CN117160463A - Preparation method and application of cerium oxide supported copper-based catalyst - Google Patents
Preparation method and application of cerium oxide supported copper-based catalyst Download PDFInfo
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- CN117160463A CN117160463A CN202311138589.7A CN202311138589A CN117160463A CN 117160463 A CN117160463 A CN 117160463A CN 202311138589 A CN202311138589 A CN 202311138589A CN 117160463 A CN117160463 A CN 117160463A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 239000010949 copper Substances 0.000 title abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910000420 cerium oxide Inorganic materials 0.000 title abstract description 9
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052802 copper Inorganic materials 0.000 title abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000000126 substance Substances 0.000 claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical class O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 4
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical class OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 22
- 239000000376 reactant Substances 0.000 claims description 20
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- -1 (4-methoxybenzyl) 2-propynyl-1-ylamine Chemical compound 0.000 claims description 9
- 238000010490 three component reaction Methods 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 5
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical class NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 claims description 5
- 230000021523 carboxylation Effects 0.000 claims description 4
- 238000006473 carboxylation reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- QYLFHLNFIHBCPR-UHFFFAOYSA-N 1-ethynylcyclohexan-1-ol Chemical compound C#CC1(O)CCCCC1 QYLFHLNFIHBCPR-UHFFFAOYSA-N 0.000 claims description 3
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 claims description 3
- PUNRPAWKFTXZIW-UHFFFAOYSA-N 3-ethylpent-1-yn-3-ol Chemical compound CCC(O)(CC)C#C PUNRPAWKFTXZIW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- IZKIWEYIOKPHLF-UHFFFAOYSA-N n-prop-2-ynylaniline Chemical compound C#CCNC1=CC=CC=C1 IZKIWEYIOKPHLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000003570 air Substances 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 1
- 229910052786 argon Inorganic materials 0.000 claims 1
- LDYSJQKNEXGCPH-UHFFFAOYSA-N n-(2-phenylethyl)prop-2-yn-1-amine Chemical compound C#CCNCCC1=CC=CC=C1 LDYSJQKNEXGCPH-UHFFFAOYSA-N 0.000 claims 1
- PDZCAXWOOIGGAM-UHFFFAOYSA-N n-prop-2-ynylcyclohexanamine Chemical compound C#CCNC1CCCCC1 PDZCAXWOOIGGAM-UHFFFAOYSA-N 0.000 claims 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 18
- 238000001354 calcination Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000012298 atmosphere Substances 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004312 hexamethylene tetramine Substances 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000006661 Meyer-Schuster rearrangement reaction Methods 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000006178 Rupe rearrangement reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000013310 covalent-organic framework Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
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- 239000012847 fine chemical Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
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Classifications
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a cerium oxide (CeO) 2 ) Preparation method and application of supported copper (Cu) based catalyst, wherein Cu in the catalyst is supported on CeO in the form of combination of Cu monoatoms and Cu nano-particles, or Cu monoatomic mixed valence combination or Cu mixed oxide combination 2 A surface. The catalyst of the invention can be used for the preparation of a catalyst for the reaction of carbon dioxide (CO 2 ) As raw materials, three different high-added value chemicals and derivative products of cyclic carbonates, oxazolidinones and alpha-hydroxyketones are prepared.
Description
Technical Field
The invention belongs to the fields of materials, catalysis and chemical industry, and in particular relates to CeO 2 A method for preparing a copper-based heterogeneous catalyst and application thereof.
Background
CO 2 Is a non-toxic harmless, cheap and easily available renewable C1 resource, and is near toFor years in CO 2 There is a great deal of interest in producing fine chemicals. CO 2 Carboxylation cyclization reactions to cyclic carbonates, oxazolidinones and their derivative components are research hotspots. CO 2 The alpha-methylene cyclic carbonate can be prepared with propargyl alcohol, is a functional organic substance widely existing in natural products or microorganisms, contains a high-activity ester group and an exocyclic carbon-carbon double bond in the structure, is easy to derivatize, is often used as an intermediate in the reaction process, and has higher bioactivity or synthesis application value. In addition, CO 2 Can also be used to prepare higher value added derivatised products such as oxazolidinones, alpha-hydroxy ketones, carbamates, asymmetric carbonates and the like, e.g. CO 2 Propargyl alcohol, H 2 The three-component derivatization reaction of O can obtain alpha-hydroxy ketone compounds.
The alpha-methylene cyclic carbonate is an important organic synthesis intermediate and a chemical intermediate, and homogeneous catalysts such as Ru (Journal ofMolecular Catalysis,1992,74 (1-3): 97-107), pd (The Journal of Organic Chemistry,1986,51 (26): 5499-5501), cu (Journal ofOrganometallic Chemistry,1997,545-546: 337-344), ag (Bulletin ofthe Chemical Society ofJapan,2011,84 (7): 698-717 and the like), phosphine (The Journal ofOrganic Chemistry,2007,72 (2): 647-649 and the like), N-heterocyclic carbene (NHC) (Angewandte Chemie,2009,121 (23): 4258-4261) and K are all frequently used at present 2 CO 3 Crown ether (Journal of Molecular Catalysis A: chemical,1999,139 (1): 1-9), dicycloguanidine (Advanced Synthesis)&Catalysis,2011,353 (1): 133-146), ag-NHC complex (Advanced Synthesis)&Catalysis,2013,355 (10): 2019-2028), N-heterocycloalkene/CO 2 Adducts (Journal of the American Chemical Society,2013,135 (32): 11996-12003) have also been developed for this reaction (ACS Catalysis,2017,7 (3): 2248-2256). Furthermore, ionic liquids (ACS Sustainable Chemistry&Reactions of Engineering,2019,7 (6): 5614-5619) or electrochemical methods (ratio Tetrahedron,2010,66 (52): 9981-9985) have also been reported. However, the prior art still has the defects, and the cost of the ionic liquid catalytic system of homogeneous catalysis is widely appliedHigh, the products, other raw materials and catalysts are difficult to separate from a homogeneous mixed system, and purification is difficult. Currently, there is a technology of immobilizing ionic liquid onto a carrier such as a covalent organic framework structural Material (MOF) (angel.chem.int.ed.2022, e 202114817), thereby realizing heterogeneous phase of a homogeneous catalyst and facilitating separation of a product from the catalyst. However, similar immobilization technology of homogeneous catalyst causes problems of complex preparation process, high cost and the like of catalytic materials, and can cause loss of catalyst molecules after multiple uses, and most of the catalyst molecules need higher CO 2 Pressure and water removal solvent. Therefore, there is an urgent need to develop a low-cost, environment-friendly preparation method and heterogeneous (heterogeneous) catalysis technology to realize CO 2 The chemical fixation is carried out on high added value products such as alpha-methylene cyclic carbonates, oxazolidinones, alpha-hydroxyketones and the like.
The alpha-hydroxy ketone is an important structure existing in various medicines and natural products, and the earliest traditional synthetic route needs to use strong acids such as highly toxic mercury salt, sulfuric acid and the like, is easy to pollute the environment and does not accord with the principle of green chemistry. Various strategies for preparing alpha-hydroxy ketone by olefin oxidation, ketone reduction, acetyl alcohol hydration and the like appear later, but Meyer-Schuster rearrangement, rupe rearrangement and the like easily occur, so that the problems of more byproducts, low product purity, low yield and the like are caused. Development of new chemical reaction catalytic systems and preparation processes is urgently needed.
Therefore, the patent can obtain the flaky cerium oxide nano-sheet supported Cu-based heterogeneous catalyst through a scientific design and a preferred stepwise reduction preparation method and a water phase impregnation reduction method combined with subsequent treatment means of different high-temperature calcination atmospheres, so as to realize the effective combination of different levels of catalytic active sites such as a nano structure, a monoatomic structure and the like and realize CO 2 And propargyl alcohol and propargylamine to prepare the alpha-methylene cyclic carbonate compound and the oxazolidinone compound by the double-molecule synergistic conversion, so that the reaction selectivity and universality can be obviously improved. In addition, the multicomponent Cu-based heterogeneous catalyst can catalyze CO 2 Propargyl alcohol, H 2 The O three-component reaction generates the alpha-hydroxy ketone compound in one step, and is a method for efficiently synthesizing the alpha-hydroxy ketone compound in a novel environment-friendly reaction catalytic system. The book is provided withPatent is development of novel heterogeneous catalyst and CO 2 Catalytic conversion technology is applied.
Disclosure of Invention
One of the problems to be solved by the invention is to solve the existing CO 2 Participating in the synthesis of cyclic carbonates and oxazolidinones, and CO 2 Propargyl alcohol compound, H 2 The catalyst for synthesizing alpha-hydroxy ketone compound by O three-component derivative reaction has the problems of harsh catalytic condition, long reaction time and insufficient active site, and provides a new catalyst and a synthesizing method thereof. In order to solve the technical problems, the invention adopts the following technical scheme:
one aspect of the invention relates to a CeO 2 A Cu-based catalyst in which Cu is supported in the form of a combination of mixed valence states of Cu monoatoms, or a combination of Cu monoatoms and Cu nanoparticles, or a combination of composite oxides of Cu 2 A surface. The catalyst of the invention has a mixed coexisting multicomponent catalytic site and a polymolecular activation characteristic, and can be used for catalyzing CO 2 And propargyl alcohol/amine compounds react to generate cyclic carbonate compounds and oxazolidinone compounds, and can also be used for catalyzing CO 2 Propargyl alcohol and H 2 O three components react to generate alpha-hydroxy copper, and CO is efficiently realized 2 The chemical fixation is three different high-added value biological medicines and organic chemical chemicals. The metal loaded by the invention is Cu, so that the cost is low, and the catalytic activity of the catalyst is further improved.
In a preferred embodiment of the present invention, the CeO 2 Has oxygen vacancies. The invention adopts CeO 2 As a support, more oxygen vacancies are provided for the metal loading, contributing to improved catalytic yields.
In a preferred embodiment of the present invention, the catalyst is a two-dimensional nano-platelet structure. For the catalyst of the invention, the catalyst is of a two-dimensional nano sheet structure, so that the catalyst has the advantages of large specific surface area and open pores, is beneficial to heat transfer, mass transfer and diffusion, and is beneficial to the rapid departure of products from a reaction place, thereby inhibiting side reactions and improving the catalytic efficiency.
In another preferred embodiment of the present invention, the loading of the metal is 0.05 to 10wt% of the total weight of the catalyst.
Another object of the present invention is to provide a process for preparing the above catalyst; the preparation method comprises the following steps: by hydrothermal method and by air and H 2 Synthesis of defect-rich CeO by two-step calcination 2 A nanosheet; dispersing the prepared carrier in alcohol solution, loading Cu metal while stirring, and adding NaBH 4 And (3) drying after reduction, and calcining the dried solid.
In a preferred embodiment of the invention, the calcination is in the presence of H 2 Ar, air or N 2 Is calcined in the atmosphere of (a). In view of improving catalytic performance and inducing formation of multicomponent Cu sites, the catalyst is preferably selected from H 2 Calcination was performed in a mixed gas atmosphere of/Ar. By reduction of H 2 Calcining to obtain monovalent monoatomic Cu 1 Site and zero-valent nanoparticle Cu n Coexisting Cu 1 +Cu n /CeO 2 Catalysts by protective atmosphere N 2 Calcining to obtain Cu with coexisting mixed valence state single atomic site 1 /CeO 2 Catalyst, cu with mixed oxide coexistent is obtained by oxidizing atmosphere Air calcination x O/CeO 2 (x=1, 2) catalyst.
In another aspect, the invention also relates to the use of the catalyst in the catalysis of propargyl alcohol compounds, propargyl amine compounds and CO 2 The reaction is carried out to generate cyclic carbonic ester, oxazolidinone compound and H 2 The O three-component derivatization reaction is used for generating alpha-hydroxy copper.
In a preferred embodiment of the invention, the catalyst catalyzes propargyl alcohol/amine compounds and CO 2 The reaction comprises the following steps: dispersing propargyl alcohol/amine compound, catalyst and auxiliary agent in solvent, and mixing with CO 2 The reaction is carried out under an atmosphere.
In a preferred embodiment of the present invention, the reaction is carried out at normal temperature and pressure.
In a preferred embodiment of the present invention, the catalyst catalyzes the reaction of a propargyl alcohol,CO 2 And H 2 The O three-component reaction comprises the following steps: propargyl alcohol compound, H 2 O, catalyst and auxiliary agent are dispersed in solvent, and CO 2 The reaction is carried out under an atmosphere.
In a preferred embodiment of the present invention, the reaction is carried out at 70-90℃under normal pressure.
In a preferred embodiment of the present invention, the propargyl alcohol/amine compounds include, but are not limited to, the following different sterically hindered, electron donating, electron deficient propargyl alcohol/amine molecules, such as: 2-methyl-3-butyn-2-ol, ethynyl cyclohexanol, 3-methyl-1-pentyn-3-ol, 3-ethyl-1-pentyn-3-ol, 3, 5-dimethyl-1-hexyn-3-ol, N- (2-propynyl) aniline, and the like.
In a preferred embodiment of the present invention, the solvent includes, but is not limited to, acetonitrile, N-dimethylformamide and other polar solvents, and the adjuvant includes, but is not limited to, 1, 8-diazabicyclo undec-7-ene (DBU).
In a preferred embodiment of the present invention, the propargyl alcohol/amine compound and CO 2 The catalytic conversion of the reaction is more than 99%, and the selectivity of the reaction is more than 92%. The propargyl alcohol compound and CO 2 And H 2 The catalytic conversion rate of the O three-component reaction is more than 99 percent, and the selectivity is more than 88 percent.
The invention has the advantages that the catalyst is a heterogeneous catalyst, and the problems of overhigh catalyst cost, harsh reaction conditions, difficult separation and purification of the catalyst and the like in the conventional homogeneous reaction system are solved to a certain extent.
To achieve the above object, ceO is preferred in the present invention 2 The preparation of Cu-based catalyst loaded with multi-component active sites and the test technical scheme of catalytic reaction are as follows:
a. adding cerium salt, a morphology guiding agent and a pH regulator into deionized water, uniformly mixing, then putting into a reaction kettle for hydrothermal synthesis, and centrifugally washing and drying to obtain white precipitate;
b. calcining the white precipitate obtained in the step a in a muffle furnace to obtain a pale yellow two-dimensional flaky cerium oxide carrier;
c. the pale yellow two-dimensional flaky cerium oxide carrier obtained in the step b is carried out at 5%H 2 Calcining in Ar mixed gas to obtain a two-dimensional flaky cerium oxide carrier rich in defects;
d. c, dispersing the powdery sample obtained in the step c in alcohol, adding a certain amount of copper salt for soaking, adding a reducing substance according to a proportion for reduction, and performing suction filtration, washing and drying to obtain a supported catalyst;
e. the catalyst obtained in step d was treated in a different atmosphere (5%H 2 /Ar、N 2 Air) to obtain three oxide supported catalysts containing multicomponent Cu sites.
Preferably, the cerium salt in the step a is one of cerium nitrate and cerium chloride.
Preferably, the morphology directing agent in step a is one of hexamethylenetetramine, cetyltrimethylammonium chloride and cetyltrimethylammonium bromide.
Preferably, the pH regulator in the step a is one of glacial acetic acid, dilute hydrochloric acid and dilute nitric acid.
Preferably, the alcohol in step c is one of ethanol, methanol and ethylene glycol.
Preferably, the copper salt in step c is one of copper nitrate, copper chloride and copper acetate.
Preferably, the reducing substance in the step c is one of citric acid, hydrazine hydrate and sodium borohydride.
The invention has the beneficial effects that:
the method adopts a water phase sodium borohydride wet impregnation method and a step reduction method of high-temperature calcination in different atmospheres to synthesize the Cu-based metal catalyst with different multicomponent active sites on the surface. Meanwhile, different calcining atmospheres regulate the number of oxygen vacancies on the carrier, so as to regulate the interaction between the carrier and metal, thereby achieving the synergistic improvement of the performance. And the reaction substrate is relatively wide, so that the method can be suitable for various propargyl alcohol and propargylamine compounds.
Drawings
Fig. 1: a reaction equation for the carboxylation cyclization reaction of propargyl alcohol with carbon dioxide.
Fig. 2: propargyl alcohol, CO 2 And H 2 O three-component reaction equation.
Fig. 3: transmission electron microscopy images of the catalytic materials prepared in examples 1,2 and 3.
Fig. 4: cu prepared in example 1 1 +Cu n /CeO 2 Spherical aberration correcting electron microscope image of catalytic material.
Fig. 5: x-ray diffraction patterns (XRD) for the catalytic materials were prepared in examples 1,2 and 3.
Fig. 6: x-ray photoelectron spectra (XPS) of Cu 2p of the catalytic materials prepared in examples 1,2 and 3 confirm the presence of mixed valence components of Cu monoatoms and Cu oxides.
Fig. 7: ceO prepared in comparative example 1 2 Transmission electron microscopy of catalytic material.
Fig. 8: the product alpha-methylene cyclic carbonate prepared in example 4 1 HNMR profile.
Fig. 9-13: example 4 expansion of the products of substrate preparation 1 HNMR profile.
Detailed Description
In order to further understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. 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.
Unless otherwise specified, all reagents involved in the examples of the present invention are commercially available products and are commercially available.
Example 1: cu (Cu) 1 +Cu n /CeO 2 Synthesis of catalyst (Cu 1 Refers to copper monoatoms, cu n Copper nanoparticles):
a. 325mg of Ce (NO) 3 ) 3 ·6H 2 Dissolving O and 736mg of hexamethylenetetramine in 15mL of methanol, adding 0.6mL of glacial acetic acid, stirring at normal temperature, and adding into high concentrationAnd (3) in a warm reaction kettle, reacting for 9 hours at 140 ℃.
b. And c, centrifugally washing the product in the step a, and drying in vacuum. Calcining the dried powder in air at 500 ℃ for 2 hours, and then in H 2 Calcining at 350 ℃ in Ar for 3 hours.
c. And c, dissolving the carrier in the step b in methanol, dropwise adding a copper acetate solution, wherein the Cu loading amount of the copper acetate solution accounts for 5wt% of the carrier, stirring for 12 hours at normal temperature, slowly dropwise adding a sodium borohydride solution with the amount of Cu atoms and other substances, stirring at normal temperature, filtering, and vacuum drying.
d. Subjecting the product of step c to H 2 Heating to 200deg.C under Ar atmosphere according to programming, and maintaining for 2 hr to obtain Cu 1 +Cu n /CeO 2 A catalyst.
Example 2: cu (Cu) 1 /CeO 2 And (3) synthesizing a catalyst:
a. the earlier steps are similar to a-c in example 1.
b. The product of step a is taken up in N 2 Heating to 200deg.C under the atmosphere according to the programming, and maintaining for 2 hr to obtain Cu 1 /CeO 2 A catalyst. As can be seen from the XPS test results of FIG. 6, cu 1 /CeO 2 Having Cu + And Cu 2+ Is a peak of the mixed valence state.
Example 3: cu (Cu) x O/CeO 2 (x=1, 2) synthesis of catalyst:
a. the earlier steps are similar to a-c in example 1.
b. Heating the product in the step a to 200 ℃ in an air atmosphere according to the programming and maintaining for 2 hours to obtain Cu x O/CeO 2 (x=1, 2) catalyst. The detection result showed that the divalent Cu atomic ratio was 42.5% and the monovalent Cu atomic ratio was 57.5%.
The morphology of the catalyst is characterized by using a transmission electron microscope, and the CeO of the two-dimensional material is shown by the material under the transmission electron microscope 2 Thin nano-hexagonal platelets (fig. 3), surface-dispersed protrusions all indicate the presence of Cu-based small particles. Example 1 in addition to the presence of Cu-based particles, there was also a dispersion of metallic Cu monoatoms, which was verified by spherical aberration microscopy (fig. 4). XRD of examples 1,2, 3 confirmed the chemical phases and compositions of the catalysts (fig. 5).Information on the electronic structure and the element valence around these catalyst surface elements (including Ce, cn, O) was obtained by XPS (fig. 6). The above results collectively demonstrate that example 1 is a coexistence of Cu monoatomic sites and nanoparticle sites; example 2 is the coexistence of Cu monatomic mixed valence sites; example 3 oxide nanoparticles Cu of different Mixed valence states x O (x=1, 2) sites coexist.
Example 4: cu (Cu) 1 +Cu n /CeO 2 In propargyl alcohol/amine and CO 2 Catalytic application in reactions
100mg of the catalyst of example 1 was weighed into a reactor, 1mmol of the reactant and 1mmol of DBU were added thereto, and 3mL of acetonitrile was added thereto. CO is blown into the reactor 2 After the gas is discharged, the upper end of the reactor is sleeved with a balloon and CO 2 The gas is inflated to a certain volume. Then reacting for 5h at 25 ℃ and a certain stirring speed. After the reaction is completed, a certain amount of internal standard biphenyl is added, the reaction solution is taken out, and clear and transparent supernatant is reserved. The catalytic performance test was performed by gas chromatography and nuclear magnetic resonance, and the yield was calculated, and the results are shown in table 1.
TABLE 1
[a] The yield represents the yield of the pure product after purification
Example 5: cu (Cu) 1 /CeO 2 In propargyl alcohol and CO 2 Catalytic application in reactions
100mg of the catalyst of example 2 was weighed into a reactor, 1mmol of the reactant 2-methyl-3-butyn-2-ol and 1mmol of DBU were added thereto, 3mL of acetonitrile was then added to the reactor, and the catalyst was sufficiently dispersed in acetonitrile by an ultrasonic machine. CO is blown into the reactor 2 After the gas is discharged, the upper end of the reactor is sleeved with a balloon and the reactor is connected with a gas supply pipeCO 2 The gas is inflated to a certain volume. Then reacting for 5h at 25 ℃ and a certain stirring speed. After the reaction is completed, a certain amount of internal standard biphenyl is added, the reaction solution is taken out, and clear and transparent supernatant is reserved. The conversion of the reactant was 77.7% as measured by gas chromatography, and the selectivity of the objective product, α -methylene cyclic carbonate, was 78.2%.
Example 6: cu (Cu) x O/CeO 2 In propargyl alcohol and CO 2 Catalytic application in reactions
100mg of the catalyst of example 3 was weighed into a reactor, 1mmol of the reactant 2-methyl-3-butyn-2-ol and 1mmol of DBU were added thereto, 3mL of acetonitrile was then added to the reactor, and the catalyst was sufficiently dispersed in acetonitrile by an ultrasonic machine. Reactor bubbling CO 2 After the gas is discharged, the upper end of the reactor is sleeved with a balloon and CO 2 The gas is inflated to a certain volume. Then reacting for 5h at 25 ℃ and a certain stirring speed. After the reaction is completed, a certain amount of internal standard biphenyl is added, the reaction solution is taken out, and clear and transparent supernatant is reserved. The conversion of the reactant was 42% as measured by gas chromatography, and the selectivity of the objective product, α -methylene cyclic carbonate, was 33%.
Three catalysts are used for catalyzing propargyl alcohol and CO 2 The catalytic properties in the reaction are shown in Table 2.
TABLE 2
The experimental results show that Cu 1 +Cu n /CeO 2 The catalyst has the best results in terms of conversion, selectivity and yield, cu 1 /CeO 2 Catalyst secondary, cu x O/CeO 2 The catalyst has relatively poor catalytic effect, but still has catalytic effect.
Example 7: c (C)u 1 +Cu n /CeO 2 In propargyl alcohol, CO 2 And H 2 Catalytic application in O three-component reaction
100mg of the catalyst from example 1 were weighed into a reactor, to which 1mmol of the reactant 2-methyl-3-butyn-2-ol, 2mmol of H were added 2 O and 1mmol of DBU, then 3mL of acetonitrile was added to the reactor and placed in an ultrasonic machine to thoroughly disperse the catalyst in acetonitrile. Reactor bubbling CO 2 After the gas is discharged, the upper end of the reactor is sleeved with a balloon and CO 2 The gas is inflated to a certain volume. Then reacting for 5h at a certain stirring speed at the temperature of 80 ℃. After the reaction is completed, a certain amount of internal standard biphenyl is added, the reaction solution is taken out, and clear and transparent supernatant is reserved. The conversion of the reactant was 99.7% as measured by gas chromatography, and the selectivity of the target product α -hydroxyketone was 88.7%.
Example 8: cu (Cu) 1 /CeO 2 In propargyl alcohol, CO 2 And H 2 Catalytic application in O three-component reaction
100mg of the catalyst from example 2 were weighed into a reactor, to which 1mmol of the reactant 2-methyl-3-butyn-2-ol, 2mmol of H were added 2 O and 1mmol of DBU, then 3mL of acetonitrile was added to the reactor and placed in an ultrasonic machine to thoroughly disperse the catalyst in acetonitrile. Reactor bubbling CO 2 After the gas is discharged, the upper end of the reactor is sleeved with a balloon and CO 2 The gas is inflated to a certain volume. Then reacting for 5h at a certain stirring speed at the temperature of 80 ℃. After the reaction is completed, a certain amount of internal standard biphenyl is added, the reaction solution is taken out, and clear and transparent supernatant is reserved. The conversion of the reactant was 93.5% as measured by gas chromatography, and the selectivity of the target product α -hydroxyketone was 88.7%.
Example 9: cu (Cu) x O/CeO 2 In propargyl alcohol, CO 2 And H 2 Catalytic application in O three-component reaction
100mg of the catalyst from example 3 were weighed into a reactor, to which 1mmol of the reactant 2-methyl-3-butyn-2-ol, 2mmol of H were added 2 O and 1mmol of DBU, then 3mL of acetonitrile was added to the reactor, and the mixture was placed in an ultrasonic machine to make the catalystSufficiently dispersed in acetonitrile. Reactor bubbling CO 2 After the gas is discharged, the upper end of the reactor is sleeved with a balloon and CO 2 The gas is inflated to a certain volume. Then reacting for 5h at a certain stirring speed at the temperature of 80 ℃. After the reaction is completed, a certain amount of internal standard biphenyl is added, the reaction solution is taken out, and clear and transparent supernatant is reserved. The conversion of the reactant was 72.7% as measured by gas chromatography, and the selectivity of the target product α -hydroxyketone was 90.1%.
The three catalysts are used for catalyzing propargyl alcohol and CO 2 And H 2 The catalytic properties in the O three-component reaction are shown in Table 3.
TABLE 3 Table 3
| Examples | Catalyst | Conversion (%) | Selectivity (%) | Yield (%) |
| 7 | Example 1 | 99.7 | 88.7 | 88.4 |
| 8 | Example 2 | 93.5 | 88.7 | 82.9 |
| 9 | Example 3 | 72.7 | 90.1 | 65.5 |
The experimental results show that Cu 1 +Cu n /CeO 2 The catalyst has the best results in terms of conversion, selectivity and yield, cu 1 /CeO 2 Catalyst secondary, cu x O/CeO 2 The catalyst has relatively poor catalytic effect, but still has catalytic effect.
Comparative example 1: ceO (CeO) 2 Preparation of the Carrier
a. 325mg of Ce (NO) 3 ) 3 ·6H 2 O and 736mg of hexamethylenetetramine are dissolved in 15mL of methanol, 0.6mL of glacial acetic acid is added, stirred, and placed in a high-temperature reaction kettle for reaction for 9h at 140 ℃.
b. And c, centrifugally washing the product in the step a, and drying in vacuum. Calcining the dried powder in air at 500 ℃ for 2 hours, and then in H 2 Calcining for 3 hours at 350 ℃ in Ar to obtain CeO 2 A carrier.
The morphology of the catalyst was characterized using transmission electron microscopy and the material was found to exhibit lamellar layers of two-dimensional material under transmission electron microscopy (fig. 7).
Comparative example 2: ceO (CeO) 2 In propargyl alcohol and CO 2 Catalytic application in reactions
100mg of the catalyst of comparative example 1 was weighed into a reactor, 1mmol of the reactant 2-methyl-3-butyn-2-ol and 1mmol of DBU were added thereto, 3mL of acetonitrile was then added to the reactor, and the catalyst was sufficiently dispersed in acetonitrile by an ultrasonic machine. CO is blown into the reactor 2 After the gas is discharged, the upper end of the reactor is sleeved with a balloon and CO 2 The gas is inflated to a certain volume. Then reacting for 5h at 25 ℃ and a certain stirring speed. After the reaction is completed, adding a certain amount of internal standard biphenyl, taking out the reaction solution, and keeping clearTransparent supernatant. The conversion of the reactant was 46.3% as measured by gas chromatography, and the selectivity of the objective product, α -methylene cyclic carbonate, was 52.8%.
Comparative example 3: commercial Cu 2 O powder in propargyl alcohol and CO 2 Catalytic application in reactions
Weigh 4.4mg commercial Cu 2 The O powder was placed in a reactor, to which was added 1mmol of the reactant 2-methyl-3-butyn-2-ol and 1mmol of DBU, and then 3mL of acetonitrile was added to the reactor, and placed in an ultrasonic machine to allow the catalyst to be sufficiently dispersed in acetonitrile. Reactor bubbling CO 2 After the gas is discharged, the upper end of the reactor is sleeved with a balloon and CO 2 The gas is inflated to a certain volume. Then reacting for 5h at 25 ℃ and a certain stirring speed. After the reaction is completed, a certain amount of internal standard biphenyl is added, the reaction solution is taken out, and clear and transparent supernatant is reserved. The conversion of the reactant was 9.9% as measured by gas chromatography, and the selectivity of the objective product, α -methylene cyclic carbonate, was 65.4%.
Comparative example 4: commercial Cu powder in propargyl alcohol and CO 2 Catalytic application in reactions
4.4mg of commercial Cu powder was weighed into a reactor, to which was added 1mmol of the reactant 2-methyl-3-butyn-2-ol and 1mmol of DBU, followed by 3mL of acetonitrile into the reactor, and placed in an ultrasonic machine to allow the catalyst to be sufficiently dispersed in acetonitrile. Reactor bubbling CO 2 After the gas is discharged, the upper end of the reactor is sleeved with a balloon and CO 2 The gas is inflated to a certain volume. Then reacting for 5h at 25 ℃ and a certain stirring speed. After the reaction is completed, a certain amount of internal standard biphenyl is added, the reaction solution is taken out, and clear and transparent supernatant is reserved. The conversion of the reactants was 79.2% by gas chromatography and the selectivity of the target product, α -methylene cyclic carbonate, was 80.9%.
Comparative examples 2, 3 and 4 in the catalysis of propargyl alcohol with CO 2 The catalytic properties in the reaction are shown in Table 2.
The foregoing describes preferred embodiments of the present invention, but is not intended to limit the invention thereto. Modifications and variations to the embodiments disclosed herein may be made by those skilled in the art without departing from the scope and spirit of the invention.
Claims (10)
1. CeO (CeO) 2 A Cu-based catalyst, wherein Cu is supported on CeO in the form of a combination of Cu monoatoms and Cu nano-particles, or a combination of mixed valence states of Cu monoatoms or a combination of Cu composite oxides 2 A surface.
2. The catalyst of claim 1, wherein the Cu is supported on CeO in the form of a combination of Cu monoatoms and Cu nanoparticles 2 A surface.
3. The catalyst according to claim 1 or 2, wherein the loading of the metallic Cu is 0.05-30wt% of the total weight of the catalyst; preferably 3.0 to 7.0wt%.
4. The catalyst of claim 1 or 2, which is a two-dimensional nano-platelet structure.
5. The method for preparing a catalyst according to any one of claims 1 to 4, which is prepared by a stepwise reduction method comprising aqueous phase sodium borohydride (NaBH 4 ) The chemical wet impregnation method is reduced and calcined at high temperature in different atmospheres, wherein the atmospheres are respectively selected from hydrogen-argon mixed gas, nitrogen or air.
6. The use of the catalyst according to any one of claims 1-4 for catalyzing carboxylation cyclization reaction of propargyl alcohol compounds and carbon dioxide to form cyclic carbonates, wherein the catalyst is used in an amount of 5-8% by mass of reactants, the reaction temperature is 20-80 ℃, the reaction pressure is 0.5-3 atm, and the reaction time is 4-8h.
7. Use according to claim 6, wherein the propargyl alcohol is selected from 2-methyl-3-butyn-2-ol, ethynyl cyclohexanol, 3-methyl-1-pentyn-3-ol, 3-ethyl-1-pentyn-3-ol and/or 3, 5-dimethyl-1-hexyn-3-ol.
8. The use of the catalyst according to any one of claims 1-4 in catalyzing the carboxylation cyclization reaction of propargylamine compounds with carbon dioxide to produce oxazolidinone compounds, wherein the catalyst is used in an amount of 5% -8% by mass of reactants, the reaction temperature is 20-80 ℃, the reaction pressure is 0.5-3 atm, and the reaction time is 4-8h.
9. Use according to claim 8, wherein the propargylamine is selected from the group consisting of N- (2-propynyl) aniline, N-phenethylprop-2-yn-1-amine, N- (prop-2-yn-1-yl) cyclohexylamine, butyl-propynyl-2-imine, (4-methoxybenzyl) 2-propynyl-1-ylamine.
10. The catalyst of any one of claims 1-4 for catalyzing propargyl alcohol and CO 2 And H 2 The application of O in three-component reaction to prepare alpha-hydroxy ketone is characterized in that the dosage of the catalyst in the reaction is 5-8% of the mass of the reactants, the reaction temperature is 70-90 ℃, the reaction pressure is 0.5-3 atm, and the reaction time is 4-8h; preferably, the propargyl alcohol is selected from 2-methyl-3-butyn-2-ol, ethynyl cyclohexanol, 3-methyl-1-pentyn-3-ol, 3-ethyl-1-pentyn-3-ol and/or 3, 5-dimethyl-1-hexyn-3-ol.
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