CN103464202B - metal catalyst compound and preparation method thereof - Google Patents
metal catalyst compound and preparation method thereof Download PDFInfo
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- CN103464202B CN103464202B CN201310460025.5A CN201310460025A CN103464202B CN 103464202 B CN103464202 B CN 103464202B CN 201310460025 A CN201310460025 A CN 201310460025A CN 103464202 B CN103464202 B CN 103464202B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000012685 metal catalyst precursor Substances 0.000 claims abstract description 38
- 239000004094 surface-active agent Substances 0.000 claims abstract description 34
- 239000003863 metallic catalyst Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000001338 self-assembly Methods 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- 239000002105 nanoparticle Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 9
- 210000002808 connective tissue Anatomy 0.000 claims description 8
- 230000010148 water-pollination Effects 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 239000003945 anionic surfactant Substances 0.000 claims description 7
- 239000003093 cationic surfactant Substances 0.000 claims description 7
- 150000002632 lipids Chemical group 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 230000004308 accommodation Effects 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 6
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 claims description 5
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims description 4
- RNPXCFINMKSQPQ-UHFFFAOYSA-N dicetyl hydrogen phosphate Chemical group CCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCC RNPXCFINMKSQPQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 229960003431 cetrimonium Drugs 0.000 claims description 3
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229950010007 dimantine Drugs 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical class [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 235000012000 cholesterol Nutrition 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000012018 catalyst precursor Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000002082 metal nanoparticle Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 150000005837 radical ions Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125773 compound 10 Drugs 0.000 description 1
- 239000004064 cosurfactant Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
The invention discloses a kind of Metal catalyst compound and preparation method thereof, first metal catalyst precursor is dissolved in cushioning liquid, then carry out adding hot reflux, ice bath and adding the steps such as surfactant, form imitated vesicle structure by surfactant self assembly in mixed liquor, part metals catalyst precursor is coated in imitated vesicle structure.Then, filter mixed liquor, removes the metal catalyst precursor outside imitated vesicle structure.Afterwards, pass into reducing gas, make metal catalyst precursor be reduced to metallic catalyst in imitated vesicle structure, and form Metal catalyst compound with imitated vesicle structure.Because metallic catalyst is completely cut off by imitated vesicle structure and external environment, and outside imitated vesicle structure, do not have metallic catalyst to be formed, thus optionally can react with specific compound in the reaction solution of complicated component.Further, the Metal catalyst compound formed can directly use as microreactor, quite convenient in the operation of catalytic reaction.
Description
Technical field
The invention belongs to catalyst field, specifically, relate to a kind of catalyst composites and preparation method thereof.
Background technology
Vesica (vesicle) is the membrane structure closed formed by the organic phospholipid molecular self-assembling of parents.Molecule one end of these chains is hydrophilic, and the other end detests water.In water, they can the rock-steady structure of spontaneous formation duplicature, thus all parts of detesting water are all hidden in film inside.A space completely cut off with extraneous solution is formed in duplicature.The physics of vesica itself, chemical property determine which Small molecular can through this duplicature enter intravesicular space or in vesica out.
The polymer vesicle be prepared from by this self-assembling technique is in recent years applied widely, such as, as pharmaceutical carrier, genophore, microreactor, or catalyst carrier etc.
Metal nanoparticle (especially transition metal nanoparticles) is custom catalysts, is widely used in the fields such as fuel cell, catalyzing manufacturing of hydrogen, petroleum chemicals synthesis, general industry and treating vehicle exhaust.If by metal nanoparticle perfectly " threadings " vesica, and do not have metal nanoparticle completely in extraneous solution outside vesica, that just only has the compound that can enter vesica just and the metal nanoparticle generation catalytic reaction of the inside.Such vesica metal nanoparticle coated with it just defines one can be carried out selective catalysis Metal catalyst compound to the specific compound in the reaction solution of complicated component.
Current industry is in the preparation method of nano particle vesica, and normally allow vesica self assembly in nano-particle solution form double membrane structure, allow the nano particle of part be coated in the space of film inside, remaining nano particle is isolated outside outermost film.But, these isolated nano particles in outside still can be attached to the periphery of the double membrane structure of vesica, so, when it is applied in drug response or catalyzing manufacturing of hydrogen reaction, these are attached to peripheral nano particle and can react by other compounds in advance and in reaction solution, thus cause reaction result not as expected or produce other unexpected accessory substances, and optionally cannot carry out catalytic reaction for specific compound, thus cause nano particle vesica to be difficult to use, and the problem of extensive use cannot be subject to.
Summary of the invention
In view of this, technical problem to be solved by this invention there is provided a kind of Metal catalyst compound and preparation method thereof, thus solves known nano particle vesica and optionally cannot carry out catalytic reaction for specific compound, and unworkable problem.
In order to solve the problems of the technologies described above, the invention discloses a kind of preparation method of Metal catalyst compound, comprising the following steps: metal catalyst precursor is dissolved in cushioning liquid and forms mixed liquor; Heating backflow mixed liquor; Mixed liquor is put into ice bath lower the temperature, and stir it; Mixed liquor is taken out from ice bath; Add surfactant in mixed liquor; Surfactant self assembly in mixed liquor forms imitated vesicle structure, and wherein part metals catalyst precursor is coated in imitated vesicle structure, and all the other are distributed in outside imitated vesicle structure; Filter mixed liquor, to remove the metal catalyst precursor be distributed in outside imitated vesicle structure; And the mixed liquor passed into after reducing gas to filtration, wherein reducing gas enters reducing metal catalyst precursor in imitated vesicle structure is metallic catalyst, to form in imitated vesicle structure the Metal catalyst compound being coated with metallic catalyst.
The present invention also discloses a kind of Metal catalyst compound, comprise a surfactant and a metallic catalyst, surfactant self assembly forms an imitated vesicle structure, this imitated vesicle structure comprises: a hydrophily adventitia and a hydrophobe inner membrance, wherein hydrophobe inner membrance is coated in hydrophily adventitia, and hydrophobe inner membrance in imitated vesicle structure around formation one accommodation space.Namely metallic catalyst is placed in described accommodation space.
Compared with existing scheme, the technique effect that the present invention obtains:
The preparation method of Metal catalyst compound disclosed by the invention, by imitated vesicle structure clad metal catalyst precursor, then the metal catalyst precursor outside vesica is eliminated, finally in imitated vesicle structure, metal catalyst precursor is reduced to metallic catalyst, can guarantee that metallic catalyst only appears in imitated vesicle structure, thus ensure that metal nano catalyst is in extraneous solution, and nonselective catalytic reaction can not occur.And rely on vesica to pass through by the selective of compound, thus effect of selective catalysis can be had for specific compound.
Accompanying drawing explanation
Fig. 1 is preparation method's flow chart of Metal catalyst compound of the present invention; And
Fig. 2 is the structural representation of Metal catalyst compound of the present invention.
Detailed description of the invention
Graphic and embodiment below will be coordinated to describe embodiments of the present invention in detail, by this to the present invention how application technology means solve technical problem and the implementation procedure reaching technology effect can fully understand and implement according to this.
Please refer to Fig. 1 and Fig. 2, the preparation method of the Metal catalyst compound disclosed by the present invention, first, metal catalyst precursor is dissolved in cushioning liquid and forms mixed liquor (S101), wherein metal catalyst precursor can be but be not limited to transition metal nanoparticles presoma, such as nano platinum particle presoma, Pd nano particle presoma, nickel nano particle presoma, Nano silver grain presoma, ruthenium nano particle presoma or cobalt nanometer particle presoma etc.Following embodiments of the invention are that nano platinum particle presoma arrives explanation as act with metal catalyst precursor, but not as limit.In addition, the pH value of the cushioning liquid used is between 6.0 ~ 8.0, and in formed mixed liquor, the concentration of metal catalyst precursor is 2.2 ~ 3.5mM, such as be dissolved in the cushioning liquid of 50ml by the metal catalyst precursor of about 150 μm of ol, the concentration forming metal catalyst precursor is the mixed liquor of 3.0mM.
Then, at the temperature of 100 DEG C, heating backflow mixed liquor (S102), such as, heat mixed liquor 2 hours, with slaking presoma under the temperature environment of 100 DEG C.Then, ice bath mixed liquor being put into 0 DEG C is lowered the temperature, and is stirred (S103), to promote the rate of temperature fall of mixed liquor.In ice bath, stir companion after 0.5 ~ 1.5 hour, from ice bath, take out mixed liquor, and be placed in room temperature and be naturally warming up to room temperature (S104); Or be heated to predetermined temperature (being such as close to or higher than room temperature).Afterwards, add surfactant to (S105) in mixed liquor, wherein, the quality concentration of volume percent of surfactant in mixed liquor is about 7 ~ 9%.In the present invention, surfactant is selected from cationic surfactant, anion surfactant or zwitterionic surfactant (lipid, such as: SPC class phosphatide) one of them, and surfactant can be but be not limited to lipid (lipid) class surfactant.What deserves to be explained is, selecting of surfactant, mainly decide according to metal catalyst precursor institute charging property own.That is, in the present invention, surfactant electrically and metal catalyst precursor electrically different, such as, when selecting electronegative metal catalyst precursor, i.e. the surfactant of select tape positive charge, vice versa.In addition, with cationic surfactant and anion surfactant unlike, zwitterionic surfactant can be applicable to metal catalyst precursor that is positively charged and negative electrical charge simultaneously.
Hold, when surfactant is added in mixed liquor, water end (W.E.) is detested because surfactant itself has a water-wet side and, therefore self assembly closed imitated vesicle structure 110 can be formed in mixed liquor, this imitated vesicle structure 110 is for having the duplicature form of a hydrophily adventitia 111 and a hydrophobe inner membrance 112, wherein hydrophobe inner membrance 112 is coated in hydrophily adventitia 111, and around formation one accommodation space 113 (as shown in Figure 2) in imitated vesicle structure 110.In addition, in this step, all right choice for use ultrasonic method or the self assembly of extrusion method cosurfactant form imitated vesicle structure, to accelerate the shaping rate of imitated vesicle structure.
In the process of above-mentioned formation imitated vesicle structure, the metal catalyst precursor be distributed in mixed liquor has part and is coated in the accommodation space of imitated vesicle structure, and remaining metal catalyst precursor is then excluded from imitated vesicle structure outer (S106).
Then, filter mixed liquor (S107), removes the metal catalyst precursor be distributed in outside imitated vesicle structure by ion-exchange, the metal catalyst precursor in mixed liquor is all coated in imitated vesicle structure, and can not be attached to outside imitated vesicle structure.Afterwards, pass into reducing gas to the mixed liquor after filtering, it carries out with speed slowly, such as, under room temperature environment, pass into the reducing gas such as hydrogen 1 ~ 2 hour with the speed of one to two bubbles per second or two to three bubbles.Molecular dimension due to reducing gas is less than the pore-size on the duplicature of imitated vesicle structure, and reducing gas can be freed in and out in imitated vesicle structure.Therefore, enter in imitated vesicle structure by reducing gas, metal catalyst precursor is reduced to metallic catalyst, to form the Metal catalyst compound 10 (as shown in Figure 2) being coated with metallic catalyst 120 in imitated vesicle structure 110, thus complete the preparation (S108) of Metal catalyst compound.
In addition, above-mentioned pass into reducing gas step before, optionally can also add auxiliary agent (such as cholesterol in mixed liquor, 1,2-DPPG or other), in order to destroy the order of the duplicature of imitated vesicle structure, thus increase the mobility of reducing gas inside and outside imitated vesicle structure, to promote the reaction rate that metal catalyst precursor is reduced to metallic catalyst further.
Based on said structure, Metal catalyst compound of the present invention by imitated vesicle structure by metallic catalyst and external environment mutually isolated, thus can directly be applied to imitated vesicle structure be microreactor catalytic reaction in.In addition, the preparation method of Metal catalyst compound of the present invention forms metallic catalyst in imitated vesicle structure, metallic catalyst can be avoided to be attached to the outer surface of imitated vesicle structure, therefore after Metal catalyst compound is formed, except guaranteeing that metallic catalyst is only formed in imitated vesicle structure, but also do not need the step of additionally carrying out the metallic catalyst removed outside imitated vesicle structure, thus simplify the preparation procedure of Metal catalyst compound.And, by the characteristic that the double membrane structure of vesica can only allow specific compound pass through, the metal nanoparticle be coated in vesica can only be reacted with this specific compound, thus allows Metal catalyst compound can carry out effect of selective catalysis to the specific compound in the reaction solution of complicated component.
Do below by way of the preparation method of some embodiments to Metal catalyst compound of the present invention and further illustrate.
The preparation of the Metal catalyst compound of embodiment one, the coated platinum nano catalyst of electronegative imitated vesicle structure:
Nano platinum particle presoma positively charged for 150 μm of ol: four ammino platinum nitrate ([Pt (NH
3)
4] (NO
3)
2) be dissolved in the 20mM trishydroxymethylaminomethane cushioning liquid of pH8.0, the concentration forming nano platinum particle presoma is the mixed liquor of 3mM.Then, heating backflow mixed liquor 2 ~ 4 hours, makes four ammino platinum nitrates dissociate and forms platinammonium [Pt (NH
3)
4]
2+.Then, mixed liquor is put into 0 DEG C of ice bath to stir 1 hour.Then, mixed liquor is taken out from ice bath, and after being naturally warmed up to room temperature, by anion surfactant: Dihexadecylphosphate (Dihexadecylphosphat, DHP) be dissolved in mixed liquor, wherein the quality concentration of volume percent of anion surfactant is about 8%.
Then, with Ultrasonic Cell Disruptor process mixed liquor, anion surfactant is formed in mixed liquor have the imitated vesicle structure of duplicature form (hydrophily adventitia and hydrophobe inner membrance), thus the platinammonium of part is coated in imitated vesicle structure, and remaining platinammonium is terminated to outside imitated vesicle structure.
Then, with the chromatographic column filter mixed liquor that corresponding ion exchange resin is filler, be such as the chromatographic column filter mixed liquor of filler with Bio-RadChelex resin, remove the platinammonium outside imitated vesicle structure, thus obtain the imitated vesicle structure being coated with platinammonium that is dispersed in mixed liquor.Afterwards, at room temperature slowly pass into hydrogen 2 hours, make platinammonium be reduced to nano platinum particle, thus obtain the Metal catalyst compound that imitated vesicle structure is coated with nano platinum particle.
The preparation of the Metal catalyst compound of embodiment two, the coated platinum nano catalyst of positively charged imitated vesicle structure:
Nanoparticle precursor electronegative for 150 μm of ol: chloroplatinic acid (H
2ptCl
6(H
2o)
6) (or potassium chloroplatinate (K
2ptCl
6)) be dissolved in the 20mM trishydroxymethylaminomethane cushioning liquid of pH8.0, the concentration forming nano platinum particle presoma is the mixed liquor of 3mM.Then, heating backflow mixed liquor 2 ~ 4 hours, makes chloroplatinic acid dissociate and forms chloroplatinic acid radical ion PtCl
6 2-.Then, mixed liquor is put into 0 DEG C of ice bath to stir 1 hour.Then, mixed liquor is taken out from ice bath, and after being naturally warmed up to room temperature, by cationic surfactant: the two octadecyldimethylamine (Diotadecyldimethylammoniumbromide of bromination, or cetrimonium bronmide (Cetryltrimethylammoniumbromide DODAB), CTAB) be dissolved in mixed liquor, the quality concentration of volume percent of its cationic surfactant is about 8%.
Then, with Ultrasonic Cell Disruptor process mixed liquor, cationic surfactant is formed in mixed liquor have the imitated vesicle structure of duplicature form (hydrophily adventitia and hydrophobe inner membrance), thus the platinammonium of part is coated in imitated vesicle structure, and remaining platinammonium is terminated to outside imitated vesicle structure.
Then, with the chromatographic column filter mixed liquor that corresponding ion exchange resin is filler, it is such as the chromatographic column filter mixed liquor of filler with Bio-RadAG50W resin, remove the chloroplatinic acid radical ion outside imitated vesicle structure, thus obtain the imitated vesicle structure being coated with chloroplatinic acid radical ion that is dispersed in mixed liquor.Afterwards, at room temperature slowly pass into hydrogen 2 hours, make chloroplatinic acid radical ion be reduced to nano platinum particle, thus obtain the Metal catalyst compound that imitated vesicle structure is coated with nano platinum particle.
Above-mentioned explanation illustrate and describes some preferred embodiments of the present invention, but as previously mentioned, be to be understood that the present invention is not limited to the form disclosed by this paper, should not regard the eliminating to other embodiments as, and can be used for other combinations various, amendment and environment, and can in invention contemplated scope described herein, changed by the technology of above-mentioned instruction or association area or knowledge.And the change that those skilled in the art carry out and change do not depart from the spirit and scope of the present invention, then all should in the protection domain of claims of the present invention.
Claims (22)
1. a preparation method for Metal catalyst compound, is characterized in that, comprises the following steps:
Be dissolved in cushioning liquid by metal catalyst precursor and form mixed liquor, described metal catalyst precursor is transition metal nanoparticles presoma;
Add mixed liquor described in hot reflux;
Described mixed liquor is put into ice bath lower the temperature, and stir described mixed liquor;
Described mixed liquor is taken out from ice bath;
Add surfactant in described mixed liquor, described surfactant be cationic surfactant, anion surfactant, zwitterionic surfactant one of them;
The self assembly in described mixed liquor of described surfactant forms imitated vesicle structure, and wherein the described metal catalyst precursor of part is coated in described imitated vesicle structure, and all the other are distributed in outside described imitated vesicle structure;
Described mixed liquor is filtered, to remove the metal catalyst precursor be distributed in outside described imitated vesicle structure with ion-exchange; And
Pass into the described mixed liquor after reducing gas to filtration, it is metallic catalyst that described reducing gas enters the described metal catalyst precursor of reduction in described imitated vesicle structure, to form the Metal catalyst compound being coated with described metallic catalyst in described imitated vesicle structure, and described metallic catalyst is transition metal nanoparticles.
2. the preparation method of Metal catalyst compound as claimed in claim 1, it is characterized in that, described metal catalyst precursor is dissolved in the step forming described mixed liquor in described cushioning liquid, be be dissolved in the described cushioning liquid of pH6.0 ~ 8.0 by described metal catalyst precursor, the concentration forming described metal catalyst precursor is the mixed liquor of 2.2 ~ 3.5mM.
3. the preparation method of Metal catalyst compound as claimed in claim 2, it is characterized in that, the pH value of described cushioning liquid is 8.0, and in described mixed liquor, the concentration of described metal catalyst precursor is 3mM.
4. the preparation method of Metal catalyst compound as claimed in claim 2, it is characterized in that, described metal catalyst precursor being dissolved in concentration is in the trishydroxymethylaminomethane cushioning liquid of 20mM.
5. the preparation method of Metal catalyst compound as claimed in claim 1, it is characterized in that, described metal catalyst precursor is nano platinum particle presoma.
6. the preparation method of Metal catalyst compound as claimed in claim 1, it is characterized in that, described transition metal nanoparticles presoma be Pd nano particle presoma, nickel nano particle presoma, Nano silver grain presoma, ruthenium nano particle presoma, cobalt nanometer particle presoma one of them.
7. the preparation method of Metal catalyst compound as claimed in claim 1, it is characterized in that, adding the step of mixed liquor described in hot reflux is add mixed liquor described in hot reflux under the temperature environment of 100 DEG C.
8. the preparation method of Metal catalyst compound as claimed in claim 7, is characterized in that, add hot reflux 2 hours.
9. the preparation method of Metal catalyst compound as claimed in claim 1, is characterized in that, described mixed liquor is put into ice bath and lowers the temperature, and the step stirring described mixed liquor is the ice bath described mixed liquor being put into 0 DEG C stirs 0.5 ~ 1.5 hour.
10. the preparation method of Metal catalyst compound as claimed in claim 1, it is characterized in that, described metal catalyst precursor is chloroplatinic acid or potassium chloroplatinate, and described surfactant is the two octadecyldimethylamine of bromination or cetrimonium bronmide.
The preparation method of 11. Metal catalyst compound as claimed in claim 1, is characterized in that, described metal catalyst precursor is four ammino platinum nitrates, and described surfactant is Dihexadecylphosphate.
The preparation method of 12. Metal catalyst compound as claimed in claim 1, it is characterized in that, described zwitterionic surfactant is lipid.
The preparation method of 13. Metal catalyst compound as claimed in claim 1, it is characterized in that, described surfactant is lipid surfactant.
The preparation method of 14. Metal catalyst compound as claimed in claim 1, it is characterized in that, the self assembly in described mixed liquor of described surfactant is formed in the step of imitated vesicle structure, uses ultrasonic method or extrusion method to assist described surfactant self assembly to form described imitated vesicle structure.
The preparation method of 15. Metal catalyst compound as claimed in claim 1, is characterized in that, add the step in described surfactant to described mixed liquor, the quality concentration of volume percent of the described surfactant in described mixed liquor is 7 ~ 9%.
The preparation method of 16. Metal catalyst compound as claimed in claim 1, is characterized in that, after adding the step in described surfactant to described mixed liquor, further comprising the steps of:
Add auxiliary agent in described mixed liquor, destroy the order of the duplicature of imitated vesicle structure, to increase the mobility of described reducing gas inside and outside described imitated vesicle structure, wherein said auxiliary agent is cholesterol or 1,2-DPPG.
The preparation method of 17. Metal catalyst compound as claimed in claim 1, it is characterized in that, the step passing into the described mixed liquor after described reducing gas to filtration is under room temperature environment, passes into reducing gas 1 ~ 2 hour with the speed of two to three bubbles per second.
The preparation method of 18. Metal catalyst compound as claimed in claim 1, it is characterized in that, described reducing gas is hydrogen.
19. 1 kinds of Metal catalyst compound, is characterized in that, are made up of surfactant and metallic catalyst,
Described surfactant self assembly forms an imitated vesicle structure, and described imitated vesicle structure comprises:
One hydrophily adventitia; And
One hydrophobe inner membrance, is coated in described hydrophily adventitia, and described hydrophobe inner membrance is in institute
State in imitated vesicle structure around formation one accommodation space;
Described metallic catalyst is positioned at described accommodation space;
Wherein, described metallic catalyst be Pd nano particle, nickel nano particle, Nano silver grain, ruthenium nano particle, cobalt nanometer particle, nano platinum particle one of them, described surfactant be cationic surfactant, anion surfactant, zwitterionic surfactant one of them.
20. Metal catalyst compound as claimed in claim 19, it is characterized in that, described metallic catalyst is nano platinum particle, described surfactant be the two octadecyldimethylamine of bromination, cetrimonium bronmide, Dihexadecylphosphate one of them.
21. Metal catalyst compound as claimed in claim 19, it is characterized in that, described zwitterionic surfactant is lipid.
22. Metal catalyst compound as claimed in claim 19, it is characterized in that, described surfactant is lipid surfactant.
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| TWI445945B (en) * | 2009-10-19 | 2014-07-21 | Nat Univ Tsing Hua | Development of phospholipid-capped gold nanoparticles (plgnps) as surface enhanced raman scattering probes |
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| Phospholipid-stabilized Au-nanoparticles;Peng He,et al;《Biomacromolecules》;20050412;第6卷(第3期);第1224页Scheme 1 * |
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