CN106964347A - 一种碳材料负载纳米Pd催化剂及其制备方法和应用 - Google Patents
一种碳材料负载纳米Pd催化剂及其制备方法和应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000010439 graphite Substances 0.000 claims abstract description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920000151 polyglycol Polymers 0.000 claims abstract description 10
- 239000010695 polyglycol Substances 0.000 claims abstract description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 8
- 230000031709 bromination Effects 0.000 claims abstract description 8
- 238000005893 bromination reaction Methods 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 5
- 238000012986 modification Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 11
- 238000000967 suction filtration Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- -1 bromo aryl compound Chemical class 0.000 claims description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 150000001540 azides Chemical class 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 4
- 229960005055 sodium ascorbate Drugs 0.000 claims description 4
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 4
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
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- 238000004140 cleaning Methods 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
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- GJMNTQBYQYGCTR-UHFFFAOYSA-N 1h-imidazole;methoxymethane Chemical class COC.C1=CNC=N1 GJMNTQBYQYGCTR-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
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- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000002604 ultrasonography Methods 0.000 abstract description 4
- BCMYXYHEMGPZJN-UHFFFAOYSA-N 1-chloro-2-isocyanatoethane Chemical compound ClCCN=C=O BCMYXYHEMGPZJN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract description 2
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
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- 229910021641 deionized water Inorganic materials 0.000 description 8
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- RHDYQUZYHZWTCI-UHFFFAOYSA-N 1-methoxy-4-phenylbenzene Chemical group C1=CC(OC)=CC=C1C1=CC=CC=C1 RHDYQUZYHZWTCI-UHFFFAOYSA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 238000004064 recycling Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- OTDGZDMGSFBZLI-UHFFFAOYSA-N 1-ethynyl-3,5-difluorobenzene Chemical class FC1=CC(F)=CC(C#C)=C1 OTDGZDMGSFBZLI-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- JXYITCJMBRETQX-UHFFFAOYSA-N 4-ethynylaniline Chemical class NC1=CC=C(C#C)C=C1 JXYITCJMBRETQX-UHFFFAOYSA-N 0.000 description 1
- NGPAOBFQERPREC-UHFFFAOYSA-N C=C.C(C)C=1C(=C(C=CC1)CC)CC Chemical compound C=C.C(C)C=1C(=C(C=CC1)CC)CC NGPAOBFQERPREC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- XQFARSXVMYNQRL-UHFFFAOYSA-N acetylene chlorobenzene Chemical group C#C.ClC1=CC=CC=C1 XQFARSXVMYNQRL-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000005418 aryl aryl group Chemical group 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
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- 239000011229 interlayer Substances 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- LSCYTCMNCWMCQE-UHFFFAOYSA-N n-methylpyridin-4-amine Chemical compound CNC1=CC=NC=C1 LSCYTCMNCWMCQE-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical class OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 235000019187 sodium-L-ascorbate Nutrition 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
本发明公开了一种碳材料负载纳米Pd催化剂及其制备方法和应用,该方法以氧化石墨为原料,通过在溶剂中超声剥离得到氧化石墨烯后,经过还原得到化学还原氧化石墨烯,再先后经过氯乙基异氰酸酯、叠氮化钠以及溴化1‑丙炔基‑3‑聚乙二醇单甲醚咪唑鎓盐修饰后,与醋酸钯和碱反应制得碳材料负载纳米Pd催化剂。由于N‑杂环卡宾以及聚乙二醇单甲醚对金属的稳定作用,从而有效防止金属Pd的流失及团聚。将上述催化剂用于铃木偶联反应具有优良的催化活性和重复性。
Description
技术领域
本发明涉及有机合成催化剂制备领域,具体涉及一种碳材料负载纳米Pd催化剂及其制备方法和应用。
背景技术
通过Pd催化Suzuki偶联反应构建分子中Aryl-aryl键是现代有机合成最重要的工具之一,在药物、农药、染料、有机导体、液晶及配体合成等领域起到不可或缺的作用。虽然许多均相催化剂对该反应有很优异的催化活性,但由于其难以从反应产物中分离以及无法重复利用等缺点,尤其Pd又为昂贵的过渡金属,且易团聚,因此该类反应中运用Pd均相催化剂在工业生产过程中具有局限性。目前为止,将催化剂负载于固体载体之上是一个可行的解决方法,目前研究的主要载体有:SiO2、活性炭、分子筛、树脂等等。但由于载体对反应进程的影响,会使催化活性降低,影响反应速率。因此有必要设计合成一种新型高效负载Pd的非均相催化剂。
石墨烯是一种单层二维的碳材料,具有许多超常的性质,比如极大的比表面积,快速的电子迁移速度,超强的机械强度和极高的化学稳定性,这些性质使石墨烯材料成为非均相催化剂理想的载体。石墨烯容易进行团聚,所以在其表面进行一些化学修饰,不仅能减少石墨烯片层间的相互作用,还可以增加对纳米颗粒的稳定作用。
目前氧化石墨负载的主要方法为:(1)河北农业大学王志等(Graphene oxidesupported N-heterocyclic carbenepalladium as a novel catalyst for the Suzuki–Miyaura reaction,RSC Adv.2013,3,21863–21868)用带氨基的咪唑型离子液体修饰氧化石墨后负载金属Pd催化Suzuki偶联反应;(2)沙希德贝赫什迪大学的Ayoob Bazgir(N-Heterocyclic carbene palladium complex supported on ionic liquid-modifiedgraphene oxide as an efficient and recyclable catalyst for Suzuki reaction,RSC Adv.2014,4,14586–14591)提出用硅烷化方法修饰氧化石墨后接枝咪唑型离子液体对金属进行负载催化Suzuki偶联反应;(3)阿米尔卡比尔理工大学Farhad Panahi等(Graphene Grafted N-Methyl-4-pyridinamine(G-NMPA):An Efficient HeterogeneousOrganocatalyst for Acetylation of Alcohols,ChemistrySelect 2017,2,474–479)先将氧化石墨氯化后连接有机催化剂实现负载。其中,方法(1)和方法(2)的非均相催化剂由于载体的引入降低了Pd的催化活性,需要在升温的条件下才能对反应进行有效催化;方法(3)由于制备过程中使用氯化亚砜,工艺条件对环境不友好。
发明内容
本发明的目的是提供一种条件温和,对环境友好,催化活性高的碳材料负载纳米Pd催化剂及其制备方法和应用。
实现本发明目的技术方案如下:
一种碳材料负载纳米Pd催化剂,该催化剂以氮杂环卡宾及乙二醇单甲醚基团修饰氧化石墨得到的碳材料为载体,以Pd纳米颗粒为活性组分。
上述催化剂的制备方法,具体步骤如下:
(1)将先后经氯化、叠氮化处理的氧化石墨置于水与乙醇的混合溶剂中配成混合溶液,超声分散均匀,加入抗坏血酸钠和硫酸铜,以及溴化1-丙炔基-3-聚乙二醇单甲醚咪唑鎓盐,室温条件下反应,反应完成后,抽滤、淋洗、干燥;
(2)取步骤(1)干燥后的粉末、醋酸钯和碳酸钾置于四氢呋喃中超声分散均匀,在氮气环境下,室温反应,反应结束后,抽滤、清洗、干燥后得到所述的催化剂。
其中,上述步骤(1)中,溴化1-丙炔基-3-聚乙二醇单甲醚咪唑鎓盐中的聚乙二醇单甲醚的分子量为200-1500。
上述步骤(1)中,先后经氯化、叠氮化处理的氧化石墨与溴化1-丙炔基-3-聚乙二醇单甲醚咪唑鎓盐的比例为100:1g/mol;先后经氯化、叠氮化处理的氧化石墨、抗坏血酸钠和硫酸铜三者的质量比为5~20:3~12:1~4,水与乙醇的混合溶剂中水和乙醇的体积比为1:1~1:3。
上述步骤(2)所用粉末、醋酸钯与碳酸钾的质量比为5~20:8~32:5~20。
上述催化剂在以溴代芳基化合物为底物的Suzuki偶联反应中的应用。
上述催化剂在催化芳基炔烃的氢硅烷化反应中的应用。
与现有技术相比,本发明的优点是:
(1)该方法与传统方法相比,催化剂制备过程条件温和,制备工艺对环境友好,催化活性较高,复用性良好。
(2)本发明所述的催化剂不仅室温条件下在绿色溶剂中对铃木偶联反应表现出良好的催化活性,还可高效催化芳基炔烃的氢硅烷化反应。
具体实施方式
实施例1
(1)称取1g氧化石墨至250mL三口烧瓶中,加入去离子水配制氧化石墨浓度为5-10mg/mL的溶液,在室温下将其超声1h,得到高度分散的氧化石墨烯溶液,向所得溶液中加入1g抗坏血酸,在100℃条件下剧烈搅拌24h,反应完成后将溶液抽滤,样品用去离子水淋洗,65℃烘干过夜,得到化学还原的氧化石墨烯粉末;
(2)将步骤(1)所得粉末300mg配制成4-5mg/mL的N,N-二甲基甲酰胺溶液超声1h,接着加入2g氯乙基异氰酸酯,在氮气氛围下室温反应24h,反应完成后将溶液抽滤,样品用二氯甲烷淋洗多次,50℃烘干过夜,得到含氯元素的碳材料粉末;
(3)将步骤(2)所得粉末200mg配制成2-3mg/mL的二甲亚砜溶液超声30min之后加入叠氮化钠800mg在50℃下搅拌反应48h,反应完成后抽滤,用去离子水和二氯甲烷淋洗后在50℃下烘干过夜,得到含叠氮基团的碳材料粉末;
(4)将步骤(3)所得粉末100mg和水与乙醇比例2:1的混合溶剂8mL配成溶液,超声1h,加入60mg抗坏血酸钠和20mg硫酸铜以及400mg溴化1-丙炔基-3-聚乙二醇200单甲醚咪唑鎓盐,室温条件下反应3天,反应完成后将反应液抽滤,用去离子水和二氯甲烷淋洗多次,50℃烘干过夜,得到连接聚乙二醇单甲醚的咪唑修饰的碳材料粉末;
(5)取步骤(4)所得粉末100mg,醋酸钯160mg和碳酸钾100mg在3mL四氢呋喃溶液中超声30min后,在氮气环境下室温反应48h,反应结束后将反应液抽滤,再用N,N-二甲基甲酰胺,去离子水和二氯甲烷淋洗多次,60℃下烘干过夜,得到负载Pd纳米颗粒的碳材料。
(6)将步骤(5)所得负载Pd纳米颗粒的碳材料催化剂2mg加入到0.5mmol 4-溴苯甲醚和0.55mmol苯硼酸以及0.75mmol碳酸钾中,用3mL水和乙醇1:1的混合溶剂中室温下反应3h,反应液离心后分离催化剂。反应液用水和乙酸乙酯萃取,分液后减压旋蒸除去有机溶剂,经柱层析得到产物4-甲氧基联苯,收率98%。
实施例2
反应步骤与实施例1完全相同,不同之处在于:
步骤(4)聚乙二醇单甲醚分子量为500,步骤(6)反应时长为4h,4-甲氧基联苯收率为95%。
实施例3
反应步骤与实施例1完全相同,不同之处在于:
步骤(4)聚乙二醇单甲醚分子量为1500,步骤(6)反应时长为6h,4-甲氧基联苯收率为92%。
实施例4
反应步骤与实施例1完全相同,不同之处在于:
步骤(5)醋酸钯的使用量80mg,4-甲氧基联苯收率为87%。
实施例5
反应步骤与实施例1完全相同,不同之处在于:
步骤(6)负载Pd纳米颗粒的碳材料用量1mg,4-甲氧基联苯收率为83%。
实施例6
反应步骤与实施例1完全相同,不同之处在于:
步骤(6)碳酸钾0.6mmol,4-甲氧基联苯收率为88%。
实施例7
反应步骤与实施例1完全相同,不同之处在于:
步骤(6)溶剂为去离子水,反应温度80℃,步骤(6)反应时长为8h,4-甲氧基联苯收率为97%。
实施例8
反应步骤与实施例1完全相同,不同之处在于:
步骤(6)溶剂为去离子水与乙醇比例为2:1,4-甲氧基联苯收率为83%。
实施例9
反应步骤与实施例1完全相同,不同之处在于:
步骤(6)溶剂为去离子水与乙醇比例为1:2,4-甲氧基联苯收率为98%。
实施例10
将所制得的催化剂0.1mg与苯乙炔0.5mmol、三乙基硅烷1.5mmol以及碘化钠0.25mmol加入到反应管中,加入1mL乙腈,室温下搅拌2h。反应结束后离心分离催化剂,将反应液用水和乙酸乙酯萃取,分液后减压旋蒸有机溶剂,经柱层析法得到产物三乙基苯乙烯基硅烷,产率为98%,Z/E构型比例为7:93。
实施例11
反应步骤与实施例10相同,不同之处在于:
底物换为4-氯苯乙炔,产率为99%,Z/E构型比例为4:96。
实施例12
反应步骤与实施例10相同,不同之处在于:
底物换为4-氨基苯乙炔,产率为98%,Z/E构型比例为15:85。
实施例13
反应步骤与实施例10相同,不同之处在于:
底物换为3,5-二氟苯乙炔,产率为99%,Z/E构型比例为1:99。
对上述实施例1中的催化剂进行复用性能考察,该催化剂离心后不经任何处理直接复用,循环使用8次后活性没有明显下降,复用性能较好。
Claims (8)
1.一种碳材料负载纳米Pd催化剂,其特征在于,该催化剂以氮杂环卡宾及乙二醇单甲醚基团修饰氧化石墨得到的碳材料为载体,以Pd纳米颗粒为活性组分。
2.如权利要求1所述的催化剂,其特征在于,由如下步骤制备:
(1)将先后经氯化、叠氮化处理的氧化石墨置于水与乙醇的混合溶剂中配成混合溶液,超声分散均匀,加入抗坏血酸钠和硫酸铜,以及溴化1-丙炔基-3-聚乙二醇单甲醚咪唑鎓盐,室温条件下反应,反应完成后,抽滤、淋洗、干燥;
(2)取步骤(1)干燥后的粉末、醋酸钯和碳酸钾置于四氢呋喃中超声分散均匀,在氮气环境下,室温反应,反应结束后,抽滤、清洗、干燥后得到所述的催化剂。
3.如权利要求2所述的催化剂,其特征在于,步骤(1)中,溴化1-丙炔基-3-聚乙二醇单甲醚咪唑鎓盐中的聚乙二醇单甲醚的分子量为200-1500。
4.如权利要求2所述的催化剂,其特征在于,步骤(1)中,先后经氯化、叠氮化处理的氧化石墨与溴化1-丙炔基-3-聚乙二醇单甲醚咪唑鎓盐的比例为100:1g/mol;先后经氯化、叠氮化处理的氧化石墨、抗坏血酸钠和硫酸铜三者的质量比为5~20:3~12:1~4;水与乙醇的混合溶剂中水和乙醇的体积比为1:1~1:3。
5.如权利要求2所述的催化剂,其特征在于,步骤(2)中,步骤(1)干燥后的粉末、醋酸钯与碳酸钾的质量比为5~20:8~32:5~20。
6.如权利要求1-5任一所述的催化剂的制备方法。
7.如权利要求1所述的催化剂在以溴代芳基化合物为底物的Suzuki偶联反应中的应用。
8.如权利要求7所述的应用,其特征在于,所述的催化剂在催化芳基炔烃的氢硅烷化反应中的应用。
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