CN101875010A - Palladium nanoparticle catalyst and preparation method as well as application thereof - Google Patents
Palladium nanoparticle catalyst and preparation method as well as application thereof Download PDFInfo
- Publication number
- CN101875010A CN101875010A CN2009101115976A CN200910111597A CN101875010A CN 101875010 A CN101875010 A CN 101875010A CN 2009101115976 A CN2009101115976 A CN 2009101115976A CN 200910111597 A CN200910111597 A CN 200910111597A CN 101875010 A CN101875010 A CN 101875010A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nanoparticle catalyst
- reaction
- preparing
- microwave
- 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
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a palladium nanoparticle catalyst and a preparation method as well as an application thereof. The preparation method comprises the following steps: controlling the pH of the reaction environment to be equal to 2; combining metal ions of different concentrations with inner N of branches; and finally, reducing the metal ions by utilizing NaBH4 to generate a metal Pd nanoparticle catalyst with different diameters (1-3nm) of particles. The catalyst has good catalytic effect on the Suzuki reaction aided by microwaves. 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%.
Claims (9)
1. Pd nanoparticle catalyst is characterized in that: adopt in the SBA-15 duct " grafting " the 4th generation polyamine dendritic amine compound fixing as the metal nanoparticle catalyst carrier, the Pd nanoparticle catalyst.
2. a method for preparing the described Pd nanoparticle catalyst of claim 1 comprises the steps:
(1) in the SBA-15 duct " grafting " the 4th generation polyamine dendritic amine compound as the metal nanoparticle catalyst carrier, and calculate branch content in the grafting;
(2) get support powder, with the hydrochloric acid solution dispersion of pH=2; Preparation K
2PdCl
4Hydrochloric acid solution, wherein the mole of Pd be approximately the branch amount of being calculated 10-40 doubly, under the room temperature this solution slowly is added dropwise to support powder and disperses in the thing, keeping the pH of reaction system constant is 2; Centrifugal and the dry yellow powder that gets in reaction back;
(3) aforementioned yellow powder is scattered in the deionized water, system is sealed; With the deionized water dissolving excessive N aBH that cooled off
4, slowly join in the sealing system by syringe; Reaction gained black solid centrifugation and vacuum drying promptly obtain the Pd nanoparticle catalyst.
3. the method for preparing the Pd nanoparticle catalyst as claimed in claim 2 is characterized in that: the mole of Pd described in the step (2) is 10 times of the branch amount calculated, and the Pd nano particle average grain diameter that obtains is 1.8 ± 0.4nm.
4. the method for preparing the Pd nanoparticle catalyst as claimed in claim 2 is characterized in that: the mole of Pd described in the step (2) is 20 times of the branch amount calculated, and the Pd nano particle average grain diameter that obtains is 2.0 ± 0.4nm.
5. the method for preparing the Pd nanoparticle catalyst as claimed in claim 2 is characterized in that: the mole of Pd described in the step (2) is 30 times of the branch amount calculated, and the Pd nano particle average grain diameter that obtains is 2.2 ± 0.4nm.
6. the method for preparing the Pd nanoparticle catalyst as claimed in claim 2 is characterized in that: the mole of Pd described in the step (2) is 40 times of the branch amount calculated, and the Pd nano particle average grain diameter that obtains is 2.7 ± 0.4nm.
7. the method for preparing the Pd nanoparticle catalyst as claimed in claim 2 is characterized in that: determine the N content of dust carrier in the described step (1) by elementary analysis, come roughly to determine the content of branch.
8. utilize right 1 described Pd nanoparticle catalyst to be used for the auxiliary Suzuki coupling reaction of microwave.
9. Pd nanoparticle catalyst as claimed in claim 7 is used for the auxiliary Suzuki coupling reaction of microwave, comprises following steps: 3mmolK
3PO
4, 0.5mol% catalyst, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101115976A CN101875010A (en) | 2009-04-29 | 2009-04-29 | Palladium nanoparticle catalyst and preparation method as well as application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101115976A CN101875010A (en) | 2009-04-29 | 2009-04-29 | Palladium nanoparticle catalyst and preparation method as well as application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101875010A true CN101875010A (en) | 2010-11-03 |
Family
ID=43017754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101115976A Pending CN101875010A (en) | 2009-04-29 | 2009-04-29 | Palladium nanoparticle catalyst and preparation method as well as application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101875010A (en) |
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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2009
- 2009-04-29 CN CN2009101115976A patent/CN101875010A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101875010A (en) | Palladium nanoparticle catalyst and preparation method as well as application thereof | |
| Yun et al. | Design and remarkable efficiency of the robust sandwich cluster composite nanocatalysts ZIF-8@ Au25@ ZIF-67 | |
| Chen et al. | Porous double-shell CdS@ C3N4 octahedron derived by in situ supramolecular self-assembly for enhanced photocatalytic activity | |
| Nabid et al. | Fe3O4–SiO2–P4VP pH‐sensitive microgel for immobilization of nickel nanoparticles: An efficient heterogeneous catalyst for nitrile reduction in water | |
| CN102205242A (en) | Method for preparing dispersed palladium nanoparticle catalyst with controllable appearance by using cucurbit[6]uril (CB[6]) | |
| Lu et al. | In situ synthesis of cobalt alginate/ammonium perchlorate composite and its low temperature decomposition performance | |
| CN105885847B (en) | A kind of cadmium sulfoselenide solid solution quantum dot and preparation method thereof and Photocatalyzed Hydrogen Production application | |
| CN110104667A (en) | A kind of magnalium hydrotalcite and preparation method and application for organic sulfur catalysis | |
| CN103359773A (en) | Preparation method of zinc oxide nanorod | |
| CN109201090A (en) | The modified BiOCl of bismuth telluride forms the preparation method of the flower-shaped catalyst of photoresponse type and its application of reduction fixed nitrogen production ammonia | |
| Zhao et al. | Transformation from 3D boron organic polymers to 1D nanorod arrays: loading highly dispersed nanometal for green catalysis | |
| CN104148084A (en) | Preparation of nano porous quaternary alloy catalyst and application thereof in production of hydrogen by virtue of ammonia borane hydrolysis | |
| CN109622037B (en) | Pd @ Co4(tpt)2(btb) composite material, and preparation method and application thereof | |
| CN116371447A (en) | double-Z heterojunction photocatalyst and preparation method and application thereof | |
| CN101786673B (en) | Synthesis method for basic cobalt carbonate ferrum nano material | |
| Aschenaki et al. | Preparation of a magnetic and recyclable superparamagnetic silica support with a boronic acid group for immobilizing Pd catalysts and its applications in Suzuki reactions | |
| CN108722486A (en) | A kind of preparation method of narrowband carbonitride modification ferrous metals organic backbone composite photo-catalyst | |
| CN105148918B (en) | Preparation method and application of Co-B/Ni-B amorphous nanosphere composite alloy catalyst | |
| Wang et al. | Integration of Au nanoparticles and metal-organic frameworks in hollow double-shelled nanoreactor for efficient tandem catalysis | |
| CN108993614B (en) | Preparation method of ball-flower-shaped zinc ion doped CdS photocatalyst | |
| Dong et al. | Two-dimensional porous Cu-CuO nanosheets: Integration of heterojunction and morphology engineering to achieve high-effective and stable reduction of the aromatic nitro-compounds | |
| CN111203279B (en) | Sandwich nano material ZIF-8@Au 25 @ ZIF-67 and preparation method and application thereof | |
| CN103111330B (en) | Preparation method of magnetic nano triphenylphosphine catalysis ligand | |
| CN111054419B (en) | For CO 2 Reduced semiconductor/g-C 3 N 4 Photocatalyst and preparation method thereof | |
| CN105435816A (en) | CdxZn1-xS nanowire compound photocatalyst and preparing method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20101103 |