CN106582710B - 一种石墨烯负载钯铜纳米催化Suzuki反应制备联苯的方法 - Google Patents
一种石墨烯负载钯铜纳米催化Suzuki反应制备联苯的方法 Download PDFInfo
- Publication number
- CN106582710B CN106582710B CN201611044914.3A CN201611044914A CN106582710B CN 106582710 B CN106582710 B CN 106582710B CN 201611044914 A CN201611044914 A CN 201611044914A CN 106582710 B CN106582710 B CN 106582710B
- Authority
- CN
- China
- Prior art keywords
- graphene
- nano capsule
- copper nano
- supported palladium
- palladium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 47
- 239000010949 copper Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 22
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title abstract description 41
- 239000004305 biphenyl Substances 0.000 title abstract description 20
- 235000010290 biphenyl Nutrition 0.000 title abstract description 20
- 238000006069 Suzuki reaction reaction Methods 0.000 title abstract description 10
- 239000002088 nanocapsule Substances 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 230000009467 reduction Effects 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 81
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 18
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 17
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 10
- PXEDJBXQKAGXNJ-QTNFYWBSSA-L disodium L-glutamate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](N)CCC([O-])=O PXEDJBXQKAGXNJ-QTNFYWBSSA-L 0.000 claims description 10
- 235000013923 monosodium glutamate Nutrition 0.000 claims description 10
- 229940073490 sodium glutamate Drugs 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 3
- DIOZVWSHACHNRT-UHFFFAOYSA-N 2-(2-prop-2-enoxyethoxy)ethanol Chemical compound OCCOCCOCC=C DIOZVWSHACHNRT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- BZVCUDFTTWZWPF-UHFFFAOYSA-M potassium;ethane-1,2-diol;hydroxide Chemical compound [OH-].[K+].OCCO BZVCUDFTTWZWPF-UHFFFAOYSA-M 0.000 claims description 2
- SNGZVXPRGLTKNU-RGMNGODLSA-N [Na].C(CC)N[C@@H](CCO)C(=O)O Chemical compound [Na].C(CC)N[C@@H](CCO)C(=O)O SNGZVXPRGLTKNU-RGMNGODLSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 150000008282 halocarbons Chemical class 0.000 abstract description 12
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 150000002940 palladium Chemical class 0.000 abstract 1
- 231100000572 poisoning Toxicity 0.000 abstract 1
- 230000000607 poisoning effect Effects 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 41
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 26
- 235000019441 ethanol Nutrition 0.000 description 25
- 239000007788 liquid Substances 0.000 description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 13
- 229910000027 potassium carbonate Inorganic materials 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 238000010792 warming Methods 0.000 description 11
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 6
- 239000002024 ethyl acetate extract Substances 0.000 description 6
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 6
- QBELEDRHMPMKHP-UHFFFAOYSA-N 1-bromo-2-chlorobenzene Chemical compound ClC1=CC=CC=C1Br QBELEDRHMPMKHP-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VOIZNVUXCQLQHS-UHFFFAOYSA-N 3-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC(Br)=C1 VOIZNVUXCQLQHS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000011280 coal tar Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- -1 γ-bromo anthracene Chemical compound 0.000 description 2
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- DZHFFMWJXJBBRG-UHFFFAOYSA-N 1-bromo-3,5-dichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Br)=C1 DZHFFMWJXJBBRG-UHFFFAOYSA-N 0.000 description 1
- XRXMNWGCKISMOH-UHFFFAOYSA-N 2-bromobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Br XRXMNWGCKISMOH-UHFFFAOYSA-N 0.000 description 1
- APSMUYYLXZULMS-UHFFFAOYSA-N 2-bromonaphthalene Chemical compound C1=CC=CC2=CC(Br)=CC=C21 APSMUYYLXZULMS-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- ATXXLNCPVSUCNK-UHFFFAOYSA-N 5-bromo-2-nitropyridine Chemical compound [O-][N+](=O)C1=CC=C(Br)C=N1 ATXXLNCPVSUCNK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229940106205 potassium 20 mg Drugs 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种石墨烯负载钯铜纳米胶囊催化Suzuki偶联反应制备联苯的方法。通过氧化石墨烯和铜盐、钯盐溶液的水热还原，经洗涤、干燥得到石墨烯负载钯铜纳米胶囊催化剂。使用石墨烯负载钯铜胶囊型纳米胶囊催化Suzuki偶联反应制备联苯反应中有良好的催化作用，实现高效催化的同时减少了钯的使用量，并减少了钯中毒。卤代烃化合物转化率超过90%，联苯化合物选择性达到95%，并对多种卤代烃化合物有良好适用性。
Description
技术领域
本发明公开了一种石墨烯负载钯铜纳米胶囊催化剂的制备方法及其在催化Suzuki偶联反应制备联苯中的应用。
背景技术
从2004年，英国曼彻斯特大学的Geim课题组利用非常简单的胶带剥离石墨的方法首次制备出了稳定的高质量的单层和少数几层石墨烯，到现在人们逐渐将其实现生产规模化和实用化，石墨烯的有关技术已经成为了化学材料研究领域中的重要研究课题。石墨烯拥有独特的二维结构和优异的物理、化学性能，这一点引发了全世界范围内对这一材料的理论与实践研究。由于其独特的二维共轭结构，石墨烯展现出诸多突出的物理化学性质。各国学者开始尝试应用化学或者物理等相关方法开发各种可靠的石墨烯制备方法。包括机械剥离法、外延生长法、化学气相沉积法、胶体溶液法以及其它一些方法。其中，化学法制备石墨烯越来越受到人们关注。石墨烯巨大的比表面积可以为金属纳米粒子的负载提供一个优良场所，并且石墨烯的片层结构可以增大与反应物的接触，有效的提高反应速率和效率。
联苯是重要的有机原料，广泛用于医药、农药、染料、液晶材料等领域。可以用来合成增塑剂、防腐剂，还可以用于制造燃料、工程塑料和高能燃料等。联苯存在于煤焦油、原油和天然气中。制备联苯，传统方法是通过各种煤焦油馏分制联苯的分离提取法；联苯在煤焦油中的质量分数为0.20%~0.40%，含量太少，此类方法已使用较少。还有石油化工上，通过苯热解制联苯的化学合成法。随着钯催化偶联反应近50年的发展，通过偶联方法合成联苯类化合物已经成为主要的合成手段。而用钯催化剂通过Suzuki偶联反应制备联苯化合物已是最经济的合成方案。为了开发出更加高效的催化剂，同时也降低钯催化剂的使用量，发展协调匹配的双金属或多金属催化剂，协助钯金属的催化作用，这类含钯复合催化材料的开发变的越来越重要。
发明内容
在本发明的目的在于发展一种石墨烯负载钯铜纳米胶囊催化Suzuki偶联反应制备联苯的方法。通过氧化石墨烯和氯化钯、硫酸铜的水热还原，经洗涤、干燥得到石墨烯负载钯铜胶囊型纳米胶囊催化剂。使用石墨烯负载钯铜纳米胶囊催化剂在 Suzuki偶联反应中有很好的催化作用，可把卤代烃化合物高选择性、高效率地合成联苯化合物。实现高效催化的同时减少了钯的使用量，并且通过钯、铜之间的电子效应，减少了钯中毒的情况发生。卤代烃化合物转化率超过90%，联苯化合物选择性达到95%，对多种卤代烃化合物有优秀的催化适用性。
为实现上述目的，本发明采用下述技术方案：
1、一种石墨烯负载钯铜纳米胶囊催化剂的制备方法，主要是由氧化石墨烯、氯化钯、硫酸铜通过水热还原反应制得，其制备方法包括以下步骤：将氯化钯乙二醇溶液逐滴加入到Hummers法制备的氧化石墨烯乙二醇浆液中，在29 oC下搅拌混合40分钟，加入硫酸铜水溶液、谷氨酸钠后，通过滴加一定浓度的氢氧化钾乙二醇溶液，调节pH至10~13，25~30 oC搅拌一定时间，移入水热釜中，180 oC下水热反应8~16小时，水、乙醇洗涤，干燥得石墨烯负载钯铜纳米胶囊催化剂。
2、石墨烯负载钯铜纳米胶囊催化剂的制备方法，10mg/mL的氧化石墨烯水溶浆液乙二醇配制后氧化石墨烯成浆液浓度为0.5~1.5mg/mL，优选0.8mg/mL~1.2 mg/mL。
3、石墨烯负载钯铜纳米胶囊催化剂的制备方法，氯化钯、硫酸铜的摩尔比为2~7:9~3,优选4~7:7~5。水溶浆液中所含氧化石墨烯质量和L-谷氨酸钠质量之比为3:5。
4、一种石墨烯负载钯铜纳米胶囊催化Suzuki偶联反应制备联苯的方法，包括下述步骤：将卤代烃化合物、苯硼酸、碳酸钾、石墨烯负载钯铜纳米胶囊催化剂置于反应装置中，卤代烃化合物：苯硼酸：碳酸钾摩尔比=1:1~3:1~6；卤代烃化合物与石墨烯负载钯铜纳米胶囊的质量比为20~200:1，优选为50~100:1；以水和乙醇体积比1:1配制溶剂加入到反应体系中，溶剂体积为1~30mL/1mmol（卤代烃化合物），优选4~12mL/1mmol（卤代烃化合物），60~100℃下加热反应4~24小时。
5、石墨烯负载钯铜纳米胶囊催化Suzuki偶联反应制备联苯的方法，卤代烃化合物包括碘苯、溴苯、γ-溴代蒽、间氯溴苯、对氯溴苯、对甲基溴苯、对溴苯甲醛、邻溴苯甲酸、α-溴代萘、β-溴代萘、间溴苯甲酸、3,5-二氯溴苯、氯苯、2-硝基-5-溴吡啶。
与现有技术相比，本发明的有益效果是：
通过氧化石墨烯和氯化钯、硫酸铜通过水热还原把氧化石墨烯和铜离子、钯离子同时原位还原，从而得到纳米尺寸的钯铜纳米胶囊均匀分散在还原石墨烯片上。反应后经水、乙醇洗，冻干得到石墨烯负载的钯铜纳米胶囊催化剂。使用所得复合催化剂在比例为1:1的水和乙醇混合液中进行反应，卤代烃化合物的转化率超过90%，联苯化合物选择性达到95%。反应完成后，回收非均相的石墨烯负载钯铜纳米胶囊催化剂，重复使用五次，卤代烃化合物的转化率仍超过90%，联苯化合物选择性仍达到95%。
具体实施方式
石墨烯负载钯铜纳米胶囊催化剂制备实例：
1、取一100mL烧杯，量取3.0mL10.0mg/mL的氧化石墨烯水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取2.8mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取0.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入50.0mg谷氨酸钠固体，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至11，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
2、取一100mL烧杯，量取1.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取3.7mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取0.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入25.0mg谷氨酸钠固体，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至13，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
3、取一100mL烧杯，量取4.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取3.7mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取0.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入75.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至13，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
4、取一100mL烧杯，量取3.0mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取2.6mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入50.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至12，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
5、取一100mL烧杯，量取1.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取2.6mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入25.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至13，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
6、取一100mL烧杯，量取4.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取2.6mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入75.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至11，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
7、取一100mL烧杯，量取3.0mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取0.5mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入50.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至11，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
8、取一100mL烧杯，量取1.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取0.5mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入25.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至11，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
9、取一100mL烧杯，量取4.5mL10.0 mg/mL的氧化石墨烯的水溶浆液，分散到30.0mL的乙二醇中，超声分散均匀，充分搅拌。量取0.5mL（6.7mg/mL）的氯化钯乙二醇溶液，逐滴加入其中，再量取1.6mL（25mg/mL）的硫酸铜水溶液缓慢加入到体系中，称取加入75.0mg谷氨酸钠缓慢加入到体系中，超声分散，搅拌40min，使体系混合均匀。然后滴加8wt%氢氧化钾的乙二醇溶液，直至溶液pH至11，搅拌30min。将混合体系移入水热釜中，180℃下通过上升热气流反应8h。降温，反复水、乙醇洗，浸泡，干燥后得到石墨烯负载钯铜纳米胶囊催化剂。
石墨烯负载钯铜纳米胶囊催化氢气还原硝基芳烃化合物制备芳基胺化合物的方法实施例：
1、取一38mL的密封管，加入94.7mg溴苯、80.8mg苯硼酸、110.0mg碳酸钾和1.4mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应8h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，碘苯的转化率为100.0%，联苯化合物的选择性为100.0%。
2、取一38mL的密封管，加入61.9mg碘苯、40.7mg苯硼酸、106.0mg碳酸钾和1.0mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应4h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，碘苯的转化率为100.0%，联苯化合物的选择性为100.0%。
3、取一38mL的密封管，加入100.6mg邻溴苯甲醛、73.0mg苯硼酸、106.0mg碳酸钾和2.0mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应8h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，邻溴苯甲醛的转化率为99.5%，联苯化合物的选择性为99.8%。
4、取一38mL的密封管，加入51.1mg间溴苯甲酸、59.3mg苯硼酸、112.0mg碳酸钾和1.0mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应10h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，间溴苯甲酸的转化率为99.6%，联苯化合物的选择性为80%。
5、取一38mL的密封管，加入98.9mg γ-溴代蒽、34.6mg苯硼酸、81.7mg碳酸钾和1.3mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应4h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，γ-溴代蒽的转化率为91.6%，联苯化合物的选择性为98.6%。
6、取一38mL的密封管，加入105.5mg间氯溴苯、85.3mg苯硼酸、157.8mg碳酸钾和1.7mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应4h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，间氯溴苯的转化率为99.9%，联苯化合物的选择性为100.0%。
7、取一38mL的密封管，加入77.2mg对溴碘苯、108.0mg苯硼酸、180.0mg碳酸钾和1.2mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应4h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，对溴碘苯的转化率为98.9%，联苯化合物的选择性为99.1%。
8、取一38mL的密封管，加入94.9mg对氯溴苯、71.0mg苯硼酸、103.2mg碳酸钾和1.1mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应4h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，碘苯的转化率为96.3%，联苯化合物的选择性为99.0%。
9、取一38mL的密封管，加入126.9mg对甲氧基溴苯、95.4mg苯硼酸、146.0mg碳酸钾和1.5mg石墨烯负载钯铜纳米胶囊催化剂，量取3.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应10h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，碘苯的转化率为98.7%，联苯化合物的选择性为99.0%。
10、取一100mL的密封管，加入1.25g溴苯、0.897g苯硼酸、1.86g碳酸钾和20mg石墨烯负载钯铜纳米胶囊催化剂，量取30mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应8h后，停止加热，自然冷却至室温。过滤，将滤出固体用乙醇和水洗涤，离心，干燥，收集固体催化剂。然后称取1.25g溴苯、0.90g苯硼酸、1.86g碳酸钾、回收的固体催化剂和30.0mL的比例为1:1的水和乙醇混合液作为溶剂加入其中。油浴升温至80℃，反应8h后，停止加热，自然冷却至室温。过滤得到滤液，并用乙酸乙酯萃取有机相，并用液相色谱和气相色谱分析，并用液相色谱和气相色谱分析，溴苯的转化率为96.0%，联苯化合物的选择性为96.5%。重复套用石墨烯负载钯铜纳米胶囊催化剂，按此方法。
上述虽然结合实施例对本发明的具体实施方式进行了描述，但并非对本发明实施方式的限定。对所属领域技术人员来说，在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围以内。
Claims (3)
1.一种石墨烯负载钯铜纳米胶囊催化剂的制备方法，其特征在于，主要是由氧化石墨烯、氯化钯、硫酸铜通过水热还原法制得，其制备方法包括以下步骤：将氯化钯乙二醇溶液逐滴加入到Hummers法制备的氧化石墨烯乙二醇浆液中，在29 ℃下搅拌混合40分钟，加入硫酸铜水溶液、谷氨酸钠后，通过滴加一定浓度的氢氧化钾乙二醇溶液，调节pH至10-13，25-30 ℃搅拌一定时间，移入水热釜中，180 ℃下水热反应8-16小时，水、乙醇洗涤，干燥得石墨烯负载钯铜纳米胶囊催化剂。
2.根据权利要求1所述的一种石墨烯负载钯铜纳米胶囊催化剂的制备方法，Hummers法制备的氧化石墨烯水溶浆液浓度为10mg/mL，乙二醇配制后的氧化石墨烯浓度为0.5-1.5mg/mL。
3.根据权利要求2所述的一种石墨烯负载钯铜纳米胶囊催化剂的制备方法，其特征在于，氯化钯：硫酸铜的摩尔比为2~7:9~3，氧化石墨烯水溶浆液中所含氧化石墨烯质量与谷氨酸钠的质量比为3:5。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611044914.3A CN106582710B (zh) | 2016-11-24 | 2016-11-24 | 一种石墨烯负载钯铜纳米催化Suzuki反应制备联苯的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611044914.3A CN106582710B (zh) | 2016-11-24 | 2016-11-24 | 一种石墨烯负载钯铜纳米催化Suzuki反应制备联苯的方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106582710A CN106582710A (zh) | 2017-04-26 |
| CN106582710B true CN106582710B (zh) | 2019-11-22 |
Family
ID=58592120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611044914.3A Expired - Fee Related CN106582710B (zh) | 2016-11-24 | 2016-11-24 | 一种石墨烯负载钯铜纳米催化Suzuki反应制备联苯的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106582710B (zh) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107195912A (zh) * | 2017-05-15 | 2017-09-22 | 上海电力学院 | 一种含有石墨烯材料的催化剂及其制备方法 |
| CN109301268B (zh) * | 2018-09-29 | 2021-09-07 | 信阳师范学院 | Li-CO2电池正极催化剂材料及其制备方法、电池正极材料以及电池 |
| CN109342745A (zh) * | 2018-12-21 | 2019-02-15 | 山东理工大学 | 一种基于PdCu@GO的夹心型电化学免疫传感器的构建方法及应用 |
| CN110090648B (zh) * | 2019-04-30 | 2021-10-29 | 皖南医学院 | 一种还原氧化石墨烯负载的铜钯氧化物纳米颗粒及其制备方法和应用 |
| CN110180587A (zh) * | 2019-06-28 | 2019-08-30 | 江西省汉高新材料有限公司 | 功能化硅纳米片负载钯催化剂的制备方法及其应用 |
| CN111203230B (zh) * | 2020-01-23 | 2022-08-23 | 陕西师范大学 | 一种Pd/FeOOH@RGO皮克林乳液及其催化碳碳偶联反应的应用 |
| CN111499566A (zh) * | 2020-04-30 | 2020-08-07 | 南京工业大学 | 一种吡啶衍生物化合物及其制备方法 |
| CN113244966B (zh) * | 2021-05-24 | 2023-04-07 | 南京邮电大学 | 一种钯镍钛乙二醇配位聚合物非均相催化剂及其制备方法和应用 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508449A (zh) * | 2012-06-29 | 2014-01-15 | 中国科学院合肥物质科学研究院 | 修饰有金属纳米粒子的石墨烯复合材料的制备方法 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014005598A1 (en) * | 2012-07-06 | 2014-01-09 | Teknologisk Institut | Method of preparing a catalytic structure |
| US20140213427A1 (en) * | 2013-01-31 | 2014-07-31 | Sunpower Technologies Llc | Photocatalyst for the Reduction of Carbon Dioxide |
-
2016
- 2016-11-24 CN CN201611044914.3A patent/CN106582710B/zh not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508449A (zh) * | 2012-06-29 | 2014-01-15 | 中国科学院合肥物质科学研究院 | 修饰有金属纳米粒子的石墨烯复合材料的制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| 石墨烯负载钯铜纳米催化剂的制备及其催化性能的研究;马静静;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20150615(第6期);第16页2.3.1节和17页2.3.2.2节 * |
| 高效催化Suzuki偶联反应的催化剂——石墨烯负载纳米Pd-Cu合金纳米复合材料;林欣燕 等;《合成化学研究》;20131231(第1期);第6页左栏第3段和右栏第4段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106582710A (zh) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106582710B (zh) | 一种石墨烯负载钯铜纳米催化Suzuki反应制备联苯的方法 | |
| CN106423204A (zh) | 一种石墨烯负载钯镍纳米合金催化还原硝基芳烃的方法 | |
| Meng et al. | Synthesis of ketones from biomass-derived feedstock | |
| CN102633821B (zh) | 由嘧啶羧酸基配体构筑的铜配合物及其制备方法与应用 | |
| CN106563507B (zh) | 纳米负载金属有机框架钯复合催化剂及制备方法与应用 | |
| Sabbatani et al. | Gold‐Catalyzed Intermolecular Synthesis of Alkylidenecyclopropanes through Catalytic Allene Activation | |
| CN105233872A (zh) | 一种Pd@MIL-101复合材料及其制备方法和应用 | |
| CN105523981B (zh) | 一种二苯碲醚衍生物及其制备方法 | |
| Rao et al. | Influence of pendent alkyl chains on Heck and Sonogashira C–C coupling catalyzed with palladium (II) complexes of selenated Schiff bases having liquid crystalline properties | |
| CN103068721A (zh) | 氢或重氢的制造方法及利用该制造方法而进行的有机化合物的氢化或重氢化 | |
| CN109053471A (zh) | 一种[60]富勒烯环戊烯衍生物的合成方法 | |
| CN106607091B (zh) | 微孔聚合物-纳米金属粒子催化剂及其制备方法和应用 | |
| Chen et al. | Poly (o-aminothiophenol)-stabilized Pd nanoparticles as efficient heterogenous catalysts for Suzuki cross-coupling reactions | |
| CN104437453B (zh) | 一种碳气凝胶催化剂及其制备方法和用途 | |
| Yoo et al. | Birch Reduction of Aromatic Compounds by Inorganic Electride [Ca2N]+• e–in an Alcoholic Solvent: An Analogue of Solvated Electrons | |
| CN102513098A (zh) | 碳纳米管负载钯复合材料的制备方法 | |
| Doroodmand et al. | Sulfonated multiwalled carbon nanotubes (MWCNTs) as a new, efficient, and recyclable heterogeneous nanocatalyst for the synthesis of amines | |
| CN103467500B (zh) | 一种铜配合物 | |
| Valentini et al. | Tailor-Made POLITAG-Pd0 Catalyst for the Low-Loading Mizoroki–Heck Reaction in γ-Valerolactone as a Safe Reaction Medium | |
| CN108786922B (zh) | 一种偶联反应用镍、钯修饰纳米二氧化硅的制备方法 | |
| CN107384357A (zh) | 聚氧乙烯‑苯磺酸盐型复合双子表面活性剂及其制备方法 | |
| Premi et al. | A nitrogen and sulphur functionalized graphene oxide–palladium nanoparticle hybrid catalyst for an efficient Heck coupling | |
| CN113694968A (zh) | 钯负载磁性UiO-66三元复合催化材料及其制备方法和应用 | |
| Jiang et al. | A strategy to facilitate reuse of palladium catalyst stabilized by block copolymer micelles | |
| CN104841429B (zh) | 一种合成气制甲醇负载型铜基催化剂及其制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191122 Termination date: 20201124 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |