CN106984326A - 一种PtPdAu/负载型纳米磁性催化剂及其制备方法 - Google Patents
一种PtPdAu/负载型纳米磁性催化剂及其制备方法 Download PDFInfo
- Publication number
- CN106984326A CN106984326A CN201710256631.3A CN201710256631A CN106984326A CN 106984326 A CN106984326 A CN 106984326A CN 201710256631 A CN201710256631 A CN 201710256631A CN 106984326 A CN106984326 A CN 106984326A
- Authority
- CN
- China
- Prior art keywords
- ptpdau
- preparation
- catalyst
- magnetic
- loaded
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 241000549556 Nanos Species 0.000 title claims description 8
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 12
- 229910052737 gold Inorganic materials 0.000 claims abstract description 11
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 239000010931 gold Substances 0.000 claims description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- -1 iron ion Chemical class 0.000 claims description 8
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000007341 Heck reaction Methods 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- B01J23/8906—Iron 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
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明公开了一种磁性PtPdAu/Fe3O4纳米催化剂的制备方法。所述催化剂载体为Fe3O4，活性组分是Pt、Pd和Au，其平均粒径分别约为10纳米、7纳米和15纳米，催化剂中Pt、Pd和Au的质量分数分别约为2.1％、4.3％和9.3％。本发明的磁性PtPdAu/Fe3O4纳米催化剂具有清洁、环保、高效而又方便的特点，并且本发明的催化剂在Heck反应中具有很高的催化活性。
Description
技术领域
本发明涉及工业催化技术领域，尤其涉及一种PtPdAu/负载型纳米磁性催化剂及其制备方法。
背景技术
近几十年来，负载型纳米催化剂已得到广泛应用。关于金属和载体间的相互作用的研究报道日益增多。众所周知，金属和载体间特殊的相互作用会影响催化剂的表面性能，进而影响它的催化活性。比如，在Al2O3载体担载金属钴的过程中钴离子会迁移到Al2O3的晶格中形成CoAl2O4化合物。铁的氧化物和过渡金属氧化物或其碳酸盐发生固-固作用形成相应的铁氧体氧化物CoFe2O4。铂、钯、金纳米微粒具有高表面能，容易发生团聚。若将铂、钯、金复合贵金属纳米微粒负载在载体上可有效地阻止其团聚，而且更有效对制备的催化剂进行分离回收。从而提高催化剂的催化活性和利用率。
Fe3O4纳米粒子显示典型的超顺磁性，在生物医学、磁记录材料、磁流体复合材料、催化剂等方面有着潜在的应用前景。
Heck反应是有机卤化物与烯烃在强碱和钯催化下生成取代烯烃的偶联反应，是过渡金属催化最重要也是应用最有前景的碳碳键形成的反应之一，在有机中间体，有机功能材料，药物，天然产物等合成中被广泛应用。
在反应中常常会遇到催化剂容易失活、回收利用率不高、破坏环境等问题，且后处理比较麻烦。本方法提供了一种清洁环保而又方便的催化剂。
发明内容
本发明专利的目的是提供一种在Heck反应中有效且易回收的具有优异催化性能的磁性PtPdAu/Fe3O4纳米催化剂的制备方法。
本发明采取的技术方案是：
本发明的PtPdAu/负载型纳米磁性催化剂载体为Fe3O4，活性组分是Pt、Pd和Au，催化剂中Pt、Pd和Au的质量分数分别为1～4％、3～6％和7～15％。
优选：催化剂中Pt、Pd和Au的质量分数分别约为2.1％、4.3％和9.3％。
活性组分Pt、Pd和Au，其平均粒径分别约为10纳米、7纳米和15纳米。
本发明的PtPdAu/负载型纳米磁性催化剂的制备方法的具体步骤如下：
(1)载体的制备及其预处理
通过水热法将铁离子前驱体氧化还原成的Fe3O4纳米颗粒，使用去离子水、无水乙醇进行清洗，直至上层液体透明，然后将其用无水乙醇定容，备用；在清洗过程中通过铁磁体对Fe3O4纳米颗粒进行分离；
(2)Pt-Pd-Au溶胶的制备
向氯铂酸、氯钯酸和氯金酸混合液中添加稳定剂，搅拌均匀后滴加还原剂溶液，继续搅拌制得稳定Pt-Pd-Au溶胶；
(3)磁性PtPdAu/Fe3O4纳米催化剂的制备
将从步骤(1)中所得的载体加入由步骤(2)制得的Pt-Pd-Au溶胶中，机械搅拌后静置，抽滤，烘干，得PtPdAu/Fe3O4催化剂。
步骤(1)中，所述的铁离子前驱体是FeCl3·6H2O、FeCl2·4H2O、FeCl2·2H2O或FeCl2。
步骤(2)中，所述的稳定剂为聚乙烯吡咯烷酮、聚乙二醇或聚乙烯醇；所述的还原剂为硼氢化钠、硼氢化钾或焦性没食子酸。
步骤(2)中，氯铂酸、氯钯酸和氯金酸混合液中摩尔比为2:1:10、当氯铂酸用量是1mol时，稳定剂用量为22mol、当氯铂酸用量是1mol时，还原剂用量为31mol。
步骤(2)中，继续搅拌0.5h。
步骤(3)中，Pt-Pd-Au溶胶与载体质量比为1：72。
本发明的PtPdAu/负载型纳米磁性催化剂可以用于Heck反应。
磁性PtPdAu/Fe3O4纳米催化剂在Heck反应中的具体步骤如下：
向三口烧瓶中加入碘苯、苯乙烯、DMF，再加入一定量的磁性PtPdAu/Fe3O4纳米催化剂，搅拌均匀后，放入油浴锅中进行反应。反应结束后，将催化剂于产物分离，催化剂留待循环使用。
本发明的积极效果如下：
本发明的磁性PtPdAu/Fe3O4纳米催化剂具有清洁、环保、可循环使用而又方便的特点，并且本发明的磁性PtPdAu/Fe3O4纳米催化剂Heck反应中反应条件要求不高，并且具有优异的催化性能。
附图说明
图1是实施例1制备的磁性PtPdAu/Fe3O4纳米催化剂的透射电镜照片。
具体实施方式
下面的实施例是对本发明的进一步详细描述。
实施例1
(1)载体的制备及其预处理
于50ml烧杯中，准确称取0.2125g的FeCl3·6H2O、0.1432g的尿素、0.1663g的聚乙烯吡咯烷酮，随后加入8.5ml的1，2-丙二醇，混合物在磁力搅拌器上搅拌直至溶液混合均匀得黄色透明溶液后转移到反应釜中，密封后在190℃下反应16h。反应结束后，冷却到室温，将产物转移到广口玻璃瓶中，用去离子水、乙醇多次洗涤，并用磁分离倾出广口瓶中的上清液。将洗涤后的黑色沉淀颗粒分散于10mL的乙醇得到Fe3O4纳米磁体材料。
(2))Pt-Pd-Au溶胶的制备
于50mL烧杯中，准确量取0.0789g的聚乙烯吡咯烷酮，用移液管量取3.86×10- 3mol/L的氯铂酸水溶液0.82mL，1.13×10-2mol/L的氯钯酸水溶液1.40mL，4.806×10-3mol/L的氯金酸水溶液3.28mL，然后在磁力搅拌器上搅拌，直至完全溶解。随后将用0.0373g硼氢化钠、1.5mL水配制的溶液逐滴加入混合液中，制得Pt-Pd-Au溶胶。
(3)磁性PtPdAu/Fe3O4纳米催化剂的制备
将(1)中制备的Fe3O4纳米颗粒于上述制得的Pt-Pd-Au溶胶，机械搅拌8小时后静置1小时，使用铁磁体将其分离，烘干得磁性PtPdAu/Fe3O4纳米催化剂。
磁性PtPdAu/Fe3O4纳米催化剂在Heck反应中的应用
向50ml三口烧瓶中加入0.14mmol的碘代苯、3ml的DMF、0.17mmol的苯乙烯、上述制得磁性PtPdAu/Fe3O4纳米催化剂，搅拌均匀后再加入2.0mmol的K2CO3，于90℃下电动搅拌9h。反应结束后，将催化剂于产物分离，催化剂留待循环使用。
碘苯的转化率约为100％，产率高达98％。
而现有催化剂的转化率和产率如表1所示：
表1
参考文献
[1]K.Karami,Z.K.Moghadam,M.Hosseini-Kharat,Catalysis Communications,43(2014)25-28.
[2]M.Bakherad,A.Keivanloo,S.Samangooei,TetrahedronLetters,53(2012)5773-5776.
[3]P.Karthikeyan,P.N.Muskawar,S.A.Aswar,P.R.Bhagat,S.K.Sythana,Journal of Molecular CatalysisA:Chemical,358(2012)112-120.
[4]F.R.Fortea-Pérez,I.Schlegel,M.Julve,Journal of OrganometallicChemistry,743(2013)102-108.
[5]F.Cuenú,R.Abonia,A.A.Cabrera,Journal ofOrganometallicChemistry,696(2011)1834-1839.
循环实验效果：催化剂循环使用六次；
表2
| 循环次数 | 1 | 2 | 3 | 4 | 5 | 6 |
| 转化率(％) | 100 | 99.01 | 98.80 | 93.88 | 87.32 | 80.74 |
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 (10)
1.一种PtPdAu/负载型纳米磁性催化剂，其特征在于：所述催化剂载体为Fe3O4，活性组分是Pt、Pd和Au，催化剂中Pt、Pd和Au的质量分数分别为1～4％、3～6％和7～15％。
2.如权利要求1所述的PtPdAu/负载型纳米磁性催化剂，其特征在于：催化剂中Pt、Pd和Au的质量分数分别约为2.1％、4.3％和9.3％。
3.如权利要求1所述的PtPdAu/负载型纳米磁性催化剂，其特征在于：活性组分是Pt、Pd和Au，其平均粒径分别约为10纳米、7纳米和15纳米。
4.一种制备如权利要求1-3任一项所述的PtPdAu/负载型纳米磁性催化剂的方法，其特征在于：所述方法的具体步骤如下：
(1)载体的制备及其预处理
通过水热法将铁离子前驱体氧化还原成的Fe3O4纳米颗粒，使用去离子水、无水乙醇进行清洗，直至上层液体透明，然后将其用无水乙醇定容，备用；在清洗过程中通过铁磁体对Fe3O4纳米颗粒进行分离；
(2)Pt-Pd-Au溶胶的制备
向氯铂酸、氯钯酸和氯金酸混合液中添加稳定剂，搅拌均匀后滴加还原剂溶液，继续搅拌制得稳定Pt-Pd-Au溶胶；
(3)磁性PtPdAu/Fe3O4纳米催化剂的制备
将从步骤(1)中所得的载体加入由步骤(2)制得的Pt-Pd-Au溶胶中，机械搅拌后静置，抽滤，烘干，得PtPdAu/Fe3O4催化剂。
5.如权利要求4所述的制备方法，其特征在于：步骤(1)中，所述的铁离子前驱体是FeCl3·6H2O、FeCl2·4H2O、FeCl2·2H2O或FeCl2。
6.如权利要求4所述的制备方法，其特征在于：步骤(2)中，所述的稳定剂为聚乙烯吡咯烷酮、聚乙二醇或聚乙烯醇；所述的还原剂为硼氢化钠、硼氢化钾或焦性没食子酸。
7.如权利要求4所述的制备方法，其特征在于：步骤(2)中，氯铂酸、氯钯酸和氯金酸混合液摩尔比为2:1:10、当氯铂酸用量是1mol时，稳定剂用量为22mol、当氯铂酸用量是1mol时，还原剂用量为31mol。
8.如权利要求4所述的制备方法，其特征在于：步骤(2)中，继续搅拌0.5h。
9.如权利要求4所述的制备方法，其特征在于：步骤(3)中，Pt-Pd-Au溶胶与载体质量比为1：72。
10.如权利要求1-3任一项所述的PtPdAu/负载型纳米磁性催化剂用于Heck反应中的用途。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710256631.3A CN106984326A (zh) | 2017-04-19 | 2017-04-19 | 一种PtPdAu/负载型纳米磁性催化剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710256631.3A CN106984326A (zh) | 2017-04-19 | 2017-04-19 | 一种PtPdAu/负载型纳米磁性催化剂及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106984326A true CN106984326A (zh) | 2017-07-28 |
Family
ID=59415750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710256631.3A Pending CN106984326A (zh) | 2017-04-19 | 2017-04-19 | 一种PtPdAu/负载型纳米磁性催化剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106984326A (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108579763A (zh) * | 2018-05-10 | 2018-09-28 | 吉林晟航科技发展有限公司 | 一种稳定性好的纳米金属催化剂及其制备方法与应用 |
| WO2019213995A1 (zh) * | 2018-05-09 | 2019-11-14 | 南通龙翔新材料科技股份有限公司 | 一种钯铂合金纳米溶胶催化剂及其制备方法 |
| CN110560165A (zh) * | 2019-09-25 | 2019-12-13 | 燕山大学 | 一种超小尺寸铂基磁性空间限域催化剂及其制备方法 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940952A (zh) * | 2010-08-17 | 2011-01-12 | 复旦大学 | 双金属纳米颗粒催化剂及其制备方法 |
-
2017
- 2017-04-19 CN CN201710256631.3A patent/CN106984326A/zh active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101940952A (zh) * | 2010-08-17 | 2011-01-12 | 复旦大学 | 双金属纳米颗粒催化剂及其制备方法 |
Non-Patent Citations (6)
| Title |
|---|
| HYON MIN SONG等: "Water-dispersable hybrid Au–Pd nanoparticles as catalysts in ethanol oxidation, aqueous phase Suzuki–Miyaura and Heck reactions", 《J. MATER. CHEM.》 * |
| MAIYONG ZHU等: "Synthesis of Porous Fe3O4 Nanospheres and Its Application for the Catalytic Degradation of Xylenol Orange", 《J. PHYS. CHEM. C》 * |
| 徐蕾等: "《负载型多酸光催化材料及应用》", 31 March 2015, 东北师范大学出版社 * |
| 朱洪法: "《催化剂载体制备及应用技术》", 31 October 2014, 石油工业出版社 * |
| 胡将军等: "《燃煤电厂 烟气脱硝催化剂》", 31 January 2014, 中国电力出版社 * |
| 胡昌义等: "《贵金属新材料》", 30 September 2015, 中南大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019213995A1 (zh) * | 2018-05-09 | 2019-11-14 | 南通龙翔新材料科技股份有限公司 | 一种钯铂合金纳米溶胶催化剂及其制备方法 |
| CN108579763A (zh) * | 2018-05-10 | 2018-09-28 | 吉林晟航科技发展有限公司 | 一种稳定性好的纳米金属催化剂及其制备方法与应用 |
| CN108579763B (zh) * | 2018-05-10 | 2021-09-17 | 吉林晟航科技发展有限公司 | 一种稳定性好的纳米金属催化剂及其应用 |
| CN110560165A (zh) * | 2019-09-25 | 2019-12-13 | 燕山大学 | 一种超小尺寸铂基磁性空间限域催化剂及其制备方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ma et al. | Preparation of high-magnetization Fe3O4–NH2–Pd (0) catalyst for Heck reaction | |
| CN105833891B (zh) | 一种功能化石墨烯支撑的镍钯双金属纳米催化剂及其制备和应用 | |
| Jiang et al. | Facile synthesis of Ag@ Pd satellites–Fe 3 O 4 core nanocomposites as efficient and reusable hydrogenation catalysts | |
| CN103272648B (zh) | 一种磁性多孔负载型金属手性催化剂及其应用 | |
| CN104043481B (zh) | 一种功能化石墨烯担载贵金属纳米晶复合催化剂的制备方法 | |
| CN108607603B (zh) | 一种co2合成炔酸催化剂及其制备和应用 | |
| CN107175105B (zh) | 石墨烯负载钯铱纳米颗粒催化剂制备方法及其甲酸氧化电催化应用 | |
| CN107597109A (zh) | 纳米金属氧化物掺杂的负载型金催化剂及其制备方法与应用 | |
| CN106984312B (zh) | 一种复合型光催化剂及其制备方法 | |
| CN106984326A (zh) | 一种PtPdAu/负载型纳米磁性催化剂及其制备方法 | |
| CN109317149A (zh) | 一种负载镍的SiO2@C核壳材料的制备方法及应用 | |
| CN104971778A (zh) | 一种四氧化三铁-聚苯胺-金纳米复合材料的制备方法及其应用 | |
| CN105879881A (zh) | PtPd/Fe3O4纳米催化剂的制备及其在HECK反应中的应用 | |
| CN106040307B (zh) | 一步水热法合成Fe3O4(PAA)@C-Au核壳结构微球的制备方法 | |
| CN110624592A (zh) | 单原子金属-氮掺杂石墨烯聚集体的合成方法及其产品和应用 | |
| Geng et al. | Rational design of CuO/SiO2 nanocatalyst with anchor structure and hydrophilic surface for efficient hydrogenation of nitrophenol | |
| Li et al. | Poly (amic acid) salt-stabilized silver nanoparticles as efficient and recyclable quasi-homogeneous catalysts for the aqueous hydration of nitriles to amides | |
| CN108031475A (zh) | 一种金负载氧化铁纳米光催化剂的制备方法 | |
| CN108636436A (zh) | 有效构筑z型三元异质结光催化剂的制备方法 | |
| CN109529879B (zh) | 一种PdNi/RGO纳米催化剂及其制备方法 | |
| CN105070924A (zh) | 一种直接甲醇燃料电池硫化钼功能化碳纳米管载Pt催化剂及其制备方法 | |
| CN105837391B (zh) | 一种无金属加氢催化剂在催化苯加氢反应中的应用 | |
| CN110560054B (zh) | 一种2，4-二硝基苯胺加氢催化剂及其制备方法和应用 | |
| Amirmahani et al. | Recent developments of metallic nanoparticles and their catalytic activity in organic reactions | |
| CN109569650B (zh) | 一种用于co偶联合成草酸酯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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170728 |