出版者・発行元：Microporous and Mesoporous Materials  

Metal-organic frameworks (MOFs) are promising candidates for membrane gas separation because of their high porosity and structural tunability. Although the appropriate size of the pore aperture of MOFs is required depending on the target molecules to separate, pore size control of MOFs occasionally influences crystal growth, preventing the fabrication of dense membranes. In this study, we present a heterobilayer membrane strategy using two isostructural MOFs. First, a MOF Kgm-OPr with fast nucleation rate was fabricated as a seed layer on an Al2O3 substrate, then the layer of Kgm-OMe or Kgm-H, which is isostructural to Kgm-OPr, was prepared on the Kgm-OPr seed layer through secondary growth. In this way, the high-quality membranes which selectively permeate CO2 over N2, CH4, and C2H4 were obtained, although all three MOFs did not form dense membranes when they were used alone. Our result would contribute to the expansion of the family of MOFs applicable to membranes for molecular separation.

DOI： 10.1016/j.micromeso.2022.111950

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記述言語：英語   出版者・発行元：Chemical Communications  

An octa-nuclear zinc (Zn8) cluster-based two-fold interpenetrated metal-organic framework (MOF) of [(CH3)2NH2]2[Zn8O3(FDC)6]·7DMF (denoted as Zn8-as; H2FDC = 9H-fluorene-2,7-dicarboxylic acid; DMF = N,N-dimethylformamide) was synthesized by the reaction of a hard base of a curved dicarboxylate ligand (H2FDC) with the borderline acid of Zn(ii) under solvothermal conditions. Zn8-as shows significant crystal volume shrinkage upon heating, yielding a solvate-free framework of [(CH3)2NH2]2[Zn8O3(FDC)6] (Zn8-de). Zn8-de displays gated adsorption for C2H2 and type-I adsorption for CO2, attributed to the framework flexibility and the different interactions between the gas molecules and the host framework.

DOI： 10.1039/d1cc05893b

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry Letters  

We demonstrate selective photo-reactions observed between the two different chemical species bearing carbon-carbon double bonds in MOF 1. 1,2-Bis(4-pyridyl)ethylene (bpe) was fixed in 1 as the organic linker, which reacted with tetramethylethylene (TME) as the guest molecule. As a result, a specific product from the radical reaction was selectively generated, whereas various side products were observed when reacted in solution. Our strategy to realize selective reactions would contribute to enforce the applicability of solid-phase reactions in synthetic chemistry.

DOI： 10.1246/cl.210525

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Communications  

We synthesized a metal-organic framework (MOF) using a ligand bearing haloalkoxy chains as a radical precursor. The radicals generated in the MOF upon photoirradiation were stable even at 250 K or under an O2 atmosphere, despite radicals generated from the ligand decomposing at 200 K; thus, the regular arrangement of radicals effectively stabilized them. Moreover, a unique photoproduct was obtained only in the MOF, indicating that the confinement effect in the nanospace enabled a specific reaction that did not occur in the bulk state. We propose a new platform for exploring chemical reactions and materials based on reactive species. This journal is

DOI： 10.1039/d1cc04267j

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry - An Asian Journal  

In this study, we report an efficient fabrication method for the membrane of a metal-organic framework (MOF) (Kgm−OEt) which is one kind of kagomé-type MOF with a two-dimensional (2D) sheet structure having one-dimensional (1D) channels suitable for separation of H2 from other larger gases. The Kgm−OEt seed layer was created on an Al2O3 substrate using layer-by-layer (LBL) growth, then a membrane was fabricated by secondary growth. The membrane on a 3-aminopropyltriethoxysilane (APTEs)-treated substrate obtained in this method was continuous and defect-free with the crystal orientation suitable for gas transportation, while the membrane grown on an unmodified substrate was loosely packed with unfavorable crystal orientation.

DOI： 10.1002/asia.202100507

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of the American Chemical Society  

Triplet carbenes (TCs) are of great interest due to their magnetic properties and reactivity, which descend from TCs' unique electronic state. However, the reactivity and stability of TCs are usually a trade-off, and it is difficult to achieve both at the same time. In this work, we were able to enhance the thermal stability of a TC species while maintaining its reactivity by confining them in the nanospace of a metal-organic framework (MOF). We synthesized a new MOF using a TC precursor; subsequently, TCs were generated by photostimulation. The TCs generated in the MOF nanospace were detectable up to 170 K, whereas their non-MOF-confined counterparts (bare ligand) could not be detected above 100 K. In addition, the reactivity of TC generated in MOF with O2 was drastically improved compared to that of bare ligand. Our approach is generally applicable to the stabilization of highly reactive species, whose reactivity needs to be preserved.

DOI： 10.1021/jacs.1c02430

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Small  

Nanoporous materials can adsorb small molecules into their nanospaces. However, the trapping of light gas molecules dissolved in solvents suffers from low concentration and poor adsorption affinity. Here, the reversible trapping and releasing of dissolved oxygen are shown through integrating photosensitization and chemical capturing abilities into a metal–organic framework (MOF), MOMF-1. 9,10-Di(4-pyridyl)anthracene (dpa) ligands in MOMF-1 generates singlet oxygen from triplet oxygen under photoirradiation without additional photosensitizers, and successively reacts with it to produce anthracene endoperoxide, forming MOMF-2, which is proved crystallographically. The reverse reaction also proceeds quantitatively by heating MOMF-2. Moreover, MOMF-1 exhibits excellent water resistance, and completely removes oxygen of ppm order concentrations in water. The new material shown in this report allows controlling of the amount of dissolved oxygen, which can be applicable in various fields relating to numerous oxidation phenomena.

DOI： 10.1002/smll.202004351

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その他リンク： https://onlinelibrary.wiley.com/doi/full-xml/10.1002/smll.202004351

記述言語：英語   出版者・発行元：Small  

Electrochemical reduction of CO2 in aqueous media is an important reaction to produce value-added carbon products in an environmentally and economically friendly manner. Various molecule-based catalytic systems for the reaction have been reported thus far. The key features of state-of-the-art catalytic systems in this field can be summarized as follows: 1) an iron-porphyrin-based scaffold as a catalytic center, 2) a dinuclear active center for the efficient activation of a CO2 molecule, and 3) a hydrophobic channel for the accumulation of CO2. This article reports a novel approach to construct a catalytic system for CO2 reduction with the aforementioned three key substructures. The self-assembly of a newly designed iron-porphyrin complex bearing bulky substituents with noncovalent interaction ability forms a highly ordered crystalline solid with adjacent catalytically active sites and hydrophobic pores. The obtained crystalline solid serves as an electrocatalyst for CO2 reduction in aqueous media. Note that a relevant iron-porphyrin complex without bulky substituents cannot form a porous structure with adjacent active sites, and the catalytic performance of the crystals of this relevant iron-porphyrin complex is substantially lower than that of the newly developed catalytic system. The present study provides a novel strategy for constructing porous crystalline solids for small-molecule conversions.

DOI： 10.1002/smll.202006150

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry Letters  

Here we report enhanced CO2 molecular recognition ability by incorporating insertion reaction into a metal porphyrin complex in a metal-organic framework (MOF). PCN-222(Cu)-INA was synthesized by the reaction of PCN-222(Cu) [Zr6O8(H2O)8- (Cu-TCPP)2], where Cu-TCPP = Cu(II) tetrakis(4-carboxyphenyl) porphyrin, and isonicotinic acid (INA). PCN-222(Cu)-INA exhibited a 1.5 times larger CO2 adsorption amount than PCN- 222(Cu) at 298K and 1 bar. The mechanism involving insertion reaction of CO2 into CuN bonds enhanced the adsorption, which was revealed by in situ IR spectroscopy and theoretical calculations.

DOI： 10.1246/cl.200785

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of the American Chemical Society  

The use of organic radicals as building blocks is an effective approach to the production of open-shell coordination polymers (CPs). Two-dimensional (2D) CPs with honeycomb spin-lattices have attracted attention because of the unique electronic structures and physical properties afforded by their structural topology. However, radical-based CPs with honeycomb spin-lattices tend to have low chemical stability or poor crystallinity, and thus novel systems with high crystallinity and persistence are in strong demand. In this study, a novel triangular organic radical possessing three pyridyl groups, tris(3,5-dichloro-4-pyridyl)methyl radical (trisPyM) was prepared. It exhibits luminescence, high photostability, and a coordination ability, allowing formation of defined and persistent 2D CPs. Optical measurements confirmed the luminescence of trisPyM both in solution and in the solid state, with emission wavelengths, λem, of 665 and 700 nm, respectively. trisPyM exhibits better chemical stability under photoirradiation than other luminescent radicals: the half-life of trisPyM in CH2Cl2 was 10 »000 times that of the tris(2,4,6-trichlorophenyl)methyl radical (TTM), a conventional luminescent radical. Complexation between trisPyM and ZnII(hfac)2 yielded a single crystal of a 2D CP trisZn, possessing a honeycomb lattice with graphene-like spin topology. The coordination structure of trisZn is stable under evacuation at 60 °C. Moreover, trisZn exhibits luminescence at 79 K, with λem = 695 nm, and is a rare example of a luminescent material among 2D radical-based CPs. Our results indicate that trisPyM may be a promising building block in the construction of a new class of 2D honeycomb CPs with novel properties, including luminescence.

DOI： 10.1021/jacs.0c13310

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Faraday Discussions  

Molecular motions taking place in the nanospace of metal-organic frameworks (MOFs) are an interesting research subject, although not yet fully investigated. In this work, we utilized in situ Raman spectroscopy in the ultralow-frequency region to investigate the libration motion (including the rotational motion of phenylene rings) of MOFs, in particular [Cu2(bdc)2(dabco)] (Cu-JAST-1), where bdc = 1,4-benzenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane. The libration mode of Cu-JAST-1 was found to be significantly suppressed by the adsorption of various guest molecules, such as CO2, Ar, and N2. In addition, an appreciable correlation between the libration mode and adsorption equilibrium time was identified, which provides useful novel tools in the design of MOFs acting as molecular adsorption and separation materials.

DOI： 10.1039/d0fd00002g

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：RSC Advances  

Here, we report the adsorptive removal of trace amounts of dimethyl sulfide (DMS) using metal-organic frameworks (MOFs). Cu2+-based MOFs with open metal sites (OMSs), [Cu3(btc)2] (HKUST-1), where btc = 1,3,5-benzenetricarboxylate, and without OMSs, [Cu2(bdc)2(dabco)] (Cu-JAST-1), where bdc = 1,4-benzenedicarboxylate and dabco = 1,4-diazabicyclo[2.2.2]octane, were investigated for the removal of DMS to compare their performance with that of Ag-Y zeolite, which is currently widely used in industry. HKUST-1 exhibited a considerably higher adsorption capacity for DMS than the other adsorbents, which was confirmed by breakthrough measurements. The adsorption state of DMS with HKUST-1 was directly revealed by single-crystal X-ray diffraction (SXRD) analysis and in situ Raman spectroscopy. In addition, it was shown that DMS can be removed by HKUST-1 even under humid conditions.

DOI： 10.1039/c9ra09702c

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1039/D0CC00932F

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CiNii Research

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of the American Chemical Society  

Reaction in well-designed solids allows yielding products with high selectivity and unique compounds that cannot be obtained in solution. However, the precise tuning of the arrangement of reactants in solids for the versatile application of solid-phase reactions remains a challenging subject. Here, a [2 + 2] photocyclization reaction at different positions of the carbon-carbon bonds is described in which the spatial arrangement of 4-styrylpyridines (4-spy) is changed by guest molecules in a flexible metal-organic framework. The 4-spy molecules undergo photodimerization between two carbon-carbon double bonds in the guest-free framework, whereas a reaction between olefinic and aromatic carbon-carbon bonds or the absence of reaction takes place in the solvent-incorporated form. This reactivity, which can be termed as "dynamic topochemistry" contributes to enforce the applicability of solid-phase reactions in synthetic chemistry.

DOI： 10.1021/jacs.9b07682

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Physical Chemistry Chemical Physics  

The ceria-based catalyst incorporated with Cr and a trace amount of Rh (Cr0.19Rh0.06CeOz) was prepared and the reversible redox performances and oxidation catalysis of CO and alcohol derivatives with O2 at low temperatures (<373 K) were investigated. In situ X-ray absorption fine structure (XAFS), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM)-EDS/EELS and temperature-programmed reduction/oxidation (TPR/TPO) revealed the structures and redox mechanisms of three metals in Cr0.19Rh0.06CeOz: dispersed Rh3+δ species (<1 nm) and Cr6-γO3-x nanoparticles (∼1 nm) supported on CeO2 in Cr0.19Rh0.06CeOz were transformed to Rh nanoclusters, Cr(OH)3 species and CeO2-x with two Ce3+-oxide layers at the surface in a concerted activation manner of the three metal species with H2

DOI： 10.1039/c9cp04625a

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of the American Chemical Society  

A layered metal-organic framework (MOF) comprising extra-large nanographene sheets, HBCMOF, was successfully synthesized using a dicarboxylic acid derivative of hexa-peri-hexabenzocoronene (HBCLH2), and its structure was characterized by single-crystal X-ray diffraction analysis. The crystal structure shows that 2D layers composed of a dinuclear Zn2+ complex unit and HBCL are located on top of each other through multiple weak interlayer bonds, affording HBCMOF, having three dimensionally connected nanopores with large nanographene surfaces. The HBC-based nanographene sheets are anchored to the MOF framework via two zinc carboxylate linkages and therefore have an axial rotational freedom. The sorption isotherms of gaseous molecules such as carbon dioxide and hydrocarbons (acetylene, propane, propylene, benzene, and cyclohexane) on HBCMOF all displayed a hysteretic profile with reversible structural changes, as observed by in situ powder X-ray diffraction studies.

DOI： 10.1021/jacs.9b07732

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemistry - An Asian Journal  

In this study, we report a facile ligand-assisted in situ hydrothermal approach for preparation of compact [Al(OH)(1,4-NDC)] (1,4-NDC=1,4-naphthalenedicarboxylate) MOF membranes on porous γ-Al2O3 substrates, which also served as the Al3+ source of MOF membranes. Simultaneously, it was observed that the heating mode exerted significant influence on the final microstructure and separation performance of [Al(OH)(1,4-NDC)] membranes. Compared with the conventional hydrothermal method, the employment of microwave heating led to the formation of [Al(OH)(1,4-NDC)] membranes composed of closely packed nanorods with superior H2/CH4 selectivity.

DOI： 10.1002/asia.201900152

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Dalton Transactions  

Herein, we developed isostructural metal-organic frameworks (MOFs) [Cu 1-x Pd x (SiF 6 )(bpy) 2 ] (bpy: 4,4′-bipyridine) (SIFSIX-1-CuPd-3, -5 and -10) containing open metal sites using a partial metal-replacement approach. Starting from the SIFSIX-1-Cu-type MOF, some of the Cu 2+ ions having octahedral geometry were successfully replaced with Pd 2+ ions having square planar geometry in different ratios, while the framework structure was maintained. The results showed that gas adsorption properties of SIFSIX-1-Cu-type MOFs can be tuned via partial metal replacement.

DOI： 10.1039/c8dt04218g

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Nature Chemistry  

The ability of porous coordination polymers to undergo reversible structural transformations in response to the presence of guest molecules has been intensively investigated for applications such as molecular separation, storage, sensing and signalling processes. Here we report on the direct observation of the highly guest-responsive nature of the surface of a single-crystalline porous coordination polymer, which consists of paddlewheel zinc clusters and two types of ligand, by in situ liquid-phase atomic force microscopy. Observations were carried out in solution at constant temperature (28 °C) by high-speed atomic force microscopy with lattice resolution. A sharp and reversible response to the presence or absence of biphenyl guest molecules was observed, under conditions that can scarcely induce the transformation of the bulk crystal. Additionally, by modulating the surface coordination equilibrium, layer-by-layer delamination events were captured in real time at every ~13 s per frame.

DOI： 10.1038/s41557-018-0170-0

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Science  

Design of the gas-diffusion process in a porous material is challenging because a contracted pore aperture is a prerequisite, whereas the channel traffic of guest molecules is regulated by the flexible and dynamic motions of nanochannels. Here, we present the rational design of a diffusion-regulatory system in a porous coordination polymer (PCP) in which flip-flop molecular motions within the framework structure provide kinetic gate functions that enable efficient gas separation and storage. The PCP shows substantial temperature-responsive adsorption in which the adsorbate molecules are differentiated by each gate-admission temperature, facilitating kinetics-based gas separations of oxygen/argon and ethylene/ethane with high selectivities of ∼350 and ∼75, respectively. Additionally, we demonstrate the long-lasting physical encapsulation of ethylene at ambient conditions, owing to strongly impeded diffusion in distinctive nanochannels.

DOI： 10.1126/science.aar6833

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記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：CrystEngComm  

In this study, it was demonstrated that the introduction of Co-Al/Mg-Al hydrotalcite-like compound buffer layers on porous α-Al2O3 substrates enabled effective manipulation of the microstructure of ZIF-7 films so that metal ions located in the inorganic buffer layers were not necessarily identical with those residing in the MOF crystals. Moreover, zinc sources were found to exert a significant influence on the final microstructure of the prepared ZIF-7 films. In addition to ZIF-7, well-intergrown ZIF-8 and HKUST-1 films could also be in situ grown on diverse HTlc buffer layer-modified α-Al2O3 substrates, which convincingly demonstrated the generality of this strategy for the facile preparation of qualified MOF films/membranes.

DOI： 10.1039/c8ce01681j

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of the American Chemical Society  

The gate-opening adsorption mechanism and sigmoidal adsorption isotherm were theoretically investigated taking CO2 adsorption into porous coordination polymers, [Fe(ppt)2]n (PCP-N, Hppt = 3-(2-pyrazinyl)-5-(4-pyridyl)-1,2,4-triazole) and [Fe(dpt)2]n (PCP-C, Hdpt = 3-(2-pyridinyl)-5-(4-pyridyl)-1,2,4-triazole) as examples, where the hybrid method consisting of dispersion-corrected DFT for infinite PCP and a post-Hartree-Fock (SCS-MP2 and CCSD(T)) method for the cluster model was employed. PCP-N has site I (one-dimensional channel), site II (small aperture to site I), and site III (small pore) useful for CO2 adsorption. CO2 adsorption at site I occurs in a one by one manner with a Langmuir adsorption isotherm. CO2 adsorption at sites II and III occurs through a gate-opening adsorption mechanism, because the crystal deformation energy (EDEF) at these sites is induced largely by the first CO2 adsorption but induced much less by the subsequent CO2 adsorption. Interestingly, nine CO2 molecules are adsorbed simultaneously at these sites because a large EDEF cannot be overcome by adsorption of one CO2 molecule but can be by simultaneous adsorption of nine CO2 molecules. For such CO2 adsorption, the Langmuir-Freundlich sigmoidal adsorption isotherm was derived from the equilibrium equation for CO2 adsorption. A very complicated CO2 adsorption isotherm, experimentally observed, is reproduced by combination of the Langmuir and Langmuir-Freundlich adsorption isotherms. In PCP-C, CO2 adsorption occurs only at site I with the Langmuir adsorption isotherm. Sites II and III of PCP-C cannot be used for CO2 adsorption because a very large EDEF cannot be overcome by simultaneous adsorption of nine CO2 molecules. Factors necessary for gate-opening adsorption mechanism are discussed on the basis of differences between PCP-N and PCP-C.

DOI： 10.1021/jacs.8b09358

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記述言語：日本語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Science  

Gate-opening gas sorption is known for metal-organic frameworks, and is associated with structural flexibility and advantageous properties for sensing and gas uptake. Here, we show that gate-opening is also possible for metal-organic polyhedra (MOPs), and depends on the molecular organisation in the lattice. Thanks to the solubility of MOPs, several interchangeable solvatomorphs of a lantern-type MOP were synthesised via treatment with different solvents. One phase obtained through use of methanol induced a gate-opening effect in the lattice in response to carbon dioxide uptake. The sorption process was thoroughly investigated with in situ powder X-ray diffraction and simultaneous adsorption experiments. Meanwhile, solution processing of this flexible phase using THF led to a permanently porous phase without a gate-opening effect. Furthermore, we find that we can change the metallic composition of the MOP, and yet retain flexibility. By showing that gate-opening can be switched on and off depending on the solvent of crystallisation, these findings have implications for the solution-based processing of MOPs.

DOI： 10.1039/c8sc02263a

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/anie.201800820

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Chemical Communications  

Kinetic stabilisation of unstable chemical species in nanospace is of potential importance in the field of materials and synthetic chemistry, and porous coordination polymers (PCPs) represent a facile platform to provide such reaction fields. Thiyl radicals are important reactive substances that often play a leading role in organic and bioorganic chemistry. However, their generation in nanospace has been barely investigated due to synthetic difficulties. Here, we report a facile methodology for the functionalisation of active thiyl substituents on PCP pore surfaces using a post-synthetic protection and deprotection technique. The thiyl radicals were generated inside a zinc(ii)-based PCP upon the deprotection of asymmetric disulfides, which were used as the protecting groups by ultraviolet light irradiation.

DOI： 10.1039/c8cc01837e

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1002/chem.201705858

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1126/sciadv.aaq1636

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.7b10110

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ACS Applied Materials and Interfaces  

A new porous coordination polymer (PCP) based on a ligand with a unique bent angle bearing a thiophene-bridged bent carboxylate ligand and the Cu2+ ion was synthesized and structurally characterized. The structure has a pillared-layer framework based on a kagomé-like layer with aromatic partition groups. It exhibits a high CO2 uptake of 180 mL(STP)/g at 1 bar, and 400 mL(STP)/g at 30 bar at 273 K. The uptakes of C2H2 and C2H4 reach 164 and 160 mL(STP)/g at 298 K and 1 bar, with good selectivity of C2H2 and C2H4 over CH4, both of which are among the highest levels of reported PCPs.

DOI： 10.1021/acsami.7b01568

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：Journal of Physical Chemistry C  

Adsorptions of CO, N2, NO, and CO2 in a paddle-wheel-type porous coordination polymer (PCP) [Cu(aip)]n (aip = 5-azidoisophthalate) were investigated with ONIOM[MP4(SDQ):ωB97XD] method using a model system consisting of two [Cu2(O2CC6H4-R)4] units (R = H and Me) and one [Cu2(O2CC6H4-R)4] unit, namely, dimer and monomer models. The experimental CO adsorption position was reproduced well by the present calculation with the dimer model. For adsorptions of CO, N2, NO, and CO2 in the dimer model, the position of gas molecule deviates from the normal one that is found in the monomer model and becomes more distant from the surrounding phenyl group(s) of the neighbor [Cu(aip)] unit. For all of these gas molecules, the calculated binding energy (BE) at the deviating adsorption position is larger than that at the normal one against our expectation that the normal position is the best for the gas adsorption. The deviation of gas adsorption position arises from the interaction between the organic linker (O2CC6H4-R moiety) and gas molecule. For all cases, the exchange repulsion with the organic linker decreases to a larger extent than the attractive electrostatic and dispersion interactions decrease when going from the normal position to the deviating one. To enhance the binding energy of gas molecule, the introduction of electron-donating substituent on phenyl moiety is computationally recommended for this PCP.

DOI： 10.1021/acs.jpcc.7b02707

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記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：ROYAL SOC CHEMISTRY  

Nano-porous coordination polymers (nano-PCPs), as a new class of crystalline material, have become a lucrative topic in coordination chemistry due to the facile tunability of their functional pore environments. However, elucidating the pathways for the rational design and preparation of nano-PCPs with various integrated properties for feasible gas separation remains a great challenge. Here, we demonstrate a new route to achieve nano-PCPs with an integrated pore system and physical properties using a reticular chemistry strategy. By optimizing the position and length of the shortest two alkyl groups in the channels, unprecedented phenomena of improved surface area, gas uptake, gas selectivity, thermal stability and chemical stability were observed in the PCPs, especially in NTU-14, the structure with a pendant ethyl group. Furthermore, the high performance of adsorption-and membrane-based separation makes NTU-14 a promising medium for CH4 purification from a mixture at room temperature.

DOI： 10.1039/c7ta02760e

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記述言語：英語   掲載種別：研究論文（学術雑誌）  

DOI： 10.1021/jacs.7b05702

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記述言語：英語  

DOI： 10.1002/anie.201611785

PubMed

記述言語：英語   掲載種別：研究論文（学術雑誌）   出版者・発行元：WILEY-V C H VERLAG GMBH  

New bis(dipyrrinato) zinc(II) complex micro- and nanosheets containing zinc(II) porphyrin (N2) are synthesized. A liquid/liquid interface method between dipyrrin porphyrin ligand L2 and zinc acetate produces N2 with a large domain size. N2 can be layered quantitatively onto a flat substrate by a modified Langmuir-Schafer method. N2 deposited on a SnO2 electrode functions as a photoanode for a photoelectric conversion system. The photoresponse of N2 covers the whole visible wavelength range (400-650 nm), with a maximum quantum efficiency of more than twice that of a bis(dipyrrinato) zinc(II) complex nanosheet without porphyrin.

DOI： 10.1002/ange.201611785

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CiNii Books

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