Mayenite-type compound containing imide anion, and method for producing same

Abstract

The invention related to a material that can stably hold an imide anion (NH.sup.2) therein even in the atmosphere or in a solvent, and a method for synthesizing the material and a use of the material. A mayenite-type compound into which imide anions are incorporated at a concentration of 110.sup.18 cm.sup.3 or more are provided. The mayenite-type compound can be produced by heating a mayenite-type compound including electrons or free oxygen ions in a cage thereof, in liquefied ammonia at 450 to 700 C. and at a pressure of 30 to 100 MPa. The compound has properties such that active imide anions can be easily incorporated into the compound and the active imide anions can be easily released in the form of ammonia from the compound, and the compound has chemical stability.

Claims

1. A mayenite-type compound, wherein imide anions are incorporated into the mayenite-type compound at a concentration of 110.sup.18 cm.sup.3 or more, and the mayenite-type compound is a compound having the same type of crystal structure as a crystal structure of mayenite.

2. A method for producing the mayenite-type compound according to claim 1 comprising: heating a mayenite-type compound including electrons or free oxygen ions in a cage thereof, in liquefied ammonia at 450 C. to 700 C. and at a pressure of 30 to 100 MPa.

3. An imide anion supplying material comprising the mayenite-type compound according to claim 1.

4. An ammonia supplying material comprising the mayenite-type compound according to claim 1.

5. The mayenite-type compound according to claim 1, wherein imide anions are incorporated into the mayenite-type compound at a concentration of 110.sup.18 cm.sup.3 to 1.110.sup.21 cm.sup.3.

6. The method according to claim 2, comprising heating a mayenite-type compound including electrons or free oxygen ions in a cage thereof, in liquefied ammonia at 450 C. to 650 C. and at a pressure of 30 to 100 MPa.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 shows a temperature programmed desorption spectrum of a compound of the present invention.

(2) FIG. 2 is a schematic view of an ammonothermal synthesis apparatus for synthesizing the compound of the present invention.

(3) FIG. 3 shows Raman spectra of the compounds of the present invention.

(4) FIG. 4 shows .sup.1H MAS NMR spectra of the compound of the present invention.

(5) FIG. 5 shows Raman spectra of the compound of the present invention after Evaluation Test 1 in which the compound is stored in the atmosphere, and Evaluation Tests 2 and 3 in which the compound is immersed in an organic solvent.

DESCRIPTION OF EMBODIMENTS

(6) Hereinafter, a mayenite-type compound containing imide anions at a concentration of 10.sup.18 cm.sup.3 or more (hereinafter, also referred to as a compound of the present invention) and a method for producing the same will be described in detail.

(7) <Production of Mayenite-Type Compound Base>

(8) Hereinafter, C12A7, which is a representative composition of the mayenite-type compound will be described in detail. However, the present invention is not limited to C12A7 and can be applied to all mayenite-type compounds having the same type of crystal structure as C12A7, such as 12SrO.7Al.sub.2O.sub.3 in which Ca is substituted with Sr. The base composed of C12A7 used as a starting material of the present invention may be a molded body of a powder, a porous body, a solid sintered body, a thin film, a solid single crystal, or the like, and the shape of the molded body may be any shape. In addition, C12A7 supported on a support composed of a different material may be used for the base.

(9) The raw materials for C12A7 are synthesized by a solid phase method, a hydrothermal method, a sol-gel method, or the like. A hydrothermal reaction is a reaction in which water participates under high temperature and high pressure conditions of 100 C. or higher and 1 atmospheric pressure or higher, and a ceramic powder can be synthesized by a reaction at a low temperature in a short period of time. A C12A7 powder having a large specific surface area (about 20 to 60 m.sup.2g.sup.1) can be obtained by using the hydrothermal synthesizing method. For example, Ca.sub.3Al.sub.2(OH).sub.12 or aluminum hydroxide as hydroxide which becomes a precursor of C12A7 can be obtained by mixing water and calcium hydroxide or aluminum hydroxide with a stoichiometric composition and heating the mixture, for example, at 150 C. for about 6 hours. The powder is subject to a vacuum evacuation treatment at 750 to 900 C. to obtain C12A7. In addition, adsorbed water, hydroxyl groups on the surface, OH.sup. in the cage, and the like can be removed and thus a reducing agent can be prevented from deactivation in a step of incorporating electrons.

(10) <Step of Incorporating Conduction Electrons and Hydrogen Anions into C12A7 Base>

(11) In the case of producing a C12A7 powder including conduction electrons, raw material powders for C12A7 with a chemical equivalent composition may be heated under a reduction atmosphere. A porous body or a solid sintered body of C12A7 including conduction electrons may be obtained by molding the material powders for C12A7 with a chemical equivalent composition and then heating the molded body with Ca, CaH.sub.2, Ti, or the like under a reduction atmosphere. Regarding bases other than a thin film and a solid single crystal, a C12A7 base including conduction electrons can be directly formed from raw materials without an intermediate step of producing a C12A7 base not including conduction electrons. When a C12A7 base including hydrogen anions is heated with Ca or the like under a hydrogen gas stream or a reduction atmosphere in the same manner, a powder, a porous body, or a solid sintered body can be synthesized.

(12) A thin film of C12A7 including conduction electrons can be produced by forming a thin film of C12A7 on a substrate of MgO, Y.sub.3Al.sub.5O.sub.12, or the like by a pulsed laser deposition (PLD) method, a sputtering method, a plasma spraying method or the like using a solid sintered body of C12A7 as a target, and then depositing C12A7 by the PLD method again to form a single body while heating the resulting thin film of C12A7 to 500 C. or higher. In the second PLD process, since C12A7 in (Non-Patent Document) plasma state works as a reducing agent, conduction electrons are incorporated into the thin film. A thin film of C12A7 including hydrogen anions can be synthesized in the same manner.

(13) In addition, a solid single crystal of C12A7 can be produced by pulling a seed crystal's rod from a melt obtained by melting raw material powders of C12A7 at about 1,600 C. to form a C12A7 single crystal (CZ method). Then, the resultant single crystal is put in a vacuum glass tube with a metal Ca powder, Ti powder, or the like, and then the glass tube is sealed. The glass tube is heated under a reduction atmosphere to incorporate conduction electrons into the solid single crystal. A solid single crystal of C12A7 including hydrogen anions can be synthesized in the same manner.

(14) The solid sintered body or solid single crystal of C12A7 including conduction electrons or hydrogen anions can be processed into a powder. Pulverizing processing can be conducted by pulverization in a mortar, pulverization using a jet mill, or the like. The size of the powder is not particularly limited and particles having a particle diameter in a range of about 100 nm to 1 mm can be obtained by these methods. Through these methods, C12A7 including conduction electrons or hydrogen anions at a concentration of 110.sup.15 cm.sup.3 or more can be produced.

(15) Irrespective of the powder, the porous body, the solid sintered body, the thin film, and the solid single crystal produced by the methods, conduction electrons may lose from the surface portion of these bases. In this case, conduction electrons can be incorporated into the outermost surface of the base at a concentration of 110.sup.15 cm.sup.3 or more by heating it in vacuum, an inert gas, or under a reduction atmosphere at the temperature range from 900 C. or higher to that lower than the melting point of the compound (1,250 C.).

(16) <Step of Incorporating Imide Anions into Mayenite-Type Compound>

(17) In the case of producing the compound of the present invention, a treatment of immersion in liquefied ammonia in a range of 450 to 700 C., more preferably in a range of 450 to 650 C., may be carried out by using a high pressure vessel such as an ammonothermal apparatus. When the temperature in the immersion treatment is 400 C. or lower, imide anions are not incorporated into the mayenite-type compound. When the temperature is higher than 700 C., it is not preferable because the decomposition reaction of the liquefied ammonia occurs.

(18) The concentration of mayenite in the liquefied ammonia is from 0.05 to 50% by weight, preferably from 0.5 to 20% by weight, and more preferably from 1 to 10% by weight with respect to ammonia. When the concentration is less than 0.05% by weight, imide ions are effectively introduced into the cage, however, it is not preferable in terms of efficiency. On the other hand, when the concentration is more than 50% by weight, a long period of time is required to introduce imide ions and thus this case is not preferable. The treatment time may be various and depends on conditions such as treatment temperature and the concentration of mayenite in the liquefied ammonia. The treatment time is not limited as long as the treatment time is 1 minute or longer at a predetermined temperature.

(19) It is considered that imide anions are incorporated in the following procedure. Ammonia reacts with oxygen ions (O.sup.2) or electrons (e) clathrated in the skeleton of the mayenite-type compound as represented by Formula 2 or 3 to provide amide anions. Further, the amide anions react with oxygen ions (O.sup.2) or electrons (e) clathrated in the skeleton as represented by Formulae 4 and 5 to provide imide anions and then the oxygen ions (O.sup.2) or the electrons (e) are substituted with the imide anions. It is considered that a reaction for generating imide anions of Formulae 4 and 5 can be conducted because the reaction pressure is about 500 times higher than in a conventional gas phase ammonia treatment.
NH.sub.3+O.sup.2.sub.cage.fwdarw.NH.sub.2.sup..sub.cage+OH.sup..sub.cage(3)
NH.sub.3+e.sub.cage.fwdarw.NH.sub.2.sup..sub.cage+H.sup..sub.cage(3)
NH.sub.2.sup..sub.cage+O.sup.2.sub.cage.fwdarw.NH.sup.2.sub.cage+OH.sup..sub.cage(4)
NH.sub.2.sup..sub.cage+2e.sub.cage.fwdarw.NH.sup.2.sub.cage+H.sup..sub.cage(5)

(20) Although nano-clathration with nanoporous materials such as organometallic complexes, supermolecules, and zeolite is effective in stabilizing or storing an unstable chemical species, a specific method of stably clathrating an imide compound has not been known. Clathration of active imide anions with a mayenite compound has been succeeded for the first time at this time. This means that an active N1 chemical species (a nitride organic reaction reagent having a CN bond forming capacity) is successfully stored.

(21) The mayenite-type compound of the present invention into which imide anions are incorporated can be applied to, for example, synthesis of primary amines formed by hydroamination of olefins having an unsaturated bond, or the like. Typically, in the reaction of halogenated alkyl and ammonia, the nucleophilicity of the produced amine is high and alkylation proceeds sequentially so that primary amines cannot be obtained. In contrast, since imide anions can conduct a selective reaction to a nucleophile portion, such as double bond, it is possible to realize a selective reaction.

(22) In addition, conventional materials do not have a property of releasing ammonia at a high temperature. This means that the compound can be used for a reductive reaction at a high temperature and can function as, for example, a promoter of a catalytic reaction such as NOx reduction.

(23) Hereinafter, the present invention will be described in detail based on examples. FIG. 2 shows a schematic view of an ammonothermal apparatus used in the test. The apparatus is configured to include a turbo molecule pump 1, an ammonia cylinder 2, a reactor 3, and an exhaust port. In addition, in order to adjust a gas flow rate or operate the apparatus safely, a mass flow controller 4, a stop valve 5, and a safety valve 6 are also used. An operation for an ammonothermal treatment is carried out after exhausting the air in the system and then sealing a predetermined amount of ammonia.

Example 1

(24) <Preparation of C12A7 Compound Including Oxygen Ions>

(25) Powders of CaCO.sub.3 and Al.sub.2O.sub.3 were mixed each other such that a ratio between Ca and Al.sub.2 is 12:7, and the mixture was heated in an alumina crucible at 1,300 C. for 6 hours. The obtained powder (referred to as C12A7:O) was pulverized with an alumina mortar.

(26) <Preparation of C12A7 Compound Including Conduction Electrons>

(27) After the obtained C12A7:O was further heated at 1,350 C. for 24 hours, the powder was inserted into a silica glass tube and heated with an equal amount of a metal Ti powder in vacuum of 110.sup.4 Pa at 1,100 C. for 24 hours. After the reaction, TiOx adhering to the surface was removed in a mechanical manner. The concentration of conduction electrons of the obtained C12A7:e was about 1.110.sup.21 cm.sup.3.

(28) <Method of Determining Content of Nitrogen Anions>

(29) The amount of nitrogen anions in the sample was measured by ion chromatography or temperature programmed desorption gas analysis according to NON-PATENT DOCUMENTs 10 and 11. The concentration of NH.sup.2 and the weight percentage of NH can be easily calculated from a chemical formula [Ca.sub.24Al.sub.28O.sub.64].sup.4+.xNH.sup.2 (x=0 to 2), when x=2, the concentration of NH.sup.2 contained is 1.1410.sup.21 cm.sup.3, and the weight percentage of NH is 1.08% by weight. [NON-PATENT DOCUMENT 10]: F. Hayashi, K. Ishizu, M. Iwamoto, Journal of American Ceramic Society, 93, 104-110 (2010). [NON-PATENT DOCUMENT 11]: F. Hayashi, Y Toda, Y Kanie, M. Kitano, Y Inoue, T. Yokoyama, M. Hara, H. Hosono, Chemical Science, 4, 3124-3130 (2013).

(30) In the former case, 5 to 30 mg of the sample was dissolved in hydrochloric acid or hydrofluoric acid, and the produced ammonium ions were analyzed with an electrical conductivity detector (CDD-10A)-mounted ion chromatography, manufactured by Shimadzu Corporation. The detection limit is 0.001% by weight and this value corresponds to a nitrogen anion concentration of 0.0110.sup.20 cm.sup.3. In addition, in the latter case, 0.5 to 10 mg of the sample was put into a TDS 1200 apparatus manufactured by ESCO, Ltd., and a temperature rising analysis for desorption gas was carried out at a temperature rising rate of 12 C./min. The result is shown in FIG. 1. The detection limit is 0.0001% by weight and this value corresponds to a nitrogen anion concentration of 0.00110.sup.20 cm.sup.3.

(31) <Liquefied Ammonia Treatment>

(32) 200 mg of C12A7:e and about 5 g of liquid NH.sub.3 were placed in a hastelloy autoclave (10 ml, manufactured by Autoclave Engineering Ltd.) and were allowed to react under the conditions of 500 C. and 45 MPa for 3 hours. Here, the pressure value significantly changes depending on the amount of NH.sub.3 to be sealed and the dead volume of the apparatus. As long as the sample is immersed in supercritical NH.sub.3, the reaction is not significantly affected by the pressure value. Hereinafter, the same will be applied to Examples 2 to 4 and Comparative Examples 1 to 4. In Table 1, the analysis result is shown. The weight percentage of NH.sup.2 was 0.021% by weight and the concentration of NH.sup.2 was 0.2210.sup.20 cm.sup.3.

Example 2

(33) A mayenite-type compound containing imide anions was prepared in the same manner as in Example 1 except that the reaction temperature was set to 600 C. and the reaction pressure was set to 55 MPa. The analysis result is shown in Table 1. The weight percentage of NH.sup.2 was 0.239% by weight and the concentration of NH.sup.2 was 2.5310.sup.20 cm.sup.3.

Example 3

(34) A mayenite-type compound containing imide anions was prepared in the same manner as in Example 1 except that the reaction temperature was set to 450 C. and the reaction pressure was set to 40 MPa. The analysis result is shown in Table 1. The weight percentage of NH.sup.2 was 0.010% by weight and the concentration of NH.sup.2 was 0.1110.sup.20 cm.sup.3.

Example 4

(35) A mayenite-type compound containing imide anions was prepared in the same manner as in Example 2 except that C12A7:O was used as a starting material. The analysis result is shown in Table 1. The weight percentage of NH.sup.2 was 0.256% by weight and the concentration of NH.sup.2 was 2.7110.sup.20 cm.sup.3.

Comparative Example 1

(36) A mayenite-type compound containing imide anions was prepared in the same manner as in Example 1 except that the reaction temperature was set to 400 C. and the reaction pressure was set to 35 MPa. The analysis result is shown in Table 1. The nitrogen species introduced was not detected at all.

Comparative Example 2

(37) A mayenite-type compound containing imide anions was prepared in the same manner as in Example 2 except that CaO was used instead of the C12A7:e powder. The analysis result is shown in Table 1. At this time, the nitrogen species introduced was not detected as in Comparative Example 1.

Comparative Example 3

(38) A mayenite-type compound containing imide anions was prepared in the same manner as in Example 2 except that Al.sub.2O.sub.3 was used instead of the C12A7:e powder. The analysis result is shown in Table 1. The nitrogen species contained was not detected as in Comparative Examples 1 and 2.

Comparative Example 4

(39) A mayenite-type compound containing imide anions was prepared in the same manner as in Example 2 except that CaO.Al.sub.2O.sub.3 was used instead of the C12A7:e powder. The analysis result is shown in Table 1. The nitrogen species contained was not detected as in Comparative Examples 1 to 3.

(40) TABLE-US-00001 TABLE 1 NH.sup.2 Weight Percentage/ Concentration/ Matrix Temperature/ C. Pressure/MPa wt % 10.sup.20 cm.sup.3 Example 1 C12A7: e 500 45 0.021 0.22 Example 2 C12A7: e 600 55 0.239 2.53 Example 3 C12A7: e 450 40 0.010 0.11 Example 4 C12A7: O 600 55 0.256 2.71 Comparative C12A7: e 400 35 0.000 0 Example 1 Comparative CaO 600 55 0.000 0 Example 2 Comparative Al.sub.2O.sub.3 600 55 0.000 0 Example 3 Comparative CaOAl.sub.2O.sub.3 600 55 0.000 0 Example 4

(41) FIG. 3 shows Raman spectra of the samples after liquefied ammonia treatment obtained in Examples 2 and 4 and Comparative Examples 1, 3, and 4. Regarding the samples obtained in Examples 2 and 3, one sharp signal belonging to NH.sup.2 ions was observed at 3,210 cm.sup.1. However, regarding the samples obtained in Comparative Examples 1, 3, and 4, NH.sup.2-derived signal was not observed. That is, it was confirmed that only the compound having a mayenite structure contains NH.sup.2.

(42) FIG. 4 shows .sup.1H MAS NMR spectra of the sample obtained in Example 4. In the preparation of the sample, .sup.15NH.sub.3 was used instead of .sup.14NH.sub.3. Regarding the sample of C12A7:O before reaction, a signal having a weak intensity near 0.7 ppm and belonging to OH.sup. by NON-PATENT DOCUMENT 12 was observed. When an ammonia treatment was carried out, the OH.sup.-derived signal intensity was increased and a new signal was observed at +5.2 ppm and 1.5 ppm. The former and the latter belong to H.sup. and NH.sup.2, respectively.

(43) [NON-PATENT DOCUMENT 12]: K. Hayashi, Journal of Solid State Chemistry, 184, 1428-1432 (2011)

(44) [Evaluation Test 1]

(45) In order to evaluate stability in the atmosphere, the sample obtained in Example 4 was used and left to stand at room temperature in the atmosphere for 40 days. After 40 days, the concentration of NH.sup.2 in the sample was 2.6510.sup.20 cm.sup.3.

(46) [Evaluation Test 2]

(47) In order to evaluate stability in a protonic polar solvent, the sample obtained in Example 4 was dispersed in a methanol (MeOH) solvent, and the dispersion was stirred for 10 minutes and then left to stand at room temperature for 10 minutes. The concentration of NH.sup.2 in the sample which had been treated with the MeOH solvent was 2.6010.sup.20 cm.sup.3.

(48) [Evaluation Test 3]

(49) In order to evaluate stability in a non-protonic polar organic solvent, the sample obtained in Example 4 was dispersed in tetrahydrofuran (THF), and the dispersion was stirred for 10 minutes and then left to stand at room temperature for 10 minutes. The concentration of NH.sup.2 in the sample which had been treated with the THF solvent was 2.6310.sup.20 cm.sup.3.

(50) In Table 2, the weight percentages and the concentrations of NH.sup.2 contained in the samples before treatment and after treatment were summarized. The concentrations of NH.sup.2 before treatment was 2.7110.sup.20 cm.sup.3 as shown in Example 4. On the other hand, as shown in Evaluation Tests 1 to 3, the concentrations of NH.sup.2 after treatment were 2.60 to 2.6510.sup.20 cm.sup.3. The reduction amounts before and after treatment were as low as about 4 to 8%, and the samples were stable in the atmosphere or in the organic solvent.

(51) TABLE-US-00002 TABLE 2 NH.sup.2 Temper- Weight ature/ Percentage/ Concentration/ Atmosphere Time C. wt % 10.sup.20 cm.sup.3 Evaluation Atmosphere 40 25 0.250 2.65 Test 1 Days Evaluation MeOH 10 25 0.246 2.60 Test 2 Minutes Evaluation THF 10 25 0.248 2.63 Test 3 Minutes

(52) FIG. 5 shows Raman spectra of the samples after Evaluation Tests 1 to 3 are carried out and the spectra were compared with the spectrum of the sample before treatment (Example 4). It was confirmed from the Raman spectra measurement that the shapes or the intensities of the NH.sup.2-derived signal rarely change before and after treatment, and the imide anions in the cage can be stably present in the atmosphere or in the organic solvent.

INDUSTRIAL APPLICABILITY

(53) The present invention makes it possible to incorporate active imide anions in a solid. It is assumed that the clathrated imide anions have high nucleophilicity due to the chemical structure thereof. The mayenite-type compound containing imide anions is stable at about 500 C. in the temperature programmed desorption analysis and thus the compound is expected to be able to be used as an organic reaction reagent for forming a CN bond which is important in organic synthetic chemistry. In addition, the nitrogen species contained can be released in the form of ammonia at 500 C. or higher (FIG. 1).