by hydrogen bonding interactions with a high C2H2 isosteric heat of adsorption (Qst) of ≈42.3 kJ mol-1 at zero loading. The pronounced discriminatory sorption behaviors lead to excellent separation performance for C2H2/CO2 and C2H2/C2H4 that surpasses many well-known sorbents. Dynamic breakthrough experiments are conducted to confirm the practical separation capability of 1, which reveal an impressive separation factor of 6.1 for equimolar C2H2/CO2 mixture. Furthermore, molecular simulation and density functional theory (DFT) calculations validate the strong binding of C2H2 stems from the chelating fix of C2H2 between SiF6 2- anion and coordinated F- anion.
ABSTRACT
Fixation of CO2 into dihydroisobenzofuran derivatives has enormous applications in both production of natural products and antidepressant drugs, and reducing the green-house effect. However, the relatively complicated multi-step processes limit the further expansion of such a valuable CO2 conversion strategy. Herein, we hierarchically modify the surface of Cu nanoparticles (NPs) with Ag NPs and the robust metal-organic framework (MOF), ZIF-8, and report the presence of the Cu-Ag yolk-shell nanoalloy based heterogeneous catalysts, Cu@Ag and Cu@Ag@ZIF-8. The latter exhibits a crystalline "raisin bread" structure and specific synergic activity for catalyzing the tandem reactions of intra-molecular H-transfer, C-C and C-O coupling, cyclization, and carboxylation from CO2, leading to the first non-homogeneous preparation of dihydroisobenzofuran derivatives in high yield, selectivity, and recyclability under mild conditions. Theoretical calculations elucidate the tandem reaction pathway synergically catalyzed by Cu@Ag@ZIF-8, which offers insights for designing multiphase catalysts towards both organic synthesis and CO2 fixation through tandem processes in one pot.
ABSTRACT
Propane (C3H8) is a widely used fuel gas. Metal-organic framework (MOF) physisorbents that are C3H8 selective offer the potential to significantly reduce the energy footprint for capturing C3H8 from natural gas, where C3H8 is typically present as a minor component. Here we report the C3H8 recovery performance of a previously unreported lonsdaleite, lon, topology MOF, a chiral metal-organic material, [Ni(S-IEDC)(bipy)(SCN)]n, CMOM-7. CMOM-7 was prepared from three low-cost precursors: Ni(SCN)2, S-indoline-2-carboxylic acid (S-IDECH), and 4,4'-bipyridine (bipy), and its structure was determined by single crystal X-ray crystallography. Pure gas adsorption isotherms revealed that CMOM-7 exhibited high C3H8 uptake (2.71 mmol g-1) at 0.05 bar, an indication of a higher affinity for C3H8 than both C2H6 and CH4. Dynamic column breakthrough experiments afforded high purity C3H8 capture from a gas mixture comprising C3H8/C2H6/CH4 (v/v/v = 5/10/85). Despite the dilute C3H8 stream, CMOM-7 registered a high dynamic uptake of C3H8 and a breakthrough time difference between C3H8 and C2H6 of 79.5 min g-1, superior to those of previous MOF physisorbents studied under the same flow rate. Analysis of crystallographic data and Grand Canonical Monte Carlo simulations provides insight into the two C3H8 binding sites in CMOM-7, both of which are driven by C-H···π and hydrogen bonding interactions.
ABSTRACT
Separation of the C8 aromatic isomers, xylenes (PX, MX, and OX) and ethylbenzene (EB), is important to the petrochemical industry. Whereas physisorptive separation is an energy-efficient alternative to current processes, such as distillation, physisorbents do not generally exhibit strong C8 selectivity. Herein, we report the mixed-linker square lattice (sql) coordination network [Zn2(sba)2(bis)]n·mDMF (sql-4,5-Zn, H2sba or 4 = 4,4'-sulfonyldibenzoic acid, bis or 5 = trans-4,4'-bis(1-imidazolyl)stilbene) and its C8 sorption properties. sql-4,5-Zn was found to exhibit high uptake capacity for liquid C8 aromatics (â¼20.2 wt %), and to the best of our knowledge, it is the first sorbent to exhibit selectivity for PX, EB, and MX over OX for binary, ternary, and quaternary mixtures from gas chromatography. Single-crystal structures of narrow-pore, intermediate-pore, and large-pore phases provided insight into the phase transformations, which were enabled by flexibility of the linker ligands and changes in the square grid geometry and interlayer distances. This work adds to the library of two-dimensional coordination networks that exhibit high uptake, thanks to clay-like expansion, and strong selectivity, thanks to shape-selective binding sites, for C8 isomers.
ABSTRACT
Chiral metal-organic materials, CMOMs, are of interest as they can offer selective binding sites for chiral guests. Such binding sites can enable CMOMs to serve as chiral crystalline sponges (CCSs) to determine molecular structure and/or purify enantiomers. We recently reported on the chiral recognition properties of a homochiral cationic diamondoid, dia, network {[Ni(S-IDEC)(bipy)(H2O)][NO3]}n (S-IDEC = S-indoline-2-carboxylicate, bipy = 4,4'-bipyridine), CMOM-5[NO3]. The modularity of CMOM-5[NO3] means there are five feasible approaches to fine-tune structures and properties via substitution of one or more of the following components: metal cation (Ni2+); bridging ligand (S-IDEC); linker (bipy); extra-framework anion (NO3-); and terminal ligand (H2O). Herein, we report the effect of anion substitution on the CCS properties of CMOM-5[NO3] by preparing and characterizing {[Ni(S-IDEC)(bipy)(H2O)][BF4]}n, CMOM-5[BF4]. The chiral channels in CMOM-5[BF4] enabled it to function as a CCS for determination of the absolute crystal structures of both enantiomers of three chiral compounds: 1-phenyl-1-butanol (1P1B); methyl mandelate (MM); ethyl mandelate (EM). Chiral resolution experiments revealed CMOM-5[BF4] to be highly selective toward the S-isomers of MM and EM with enantiomeric excess, ee, values of 82.6 and 78.4%, respectively. The ee measured for S-EM surpasses the 64.3% exhibited by [DyNaL(H2O)4] 6H2O and far exceeds that of CMOM-5[NO3] (6.0%). Structural studies of the binding sites in CMOM-5[BF4] provide insight into their high enantioselectivity.
ABSTRACT
We report that linker ligand substitution involving just one atom induces a shape-memory effect in a flexible coordination network. Specifically, whereas SIFSIX-23-Cu, [Cu(SiF6 )(L)2 ]n , (L=1,4-bis(1-imidazolyl)benzene, SiF6 2- =SIFSIX) has been previously reported to exhibit reversible switching between closed and open phases, the activated phase of SIFSIX-23-CuN , [Cu(SiF6 )(LN )2 ]n (LN =2,5-bis(1-imidazolyl)pyridine), transformed to a kinetically stable porous phase with strong affinity for CO2 . As-synthesized SIFSIX-23-CuN , α, transformed to less open, γ, and closed, ß, phases during activation. ß did not adsorb N2 (77â K), rather it reverted to α induced by CO2 at 195, 273 and 298â K. CO2 desorption resulted in α', a shape-memory phase which subsequently exhibited type-I isotherms for N2 (77â K) and CO2 as well as strong performance for separation of CO2 /N2 (15/85) at 298â K and 1â bar driven by strong binding (Qst =45-51â kJ/mol) and excellent CO2 /N2 selectivity (up to 700). Interestingly, α' reverted to ß after re-solvation/desolvation. Molecular simulations and density functional theory (DFT) calculations provide insight into the properties of SIFSIX-23-CuN .
ABSTRACT
Chiral metal-organic materials (CMOMs), can offer molecular binding sites that mimic the enantioselectivity exhibited by biomolecules and are amenable to systematic fine-tuning of structure and properties. Herein, we report that the reaction of Ni(NO3)2, S-indoline-2-carboxylic acid (S-IDECH), and 4,4'-bipyridine (bipy) afforded a homochiral cationic diamondoid, dia, network, [Ni(S-IDEC)(bipy)(H2O)][NO3], CMOM-5. Composed of rod building blocks (RBBs) cross-linked by bipy linkers, the activated form of CMOM-5 adapted its pore structure to bind four guest molecules, 1-phenyl-1-butanol (1P1B), 4-phenyl-2-butanol (4P2B), 1-(4-methoxyphenyl)ethanol (MPE), and methyl mandelate (MM), making it an example of a chiral crystalline sponge (CCS). Chiral resolution experiments revealed enantiomeric excess, ee, values of 36.2-93.5%. The structural adaptability of CMOM-5 enabled eight enantiomer@CMOM-5 crystal structures to be determined. The five ordered crystal structures revealed that host-guest hydrogen-bonding interactions are behind the observed enantioselectivity, three of which represent the first crystal structures determined of the ambient liquids R-4P2B, S-4P2B, and R-MPE.
ABSTRACT
Formamides have critical application value in the chemical industry serving as solvents or reagents for the synthesis of pharmaceuticals, agrochemicals, and dyes. Herein, we selected a green-synthesis produced aluminum-based metal-organic framework (Al-MOF) material CAU-10pydc as a catalyst to study its performance in CO2 formylation reaction. At room temperature and in the green solvent acetonitrile, CAU-10pydc could highly effectively catalyze the reaction of CO2 and N-methylaniline to N-methyl-N-phenylformamide under mild conditions. CAU-10pydc could maintain its efficient catalytic performance after five catalytic cycles, and PXRD and SEM measurements demonstrated that CAU-10pydc is stable after cyclic catalysis. The universality of this catalyst was illustrated by nine substrates with high yields. The reaction mechanism was further analyzed by DFT calculations. To our knowledge, this work is the first example of a CO2 formylation reaction being catalyzed highly effectively by an Al-MOF under green conditions.
ABSTRACT
Ultramicroporous materials can be highly effective at trace gas separations when they offer a high density of selective binding sites. Herein, we report that sql-NbOFFIVE-bpe-Cu, a new variant of a previously reported ultramicroporous square lattice, sql, topology material, sql-SIFSIX-bpe-Zn, can exist in two polymorphs. These polymorphs, sql-NbOFFIVE-bpe-Cu-AA (AA) and sql-NbOFFIVE-bpe-Cu-AB (AB), exhibit AAAA and ABAB packing of the sql layers, respectively. Whereas NbOFFIVE-bpe-Cu-AA (AA) is isostructural with sql-SIFSIX-bpe-Zn, each exhibiting intrinsic 1D channels, sql-NbOFFIVE-bpe-Cu-AB (AB) has two types of channels, the intrinsic channels and extrinsic channels between the sql networks. Gas and temperature induced transformations of the two polymorphs of sql-NbOFFIVE-bpe-Cu were investigated by pure gas sorption, single-crystal X-ray diffraction (SCXRD), variable temperature powder X-ray diffraction (VT-PXRD), and synchrotron PXRD. We observed that the extrinsic pore structure of AB resulted in properties with potential for selective C3H4/C3H6 separation. Subsequent dynamic gas breakthrough measurements revealed exceptional experimental C3H4/C3H6 selectivity (270) and a new benchmark for productivity (118 mmol g-1) of polymer grade C3H6 (purity >99.99%) from a 1:99 C3H4/C3H6 mixture. Structural analysis, gas sorption studies, and gas adsorption kinetics enabled us to determine that a binding "sweet spot" for C3H4 in the extrinsic pores is behind the benchmark separation performance. Density-functional theory (DFT) calculations and Canonical Monte Carlo (CMC) simulations provided further insight into the binding sites of C3H4 and C3H6 molecules within these two hybrid ultramicroporous materials, HUMs. These results highlight, to our knowledge for the first time, how pore engineering through the study of packing polymorphism in layered materials can dramatically change the separation performance of a physisorbent.
ABSTRACT
A molecular porous material, MPM-2, comprised of cationic [Ni2 (AlF6 )(pzH)8 (H2 O)2 ] and anionic [Ni2 Al2 F11 (pzH)8 (H2 O)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 C2 H2 over CO2 thanks to a high (ΔQst )AC [Qst (C2 H2 ) - Qst (CO2 )] of 13.7 kJ mol-1 at low coverage. Dynamic column breakthrough experiments on MPM-2 demonstrated the separation of C2 H2 from a 1:1 C2 H2 /CO2 mixture at 298 K with effluent CO2 purity of 99.995% and C2 H2 purity of >95% after temperature-programmed desorption. C-H···F interactions between C2 H2 molecules and F atoms of AlF6 3- are found to enable high selectivity toward C2 H2 , as determined by density functional theory simulations.
ABSTRACT
A series of catecholate-functionalized titanium-oxo clusters (TOCs), PTC-271 to PTC-277, with atomically precise structures were synthesized and characterized, including distinctive "boat" and "chair" conformations in PTC-273 and PTC-274, respectively. These cluster compounds are prominent for their ultralow optical band gaps, as is visually evident from the rather unusual black TOCs (B-TOCs), PTC-272 to PTC-277. The cluster structures were found to be ultrastable with respect to air, water, organic solvents, and even acidic or basic aqueous solutions in a wide pH range (pH 0-13), owing to the stabilizing effects of catecholate and its derivatives, as well as the carboxylate ligands. Another prominent feature is the occurrence of third-order nonlinear optical (NLO) performance, which has previously been unreported in the field of homometallic titanium-oxo clusters. Open-aperture Z-scan experiments show significant solid-state optical limiting (OL) applications of these B-TOCs, with high laser irradiation stability and low minimum normalized transmittance (Tmin) of PTC-273 as â¼0.17. Meanwhile, theoretical calculations indicate that the smaller band gaps of B-TOCs were beneficial for strengthening the NLO response. This work not only represents a significant milestone in the construction of stable low-band gap black titanium oxide materials but also contributes to the mechanism insights into their optical applications.
ABSTRACT
Understanding soil microbial element limitation and its relation with the microbial community can help in elucidating the soil fertility status and improving nutrient management of planted forest ecosystems. The stand age of a planted forest determines the aboveground forest biomass and structure and underground microbial function and diversity. In this study, we investigated 30 plantations of Camellia oleifera distributed across the subtropical region of China that we classified into four stand ages (planted <9 years, 9-20 years, 21-60 years, and >60 years age). Enzymatic stoichiometry analysis showed that microbial metabolism in the forests was mainly limited by C and P. P limitation significantly decreased and C limitation slightly increased along the stand age gradient. The alpha diversity of the soil microbiota remained steady along stand age, while microbial communities gradually converged from scattered to clustered, which was accompanied by a decrease in network complexity. The soil bacterial community assembly shifted from stochastic to deterministic processes, which probably contributed to a decrease in soil pH along stand age. Our findings emphasize that the stand age regulated the soil microbial metabolism limitation and community assembly, which provides new insight into the improvement of C and P management in subtropical planted forest.
ABSTRACT
Selective separation of propyne/propadiene mixture to obtain pure propadiene (allene), an essential feedstock for organic synthesis, remains an unsolved challenge in the petrochemical industry, thanks mainly to their similar physicochemical properties. We herein introduce a convenient and energy-efficient physisorptive approach to achieve propyne/propadiene separation using microporous metal-organic frameworks (MOFs). Specifically, HKUST-1, one of the most widely studied high surface area MOFs that is available commercially, is found to exhibit benchmark performance (propadiene production up to 69.6 cm3/g, purity > 99.5%) as verified by dynamic breakthrough experiments. Experimental and modeling studies provide insight into the performance of HKUST-1 and indicate that it can be attributed to a synergy between thermodynamics and kinetics that arises from abundant open metal sites and cage-based molecular traps in HKUST-1.
ABSTRACT
Closed-to-open structural transformations in flexible coordination networks are of potential utility in gas storage and separation. Herein, we report the first example of a flexible SiF62--pillared square grid material, [Cu(SiF6)(L)2]n (L = 1,4-bis(1-imidazolyl)benzene), SIFSIX-23-Cu. SIFSIX-23-Cu exhibits reversible switching between nonporous (ß1) and several porous (α, γ1, γ2, and γ3) phases triggered by exposure to N2, CO2, or H2O. In addition, heating ß1 to 433 K resulted in irreversible transformation to a closed polymorph, ß2. Single-crystal X-ray diffraction studies revealed that the phase transformations are enabled by rotation and geometrical contortion of L. Density functional theory calculations indicated that L exhibits a low barrier to rotation (as low as 8 kJmol-1) and a rather flat energy surface. In situ neutron powder diffraction studies provided further insight into these sorbate-induced phase changes. SIFSIX-23-Cu combines stability in water for over a year, high CO2 uptake (ca. 216 cm3/g at 195 K), and good thermal stability.
ABSTRACT
Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas-storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate-opening and gate-closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine-tune gate-opening and gate-closing pressure. Specifically, three variants of a previously reported pcu-topology MOF, X-pcu-5-Zn, have been prepared: X-pcu-6-Zn, 6=1,2-bis(4-pyridyl)ethane (bpe), X-pcu-7-Zn, 7=1,2-bis(4-pyridyl)acetylene (bpa), and X-pcu-8-Zn, 8=4,4'-azopyridine (apy). Each exhibited switching isotherms but at different gate-opening pressures. The N2 , CO2 , C2 H2 , and C2 H4 adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6, afforded lower gate-opening and gate-closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.
ABSTRACT
Pinene is a family of bicyclic monoterpenes found in nature, which exhibits important applications in chemical industry and biomedicine; however, the discrimination methods used for pinene enantiomers are still rare. The alpha- and beta-pinene enantiomers were recognized and discriminated via an electrochemical method for the first time based on a cyclodextrin metal-organic framework (CD-MOF) as an electrochemical chiral sensor.
Subject(s)
Bridged Bicyclo Compounds/chemistry , Cyclodextrins/chemistry , Metal-Organic Frameworks/chemistry , Monoterpenes/chemistry , Bicyclic Monoterpenes , Electrochemical Techniques , Electrodes , Oxidation-Reduction , StereoisomerismABSTRACT
We report herein the previously unknown structures of the pneumococcal capsular polysaccharides serotype 33C and 33D, and a revised structure of serotype 33B. The syntenic pair 33B/33D has nearly identical polysaccharide repeat units with the exception of one sugar residue (â2-α-Glcp in 33B and â2-α-Galp in 33D). Serotype 33C is structurally more similar to 33B/33D than 33A/33F, in that it also possesses a backbone ribitol-phosphate group and a â3-ß-GalpNAc residue, both of which are absent in the repeat units of 33A/33F. Serotype 33C is notably different from all other serogroup 33 polysaccharides, as there is no â3-ß-Glcp residue and the location of the O-acetylation of the â5-ß-Galf residue (O-6) differs from the other serogroup 33 polysaccharides (O-2). This completes the structural assignments of polysaccharides within serogroup 33 and provides a framework for understanding the recognition of epitopes by serogroup 33 typing sera based on observed cross-reactivities reported in the literature.
Subject(s)
Bacterial Capsules/chemistry , Polysaccharides/chemistry , Streptococcus pneumoniae/chemistry , Acetylation , Epitopes/chemistry , Epitopes/immunology , Ribitol/chemistry , Serotyping , Streptococcus pneumoniae/genetics , Streptococcus pneumoniae/immunologyABSTRACT
In order to better understand cross-reactions of serogroup 33 polysaccharides and the typing sera, the structure of pneumococcal capsular polysaccharide serotype 33A was elucidated. Serotype 33A has been shown to have an identical polysaccharide backbone as that of serotype 33F, with two additional sites of O-acetylation at C5, and C6 of the 3-ß-Galf residue in serotype 33A. This finding is consistent with the presence of an additional functional acetyltransferase gene (wcjE) in the cps biosynthetic locus of serotype 33A compared to 33F. The identical polysaccharide backbone with at least one common O-acetylation site (C2 of 5-ß-Galf) shared by serotype 33A and 33F polysaccharides is proposed to be the epitope recognized by typing serum 33b. In addition, a 5,6-di-O-acetylated â3)-ß-d-Galf5,6Ac-(1â3)-ß-d-Glcp-(1â disaccharide unit, a common structural motif present in serotypes 33A, 20, and 35A polysaccharides, is proposed to be the antigenic determinant recognized by typing serum 20b.