WO2022230898A1 - 含窒素化合物の製造方法 - Google Patents
含窒素化合物の製造方法 Download PDFInfo
- Publication number
- WO2022230898A1 WO2022230898A1 PCT/JP2022/018933 JP2022018933W WO2022230898A1 WO 2022230898 A1 WO2022230898 A1 WO 2022230898A1 JP 2022018933 W JP2022018933 W JP 2022018933W WO 2022230898 A1 WO2022230898 A1 WO 2022230898A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nitrogen
- containing compound
- electrode
- reducing agent
- producing
- Prior art date
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- -1 nitrogen-containing compound Chemical class 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 55
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000004913 activation Effects 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 132
- 229910021529 ammonia Inorganic materials 0.000 claims description 66
- 239000003960 organic solvent Substances 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
- 239000011733 molybdenum Substances 0.000 claims description 17
- XQKBFQXWZCFNFF-UHFFFAOYSA-K triiodosamarium Chemical compound I[Sm](I)I XQKBFQXWZCFNFF-UHFFFAOYSA-K 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 7
- KZCDXNZVNRLDFN-UHFFFAOYSA-N chromium(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene Chemical compound [Cr+2].CC=1C(C)=C(C)[C-](C)C=1C.CC=1C(C)=C(C)[C-](C)C=1C KZCDXNZVNRLDFN-UHFFFAOYSA-N 0.000 claims description 5
- NGJVBICXQZVNEF-UHFFFAOYSA-N cobalt(2+);1,2,3,4,5-pentamethylcyclopenta-1,3-diene Chemical compound [Co+2].CC=1C(C)=C(C)[C-](C)C=1C.CC=1C(C)=C(C)[C-](C)C=1C NGJVBICXQZVNEF-UHFFFAOYSA-N 0.000 claims description 5
- ILZSSCVGGYJLOG-UHFFFAOYSA-N cobaltocene Chemical compound [Co+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 ILZSSCVGGYJLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 claims 1
- 150000002830 nitrogen compounds Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 46
- 239000002904 solvent Substances 0.000 description 18
- 239000003446 ligand Substances 0.000 description 17
- 238000006722 reduction reaction Methods 0.000 description 15
- 238000005868 electrolysis reaction Methods 0.000 description 13
- 239000000654 additive Substances 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 10
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- 210000000080 chela (arthropods) Anatomy 0.000 description 9
- 238000003487 electrochemical reaction Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 230000001737 promoting effect Effects 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 150000002751 molybdenum Chemical class 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
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- 150000001298 alcohols Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/16—Hydrazine; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/13—Organo-metallic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
Definitions
- the present invention relates to a method for producing a nitrogen-containing compound.
- Ammonia is an important chemical raw material that is used as a basic material for fertilizers and chemical products.In recent years, its use as a coal-fired power generation co-combustion and energy carrier has also attracted attention. Conventionally, ammonia is produced by the Haber-Bosch process.
- the Haber-Bosch process is a method of producing ammonia by reacting nitrogen gas and hydrogen gas in the presence of an iron-based catalyst.
- the Haber-Bosch method is a method of synthesizing ammonia at high temperature and high pressure, it consumes a large amount of energy and requires a large-sized apparatus made of special materials. Furthermore, there is also the problem that a large amount of carbon dioxide, which is a greenhouse gas, is emitted when hydrogen gas is obtained from natural gas containing methane (CH 4 ) as a main component. Therefore, it is desired to develop a method for producing ammonia from nitrogen and water under mild reaction conditions.
- CH 4 natural gas containing methane
- Patent Documents 1 and 2 and Non-Patent Document 1 disclose a method for producing ammonia from nitrogen and water using a molybdenum complex catalyst. These documents describe that ammonia can be produced at normal temperature and normal pressure.
- the present inventors have studied a method for further improving the amount of ammonia produced by the methods for producing ammonia described in Patent Documents 1 and 2 and Non-Patent Document 1.
- the present invention has been made in view of the above circumstances, and provides a method for producing a nitrogen-containing compound, which improves the production amount of the nitrogen-containing compound.
- the inventors of the present invention have found that a nitrogen-containing compound is synthesized from nitrogen and a proton source, and at the same time, the reducing agent oxidized in the synthesis reaction of the nitrogen-containing compound is reduced by an electrolysis method, thereby improving the production amount of the nitrogen-containing compound. I found out what I can do.
- the present invention includes the following aspects.
- [1] a step of synthesizing a nitrogen-containing compound from nitrogen and a proton source in the presence of a nitrogen-activating catalyst and a reducing agent, and simultaneously reducing the reducing agent oxidized in the synthesis reaction of the nitrogen-containing compound by an electrolysis method;
- a method for producing a nitrogen-containing compound comprising: [2] The method for producing a nitrogen-containing compound according to [1] above, wherein the reducing agent has an oxidation-reduction potential of ⁇ 0.40 V vs SCE or less and contains a compound soluble in an organic solvent.
- FIG. 1 is a schematic diagram showing an example of an electrolytic cell used in the method for producing a nitrogen-containing compound according to the present disclosure.
- FIG. 2 is a diagram showing the results of cyclic voltammetry measurement of samarium iodide.
- a nitrogen-containing compound is synthesized from nitrogen and a proton source in the presence of a nitrogen activation catalyst and a reducing agent, and at the same time, the reducing agent oxidized in the synthesis reaction of the nitrogen-containing compound. is reduced by an electrolytic method.
- “simultaneously” means that the steps are performed in the same system. It is preferred that the time interval between the synthesis of the nitrogen-containing compound and the reduction of the oxidized reducing agent is short.
- synthesis of a nitrogen-containing compound from nitrogen and a proton source is carried out in the presence of a nitrogen-activating catalyst and a reducing agent. Specifically, it is considered to include electron donation from a reducing agent and the production reaction of a nitrogen-containing compound.
- the production reaction of nitrogen-containing compounds proceeds in the presence of a nitrogen-activated catalyst, and is thought to proceed, for example, by a proton-coupled electron transfer (PCET) reaction coupled with electron donation from a reducing agent.
- PCET proton-coupled electron transfer
- the reduction of the oxidized reducing agent by the electrolysis method is considered to proceed as a cathodic reaction of the electrolysis method. Any reaction can be selected for the anodic reaction paired with the cathodic reaction.
- reaction shown in (2) below includes the electron donation from the reducing agent that proceeds in conjunction with the NH 3 formation reaction, that is, the reaction shown in (1) below.
- Electron donation from reducing agent Red ⁇ Ox+e ⁇ (2) NH 3 production reaction N 2 +6Red+6H + ⁇ (Cat) ⁇ 2NH 3 +6Ox (3) Reduction reaction of reducing agent (cathode reaction) Ox + e - ⁇ Red
- Red is a reducing agent
- Ox is an oxidized reducing agent
- Cat is a nitrogen activation catalyst.
- Protons H 2 + in reaction (2) can be supplied from a proton source added in the cathode chamber or from the anode chamber through a diaphragm.
- an electrolysis cell as a nitrogen-containing compound production apparatus
- a molybdenum complex hereinafter also referred to as "Mocat”
- Mocat molybdenum complex
- iodide as a reducing agent
- water can be used as a proton source, so a nitrogen-containing compound such as ammonia can be synthesized from nitrogen without going through the generation of hydrogen gas. Therefore, the process of obtaining hydrogen gas from natural gas containing methane (CH 4 ) as a main component can be omitted, and the problem of a large amount of carbon dioxide, which is a greenhouse gas, is less likely to occur. Furthermore, the method for producing a nitrogen-containing compound of the present disclosure allows the synthesis reaction of the nitrogen-containing compound to proceed under mild reaction conditions, so that energy consumption is small, large-sized equipment made of special materials can be omitted, and industrial It can be said that it is excellent in terms of productivity.
- a nitrogen-containing compound such as ammonia can be synthesized from nitrogen without going through the generation of hydrogen gas. Therefore, the process of obtaining hydrogen gas from natural gas containing methane (CH 4 ) as a main component can be omitted, and the problem of a large amount of carbon dioxide, which is a greenhouse gas, is less likely to occur.
- Proton sources in the method for producing a nitrogen-containing compound of the present disclosure include water, alcohols such as methanol, ethanol, propanol, butanol, trifluoroethanol, phenol, and ethylene glycol, hydrogenated lutidine, hydrogenated picoline, Hydrogenated forms of collidine and the like can be mentioned, and water is preferable.
- the proton source may be contained in at least one of the catholyte and the anolyte as an anode solvent and/or a catholyte solvent, which will be described later, or may be contained in at least one of the catholyte and the anolyte as an additive, which will be described later. may be included in
- examples of the nitrogen-containing compound in the method for producing a nitrogen-containing compound of the present disclosure include ammonia, silylamine, hydrazine and the like, with ammonia being preferred.
- the nitrogen activation catalyst in the method for producing a nitrogen-containing compound of the present disclosure is not particularly limited as long as it is a catalyst capable of activating nitrogen. More preferably, it is an organometallic complex that can cleave the nitrogen triple bond and is soluble in an organic solvent.
- "soluble in an organic solvent” means, for example, that a nitrogen-activating catalyst is mixed in an organic solvent in an amount that gives a concentration of 0.1 mmol/L, and dissolution can be confirmed visually.
- the central metal of the metal complex that activates nitrogen include Ti, V, Mo, Fe, Mn, Co, Pt, Ir, and W, with Mo being preferred.
- ligands of metal complexes that activate nitrogen include halide ions, tertiary phosphines, and the like.
- a ligand to which a position atom is bound) and a halide ion more preferably a PCP (phosphorus-carbon-phosphorus) type pincer ligand or a PNP (phosphorus-nitrogen-phosphorus) type pincer ligand
- a combination with a halide ion more preferably a combination of a PCP-type pincer ligand and a halide ion.
- a complex corresponding to solubility in an organic solvent and reactivity with a reducing agent can be preferably used.
- a molybdenum complex in which the central metal is Mo is preferable, a molybdenum complex having a pincer ligand and a halide ion as a ligand is more preferable, and PCP is used as a ligand.
- a molybdenum complex having a PNP-type pincer ligand or a PNP-type pincer ligand and a halide ion is more preferred, and a molybdenum complex having a PCP-type pincer ligand and a halide ion as ligands is more preferred.
- molybdenum complexes having a PNP-type pincer ligand and a halide ion as ligands include molybdenum complexes represented by the following formulas (1), (5), and (6).
- Molybdenum complexes having a PCP-type pincer ligand and a halide ion as ligands include, for example, molybdenum complexes represented by the following formula (2) or (3).
- Other molybdenum complexes include molybdenum complexes represented by the following formula (4).
- R 1 to R 4 each independently represent hydrogen or a chain, cyclic or branched hydrocarbon group having 1 to 14 carbon atoms
- R 5 is hydrogen or a cyclic It is a group substituting hydrogen and represents a chain, cyclic or branched hydrocarbon group having 1 to 14 carbon atoms
- each X is independently selected from the group consisting of fluorine, chlorine, bromine and iodine. represents a halide ion.
- R 1 and R 2 and/or R 3 and R 4 may combine with each other to form a ring, and PR 1 R 2 and PR 3 R 4 may be the same or different. and R 1 to R 4 may all be the same or at least partially different.
- the “chain, cyclic or branched hydrocarbon group having 1 to 14 carbon atoms” for R 1 to R 5 is, for example, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, selected from the group consisting of alkynyl groups of ⁇ 6, cycloalkyl groups of 3 to 6 carbon atoms, cycloalkenyl groups of 3 to 6 carbon atoms, cycloalkynyl groups of 3 to 6 carbon atoms, and aryl groups of 6 to 14 carbon atoms; can do.
- R 1 to R 4 are preferably alkyl groups having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms.
- R 1 to R 4 are preferably butyl groups, more preferably tert-butyl groups.
- these R5 's may combine with each other to form a ring.
- 2 or 3 R5's they may be all the same or at least partially different.
- X is preferably bromine, chlorine or iodine, more preferably chlorine or iodine.
- X 3 in the formula means that three X's are bonded to Mo.
- R 1 to R 5 and X are the same as in formula (1) above.
- R 1 to R 5 and X are the same as in formula (1) above.
- R 1 to R 3 are the same as in formula (1) above.
- R 1 to R 5 and X are the same as in formula (1) above.
- R 1 to R 5 and X are the same as in formula (1) above.
- the concentration of the nitrogen activation catalyst in the catholyte is not particularly limited, it is, for example, 0.1 mmol/L or more and 1 mol/L or less from the viewpoint of promoting the synthesis reaction of the nitrogen-containing compound.
- the reducing agent in the method for producing a nitrogen-containing compound of the present disclosure is not particularly limited as long as it is a compound capable of reducing a nitrogen-activating catalyst. Compounds that have an electric potential and are soluble in organic solvents are preferred.
- the reduction potential of the reducing agent of the present disclosure is preferably nobler than the proton source or proton reduction reaction, which is a competing reaction, and is nobler than ⁇ 2.0 V vs SCE. side is more preferred.
- the redox potential of the reducing agent is measured by a cyclic voltammetry (CV) method, for example, using an Ag/Ag + electrode as a reference electrode, and converted to a SCE (Saturated Calomel Electrode) reference potential. It can be determined, and more specifically, it can be measured by the method described in Examples below.
- soluble in an organic solvent means, for example, that a reducing agent can be mixed with an organic solvent in an amount such that the concentration becomes 0.1 mmol/L, and dissolution can be visually confirmed.
- the reducing agent of the present disclosure includes, for example, at least one selected from the group consisting of samarium iodide, decamethylcobaltocene, cobaltocene, and decamethylchromocene.
- concentration of the reducing agent in the catholyte is not particularly limited, it is, for example, 0.1 mmol/L or more and 1 mol/L or less from the viewpoint of promoting the synthesis reaction of the nitrogen-containing compound.
- FIG. 1 is a schematic diagram showing an example of an electrolytic cell 10 used in the method for producing a nitrogen-containing compound according to the present disclosure.
- the electrolytic cell 10 includes, for example, a cathode section including a cathode electrode 1 and a cathode chamber 4, an anode section including an anode electrode 2 and an anode chamber 5, a diaphragm 3 positioned between the cathode portion and the anode portion, Prepare. Further, a power source 6 capable of applying voltage to the cathode electrode 1 and the anode electrode 2 may be further provided.
- Nitrogen-activated catalyst, reducing agent, proton source and solvent are added to cathode chamber 4 .
- the nitrogen activation catalyst is, for example, an organometallic complex that can cleave a nitrogen triple bond, and is preferably soluble in an organic solvent.
- the nitrogen activation catalyst reacts with the nitrogen molecules supplied to the cathode chamber 4 to activate the nitrogen molecules and form metal-nitrogen bonds. Protons are supplied to this nitrogen from a proton source, electrons are supplied by a reducing agent, and the metal is repeatedly reduced, thereby producing a nitrogen-containing compound.
- the oxidized reducing agent is reduced at the cathode electrode 1 and reused.
- Cathode chamber 4 can contain a compound that increases conductivity.
- the catholyte refers to a liquid used in the cathode section (cathode chamber), and includes, for example, a solvent such as a nitrogen activation catalyst, a reducing agent, and optionally a proton source, additives, and the like.
- the anolyte is a liquid used in the anode part (anode chamber), and is, for example, a solvent or a liquid obtained by adding an additive, a proton source, etc.
- (Cathode electrode 1) At the cathode electrode 1, in addition to the reduction reaction of the reducing agent such as (3) or (C) described above, a reduction reaction of the proton source added to the cathode chamber 4 (for example, 2H 2 O+2e ⁇ ⁇ H 2 +2OH ⁇ ) and a reduction reaction (for example, 2H + +2e ⁇ ⁇ H 2 ) of protons donated from the anode chamber 5 to the cathode chamber 4 through the diaphragm. Therefore, it is preferable to select the cathode electrode 1 having a high overvoltage with respect to the competitive reaction so that the reduction reaction of the reducing agent such as (3) or (C) above is given priority.
- the reduction reaction of the reducing agent such as (3) or (C) above is given priority.
- Examples of such a cathode electrode 1 include a titanium electrode, a vanadium electrode, a manganese electrode, an iron electrode, a cobalt electrode, a nickel electrode, a copper electrode, a zinc electrode, a gallium electrode, a niobium electrode, a molybdenum electrode, a silver electrode, an indium electrode, A tin electrode, a lead electrode, a bismuth electrode, an aluminum electrode, a carbon electrode, an electrode combining these, and the like can be mentioned.
- a titanium electrode is preferable from the viewpoint of further promoting the reaction at the cathode electrode 1 .
- anode electrode 2 As the anode electrode 2, from the viewpoint of promoting the reaction on the anode electrode 2, it is preferable to use an anode electrode 2 with a low reaction overvoltage. For example, when the reaction “4OH ⁇ ⁇ O 2 +2H 2 O+4e ⁇ ” is selected for the reaction on the anode electrode 2, from the viewpoint of promoting the reaction on the anode electrode 2, the anode electrode 2 with a low oxygen generation overvoltage is selected.
- anode electrode 2 examples include rhodium electrode, palladium electrode, iridium electrode, ruthenium electrode, platinum electrode, gold electrode, titanium electrode, nickel electrode, cobalt electrode, manganese electrode, copper electrode, zinc electrode, tin electrode, Examples include iron electrodes, lanthanum electrodes, strontium electrodes, chromium electrodes, calcium electrodes, barium electrodes, cerium electrodes, bismuth electrodes, tungsten electrodes, carbon electrodes and electrodes in which these are combined. Among these, a nickel electrode is preferable from the viewpoint of further promoting the reaction at the anode electrode 2 .
- the diaphragm 3 serves to prevent the catalyst and reducing agent from moving from the cathode chamber 4 to the anode chamber 5 . Also, depending on the type of reducing agent, proton source, and anode reaction used, it is responsible for proton transfer from the anode chamber 5 to the cathode chamber 4 or OH ⁇ ion transfer from the cathode chamber 4 to the anode chamber 5 . In addition, when the reaction at the cathode occurs in an organic solvent, it is preferable to select a diaphragm that is chemically and/or physically stable in an organic solvent, i.e., a diaphragm that is less likely to dissolve and/or swell in an organic solvent.
- diaphragm 3 examples include inorganic membranes such as glass filters and zeolite membranes having the above physical properties; ion exchange membranes such as anion exchange membranes, cation exchange membranes and bipolar membranes; and the like.
- a diaphragm may be used individually by 1 type, or may use 2 or more types together.
- the thickness of the diaphragm 3 is not particularly limited, it is, for example, 10 ⁇ m or more and 5000 ⁇ m or less from the viewpoint of ionic conductivity and chemical and physical stability.
- an additive capable of improving electrical conductivity without inhibiting the synthesis reaction of the nitrogen-containing compound may be added to the catholyte and/or the anolyte.
- additives include metal halide salts such as lithium iodide, sodium iodide, potassium iodide, lithium chloride, sodium chloride and potassium chloride; dimethylanilinium borate, tetrabutylammonium hexafluorophosphate, ammonium hexafluorophosphate, [LutH]OTf (hydrogenated lutidine trifluoromethanesulfonate), [ColH]OTf (hydrogenated collidine trifluoromethanesulfonate), [PicH]OTf (hydrogenated picoline trifluoromethanesulfonate) , 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfon
- An additive may be used individually by 1 type, or may use 2 or more types together. Moreover, when using an organic solvent as a solvent, it is good also considering water as an additive.
- concentration of the additive in the catholyte or anolyte is not particularly limited, it is, for example, 0.1 mmol/L or more and 3 mol/L or less from the viewpoint of promoting the synthesis reaction of the nitrogen-containing compound.
- the solvent (cathode solvent) used in the catholyte is preferably a solvent that can dissolve the nitrogen-activated catalyst, for example, a solvent with a solubility parameter of 20 (cal/cm 3 ) 1/2 or less, and that is stable even when voltage is applied. Organic solvents having a wide potential window are preferred.
- a "solubility parameter (SP value)" as used herein is a value introduced by Hildebrand and defined by regular solution theory.
- organic solvents examples include ethers such as dibutyl ether, diethyl ether, dimethoxyethane, 1,4-dioxane and tetrahydrofuran; methanol, ethanol, propanol, isopropanol, butanol, trifluoroethanol, phenol, ethylene glycol and the like. nitriles such as acetonitrile; alkanes such as n-hexane; carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl carbonate and methyl propyl carbonate. Among these, tetrahydrofuran and/or dimethoxyethane are preferred.
- a solvent may be used individually by 1 type, or may use 2 or more types together.
- anode solvent examples of the solvent (anode solvent) used in the anolyte include water and organic solvents containing water.
- organic solvent used in the anode part examples include the same organic solvents as those exemplified for the cathode solvent.
- ⁇ Reaction conditions> selecting a voltage that maximizes the current value for electrochemically reducing the reducing agent and suppresses competitive reactions and reduction deposition of the reducing agent and the proton source. is preferred. Specifically, the voltage is more preferably 5.0 V or less, still more preferably 4.5 V or less, even more preferably 4.0 V or less, and even more preferably 3.5 V or less. .
- the synthesis of a nitrogen-containing compound can proceed under relatively mild conditions, for example, in the range of ⁇ 80° C. or higher and 100° C. or lower and 0.10 MPa or higher and 0.20 MPa or lower. can be done with The temperature is preferably -60°C or higher and 70°C or lower, more preferably -40°C or higher and 60°C or lower.
- Example 1 An electrolysis cell (made of Pyrex glass, H type cell) shown in FIG. 1 was used.
- An anion exchange membrane manufactured by Astom Co., Ltd., product name: “Neosepta ASE-A-5142 membrane", thickness: 150 ⁇ m
- a nickel (Ni) electrode is used as the anode electrode (manufactured by Nilaco Corporation, product name: " Nickel 100 mesh")
- a titanium (Ti) electrode manufactured by Taiyo Wire Mesh Co., Ltd., product name: "fine titanium fiber processed product ST/Ti 0.2 mm" was used as the cathode electrode.
- FIG. 2 shows the CV measurement results of samarium iodide) 0 .06 mmol, 40 mL of dehydrated and deoxygenated dimethoxyethane (DME, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a solvent, and tetrabutylammonium hexafluorophosphate ( Bu4NPF6 , manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as an additive. ) and 500 mg of lithium iodide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
- DME dehydrated and deoxygenated dimethoxyethane
- Bu4NPF6 tetrabutylammonium hexafluorophosphate
- a voltage of 3.5 V was applied between the anode electrode and the cathode electrode of the electrolysis cell for 4 hours of energization treatment to carry out an ammonia synthesis reaction.
- 10 mL of 0.02 mol/L sulfuric acid was added to the cathode chamber to stop the reaction, and the ammonia produced was quantified by ion chromatography.
- the amount of ammonia produced was 0.031 mmol. Since the amount of ammonia produced from the chemical reaction calculated from the amount of samarium iodide used was 0.010 mmol, 0.021 mmol of ammonia was produced by the electrochemical reaction.
- t Bu represents a tert-butyl group.
- the redox potential of the reducing agent was measured by cyclic voltammetry (CV) method. CV was measured using the following apparatus and conditions. The redox potential of the resulting reducing agent was converted from the Ag/Ag + standard to the SCE standard potential.
- Measuring device/potentiostat manufactured by Touhou Giken Co., Ltd., product name “8CHANNEL POTENTIOSTAT/GALVANOSTAT MODEL PS-08”
- Working electrode glassy carbon electrode (manufactured by BAS Co., Ltd., OD: 6 mm, ID: 3 mm)
- Counter electrode platinum electrode (manufactured by BAS Co., Ltd., length 5 cm, electrode part diameter 0.5 mm)
- Reference electrode Non-aqueous solvent-based reference electrode (BAS Co., Ltd., Ag/Ag + , RE-7) Measurement conditions Supporting electrolyte: 0.1 M tetrabutylammonium hexafluorophosphate Sweeping rate: 100 mV/sec Solvent: dimethoxyethane Measurement was performed in a glove box purged with nitrogen gas. ⁇ Reducing agent concentration: 10 mM
- Example 2 The procedure was the same as in Example 1, except that "dehydrated and deoxygenated dimethoxyethane (DME)" put into the cathode chamber was changed to "dehydrated and deoxygenated tetrahydrofuran (THF, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.)". and produced ammonia.
- the amount of ammonia produced was 0.031 mmol. Since the amount of ammonia produced from the chemical reaction calculated from the amount of samarium iodide used was 0.010 mmol, 0.021 mmol of ammonia was produced by the electrochemical reaction.
- Example 3 Production of ammonia in the same manner as in Example 1, except that "0.5 mL of ionic liquid BMI-TFSA (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide)" was added to the cathode chamber. performed. The amount of ammonia produced was 0.035 mmol. Since the amount of ammonia produced from the chemical reaction calculated from the amount of samarium iodide used was 0.010 mmol, 0.025 mmol of ammonia was produced by the electrochemical reaction.
- BMI-TFSA 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide
- Comparative example 1 Ammonia was produced in the same manner as in Example 1, except that no voltage was applied between the anode electrode and the cathode electrode of the electrolytic cell. The amount of ammonia produced was 0.010 mmol, which was equal to the amount of ammonia produced from the chemical reaction calculated from the amount of samarium iodide.
- Example 4 Ammonia was removed in the same manner as in Example 1, except that "0.010 mmol of the molybdenum complex represented by the formula (A)" placed in the cathode chamber was changed to "0.010 mmol of the molybdenum complex represented by the following formula (B)". manufactured.
- the amount of ammonia produced was 0.029 mmol. Since the amount of ammonia produced from the chemical reaction calculated from the amount of samarium iodide used was 0.010 mmol, 0.019 mmol of ammonia was produced by the electrochemical reaction.
- Comparative example 2 Ammonia was produced in the same manner as in Example 4, except that no voltage was applied between the anode and cathode electrodes of the electrolytic cell. The amount of ammonia produced was 0.010 mmol.
- Example 5 Ammonia was removed in the same manner as in Example 1, except that "0.010 mmol of the molybdenum complex represented by the formula (A)" placed in the cathode chamber was changed to "0.010 mmol of the molybdenum complex represented by the following formula (C)". manufactured.
- the amount of ammonia produced was 0.034 mmol. Since the amount of ammonia produced from the chemical reaction calculated from the amount of samarium iodide used was 0.010 mmol, 0.024 mmol of ammonia was produced by the electrochemical reaction.
- Comparative example 3 Ammonia was produced in the same manner as in Example 5, except that no voltage was applied between the anode electrode and the cathode electrode of the electrolytic cell. The amount of ammonia produced was 0.011 mmol.
- Example 6 "0.06 mmol of samarium iodide" placed in the cathode chamber was changed to "0.06 mmol of decamethylcobaltocene (CoCp * 2 , manufactured by Sigma-Aldrich Co., Ltd., reduction potential is -1.50 V vs SCE)", and an additive was added to the cathode chamber.
- Ammonia was produced in the same manner as in Example 1, except that 0.06 mmol of [ColH]OTf was added. The amount of ammonia produced was 0.036 mmol. Since the amount of ammonia produced from the chemical reaction calculated from the amount of decamethylcobaltocene used was 0.020 mmol, 0.016 mmol of ammonia was produced by the electrochemical reaction.
- Example 7 "0.06 mmol of samarium iodide" placed in the cathode chamber was changed to "0.06 mmol of decamethylchromocene (CrCp * 2 , manufactured by Sigma-Aldrich Co., Ltd., reduction potential is -1.10 V vs SCE)", and an additive was added to the cathode chamber.
- Ammonia was produced in the same manner as in Example 1, except that 0.06 mmol of [ColH]OTf was added. The amount of ammonia produced was 0.035 mmol. Since the amount of ammonia produced from the chemical reaction calculated from the amount of decamethylchromocene used was 0.020 mmol, 0.015 mmol of ammonia was produced by the electrochemical reaction.
- Example 8 “0.06 mmol of samarium iodide” placed in the cathode chamber was changed to “0.06 mmol of cobaltocene (CoCp 2 , manufactured by Sigma-Aldrich, reduction potential is ⁇ 0.90 V vs SCE)”, and [ColH ] Ammonia was produced in the same manner as in Example 1, except that 0.06 mmol of OTf was added. The amount of ammonia produced was 0.028 mmol. Since the amount of ammonia produced from the chemical reaction calculated from the amount of cobaltocene used was 0.020 mmol, 0.008 mmol of ammonia was produced by the electrochemical reaction.
- Example 9 Ammonia was produced in the same manner as in Example 1, except that the cathode electrode was changed from a titanium electrode to a carbon (C) electrode (carbon paper, manufactured by Toray Industries, Inc., product name: "TGP-H-060”). .
- the amount of ammonia produced was 0.032 mmol. Since the amount of ammonia produced from the chemical reaction calculated from the amount of samarium iodide used was 0.010 mmol, 0.022 mmol of ammonia was produced by the electrochemical reaction.
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Abstract
Description
従来、アンモニアはハーバー・ボッシュ法により製造されている。ハーバー・ボッシュ法は、鉄系触媒の存在下、窒素ガスと水素ガスとを反応させることによってアンモニアを製造する方法である。
そのため、穏和な反応条件下で、窒素と水からアンモニアを製造する方法の開発が望まれている。
本発明は上記事情に鑑みてなされたものであり、含窒素化合物の生産量を向上させる、含窒素化合物の製造方法を提供するものである。
〔1〕 窒素活性化触媒及び還元剤の存在下で、窒素とプロトン源から含窒素化合物を合成しつつ同時に、前記含窒素化合物の合成反応で酸化した前記還元剤を電解法により還元する工程を含む、含窒素化合物の製造方法。
〔2〕 前記還元剤は、-0.40VvsSCE以下に酸化還元電位を持ち、かつ、有機溶媒に可溶な化合物を含む、前記〔1〕に記載の含窒素化合物の製造方法。
〔3〕 前記還元剤は、ヨウ化サマリウム、デカメチルコバルトセン、コバルトセン、及びデカメチルクロモセンからなる群から選択される少なくとも一種を含む、前記〔1〕又は〔2〕に記載の含窒素化合物の製造方法。
〔4〕 前記窒素活性化触媒がモリブデン錯体を含む、前記〔1〕~〔3〕のいずれかに記載の含窒素化合物の製造方法。
〔5〕 前記含窒素化合物がアンモニアを含む、前記〔1〕~〔4〕のいずれかに記載の含窒素化合物の製造方法。
〔6〕 前記プロトン源が水を含む、前記〔1〕~〔5〕のいずれかに記載の含窒素化合物の製造方法。
本開示の含窒素化合物の製造方法は、窒素活性化触媒及び還元剤の存在下で、窒素とプロトン源から含窒素化合物を合成しつつ同時に、前記含窒素化合物の合成反応で酸化した前記還元剤を電解法により還元する工程を含む。
ここで、「同時に」とは、前記工程が同一の系内で実施されることを意味する。含窒素化合物の合成と酸化した還元剤の還元との時間の間隔が短いことが好ましい。
含窒素化合物の生成反応は、窒素活性化触媒の存在下で進行し、例えば還元剤からの電子供与と共役したプロトン共役電子移動(PCET)反応により進行すると考えられる。
酸化した還元剤の電解法による還元は、電解法のカソード反応として進行すると考えられる。カソード反応と対になるアノード反応には、任意の反応を選択できる。
(1)還元剤からの電子供与
Red→Ox+e-
(2)NH3生成反応
N2+6Red+6H+→(Cat)→2NH3+6Ox
(3)還元剤の還元反応(カソード反応)
Ox+e-→Red
ここで、Redは還元剤、Oxは酸化した還元剤、Catは窒素活性化触媒を示す。
(2)の反応におけるプロトンH+は、カソード室内に添加されたプロトン源から、又はアノード室から隔膜を通じて供与することができる。
(A)SmI2+H2O→SmI2(H2O)→SmI2(OH)+H++e-
(B)NH3生成反応
N2+6SmI2+6H2O→(プロトン共役電子移動(PCET)反応+Mocat)→2NH3+6SmI2(OH)
(C)ヨウ化サマリウムの還元反応(カソード反応)
SmI2(OH)+e-→SmI2+OH-
また、本開示の含窒素化合物の製造方法では、プロトン源として水を使用することができるため、水素ガスの生成を経由せずに、窒素からアンモニア等の含窒素化合物を合成することができる。そのため、メタン(CH4)を主成分とする天然ガスから水素ガスを得る工程を省略でき、温室効果ガスである二酸化炭素が多量に排出されるという問題も起きにくい。
さらに、本開示の含窒素化合物の製造方法は、穏和な反応条件下で含窒素化合物の合成反応を進めることができるため、エネルギー消費量が少なく、大型で特殊な材質の装置も省略でき、工業的生産性に優れているといえる。
また、本開示の含窒素化合物の製造方法における含窒素化合物としては、例えば、アンモニア、シリルアミン、ヒドラジン等が挙げられ、アンモニアが好ましい。
本開示の含窒素化合物の製造方法における窒素活性化触媒は、窒素を活性化できる触媒であれば特に限定されないが、例えば、窒素を活性化する金属錯体が挙げられ、好ましくは窒素三重結合を切断できる有機金属錯体であり、より好ましくは、窒素三重結合を切断でき、かつ、有機溶媒に可溶な有機金属錯体である。ここで、「有機溶媒に可溶」とは、例えば有機溶媒に、濃度が0.1mmol/Lとなる分量で窒素活性化触媒を混合し、目視で溶解を確認できることが挙げられる。
窒素を活性化する金属錯体の中心金属としては、例えば、Ti、V、Mo、Fe、Mn、Co、Pt、Ir、W等が挙げられ、好ましくはMoである。
窒素を活性化する金属錯体の配位子としては、例えばハロゲン化物イオン、第三級ホスフィン等が挙げられ、好ましくはピンサー配位子(すなわち中心金属を含む同一平面上の3方向から3つの配位原子が結合する配位子)とハロゲン化物イオンとの組み合わせであり、より好ましくはPCP(リン-炭素-リン)型ピンサー配位子又はPNP(リン-窒素-リン)型ピンサー配位子とハロゲン化物イオンとの組み合わせであり、更に好ましくはPCP型ピンサー配位子とハロゲン化物イオンとの組み合わせである。
窒素を活性化する金属錯体としては、有機溶媒への溶解性、還元剤との反応性に対応した錯体を好適に用いることができる。
窒素を活性化する金属錯体としては、これらの中でも中心金属がMoであるモリブデン錯体が好ましく、配位子としてピンサー配位子とハロゲン化物イオンとを有するモリブデン錯体がより好ましく、配位子としてPCP型ピンサー配位子又はPNP型ピンサー配位子とハロゲン化物イオンとを有するモリブデン錯体が更に好ましく、配位子としてPCP型ピンサー配位子とハロゲン化物イオンとを有するモリブデン錯体が更に好ましい。
配位子としてPNP型ピンサー配位子とハロゲン化物イオンとを有するモリブデン錯体としては、例えば、下記式(1)、(5)、又は(6)で示されるモリブデン錯体が挙げられる。また、配位子としてPCP型ピンサー配位子とハロゲン化物イオンとを有するモリブデン錯体としては、例えば、下記式(2)又は(3)で示されるモリブデン錯体が挙げられる。また、その他のモリブデン錯体としては、下記式(4)で示されるモリブデン錯体が挙げられる。
ここで、R1とR2、及び/又はR3とR4は、互いに結合して環を形成していてもよく、PR1R2とPR3R4とは同じであっても異なっていてもよく、R1~R4は全て同じでも少なくとも一部が異なっていてもよい。
R1~R5における「炭素数1~14の鎖状、環状若しくは分岐状の炭化水素基」は、例えば、炭素数1~6のアルキル基、炭素数2~6のアルケニル基、炭素数2~6のアルキニル基、炭素数3~6のシクロアルキル基、炭素数3~6のシクロアルケニル基、炭素数3~6のシクロアルキニル基、及び炭素数6~14のアリール基からなる群より選択することができる。これらの中でも、R1~R4としては、炭素数1~6のアルキル基が好ましく、炭素数1~4のアルキル基がより好ましい。また、R1~R4としては、ブチル基が好ましく、tert-ブチル基がより好ましい。
また、R5が2又は3個存在する場合には、これらのR5が互いに結合して環を形成していてもよい。また、R5が2又は3個存在する場合には、これらは、全て同じでも、少なくとも一部が異なっていてもよい。
Xは臭素、塩素又はヨウ素が好ましく、塩素又はヨウ素がより好ましい。
ここで、式中のX3はMoにXが3つ結合していることを意味する。
本開示の含窒素化合物の製造方法における還元剤は、窒素活性化触媒を還元できる化合物であれば特に限定されないが、含窒素化合物の合成反応を促進する観点から、-0.40VvsSCE以下に酸化還元電位を持ち、かつ、有機溶媒に可溶な化合物が好ましい。また、含窒素化合物の合成反応を促進する観点から、本開示の還元剤の還元電位が競合反応であるプロトン源又はプロトンの還元反応よりも貴側であることが好ましく、-2.0VvsSCEより貴側であることがより好ましい。
還元剤の酸化還元電位は、サイクリックボルタンメトリー(CV)法により、例えば、参照電極としてAg/Ag+電極を用いて測定し、SCE(飽和カロメル電極;Saturated Calomel Electrode)基準の電位に変換して求めることができ、より具体的には、後述する実施例に記載の方法により測定することができる。
また、「有機溶媒に可溶」とは、例えば有機溶媒に、濃度が0.1mmol/Lとなる分量で還元剤を混合し、目視で溶解を確認できることが挙げられる。
本開示の還元剤として、例えば、ヨウ化サマリウム、デカメチルコバルトセン、コバルトセン、及びデカメチルクロモセンからなる群から選択される少なくとも一種が挙げられる。
カソード液中の還元剤の濃度は特に限定されないが、含窒素化合物の合成反応を促進する観点から、例えば、0.1mmol/L以上1mol/L以下である。
本開示の含窒素化合物の製造方法は、例えば、電気分解用セルを用いて実施することができる。図1は、本開示に係る含窒素化合物の製造方法で用いられる電気分解用セル10の一例を示す模式図である。
電気分解用セル10は、例えば、カソード電極1及びカソード室4を含むカソード部と、アノード電極2及びアノード室5を含むアノード部と、カソード部とアノード部との間に位置する隔膜3と、を備える。また、カソード電極1及びアノード電極2に対して電圧を印加できる電源6を更に備えてもよい。
窒素活性化触媒、還元剤、プロトン源及び溶媒はカソード室4に添加する。窒素活性化触媒は、例えば、窒素三重結合を切断できる有機金属錯体であり、有機溶媒に可溶なものであるものが好ましい。
窒素活性化触媒は、カソード室4に供給された窒素分子と反応して窒素分子を活性化し、金属窒素結合を形成する。この窒素にプロトン源からプロトンが供給され、かつ還元剤により電子が供給され、金属が還元されることを繰り返し、含窒素化合物が生成する。酸化した還元剤は、カソード電極1で還元され、再利用される。カソード室4には電導性を上げる化合物を入れることができる。アノード室5には水又は有機溶媒を用いることができる。
なお、電気分解用セル10のカソード室4にて還元剤を再利用することに加えて、酸化した還元剤の一部を電気分解用セル10とは異なる電気分解用セルにて再生し、再度電気分解用セル10のカソード室4に投入することも可能である。
ここで、本明細書において、カソード液とは、カソード部(カソード室)で用いられる液体のことをいい、例えば、溶媒に窒素活性化触媒、還元剤、必要に応じてプロトン源、添加剤等を添加した液体であり、アノード液とは、アノード部(アノード室)で用いられる液体のことをいい、例えば、溶媒、又は溶媒に添加剤、プロトン源等を添加した液体のことをいう。
カソード電極1では、上述の(3)又は(C)のような還元剤の還元反応に加えて、競合反応としてカソード室4に添加されたプロトン源の還元反応(例えば2H2O+2e-→H2+2OH-)及び、アノード室5から隔膜を通じてカソード室4に供与されるプロトンの還元反応(例えば2H++2e-→H2)が起こる。
そのため、上述の(3)又は(C)のような還元剤の還元反応が優先されるように、競合反応に対して過電圧の高いカソード電極1を選択することが好ましい。
このようなカソード電極1としては、例えば、チタン電極、バナジウム電極、マンガン電極、鉄電極、コバルト電極、ニッケル電極、銅電極、亜鉛電極、ガリウム電極、ニオブ電極、モリブデン電極、銀電極、インジウム電極、スズ電極、鉛電極、ビスマス電極、アルミニウム電極、炭素電極及びこれらを組み合わせた電極等が挙げられる。これらの中でも、カソード電極1での反応をより一層促進する観点から、チタン電極が好ましい。
アノード電極2としては、アノード電極2上での反応を促進する観点から、反応過電圧の低いアノード電極2を用いることが好ましい。例えば、アノード電極2上での反応に「4OH-→O2+2H2O+4e-」の反応を選択した場合、アノード電極2上での反応を促進する観点から、酸素生成過電圧の低いアノード電極2を用いることが好ましい。
このようなアノード電極2としては、例えば、ロジウム電極、パラジウム電極、イリジウム電極、ルテニウム電極、白金電極、金電極、チタン電極、ニッケル電極、コバルト電極、マンガン電極、銅電極、亜鉛電極、スズ電極、鉄電極、ランタン電極、ストロンチウム電極、クロム電極、カルシウム電極、バリウム電極、セリウム電極、ビスマス電極、タングステン電極、炭素電極及びこれらを組み合わせた電極等が挙げられる。これらの中でも、アノード電極2での反応をより一層促進する観点から、ニッケル電極が好ましい。
隔膜3は触媒及び還元剤がカソード室4からアノード室5へ移動することを防止する役割を持つ。また、用いる還元剤、プロトン源、アノード反応の種類によっては、アノード室5からカソード室4へのプロトン移動、又はカソード室4からアノード室5へのOH-イオン移動を担う。また、カソード部での反応が有機溶媒中で起こる場合は、有機溶媒中でも化学的及び/又は物理的に安定な隔膜すなわち有機溶媒中でも溶解及び/又は膨潤が起こり難い隔膜を選択することが好ましい。
隔膜3としては、例えば、上記物性を有するガラスフィルター、ゼオライト膜等の無機膜;アニオン交換膜、カチオン交換膜、バイポーラー膜等のイオン交換膜;等が挙げられる。隔膜は1種単独で用いても、2種以上を併用してもよい。
隔膜3の厚みは特に限定されないが、イオン電導性、並びに、化学的及び物理的安定性の観点から、例えば、10μm以上5000μm以下である。
含窒素化合物の合成反応を促進する観点から、含窒素化合物の合成反応を阻害せず、電気伝導性を向上できるような添加剤をカソード液及び/又はアノード液に添加してもよい。
このような添加剤としては、例えば、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム、塩化リチウム、塩化ナトリウム、塩化カリウム等のハロゲン化金属塩;ジメチルアニリニウムボレート、テトラブチルアンモニウムヘキサフルオロホスファート、アンモニウムヘキサフルオロリン酸、[LutH]OTf(トリフルオロメタンスルホン酸ルチジン水素化体)、[ColH]OTf(トリフルオロメタンスルホン酸コリジン水素化体)、[PicH]OTf(トリフルオロメタンスルホン酸ピコリン水素化体)、1-ヘキシル-3-メチルイミダゾリウム ビス(トリフルオロメチルスルホニル)イミド、1-ブチル-3-メチルイミダゾリウム ビス(トリフルオロメチルスルホニル)アミド(イオン液体)等のカチオンとアニオンのコンプレックスである化合物;水酸化ナトリウム、水酸化カリウム等の塩基性化合物等が挙げられる。添加剤は1種単独で用いても、2種以上を併用してもよい。
また、溶媒として有機溶媒を用いる場合、水を添加剤としてもよい。
カソード液又はアノード液中の添加剤の濃度は特に限定されないが、含窒素化合物の合成反応を促進する観点から、例えば、0.1mmol/L以上3mol/L以下である。
カソード液で用いられる溶媒(カソード溶媒)は、窒素活性化触媒を溶解できる、例えば溶解度パラメータが20(cal/cm3)1/2以下の溶媒を選択することが望ましく、かつ電圧印加時でも安定な電位窓を有する有機溶媒が好ましい。本明細書における「溶解度パラメータ(SP値)」とは、ヒルデブラント(Hildebrand)によって導入され、正則溶液論により定義された値である。
このような有機溶媒としては、例えば、ジブチルエーテル、ジエチルエーテル、ジメトキシエタン、1,4-ジオキサン、テトラヒドロフラン等のエーテル類;メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、トリフルオロエタノール、フェノール、エチレングリコール等のアルコール類;アセトニトリル等のニトリル類;n-ヘキサン等のアルカン類;エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、エチルカーボネート、メチルプロピルカーボネート等のカーボネート類等が挙げられる。これらの中でも、テトラヒドロフラン及び/又はジメトキシエタンが好ましい。溶媒は1種単独で用いても、2種以上を併用してもよい。
アノード液で用いられる溶媒(アノード溶媒)としては、例えば、水、水を含む有機溶媒が挙げられる。アノード部で用いられる有機溶媒としては、カソード溶媒で例示した有機溶媒と同様のものが挙げられる。
本開示の含窒素化合物の製造方法において、還元剤を電気化学的に還元する電流値を最大化しつつ、競合反応、並びに、還元剤及びプロトン源の還元析出を抑制するような電圧を選択することが好ましい。
具体的には、電圧は5.0V以下であることがより好ましく、4.5V以下であることが更に好ましく、4.0V以下であることが更に好ましく、3.5V以下であることが更に好ましい。
図1に示す電気分解用セル(Pyrexガラス製、H型セル)を用いた。前記セルの隔膜にアニオン交換膜(株式会社アストム製、製品名:「ネオセプタASE-A-5142膜」、厚み:150μm)、アノード電極にニッケル(Ni)電極(株式会社ニラコ製、製品名:「ニッケル100 mesh」)、カソード電極にチタン(Ti)電極(太陽金網株式会社製、製品名:「微細チタン繊維加工品ST/Ti 0.2mm」)をそれぞれ用いた。
前記H型セルのアノード室に、脱酸素した0.2mol/Lの水酸化カリウム(KOH、富士フィルム和光純薬株式会社製)水溶液40mLを入れ、カソード室に、窒素活性化触媒として下記式(A)で示されるモリブデン錯体0.010mmol、還元剤としてヨウ化サマリウム(東京化成工業株式会社製、SmI2、還元電位が-0.70VvsSCE、図2にヨウ化サマリウムのCV測定結果を示す)0.06mmol、溶媒として脱水及び脱酸素したジメトキシエタン(DME、富士フィルム和光純薬株式会社製)40mL、添加剤としてテトラブチルアンモニウムヘキサフルオロホスファート(Bu4NPF6、富士フィルム和光純薬株式会社製)200mg及びヨウ化リチウム(富士フィルム和光純薬株式会社製)500mgをそれぞれ入れた。
次いで、前記電気分解用セルのアノード電極とカソード電極との間に3.5Vの電圧を印加して、4時間通電処理し、アンモニアの合成反応を行った。その後、カソード室に、0.02mol/Lの硫酸10mLを添加し、反応を停止し、イオンクロマトグラフィーにより生成したアンモニアを定量した。
アンモニアの生成量は0.031mmolであった。使用したヨウ化サマリウム量から計算したアンモニアの化学反応由来の生成量は0.010mmolであるため、電気化学反応により0.021mmolのアンモニアが生成された。
ここで、上記式(A)で示されるモリブデン錯体は、非特許文献 Y. Ashida, Y. Nishibayashi et al., “Molybdenum-catalysed ammonia production with samarium diiodide and alcohols or water”, Nature, 568, 536 (2019)の記載に従って製造した。
tBuはtert-ブチル基を示す。
測定装置
・ポテンショスタット:株式会社東方技研製、製品名「8CHANNEL POTENTIOSTAT/GALVANOSTAT MODEL PS-08」
・作用電極:グラッシーカーボン電極(ビー・エー・エス株式会社製、OD:6mm、ID:3mm)
・カウンター電極:白金電極(ビー・エー・エス株式会社製、長さ5cm、電極部直径0.5mm)
・参照電極:非水溶媒系参照電極(ビー・エー・エス株式会社製、Ag/Ag+、RE-7)
測定条件
・支持電解質:0.1M ヘキサフルオロリン酸テトラブチルアンモニウム
・掃引速度:100mV/秒
・溶媒:ジメトキシエタン
・窒素ガスで置換したグローブボックス中で測定を行った。
・還元剤濃度:10mM
カソード室に入れた「脱水及び脱酸素したジメトキシエタン(DME)」を「脱水及び脱酸素したテトラヒドロフラン(THF、富士フィルム和光純薬株式会社製)」に変更した以外は、実施例1と同様にしてアンモニアの製造を行った。アンモニアの生成量は0.031mmolであった。使用したヨウ化サマリウム量から計算したアンモニアの化学反応由来の生成量は0.010mmolであるため、電気化学反応により0.021mmolのアンモニアが生成された。
カソード室に「イオン液体であるBMI-TFSA(1-ブチル-3-メチルイミダゾリウム ビス(トリフルオロメチルスルホニル)アミド)0.5mL」を追加した以外は、実施例1と同様にしてアンモニアの製造をおこなった。アンモニアの生成量は0.035mmolであった。使用したヨウ化サマリウム量から計算したアンモニアの化学反応由来の生成量は0.010mmolであるため、電気化学反応により0.025mmolのアンモニアが生成された。
前記電気分解用セルのアノード電極とカソード電極との間に電圧を印加しない以外は、実施例1と同様にしてアンモニアの製造をおこなった。アンモニアの生成量は0.010mmolであり、ヨウ化サマリウム量から計算したアンモニアの化学反応由来の生成量と等しかった。
カソード室に入れた「式(A)で示されるモリブデン錯体0.010mmol」を「下記式(B)で示されるモリブデン錯体0.010mmol」に変更した以外は、実施例1と同様にしてアンモニアの製造を行った。アンモニアの生成量は0.029mmolであった。使用したヨウ化サマリウム量から計算したアンモニアの化学反応由来の生成量は0.010mmolであるため、電気化学反応により0.019mmolのアンモニアが生成された。
前記電気分解用セルのアノード電極とカソード電極との間に電圧を印加しない以外は、実施例4と同様にしてアンモニアの製造をおこなった。アンモニアの生成量は0.010mmolであった。
カソード室に入れた「式(A)で示されるモリブデン錯体0.010mmol」を「下記式(C)で示されるモリブデン錯体0.010mmol」に変更した以外は、実施例1と同様にしてアンモニアの製造を行った。アンモニアの生成量は0.034mmolであった。使用したヨウ化サマリウム量から計算したアンモニアの化学反応由来の生成量は0.010mmolであるため、電気化学反応により0.024mmolのアンモニアが生成された。
ここで、上記式(C)で示されるモリブデン錯体は、非特許文献 A. Eizawa, Y. Nishibayashi et al., “Remarkable catalytic activity of dinitrogen-bridged dimolybdenum complexes bearing NHC-based PCP-pincer ligands toward nitrogen fixation”, Nature Communications, 8, 14874 (2017)の記載に従って製造した。
前記電気分解用セルのアノード電極とカソード電極との間に電圧を印加しない以外は、実施例5と同様にしてアンモニアの製造をおこなった。アンモニアの生成量は0.011mmolであった。
カソード室に入れた「ヨウ化サマリウム0.06mmol」を「デカメチルコバルトセン(CoCp* 2、シグマアルドリッチ社製、還元電位が-1.50VvsSCE)0.06mmol」に変更し、カソード室に添加剤として[ColH]OTf0.06mmolを追加した以外は、実施例1と同様にしてアンモニアの製造を行った。アンモニアの生成量は0.036mmolであった。使用したデカメチルコバルトセン量から計算したアンモニアの化学反応由来の生成量は0.020mmolであるため、電気化学反応により0.016mmolのアンモニアが生成された。
カソード室に入れた「ヨウ化サマリウム0.06mmol」を「デカメチルクロモセン(CrCp* 2、シグマアルドリッチ社製、還元電位が-1.10VvsSCE)0.06mmol」に変更し、カソード室に添加剤として[ColH]OTf0.06mmolを追加した以外は、実施例1と同様にしてアンモニアの製造を行った。アンモニアの生成量は0.035mmolであった。使用したデカメチルクロモセン量から計算したアンモニアの化学反応由来の生成量は0.020mmolであるため、電気化学反応により0.015mmolのアンモニアが生成された。
カソード室に入れた「ヨウ化サマリウム0.06mmol」を「コバルトセン(CoCp2、シグマアルドリッチ社製、還元電位が-0.90VvsSCE)0.06mmol」に変更し、カソード室に添加剤として[ColH]OTf0.06mmolを追加した以外は、実施例1と同様にしてアンモニアの製造を行った。アンモニアの生成量は0.028mmolであった。使用したコバルトセン量から計算したアンモニアの化学反応由来の生成量は0.020mmolであるため、電気化学反応により0.008mmolのアンモニアが生成された。
カソード電極をチタン電極から炭素(C)電極(カーボンペーパー、東レ株式会社製、製品名:「TGP-H-060」)に変更した以外は、実施例1と同様にしてアンモニアの製造を行った。アンモニアの生成量は0.032mmolであった。使用したヨウ化サマリウム量から計算したアンモニアの化学反応由来の生成量は0.010mmolであるため、電気化学反応により0.022mmolのアンモニアが生成された。
2 アノード電極
3 隔膜
4 カソード室
5 アノード室
6 電源
10 電気分解用セル
Claims (6)
- 窒素活性化触媒及び還元剤の存在下で、窒素とプロトン源から含窒素化合物を合成しつつ同時に、前記含窒素化合物の合成反応で酸化した前記還元剤を電解法により還元する工程を含む、含窒素化合物の製造方法。
- 前記還元剤は、-0.40VvsSCE以下に酸化還元電位を持ち、かつ、有機溶媒に可溶な化合物を含む、請求項1に記載の含窒素化合物の製造方法。
- 前記還元剤は、ヨウ化サマリウム、デカメチルコバルトセン、コバルトセン、及びデカメチルクロモセンからなる群から選択される少なくとも一種を含む、請求項1又は2に記載の含窒素化合物の製造方法。
- 前記窒素活性化触媒がモリブデン錯体を含む、請求項1~3のいずれかに記載の含窒素化合物の製造方法。
- 前記含窒素化合物がアンモニアを含む、請求項1~4のいずれかに記載の含窒素化合物の製造方法。
- 前記プロトン源が水を含む、請求項1~5のいずれかに記載の含窒素化合物の製造方法。
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