Mof-type layered coordination polymers of manganese, method of their preparation, modification and use thereof

Abstract

The invention solves the problem of the development of microporous layered MOF-type manganese materials based on isonicotinate anions, their synthesis and modification with selected ionic substances and application associated with the adsorption of the molecules and the construction of solid superionic conductors.

Claims

1. A layered MOF-type coordination polymer of manganese defined by the general formula 1:
{[Mn.sub.2(ina).sub.4(L).sub.x].yS}.sub.n in which: ina is an isonicotinic acid anion; L is a neutral molecule of a solvent selected from the group consisting of C.sub.1-C.sub.12 alcohols or water; S independently denotes inert solvent molecule selected from the group consisting of C.sub.1-C.sub.12 alcohols or water; x varies from 0 to 2; y Independently varies in the range from 0 to 4; n denotes a polymeric structure of the general formula, wherein the layered MOF-type coordination polymer is a two-dimensional network.

2. The layered polymer according to claim 1, characterized in that L means water, S is ethanol, x=2, y=2.

3. The layered polymer according to claim 1, characterized in that L means water, x=2, y=0.

4. The layered polymer according to claim 1, characterized in that S is ethanol, x=0, y=2.

5. The layered polymer according to claim 1, characterized in that x=0, y=0.

6. A method for producing the layered MOF-type coordination polymer of claim 1, characterized in that isonicotinic acid hydrazide is condensed through a condensation reaction with a lower ketone or aldehyde under anaerobic or aerobic conditions or in air, wherein the condensation reaction is carried out at 1:1 molar ratio of an aldehyde or ketone with isoniazid or at a stoichiometric excess of one of the reactants, in a C.sub.1-C.sub.12 alcohol or aqueous-alcoholic solution, formed by mixing of C.sub.1-C.sub.12 alcohol and water in any ratio, and in a second stage to prevent the deprotonation of the resulting hydrazide-hydrazone, an acidic substance and a salt of manganese(II) are added, wherein the second stage is carried out at a molar ratio 1:2:2 of manganese to isoniazid to acid or at a stoichiometric excess or a deficiency of the acid.

7. The method according to claim 6, characterized in that, as a manganese(II) salt, manganese(II) actetate hydrated or anhydrous is used.

8. The method according to claim 6, wherein the method is carried out in the temperature range of 130 C. to 260 C. and in the pressure range of 0.01 to 1 MPa.

9. The method according to claim 6 characterized in that as a factor preventing hydrazide-hydrazone deprotonation, acetic acid is used.

10. The method according to claim 6 characterized in that the resulting compounds are heated to temperatures not exceeding 400 C. and/or subjected to reduced pressure and/or contacted with a strong dehydrating agent in the form of phosphorus pentoxide P.sub.4O.sub.10.

11. A method of modifying the layered MOF-type coordination polymer of claim 1 by with an ionic substance to form a modified compound characterized in that the modifying is carried out by grinding of the layered MOF-type coordination polymer in a mortar or a ball mill with the ionic substance without solvent or with addition of solvent in an amount of up to 10 l per 1 mg of solid reactants (liquid-assisted grinding method), wherein grinding in a mortar or ball mill is carried out at a molar ratio of the coordination polymer to the ionic substance in the range from 10:1 to 1:10, and in the case of using LAG method (liquid-assisted grinding method), solvent is eventually removed by evaporation which occurs during the grinding.

12. The method according to claim 11 characterized in that as a solvent in the LAG method C.sub.1-C.sub.12 alcohol or aqueous-alcoholic solution formed by mixing C.sub.1-C.sub.12 alcohol and water in any ratio, is used.

13. The method according to claim 11 characterized in that the modifying with addition of solvent is carried out at a molar ratio of the coordination polymer to the ionic substance in the range from 100:1 to 1:100, wherein the modifying is carried out in the temperature range of 130 C. to 260 C. and in the pressure range of 0.01 to 1 MPa.

14. The method according to claim 11 wherein the solvent is pyridine, N,N-dimethylformamide, N,N-diethylformamide, N,N-imethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, dimethyl carbonate, diethyl carbonate, C.sub.1-C.sub.12 alcohols, water, halogenated alkanes, acetonitrile, tetrahydrofuran or mixtures thereof.

15. The method according to claim 11 wherein the ionic substance is a compound containing at least one anion from the group: halides (fluorides, chlorides, bromides, iodides), hydroxides, nitrates, sulfates, bisulfates, thiosulphates, phosphates, hydrophosphates, carbonates, bicarbonates, chlorates, bromates, iodates, thiocyanates, cyanides, cyanates, chromates, dichromates, silicates, arsenates, acetates, formates, oxalates, citrates, sulfides, hexafluorophosphates, tetrafluoroborates, tetraphenylborates, molybdates, tungstates, vanadates, phthalates, hydrogen phthalates, terephthalates, and containing at least one cation from the group: ammonium, alkylammonium, hydrogen, lithium, sodium, or potassium.

16. A method for detecting, capture, separating or storage of a molecule comprising contacting the layered MOF-type manganese coordination polymer of claim 1 with the molecule to form a modified compound.

17. The method according to claim 11 characterized in that the modified compound is used for the preparation of superionic or ionic-electronic conductors, or for construction of batteries, supercapacitors or fuel cells.

18. The method of claim 16, wherein said molecule is hydrogen, carbon dioxide, carbon monoxide, an alcohol, water, or a hydrocarbon or any combination thereof.

Description

(1) In the following detailed description, reference is made to the accompanying drawings, which form a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. The following detailed description, therefore, is not to be taken in a limiting sense, and the scope of the present invention is defined by the appended claims.

(2) FIG. 1 shows the crystal structure of 2D {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n MOF. (a) Single layer with dinuclear Mn.sub.2 nodes and their fourfold connectivity with isonicotinate linkers (EtOH guest molecules have been omitted) (left) viewed along the crystallographic a axis (H atoms omitted), and (right) represented in a spacefill model showing rectangular open channels. (b) Stacked layers viewed along the crystallographic c axis. (Left) Coordinated H.sub.2O molecules occupying the interlayer region and EtOH guest molecules are clearly visible. (Right) Sequence of interlayer hydrogen-bonds involving H.sub.2O, EtOH and framework free oxygen atoms of carboxylate groups, is indicated as a line between atoms shown as balls.

(3) FIG. 2 shows TG and dTG curves for {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n showing stepwise weight loss upon heating.

(4) FIG. 3 shows the observed (black line) and calculated (gray line) PXRD patterns of {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n along with the difference curve (bottom black line).

(5) FIG. 4 shows {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n (JUIK-2) formation upon 5 min LAG (EtOH) grinding of {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n (JUIK-1) and NH.sub.4SCN at various stoichiometries (given as {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n to NH.sub.4SCN ratio). a) IR-ATR spectra of ground reactants (top to bottom): 1:3.5; 1:2.7; 1:2 (pure {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n); 1:1; 1:0.5; initial {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n; initial NH.sub.4SCN. Dotted lines indicate selected wavenumbers of initial reactants and {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n. b) PXRD patterns (top to bottom): 1:2 (pure {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n); 1:0.5 (mixture of {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n and unreacted {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n); initial {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n; initial NH.sub.4SCN. Characteristic reflections of {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n and {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n are labeled *.

(6) FIG. 5 shows proton conduction in {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n a) Arrhenius plots for a (1).fwdarw.(2).fwdarw.(3) sequence: (1) as-synthesized (circles); (2) dried for 3 h at 60 C., 25 mbar and kept in air at approx. 40% RH for 4 days (squares); (3) kept over water in a closed vial for 16 h at 40 C. and kept in air at approx. 40% RH for 4 days (triangles). Open and closed symbols denote cooling and heating cycles, respectively.

(7) FIG. 6 shows selective CO.sub.2 vs N.sub.2 adsorption for activated {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n. CO.sub.2 and N.sub.2 adsorption isotherms at 195 K and 77 K, respectively.

(8) The invention is illustrated by the following examples not limiting in any way the scope of its protection.

EXAMPLE 1

(9) Compound {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n, in which (L=H.sub.2O; S=EtOH; x=2; y=2).

(10) Isonicotinic acid hydrazide (isoniazid) (274 mg; 2.00 mmol) was dissolved in 92% ethanol (40 mL) containing acetone (700 L; 10.0 mmol) and was heated under reflux for about 10 minutes. Then 80% acetic acid (215 L; 3.00 mmol) and [Mn(CH.sub.3COO).sub.2].4H.sub.2O (245 mg; 1.00 mmol) were added. Refluxing the resulting pale yellow solution was continued for about 10 minutes. Then the solution was left for crystallization. After approximately 6 days dark yellow crystals were filtered, washed with ethanol and dried in air at room temperature. Yield: 200 mg; 55%.

(11) Elemental analysis: Calculated for C.sub.28H.sub.32Mn.sub.2N.sub.4O.sub.12: C, 46.29; H, 4.44; N, 7.71. Found: C, 45.99; H, 4.53; N, 7.70%. IR (ATR, cm.sup.1): v(COO).sub.as 1643 s 1599 vs, v(COO).sub.s 1415 s 1396 vs, v(CO.sub.etanol) 1049 w, v(CH.sub.etanol) 2972 w, v(OH) 3271 m br. Magnetic moment (298 K): .sub.eff=5.7.sub.B. Surface area S.sub.BET-N2=11 m.sup.2/g (in 196 C., the average of three, single point measurements for p/p.sub.0=0.1; 0.2; 0.3). UV-vis (solid state) , nm: 447, 441, 419, 400, 310 sh, 269, 214.

(12) Crystallographic data (SCXRD): monoclinic, space group P2.sub.1/c, a=10.869(5), b=12.130(5), c=13.783(4) , =117.75(2), V=1608.2(11) .sup.3, T=293(2) K, Z=4, D.sub.C=1.500 Mg m.sup.3, =6.974 mm.sup.1, 22994 reflections measured, 3093 reflections unique (R.sub.int=0.0405), 2776 reflections observed [I>2(I)]. R.sub.1=0.0329; wR.sub.2=0.0832 [for 2776 reflections observed].

(13) Single-crystal XRD revealed that the isonicotinate ligands in {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n function as .sub.3 and .sub.2 linkers between the carboxylate-bridged dinuclear Mn.sup.II clusters and act as nodes in the layered framework of a (4,4)-topology (FIG. 1). The framework also exhibits 1D channels of approximately 3.72.9 .sup.2, which were occupied by EtOH guest molecules. The non-polar ethyl groups were directed inside the 10.8 -thick layers. In contrast, the hydroxyl groups of the ethanol units were involved in strong hydrogen-bonds (OH . . . O distances range from 2.666 to 2.786 ) with both the framework free carboxylate groups and coordinated H.sub.2O guest molecules. The structural flexibility of the framework arises from its interlayer hydrogen-bonding acceptor sites and labile guest molecules that can be easily and selectively removed.

(14) TGA/QMS for {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n revealed a stepwise weight loss (FIG. 2) with an approximate plateau in the range 170-400 C., upon heating. The first distinct step with a maximum at 151 C. corresponds to the loss of two solvate ethanol and two coordination water molecules per formula unit (found: 18.3%, m/z=14 [CH.sub.2].sup.+, 15 [CH.sub.3].sup.+, 17 [OH].sup.+, 18 [H.sub.2O].sup.+; calculated weight-loss: 17.6%). The final distinct step occurring at 433 C. was assigned to the loss of carboxylate groups (found: 45.1%, m/z=28 [CO].sup.+, 44 [COO].sup.+) and is associated with a decomposition of the compound.

EXAMPLE 2

(15) Compound {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2]}.sub.n, in which (L=H.sub.2O; x=2; y=0).

(16) Yellow powdered compound {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n (101.7 mg; 0.2800 mmol) was heated for approx. 1 hour at 150 C., after that the sample was immediately weighed. Weight loss of 18.3 mg corresponding to the release of two water molecules and two ethanol molecules per one formula unit of [Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH was observed. The resulting pale yellow powder of {[Mn.sub.2(ina).sub.4]}.sub.n (x=0; y=0) (83.4 mg; 0.279 mmol) was exposed to air for about 1 hour at room temperature. Weight gain of 4.9 g corresponding to the uptake of two water molecules per one unit of [Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH was observed. The resulting pale yellow powder of {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2]}.sub.n was obtained (88.3 mg; 0.278 mmol). Yield: 100%.

(17) Elemental analysis: Calculated for C.sub.24H.sub.20Mn.sub.2N.sub.4O.sub.10: C, 45.44; H, 3.18; N, 8.83. Found: C, 45.61; H, 3.10; N, 9.01%. IR (ATR, cm.sup.1): v(COO).sub.as 1609 s, v(COO).sub.s 1405 s 1394 vs, UV-vis (solid state) , nm: 390 sh, 310 sh, 272, 210.

EXAMPLE 3

(18) Compound {[Mn.sub.2 (ina).sub.4].2EtOH}.sub.n, in which (x=0; S=EtOH; y=2).

(19) Yellow powdered compound {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n (82.7 mg; 0.228 mmol) was placed in a desiccator over P.sub.4O.sub.10 under reduced pressure (p40 hPa) at room temperature for about 24 hours. Weight loss of 4.1 mg corresponding to the release of two water molecules per one formula unit of [Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH was observed. The resulting yellow powder of {[Mn.sub.2 (ina).sub.4].2EtOH}.sub.n was obtained (78.6 mg; 0.228 mmol). Yield: 100%.

(20) {[Mn.sub.2(ina).sub.4].2EtOH}.sub.n was exposed to air for about 1 hour at room temperature. Weight regain of 4.1 g corresponding to the uptake of two water molecules per one unit of [Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH was observed. The resulting yellow powder of {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n was obtained (82.7 mg; 0.228 mmol). Yield: 100%. Compound identification was based on the IR spectrum.

EXAMPLE 4

(21) Modification of {[Mn.sub.2(ina).sub.4(H.sub.2O.sub.2).sub.2].2EtOH}.sub.n compound with ammonium thiocyanate (by mechanochemical method in LAG variant).

(22) {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n compound (80.0 mg; 0.220 mmol) and NH.sub.4SCN (33.5 mg; 0.440 mmol) were ground in an agate mortar at room temperature in air for about 20 minutes in 4 cycles, 5 minutes each. In each cycle approximately 100-120 L of 92% ethanol was added to the system (mechanochemical method in LAG variant). Light yellow powder of {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n was obtained. Yield: 99.4 mg; 100%.

(23) It has been confirmed by IR spectroscopy that after 1 minute of neat grinding (NG) the product is already formed.

(24) Elemental analysis: Calculated for C.sub.14H.sub.16N.sub.6O.sub.4S.sub.2Mn: C, 37.25; H, 3.57; N, 18.62; S, 14.21. Found: C, 36.89; H, 3.51; N, 18.46; S, 14.29%. IR (ATR, cm.sup.1): v(COO).sub.as 1580 vs v(COO).sub.s 1408 s, (NH).sub.ammonium 1479 m 1437 s, v(SCN) 2103 vs, v(NH.sub.ammonium) 3236 m 3186 m. UV-vis (solid state) , nm: 310 sh, 268, 230, 211.

(25) Crystallographic data (PXRD): monoclinic, space group P2.sub.1/c, a=9.72, b=14.1, c=7.15 , =97.9, V=968 .sup.3, T=293 K. The PXRD pattern for the {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n is presented on FIG. 3.

(26) The stoichiometry of the reaction (1:2; {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n to NH.sub.4SCN) as well as the formation of a new, crystalline phase of {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n can be detected by IR spectroscopy and powder X-ray diffraction (FIG. 4). Reactions carried out at higher stoichiometries of NH.sub.4SCN give mixtures of the thiocyanate and {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n, whereas all reactions with lower stoichiometry of NH.sub.4SCN lead to mixtures of the unreacted {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n and {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n, whose amount is limited by the thiocyanate.

EXAMPLE 5

(27) Proton conductivity of {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n compound.

(28) The proton conductivity of {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n and {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n was evaluated by AC 4-probe method performed on powdered sample pressed between two gold electrodes in a sealed glass tube within temperature range +5 C. and +30 C. {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n, precursor of {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n, was not conductive, i.e. the conductivity was lower than S<10.sup.7 S cm.sup.1. However, the proton conductivity of as-synthesized {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n was found to be 7.010.sup.4 S cm.sup.1 at 25 C., estimated from the linear fit of the Arrhenius plot in FIG. 5. This proton conductivity is among the highest reported for MOFs so far ((a) Ramaswamy, P.; Wong, N. E.; Shimizu, G. K. H. Chem. Soc. Rev. 2014, 43, 5913. (b) Horike, S.; Umeyama, D.; Kitagawa, S. Acc. Chem. Res. 2013, 46, 2376-2384. (c) Yoon, M.; Suh, K.; Natarajan, S.; Kim, K. Angew. Chem. Int. Ed. 2013, 52, 2688). To gain more insight into the conducting process, the sample of {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n was dried and then stepwise humidified. It has been observed that the dried sample (3 h at 60 C., 25 mbar) was not conductive (S<10.sup.7 S cm.sup.1). This finding indicates the presence of interlayer water molecules that play an important role in creating the proton-conducting pathways in {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n (the formula of the compound may also be presented as {(NH.sub.4).sub.2[Mn(ina).sub.2(NCS).sub.2]}.sub.n.xH.sub.2O). These water molecules (xH.sub.2O) are adsorbed on its layers and disordered, and as such cannot be included in the X-ray crystal structure, elucidated from the PXRD data. On the other hand, when the dried sample was conditioned in air at approx. 40% RH (relative humidity), only a partial restoration (1.210.sup.6 S cm.sup.1 at 25 C.) of conductivity was observed (FIG. 5). In contrast, when this sample was further exposed to 100% RH followed by conditioning at approx. 40% RH, its degree of hydration was (FIG. 5). Both the reversibility of proton conductivity property as well as the stability under high humidity extending to soaking in water, are desirable features of {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n in the context of its fuel cells applications.

(29) The Arrhenius plots of the proton conductivity allow for calculation of the activation energy (E.sub.a) for {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n samples. The obtained value of 0.20 eV for the as-synthesized material indicates the Grotthuss mechanism of proton conduction involving rotational movements of NH.sub.3/NH.sub.4.sup.+ and H.sub.2O/H.sub.3O.sup.+ moieties (Kreuer K.-D.; Rabenau A.; Weppner Angew. Chem. Int. Ed. 1982, 21, 208). In contrast, the sample with partially recovered hydration and resulting restored conductivity exhibits higher E.sub.a=0.64 eV suggesting that proton conduction in {(NH.sub.4).sub.2[Mn(ina).sub.4(SCN).sub.2]}.sub.n includes another process involving translational movements of the aforementioned molecules/ions (vehicle mechanism).

EXAMPLE 6

(30) CO.sub.2 and N.sub.2 adsorption isotherms for activated {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n (FIG. 6)

(31) {[Mn.sub.2(ina).sub.4(H.sub.2O).sub.2].2EtOH}.sub.n was degassed at 150 C. for 1 hour prior to analysis. Measurements were performed in triplicates on degassed samples at 195K (CO.sub.2) and 77K (N.sub.2) over a pressure range of 0.01-0.90 bar. The data reflects the average volumes at STP (cm.sup.3/g).