CN116603573A - 一种金属钯纳米团簇及其制备方法 - Google Patents
一种金属钯纳米团簇及其制备方法 Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 14
- 101150003085 Pdcl gene Proteins 0.000 claims abstract description 13
- HJPHBJYOODQSLK-UHFFFAOYSA-N dicyclohexyl(oxo)phosphanium Chemical compound C1CCCCC1[P+](=O)C1CCCCC1 HJPHBJYOODQSLK-UHFFFAOYSA-N 0.000 claims abstract description 10
- TWKVUTXHANJYGH-UHFFFAOYSA-L allyl palladium chloride Chemical class Cl[Pd]CC=C.Cl[Pd]CC=C TWKVUTXHANJYGH-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012696 Pd precursors Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- WVUCNNGUXNXOBY-UHFFFAOYSA-N 1,3-dimethoxy-5-nitrobenzene Chemical compound COC1=CC(OC)=CC([N+]([O-])=O)=C1 WVUCNNGUXNXOBY-UHFFFAOYSA-N 0.000 description 2
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- WNRGWPVJGDABME-UHFFFAOYSA-N 3,5-Dimethoxyaniline Chemical compound COC1=CC(N)=CC(OC)=C1 WNRGWPVJGDABME-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- -1 i.e. Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—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
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
本发明提供了一种金属钯纳米团簇及其制备方法,属于有机合成技术领域。本发明采用非均相法以烯丙基氯化钯二聚体[PdCl(C3H5)]2和二环己基膦氧化物为起始原料,制备金属钯纳米团簇。将其用于选择性催化加氢过程中,具有反应活性高、粒径均匀、不易失活的特点,与水表现出了优异的协同效应,且易于回收,可重复使用。其制备方法无需无水无氧条件,简单、安全、可操作性强。
Description
技术领域
本发明涉及一种金属钯纳米团簇及其制备的方法,属于有机合成技术领域。
背景技术
纳米颗粒作为一种新兴的催化剂,在有机催化反应中经常表现出优异的活性、稳定性和选择性,引起了研究者的广泛关注。其中,纳米钯催化剂在各种反应中都被认为是优良的催化剂,包括碳-碳键偶联反应、CO氧化、H2和O2直接合成H2O2、硝基还原、醇氧化成醛、碳-氯键活化、异丙醇选择性催化氧化等。特别是钯纳米团簇表现出比均相催化剂更好的催化性能,已成为催化研究中最引人注目的体系之一。
传统的纳米团簇合成方法包括聚合物、有机配体、表面活性剂等,然而,在有机配体的选择中次级膦氧(SPOs)作为一种优良的纳米团簇配体稳定剂却没有在纳米团簇合成中得到应用。SPOs通常对空气和水更稳定,供体性能强,这意味着制备条件比三价膦配体更容易。
虽然有许多关于SPO-M在各种有机反应中的催化作用报道,但目前SPOs作为配体稳定剂合成金属纳米团簇的报道相对较少。因此,探索将其应用于合成钯纳米团簇的构筑具有开发应用价值。
发明内容
本发明的目的在于提供一种催化效果好的金属钯纳米团簇;另一目的在于提供其制备的方法。
为实现本发明目的,本发明以烯丙基氯化钯二聚体[PdCl(C3H5)]2和二环己基膦氧化物为起始原料,制备金属钯纳米团簇。
所述金属钯纳米团簇通过如下方法制备而成:
(1)以烯丙基氯化钯二聚体[PdCl(C3H5)]2和二环己基膦氧化物为起始原料,在二氯甲烷溶液中搅拌反应,反应结束后,经旋蒸、过滤得到黄色固体,即钯前体配合物{PdCl2[Cy2(O)H]2};烯丙基氯化钯二聚体、二环己基膦氧化物的摩尔比为1:2.5。
(2)将钯前体配合物{PdCl2[Cy2(O)H]2}溶解在H2O:二氯甲烷(DCM)(体积比=1:2)的混合溶剂中,并在冰浴中冷却;将NaBH4溶解于甲醇溶液中,然后分批滴入反应体系中至反应充分;将反应液旋干、洗涤、真空下干燥得到目标物钯纳米团簇;钯前体配合物、硼氢化钠的摩尔比为1:1.5。
通过ICP测得该钯纳米团簇的钯含量为12%~13%。
该钯纳米团簇催化剂可以应用于硝基化合物选择性催化加氢,反应路线如下:
R1代表氢、卤素、甲氧基、C1-3烷基;在苯环上单取代或双取代。
本发明优点:首次采用非均相法制备了二环己基膦氧稳定的钯纳米团簇,得到的五价膦配位钯纳米团簇具有反应活性高、粒径均匀、不易失活的特点。在选择性催化加氢过程中,该催化剂与水表现出了优异的协同效应,水和中心金属表面配体可以加速底物的吸收和氢分子在钯纳米团簇表面的协同活化,选择性好,收率高,达92%以上,反应条件温和;且该钯纳米团簇催化剂易于回收,可重复使用。另外,其制备方法无需无水无氧条件,方法简单、安全、可操作性强,便于工业化应用。
附图说明
图1是本发明制备的钯纳米团簇的TEM照片,由图可知,本发明合成的钯纳米团簇为纳米级。
图2是是本发明制备的钯纳米团簇的TEM局部放大后照片。
具体实施方式
下面结合具体的实施例对本发明作进一步详细的说明。
实施例1:
钯前体配合物的合成
向反应瓶中添加烯丙基氯化钯二聚体[PdCl(C3H5)]2 366mg(1.0mmol),二环己基膦氧化物536mg(2.5mmol)和CH2Cl2(15mL),搅拌反应5h,反应结束后,通过旋蒸除去一半溶剂,然后加入15mL正己烷,并在-20℃的冰箱中过夜。过滤后,得到黄色固体516mg(0.85mmol),即钯前体配合物,收率为85%。
实施例2:
钯纳米团簇的合成
将上述钯前体配合物{PdCl2[Cy2(O)H]2}(0.3mmol,182mg)溶解在H2O:DCM(6mL:12mL)的混合溶剂中,并在冰浴中冷却至0℃。将NaBH4(18mg,0.45mmol,1.5eq)溶解于甲醇(10mL)溶液中,然后将其分批滴加至反应液中,室温下反应0.5h至反应充分。将反应液旋干、洗涤、真空下干燥后得到钯纳米团簇。通过ICP测得该钯纳米团簇的钯含量为12.42%。
实施例3:
钯纳米团簇对硝基苯的选择性催化加氢
在10ml烧瓶中加入1mmol底物硝基苯和5ml溶剂水,1mg本发明制备的钯纳米团簇;搅拌下通入适量H2,反应20h左右,气相检测反应进程,反应完全后用DCM萃取,有机相用无水MgSO4干燥,减压蒸馏除去有机溶剂,通过柱层析纯化得到目标产物苯胺86mg(0.92mmol),收率:92%。核磁数据:1H NMR(400MHz,CDCl3)δ=3.52(s,br,2H),6.59(d,J=8.0Hz,2H),6.71(t,J=8.0Hz,1H),7.10(t,J=8.0Hz,2H);13C NMR(100MHz,CDCl3)δ=115.00(s,2CH),118.33(s,CH),129.19(s,2CH),146.42(s,C)。
实施例4:
钯纳米团簇对4-硝基甲苯的选择性催化加氢
在10ml烧瓶中加入1mmol底物对硝基甲苯和5ml溶剂水,1mg本发明制备的钯纳米团簇;搅拌下通入适量H2,反应20h左右,气相检测反应进程,反应完全后用DCM萃取,有机相用无水MgSO4干燥,减压蒸馏除去有机溶剂,通过柱层析纯化得到目标产物对甲苯胺102mg(0.95mmol),收率:95%。核磁数据:1H NMR(400MHz,CDCl3)δ=2.35(d,J=8.0Hz,3H),3.59(s,br,2H),6.66-6.69(m,2H),7.05-7.08(m,2H);13C NMR(100MHz,CDCl3)δ=20.39(s,CH3),115.18(s,2CH),127.55(s,C),129.68(s,2CH),143.88(s,C)。
实施例5:
钯纳米团簇对4-溴硝基苯的选择性催化加氢
在10ml烧瓶中加入1mmol底物4-溴硝基苯和5ml溶剂水,1mg本发明制备的钯纳米团簇;搅拌下通入适量H2,反应20h左右,气相检测反应进程,反应完全后用DCM萃取,有机相用无水MgSO4干燥,减压蒸馏除去有机溶剂,通过柱层析纯化得到目标产物对溴苯胺158mg(0.92mmol),收率:92%。核磁数据:1H NMR(400MHz,CDCl3)δ=3.62(s,br,2H),6.51(d,J=8.0Hz,2H),7.20(d,J=8.0Hz,2H);13C NMR(100MHz,CDCl3)δ=110.05(s,C),116.73(s,2CH),131.97(s,C),145.49(s,C)。
实施例6:
钯纳米团簇对4-硝基苯甲醚的选择性催化加氢
在10ml烧瓶中加入1mmol底物4-硝基苯甲醚和5ml溶剂水,1mg本发明制备的钯纳米团簇;搅拌下通入适量H2,反应20h左右,气相检测反应进程,反应完全后用DCM萃取,有机相用无水MgSO4干燥,减压蒸馏除去有机溶剂,通过柱层析纯化得到目标产物4-甲氧基苯胺118mg(0.96mmol),收率:96%。核磁数据:1H NMR(400MHz,CDCl3)δ=3.41(s,br,2H),3.71(s,3H),6.61(d,J=8.0Hz,2H),6.73(d,J=4.0Hz,2H);13C NMR(100MHz,CDCl3)δ=55.71(s,CH3),114.80(s,2CH),116.39(s,2CH),140.05(s,C),152.71(s,C)。
实施例7:
钯纳米团簇对1,3-二甲氧基-5-硝基苯的选择性催化加氢
在10ml烧瓶中加入1mmol底物对1,3-二甲氧基-5-硝基苯和5ml溶剂水,1mg本发明制备的钯纳米团簇;搅拌下通入适量H2,反应20h左右,气相检测反应进程,反应完全后用DCM萃取,有机相用无水MgSO4干燥,减压蒸馏除去有机溶剂,通过柱层析纯化得到目标产物3,5-二甲氧基苯胺144mg(0.94mmol),收率:94%。核磁数据:1H NMR(400MHz,CDCl3)δ=3.68(s,6H),3.73(s,br,2H),5.82(s,2H),5.90(s,1H);13C NMR(100MHz,CDCl3)δ=54.92(s,2CH3),90.62(s,CH),93.50(s,2CH),148.57(s,C),161.54(s,C)。
实施例8:
钯纳米团簇循环催化验证实验
以4-硝基甲苯为催化底物,取5mg本发明制备的钯纳米团簇,每次取10mmol 4-硝基甲苯,按照上述方法平行做六次钯纳米团簇循环催化反应,每次催化用的钯纳米团簇为上次实验回收所得。
循环使用次数 | 1 | 2 | 3 | 4 | 5 | 6 |
产率 | 95% | 95% | 94% | 93% | 92% | 90% |
本发明制备的钯纳米团簇重复使用6次后,产品收率仍可达90%,因此,该钯纳米团簇催化剂稳定性好,易于重复回收利用。
Claims (7)
1.一种金属钯纳米团簇,其特征在于,通过如下方法制备而成:
(1)以烯丙基氯化钯二聚体[PdCl(C3H5)]2和二环己基膦氧化物为起始原料,在二氯甲烷溶液中搅拌反应,反应结束后,经旋蒸,过滤得到钯前体配合物{PdCl2[Cy2(O)H]2};
(2)将钯前体配合物{PdCl2[Cy2(O)H]2}溶解在H2O:DCM的混合溶剂中,并在冰浴中冷却;将NaBH4溶解于甲醇溶液中,然后分批滴入反应体系中至反应充分;将反应液旋干、洗涤、真空下干燥后得到钯纳米团簇。
2.根据权利要求1所述的金属钯纳米团簇,其特征在于,所述的烯丙基氯化钯二聚体、二环己基膦氧化物的摩尔比为1:2.5。
3.根据权利要求1所述的金属钯纳米团簇,其特征在于,所述的钯前体配合物、硼氢化钠的摩尔比为1:1.5。
4.制备如权利要求1所述的金属钯纳米团簇的方法,其特征在于,通过如下方法实现:
(1)以烯丙基氯化钯二聚体[PdCl(C3H5)]2和二环己基膦氧化物为起始原料,在二氯甲烷溶液中搅拌反应,反应结束后,经旋蒸,过滤得到钯前体配合物{PdCl2[Cy2(O)H]2};
(2)将钯前体配合物{PdCl2[Cy2(O)H]2}溶解在H2O:DCM的混合溶剂中,并在冰浴中冷却;将NaBH4溶解于甲醇溶液中,然后分批滴入反应体系中至反应充分;将反应液旋干、洗涤、真空下干燥后得到钯纳米团簇。
5.根据权利要求4所述的金属钯纳米团簇的制备方法,其特征在于,所述的烯丙基氯化钯二聚体、二环己基膦氧化物的摩尔比为1:2.5。
6.根据权利要求4所述的金属钯纳米团簇的制备方法,其特征在于,所述的钯前体配合物、硼氢化钠的摩尔比为1:1.5。
7.根据权利要求1、2或3所述的金属钯纳米团簇的应用,其特征在于,作为催化剂,将其应用于如下反应的催化加氢中;
R1代表氢、卤素、甲氧基或C1-3烷基;在苯环上单取代或双取代。
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