CN108786922A - 一种偶联反应用镍、钯修饰纳米二氧化硅的制备方法 - Google Patents
一种偶联反应用镍、钯修饰纳米二氧化硅的制备方法 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 14
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- 238000005859 coupling reaction Methods 0.000 title claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
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- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 22
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- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 10
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- 125000003368 amide group Chemical group 0.000 claims description 6
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- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 20
- 238000004587 chromatography analysis Methods 0.000 description 16
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
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- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical class CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
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- 125000005619 boric acid group Chemical group 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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Abstract
本发明公开了一种偶联反应用镍、钯修饰纳米二氧化硅的制备方法,具体制备步骤如下:将气相纳米二氧化硅,超声分散,加入KH550和水,搅拌回流,反应后抽滤,滤饼干燥得氨基修饰的二氧化硅;乙醇中依次加入二苯基膦与甲醛水溶液,加入所得的二氧化硅继续反应,反应完后抽滤,洗涤,滤饼干燥,得氨基膦配体修饰的二氧化硅;将氨基膦配体修饰的二氧化硅于二氯甲烷中超声处理,将Pd(CH3CN)2Cl2于二氯甲烷的溶液加入上混合液中,将NiCl2.6H2O于乙醇的溶液加入混合液,反应后抽滤,洗涤,滤饼真空干燥,得纳米催化剂。通过纳米二氧化硅表面修饰引入氨基膦配体,再分别与金属镍和钯配位,制备复合型催化剂,催化活性较高。
Description
技术领域
本发明涉及一种偶联反应用镍、钯修饰纳米二氧化硅的制备方法,具体涉及化工用品的制备技术领域。
背景技术
1979年,日本的北海道大学的Suzuki和Miyaura等人首次发现了钯催化的有机硼酸与卤代烃的偶联反应。这一类反应在有机合成中的作用非常广泛,被命名为Suzuki反应[1,2]。在Suzuki反应中,常用的催化剂为含贵金属钯盐、环钯化合物和钯配合物,钯催化剂有两种形式:均相催化剂和非均相催化剂。均相催化剂普遍存在如下缺点:催化剂不能回收,既提高了反应成本,又造成了产品的重金属污染,这对重金属含量要求较高的医药行业和精细化学品而言是致命的缺点。因此,从环境和工业应用的角度来看,Suzuki偶联反应的最新热点是设计合成出高活性且易于回收的多相催化剂[3,4]。
早在1979年,Suzuki等人发现三苯基膦作为配体的钯催化偶联反应表现出很高的活性[5]。进一步的研究发现膦配体具有丰富的电子,在反应过程中可以很好的稳定和活化金属钯,因此膦配体是钯催化的Suzuki偶联反应中的一种重要有机配体。另一方面,大部分膦配体对于氧气敏感,所以膦配体往往用于Suzuki偶联反应的均相催化中。在非均相催化中,载体中含有膦配体的研究较少,Marck等人发现,在钯的多相催化剂(Pd/C)中添加三苯基膦取得了较好的催化效果[6]。本发明在于针对上述现有技术的不足,提供一种简单的制备含有膦配体的Suzuki偶联反应钯、镍复合纳米二氧化硅催化剂。
[1] Miyaura N, Yamada K, Suzuki A. Tetrahedron Letters. 1979, 20(36):3437-3440。
[2] Miyaura N, Suzuki A. Chemical reviews. 1995, 95(7):2457-2483。
[3] Ganapathy D, Sekar G. Catal. Commun. 2013, 39, 50。
[4] Hoseini S J, Dehghani M, Nasrabadi H. Catalysis Science &Technology. 2014, 4(4): 1078-1083。
[5] Miyaura N, Suzuki A. Jouanal of the Chemical Society, ChemicalCommunications. 1979, 19, 866-867。
[6] Zapf A, Beller M. Topocs in Catalysis, 2002, 19(1):101-109。
发明内容
本发明的目的在于提供一种偶联反应用镍、钯修饰纳米二氧化硅的制备方法。
为实现上述目的,本发明提供如下技术方案:一种偶联反应用镍、钯修饰纳米二氧化硅的制备方法具体步骤如下:
步骤一、将5.0克气相纳米二氧化硅,原生粒径12 nm,于200毫升乙醇中超声分散10分钟,然后加入1.500 g 6.787 mmol的KH550和水3毫升,氮气保护下搅拌回流4小时,待混合液冷却以后抽滤,分别以乙醇与二氯甲烷100毫升各洗涤两次,滤饼60℃下真空干燥6小时,得氨基修饰的二氧化硅4.950克;
步骤二、氮气保护下,在20毫升乙醇中依次加入 5.40 mmol的二苯基膦1.000 g与浓度为35%的5.60 mmol的甲醛水溶液0.454 g,所得的混合溶液搅拌30分钟,将氨基修饰的二氧化硅2.000克于100毫升乙醇中超声分散10分钟,将所得悬浊液加入上混合液中,室温搅拌10小时以后抽滤,以乙醇/二氯甲烷体积比为1/1,100毫升洗涤四次,滤饼室温下真空干燥6小时,得氨基膦配体修饰的二氧化硅2.000克;
步骤三、将氨基膦配体修饰的纳米二氧化硅0.500克于100毫升二氯甲烷中超声处理10分钟,氮气保护下,将15 mg Pd(CH3CN)2Cl2于5毫升二氯甲烷的溶液加入上混合液中,室温反应6小时以后将200 mg NiCl2.6H2O于10毫升乙醇的溶液加入混合液,继续反应12小时以后抽滤,以乙醇和二氯甲烷100毫升分别洗涤两次,滤饼室温下真空干燥6小时,即得到最终的纳米催化剂。
作为优选,所述的纳米二氧化硅及负载上的活性组分组成催化剂,其中活性组分为膦配位的二价钯;所述催化剂中钯的百分含量为0.5%,镍的百分含量为1.95%。
本发明具体制备步骤的化学反应式如下所示:
与现有技术相比,本发明的有益效果如下:通过纳米二氧化硅表面修饰引入氨基膦配体,再分别与金属镍和钯配位,制备含有镍钯两种金属配合物结构的复合型催化剂;催化剂含钯量低,降低了催化剂的生产成本;催化活性较高,在含氧、含水的温和条件下可达到较好的催化效果,对于基团的耐受性较强;催化剂可以重复使用。
附图说明
图1为本发明制备的纳米催化剂扫描电镜图;
图2为本发明制备的纳米催化剂透射电镜图;
图3为本发明制备的纳米催化剂X射线能谱图;
图4为本发明制备的纳米催化剂的红外光谱图;
图5为本发明制备的纳米催化剂的XRD衍射图;
图6为本发明实施例1反应液的色谱图;
图7为本发明实施例2反应液的色谱图;
图8为本发明实施例3反应液的色谱图;
图9为本发明实施例4反应液的色谱图;
图10为本发明实施例5反应液的色谱图;
图11为本发明实施例6反应液的色谱图;
图12为本发明实施例7反应液的色谱图;
图13为本发明实施例8反应液的色谱图。
具体实施方式
下面将结合本发明具体实施方式与实施例,对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本具体实施方式一种偶联反应用镍、钯修饰纳米二氧化硅的制备方法具体步骤如下:步骤一、将5.0克气相纳米二氧化硅,原生粒径12 nm,于200毫升乙醇中超声分散10分钟,然后加入1.500 g 6.787 mmol的KH550和水3毫升,氮气保护下搅拌回流4小时,待混合液冷却以后抽滤,分别以乙醇与二氯甲烷100毫升各洗涤两次,滤饼60℃下真空干燥6小时,得氨基修饰的二氧化硅4.950克;
步骤二、氮气保护下,在20毫升乙醇中依次加入 5.40 mmol的二苯基膦1.000 g与浓度为35%的5.60 mmol的甲醛水溶液0.454 g,所得的混合溶液搅拌30分钟,将氨基修饰的二氧化硅2.000克于100毫升乙醇中超声分散10分钟,将所得悬浊液加入上混合液中,室温搅拌10小时以后抽滤,以乙醇/二氯甲烷体积比为1/1,100毫升洗涤四次,滤饼室温下真空干燥6小时,得氨基膦配体修饰的二氧化硅2.000克;
步骤三、将氨基膦配体修饰的纳米二氧化硅0.500克于100毫升二氯甲烷中超声处理10分钟,氮气保护下,将15 mg Pd(CH3CN)2Cl2于5毫升二氯甲烷的溶液加入上混合液中,室温反应6小时以后将200 mg NiCl2.6H2O于10毫升乙醇的溶液加入混合液,继续反应12小时以后抽滤,以乙醇和二氯甲烷100毫升分别洗涤两次,滤饼室温下真空干燥6小时,即得到最终的纳米催化剂。
作为优选,所述的纳米二氧化硅及负载上的活性组分组成催化剂,其中活性组分为膦配位的二价钯;所述催化剂中钯的百分含量为0.5%,镍的百分含量为1.95%。
具体制备步骤的化学反应式如下所示:
下面结合附图对本具体实施方式所合成的催化剂结构做进一步说明。
图1和图2分别为纳米催化剂的扫描电子显微镜以及透射电子显微镜图片,展示了催化剂外观为均匀的颗粒,直径约12nm。
图3为纳米催化剂的能谱图,图中明显的显示出催化剂中含有C、N、O、Si、P、Cl、Ni等元素,由于含钯量极低,因此在能谱图中无信号显示。金属镍(1.95%)和钯(0.5%)的精确含量通过ICP-Ms测得。
图4为纳米催化剂的红外光谱图。图中除了3442cm-1以及1104cm-1等处有SiO2相关吸收峰之外,还存在着696 cm-1以及1438cm-1等处与有机基团苯环相关的特征吸收。
图5为纳米催化剂的XRD单晶衍射图。由于原料是无定型纳米二氧化硅,因此其单晶衍射图峰高不明显,其在22°处有微弱的峰,正是无定型二氧化硅的特征峰。
本具体实施方式所指的纳米催化剂被用于如下所示的反应中;
本具体实施方式所指的纳米催化剂催化效果如表一所列。
表一、本具体实施方式所指的纳米催化剂催化效果表。
实施例1
在一小反应管内依次加入本具体实施方式制备的纳米催化剂(5mg)、苯硼酸(94 mg,0.75 mmol)、碳酸钾(138 mg, 1.00 mmol)、溴苯(52μl,0.50 mmol)以及内标化合物萘(64mg,0.50 mmol),最后加入乙醇、水体积比为3/2的混合溶剂4 mL,60℃反应8小时以后对反应液进行气相色谱分析,反应结果如下图6所示。色谱图中,溴苯的保留时间为5.1min,内标物萘保留时间为7.8 min,产物联苯保留时间为9.3 min,色谱产率为96%。
实施例2
在一小反应管内依次加入本具体实施方式制备的纳米催化剂(5mg)、苯硼酸(94 mg,0.75 mmol)、甲醇钠(54 mg, 1.00 mmol)、溴苯(52μl,0.50 mmol)以及内标化合物萘(64mg,0.50 mmol),最后加入乙醇4 mL,60℃反应8小时以后对反应液进行气相色谱分析,反应结果如下图7所示。色谱图中,溴苯的保留时间为5.1 min,内标物萘保留时间为7.8 min,产物联苯保留时间为9.3 min,色谱产率为80%。
实施例3
在一小反应管内依次加入本具体实施方式制备的纳米催化剂(5mg)、苯硼酸(94 mg,0.75 mmol)、碳酸钾(138 mg, 1.00 mmol)、4-甲基溴苯(61μl,0.50 mmol)以及内标化合物萘(64 mg,0.50 mmol),最后加入乙醇、水体积比为3/2的混合溶剂4 mL,60℃反应8小时以后对反应液进行气相色谱分析,反应结果如下图8所示。色谱图中,4-甲基溴苯的保留时间为6.4 min,内标物萘保留时间为7.8 min,产物4-甲基-1,1‘-联苯的保留时间为10.0 min,色谱产率为78%。
实施例4
在一小反应管内依次加入本具体实施方式制备的纳米催化剂(5mg)、苯硼酸(94 mg,0.75 mmol)、碳酸钾(138 mg, 1.00 mmol)、4-甲氧基溴苯(63μl,0.50 mmol)以及内标化合物萘(64 mg,0.50 mmol),最后加入乙醇、水体积比为3/2的混合溶剂4 mL,60℃反应8小时以后对反应液进行气相色谱分析,反应结果如下图9所示。色谱图中,内标物萘保留时间为7.8 min,产物4-甲氧基-1,1‘-联苯的保留时间为11.0 min,色谱产率为92%。
实施例5
在一小反应管内依次加入本具体实施方式制备的纳米催化剂(5mg)、苯硼酸(94 mg,0.75 mmol)、碳酸钾(138 mg, 1.00 mmol)、4-腈基溴苯(63μl,0.50 mmol)以及内标化合物萘(64 mg,0.50 mmol),最后加入乙醇、水体积比为3/2的混合溶剂4 mL,60℃反应8小时以后对反应液进行气相色谱分析,反应结果如下图10所示。色谱图中,内标物萘保留时间为7.8 min,产物4-腈基-1,1‘-联苯的保留时间为11.5 min,色谱产率为98%。
实施例6
在一小反应管内依次加入本发明所指的催化剂(5mg)、苯硼酸(94 mg,0.75 mmol)、碳酸钾(138 mg, 1.00 mmol)、碘苯(56μl,0.50 mmol)以及内标化合物萘(64 mg,0.50mmol),最后加入乙醇、水体积比为3/2的混合溶剂4 mL,室温反应8小时以后对反应液进行气相色谱分析,反应结果如下图11所示。色谱图中,碘苯的保留时间为6.4min,内标物萘保留时间为7.8 min,产物联苯的保留时间为9.3 min,色谱产率为96%。
实施例7
在一小反应管内依次加入本具体实施方式制备的纳米催化剂(5mg)、4-氯苯硼酸(102mg,0.75 mmol)、碳酸钾(138 mg, 1.00 mmol)、溴苯(52μl,0.50 mmol)以及内标化合物萘(64 mg,0.50 mmol),最后加入乙醇、水体积比为3/2的混合溶剂4 mL,60℃反应8小时以后对反应液进行气相色谱分析,反应结果如下图12所示。色谱图中,溴苯的保留时间为5.0min,内标物萘保留时间为7.6 min,产物4-氯-1,1‘-联苯的保留时间为10.4 min,色谱产率为50%。
实施例8
在一小反应管内依次加入本具体实施方式制备的纳米催化剂(5mg)、3-氟苯硼酸(105mg,0.75 mmol)、碳酸钾(138 mg, 1.00 mmol)、溴苯(52μl,0.50 mmol)以及内标化合物萘(64 mg,0.50 mmol),最后加入乙醇、水体积比为3/2的混合溶剂4 mL,60℃反应8小时以后对反应液进行气相色谱分析,反应结果如下图13所示。色谱图中,溴苯的保留时间为5.0min,内标物萘保留时间为7.6 min,产物3-氟-1,1‘-联苯的保留时间为10.4 min,色谱产率为75%。
实施例9
在一小反应管内依次加入本具体实施方式制备的纳米催化剂(50mg)、苯硼酸(940mg,7.5 mmol)、碳酸钾(1.38 g, 10.0 mmol)、溴苯(520μl,5.0 mmol)最后加入乙醇、水体积比为3/2的混合溶剂40 mL,60℃反应8小时。反应完后旋转蒸发除去乙醇,加水20mL,以乙酸乙酯20mL萃取三次,合并有机相,以饱和食盐水50mL洗涤两次,有机相以无水硫酸镁干燥,悬干后通过一8cm长硅胶柱纯化(石油醚淋洗)以除去微量的杂质,最终得产品732 mg,收率95%。
实施例10
在一小反应管内依次加入实例9中使用过一次的纳米催化剂约(50mg)、苯硼酸(940mg,7.5 mmol)、碳酸钾(1.38 g, 10.0 mmol)、溴苯(520μl,5.0 mmol)最后加入乙醇、水体积比为3/2的混合溶剂40 mL,60℃反应8小时。反应完后旋转蒸发除去乙醇,加水20mL,以乙酸乙酯20mL萃取三次,合并有机相,以饱和食盐水50mL洗涤两次,有机相以无水硫酸镁干燥,悬干后通过一8cm长硅胶柱纯化(石油醚淋洗)以除去微量的杂质,最终得产品640 mg,收率82%。
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (2)
1.一种偶联反应用镍、钯修饰纳米二氧化硅的制备方法,其特征在于:具体制备步骤如下:
步骤一、将5.0克气相纳米二氧化硅,原生粒径12 nm,于200毫升乙醇中超声分散10分钟,然后加入1.500 g 6.787 mmol的KH550和水3毫升,氮气保护下搅拌回流4小时,待混合液冷却以后抽滤,分别以乙醇与二氯甲烷100毫升各洗涤两次,滤饼60℃下真空干燥6小时,得氨基修饰的二氧化硅4.950克;
步骤二、氮气保护下,在20毫升乙醇中依次加入 5.40 mmol的二苯基膦1.000 g与浓度为35%的5.60 mmol的甲醛水溶液0.454 g,所得的混合溶液搅拌30分钟,将氨基修饰的二氧化硅2.000克于100毫升乙醇中超声分散10分钟,将所得悬浊液加入上混合液中,室温搅拌10小时以后抽滤,以乙醇/二氯甲烷体积比为1/1,100毫升洗涤四次,滤饼室温下真空干燥6小时,得氨基膦配体修饰的二氧化硅2.000克;
步骤三、将氨基膦配体修饰的纳米二氧化硅0.500克于100毫升二氯甲烷中超声处理10分钟,氮气保护下,将15 mg Pd(CH3CN)2Cl2于5毫升二氯甲烷的溶液加入上混合液中,室温反应6小时以后将200 mg NiCl2.6H2O于10毫升乙醇的溶液加入混合液,继续反应12小时以后抽滤,以乙醇和二氯甲烷100毫升分别洗涤两次,滤饼室温下真空干燥6小时,即得到最终的纳米催化剂。
2.根据权利要求1所述的一种偶联反应用镍、钯修饰纳米二氧化硅的制备方法,其特征在于:所述的纳米二氧化硅及负载上的活性组分组成催化剂,其中活性组分为膦配位的二价钯;所述催化剂中钯的百分含量为0.5%,镍的百分含量为1.95%。
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CN114634584B (zh) * | 2022-02-18 | 2023-03-03 | 南昌工程学院 | 一种含苯基磷配体的磁性壳聚糖材料的制备方法 |
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