CN101875010A - A kind of palladium nanoparticle catalyst and its preparation method and application - Google Patents
A kind of palladium nanoparticle catalyst and its preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title abstract description 20
- 229910052763 palladium Inorganic materials 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 210000001787 dendrite Anatomy 0.000 claims abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000412 dendrimer Substances 0.000 claims description 8
- 229920000736 dendritic polymer Polymers 0.000 claims description 8
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002082 metal nanoparticle Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- 239000000243 solution Substances 0.000 claims 3
- 239000012074 organic phase Substances 0.000 claims 2
- 101150003085 Pdcl gene Proteins 0.000 claims 1
- 238000000921 elemental analysis Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 229910021645 metal ion Inorganic materials 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 208000035126 Facies Diseases 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 239000011943 nanocatalyst Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000003810 ethyl acetate extraction Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000010812 external standard method Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LBBMOAOCCQOIAQ-UHFFFAOYSA-N methoxy(phenyl)borinic acid Chemical compound COB(O)C1=CC=CC=C1 LBBMOAOCCQOIAQ-UHFFFAOYSA-N 0.000 description 2
- KNPNGMXRGITFLE-UHFFFAOYSA-N methylperoxy(phenyl)borinic acid Chemical compound COOB(O)C1=CC=CC=C1 KNPNGMXRGITFLE-UHFFFAOYSA-N 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
本发明涉及一种钯纳米颗粒催化剂及其制备方法和用途。控制反应环境pH＝2，使不同浓度金属离子与树枝内部N结合，最后利用NaBH4还原金属离子生成粒径(1-3nm)不同的金属Pd纳米颗粒催化剂。此种催化剂对微波辅助进行Suzuki反应具有优良的催化效果。本方法具有工艺简单，操作方便，形貌可控，应用效果好等特点。
The invention relates to a palladium nanoparticle catalyst and its preparation method and application. Control the pH of the reaction environment to 2, make different concentrations of metal ions combine with N inside the dendrites, and finally use NaBH 4 to reduce the metal ions to generate metal Pd nanoparticle catalysts with different particle sizes (1-3nm). This kind of catalyst has excellent catalytic effect on microwave-assisted Suzuki reaction. The method has the characteristics of simple process, convenient operation, controllable shape, good application effect and the like.
Description
Technical field
The present invention relates to a kind of preparation method of palladium nanoparticle catalyst, specifically, utilize the internal cavities that grafts in the dendrimer among the mesoporous SBA-15 exactly, prepare the nanocatalyst that can be used for the auxiliary Suzuki reaction of catalysis microwave, belong to the catalyst material field.
Background technology
Coupling reactions such as Suzuki are extremely important intermediate reaction processes in the organic reaction always.At present, this type of reaction and correlated response thereof have been widely used in the methods such as pharmacy new material preparation, and application mode constantly weeds out the old and bring forth the new, and far-reaching using value is arranged.
What catalysis suzuki reacted mainly is to be the catalyst of representative with noble metals such as palladiums, and general catalyst can be divided into homogeneous catalyst and different-phase catalyst.Homogeneous catalyst has the reaction rate height, consumption is few, the output height, advantages such as mild condition, but its difficulty is separated with product, and easily shortcoming such as pollution products has hindered its application in industrial aspect, though and different-phase catalyst reaction rate slower than homogeneous phase, but being easy to separate advantages such as (general using are filtered, means such as magnetic force absorption), it make it especially be subjected to the industry favor.
Up to the present, nano particle has obtained deep research as branch important in the different-phase catalyst.The internal cavities of dendrimer both can be used as the template that forms nano particle, also can be in reaction as nano-reactor and can be used as metal " anchor point ", the protection nano particle avoids running off.But end group is that amino polyamine amine dendrimer is under neutrallty condition, very easily with Pd
2+Deng the precious metal ion combination, cause the inner N atom of branch can not with the metal ion combination, after reduction, metal simple-substance can only be reunited at the end of branch compound, make dendrimer lose the effect of template and " anchor point ", and nano particle pattern of Xing Chenging and size are uncontrollable in this case, influence its application.At this kind situation, among the present invention, before carrier and metal ion combination, regulate pH=2 earlier, make end group amino protonated, lose ability, and inner N is uninfluenced in conjunction with the ability of metal simultaneously in conjunction with metal, metal nanoparticle just can successfully be wrapped in dendrimer inside like this, has realized that particle diameter is controlled.
Also utilize the characteristics of heating using microwave among the present invention, will be prepared into catalyst and be applied in the microwave assisted reaction reaction be finished at short notice rapidly, shorten the reaction time.The result proves: reaction has good catalytic effect to the palladium nanoparticle catalyst of preparation to Suzuki.The method catalyst amount is few, and it is higher to recycle number of times and since reaction system with water and ethanol as solvent, environmental pollution is seldom.
Summary of the invention
The invention provides and a kind ofly prepare the method for palladium nanoparticle catalyst and expand its scope of application
Its feature mainly contains: utilize the existing preparation method improved in the SBA-15 duct " grafting " four generation the dendriform compound as the metal nanoparticle catalyst carrier.Thereafter, control reaction environment pH=2 combines the inner N of variable concentrations metal ion and branch, utilizes NaBH at last
4The reducing metal ion generates the different metal nanoparticle catalyst of particle diameter (1-3nm).By test, innovation uses this kind catalyst to the auxiliary Suzuki reaction of microwave, and good catalytic effect is arranged.It is simple that this method has technology, easy to operate, and pattern is controlled, characteristics such as applied range.
Concrete processing step is:
1. at first prepare grow in the SBA-15 duct the 4th generation polyamine amine dendrimer, with this as support powder.
2. utilize elementary analysis to determine N content in the support powder, thereby extrapolate the quantity of branch.
3. get the 0.1g support powder, the hydrochloric acid solution dispersion with 50ml pH=2 utilizes the sonic oscillation aid dispersion in case of necessity.Equally, with same hydrochloric acid solution 5ml dissolving certain mass K
2PdCl
4(metal: the branch More is than=10: 1,20: 1,30: 1 and 40: 1).After the dissolving, this drips of solution is added in the powder dispersed mixture fully, the control temperature is a room temperature, reaction 12h.In course of reaction, keep the pH of reaction system constant is 2.After reaction finished, centrifugal drying obtained yellow solid.
4. utilize magnetic agitation and sonic oscillation, again yellow solid is scattered in the deionized water, and seal with the sealing plug.The deionized water dissolving excessive N aBH that cooled off with the 5ml refrigerator
4, slowly join in the sealing system reaction 12h by syringe.Reaction gained black solid is equally by sonic oscillation and centrifugation, and final drying obtains.
The preparation method of nanometer palladium beaded catalyst provided by the present invention has the following advantages:
(1) Zhi Bei metal nanoparticle is not easy to reunite, and monodispersity is fine.
(2) by changing the amount of reacting metal, the size that can suitably regulate metal nanoparticle, thus realize that form is controlled.
(3) nanocatalyst for preparing with the method stable fine in catalytic reaction is not easy to run off, and guarantees recycled for multiple times and pollution products not.
Under nitrogen protection, with 3mmolK
3PO
4, 0.005g catalyst (0.5mol%), 1.05mmol aromatic boric acid add has in the 20ml microwave reaction bottle of 1.8ml deionized water, 1.2ml ethanol, wait to be uniformly dispersed, and add iodobenzene 1mmol, put into microwave reactor after the sealing, 100 ℃ of reaction 30min.
Reaction is used the ethyl acetate extraction organic facies after finishing, after the inorganic water that contains catalyst fines passes through centrifugation and washes three times ethanol and washes twice, and the heating recovery catalyst.Organic facies extracts prior to saturated aqueous common salt, utilizes anhydrous sodium sulfate to carry out drying then.Through decompression distillation, it is to be measured to obtain product.
Description of drawings
Fig. 1 Pd nanocatalyst X-ray powder diffraction figure.
Fig. 2 Pd nanocatalyst EDS collection of illustrative plates.
Fig. 3 metal Pd: the branch More is than the projection electromicroscopic photograph of=10: 1 nanocatalyst for preparing.
Fig. 4 metal Pd: the branch More distributes than the particle diameter of nano particle in=10: 1 nanocatalyst for preparing.
The comparison of Fig. 5 catalyst circulation access times and conversion ratio.
The specific embodiment
Embodiment 1: utilize the catalyst iodobenzene and the auxiliary Suzuki coupling reaction of phenyl boric acid microwave that make
Under the nitrogen protection, with 0.8gK
3PO
4, 0.005g catalyst (0.5mol%), 0.128g phenyl boric acid (1.05mmol) add has in the 20ml microwave reaction bottle of 1.8ml deionized water, 1.2ml ethanol, wait to be uniformly dispersed, add iodobenzene 1mmol, put into microwave reactor after the sealing, 100 ℃ of reaction 30min.Reaction is used the ethyl acetate extraction organic facies after finishing, after the inorganic water that contains catalyst fines passes through centrifugation and washes three times ethanol and washes twice, and the heating recovery catalyst.Organic facies extracts prior to saturated aqueous common salt, utilizes anhydrous sodium sulfate to carry out drying then.Through decompression distillation, it is to be measured to obtain product.Productive rate utilizes the external standard method in the gas-chromatography to record, productive rate＞99%.
Thereafter, utilize the catalyst that reclaims to proceed the catalytic reaction of embodiment 1, behind five secondary responses, productive rate does not significantly reduce.
Embodiment 2: utilize the catalyst iodobenzene make and to the auxiliary Suzuki reaction of methylphenylboronic acid microwave
Under the nitrogen protection, 0.8gK
3PO
4, 0.005g catalyst (0.5mol%), 1.05mmol add methylphenylboronic acid 1.05mmol has in the 20ml microwave reaction bottle of 1.8ml deionized water, 1.2ml ethanol, wait to be uniformly dispersed, add iodobenzene 1mmol, put into microwave reactor after the sealing, 100 ℃ of reaction 30min.
Reaction is used the ethyl acetate extraction organic facies after finishing, after the inorganic water that contains catalyst fines passes through centrifugation and washes three times ethanol and washes twice, and the heating recovery catalyst.Organic facies extracts at this prior to saturated aqueous common salt, utilizes anhydrous sodium sulfate to carry out drying then.Through decompression distillation, it is to be measured to obtain product.Productive rate utilizes the external standard method in the gas-chromatography to record, productive rate 91%.
Embodiment 3: utilize to make the catalyst iodobenzene and the methoxyphenylboronic acid microwave is assisted the Suzuki reaction
Under the nitrogen protection, 0.8gK
3PO
4, 0.005g catalyst (0.5mol%), 1.05mmol add methoxyphenylboronic acid 1.05mmol has in the 20ml microwave reaction bottle of 1.8ml deionized water, 1.2ml ethanol, wait to be uniformly dispersed, add iodobenzene 1mmol, put into microwave reactor after the sealing, 100 ℃ of reaction 30min.
Reaction is used the ethyl acetate extraction organic facies after finishing, after the inorganic water that contains catalyst fines passes through centrifugation and washes three times ethanol and washes twice, and the heating recovery catalyst.Organic facies extracts at this prior to saturated aqueous common salt, utilizes anhydrous sodium sulfate to carry out drying then.Through decompression distillation, it is to be measured to obtain product.Productive rate utilizes the external standard method in the gas-chromatography to record, productive rate 99%.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370821A (en) * | 2011-01-19 | 2013-10-23 | Utc电力公司 | Shape controlled palladium and palladium alloy nanoparticle catalyst |
| CN105399635A (en) * | 2015-12-15 | 2016-03-16 | 上海师范大学 | Microwave synthesis method of 2-nitro-3',4',5'-trifluoro-1,1'-biphenyl |
| US9663600B2 (en) | 2012-12-21 | 2017-05-30 | Audi Ag | Method of fabricating an electrolyte material |
| US9923224B2 (en) | 2012-12-21 | 2018-03-20 | Audi Ag | Proton exchange material and method therefor |
| US9923223B2 (en) | 2012-12-21 | 2018-03-20 | Audi Ag | Electrolyte membrane, dispersion and method therefor |
| CN108201897A (en) * | 2018-02-01 | 2018-06-26 | 黑龙江省科学院石油化学研究院 | The method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts |
| US10505197B2 (en) | 2011-03-11 | 2019-12-10 | Audi Ag | Unitized electrode assembly with high equivalent weight ionomer |
| CN107983357B (en) * | 2017-12-08 | 2021-05-18 | 西安近代化学研究所 | Catalyst for synthesizing propane diamine and preparation method thereof |
| CN113248346A (en) * | 2021-05-26 | 2021-08-13 | 华东师范大学 | Preparation method of 1, 4-cyclohexanedimethanol |
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| CN1958156A (en) * | 2006-10-27 | 2007-05-09 | 中国科学院上海硅酸盐研究所 | Pd(0) Gn-PAMAM mesoporous catalyst in use for hydrogenation reaction of unsaturated hydrocarbon, and preparation method |
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2009
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Patent Citations (1)
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| CN1958156A (en) * | 2006-10-27 | 2007-05-09 | 中国科学院上海硅酸盐研究所 | Pd(0) Gn-PAMAM mesoporous catalyst in use for hydrogenation reaction of unsaturated hydrocarbon, and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 张涛等: "SBA-15负载钯催化剂的制备及其在超临界二氧化碳介质中催化Suzuki偶联反应的研究", 《分子科学学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370821A (en) * | 2011-01-19 | 2013-10-23 | Utc电力公司 | Shape controlled palladium and palladium alloy nanoparticle catalyst |
| US10505197B2 (en) | 2011-03-11 | 2019-12-10 | Audi Ag | Unitized electrode assembly with high equivalent weight ionomer |
| US9663600B2 (en) | 2012-12-21 | 2017-05-30 | Audi Ag | Method of fabricating an electrolyte material |
| US9923224B2 (en) | 2012-12-21 | 2018-03-20 | Audi Ag | Proton exchange material and method therefor |
| US9923223B2 (en) | 2012-12-21 | 2018-03-20 | Audi Ag | Electrolyte membrane, dispersion and method therefor |
| CN105399635A (en) * | 2015-12-15 | 2016-03-16 | 上海师范大学 | Microwave synthesis method of 2-nitro-3',4',5'-trifluoro-1,1'-biphenyl |
| CN107983357B (en) * | 2017-12-08 | 2021-05-18 | 西安近代化学研究所 | Catalyst for synthesizing propane diamine and preparation method thereof |
| CN108201897A (en) * | 2018-02-01 | 2018-06-26 | 黑龙江省科学院石油化学研究院 | The method that ultrasonic wave added local reduction way prepares SBA-15 loaded nanometer palladium catalysts |
| CN113248346A (en) * | 2021-05-26 | 2021-08-13 | 华东师范大学 | Preparation method of 1, 4-cyclohexanedimethanol |
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Application publication date: 20101103 |