CN113244957B - Polymeric carbene iridium catalyst and preparation method and application thereof - Google Patents
Polymeric carbene iridium catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 33
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 77
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 42
- 238000005984 hydrogenation reaction Methods 0.000 claims description 42
- ORBBTCHHNMWMCP-UHFFFAOYSA-K cycloocta-1,5-diene trichloroiridium Chemical compound [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1 ORBBTCHHNMWMCP-UHFFFAOYSA-K 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 16
- 125000006310 cycloalkyl amino group Chemical group 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 10
- 239000003446 ligand Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 9
- 235000019253 formic acid Nutrition 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- -1 (amino) carbenes Chemical class 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229910052987 metal hydride Inorganic materials 0.000 description 5
- 150000004681 metal hydrides Chemical class 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- VUFNLQXQSDUXKB-DOFZRALJSA-N 2-[4-[4-[bis(2-chloroethyl)amino]phenyl]butanoyloxy]ethyl (5z,8z,11z,14z)-icosa-5,8,11,14-tetraenoate Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(=O)OCCOC(=O)CCCC1=CC=C(N(CCCl)CCCl)C=C1 VUFNLQXQSDUXKB-DOFZRALJSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- JDZNTUQRMDAIRO-UHFFFAOYSA-N dimethylmyleran Chemical compound CS(=O)(=O)OC(C)CCC(C)OS(C)(=O)=O JDZNTUQRMDAIRO-UHFFFAOYSA-N 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical compound OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 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
- B01J31/2265—Carbenes or carbynes, i.e.(image)
- B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- 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
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
- B01J2531/0233—Aza-Cp ligands, i.e. [CnN(5-n)Rn]- in which n is 0-4 and R is H or hydrocarbyl, or analogous condensed ring systems
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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
The invention provides a polymeric carbene iridium catalyst, a preparation method and application thereof, wherein the polymeric carbene iridium catalyst has a chemical structural formula as follows:
wherein the method comprises the steps of
The polymerization carbene iridium catalyst is a heterogeneous catalyst, so that water can be used as a solvent in the actual catalytic reaction process, the hydrophobicity and the thermal stability of the polymerization carbene iridium catalyst are obviously enhanced, and the protection of Ir-H bonds is very favorable.
Description
Technical Field
The invention relates to the field of preparation of polymeric carbene iridium catalysts, in particular to a polymeric carbene iridium catalyst, and a preparation method and application thereof.
Background
Formic acid (Formic acid), commonly known as Formic acid, is the simplest organic carboxylic acid, and contains both carboxyl groups and aldehyde groups in its molecule as compared with other organic acids, so Formic acid has both acid properties and aldehyde properties. As an important chemical raw material, formic acid has wide application in rubber, leather making, medicine, pesticide, dye, fuel cell, catalytic hydrogen production, agriculture, environmental protection and other industries, and in recent years, the demand of domestic formic acid has been increasing at a speed of more than 10%. Notably, the industry currently producing formic acid by methanol carbonylationThe method is neither environment-friendly nor economical. In the past decades, CO 2 Is considered a promising carbon source due to its non-toxic, readily available and renewable nature. Thus CO 2 Hydrogenation to produce formic acid is a promising alternative.
CO 2 The hydrogenation reaction for preparing formic acid needs to add an alkaline solvent into a reaction system, so that the reaction is thermodynamically feasible. Meanwhile, the addition of weak base can not only form formate with generated formic acid to promote the reaction to be continuously carried out to the right, but also enable the generated formate to be easily separated from a reaction system and then decomposed, so that on one hand, formic acid is obtained, on the other hand, alkali is recovered, and the recycling of the alkali is realized. Research shows that noble metal catalysts (Ir, ru, rh, etc.) and inexpensive transition metals (Cu, fe, etc.) have certain activities for hydrogenation reactions, but the disadvantage is that the catalytic reactions are usually carried out at higher reaction temperatures. Cyclo (alkyl) (amino) carbenes (CAACs) proved to be excellent ligands for transition metals, and are widely used in the catalytic field because of their greater advantage in activating small molecules and hot strong bonds.
In CO 2 During hydrogenation, metal and H 2 The interaction to form metal hydrides (M-Hs) is critical and then CO 2 May be inserted into the M-H bond. In general, M-Hs are unstable in water, except for water-soluble ligands (e.g., tppms, tppts, pta) or polar substituents such as acidic (-SO) 3 H、-CO 2 H) Alkaline (-NR) 2 ) In addition, the catalysts used at present can only be used in organic solvents. Exploring catalyst pairs containing high stability M-Hs active centers to enhance CO 2 The hydrogenation efficiency has important significance.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a novel structure of polymeric carbene iridium catalyst which is heterogeneous and can be prepared by using water as solvent and sodium hydroxide as alkali to react CO at room temperature 2 The catalyst is converted into formate, the defect that organic solvent is needed to be used as solvent in the prior art of adopting homogeneous catalyst is overcome, and the catalyst is green and environment-friendlyThe hydrophobicity and the thermal stability of the catalyst are obviously enhanced, which is very beneficial to the protection of Ir-H bonds.
The second aim of the invention is to provide a preparation method of the polymeric carbene iridium catalyst, which is simple, has tight connection before and after operation steps and is worthy of wide popularization and application.
The third object of the present invention is to provide the application of the above-mentioned polymeric carbene iridium catalyst, and the reaction process has the advantages of mild condition, fast reaction rate, environmental protection, etc. compared with the conventional reaction process, and is CO 2 The hydrogenation preparation of formate provides a new efficient and feasible method.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a polymeric carbene iridium catalyst, which has a chemical structural formula as follows:
In the prior art, M-Hs are unstable in water, except for water-soluble ligands (e.g., tppms, tppts, pta) or polar substituents such as acidic (-SO) 3 H、-CO 2 H) Alkaline (-NR) 2 ) In addition, the catalyst commonly used in the prior art can only be used in an organic solvent, and the stability and catalytic performance of the catalyst are general, so that the invention provides a heterogeneous catalyst for solving the technical problems, and the catalyst belongs to a polymeric carbene iridium catalyst, can still have high catalytic effect under the condition of taking water as a solvent, and has relatively strong hydrophobicity and thermal stability.
Preferably, as a further implementation scheme, the catalyst of the invention is mainly prepared from raw materials of a cycloalkylamino carbene ligand, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, wherein the cycloalkylamino carbene ligand is a carbene iridium catalyst which is frequently used as a catalyst in the prior art, and the structure of the catalyst also belongs to the prior art.
Preferably, as a further embodiment, the molar ratio of the cycloalkylamino carbene ligand, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride is 1: (1-10): (1-10):1. The proportion of raw materials of the synthetic catalyst has a certain influence on the catalytic effect of the catalyst, particularly the proportion of dimethoxymethane and benzene, can influence the dispersion degree of metal elements in the polymer, and the catalyst clusters can be reduced in activity due to the small dispersion degree, and the catalyst concentration can be reduced and is unfavorable for the reaction due to the high dispersion degree, so that the catalyst concentration is preferably controlled in a proper proportion range.
The invention also provides a preparation method of the polymeric carbene iridium catalyst, which comprises the following steps:
all the raw materials are reacted and synthesized at the temperature of 60-150 ℃, and the reaction chemical equation is as follows:
in the specific preparation process, the operating conditions are preferably controlled appropriately, for example, the preparation temperature is generally controlled to be 60-150 ℃, and the temperature needs to be controlled in a relatively appropriate range because the reaction itself is exothermic from the thermodynamic point of view although the reaction is accelerated by the temperature rise.
Preferably, as a further embodiment, the reaction time is from 40 to 80 hours. The reaction time should also be controlled within a suitable range because, although the reaction proceeds in the forward direction by extending the reaction time, the reaction approaches equilibrium after the time increases to some extent, and the increase in catalytic effect decreases.
The invention can catalyze CO by the polymeric carbene iridium catalyst 2 Hydrogenation formate preparationAspects are useful for applications.
Preferably, CO is catalyzed 2 In the reaction process of preparing formate by hydrogenation, the dosage of the polymeric carbene iridium catalyst is 0.000002mmol-0.0002mmol of catalyst per milliliter of solvent based on the molar quantity of iridium.
Preferably, as a further embodiment, the catalytic CO 2 The reaction temperature for preparing formate by hydrogenation is 30-100 ℃.
Preferably, as a further embodiment, the catalytic CO 2 The reaction time for preparing formate by hydrogenation is 12h-48h, and the reaction pressure is 5-7MPa.
Preferably, as a further embodiment, the CO 2 And H is 2 The inlet volume ratio of (2) is 1: (2-3).
Catalytic CO 2 After the reaction for preparing formate by hydrogenation is finished, TON of the reaction can be calculated by the following formula:
wherein TON represents the conversion number of the substrate per mole of the catalyst per unit activity center, n 1 Indicating the amount of formate material produced, n cat Indicating the amount of iridium-containing material in the catalyst used. The formate amount is measured by a hydrogen spectrum nuclear magnetic internal standard method, wherein the internal standard is isopropanol and deuterium water is locked in the field.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention provides a heterogeneous polymerization carbene iridium catalyst with a novel structure, which can take water as a solvent and sodium hydroxide as alkali to carry out CO at room temperature 2 Is converted into formate.
(2) The polymeric carbene iridium catalyst disclosed by the invention has better solubility in a reaction system and better applicability to the current mainstream production process.
(3) The preparation method of the polymeric carbene iridium catalyst provided by the invention is simple, the operation steps are tightly connected before and after, and the catalyst is worthy of wide popularization and application.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to designate like parts throughout the figures. In the drawings:
FIG. 1 is a nuclear magnetic resonance spectrum of a polymeric carbene iridium catalyst provided in example 1 of the present invention;
fig. 2 is an infrared spectrum of the polymeric card funeral iridium catalyst provided in embodiment 1 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
In order to more clearly illustrate the technical scheme of the invention, the following description is given by way of specific examples.
EXAMPLE 1 catalytic CO 2 The reaction process for preparing formate by hydrogenation is as follows:
into a 500mL autoclave, 0.0001mmol of catalyst, 5g of sodium hydroxide and 50mL of water were charged, and CO was introduced after the air was removed 2 2MPa and H 2 The raw materials of the synthesis catalyst are cycloalkyl amino carbene, dimethoxy methane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, and the synthesis condition is 60 ℃ for 40h. CO 2 The reaction temperature of the formate preparation by hydrogenation is 30 ℃, and a sample is taken out for testing after 12 hours of reaction. Under these conditions, TON was 5760, and the confirmation pattern of the resulting catalyst is shown in FIGS. 1-2, in which the formants at 1, 2, 3, 4 and 5 are assigned to carbon, cyclooctadiene, aromatic carbon, quaternary carbon and methylene carbon, respectively.
EXAMPLE 2 catalytic CO 2 The reaction process for preparing formate by hydrogenation is as follows:
into a 500mL autoclave, 0.0001mmol of catalyst, 5g of sodium hydroxide and 50mL of water were charged, and CO was introduced after the air was removed 2 2MPa and H 2 The raw materials of the synthesis catalyst are cycloalkyl amino carbene, dimethoxy methane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:10:10:1, and the synthesis condition is 60 ℃ for 40h. CO 2 The reaction temperature of the formate preparation by hydrogenation is 30 ℃, and a sample is taken out for testing after 12 hours of reaction. Under this condition, TON obtained was 4560.
EXAMPLE 3 catalytic CO 2 The reaction process for preparing formate by hydrogenation is as follows:
into a 500mL autoclave, 0.0001mmol of catalyst, 5g of sodium hydroxide and 50mL of water were charged, and CO was introduced after the air was removed 2 2MPa and H 2 The raw materials of the synthesis catalyst are cycloalkyl amino carbene, dimethoxy methane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, and the synthesis condition is 150 ℃ for 40h. CO 2 The reaction temperature of the formate preparation by hydrogenation is 30 ℃, and a sample is taken out for testing after 12 hours of reaction. Under this condition, TON obtained was 5660.
EXAMPLE 4 catalytic CO 2 The reaction process for preparing formate by hydrogenation is as follows:
into a 500mL autoclave, 0.0002mmol of catalyst, 5g of sodium hydroxide and 50mL of water were charged, and CO was introduced after the air was removed 2 2MPa and H 2 The raw materials of the synthesis catalyst are cycloalkyl amino carbene, dimethoxy methane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, and the synthesis condition is 60 ℃ for 80 hours. CO 2 The reaction temperature of the formate preparation by hydrogenation is 30 ℃, and a sample is taken out for testing after 12 hours of reaction. Under this condition, TON was obtained to be 6400.
EXAMPLE 5 catalysis of CO 2 The reaction process for preparing formate by hydrogenation is as follows:
into a 500mL autoclave, 0.0001mmol of catalyst, 5g of sodium hydroxide and 50mL of water were charged, and CO was introduced after the air was removed 2 2MPa and H 2 The raw materials of the synthesis catalyst are cycloalkyl amino carbene, dimethoxy methane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, and the synthesis condition is 60 ℃ for 40h. CO 2 The reaction temperature of the hydrogenation formate preparation is 100 ℃, and a sample is taken out for testing after 12 hours of reaction. Under this condition, TON was obtained as 7970.
EXAMPLE 6 catalysis of CO 2 The reaction process for preparing formate by hydrogenation is as follows:
into a 500mL autoclave, 0.0001mmol of catalyst, 5g of sodium hydroxide and 50mL of water were charged, and CO was introduced after the air was removed 2 2MPa and H 2 4MPa, the raw material of the synthetic catalyst is cycloalkyl amino cardThe molar ratio of the guest, the dimethoxymethane, the benzene and the 1, 5-cyclooctadiene iridium chloride is 1:1:1:1, and the synthesis condition is 60 ℃ for 40h. CO 2 The reaction temperature of the formate preparation by hydrogenation is 30 ℃, and a sample is taken out for testing after 48 hours of reaction. Under this condition, TON was obtained as 7880.
EXAMPLE 7 catalysis of CO 2 The reaction process for preparing formate by hydrogenation is as follows:
into a 500mL autoclave, 0.0001mmol of catalyst, 5g of sodium hydroxide and 50mL of water were charged, and CO was introduced after the air was removed 2 2MPa and H 2 The raw materials of the synthesis catalyst are cycloalkyl amino carbene, dimethoxy methane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:1:1:1, and the synthesis condition is 60 ℃ for 40h. CO 2 The reaction temperature of the formate preparation by hydrogenation is 30 ℃, and a sample is taken out for testing after 12 hours of reaction. Under this condition, TON obtained was 3280.
EXAMPLE 8 catalysis of CO 2 The reaction process for preparing formate by hydrogenation is as follows:
into a 500mL autoclave, 0.0005mmol of catalyst, 5g of sodium hydroxide and 50mL of water were introduced, and CO was introduced after the air was removed 2 2MPa and H 2 The raw materials of the synthesis catalyst are cycloalkyl amino carbene, dimethoxy methane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:5:5:1, and the synthesis condition is 100 ℃ for 60 hours. CO 2 The reaction temperature of the hydrogenation formate is 50 ℃, and a sample is taken out for testing after 24 hours of reaction. Under this condition, TON was obtained as 5890.
EXAMPLE 9 catalysis of CO 2 The reaction process for preparing formate by hydrogenation is as follows:
into a 500mL autoclave, 0.00002mmol of catalyst, 5g of sodium hydroxide and 50mL of water were added, and CO was introduced after the air was removed 2 2MPa and H 2 The raw materials of the synthesis catalyst are cycloalkyl amino carbene, dimethoxy methane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:10:10:1, and the synthesis condition is 150 ℃ for 80 hours. CO 2 The reaction temperature of the hydrogenation formate preparation is 100 ℃, and a sample is taken out for testing after 48 hours of reaction. Under this condition, TON was obtained as 10680.
Example 10 catalysis of CO 2 The reaction process for preparing formate by hydrogenation is as follows:
into a 500mL autoclave, 0.0005mmol of catalyst, 5g of sodium hydroxide and 50mL of water were introduced, and CO was introduced after the air was removed 2 2MPa and H 2 The raw materials of the synthesis catalyst are cycloalkyl amino carbene, dimethoxy methane, benzene and 1, 5-cyclooctadiene iridium chloride, the molar ratio is 1:2:2:1, and the synthesis condition is 70 ℃ for 60 hours. CO 2 The reaction temperature of the formate preparation by hydrogenation is 70 ℃, and a sample is taken out for testing after 36 hours of reaction. Under this condition, TON was 7650.
Experimental example 1
The following process steps are adopted to catalyze CO 2 Formate is produced by hydrogenation, and TON obtained by the reaction is compared by changing the mole ratio of raw materials.
The specific process comprises the following steps: the molar ratios of cycloalkylamino carbene, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride were respectively according to the following Table 1, with synthesis conditions of 100℃for 70h. Reaction conditions: 0.00001mmol catalyst, 0.5g sodium hydroxide and 5mL water, CO 2 2MPa，H 2 4MPa。CO 2 The reaction temperature of the hydrogenation formate preparation is 100 ℃, and a sample is taken out for testing after 48 hours of reaction.
TABLE 1 influence of different molar ratios on reaction TON
| CAAC, DMM, benzene, irCOD/synthetic molar ratio | TON |
| 1:1:1:1 | 8500 |
| 1:2:2:1 | 10200 |
| 1:5:5:1 | 13400 |
| 1:8:8:1 | 11300 |
| 1:10:10:1 | 7800 |
As can be seen from table 1 above, adjusting the ratio of dimethoxymethane to benzene can affect the degree of dispersion of metal elements in the polymer, and too small a degree of dispersion may cause the catalyst clusters to decrease in activity, and too high a degree of dispersion may cause the catalyst concentration to decrease and be unfavorable for the reaction.
Experimental example 2
The following process steps are adopted to catalyze CO 2 Formate is prepared by hydrogenation, and TON obtained by the reaction is compared by changing the reaction temperature.
The specific process comprises the following steps: the molar ratio of the cycloalkylamino carbene, the dimethoxymethane, the benzene and the 1, 5-cyclooctadiene iridium chloride is 1:5:5:1, and the synthesis condition is 100 ℃ for 70h. Reaction conditions: 0.00001mmol catalyst, 0.5g sodium hydroxide and 5mL water, CO 2 2MPa，H 2 4MPa。CO 2 The formate is prepared by hydrogenation, the specific reaction temperature is shown in the following table 2, and a sample is taken out for testing after 48 hours of reaction.
TABLE 2 influence of reaction temperature on reaction TON
| Hydrogenation reaction temperature | TON |
| 30 | 5900 |
| 50 | 7200 |
| 70 | 9900 |
| 90 | 14600 |
| 100 | 13400 |
As can be seen from Table 2 above, an increase in temperature is advantageous for accelerating the reaction, but the reaction itself is exothermic from a thermodynamic point of view, so that the effect is slightly reduced when the temperature reaches a certain limit.
Experimental example 3
The following process steps are adopted to catalyze CO 2 Formate is prepared by hydrogenation, and TON obtained by the reaction is compared by changing the reaction time.
The specific process comprises the following steps: the molar ratio of the cycloalkylamino carbene, the dimethoxymethane, the benzene and the 1, 5-cyclooctadiene iridium chloride is 1:5:5:1, and the synthesis condition is 100 ℃ for 70h. Reaction conditions: 0.00001mmol catalyst, 0.5g sodium hydroxide and 5mL water, CO 2 2MPa，H 2 4MPa。CO 2 The specific reaction temperature is 90 ℃, the reaction time is shown in the following table 3, and a sample is taken out for testing after the reaction.
TABLE 3 influence of reaction time on reaction TON
| Hydrogenation reaction time | TON |
| 12 | 4300 |
| 18 | 6700 |
| 24 | 9700 |
| 36 | 13500 |
| 48 | 14600 |
As can be seen from table 3 above, the reaction proceeds forward with prolonged reaction time, but the reaction approaches equilibrium after the time increases to some extent, and the catalytic effect increases less.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. The polymeric carbene iridium catalyst is characterized by having a chemical structural formula:
The polymerization carbene iridium catalyst is prepared from raw materials of a cycloalkyl amino carbene ligand, dimethoxymethane, benzene and 1, 5-cyclooctadiene iridium chloride, wherein the molar ratio of the cycloalkyl amino carbene ligand to the dimethoxymethane to the benzene to the 1, 5-cyclooctadiene iridium chloride is 1: (1-10): (1-10) 1;
the polymerization carbene iridium catalyst can take water as a solvent, sodium hydroxide as alkali, and CO is prepared at room temperature 2 Is converted into formate.
2. The method for preparing the polymeric carbene iridium catalyst according to claim 1, which is characterized by comprising the following steps:
all the raw materials are reacted and synthesized at the temperature of 60-150 ℃, and the reaction chemical equation is as follows:
3. the preparation method according to claim 2, wherein the reaction time is 40-80h.
4. The polymeric carbene iridium catalyst of claim 1 or the polymeric carbene iridium catalyst prepared by the preparation method of any one of claims 2 to 3 in the catalysis of CO 2 The application of hydrogenation to formate preparation.
5. The use according to claim 4, characterized in that CO is catalyzed 2 In the reaction process of preparing formate by hydrogenation, the dosage of the polymeric carbene iridium catalyst is 0.000002mmol-0.0002mmol of catalyst per milliliter of solvent based on the molar quantity of iridium.
6. The use according to claim 4, characterized in that CO is catalyzed 2 The reaction temperature for preparing formate by hydrogenation is 30-100 ℃.
7. According to claim4, characterized in that it catalyzes the CO 2 The reaction time for preparing formate by hydrogenation is 12h-48h, and the reaction pressure is 5-7MPa.
8. The use according to claim 4, wherein the CO is 2 And H is 2 The inlet volume ratio of (2) is 1: (2-3).
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| CN111205198A (en) * | 2020-01-24 | 2020-05-29 | 复旦大学 | Method for preparing formamide compound by catalyzing carbon dioxide hydrogenation with porous material |
| CN111841641A (en) * | 2020-07-20 | 2020-10-30 | 浙江大学 | Preparation method and application of N-heterocyclic carbene modified nickel-iridium diatomic carbon-based catalyst |
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| WO2008105430A1 (en) * | 2007-02-27 | 2008-09-04 | Zeon Corporation | Polymerizable composition |
| CN111205198A (en) * | 2020-01-24 | 2020-05-29 | 复旦大学 | Method for preparing formamide compound by catalyzing carbon dioxide hydrogenation with porous material |
| CN111841641A (en) * | 2020-07-20 | 2020-10-30 | 浙江大学 | Preparation method and application of N-heterocyclic carbene modified nickel-iridium diatomic carbon-based catalyst |
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| Dejin Zhang et al..Efficient methanol carbonylation to methyl acetate catalyzed by a cyclic(alkyl)(amino)carbine iridium complex.Catalysis Science & Technology.2020,Fig. 1. * |
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