CN103386494B - Preparation taking chirality rare earth organic phospho acid coil material as the noble metal nano composite of carrier - Google Patents
Preparation taking chirality rare earth organic phospho acid coil material as the noble metal nano composite of carrier Download PDFInfo
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- CN103386494B CN103386494B CN201310311723.9A CN201310311723A CN103386494B CN 103386494 B CN103386494 B CN 103386494B CN 201310311723 A CN201310311723 A CN 201310311723A CN 103386494 B CN103386494 B CN 103386494B
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Abstract
The present invention proposes class structure composition taking chirality rare earth organic phospho acid coil material as the noble metal nano composite of carrier and preparation method thereof. Can obtain by changing source metal the composite that contains different noble metal nano particles. What preparation method adopted is low-temperature atmosphere-pressure reducing process with low cost, good dispersion. The diameter of these noble metal nano particles is between 2～30nm.
Description
Technical field
The present invention relates to the noble metal nano composite wood of a class taking chirality rare earth organic phospho acid coil material as carrierStructure composition of material and preparation method thereof.
Background technology
Helical structure is of common occurrence in occurring in nature or artificial structure. From the double helix knot of DNA molecularStructure, all closely bound up with helical structure to the spiral growth of climbing plant or even the eddy structure in the milky way galaxy. PeopleThe synthetic material with macroscopical Spiral morphology of work has in fields such as chiral Recognition, chiral separation and chiral catalysisVery important potential application foreground, and can the chirality problem in life science and pharmacy be provided reference and be openedShow.
Noble metal nano particles not only has small-size effect, skin effect, the quantum size of general nano particleThe character such as effect and macro quanta tunnel effect, also has unique optics, electricity, catalytic property, can be extensiveBe applied to catalysis material, battery electrode material, low temperature Heat Conduction Material and conductive material etc. Therefore nano-noble metalPreparation and improvement technology get more and more people's extensive concerning. Noble metal nano particles is loaded on macroscopical conveyor screwLikely bring new physics or chemical functional, as chiral catalysis with separate etc., thereby will greatly widen this class materialApplication and the application mode of material.
Summary of the invention
The object of the invention is to propose the noble metal of a class taking chirality organic phospho acid rare earth coil material as carrierNano composite material and synthetic method thereof. Wherein noble metal nano particles comprises in Ag, Au, Pt nano particleOne or more, its carrier is the Ln that consists of with macroscopical Spiral morphologyx[RCH2(PO3H)m]y(H2O)z(wherein R=organic group; Ln is rare earth ion) chirality rare earth organic phospho acid compound.
Technical scheme of the present invention is as follows:
Advanced composite material (ACM) is to have the chirality rare earth organic phospho acid compound of macroscopical helical structureLnx[RCH2(PO3H)m]y(H2O)zAs carrier, it uses the not raw material of isomorphism type can obtain respectively having left handThe material of spiral and right-handed helix structure, these spirochetal diameters are greatly between 3～6 μ m, and length isBetween 100～300 μ m.
Described chirality rare earth organic phospho acid compound L nx[RCH2(PO3H)m]y(H2O)zCoil material carrier, itsComposition structure mainly includes machine phosphonic acid RCH2(PO3H2)n, rare earth ion and hydrone three parts. Organic phospho acid RCH2(PO3H2)nIn R group be the organic group (R=R/S-C that has asymmetric carbon atom6H5CHCH3NH、R/S-C10H9CHCH3NH、R/S-C4H7NCOOH、R/S-C5H9NCOOH etc.), n PO3H2And haveMachine group CH2In C atom be connected, RCH in the time of n=12PO3H2For organic mono phosphonic acid, in the time of n=2RCH2PO3H2For organic diphosphonic acid, by that analogy. Ln is rare earth ion, as Eu, Gd, Tb, Dy,Ho etc.
The noble metal nano particles of load in described composite, wherein, described noble metal comprise Ag, Au,One or more in Pt. The size of nano particle is 2～30nm.
Described to there is the rare earth organic phospho acid compound L n of macroscopical helical structurex[RCH2(PO3)m]y(H2O)zFor the synthetic method of the composite of carrier, wherein, described synthetic method is made up of the following step
Step 1. is by the salt that contains metal ion or acid-soluble in appropriate ethanol, rare with the chirality of appropriate massSoil organic phospho acid coil material mixes, fully stirs at ambient temperature,
The suspension of step 1 gained is carried out centrifugation by step 2., after cleaning, separates and adhered to ethanolSlaine or acid chirality rare earth organic phospho acid coil material,
The product of step 2 gained is scattered in ethanol by step 3., adds the PVP(of suitable amount of substance poly-Vinylpyrrolidone) or NaBH4, be heated to 60 DEG C, at this temperature, react the regular hour,
Step 4. is the product centrifugation of step 3 gained, the solids obtaining with appropriate amount, ethanol is clearWash vacuum drying.
Principle of the present invention
Compared with the noble metal granule of macro-scale, the ratio of the volume that noble metal nano particles sharply reduces and increaseSurface area, make its small-size effect not only with general nano particle, skin effect, quantum size effect andThe character such as macro quanta tunnel effect, also have the character such as unique optics, electricity, catalysis. But, nanometerThe character that material is easily reunited has affected its performance. By using suitable carrier, can increase the steady of nano particleQualitative. Using chirality rare earth organic phospho acid coil material is carrier, greatly improved nano particle dispersiveness andStability.
Advantage of the present invention
1, pass through the configuration of the R group that changes organic phospho acid, can realize chirality organic phospho acid rare earth coil materialThe regulation and control of the hand of spiral in carrier.
2,, by changing the kind of rare earth ion, can realize chirality organic phospho acid rare earth coil material carrier compositionThe modulation of composition.
3, the source metal using by change, can obtain the noble metal nano particles of heterogeneity.
4, the reducing condition of low-temperature atmosphere-pressure is easy to realize, with low cost.
Brief description of the drawings
Below in conjunction with accompanying drawing, the present invention is described in further detail:
Fig. 1 is right-handed helix R-[Tb (C in embodiment 16H5CHCH3NHCH2PO3H)3](H2O)xMultiple with AgThe transmission electron microscope picture of condensation material.
Fig. 2 is right-handed helix R-[Tb (C in embodiment 26H5CHCH3NHCH2PO3H)3](H2O)xMultiple with AuThe transmission electron microscope picture of condensation material.
Fig. 3 is right-handed helix R-[Tb (C in embodiment 16H5CHCH3NHCH2PO3H)3](H2O)xMultiple with AgThe feature structure figure of condensation material.
Detailed description of the invention
For making the present invention easier to understand, describe the present invention in detail below in conjunction with drawings and Examples, thisA little embodiment only play illustrative effect, are not limited to range of application of the present invention, not mentioned in the following exampleSpecific experiment method, conventionally carry out according to normal experiment method.
The carrier of selecting in the embodiment of the present invention is right-handed helix rare earth organic phospho acid material, and its chemical formula is[Tb(C6H5CHCH3NHCH2PO3H)3](H2O)x, structural formula is as shown in (I):
Embodiment
Embodiment 1: right-handed helix R-[Tb (C6H5CHCH3NHCH2PO3H)3](H2O)xWith closing of Ag compositeBecome
By AgNO3(0.1mmol, 0.0170g) is dissolved in 10mL ethanol, adds 0.01g chirality organic phosphineAcid rare earth coil material, fully stirs 0.5～1 hour, then, by the suspension centrifugation of gained, obtainsSolid is cleaned with ethanol, separates. PVP (polyvinylpyrrolidone, 0.112g) is dissolved in 10mL ethanol,Before the solid of gained add wherein, be heated to 60 DEG C, and keep 1 hour, will be suspended after being cooled to room temperatureLiquid centrifugation obtains solid, uses ethanol to clean, and vacuum drying, obtains right-handed helixR-[Tb(C6H5CHCH3NHCH2PO3H)3](H2O)xWith Ag composite, its feature structure as shown in Figure 3.EDX carries out elemental composition analysis (%): C, 41.9; O, 11.10; P, 7.60; Tb, 25.70; Ag,13.80. Ultraviolet spectra (ethanolic solution): 432nm place is Nano silver grain characteristic absorption. Load on conveyor screwDiameter of nano particles greatly between 5～20nm.
Embodiment 2: right-handed helix R-[Tb (C6H5CHCH3NHCH2PO3H)3](H2O)xWith closing of Au compositeBecome
By HAuCl4(0.1mmol, 0.0411g) is dissolved in 10mL ethanol, adds 0.01g chirality organic phospho acidRare earth coil material, fully stirs 0.5～1 hour, and then, by the suspension centrifugation of gained, what obtain consolidatesBody is cleaned with ethanol, separates. PVP (polyvinylpyrrolidone, 0.112g) is dissolved in 10mL ethanol,Before the solid of gained add wherein, be heated to 60 DEG C, and keep 1 hour, will be suspended after being cooled to room temperatureLiquid centrifugation obtains solid, uses ethanol to clean, vacuum drying. EDX carries out elemental composition analysis (%):C, 42.8; N, 2.60; O, 11.50; P, 9.10; Tb, 32.40; Au, 1.60. Ultraviolet spectra (ethanolSolution): 551nm place is golden nanometer particle characteristic absorption. Load on diameter of nano particles on conveyor screw aboutBetween 2～30nm.
The foregoing is only preferred embodiments of the present invention, not in order to limit the present invention, all of the present inventionWithin spirit and principle, any amendment of doing, be equal to replacement, improvement etc., all should be included in guarantor of the present inventionWithin protecting scope.
Claims (5)
1. the noble metal nano composite taking chirality organic phospho acid rare earth coil material as carrier, compositionStructure is that carrier is chirality organic phospho acid rare earth coil material, and noble metal nano particles is by electrostatic interaction and macroscopic viewConveyor screw combines, and has following feature structure:
Wherein noble metal nano particles comprises Ag, Au, one or more in Pt nano particle; Carrier is handProperty organic phospho acid rare earth coil material, its chemical formula is [Ln (C6H5CHCH3NHCH2PO3H)3](H2O)x，Wherein Ln be rare earth ion La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm,Yb、Lu。
2. chirality organic phospho acid rare earth coil material carrier according to claim 1, Ln is rare earth ionLa、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu。
3. chirality organic phospho acid rare earth coil material carrier according to claim 1, is characterized in that,Conveyor screw has left hand helix or right-handed helix structure, these spirochetal diameters between 3～6 μ m, andLength is between 100～300 μ m.
4. noble metal nano particles according to claim 1, is characterized in that, described noble metal comprisesAg, Au, one or more in Pt, the size of noble metal nano particles is between 2～30nm.
5. according to claim 1ly receive taking chirality organic phospho acid rare earth coil material as the noble metal of carrierNano composite material, is characterized in that, preparation method is as follows:
The ethanolic solution of configuration 0.01M metal ion, by 0.01g chirality organic phospho acid rare earth coil materialBe dispersed in above-mentioned solution, fully stir 0.5-1 hour, centrifugation, is used ethanol to clean, and will clean pointFrom coil material add 10mL0.1MPVP or NaBH4In ethanolic solution, heat 1 hour at 60 DEG C,Centrifugation, is used ethanol to clean.
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| CN105618783A (en) * | 2015-01-28 | 2016-06-01 | 江苏科技大学 | Preparation method for silver nanoparticles with optical activity |
| WO2019194509A1 (en) * | 2018-04-06 | 2019-10-10 | 서울대학교산학협력단 | Three-dimensional chiral nanostructure |
| CN109956968B (en) * | 2019-03-29 | 2021-05-28 | 宿迁学院 | Preparation method of terbium organic phosphonic acid complex and application of terbium organic phosphonic acid complex in water body detection |
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| CN1739896A (en) * | 2005-09-22 | 2006-03-01 | 中国科学院生态环境研究中心 | The multiple method of metal nanoparticles of preparation on ion exchange resin carrier |
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| CN1739896A (en) * | 2005-09-22 | 2006-03-01 | 中国科学院生态环境研究中心 | The multiple method of metal nanoparticles of preparation on ion exchange resin carrier |
Non-Patent Citations (2)
| Title |
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| （2-吡啶甲基）胺基甲基膦酸与草酸配体的同构稀土（Gd，Tb）化合物的合成、结构、磁学和荧光性质;刘美娟等;《无机化学学报》;20120930;第28卷(第9期);2017-2024 * |
| Homochiral zinc phosphonates with layered and open framework structures using polycarboxylate as second linkers;Xun-Gao Liu et al.;《Dalton Transactions》;20090930;9837-9842 * |
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