CN109847797A - A kind of preparation method and applications for the gold nano catalyst that porphyrin is stable - Google Patents
A kind of preparation method and applications for the gold nano catalyst that porphyrin is stable Download PDFInfo
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- CN109847797A CN109847797A CN201910081031.7A CN201910081031A CN109847797A CN 109847797 A CN109847797 A CN 109847797A CN 201910081031 A CN201910081031 A CN 201910081031A CN 109847797 A CN109847797 A CN 109847797A
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- porphyrin
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Abstract
The present invention provides a kind of gold nano catalysts that porphyrin is stable, using tetrahydroxy tetraphenylporphyrin as the carrier for stablizing nanoparticle, oxygen atom and gold nanoparticle on the hydroxyl of phenyl porphyrin structure phenyl ring periphery interact, strong interaction between nitrogen amine and metal and the effect due to macromolecular phenyl porphyrin, effectively stabilize gold nano grain.And the steric factor of four hydroxyls existing for the big ring phenyl ring periphery of porphyrin and big ring can efficiently control aggregation.The stable nanoparticle of porphyrin shows better electric charge transfer power and good electronic media.Synthesized gold nanoparticle has the distribution relatively uniform, partial size is narrow.
Description
Technical field
The invention belongs to field of functional materials, in particular to a kind of porphyrin stablize gold nano grain method for preparing catalyst and
It is applied.
Background technique
The research and development of nanotechnology provides more wide application space for nano material, in numerous nano materials
In, Jenner's wood particle is affine with its good stability, small-size effect, skin effect, optical effect and special biology
The features such as effect, becomes the research of optics, electronics, catalysis, biological medicine etc. and using hot spot.Gold nano grain ratio
Surface area is big, good biocompatibility, and electric conductivity is high, the electron transport rate of porphyrin can be largely improved, to increase
Its strong catalytic performance.This body structure of tetrahydroxy tetraphenylporphyrin is very stable, and there are many site that can form hydrogen bond with gold atom, can
Dispersion gold nanoparticle well.
Summary of the invention
Based on the above background, the object of the present invention is to provide a kind of preparation method of gold nano grain that porphyrin is stable and its
Using.
The stable gold nano grain catalyst of the porphyrin of the invention, using porphyrin and gold chloride as raw material, go from
After mixing in sub- water, gold nano grain is obtained with sodium borohydride reduction.It is preferable that catalytic performance test shows that the catalyst has
It is catalyzed the performance of sodium borohydride reduction p-nitrophenol.
The preparation method of the stable gold nano grain catalyst of the porphyrin, including following preparation step:
(1) tetrahydroxy tetraphenylporphyrin is dissolved in solvent, is stirred until homogeneous under ice bath environment, is then added four
Water chlorauric acid solution is stirred until homogeneous mixing under ice bath environment；
(2) sodium borohydride solution is added in the mixed solution of step (1), reacts 1-5 hours under ice bath environment, instead
After answering, the stable gold nano grain solution of porphyrin can be obtained.
The amount of the substance of tetrahydroxy tetraphenylporphyrin is 1.5 × 10 in the solution-4-1×10-3mmol；Four water gold chlorides
The amount of the substance of solution is 1.5 × 10-4-1×10-3mmol；The amount of the substance of sodium borohydride solution is 1.5 × 10-4-1×10- 2mmol。
Solvent described in step (1) includes ethyl alcohol, methanol, any one in isopropanol.
Four water chlorauric acid solutions described in step (1) are added by the way of being added dropwise, and wherein rate of addition is 2-
10min/ml。
Sodium borohydride solution described in step (2) is added by the way of being added dropwise, and wherein rate of addition is 2-10min/
ml。
Technical solution of the present invention is by the stable gold nano grain catalyst of the porphyrin in sodium borohydride reduction to nitre
Application in base phenol.
The stable gold nano grain catalyst of the porphyrin catalysis sodium borohydride reduction p-nitrophenol in step such as
Under:
Step 1: by 1.5 × 10-4-1×10-3Mmol p-nitrophenol is dissolved in deionized water, ultrasonic to completely molten
Solution；
Step 2: by 1.5 × 10-3-1×10-1Mmol sodium borohydride, which is dissolved in deionized water, to be dissolved；
Step 3: it takes p-nitrophenyl phenol solution in step 1 that sodium borohydride solution in step 2 is added in cuvette, mixes
It closes uniform.
Step 4: the stable gold nano grain catalyst of porphyrin is added in mixed solution described in step 3, use is ultraviolet
The absorption peak of visible light photometer measurement p-nitrophenol ultraviolet-visible absorption changes.
Metal nano catalyst is widely used in the reaction that p-nitrophenol is reduced into para-aminophenol, this is anti-
The property for coping with metal nano catalyst surface is very sensitive.A universal cause specific of this catalysis reaction can exactly lead to
Uv-vis spectra analysis detection is crossed, reaction process is very convenient.Wavelength be 400nm and 300nm at typical absorption band most
Big value is directly related with p-nitrophenol and para-aminophenol respectively.The color change of yellow solution can intuitively be embodied and be reacted
Journey.
The addition magnitude relation of p-nitrophenol, the sodium borohydride is molar ratio 1:50-100, the stable Jenner of porphyrin
Rice catalyst is molar ratio 0.1-10% relative to the addition magnitude relation of p-nitrophenol.
Detailed description of the invention
Fig. 1 is the novel gold nano grain catalyst transmission electron microscope that the embodiment of the present invention 1 is prepared.
Fig. 2 is the new catalyst nano particle size statistical chart that the embodiment of the present invention 1 is prepared.
Fig. 3 is the novel gold nano grain UV-vis absorption spectrum figure that the embodiment of the present invention 1 is prepared.
Fig. 4 is the novel gold nano grain catalysis sodium borohydride reduction p-nitrophenol that the embodiment of the present invention 1 is prepared
UV-vis absorption spectrum figure.
Specific embodiment
Embodiment 1
The preparation method that the present invention uses includes the following steps
Step 1: by 2.5 × 10-4The porphyrin of mmol is dissolved in ethyl alcohol (1mL), and stirring is to being completely dissolved；
Step 2: the deionized water of 7mL is added in the resulting solution of step 1, is stirred evenly；
Step 3: by 2.5 × 10-4The four water gold chlorides of mmol are dissolved in deionized water (1mL), and are slowly added into step
In rapid two resulting mixed solution；
Step 4: by 7.5 × 10-3The sodium borohydride of mmol is dissolved in 1mL deionized water, and is slowly added into step 3
In resulting mixed solution, react 2-5 hours.The stable gold nano grain catalyst of porphyrin can be obtained.
Fig. 1 is the transmission electron microscope figure of new catalyst prepared by the present invention.By the picture of transmission electron microscope
As can be seen that obtained gold nano grain is uniformly dispersed, and grain diameter is small.
Fig. 2 is new catalyst nano particle size statistical chart prepared by the present invention, thus catalyst nano-particles partial size
It is small that statistical chart can be seen that this catalyst granules partial size, average grain diameter 3.25nm.
Fig. 3 is the UV-vis absorption spectrum figure of new catalyst prepared by the present invention.
Embodiment 2
The preparation method that the present invention uses includes the following steps
Step 1: by 5 × 10-3The porphyrin of mmol is dissolved in ethyl alcohol (1mL), and stirring is to being completely dissolved；
Step 2: the deionized water of 10mL is added in the resulting solution of step 1, is stirred evenly；
Step 3: by 5 × 10-3The four water gold chlorides of mmol are dissolved in deionized water (2mL), and are slowly added into step
In two resulting mixed solutions；
Step 4: by 5 × 10-2The sodium borohydride of mmol is dissolved in 1mL deionized water, and is slowly added into step 3 institute
In the mixed solution obtained, react 2-5 hours.The stable gold nano grain catalyst of porphyrin can be obtained.
Embodiment 3
Sodium borohydride reduction p-nitrophenyl is catalyzed using the stable gold nano catalyst of the resulting porphyrin of the embodiment of the present invention 1
Application in phenol.
Include the following steps:
Step 1: by 2.5 × 10-4Mmol p-nitrophenol is dissolved in 0.1mL deionized water, ultrasound to dissolution；
Step 2: by 2.5 × 10-2Mmol sodium borohydride is dissolved in 1mL deionized water, stirring to dissolution；
Step 3: it takes in step 1 in p-nitrophenyl phenol solution and cuvette, sodium borohydride solution in step 2 is added, mix
It closes uniform.
Step 4: the gold nano grain catalyst for taking 0.5mL porphyrin stable is added in mixed solution described in step 3, uses
The absorption peak of ultraviolet-visible photometer measurement p-nitrophenol ultraviolet-visible absorption changes.
Fig. 4 is the stable gold nano catalyst catalysis sodium borohydride reduction p-nitrophenol reaction of porphyrin prepared by the present invention
UV-vis absorption spectrum figure.From figure can, within 11 minutes, paranitroanilinum can be reduced into completely.
Embodiment 4
Sodium borohydride reduction p-nitrophenyl is catalyzed using the stable gold nano catalyst of the resulting porphyrin of the embodiment of the present invention 2
Application in phenol.
Include the following steps:
Step 1: by 5 × 10-4Mmol p-nitrophenol is dissolved in 0.1mL deionized water, ultrasound to dissolution；
Step 2: by 5 × 10-2Mmol sodium borohydride is dissolved in 1mL deionized water, stirring to dissolution；
Step 3: it takes in step 1 in p-nitrophenyl phenol solution and cuvette, sodium borohydride solution in step 2 is added, mix
It closes uniform.
Step 4: the gold nano grain catalyst for taking 0.68mL porphyrin stable is added in mixed solution described in step 3,
Changed with the absorption peak of ultraviolet-visible photometer measurement p-nitrophenol ultraviolet-visible absorption.The catalysis restores p-nitrophenyl
Phenol can be reduced into completely paranitroanilinum in 8 minutes.
Claims (8)
1. a kind of gold nano grain preparation method that porphyrin is stable, which comprises the following steps:
(1) tetrahydroxy tetraphenylporphyrin is dissolved in solvent, is stirred until homogeneous under ice bath environment, is then added four water chlorine
Auric acid solution is stirred until homogeneous mixing under ice bath environment；
(2) sodium borohydride solution is added in the mixed solution of step (1), is reacted 1-5 hours under ice bath environment, reaction knot
The stable gold nano grain solution of porphyrin can be obtained in Shu Hou.
2. the preparation method of the stable gold nano grain of porphyrin according to claim 1, which is characterized in that four hydroxyls
The amount of the substance of base tetraphenylporphyrin is 1.5 × 10-4-1×10-3mmol；The amount of the substance of four water chlorauric acid solutions be 1.5 ×
10-4-1×10-3mmol；The amount of the substance of sodium borohydride solution is 1.5 × 10-4-1×10-2mmol。
3. the preparation method of the stable gold nano grain of porphyrin according to claim 1, which is characterized in that in step (1)
The solvent includes ethyl alcohol, methanol, any one in isopropanol.
4. the preparation method of the stable gold nano grain of porphyrin according to claim 1, which is characterized in that in step (1)
The four water chlorauric acid solutions are added by the way of being added dropwise, and wherein rate of addition is 2-10min/ml.
5. the preparation method of the stable gold nano grain of porphyrin according to claim 1, which is characterized in that in step (2)
The sodium borohydride solution is added by the way of being added dropwise, and wherein rate of addition is 2-10min/ml.
6. the stable gold nano grain of the porphyrin of any one of -5 preparations is restored as reducing agent in catalysis according to claim 1
Application on p-nitrophenol.
7. application according to claim 6, which is characterized in that the stable gold nano catalyst of porphyrin is in sodium borohydride reduction
The step of p-nitrophenol, is as follows:
Step 1: p-nitrophenol is dissolved in deionized water, ultrasound to dissolution；
Step 2: by 1.5 × 10-3-1×10-1Mmol sodium borohydride is dissolved in deionized water, stirring to dissolution；
Step 3: take p-nitrophenyl phenol solution in step 1 that sodium borohydride solution in step 2 is added in cuvette, mixing is equal
It is even；
Step 4: the stable gold nano grain catalyst of porphyrin is added in mixed solution described in step 3, UV, visible light is used
The absorption peak of light photometer measurement p-nitrophenol ultraviolet-visible absorption changes.
8. application as claimed in claim 6, which is characterized in that the amount of the substance of the stable gold nano grain catalyst of porphyrin is pair
The 0.1-10% of nitrophenol.
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Cited By (3)
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| CN110270372A (en) * | 2019-06-21 | 2019-09-24 | 三峡大学 | The preparation method and application of gold nano grain |
| CN111205476A (en) * | 2020-02-28 | 2020-05-29 | 三峡大学 | Preparation method of spherical porphyrin |
| CN113563583A (en) * | 2021-08-03 | 2021-10-29 | 扬州大学 | Method for synthesizing melanin |
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| CN110270372A (en) * | 2019-06-21 | 2019-09-24 | 三峡大学 | The preparation method and application of gold nano grain |
| CN111205476A (en) * | 2020-02-28 | 2020-05-29 | 三峡大学 | Preparation method of spherical porphyrin |
| CN113563583A (en) * | 2021-08-03 | 2021-10-29 | 扬州大学 | Method for synthesizing melanin |
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