WO2020009166A1 - ポリオキソメタレート化合物及びその製造方法、ポリオキソメタレート化合物の焼成体、並びに、反応触媒 - Google Patents
ポリオキソメタレート化合物及びその製造方法、ポリオキソメタレート化合物の焼成体、並びに、反応触媒 Download PDFInfo
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- WO2020009166A1 WO2020009166A1 PCT/JP2019/026522 JP2019026522W WO2020009166A1 WO 2020009166 A1 WO2020009166 A1 WO 2020009166A1 JP 2019026522 W JP2019026522 W JP 2019026522W WO 2020009166 A1 WO2020009166 A1 WO 2020009166A1
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- polyoxometalate
- substituted
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- 239000013460 polyoxometalate Substances 0.000 title claims abstract description 183
- 150000001875 compounds Chemical class 0.000 title claims abstract description 96
- 239000007809 chemical reaction catalyst Substances 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 161
- 239000002184 metal Substances 0.000 claims abstract description 161
- 125000004429 atom Chemical group 0.000 claims abstract description 131
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 122
- 239000013110 organic ligand Substances 0.000 claims abstract description 69
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 230000007547 defect Effects 0.000 claims abstract description 42
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 23
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 23
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 150000004696 coordination complex Chemical class 0.000 claims description 20
- 230000002950 deficient Effects 0.000 claims description 20
- 238000006467 substitution reaction Methods 0.000 claims description 17
- 150000003624 transition metals Chemical group 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 150000003973 alkyl amines Chemical class 0.000 claims description 9
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000011941 photocatalyst Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 53
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000002244 precipitate Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 18
- 239000012528 membrane Substances 0.000 description 15
- 238000000921 elemental analysis Methods 0.000 description 14
- 125000005842 heteroatom Chemical group 0.000 description 12
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 6
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 6
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- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
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- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- -1 Cs + Chemical class 0.000 description 3
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000009102 absorption Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004455 differential thermal analysis Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052732 germanium Chemical group 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000004294 195Pt NMR spectroscopy Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- DQLATGHUWYMOKM-UHFFFAOYSA-L cisplatin Chemical compound N[Pt](N)(Cl)Cl DQLATGHUWYMOKM-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
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- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
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- Y02E60/30—Hydrogen technology
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Definitions
- the present invention relates to a polyoxometalate compound and a method for producing the same, a fired body of the polyoxometalate compound, and a reaction catalyst.
- Polyoxometalate compounds are metal oxides containing polyoxometalate ions composed of a number of basic units such as tetrahedrons formed by coordination bonding of oxygen atoms to metal atoms.
- a metal-substituted polyoxometalate compound having various functions given by deleting a part of the basic unit of a polyoxometalate ion containing a hetero atom and introducing various substitution structures into the generated defect sites. can be obtained.
- a platinum-coordinated polyoxometalate containing a phosphorus atom as a hetero atom and introducing a chemical species containing divalent platinum (Pt (II)) into a defect site generates hydrogen from water by irradiation with visible light. It has been reported that it functions as a photosensitizer and a cocatalyst in the photoreaction to be carried out (Non-Patent Document 1).
- a reaction catalyst used for various chemical reactions such as a photocatalyst for generating hydrogen from water by irradiation with visible light preferably has high catalytic activity.
- One aspect of the present invention relates to a metal-substituted polyoxometalate and a polyoxometalate compound having a counter ion thereof. Another aspect of the present invention relates to a method for producing a polyoxometalate compound.
- a method according to one aspect of the present invention provides a method for preparing a polyoxometalate and a metal complex in a reaction solution containing a polyoxometalate having one or more defect sites and a metal complex having a central metal and an organic ligand. To produce a metal-substituted polyoxometalate.
- the metal-substituted polyoxometalate has a polyoxometalate having one or more defect sites, a substituted metal atom introduced into the defective site, and an organic ligand coordinated to the substituted metal atom.
- the substituted metal atom is divalent platinum or palladium.
- the organic ligand may be a bidentate ligand having an aliphatic heterocycle containing two nitrogen atoms coordinated to a substituted metal atom.
- one substitution metal atom is introduced into each of one or more defect sites.
- the organic ligand may be two ammonia, two alkylamines having 1 to 3 carbon atoms, or one ethylenediamine coordinated to one central metal or one substituted metal atom. Good.
- the metal-substituted polyoxometalate may be generated in a reaction solution at 25 ° C. or lower.
- the metal-substituted polyoxometalate includes a polyoxometalate having one or more defect sites, a first substituted metal atom introduced into the defect site, A first organic ligand coordinated to one substituted metal atom, a second substituted metal atom introduced to the defect site, and a second organic coordinate coordinated to the second substituted metal atom With child.
- the first substituted metal atom is a divalent platinum atom and the second substituted metal atom is divalent palladium, or the first substituted metal atom is divalent palladium and the second substituted metal atom is It is divalent platinum.
- One first substitution metal atom and one second substitution metal atom are introduced into each of the one or more defect sites.
- Such a binuclear polyoxometalate compound includes, for example, a metal-substituted polyoxometalate having a first substituted metal atom and a mononuclear polyoxometalate compound having a counter ion thereof, and a central metal.
- a mononuclear polyoxometalate compound and a metal complex in a reaction solution containing a metal complex having a first substituted metal atom and a second substituted metal atom that is a central metal It can be produced by a method including a step of producing a binuclear polyoxometalate compound.
- reaction catalyst containing any of the above-described polyoxometalate compounds.
- This reaction catalyst can exhibit high catalytic activity, for example, as a photocatalyst for generating hydrogen from water, a hydrogenation reaction catalyst, an exhaust gas purification catalyst, or an electrode catalyst for a fuel cell.
- a polyoxometalate compound having high activity as a reaction catalyst used for a chemical reaction such as a photocatalyst for generating hydrogen from water and a fired body thereof are provided.
- the reaction catalyst according to the present invention is also excellent in that high catalytic activity can be maintained at a high temperature for a long period of time.
- FIG. 3 is a schematic diagram showing one embodiment of a substituted metal atom introduced into a defect site of polyoxometalate and an organic ligand coordinated with the substituted metal atom. It is a schematic diagram which shows one Embodiment of a binuclear type polyoxometallate compound. It is a 31 P NMR spectrum of Cs-P-1Pt-NH 3 . It is a graph showing the relationship between the ratio and the reaction time of Cs-P-1Pt-NH 3 .
- TMA-P-1Pt-ppz It is an infrared absorption spectrum of TMA-P-1Pt-ppz and K 7 [PW 11 O 39 ] ⁇ 13H 2 O. It is a 31 P NMR spectrum of TMA-P-1Pt-ppz. It is a 31 P NMR spectrum of Cs-P-1Pt-NH 3 and TMA-P-1Pt-ppz after standing at 50 ⁇ 2 ° C. for 24 hours. It is a 31 P NMR spectrum of TMA-P-1Pt (NH 3 ) -1Pd (bpy). It is a graph which shows the relationship between the catalyst rotation speed of the fired body of a polyoxometalate compound, and light irradiation time.
- the polyoxometalate compound according to one embodiment has a metal-substituted polyoxometalate and a counter ion thereof.
- the counterion is generally a cation because the metal-substituted polyoxometalate is an anion.
- the counter ion is not particularly limited, but is, for example, a metal cation such as Cs + , K + , Na + and Li + , an alkylammonium such as ammonium and tetramethylammonium, a proton (H + ), or a combination thereof. There may be.
- the metal-substituted polyoxometalate has a polyoxometalate having a defective site, a substituted metal atom introduced into the defective site, and an organic ligand coordinated to the substituted metal atom.
- the substituted metal atom is usually divalent platinum (Pt (II)) or palladium (Pd (II)).
- Polyoxometalate is generally an anion formed by condensing oxo acid of a transition metal atom, and may contain a hetero atom which is an element different from the transition metal atom.
- the polyoxometalate containing a hetero atom includes, for example, a hetero atom, a plurality of transition metal atoms, and a plurality of oxygen atoms bonded to the hetero atom or the transition metal atom.
- a plurality of transition metal atoms are bonded to a hetero atom via an oxygen atom.
- the number of heteroatoms contained in one molecule of the polyoxometalate compound is usually one.
- the polyoxometalate compound may form a hydrate.
- the polyoxometalate can be, for example, a Keggin type, a Dawson type, an Anderson type, or a Waugh type. In this embodiment, the polyoxometalate is most typical. It is a Keggin type.
- a metal-substituted polyoxometalate having a Keggin-type polyoxometalate having one defect site is represented by, for example, the following formula (1): [XM 11 O 39 ⁇ M 1 (L 1 ) p ⁇ ] n -... (1) Can be represented by In the formula, X represents a hetero atom, M represents a transition metal atom, M 1 represents a substituted metal atom, and L 1 represents an organic ligand coordinated to the substituted metal atom M 1 .
- n represents an integer of 1 to 10.
- M is a tungsten atom (W)
- n is usually 3, 4 or 5.
- n is 5 when X is a phosphorus atom
- n is 6 when X is a silicon atom or a germanium atom
- n is 7 when X is a boron atom or an aluminum atom.
- p is 1 or 2, and corresponds to the number of organic ligands L 1 coordinated to one substituted metal atom M 1 .
- p is 2
- p is 1
- the bidentate ligand herein is used as a term including a chelate ligand.
- the hetero atom can be selected from, for example, a phosphorus atom (P), a silicon atom (Si), a germanium atom (Ge), an aluminum atom (Al), and a boron atom (B).
- P phosphorus atom
- Si silicon atom
- Ge germanium atom
- Al aluminum atom
- B boron atom
- transition metal atom examples include a tungsten atom (W) and a molybdenum atom (Mo).
- W tungsten atom
- Mo molybdenum atom
- the transition metal atom is a tungsten atom
- the polyoxometalate compound and its calcined product tend to easily exhibit higher photocatalytic activity as a reaction catalyst.
- FIG. 1 is a schematic diagram showing one embodiment of a metal-substituted polyoxometalate constituting a polyoxometalate compound.
- Substituted metal atom M 1 is a bivalent platinum or palladium.
- the polyoxometalate 3 has one basic unit 3A formed by a hetero atom and an oxygen atom, and 11 basic units 3B formed around a basic unit 3A and formed by a transition metal atom and an oxygen atom. And a Keggin-type polyoxometalate having one defective site 10.
- the basic unit 3A is an oxide represented by XO 4 (X represents a hetero atom), and has a tetrahedral structure.
- the basic unit 3B is a metal oxide represented by MO 6 (M represents a transition metal atom), and has an octahedral structure.
- Organic ligand L 1 may be a bidentate ligand having an aliphatic heterocycle containing two nitrogen atoms coordinated to one substituted metal atom M 1 .
- An aliphatic heterocyclic ring of the bidentate ligand as the organic ligand L 1 has two nitrogen atoms and two or three carbon atoms continuously arranged between the two nitrogen atoms. And an atom may be included as an atom constituting the ring.
- Examples of such an organic ligand having an aliphatic hetero ring include a compound represented by the following formula (L1), (L2), (L3) or (L4).
- R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (eg, a methyl group).
- FIG. 2 is a schematic diagram showing an embodiment of a substituted metal atom introduced into a defective site of polyoxometalate and an organic ligand coordinated with the substituted metal atom.
- FIG. 2 shows an example of a structure estimated when the transition metal atom of polyoxometalate is tungsten, the substituted metal atom is platinum, and the organic ligand is N, N'-dimethylpiperazine. Is not limited to this.
- one platinum atom as a substitution metal atom is bonded to an oxygen atom of the basic unit 3B adjacent to the defect site.
- Two nitrogen atoms in N, N'-dimethylpiperazine as an organic ligand are coordinate-bonded to one platinum atom. Since the organic ligand has a bulky aliphatic heterocycle, it is difficult to introduce the second substituted metal atom into the defect site, which is considered to contribute to the improvement of the thermal stability of the polyoxometalate compound. .
- the organic ligand L 1 may be two ammonia (NH 3 ), two alkylamines having 1 to 3 carbon atoms, or one ethylenediamine.
- the alkylamine having 1 to 3 carbon atoms may be, for example, methylamine, ethylamine or n-propylamine.
- the organic ligand is a relatively non-bulk compound such as these, for example, by controlling the reaction temperature for producing a metal-substituted polyoxometalate as described below, decomposition, or to the defect site By suppressing the introduction of the second substituted metal atom, a mononuclear metal-substituted polyoxometalate can be obtained with a high yield.
- the organic ligand further introduces a second substituted metal atom into the deficient site of the mononuclear metal-substituted polyoxometalate, which is a compound of these compounds, whereby two deficient sites are introduced into one deficient site.
- a polyoxometalate compound having a metal-substituted polyoxometalate into which a substituted metal atom has been introduced can be easily obtained.
- Such a metal-substituted polyoxometalate in which two substitution metal atoms are introduced into one defect site and a polyoxometalate compound having the same are referred to herein as “binuclear”. There is that.
- the binuclear metal-substituted polyoxometalate is, for example, represented by the formula (2): [XM 11 O 39 ⁇ M 1 (L 1 ) p ⁇ ⁇ M 2 (L 2 ) q ⁇ ] n -... (2) It is represented by In the formula (2), X, M and p are defined as in the formula (1). When X is a phosphorus atom, n is 3, when X is a silicon atom or a germanium atom, n is 4, and when X is a boron atom or an aluminum atom, n is 5.
- M 1 and L 1 are a first substituted metal atom and a first organic ligand, respectively.
- M 2 represents a second substituted metal atom
- L 2 represents a second organic ligand
- q is 1 or 2.
- q is 2
- q is 1
- the bidentate ligand here is also used as a term including a chelate ligand.
- FIG. 3 is a schematic diagram showing one embodiment of the metal-substituted polyoxometalate constituting the binuclear polyoxometalate compound.
- Metal-substituted polyoxometalate 22 shown in FIG. 3 one of polyoxometalates 3 with defects sites 10, first-substituted metal atom M 1 and the first substituted metal atom introduced into the defect site 10 A first organic ligand L 1 coordinated to M 1 , and a second organic ligand L 2 coordinated to a second substituted atom M 2 and a second substituted metal atom M 2 introduced into the defect site 10. and a ligand L 2.
- the polyoxometalate 3 of the metal-substituted polyoxometalate 22 has the same configuration as the polyoxometallate 3 in FIG.
- the second replacement metal atom M 2 is the divalent palladium.
- first substituted metal atom M 1 is a bivalent palladium
- second substituted metal atom M 2 is platinum.
- the first organic ligand L 1 in FIG. 3 may be the same compound with an organic ligand L 1 in FIG. 1.
- the first organic ligand L 1 is two ammonia (NH 3 ), two alkylamines having 1 to 3 carbon atoms, or one ethylenediamine
- the second substituted metal atom M 2 is particularly Can be easily introduced.
- the second organic ligand L 2 may be a compound similar to the first organic ligand L 1 , or another compound capable of coordinating with the second substituted metal atom M 2 . It may be any monodentate or bidentate ligand.
- the second organic ligand L 2 may be two ammonia (NH 3 ), two alkylamines having 1 to 3 carbon atoms, or one ethylenediamine, or 2,2′- It may be a nitrogen-containing heteroaromatic compound such as bipyridine.
- Polyoxometallate can have more than one missing site.
- the polyoxometalate has two or more defect sites, one defect metal atom or two different substitution metal atoms (a first substitution metal atom and a second substitution metal atom) are present at each defect site. be introduced.
- the polyoxometalate may have two or three defect sites.
- Mononuclear polyoxometalate compound for example, in a reaction solution containing a polyoxometalate having one or more defect sites and a metal complex having a central metal and an organic ligand, polyoxometalate and It can be produced by a method including a step of producing a metal-substituted polyoxometalate by reacting with a metal complex.
- the counter ion of the metal-substituted polyoxometalate can be introduced by adding a compound (salt) containing the counter ion to the reaction solution after the completion of the reaction.
- the reaction solution usually further contains water as a reaction solvent.
- the temperature of the reaction solution may be 25 ° C. or lower, or 23 ° C. or lower. This makes it possible to obtain a mononuclear metal-substituted polyoxometalate in high yield while suppressing the production of a binuclear metal-substituted polyoxometalate into which two substituted metal atoms have been introduced. .
- the lower limit of the temperature of the reaction solution may be 10 ° C. or higher, 15 ° C. or higher, or 18 ° C. or higher to maintain an appropriate reaction rate.
- the temperature of the reaction solution may be kept constant or may fluctuate.
- the reaction time can be adjusted so that the ratio of the desired mononuclear metal-substituted polyoxometalate is increased.
- the reaction time may be 25 to 30 hours.
- the temperature of the reaction solution may be 5 to 90 ° C.
- the reaction time may be 0.5 to 90 ° C. It may be up to 24 hours.
- Polyoxometalate having a defective site for introducing a substituted metal atom can be synthesized by a usual method.
- a metal complex used for synthesizing a mononuclear polyoxometalate compound has a central metal serving as a substituted metal atom and an organic ligand coordinated to the central metal.
- the central metal is divalent platinum or palladium, and the organic ligand is as described above.
- the metal complex may be, for example, a complex represented by the formula: M 1 Cl 2 (L 1 ) p .
- M 1 , L 1 and p are defined in the same manner as in the equation (1).
- Examples of metal complexes having two ammonias, two alkylamines having 1 to 3 carbon atoms, or one ethylenediamine as an organic ligand include cis-Pt II (NH 3 ) 2 Cl 2. .
- the binuclear polyoxometalate compound is, for example, a mononuclear polyoxometalate having a first substituted metal atom and a first organic ligand and a metal-substituted polyoxometalate having the first organic ligand by the same method as described above. And a step of obtaining a polyoxometalate compound of the above, in a reaction solution containing a mononuclear polyoxometalate compound and a metal complex having a central metal, a mononuclear polyoxometalate compound and a metal complex Reacting to produce a binuclear polyoxometalate compound having a first substituted metal atom and a second substituted metal atom.
- the counter ion of the binuclear metal-substituted polyoxometalate can be introduced by adding a compound (salt) containing the counter ion to the reaction solution after the completion of the reaction.
- the reaction solution usually further contains water as a reaction solvent.
- a metal complex used for synthesizing a binuclear polyoxometalate compound has a central metal serving as a second substituted metal atom and a second organic ligand coordinated to the central metal.
- the central metal is selected from platinum and palladium different from the first substituted metal atom.
- the metal complex may be, for example, a complex represented by the formula: M 2 Cl 2 (L 2 ) q .
- M 2 , L 2 and q are defined in the same manner as in the formula (2).
- Examples of metal complexes include Pd II (bpy) Cl 2 .
- the temperature and reaction time of the reaction solution for introducing the second substituted metal atom may be adjusted depending on the reactivity of a metal complex having the second substituted metal atom as a central metal. Usually, the temperature of the reaction solution is adjusted to 5 to 90 ° C., and the reaction time is adjusted to 1 second to 10 minutes.
- ⁇ Fired body of polyoxometalate compound By firing the polyoxometalate compound according to the above embodiment, a fired body is obtained.
- the firing of the polyoxometalate compound may be performed in an air atmosphere or an inert gas atmosphere, or may be performed under an atmosphere of atmospheric pressure, reduced pressure, or increased pressure.
- "calcining a polyoxometalate compound” means to heat the polyoxometalate compound to such an extent that some chemical property changes irreversibly. For example, heating a polyoxometalate compound to 200 ° C. or higher usually corresponds to firing the polyoxometalate compound.
- the polyoxometalate compound can be fired so that at least a part of the organic ligand bonded to the substituted metal atom is eliminated.
- the polyoxometalate compound after the elimination of the organic ligand can exhibit higher activity as a reaction catalyst. From such a viewpoint, the polyoxometalate compound may be fired until the organic ligand is substantially not contained.
- the organic ligand can be easily eliminated by heating the polyoxometalate compound to 200 ° C. or higher.
- the heating temperature for firing may be 250 ° C. or higher.
- the upper limit of the heating temperature is not particularly limited, but may be 1000 ° C. or lower, or 550 ° C. or lower.
- the heating time for calcination may be appropriately adjusted so as to increase the catalytic activity of the calcined body, and may be, for example, 1 to 20 hours.
- the fired body usually contains a substituted metal atom, and a transition metal derived from polyoxometalate, the molar ratio of the substituted metal atom in the fired body and the transition metal atom derived from polyoxometalate, polyoxometalate
- the molar ratio of the substituted metal atom to the transition metal atom derived from polyoxometalate in the compound is substantially the same.
- the reaction catalyst according to one embodiment contains the oxometalate compound according to the embodiment described above or a calcined product thereof.
- This reaction catalyst can exhibit high catalytic activity, for example, as a photocatalyst for advancing a photoreaction by irradiation with visible light.
- photocatalyst is used as a term that includes not only a catalyst directly involved in a photoreaction but also a photosensitizer.
- the reaction catalyst according to this embodiment may function as a photocatalyst and a photosensitizer to allow a photoreaction to proceed even when no other photosensitizer is present.
- the reaction catalyst according to the present embodiment can be used, for example, as an oxidation reaction or hydrogenation reaction catalyst, an exhaust gas purification catalyst, or an electrode catalyst for a fuel cell.
- Measurement method 1-1 NMR Spectrum The NMR spectrum of each nuclide was measured using an FT NMR apparatus ECA-600 manufactured by JEOL Ltd. 1-2. Elemental analysis C, H and N were quantified by using a Thermo FA's Flash FA. P, Pt and K were quantified using Optima 2100DV manufactured by PerkinElmer. 1-3. Infrared absorption spectrum The infrared absorption spectrum was measured using Spectrum 100 FTIR manufactured by PerkinElmer. 1-4. Thermogravimetric-differential thermal analysis (TG / DTA) Thermogravimetric-differential thermal analysis was performed using a differential thermal balance Thermo plus EVO2 TG-DTA 81205Z manufactured by Rigaku Corporation.
- TG / DTA Thermogravimetric-differential thermal analysis was performed using a differential thermal balance Thermo plus EVO2 TG-DTA 81205Z manufactured by Rigaku Corporation.
- FIG. 4 is the 31 P NMR spectrum of the product.
- a signal assigned to Cs-P-1Pt-NH 3 was observed at -11.48 ppm, assigned to Cs-P-2Pt-NH 3 at -12.81 ppm and [ ⁇ -PW 11 O 39 ] 7- at -10.67 ppm The observed signal was also slightly observed.
- the abundance ratio of [ ⁇ -PW 11 O 39 ] 7- : Cs-P-1Pt-NH 3 : Cs-P-2Pt-NH 3 determined from the integrated intensity of each signal was 0.06: 1.00: 0.02.
- FIG. 5 is a graph showing the relationship between the ratio of Cs-P-1Pt-NH 3 and the reaction time. In the case of a reaction temperature of 20 ° C., it was confirmed that a mononuclear Cs-P-1Pt-NH 3 can be obtained with a particularly high yield by setting the reaction time to about 25 to 30 hours.
- TG / DTA Thermogravimetric / differential thermal analysis
- FIG. 6 is an infrared absorption spectrum of the product (TMA-P-1Pt-ppz) and K 7 [PW 11 O 39 ] ⁇ 13H 2 O.
- (A) shows TMA-P-1Pt-NH 3
- (b) shows K 7 [PW 11 O 39 ] ⁇ 13H 2 O.
- TMA-P-1Pt-ppz showed absorptions derived from [(CH 3 ) 4 N] + and Me 2 ppz near 1488 cm ⁇ 1 .
- FIG. 7 is a 31 P NMR spectrum of TMA-P-1Pt-ppz. (A) it is measured data in D 2 O, (b) is measured data in DMSO-d 6. The NMR spectrum data containing other nuclides is shown below.
- FIG. 8 is a 31 P NMR spectrum of each polyoxometalate compound after standing at 50 ⁇ 2 ° C. for one day.
- signals of [PW 11 O 39 ] 7- and Cs-P-2Pt-NH 3 appear, and decomposition of Cs-P-1Pt-NH 3 is It was suggested that it had progressed slowly.
- the deposited yellow precipitate was collected with a membrane filter and washed with a small amount of ethanol.
- the obtained crude product (0.3823 g) was dissolved in 90 mL of water at 80 ° C, and the solution was left in a refrigerator at about 5 ° C for 9 days.
- the precipitated yellow precipitate was collected with a membrane filter to obtain 0.2861 g of a product. From the analysis results including the following elemental analysis, it was confirmed that binuclear Cs-Ge-2Pt-bpy was obtained.
- the deposited yellow precipitate was collected with a membrane filter and washed with a small amount of ethanol.
- the obtained crude product (0.3626 g) was dissolved in 90 mL of water at 90 ° C, and the solution was left in a refrigerator at about 5 ° C for 5 days.
- the precipitated yellow crystals were collected with a membrane filter to obtain 0.2248 g of a product. From the analysis results including the following elemental analysis, it was confirmed that binuclear Cs-Ge-2Pt-phen was obtained.
- FIG. 9 is the 31 P NMR spectrum of the product.
- a signal derived from TMA-P-1Pt (NH 3 ) -1Pd (bpy) was observed at -12.14 ppm.
- a signal of [PW 11 O 39 ⁇ Pd (bpy) ⁇ 2 ] 3- was observed at -11.99 ppm, and a signal of [PW 11 O 39 ⁇ Pt (NH 3 ) 2 ⁇ 2 ] 3- was observed at -12.37 ppm.
- the 31 P NMR spectra of the product were measured in dimethyl sulfoxide (DMSO) -d 6.
- DMSO dimethyl sulfoxide
- a signal derived from Cs-P-1Pt (NH 3 ) -1Pd (bpy) was observed at -12.15 ppm, and (PW 11 O 39 (Pd (bpy) 2 ⁇ 2 ] 3- signal was observed.
- the reaction solution was irradiated with light of 440 nm or more in an environment of 25 ° C., and the amount of hydrogen generated by the photocatalytic reaction was quantified.
- the amount of H 2 generated after 1 hour and the catalyst rotation number (TON, 2 ⁇ (H 2 generation amount (mol) / Pt atomic weight (mol))) as an index of the photocatalytic activity were measured.
- the photocatalytic activity of Cs-P-2Pd-bpy, a binuclear palladium synthesized by the method described above, and a commercially available platinum black were similarly evaluated.
- the mononuclear polyoxometalate compounds TMA-P-1Pt-ppz and Cs-P-1Pt-NH 3 are different from the binuclear Cs-P-2Pt-NH 3
- the catalyst rotation speed was significantly higher.
- the binuclear platinum-palladium TMA-P-1Pt (NH 3 ) -1Pd (bpy) exhibited an even more markedly improved catalyst speed.
- Photocatalytic reaction that generates hydrogen from water by mixing 2.0 ⁇ mol of each polyoxometalate compound containing platinum atoms, 2.5 ⁇ mol of eosin Y, 10 mL of water, and 100 mM of triethanolamine (TEA) was prepared.
- the reaction solution was irradiated with light of 400 nm or more in an environment of 25 ° C., and the amount of hydrogen generated by the photocatalytic reaction was quantified.
- the amount of H 2 generated by the reaction for one hour and the number of catalyst rotations (TON, 2 ⁇ (H 2 generation (mol) / Pt atomic weight (mol)) as an index of photocatalytic activity were measured. Show.
- TMA-P-1Pt-ppz which is a mononuclear polyoxometalate compound has a remarkably high catalyst rotation speed as compared with various binuclear polyoxometalate compounds. Indicated.
- the amount of the polyoxometalate fired body was adjusted to an amount corresponding to 0.6 ⁇ mol of platinum atoms shown in Table 3.
- the reaction solution was irradiated with light of 400 nm or more in an environment of 25 ° C., and the amount of hydrogen generated by the photocatalytic reaction was quantified.
- FIG. 10 is a graph showing the relationship between the catalyst rotation speed TON and the light irradiation time.
- Cs-P-1Pt-300 (5h) showed a tendency that the photocatalytic activity was less likely to decrease than Cs-P-2Pt-300 (5h).
- 3 Polyoxometalate, 3A, 3B: Basic unit, 10: Deletion site, 21: Metal-substituted polyoxometalate (mononuclear type), 22: Metal-substituted polyoxometalate (binuclear type), M 1 ... (First) substituted metal atom, M 2 ... Second substituted metal atom, L 1 ... (First) organic ligand, L 2 ... Second organic ligand.
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Abstract
Description
Me2ppz:N,N'-dimethylpiperazine
bpy:2,2'-bipyridine
phen:1,10-phenanthroline
TMA:tetramethylammonium
Cs-P-1Pt-NH3:Cs5[α-PW11O39{cis-PtII(NH3)2}]、又はその水和物
Cs-P-2Pt-NH3:Cs3[α-PW11O39{cis-PtII(NH3)2}2]、又はその水和物
TMA-P-1Pt-ppz:[(CH3)4N]4H[α-PW11O39{cis-PtII(Me2ppz)}]、又はその水和物
TMA-P-1Pt(NH3)-1Pd(bpy):[(CH3)4N]3[α-PW11O39{PtII(NH3)2}{PdII(bpy)}]、又はその水和物
Cs-P-1Pt(NH3)-1Pd(bpy):Cs3[α-PW11O39{PtII(NH3)2}{PdII(bpy)}]、又はその水和物
Cs-P-2Pd-bpy:Cs3[α-PW11O39{PdII(bpy)}2]・10H2O
TMA-Al-2Pt-NH3:[(CH3)4N]4H[α-AlW11O39{cis-PtII(NH3)2}2}]・11H2O
TMA-B-2Pt-NH3:[(CH3)4N]4H[α-BW11O39{cis-PtII(NH3)2}2}]・9H2O
Cs-Ge-2Pt-bpy:Cs4[α-GeW11O39{cis-PtII(bpy)}2]・10H2O
Cs-Ge-2Pt-phen:Cs3.5H0.5[α-GeW11O39{cis-PtII(phen)}2]・3H2O
TMA-P-2Pt-NH3:[(CH3)4N]3[α-PW11O39{cis-PtII(NH3)2}2]・10H2O
TMA-Si-2Pt-NH3:[(CH3)4N]4[α-SiW11O39{cis-PtII(NH3)2}2]・13H2O
TMA-Ge-2Pt-NH3:[(CH3)4N]4[α-GeW11O39{cis-PtII(NH3)2}2]・11H2O
一実施形態に係るポリオキソメタレート化合物は、金属置換ポリオキソメタレート及びその対イオンを有する。
[XM11O39{M1(L1)p}]n- ・・・(1)
で表すことができる。式中、Xはヘテロ原子を示し、Mは遷移金属原子を示し、M1は置換金属原子を示し、L1は置換金属原子M1に配位結合した有機配位子を示す。nは1~10の整数を示す。Mがタングステン原子(W)である場合、nは通常3、4又は5である。例えば、Xがリン原子である場合、nは5であり、nはXがケイ素原子又はゲルマニウム原子である場合、nは6であり、Xがホウ素原子又はアルミニウム原子である場合、nは7である。pは1又は2であり、1個の置換金属原子M1に配位結合した有機配位子L1の数に相当する。一般に、有機配位子L1が単座配位子であるとき、pは2であり、有機配位子Lが二座配位子であるとき、pは1である。ここでの二座配位子は、キレート配位子も含む用語として用いられる。
[XM11O39{M1(L1)p}{{M2(L2)q}]n- ・・・(2)
で表される。式(2)中、X、M及びpは式(1)と同様に定義される。Xがリン原子である場合、nは3であり、Xがケイ素原子又はゲルマニウム原子である場合、nは4であり、Xがホウ素原子又はアルミニウム原子である場合、nは5である。M1及びL1は、それぞれ第1の置換金属原子及び第1の有機配位子であり、これらは単核型の金属置換ポリオキソメタレートでは単に「置換金属原子」及び「有機配位子」と称されていたものである。M2は第2の置換金属原子を示し、L2は第2の有機配位子を示し、qは1又は2である。第2の有機配位子L2が単座配位子であるとき、qは2であり、第2の有機配位子L2が二座配位子であるとき、qは1である。ここでの二座配位子も、キレート配位子を含む用語として用いられる。
単核型のポリオキソメタレート化合物は、例えば1個以上の欠損サイトを有するポリオキソメタレートと中心金属及び有機配位子を有する金属錯体とを含有する反応液中で、ポリオキソメタレートと金属錯体とを反応させて、金属置換ポリオキソメタレートを生成させる工程を含む方法により、製造することができる。金属置換ポリオキソメタレートの対イオンは、反応終了後、対イオンを含む化合物(塩)を反応液に加えることにより、導入することができる。反応液は、通常、反応溶媒としての水を更に含む。
以上の実施形態に係るポリオキソメタレート化合物を焼成することにより、焼成体が得られる。ポリオキソメタレート化合物の焼成は、空気雰囲気又は不活性ガス雰囲気で行ってもよいし、大気圧、減圧、又は加圧の雰囲気下で行ってもよい。本明細書において、「ポリオキソメタレート化合物を焼成する」とは、ポリオキソメタレート化合物を、何らかの化学的な性質が不可逆的に変化する程度に加熱することを意味する。例えば、ポリオキソメタレート化合物を200℃以上に加熱することは、通常、ポリオキソメタレート化合物を焼成することに該当する。
一実施形態に係る反応触媒は、以上説明した実施形態に係るオキソメタレート化合物又はその焼成体を含有する。この反応触媒は、例えば可視光照射により光反応を進行させるための光触媒として、高い触媒活性を発現することができる。本明細書において、「光触媒」は、光反応に直接関与する触媒だけでなく、光増感剤も含む用語として使用される。本実施形態に係る反応触媒は、他の光増感剤が存在しない場合であっても、光触媒及び光増感剤として機能して光反応を進行させることができる場合がある。本実施形態に係る反応触媒は、例えば酸化反応若しくは水素化反応の触媒、排ガス浄化用触媒、又は燃料電池用電極触媒としても用いられ得る。
1-1.NMRスペクトル
各核種のNMRスペクトルは、日本電子株式会社製のFT NMR装置ECA-600を用いて測定した。
1-2.元素分析
C、H及びNは、サーモエレクトロン社製のFlash FAを用いて定量した。P、Pt及びKは、パーキンエルマー社製のOptima 2100DVを用いて定量した。
1-3.赤外吸収スペクトル
赤外吸収スペクトルは、パーキンエルマー社製のSpectrum 100 FTIRを用いて測定した。
1-4.熱重量-示差熱分析(TG/DTA)
株式会社リガク製の示差熱天秤Thermo plus EVO2 TG-DTA 81205Zを用いて熱重量-示差熱分析を行った。
2-1.Cs-P-1Pt-NH3(Cs5[α-PW11O39{cis-PtII(NH3)2}]・6H2O)
<合成>
cis-ジアンミンジクロロ白金(II)(cis-PtII(NH3)2Cl2;0.0604 g; 0.201 mmol; MW: 300.05)を室温で水150 mLに溶解した。そこに、K7[PW11O39]・10H2O(0.3172 g; 0.101 mmol; MW: 3131.031)を室温で水15.0 mLに溶解した溶液を加え、得られた反応液を20±2 ℃の水浴中で27時間攪拌した。反応液を氷浴に移し、攪拌しながら、塩化セシウム(0.7531g; 4.47 mmol; MW: 168.36)を水3 mLに溶解した溶液を加えた。反応液を氷浴中で更に20分間攪拌してから、エタノール540 mLを加え、反応液を10分間攪拌した。生成した沈殿物をメンブレンフィルターで回収した。回収した沈殿物を吸引乾燥し、次いで凍結乾燥して、Cs-P-1Pt-NH3を含む生成物(黄色粉体、収量0.3547g)を得た。
反応温度を20℃、反応時間を15時間、18時間、21時間、24時間、27時間、30時間又は33時間として、上記と同様にcis-PtII(NH3)2Cl2とK7[PW11O39]との反応を行った。生成物の31P NMRを測定し、[α-PW11O39]7-のシグナルに対するCs-P-1Pt-NH3のシグナルの積分強度比をCs-P-1Pt-NH3の比率として求めた。図5は、Cs-P-1Pt-NH3の比率と反応時間との関係を示すグラフである。反応温度20℃の場合、反応時間を25~30時間程度とすることで、特に高い収率で単核体のCs-P-1Pt-NH3が得られることが確認された。
cis-[PtIICl2(Me2ppz)](0.0758 g; 0.2mmol MW : 380.176)を50℃の水35 mLに溶解した。得られた溶液を、K7[PW11O39]・13H2O (0.643 g;0.2 mmol; MW : 3185.08)を室温で水5 mLに溶解した溶液に加えた。得られた反応液を25℃で24時間攪拌した。固体の(CH3)4NBr (1.035g; 9.4 mmol)を加え、反応液を25℃で更に24時間攪拌した。析出した黄色沈殿物をメンブレンフィルターで回収し、エタノールで洗浄した。この時点で、0.437 gの粗生成物が得られた。粗生成物を50℃の水20 mLに溶解し、溶液を冷蔵庫中に一晩静置した。析出した黄色沈殿物をメンブレンフィルターで回収し、回収した沈殿物をエタノールで洗浄して、TMA-P-1Pt-ppzを含む生成物を得た(収量0.1447 g)。下記の元素分析の結果から、単核体のTMA-P-1Pt-ppzがほぼ選択的に得られたことが確認された。
元素分析:
found: C, 7.78; H, 1.89; N, 2.48; P, 0.98; Pt, 5.76; K, <0.1%.
Calculations for [(CH3)4N]4H[PW11O39{Pt(Me2ppz)}]・5H2O = H73C22N6Pt1O44P1W11(MW: 3374.129): C, 7.83; H, 2.18; N, 2.49; P, 0.92; Pt, 5.78; K, 0%.
生成物(TMA-P-1Pt-ppz)の大気囲気下でのTG/DTA分析の結果、92.5℃未満の温度で5分子の水にほぼ相当する2.90%の重量減少が観測された。更に、273.8℃と374.9℃の2つの発熱ピークを伴って13.03%の重量減少が観測され、これは4分子の[(CH3)4N]+と1分子のMe2ppzに相当すると考えられる。
図6は、生成物(TMA-P-1Pt-ppz)及びK7[PW11O39]・13H2Oの赤外吸収スペクトルである。(a)はTMA-P-1Pt-NH3、(b)はK7[PW11O39]・13H2Oを示す。TMA-P-1Pt-ppzは、1488 cm-1付近に[(CH3)4N]+とMe2ppzに由来する吸収を示した。
図7は、TMA-P-1Pt-ppzの31P NMRスペクトルである。(a)はD2O中での測定データで、(b)はDMSO-d6中での測定データである。その他の核種を含むNMRスペクトルデータを以下に示す。
13C NMR (DMSO-d6, 23.4℃) :δ57.7 ([(CH3)4N]+),50.9 and 51.4 (-CH2CH2- groups in Me2ppz),21.7 ((CH3)2ppz)
31P NMR: (D2O, 21.3℃): δ-12.03
31P NMR: (DMSO-d6, 22.6℃): δ-11.75
195Pt NMR (DMSO-d6, 20.7℃): δ-1326
10.5 mgのCs-P-1Pt-NH3、及び4.4 μmolのTMA-P-1Pt-ppzを、それぞれ600 μLのD2Oに溶解させた。得られた溶液を50±2℃の環境下に静置した。図8は、50±2℃で1日静置後の各ポリオキソメタレート化合物の31P NMRスペクトルである。(a)のCs-P-1Pt-NH3の場合、[PW11O39]7-及びCs-P-2Pt-NH3のシグナルが現れており、Cs-P-1Pt-NH3の分解が徐々に進行したことが示唆された。一方、(b)のTMA-P-1Pt-ppzの場合、分解はほとんど認められなかった。TMA-P-1Pt-ppzは、50±2℃で7日間静置後も実質的に分解せず、高い熱安定性を有することが確認された。
3-1.TMA-Al-2Pt-NH3([(CH3)4N]4H[α-AlW11O39{cis-PtII(NH3)2}2}]・11H2O)
cis-PtII(NH3)2Cl2(0.120 g; 0.40 mmol)を水140 mLに溶解して得た溶液に、K9[α-AlW11O39]・13H2O(0.665 g;0.20 mmol)を加えた。得られた反応液を60℃で2時間攪拌すると、黄色沈殿物が析出した。沈殿物をメンブレンフィルターで除去し、濾液に固体の(CH3)4NCl(8.772 g: 80 mmol)を加えた。25℃で3日間の攪拌の後、析出した黄色沈殿物をメンブレンフィルターで回収した。得られた粗生成物(0.347 g)を70℃の水10.4 mLに溶解し、エタノールを用いた25℃での蒸気拡散によって精製した。5日放置後、黄色結晶を、メンブレンフィルターで回収し、エタノール10 mLで洗浄した。この結晶化を2回行い、0.1110 gの黄色単結晶を得た。下記の元素分析を含む分析結果から、二核体のTMA-Al-2Pt-NH3が得られたことが確認された。
元素分析:
found: C, 5.37; H, 2.16; N, 3.07; Al, 0.65; Pt, 10.53; K,<0.1%.
Calculations for [(CH3)4N]4H[AlW11O39{cis-Pt(NH3)2}2]・xH2O (x=11) = C16H83N8Pt2O50Al1W11: C, 5.30; H, 2.31; N, 3.09; Al, 0.74; Pt, 10.76; K, 0%.
K8H[α-BW11O39]・16H2O(0.661 g;0.20 mmol)を水40 mLに溶解させた。この溶液を、cis-PtII(NH3)2Cl2(0.121 g; 0.40 mmol)を水150 mLに溶解して得た溶液に加えた。得られた反応液を25℃で10日間攪拌すると、黄色沈殿物が析出した。沈殿物をメンブレンフィルターで除去し、濾液に固体の(CH3)4NCl(3.52 g: 32.1 mmol)を加え、濾液を氷冷しながら2時間の攪拌した。その後、析出した黄色沈殿物をメンブレンフィルターで回収し、少量のエタノールで洗浄した。得られた粗生成物(0.5458 g)を70℃の水25 mLに溶解し、冷蔵庫中に7~10日放置した。析出した黄色結晶をメンブレンフィルターで回収し、少量のエタノールで洗浄した。この結晶化による精製を2回行い、0.2255 gの生成物の結晶を得た。
下記の元素分析を含む分析結果から、二核体のTMA-Al-2Pt-NH3が得られたことが確認された。
元素分析:
found: C, 5.32; H, 2.02; N, 3.07; B, 0.29; Pt, 10.84; K,<0.1%
Calculations for [(CH3)4N]4H[α-BW11O39{cis-Pt(NH3)2}2]・xH2O (x=9) = C16H79N8Pt2O48B1W11: C, 5.38; H, 2.23; N, 3.13; B, 0.30; Pt, 10.91; K, 0%
K6Na2[α-GeW11O39]・12H2O(0.3286 g;0.10 mmol)を水200 mLに溶解して得た溶液に、cis-PtII(bpy)2Cl2(0.0844 g; 0.20 mmol)を加えた。得られた反応液を90℃で2時間攪拌した後、固体のCsCl(2.08 g; 12 mmol)を反応液に加え、反応液を25℃で1日攪拌した。析出した黄色沈殿物をメンブレンフィルターで回収し、少量のエタノールで洗浄した。得られた粗生成物(0.3823 g)を80℃の水90 mLに溶解し、溶液を約5℃の冷蔵庫中に9日放置した。析出した黄色沈殿物をメンブレンフィルターで回収し、0.2861 gの生成物を得た。下記の元素分析を含む分析結果から、二核体のCs-Ge-2Pt-bpyが得られたことが確認された。
元素分析:
found: C, 5.91; H, 0.56; N, 1.36; Ge, 1.74; Pt, 9.48; Cs, 12.5; K,<0.1; Na,<0.1%
Calculations for Cs4[GeW11O39{Pt(bpy)}2]・xH2O (x=10) = C20H36Cs4N4Pt2O49Ge1W11: C, 5.81; H, 0.88; N, 1.36; Ge, 1.76; Pt, 9.44; Cs, 12.86; K, 0; Na, 0%
K6Na2[α-GeW11O39]・12H2O(0.3290 g;0.10 mmol)を水200 mLに溶解して得た溶液に、cis-PtII(phen)2Cl2(0.0905 g; 0.20 mmol)を加えた。得られた反応液を90℃で8時間攪拌した後、固体のCsCl(2.08 g; 12 mmol)を反応液に加え、反応液を25℃で2日攪拌した。析出した黄色沈殿物をメンブレンフィルターで回収し、少量のエタノールで洗浄した。得られた粗生成物(0.3626 g)を90℃の水90 mLに溶解し、溶液を約5℃の冷蔵庫中に5日放置した。析出した黄色結晶をメンブレンフィルターで回収し、0.2248 gの生成物を得た。下記の元素分析を含む分析結果から、二核体のCs-Ge-2Pt-phenが得られたことが確認された。
元素分析:
found: C, 7.04; H, 0.55; N, 1.35; Ge, 1.75; Pt, 9.53; Cs, 12.0; K,<0.1; Na,<0.1%
Calculations for Cs3.5H0.5[GeW11O39{Pt(phen)}2]・xH2O (x=3) = C24H22.5Cs3.5N4Pt2O42Ge1W11: C, 7.23; H, 0.57; N, 1.40; Ge, 1.82; Pt, 9.78; Cs, 11.66; K, 0; Na, 0%
4-1.TMA-P-1Pt(NH3)-1Pd(bpy)([(CH3)4N]3[α-PW11O39{PtII(NH3)2}{PdII(bpy)}])
0.1826 gのCs-P-1Pt-NH3(MW: 3678.95, 0.050mmol)を蒸留水50 mLに溶解して、淡黄色透明な溶液を得た。この溶液を、0.0163 gのPdII(bpy)Cl2(MW:333.51, 0.049 mmol)を蒸留水50 mLに90℃の湯浴で溶解させて得た淡黄色透明の溶液に、氷浴中で加えた。得られた反応液を3分間攪拌してから、テトラメチルアンモニウムクロリド 3.948 g(MW:109.60, 36 mmol)を加え、白黄色の沈殿物を析出させた。沈殿物をメンブレンフィルターによって回収し、エタノールで洗浄した。洗浄後の沈殿物を吸引乾燥し、続いて凍結乾燥して、TMA-P-1Pt(NH3)-1Pd(bpy)を含む生成物を得た(収量0.0733g)。
元素分析
found:P 0.72%; Pt 5.03%; Pd 3.93%
calculated for [(CH3)4N]3[PW11O39{Pt(NH3)2}{Pd(N2C10H8)}]0.81[PW11O39{Pd(N2C10H8)}2]0.18[PW11O39{Pt(NH3)2}2]0.01・2H2O:P0.90%; Pt 4.72%; Pd 3.63% = C23.7H54.34N7O41P1Pd1.17Pt0.83W11(MW 3433.096)
0.1839 gのCs-P-1Pt-NH3(MW: 3678.95, 0.050mmol)を蒸留水50 mLに溶解して、淡黄色透明な溶液を得た。この溶液を、0.0167 gのPdII(bpy)Cl2(MW:333.51, 0.051 mmol)を蒸留水50 mLに90℃の湯浴で溶解させて得た淡黄色透明の溶液に、氷浴中で加えた。得られた反応液を3分間攪拌してから、塩化セシウム3.800 g(MW:168.36, 22.6 mmol)を加え、白黄色の沈殿物を析出させた。沈殿物をメンブレンフィルターによって回収し、エタノールで洗浄した。洗浄後の沈殿物を吸引乾燥し、続いて凍結乾燥して、Cs-P-1Pt(NH3)-1Pd(bpy)を含む生成物を得た(収量0.1284g)。
5-1.ポリオキソメタレート化合物
試験1
0.2~3.0 μmolの白金原子を含む量の各ポリオキソメタレート化合物、2.5 μmolのエオシンY、2.5 μmolのK5SiW11{Al(OH2)}O39]・7H2O、50 mgのTiO2粒子(anatase:rutile = 80:20)、10 mLの水、及び100 mMのトリエタノールアミン(TEA)を混合して、水から水素を生成する光触媒反応のための反応液を調製した。ポリオキソメタレート化合物の量は、表1に示す0.2~0.6 μmolの白金原子に相当する量に調整した。
反応液に、25 ℃の環境下で、440 nm以上の光を照射し、光触媒反応によって生成した水素の量を定量した。1時間後のH2生成量と、光触媒活性の指標としての触媒回転数(TON、2×(H2生成量(mol)/Pt原子量(mol))を測定した。比較のため、上記と同様の方法で合成したパラジウムの二核体であるCs-P-2Pd-bpy、及び市販のplatinum blackについても、同様に光触媒活性を評価した。
TMA-Al-2Pt-NH3、TMA-B-2Pt-NH3、Cs-Ge-2Pt-bpy、及びCs-Ge-2Pt-phenと、これらと同様の方法で合成したTMA-P-2Pt-NH3([(CH3)4N]3[α-PW11O39{cis-PtII(NH3)2}2]・10H2O)、TMA-Si-2Pt-NH3([(CH3)4N]4[α-SiW11O39{cis-PtII(NH3)2}2]・13H2O)、及びTMA-Ge-2Pt-NH3([(CH3)4N]4[α-GeW11O39{cis-PtII(NH3)2}2]・11H2O)の光触媒活性を以下の手順で評価した。TMA-P-1Pt-ppzの光触媒活性も同様に評価し、2核体の光触媒活性と比較した。
Cs-P-1Pt-NH3、Cs-P-2Pt-NH3及びCs-P-1Pt(NH3)-1Pd(bpy)を、それぞれるつぼ中で加熱することにより焼成して、これらポリオキソメタレート化合物の焼成体を得た。焼成の条件は以下のとおりである。
Cs-P-1Pt-NH3:300℃,5時間
Cs-P-2Pt-NH3:300℃,5時間
Cs-P-1Pt(NH3)-1Pd(bpy):500℃,5時間
以下、それぞれの焼成体を「Cs-P-1Pt-300(5h)」、「Cs-P-2Pt-300(5h)」及び「Cs-P-1Pt(NH3)-1Pd(bpy)-500(5h)」と略記する。
反応液に、25 ℃の環境下で、400 nm以上の光を照射し、光触媒反応によって生成した水素の量を定量した。6時間後のH2生成量と、光触媒活性の指標としての触媒回転数(TON、2×(H2生成量(mol)/Pt原子量(mol))を測定した。比較のため、焼成前の白金二核型ポリオキソメタレート化合物Cs-P-2Pt-NH3および市販のplatinum blackについても、同様に光触媒活性を評価した。各焼成体は非常に高い触媒回転数を示した。
Claims (14)
- 金属置換ポリオキソメタレート及びその対イオンを有するポリオキソメタレート化合物であって、
前記金属置換ポリオキソメタレートが、
1個以上の欠損サイトを有するポリオキソメタレートと、
前記欠損サイトに導入された置換金属原子と、
前記置換金属原子に配位結合した有機配位子と、
を有し、
前記置換金属原子が2価の白金又はパラジウムであり、
前記有機配位子が、前記置換金属原子に配位結合した2個の窒素原子を含む脂肪族ヘテロ環を有する、二座配位子であり、
1個以上の前記欠損サイトのそれぞれに1個の前記置換金属原子が導入されている、
ポリオキソメタレート化合物。 - 1個以上の欠損サイトを有するポリオキソメタレートと中心金属及び有機配位子を有する金属錯体とを含有する反応液中で、前記ポリオキソメタレートと前記金属錯体とを反応させて、金属置換ポリオキソメタレートを生成させる工程を備え、
前記金属置換ポリオキソメタレートが、
前記ポリオキソメタレートと、
前記欠損サイトに導入された前記中心金属である置換金属原子と、
前記置換金属原子に配位結合した前記有機配位子と、
を有し、
前記中心金属及び前記置換金属原子が2価の白金又はパラジウムであり、
前記有機配位子が、1個の前記中心金属又は1個の前記置換金属原子に配位結合した2個の窒素原子を含む脂肪族ヘテロ環を有する、二座配位子であり、
前記金属置換ポリオキソメタレートにおいて、1個以上の前記欠損サイトのそれぞれに1個の前記置換金属原子が導入されている、
請求項1に記載のポリオキソメタレート化合物を製造する方法。 - 前記有機配位子がN,N’-ジメチルピペラジンである、請求項2に記載の方法。
- 金属置換ポリオキソメタレート及びその対イオンを有するポリオキソメタレート化合物であって、
前記金属置換ポリオキソメタレートが、
1個以上の欠損サイトを有するポリオキソメタレートと、
前記欠損サイトに導入された第1の置換金属原子と、
前記第1の置換金属原子に配位結合した第1の有機配位子と、
前記欠損サイトに導入された第2の置換金属原子と、
前記第2の置換金属原子に配位結合した第2の有機配位子と、
を有し、
前記第1の置換金属原子が2価の白金原子で、前記第2の置換金属原子が2価のパラジウムである、又は、前記第1の置換金属原子が2価のパラジウムで、前記第2の置換金属原子が2価の白金であり、
1個以上の前記欠損サイトのそれぞれに1個の前記第1の置換金属原子及び1個の前記第2の置換金属原子が導入されている、
ポリオキソメタレート化合物。 - 第1の置換金属原子を有する金属置換ポリオキソメタレート及びその対イオンを有する単核型のポリオキソメタレート化合物と中心金属を有する金属錯体とを含有する反応液中で、前記単核型のポリオキソメタレート化合物と前記金属錯体とを反応させて、前記第1の置換金属原子、及び前記中心金属である第2の置換金属原子を有する二核型のポリオキソメタレート化合物を生成させる工程を備え、
前記単核型のポリオキソメタレート化合物の金属置換ポリオキソメタレートが、
1個以上の欠損サイトを有するポリオキソメタレートと、
前記欠損サイトに導入された前記第1の置換金属原子と、
前記第1の置換金属原子に配位結合した第1の有機配位子と、
を有し、
前記金属錯体が、
前記中心金属と、
前記中心金属に配位結合した第2の有機配位子と、
を有し、
前記第1の置換金属原子が2価の白金で、前記中心金属及び前記第2の置換金属原子が2価のパラジウムである、又は、前記第1の置換金属原子がパラジウムで、前記中心金属及び前記第2の置換金属原子が2価の白金であり、
前記単核型のポリオキソメタレート化合物において、1個以上の前記欠損サイトのそれぞれに1個の前記第1の置換金属原子が導入されており、
前記二核型のポリオキソメタレート化合物において、1個以上の前記欠損サイトのそれぞれに1個の前記第1の置換金属原子及び1個の前記第2の置換金属原子が導入されている、
請求項4に記載のポリオキソメタレート化合物を製造する方法。 - 前記第1の有機配位子が、1個の前記第1の置換金属原子に配位結合した、2個のアンモニア、2個の炭素数1~3のアルキルアミン、又は1個のエチレンジアミンである、請求項5に記載の方法。
- 1個以上の欠損サイトを有するポリオキソメタレートと中心金属及び有機配位子を有する金属錯体とを含有する反応液中で、前記ポリオキソメタレートと前記金属錯体とを反応させて、金属置換ポリオキソメタレートを生成させる工程を備え、
前記金属置換ポリオキソメタレートが、
前記ポリオキソメタレートと、
前記欠損サイトに導入された前記中心金属である置換金属原子と、
前記置換金属原子に配位結合した前記有機配位子と、
を有し、
前記中心金属及び前記置換金属原子が2価の白金又はパラジウムであり、
前記有機配位子が、1個の前記中心金属又は1個の前記置換金属原子に配位結合した、2個のアンモニア、2個の炭素数1~3のアルキルアミン、又は1個のエチレンジアミンであり、
前記金属置換ポリオキソメタレートにおいて、1個以上の前記欠損サイトのそれぞれに1個の前記置換金属原子が導入されており、
25℃以下の前記反応液中で前記金属置換ポリオキソメタレートを生成させる、
ポリオキソメタレート化合物を製造する方法。 - 金属置換ポリオキソメタレート及びその対イオンを有するポリオキソメタレート化合物を含有する、反応触媒であって、
前記金属置換ポリオキソメタレートが、
1個以上の欠損サイトを有するポリオキソメタレートと、
前記欠損サイトに導入された置換金属原子と、
該置換金属原子に配位結合した有機配位子と、
を有し、
前記置換金属原子が2価の白金又はパラジウムであり、
1個以上の前記欠損サイトのそれぞれに1個の前記置換金属原子が導入されている、
反応触媒。 - 請求項1又は4に記載のポリオキソメタレート化合物を含有する、反応触媒。
- 金属置換ポリオキソメタレート及びその対イオンを有するポリオキソメタレート化合物の焼成体であって、
前記金属置換ポリオキソメタレートが、
1個以上の欠損サイトを有するポリオキソメタレートと、
前記欠損サイトに導入された置換金属原子と、
該置換金属原子に配位結合した有機配位子と、
を有し、
前記置換金属原子が2価の白金又はパラジウムであり、
1個以上の前記欠損サイトのそれぞれに1個の前記置換金属原子が導入されている、
ポリオキソメタレート化合物の焼成体。 - 請求項1又は4に記載のポリオキソメタレート化合物の焼成体。
- 当該焼成体が、前記置換金属原子、及び前記ポリオキソメタレートに由来する遷移金属原子を含み、前記置換金属原子と前記遷移金属原子とのモル比が1:11である、請求項10又は11に記載の焼成体。
- 請求項10~12のいずれか一項に記載のポリオキソメタレート化合物の焼成体を含有する、反応触媒。
- 水から水素を発生させるための光触媒、水素化反応触媒、排ガス浄化用触媒、又は燃料電池用電極触媒である、請求項8、9又は13に記載の反応触媒。
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