CN117659098A - Tridentate phosphine ligand ferrous metal catalyst and preparation method and application thereof - Google Patents
Tridentate phosphine ligand ferrous metal catalyst and preparation method and application thereof Download PDFInfo
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- CN117659098A CN117659098A CN202311571611.7A CN202311571611A CN117659098A CN 117659098 A CN117659098 A CN 117659098A CN 202311571611 A CN202311571611 A CN 202311571611A CN 117659098 A CN117659098 A CN 117659098A
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 33
- 239000003446 ligand Substances 0.000 title claims abstract description 32
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 36
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 18
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000019253 formic acid Nutrition 0.000 claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 107
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 41
- 239000011259 mixed solution Substances 0.000 claims description 28
- -1 transition metal salt Chemical class 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000376 reactant Substances 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002848 electrochemical method Methods 0.000 claims description 4
- 238000003487 electrochemical reaction Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 125000002971 oxazolyl group Chemical group 0.000 claims description 4
- 238000010408 sweeping Methods 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000007942 carboxylates Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims 1
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000005311 nuclear magnetism Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- JGTMRPIQDKGXCD-UHFFFAOYSA-N acetonitrile;iron Chemical compound [Fe].CC#N JGTMRPIQDKGXCD-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012223 aqueous fraction Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000001536 pulsed discharge helium ionisation detection Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/085—Organic compound
-
- 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
- C25B3/07—Oxygen containing 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
- C25B3/26—Reduction of carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the technical field of electrochemistry, in particular to a tridentate phosphine ligand ferrous metal catalyst, a preparation method and application thereof. The catalyst is a hexacoordinated octahedral model structure shown in a formula I, and the structural formula is shown in the formula I:the invention also discloses a preparation method of the tridentate phosphine ligand metal catalyst, which comprises the following steps ofThe catalyst can effectively reduce carbon dioxide into formic acid, and the selectivity of the catalyst reaches 85 percent.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a tridentate phosphine ligand ferrous metal catalyst, a preparation method and application thereof.
Background
The industrial revolution has led to the large-scale use of fossil fuels, which brings many benefits to people, and also creates CO 2 Excessive emissions of (2), thus causing global ecological environment deterioration. If the carbon-oxygen source is used as a carbon oxygen source, various chemicals and materials are synthesized, two major crisis of environment and energy can be relieved at the same time, and the sustainable development goal of human beings is met.
Chemical reactions that are difficult to directly oxidize or reduce under ordinary conditions can be achieved using electrolytic methods. The existing catalysts for carbon dioxide electroreduction mainly comprise a heterogeneous nano catalyst and a homogeneous molecular catalyst. Wherein the productivity of the nano catalyst is relatively high, but the product is various, and the selectivity is poor; while molecular catalysts are generally higher in selectivity but lower in yield.
Electrocatalytic reduction of CO in molecular catalysts 2 The catalyst with good effect is basically noble metals such as ruthenium, iridium, palladium and the like. While less research is directed to inexpensive metals, and inexpensive metal-based catalysts generally have significantly lower yields and poorer selectivities than noble metals, which limits the application and development of inexpensive metals in the electrocatalytic reduction of carbon dioxide.
Therefore, the invention provides a tridentate phosphine ligand iron cheap metal catalyst, and a preparation method and application thereof.
Disclosure of Invention
It is an object of the present invention to provide a tridentate phosphine ligand ferrous metal catalyst.
Another object of the invention is to provide a method for preparing a tridentate phosphine ligand ferrous metal catalyst.
A third object of the present invention is to provide the use of a tridentate phosphine ligand ferrous metal catalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a tridentate phosphine ligand metal catalyst which is a hexacoordinated octahedral model structure shown in a formula I,
wherein R is 1 、R 2 、R 3 Each independently of the others can be the same or different hydrogen atom, C1-C12 alkyl, alkoxy, phenylBenzyl, amino, pyridyl, oxazolyl; ln is a transition metal;
L 1 、L 2 each L 3 Independently may be the same or different halogen atom, acetonitrile molecule, carboxylate group, methanol molecule, water molecule or tetrahydrofuran group.
The R is 1 、R 2 、R 3 Each independently represents a hydrogen atom, a phenyl group, a benzyl group, an amino group, a pyridyl group, an oxazolyl group, a 6 alkyl group or a C1-C6 alkoxy group;
ln is iron, cobalt or nickel.
In the catalyst, the introduction of alkyl increases the solubility of the system, so that the alkyl is maximally dissolved in the solution; if aryl is introduced, the conjugated system with large aryl reduces the solubility of the system, so that the conjugated system is easy to load on the surface for catalytic reaction.
The preparation method of the tridentate phosphine ligand metal catalyst comprises the steps of mixing a reactant A and a solvent M to obtain a white suspension B; mixing transition metal salt and a solvent N to obtain a mixed solution C; mixing the mixed solution C and the suspension B at room temperature for reaction for 30 min-1 h to obtain a metal catalyst; wherein, the structural formula of the reactant A is as follows:the solvent M and the solvent N may be the same or different and are each selected from acetonitrile, tetrahydrofuran or toluene.
The transition metal is iron, cobalt or nickel.
The ferric salt is ferric tetrafluoroborate hexahydrate, ferric tetra-acetonitrile trifluoromethane sulfonate, ferric acetate or ferric halide. The ferric salt has small steric hindrance, small electronegativity and strong coordination capability, and is easy to coordinate with the reactant A.
The final concentration of the reactant A in the white suspension B is 1mM-5M, and the final concentration of the transition metal salt in the mixed solution C is 1mM-5mM;
the concentration ratio of the mixed solution C to the suspension B is 1:1-1:1.2.
Further, the mixing mode of the reactant A and the solvent M is as follows: the solvent M and the reactant a are mixed and stirred so that the reactant a and the solvent M are more fully mixed into a uniform suspension. The person skilled in the art can adjust the amounts of the reactant a and the solvent according to the actual situation, so that the reactant a and the solvent can be mixed to form a suspension.
The molar mass ratio of the ferric salt to the reactant A is 1:1-1:10; in the actual reaction, one equivalent of reactant A and one equivalent of ferric salt are subjected to coordination reaction according to the ratio of 1:1, no matter whether the ferric salt or the excessive amount of reactant A has no influence on the actual reaction result, therefore, the molar mass ratio is illustrative and not restrictive, the protection scope of the invention is not limited, and the use amount of the reactant A and the ferric salt can be adjusted according to the actual situation by a person skilled in the art.
The mixing mode of the mixed solution C and the suspension B is as follows: slowly dripping the mixed solution C into the suspension B and continuously stirring, so as to ensure that the reactant A is in an excessive state and the metal can be fully coordinated.
When the mixed solution C and the suspension B are mixed, the concentration ratio of the mixed solution C to the suspension B is 1:1-1:1.2. On the premise of 1:5-1:10; within this volume ratio, the insoluble reactant a is mixed more uniformly and reacted more fully in as much of the solution as possible.
The condition of the mixing reaction of the mixed solution C and the suspension B is that stirring reaction is carried out for 30 min-1 h at room temperature. In the present invention, the stirring rate is not limited, and the reaction may be not affected.
The application of the tridentate phosphine ligand ferrous metal catalyst in electrocatalytic reduction of carbon dioxide.
A method for preparing formic acid by electrocatalytic reduction of carbon dioxide comprises the steps of dissolving tetrabutylammonium hexafluorophosphate in acetonitrile to obtain a mixed solution D, mixing the mixed solution D with a catalyst to obtain a mixed solution E, and carrying out electrochemical catalytic reaction on the mixed solution E by carbon dioxide to obtain the formic acid.
Adding water into the mixed solution E during the electrochemical reaction system to enable the volume fraction of the water in the reaction system to be 1-10%vol; the addition amount of the catalyst in the electrochemical reaction system is 0.1mM-5mM,
the CO is introduced into 2 The electrochemical characterization is carried out by introducing CO 2 The time of the process is 5 min-20 min, the sweeping speed is 10 mv-100 mv, the applied voltage is-1.05V to-1.55V (V vs. NHE), and the electrified electrolysis time is 1 h-8 h.
The condition of electrochemical characterization by passing Ar is that the time of passing Ar is 5 min-20 min, the sweeping speed is 10 mv-100 mv, the applied voltage is-1.05V-1.55V (V vs. NHE), the time of passing Ar is 1 h-8 h, and the gas phase electrolysis product is detected by gas chromatography; spin-drying the liquid, making hydrogen spectrum nuclear magnetism, and detecting the liquid phase product.
The CO is introduced into 2 The electrochemical characterization is carried out by introducing CO 2 The time of (2) is 5-20 min, the sweeping speed is 10-100 mv, the applied voltage is-1.05V to-1.55V (V vs. NHE), the electrified electrolysis time is 1-8 h, and the gas phase electrolysis product is detected by gas chromatography; spin-drying the liquid, making hydrogen spectrum nuclear magnetism, and detecting the liquid phase product.
In addition, unless otherwise specified, all raw materials used in the present invention are commercially available, and any ranges recited in the present invention include any numerical value between the end values and any sub-range constituted by any numerical value between the end values or any numerical value between the end values.
The beneficial effects of the invention are as follows:
(1) The tridentate phosphine ligand metal catalyst provided by the invention has the advantages that the supporting ligand is directly purchased from the market, and the ligand synthesis time is saved.
(2) The preparation method of the tridentate phosphine ligand metal catalyst is prepared in one step, and has the advantages of simple operation, high economic efficiency and good environmental protection.
(3) The three phosphine atoms in the structure of the tridentate phosphine ligand metal catalyst are coordinated with the metal center, and three flexible coordination sites are provided for carbon dioxide to react.
(4) The tridentate phosphine ligand metal catalyst can effectively and selectively reduce carbon dioxide into formic acid, and the selectivity performance of the catalyst reaches 85 percent.
(5) The tridentate phosphine ligand metal catalyst of the present invention has little activity in catalyzing hydrogen production.
Drawings
FIG. 1 is a synthetic route for the tridentate phosphine ligand iron-based acetonitrile complex of example 1 of the present invention.
FIG. 2 is a schematic view showing the crystal structure of the tridentate phosphine ligand iron-based acetonitrile complex in example 1 of the present invention.
FIG. 3 is an electrochemical cyclic voltammogram of a tridentate phosphine ligand iron-based metal catalyst of comparative example 2 of the present invention.
FIG. 4 is a graph showing electrochemical cyclic voltammetry of 2.5mM symmetric tetradentate phosphine ligand iron-based metal catalyst in acetonitrile of 0.1M tetrabutylammonium hexafluorophosphate with addition of 0-10% vol water under Ar atmosphere in example 3 of the present invention.
FIG. 5 is a graph of CO in example 4 of the present invention 2 Electrochemical cyclic voltammogram of 2.5mM symmetric tetradentate phosphine ligand iron-based metal catalyst in 0.1M acetonitrile of tetrabutylammonium hexafluorophosphate with addition of 0-10% vol water in the atmosphere.
FIG. 6 shows the product distribution of the catalyst concentration of 2.5Mm, with no water added, for varying the potentials of-1.15V to 1.55V vs. NHE in example 5 of the present invention.
FIG. 7 is a distribution of the electrolytic product of phosphine ligand iron-based metal catalyst in acetonitrile of 0.1M tetrabutylammonium hexafluorophosphate when water was added in a volume fraction of 0 to 10% vol with a control potential of-1.25V vs. NHE in example 6 of the present invention.
FIG. 8 is an electrolytic product distribution of a tridentate phosphine ligand iron-based metal catalyst in 0.1M tetrabutylammonium hexafluorophosphate acetonitrile with a control potential of-1.25V vs. NHE, varying the catalyst concentration from 0.5mMl to 5mMl, in example 7 of the present invention.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
In the invention, the preparation method is a conventional method unless specified otherwise, the percentages are mass percentages unless specified otherwise, the units M are mol/L unless specified otherwise, the reaction conditions are normal temperature and normal pressure conditions, the used medicines and solvents are all from the market, the catalyst synthesis is carried out in a glove box, acetonitrile is obtained by a solvent purification system, and deionized water is obtained by a Master-S15 UV Water Purification system of an ultrapure water machine. Other cases are not illustrated and are used without treatment.
Electrochemical experiments in the present invention all used a CHI 705E electrochemical workstation (CH Instruments, inc., TX). The three electrode system included a glassy carbon working electrode, a platinum wire counter electrode, and a silver/silver nitrate reference electrode (BASi, 10mM silver nitrate, 0.1M acetonitrile solution of tetrabutylammonium hexafluorophosphate, 0.55V vs NHE) gas filled in two separate cells. Before each test, the glassy carbon electrode (BAsi, 7.1mm 2 ) All were polished with 0.05 μm aluminum paste to give a mirror image surface, and then sonicated with ultrapure water and acetone. For cyclic voltammetry experiments, one side of the working electrode and the counter electrode, the other side of the reference electrode. For the electrolysis experiments, the reference electrode and the counter electrode on one side and the working electrode on the other side were converted to a standard hydrogen potential NHE by adding 0.55V. The gas phase product was detected by Varian 8610C-GC, which was equipped with a molecular sieve and a PDHID detector. The electrochemical test is carried out under mild conditions, if no special statement is made, accidents such as severe temperature rise and the like can not occur.
Example 1
Tridentate phosphine ligand iron-acetonitrile metal catalyst, i.e. 1 MeCN The structural formula is as follows:
compound 1 MeCN The synthetic route of (2) is shown in figure 1, and specifically comprises the following steps:
the reactant A is weighed in a glove box(1.0 mmol) in a 25ml single-port bottle, 10ml acetonitrile was added and mixed uniformly to form a white suspension, and [ Fe (H) 2 O) 6 ](BF 4 ) 2 (1.0 mmol) was dissolved in 5ml of acetonitrile, and the dissolved [ Fe (H) 2 O) 6 ](BF 4 ) 2 Slowly dripping into the obtained white suspension, and continuously stirring. And (3) in the dripping process, the suspension is found to be continuously dissolved and finally becomes transparent orange-yellow solution, stirring is continued for 1h until the reaction is complete, filtering is carried out, a vacuum pump is used for pumping acetonitrile serving as a solvent, and finally orange-yellow solid powder is obtained.
Recrystallizing the solid powder with acetonitrile and diethyl ether to obtain pale yellow crystals, separating solid from liquid, and pumping the solid to obtain product 1 MeCN The yield was 93%. For the prepared 1 MeCN By performing X-ray single crystal diffraction, as shown in FIG. 2, compound 1 was analyzed MeCN As pale yellow crystals obtained by slow diffusion of diethyl ether into acetonitrile at room temperature, the crystal structure showed 1 MeCN The middle iron atom being represented by ligand L 1 Three acetonitrile molecules form a hexacoordinated octahedral structure.
Example 2
For example 1 MeCN Electrochemical performance characterization:
to 2.5mL of acetonitrile containing 0.1M tetrabutylammonium hexafluorophosphate was added 1 obtained in example 1 MeCN A mixed solution was obtained, wherein the concentration of the mixed solution was 2.5mM (i.e., 2.5mmol of 1 per L of acetonitrile of tetrabutylammonium hexafluorophosphate) MeCN ) After 10min Ar is passed, the electrochemical CV is swept at a sweep speed of 100 mV/s; after that, after 10min of carbon dioxide exchange, the electrochemical CV was swept at a sweep rate of 100 mV/s.
Characterization results are shown in FIG. 3, cyclic Voltammograms (CV) of the compounds in acetonitrile solution of Ar or CO 2 Obtaining the product; wherein under Ar, compound 1 MeCN There are four sets of electroreduction peaks, belonging to the reduction electron pair of Fe (III)/Fe (II) (peak I), the reduction electron pair of Fe (II)/Fe (I) (peak II) and the reduction electron pair of Fe (I)/Fe (0) (peak III), respectively, and the peak at-0.25V is the peak of the negative hydrogen compound.
When the solution is filled with CO 2 After that, the catalytic current density at Fe (I)/Fe (0) was significantly enhanced, 2.25 times higher than that under Ar, indicating that Fe (I)/Fe (0) is the electrocatalytic peak of carbon dioxide and the electrocatalytic activity of carbon dioxide is very strong. When no catalyst is added to the system, the current in CV is not changed obviouslyAnd (5) melting.
Example 3
Under the Ar atmosphere, water with different volume fractions is added to the mixture of the mixture 1 prepared in the example 1 MeCN The electrochemical performance of (a) is affected by the following steps:
to 2.5mL of acetonitrile containing 0.1M tetrabutylammonium hexafluorophosphate was added 1 obtained in example 1 MeCN A mixed solution was obtained, wherein the concentration of the mixed solution was 2.5mM (i.e., 2.5mmol of 1 per L of acetonitrile of tetrabutylammonium hexafluorophosphate) MeCN ) After 10min Ar, the electrochemical CV was swept at a sweep rate of 100 mV/s. Then, water was added to the mixture in different volume fractions, wherein each of the water was 0% vol, 1% vol, 5% vol, and 10% vol based on the volume of the mixture, and the electrochemical CV was swept at a sweep rate of 100 mV/s.
FIG. 4 shows 2.5mM 1 under Ar MeCN CV in acetonitrile of 0-10% water. The peak height of Fe (I)/Fe (0) was hardly changed as compared with the dry case, which is described as 1 MeCN Not a hydrogen-producing catalyst.
Example 4
Inspection of CO 2 Under atmosphere, different volume fractions of water were added to the mixture of 1 prepared in example 1 MeCN The electrochemical performance of (a) is affected by the following steps:
to 2.5mL of acetonitrile containing 0.1M tetrabutylammonium hexafluorophosphate was added 2.5mM of 1 obtained in example 1 MeCN Then, water was added to the system in various volume fractions so that the water in the system was 0% vol, 1% vol, 3% vol, 5% vol, 7% vol, 10% vol, and after passing carbon dioxide for 5 minutes, the electrochemical CV was swept at a sweep rate of 100 mV/s.
The results are shown in FIG. 5:
in CO 2 In the case where the water fraction was increased from 0 to 10%, the Fe (II)/Fe (0) was increased, but the increase was not very significant, indicating that the addition of water was to the system CO 2 The promotion effect under the condition is not great.
Example 5
Control potential electrolysis experiments:
to 2.5mL of acetonitrile containing 0.1M tetrabutylammonium hexafluorophosphate was added 1 obtained in example 1 MeCN Obtaining a mixed solution, whereinThe concentration of the mixture was 2.5mM (i.e., 2.5mmol of 1 per L of acetonitrile of tetrabutylammonium hexafluorophosphate) MeCN ) After introducing carbon dioxide for 15min, sealing the electrolytic cell, electrolyzing, stopping electrolysis when the electrolysis electric quantity reaches 1.0-2.0 ℃, pumping 2mL of gas phase gas by using a sample injection needle, and pumping into gas chromatography to detect a gas phase electrolysis product; then, 1mL of liquid phase was spin-dried, 10. Mu.L of a 100mM standard solution of N, N-dimethylformamide in acetonitrile was added to prepare a hydrogen spectrum nuclear magnetism, and the liquid phase product was detected.
The effect of different potentials was examined: the control potentials are respectively: -1.15v vs. nhe, -1.25v vs. nhe, -1.35v vs. nhe, -1.45v vs. nhe, -1.55v vs. nhe.
The gas produced in the electrochemical cell was analyzed by gas chromatography and the liquid phase solution was characterized by nuclear magnetic NMR.
As a result, as shown in FIG. 6, the best electrolysis was performed at-1.25V vs. NHE for 2 hours, resulting in a formic acid selectivity of 85%.
Example 6
The effect of the addition of different volume fractions of water on the electrolysis product was examined, and the Controlled Potential Electrocatalytic (CPE) experiment was performed at-1.25V vs NHE, i.e. the method steps were identical to example 5, except that: to the mixture was added water in an amount of 0% by volume, 1% by volume, 3% by volume, 5% by volume, 7% by volume, and 10% by volume, respectively, and then carbon dioxide was introduced for electrolysis.
Controlled Potential Electrocatalysis (CPE) experiments were performed at-1.25V vs NHE and the results are shown in FIG. 7 where the Faraday efficiency of formic acid decreases with increasing water addition, H 2 The faraday efficiency of (c) gradually increases, but formic acid is still the absolute main product.
Example 7
The effect of catalyst concentration on the electrolysis product was examined, and the potentiometric electro-Catalysis (CPE) experiment was performed at-1.25V vs NHE, with no water added to the reaction system, i.e. the method steps were identical to example 5, except that: the concentrations of the catalyst in the mixture were controlled to be 0mM, 0.5mM, 1mM, 2.5mM and 5mM, respectively, and then electrolysis was performed by passing carbon dioxide.
Controlled Potential Electrocatalysis (CPE) experiments at-1.25V vs NHE, the results are shown in FIG. 8, formic acid and H with increasing catalyst concentration 2 Almost no change in faraday efficiency, and the catalyst concentration had little effect on the product distribution.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (10)
1. A tridentate phosphine ligand metal catalyst is characterized in that the catalyst is of a hexacoordinated octahedral model structure shown in a formula I,
wherein R is 1 、R 2 、R 3 Each independently of the others may be the same or different a hydrogen atom, a C1-C12 alkyl group, an alkoxy group, a phenyl group, a benzyl group, an amine group, a pyridyl group, an oxazolyl group; ln is a transition metal;
L 1 、L 2 each L 3 Independently may be the same or different halogen atom, acetonitrile molecule, carboxylate group, methanol molecule, water molecule or tetrahydrofuran group.
2. The tridentate phosphine ligand metal catalyst of claim 1 wherein R is 1 、R 2 、R 3 Each independently represents a hydrogen atom, a phenyl group, a benzyl group, an amino group, a pyridyl group, an oxazolyl group, a 6 alkyl group or a C1-C6 alkoxy group;
ln is iron, cobalt or nickel.
3. A tridentate phosphine ligand metal according to claim 1The preparation method of the catalyst is characterized in that a reactant A and a solvent M are mixed to obtain a white suspension B; mixing transition metal salt and a solvent N to obtain a mixed solution C; mixing the mixed solution C and the suspension B at room temperature for reaction for 30 min-1 h to obtain a metal catalyst; wherein, the structural formula of the reactant A is as follows:the solvent M and the solvent N may be the same or different and are each selected from acetonitrile, tetrahydrofuran or toluene.
4. A method of preparation according to claim 3, wherein the transition metal is iron, cobalt or nickel.
5. The method of claim 4, wherein the iron salt is iron tetrafluoroborate hexahydrate, iron tetra acetonitrile trifluoromethane sulfonate, iron acetate or iron halide.
6. The method according to claim 3, wherein the final concentration of reactant A in the white suspension B is 1mM-5M, and the final concentration of transition metal salt in the mixed solution C is 1mM-5mM;
the concentration ratio of the mixed solution C to the suspension B is 1:1-1:1.2.
7. Use of a tridentate phosphine ligand ferrous metal catalyst according to claim 1 in the electrocatalytic reduction of carbon dioxide.
8. A method for preparing formic acid by electrocatalytic reduction of carbon dioxide is characterized by comprising the following steps: and dissolving tetrabutylammonium hexafluorophosphate in acetonitrile to obtain a mixed solution D, mixing the mixed solution D with the catalyst of claim 1 to obtain a mixed solution E, and carrying out electrochemical catalytic reaction on the mixed solution E by carbon dioxide to obtain formic acid.
9. The method of manufacturing according to claim 8, wherein: adding water into the mixed solution E during the electrochemical reaction system to enable the volume fraction of the water in the reaction system to be 1-10%vol; the addition amount of the catalyst in the electrochemical reaction system is 0.1mM-5mM.
10. The method of manufacturing according to claim 8, wherein: the CO is introduced into 2 The electrochemical characterization is carried out by introducing CO 2 The time of the process is 5 min-20 min, the sweeping speed is 10 mv-100 mv, the applied voltage is-1.05V to-1.55V (V vs. NHE), and the electrified electrolysis time is 1 h-8 h.
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