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1.
Inorg Chem ; 2020 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-32663400

RESUMO

Four new layered flexible metal-organic frameworks (MOFs) containing a diacylhydrazone moiety, namely, guest-filled [Zn2(iso)2(tdih)2]n (1), [Zn2(NH2iso)2(tdih)2]n (2), [Cd2(iso)2(tdih)2]n (3) and [Cd2(NH2iso)2(tdih)2]n (4) were synthesized using terephthalaldehyde di-isonicotinoylhydrazone (tdih) as a linear ditopic linker as well as isophtalate (iso) or 5-aminoisophthalate (NH2iso) as angular colinkers. The MOFs with hexacoordinated cadmium centers feature two-dimensional pore systems as compared to the MOFs with pentacoordinated zinc centers showing either zero-dimensional or mixed zero-/one-dimensional voids, as evidenced by single-crystal X-ray diffraction. In contrast to the frameworks based on isophtalates which do not show any significant gas uptakes, introduction of amino-substituted linker enables CO2 adsorption. Gently activated aminoisophthalate-based frameworks, that is, guest-exchanged in methanol and heated to 100 °C, show reversible gated CO2 adsorptions at 195 K, whereas the increase of activation temperature to 150 °C or more leads to one-step isotherms and lower adsorption capacities. X-ray diffraction and IR spectroscopy reveal significant structural differences in interlayer hydrogen bonding upon activation of materials at higher temperatures. The work emphasizes the role of hydrogen bonds in crystal engineering of layered materials and the importance of activation conditions in such systems.

2.
Chem Commun (Camb) ; 56(59): 8269-8272, 2020 Jul 23.
Artigo em Inglês | MEDLINE | ID: mdl-32568349

RESUMO

Experimental in situ observations of phase coexistence in switchable metal-organic frameworks are reported to provide a fundamental understanding of dynamic adsorbents that can change their pore structure in response to external stimuli. A prototypical flexible pillared layer framework DUT-8(Ni) (DUT = Dresden University of Technology) was studied under hydrostatic pressure by in situ Raman spectroscopy on single crystals. The closing transition of the open pore phase (op) containing DMF in the pores in silicon oil as a pressure transmitting fluid, as well as the closed pore phase (cp) to op transition under pressure in methanol, were studied. Phase coexistences during both transitions were observed.

3.
Chem Commun (Camb) ; 2020 Jun 04.
Artigo em Inglês | MEDLINE | ID: mdl-32497159

RESUMO

We evaluate experimentally the force exerted by flexible metal-organic frameworks through expansion for a representative model system, namely MIL-53(Al). The results obtained are compared with data collected from intrusion experiments while molecular simulations are performed to shed light on the re-opening of the guest-loaded structure. The critical impact of the transition stimulating medium on the magnitude of the expansion force is demonstrated.

4.
Nat Commun ; 11(1): 1590, 2020 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-32221287

RESUMO

Amongst various porous materials, noble metal aerogels attract wide attention due to their concurrently featured catalytic properties and large surface areas. However, insufficient understanding and investigation of key factors (e.g. reductants and ligands) in the fabrication process limits on-target design, impeding material diversity and available applications. Herein, unveiling multiple roles of reductants, we develop an efficient method, i.e. the excessive-reductant-directed gelation strategy. It enables to integrate ligand chemistry for creating gold aerogels with a record-high specific surface area (59.8 m2 g-1), and to expand the composition to all common noble metals. Moreover, we demonstrate impressive electrocatalytic performance of these aerogels for the ethanol oxidation and oxygen evolution reaction, and discover an unconventional organic-ligand-enhancing effect. The present work not only enriches the composition and structural diversity of noble metal aerogels, but also opens up new dimensions for devising efficient electrocatalysts for broad material systems.

5.
Artigo em Inglês | MEDLINE | ID: mdl-31917504

RESUMO

Functional materials that respond to chemical or physical stimuli through reversible structural transformations are highly desirable for the integration into devices. Now, a new stable and flexible eightfold interpenetrated three-dimensional (3D) metal-organic framework (MOF) is reported, [Zn(oba)(pip)]n (JUK-8) based on 4,4'-oxybis(benzenedicarboxylate) (oba) and 4-pyridyl functionalized benzene-1,3-dicarbohydrazide (pip) linkers, featuring distinct switchability in response to guest molecules (H2 O and CO2 ) or temperature. Single-crystal X-ray diffraction (SC-XRD), combined with density functional theory (DFT) and grand canonical Monte Carlo (GCMC) simulations, reveal a unique breathing mechanism involving collective motions of eight mixed-linker diamondoid subnetworks with only minor displacements between them. The pronounced stepwise volume change of JUK-8 during water adsorption is used to construct an electron conducting composite film for resistive humidity sensing.

6.
Inorg Chem ; 59(1): 350-359, 2020 Jan 06.
Artigo em Inglês | MEDLINE | ID: mdl-31820946

RESUMO

In situ formation of imine-based organic linkers facilitates the formation of metal-organic frameworks (MOFs), in particular if linker solubility hampers the direct synthesis. The reaction of ZrCl4 with 4-formylbenzoic acid or 4-formyl-3-hydroxybenzoic acid as the aldehyde source and 4-aminobenzoic acid as the amine source is shown to produce zirconium MOFs isoreticular to UiO-66 (PCN-161 and a novel DUT-133, [Zr6O4(OH)4(C15H9NO5)6], respectively). A similar reaction with p-phenylenediamine as the amine-containing building block gave 2-fold interpenetrated framework (PCN-164). Detailed characterization, including single crystal and powder X-ray diffraction, water stability tests, thermal stability, and in situ 1H and 13C NMR were performed to elucidate the formation mechanism of zirconium MOFs containing imine-based linkers. The resulting zirconium MOFs were evaluated as potential materials for CO2 capture and as ethylene oligomerization catalysts with anchored nickel as the active species.

7.
Beilstein J Nanotechnol ; 10: 1737-1744, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31501745

RESUMO

In this contribution we analyze the influence of adsorption cycling, crystal size, and temperature on the switching behavior of the flexible Zr-based metal-organic framework DUT-98. We observe a shift in the gate-opening pressure upon cycling of adsorption experiments for micrometer-sized crystals and assign this to a fragmentation of the crystals. In a series of samples, the average crystal size of DUT-98 crystals was varied from 120 µm to 50 nm and the obtained solids were characterized by X-ray diffraction, infrared spectroscopy, as well as scanning and transmission electron microscopy. We analyzed the adsorption behavior by nitrogen and water adsorption at 77 K and 298 K, respectively, and show that adsorption-induced flexibility is only observed for micrometer-sized crystals. Nanometer-sized crystals were found to exhibit reversible type I adsorption behavior upon adsorption of nitrogen and exhibit a crystal-size-dependent steep water uptake of up to 20 mmol g-1 at 0.5 p/p 0 with potential for water harvesting and heat pump applications. We furthermore investigate the temperature-induced structural transition by in situ powder X-ray diffraction. At temperatures beyond 110 °C, the open-pore state of the nanometer-sized DUT-98 crystals is found to irreversibly transform to a closed-pore state. The connection of crystal fragmentation upon adsorption cycling and the crystal size dependence of the adsorption-induced flexibility is an important finding for evaluation of these materials in future adsorption-based applications. This work thus extends the limited amount of studies on crystal size effects in flexible MOFs and hopefully motivates further investigations in this field.

8.
Nat Commun ; 10(1): 3632, 2019 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-31406113

RESUMO

Switchable metal-organic frameworks (MOFs) have been proposed for various energy-related storage and separation applications, but the mechanistic understanding of adsorption-induced switching transitions is still at an early stage. Here we report critical design criteria for negative gas adsorption (NGA), a counterintuitive feature of pressure amplifying materials, hitherto uniquely observed in a highly porous framework compound (DUT-49). These criteria are derived by analysing the physical effects of micromechanics, pore size, interpenetration, adsorption enthalpies, and the pore filling mechanism using advanced in situ X-ray and neutron diffraction, NMR spectroscopy, and calorimetric techniques parallelised to adsorption for a series of six isoreticular networks. Aided by computational modelling, we identify DUT-50 as a new pressure amplifying material featuring distinct NGA transitions upon methane and argon adsorption. In situ neutron diffraction analysis of the methane (CD4) adsorption sites at 111 K supported by grand canonical Monte Carlo simulations reveals a sudden population of the largest mesopore to be the critical filling step initiating structural contraction and NGA. In contrast, interpenetration leads to framework stiffening and specific pore volume reduction, both factors effectively suppressing NGA transitions.

9.
Chem Commun (Camb) ; 55(62): 9140-9143, 2019 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-31304489

RESUMO

Selective 13C-labelling of carboxylate carbons in the linker molecules of flexible metal-organic frameworks (MOFs) makes solid-state NMR spectroscopy very powerful to investigate solvent-induced local structural changes as demonstrated by 13C and 1H NMR spectroscopy on the pillared layer MOF DUT-8(Ni). Selective identification of polar solvent-node interactions becomes feasible.

10.
ACS Appl Mater Interfaces ; 11(23): 20915-20922, 2019 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-31117471

RESUMO

Highly selective electrooxidation catalysts were synthesized by functionalizing a commercially available reference electrooxidation catalyst (Pt/Vulcan XC 72R) with a coating of the highly hydrophobic porous zeolitic imidazolate framework ZIF-8, an adsorbent with high affinity for the extraction of aliphatic alcohols from water. According to cyclovoltammetric studies in alkaline media at 25 °C, the ZIF-8 functionalized catalyst shows a high selectivity for the electrooxidation of small alcohols such as ethanol and methanol over more hydrophobic alcohols ( n-butanol, n-propanol). In contrast, the noncoated reference catalyst (Pt/Vulcan XC 72R) oxidizes all investigated alcohols with comparable current densities. Tafel curves confirm these observations and indicate a limited conversion of long chain alcohols, especially n-butanol, caused by the high affinity of the ZIF-8 for this molecule resulting in significant diffusion limitations.

11.
Chem Commun (Camb) ; 55(43): 6042-6045, 2019 May 28.
Artigo em Inglês | MEDLINE | ID: mdl-31065638

RESUMO

The identification and quantification of reaction intermediates and products in a time-resolved fashion is of great value for the understanding of mechanisms underlying the electro-catalytic oxidation of alcohols. Using a newly developed in situ cell, the identification of different intermediates, products, and side products became possible by monitoring the ethanol electro-oxidation in operando by 13C NMR spectroscopy.

12.
Inorg Chem ; 58(7): 4561-4573, 2019 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-30869884

RESUMO

A Cu2+-doped metal-organic framework (DUT-8(Ni0.98Cu0.02), M2(NDC)2DABCO, M = Ni, Cu, NDC = 2,6-napththalene dicarboxylate, DABCO = 1,4-diazabicyclo[2.2.2]octane, DUT = Dresden University of Technology) was synthesized in the form of large (>1 µm) and small crystals (<1 µm) to analyze their switchability by X-band continuous wave (cw) electron paramagnetic resonance (EPR) spectroscopy. The large crystals are flexible and in a porous open pore (op) phase after solvation in N, N-dimethylformamide (DMF), but in the activated solvent-free form, a nonporous closed pore (cp) phase forms. EPR measurements of the rigid Ni-free DUT-8(Cu) show a characteristic electron spin S = 1 room temperature signal of the antiferromagnetically coupled Cu2+-Cu2+ paddlewheel building unit of this metal-organic framework. None of the mixed metal DUT-8(Ni0.98Cu0.02) materials showed comparable signals, indicating the absence of dimeric Cu2+-Cu2+ paddlewheel units in the materials. Instead, characteristic electron spin S = 3/2 signals are detected for all DUT-8(Ni0.98Cu0.02) samples at temperatures T < 77 K, which can be assigned to ferromagnetically coupled mixed metal Ni2+-Cu2+ paddlewheel units. Those signals differ characteristically for the op and cp phase and enable monitoring the reversible op-cp transition during the de-/adsorption of DMF.

13.
Angew Chem Int Ed Engl ; 58(21): 6896-6900, 2019 May 20.
Artigo em Inglês | MEDLINE | ID: mdl-30864202

RESUMO

Covalent organic frameworks (COFs) have garnered immense scientific interest among porous materials because of their structural tunability and diverse properties. However, the response of such materials toward laser-induced nonlinear optical (NLO) applications is hardly understood and demands prompt attention. Three novel regioregular porphyrin (Por)-based porous COFs-Por-COF-HH and its dual metalated congeners Por-COF-ZnCu and Por-COF-ZnNi-have been prepared and present excellent NLO properties. Notably, intensity-dependent NLO switching behavior was observed for these Por-COFs, which is highly desirable for optical switching and optical limiting devices. Moreover, the efficient π-conjugation and charge-transfer transition in ZnCu-Por-COF enabled a high nonlinear absorption coefficient (ß=4470 cm/GW) and figure of merit (FOM=σ1 /σo , 3565) value compared to other state-of-the-art materials, including molecular porphyrins (ß≈100-400 cm/GW), metal-organic frameworks (MOFs; ß≈0.3-0.5 cm/GW), and graphene (ß=900 cm/GW).

14.
Dalton Trans ; 48(10): 3415-3421, 2019 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-30788474

RESUMO

Catalytic ethylene oligomerization proceeds under mild conditions with high activity using porous or non-porous nickel-based coordination polymers/metal-organic frameworks (MOFs) as catalysts. The role of MOFs as catalyst precursors and the crucial impact of metal coordination on the catalyst activity and leaching are elucidated by comparing MOFs constructed from different clusters and linkers. The stronger the coordination bond of organic linkers to the Ni center, the lower the catalytic activity of the MOF, as shown for CPO-27(Ni). The highest activity and stability were obtained with the [Ni3(ndc)3(DMF)2((CH3)2NH)2]n catalyst.

15.
Dalton Trans ; 48(11): 3601-3609, 2019 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-30698578

RESUMO

New redox active 1D helical coordination polymers M(fcdHp) (M(ii) = Zn(1), Co(2)) have been obtained by utilizing the 1,1'-ferrocenylenbis(H-phosphinic) acid (H2fcdHp) ligand and Zn or Co nitrate salts. Complexes 1 and 2 are isomorphic, crystallizing in the chiral space groups P4122 and P4322, respectively. Their redox, electrocatalytic and other properties are described. These compounds incorporated into carbon paste electrodes and exhibited reversible redox reactions, arising from the ferrocenyl moiety. These coordination polymers are efficient as electrocatalysts for the reduction of protons to hydrogen. Using N,N-dimethylformamidium ([DMF(H)+]) as the acid in the acetonitrile solution, Co CP (2) displays a turnover frequency of 300 s-1, which is among the fastest rates reported for any CP electrocatalyst in CH3CN. This high rate of catalytic reaction comes at the cost of the 820-840 mV overpotential at the potential of catalysis. As the hydrogen evolution reaction (HER) catalysts, the CPs exhibited in 0.5 M H2SO4 the overpotential η10 of 340 or 450 mV, onset overpotential of 220 or 300 mV (vs. RHE), Tafel slope of 110 or 120 mV dec-1, correspondingly for 1 and 2, and considerable long-term stability for the HER.

16.
Langmuir ; 35(8): 3162-3170, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30695636

RESUMO

Metal-organic frameworks are promising candidates for selective separation processes such as CO2 removal from methane (natural gas sweetening). Framework flexibility, that is, the ability of a MOF lattice to change its structure as a function of parameters like pressure, temperature, and type of adsorbed molecules, is only observed for some special compounds. The main question of our present work is: does framework flexibility influence the adsorption selectivity? As a direct quantitative method to monitor the adsorption of both, carbon dioxide and methane, we make use of high-pressure in situ 13C NMR spectroscopy of 13CO2/13CH4 gas mixtures. This method allows to distinguish between the two gases as well as between adsorbed molecules and the interparticle gas phase. Gas mixture adsorption is studied under isothermal conditions. The selectivity factor for CO2 adsorption from CO2/CH4 mixtures is measured as a function of total gas pressure. The flexible material SNU-9 as well as the flexible and the nonflexible variant of DUT-8(Ni) are compared. Maximum selectivity factors for CO2 are observed for the flexible variant of DUT-8(Ni) in its open, large-pore state. In contrast, the rigid variant of DUT-8(Ni) and SNU-9 especially in its intermediate state exhibits lower adsorption selectivity factors. This observation indicates significant influence of the framework elasticity on the adsorption selectivity.

17.
Chemistry ; 24(70): 18629-18633, 2018 Dec 12.
Artigo em Inglês | MEDLINE | ID: mdl-30284341

RESUMO

The successful incorporation of a thermally fragile imidazolium moiety into a covalent triazine framework resulted in a heterogeneous organocatalyst active in carbene-catalyzed umpolung reaction. The structural integrity of the imidazolium moiety was confirmed by combining solid-state NMR and XPS experiments.

18.
Phys Chem Chem Phys ; 20(38): 25039-25043, 2018 Oct 03.
Artigo em Inglês | MEDLINE | ID: mdl-30246822

RESUMO

The pressure dependence of the 129Xe chemical shift in the metal-organic frameworks (MOFs) UiO-66 and UiO-67 (UiO - University of Oslo) has been investigated using both theory and experiment. The resulting chemical shift isotherms were analyzed with a theoretical approach based on model systems (as proposed by K. Trepte, J. Schaber, S. Schwalbe, F. Drache, I. Senkovska, S. Kaskel, J. Kortus, E. Brunner and G. Seifert, Phys. Chem. Chem. Phys., 2017, 19, 10020-10027) and experimental 129Xe NMR measurements at different pressures. All investigations were carried out at T = 237 K while the pressure range was chosen according to the maximum pressure at which Xe liquifies (p0 = 1.73 MPa or 17.3 bar), thus 0 < p ≤ p0. The theoretically predicted chemical shift isotherms agree well with the experimental ones. Additionally, a comparison of the chemical shift isotherms with volumetric adsorption isotherms was carried out to determine the similarities and differences of both isotherms.

19.
Angew Chem Int Ed Engl ; 57(42): 13780-13783, 2018 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-30160076

RESUMO

A new mesoporous metal-organic framework (MOF; DUT-60) was conceptually designed in silico using Zn4 O6+ nodes, ditopic and tritopic linkers to explore the stability limits of framework architectures with ultrahigh porosity. The robust ith-d topology of DUT-60 provides an average bulk and shear modulus (4.97 GPa and 0.50 GPa, respectively) for this ultra-porous framework, a key prerequisite to suppress pore collapse during desolvation. Subsequently, a cluster precursor approach, resulting in minimal side product formation in the solvothermal synthesis, was used to produce DUT-60, a new crystalline framework with the highest recorded accessible pore volume (5.02 cm3 g-1 ) surpassing all known crystalline framework materials.

20.
Nat Commun ; 9(1): 1573, 2018 04 20.
Artigo em Inglês | MEDLINE | ID: mdl-29679030

RESUMO

Negative gas adsorption (NGA) in ordered mesoporous solids is associated with giant contractive structural transitions traversing through metastable states. Here, by systematically downsizing the crystal dimensions of a mesoporous MOF (DUT-49) from several micrometers to less than 200 nm, counterintuitive NGA phenomena are demonstrated to critically depend on the primary crystallite size. Adsorbing probe molecules, such as n-butane or nitrogen, gives insights into size-dependent activation barriers and thermodynamics associated with guest-induced network contraction. Below a critical crystal size, the nitrogen adsorption-induced breathing is completely suppressed as detected using parallelized synchrotron X-ray diffraction-adsorption instrumentation. In contrast, even the smallest particles show NGA in the presence of n-butane, however, associated with a significantly reduced pressure amplification. Consequently, the magnitude of NGA in terms of amount of gas expulsed and pressure amplification can be tuned, potentially paving the way towards innovative concepts for pressure amplification in micro- and macro-system engineering.

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