CN109954517A - A kind of Au@NH2- MIL-125 nanometers of enzyme catalysts and preparation method thereof - Google Patents
A kind of Au@NH2- MIL-125 nanometers of enzyme catalysts and preparation method thereof Download PDFInfo
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- CN109954517A CN109954517A CN201910351250.2A CN201910351250A CN109954517A CN 109954517 A CN109954517 A CN 109954517A CN 201910351250 A CN201910351250 A CN 201910351250A CN 109954517 A CN109954517 A CN 109954517A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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Abstract
The present invention relates to a kind of Au@NH2- MIL-125 nanometers of enzyme catalysts and preparation method thereof, belong to technical field of nano material.Au nanoparticle is distributed to NH by the method for impregnating, restoring2On-MIL-125, Au@NH is prepared2- MIL-125 nanometers of enzyme catalysts.The NH that the present invention uses2- MIL-125 material has hierarchical porous structure and bigger serface, has good stabilization and peptizaiton to Au nanoparticle.The Au@NH2In-MIL-125 nanometers of enzyme catalysts, the Au NH that provides2- MIL-125 nano enzyme catalyst granules is small, and partial size is 200-500nm round sheet or polyhedral structure, is conducive to the active site for increasing catalyst, Au nanoparticle and NH2- MIL-125 has concerted catalysis effect, and a variety of substrates are shown with the catalytic action of high-efficiency broad spectrum；Heretofore described Au@NH2The process of preparing of-MIL-125 nanometers of enzyme catalysts is simple, economically feasible.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of Au@NH2- MIL-125 nanometers of enzyme catalysts and its
Preparation method.
Background technique
Nature all life phenomenon is all related with enzyme.Native enzyme is a kind of with catalysis based on protein
Biomolecule, catalysis feature are that high-efficient, substrate is single-minded.However, since most of native enzymes are all protein, encounter heat,
The non-physiological condition such as acid, alkali, is easy to happen structure change and loses catalytic activity.In addition, the content of native enzyme in vivo
It is very low, it is difficult largely to obtain, thus it is expensive.In order to improve the stability of enzyme and reduce cost, biochemist is being sought always
Ask by full chemistry synthesis or semisynthesis prepare artificial mimic enzyme, generally use organic double compound, as cyclodextrin, crown ether,
Porphyrin etc., and achieve a series of progress.Before nano enzyme appearance, analogue enztme generally refers to above-mentioned enzyme.
Gold is used as simulated enzyme catalyst, and in bio-sensing, environmental science, the multiple fields such as biomedical and food safety have
Many applications are acted on, there are two types of tools to improve the catalytic activity of the enzyme mimics based on nano material based on concerted catalysis
The nanocomposite of component prepares meaningful target.
Summary of the invention
The present invention provides a kind of Au@NH2- MIL-125 nanometers of enzyme catalysts and preparation method thereof.
Inventive concept of the invention is: by solid material with unique properties as supported on carriers high degree of dispersion
Au nanoparticle, carrier can not only be used to stablize nanogold, while can also generate synergistic effect with nanogold, improve composite wood
The whole catalytic effect of material.The carrier NH that the present invention uses2- MIL-125 is a kind of metal-organic framework materials, is had porous
Property, high specific surface area and biocompatibility.NH simultaneously2- MIL-125 has certain duct size, so as to realize gold
The determinate growth for belonging to nanoparticle Au, to generate monodispersed metal Au nano particle.
The present invention specifically adopts the following technical scheme that, a kind of Au@NH2- MIL-125 nanometers of enzyme catalysts, Au nanoparticle
It is highly dispersed to NH2On-MIL-125, Au Nanoparticle Size is 5-50nm, mass content 0.1-20%.Used NH2-
MIL-125 pattern is round sheet or octahedron, and size is in 200-500nm.
Above-mentioned Au@NH2The preparation method of-MIL-125 nanometers of enzyme catalysts, includes the following steps:
S1.NH2The synthesis of-MIL-125
DMF and methanol are mixed, 2- amino terephthalic acid (TPA) then is added after stirring 10-20 minutes, titanium is then added
Sour four butyl esters, 2- amino terephthalic acid (TPA) and butyl titanate molar ratio are as follows: 4:1-5:1 is stirred for 30 minutes, by precursor solution
It is transferred in the stainless steel autoclave of teflon lining, and is heated 72 hours at 150-160 DEG C in electric furnace.After reaction, lead to
It crosses and product is collected by centrifugation and is washed for several times with methanol, be then dried overnight sample at 105 DEG C.In order to realize that sample activates,
Solid after synthesis is heated 12 hours at 200 DEG C in air.
S2.Au@NH2The synthesis of-MIL-125
Firstly, under ultrasonic wave effect, by 5mg NH2- MIL-125 is dissolved in 5.76ml water.Secondly, 120 μ L are added
HAuCl4(1wt%), and kept for 5 minutes under ultrasound.Finally, 360 μ L sodium borohydrides or trisodium citrate are rapidly joined molten
It in liquid and is ultrasonically treated 20 minutes, until the color of solution becomes stable darkviolet.Product is collected by centrifugation, with methanol and washing
It washs for several times, it is dry.
DMF and methanol mix ultrasonic mixing, 2- amino terephthalic acid (TPA), butyl titanate ultrasonic dissolution in the step S1
At clear solution.
In the step S2, sodium borohydride or trisodium citrate in three seconds in being all added into solution and be ultrasonically treated 20
Minute.
As a preferred embodiment of the invention, Au@NH2- MIL-125 nanometers of enzyme catalysts the preparation method is as follows:
S1. 2- amino terephthalic acid (TPA) (0.543 gram, 3mmol) is dissolved in containing molten in DMF (9ml) and MeOH (1ml)
In liquid.Then by butyl titanate Ti (OC4H9)4(0.26ml, 0.75mmol) is added in the solution.By said mixture in room
It temperature lower ultrasonic treatment 10 minutes, is then transferred into 50ml Teflon lining and is heated 72 hours at 150 DEG C.Finally, passing through
Yellow powder obtained is collected by centrifugation, is washed respectively with DMF and MeOH, and is dried in vacuo at 60 DEG C；
S2. Au@NH is synthesized by ultrasonic method2-MIL-125.Firstly, under ultrasonic wave effect, by 5mg NH2-MIL-
125 are dissolved in 5.76ml water.Secondly, 120 μ L HAuCl are added4(1wt%), and kept for 5 minutes under ultrasound.Finally, will
360 μ L trisodium citrates are rapidly joined in solution and are ultrasonically treated 20 minutes, until the color of solution becomes stable darkviolet.
Product is collected by centrifugation, for several times with methanol and water washing.
A kind of composite Nano enzyme catalyst is claimed in the present invention simultaneously, including the Au@NH using above method preparation2-
Acceptable auxiliary material in MIL-125 nanometers of enzyme catalysts and catalyst.
Au nanoparticle is distributed to NH by the present invention2On-MIL-125 nanoparticle, metal-organic framework materials NH is utilized2-
The limit threshold effect of the hierarchical porous structure of MIL-125 and nano pore limitation Au nanoparticle grows up and reunites, carrier NH2-
The porosity of MIL-125 is conducive to Au+The diffusion of ion；And NH2- MIL-125 carrier has Au nanoparticle preferably steady
It is set for using, so that monodispersed Au nanoparticle be prepared, further obtains efficient Au@NH2The compound of-MIL-125 is received
Rice enzyme catalyst.
Compared with prior art, the invention has the following advantages that
1, Au@NH provided by the invention2- MIL-125 nano enzyme method for preparing catalyst, synthesis condition is mild, technique side
Method is simple, economically feasible.
2, Au@NH provided by the invention2In-MIL-125 nanometers of enzyme catalysts, Au nanoparticle high degree of dispersion and NH2-
MIL-125 has concerted catalysis effect, is conducive to the nanometer enzyme catalyst for preparing high-efficiency broad spectrum.
3, Au@NH provided by the invention2- MIL-125 nano enzyme catalyst granules is small, and partial size is 200-500nm circle medicine
Piece or dodecahedron structure are conducive to the active site for increasing catalyst, Au nanoparticle and NH2There is-MIL-125 collaboration to urge
A variety of substrates are shown the catalytic action of high-efficiency broad spectrum by change effect.
Detailed description of the invention
Fig. 1 nanometer enzyme catalyst Au NH2SEM (A), the TEM of-MIL-125 schemes (B)；
Fig. 2 nanometer enzyme catalyst Au NH2The catalytic effect of-MIL-125, detection hydrogen peroxide and detection limit.
Specific embodiment
Technical solution of the present invention is described in further detail below in conjunction with specific embodiment, but is not limited of the invention
Protection scope.
Embodiment 1 prepares Au@NH using impregnation-reduction method2- MIL-125 nanometers of enzyme catalysts
S1. 2- amino terephthalic acid (TPA) (0.543 gram, 3mmol) is dissolved in containing molten in DMF (9ml) and MeOH (1ml)
In liquid.Then by butyl titanate Ti (OC4H9)4(0.26ml, 0.75mmol) is added in the solution.By said mixture in room
It temperature lower ultrasonic treatment 10 minutes, is then transferred into 50ml Teflon lining and is heated 72 hours at 150 DEG C.Finally, passing through
Yellow powder obtained is collected by centrifugation, is washed respectively with DMF and MeOH, and is dried in vacuo at 60 DEG C；
S2. Au@NH is synthesized by ultrasonic method2-MIL-125.Firstly, under ultrasonic wave effect, by 5mg NH2-MIL-
125 are dissolved in 5.76ml water.Secondly, the 120 μ L HAuCl of concentration 1wt%4, and kept for 5 minutes under ultrasound.Finally, will
360 μ L trisodium citrates are rapidly joined in solution and are ultrasonically treated 20 minutes, until the color of solution becomes stable darkviolet.
Product is collected by centrifugation, for several times with methanol and water washing.
Embodiment 2
Using the Au@NH prepared in colorimetric evaluation embodiment 12Effect of-the MIL-125 to detection hydrogen peroxide, test knot
Fruit is as shown in Figure 2.
Colorimetric detection hydrogen peroxide takes 20 μ LTMB (15mmol) and 20 μ L Au@NH2- MIL-125 (3mg/mL) is added to
3mL acetate buffer solution (pH=4.0).Various concentration hydrogen peroxide is added in above-mentioned buffer solution, is passed through after five minutes
UV- visible absorption spectra monitors the absorbance change at 651nm.
Claims (7)
1. a kind of Au@NH2- MIL-125 nanometers of enzyme catalysts, which is characterized in that Au nanoparticle is highly dispersed to NH2-MIL-
On 125, Au Nanoparticle Size is 5-50nm, mass content 0.1-20%.
2. Au@NH according to claim 12- MIL-125 nanometers of enzyme catalysts, which is characterized in that used NH2-
MIL-125 pattern is round sheet or octahedron, and size is in 200-500nm.
3. a kind of Au@NH2The preparation method of-MIL-125 nanometers of enzyme catalysts, which is characterized in that preparation method includes following step
It is rapid:
S1.NH2The synthesis of-MIL-125
DMF and methanol are mixed, then sequentially add 2- amino terephthalic acid (TPA), butyl titanate after stirring 10-20 minutes,
2- amino terephthalic acid (TPA) and butyl titanate molar ratio are as follows: 4:1-5:1 is stirred for 30 minutes, precursor solution is transferred to spy
In the stainless steel autoclave of fluon lining, and heated 72 hours at 150 DEG C in electric furnace；After reaction, produced by being collected by centrifugation
Object is simultaneously washed for several times with methanol, is then dried overnight sample at 105 DEG C；In order to realize that sample activates, by consolidating after synthesis
Body heats 12 hours at 200 DEG C in air；
S2.Au@NH2The synthesis of-MIL-125
Firstly, under ultrasonic wave effect, by 5mgNH2- MIL-125 is dissolved in 5.76ml water；Secondly, being added concentration 1wt%'s
120μLHAuCl4, and kept for 5 minutes under ultrasound；Finally, 360 μ L sodium borohydrides or trisodium citrate are rapidly joined solution
In and be ultrasonically treated 20 minutes, until the color of solution becomes stable darkviolet, product is collected by centrifugation, with methanol and water washing
For several times, dry.
4. a kind of Au@NH according to claim 32The preparation method of-MIL-125 nanometers of enzyme catalysts, which is characterized in that
DMF and methanol mixing ultrasonic mixing, 2- amino terephthalic acid (TPA), butyl titanate ultrasonic dissolution are molten at clarifying in the step S1
Liquid.
5. a kind of Au@NH according to claim 32The preparation method of-MIL-125 nanometers of enzyme catalysts, which is characterized in that
In the step S1, in DMF and methanol mixed solution, the ratio of DMF and methanol mixed volume is 9:1.
6. a kind of Au@NH according to claim 32The preparation method of-MIL-125 nanometers of enzyme catalysts, which is characterized in that
Specific step is as follows:
S1. 3mmol2- amino terephthalic acid (TPA) is dissolved in DMF and MeOH mixed solution, mixed solution DMF is 9ml, MeOH
For 1ml；Then 0.75mmol butyl titanate is added in the solution；Said mixture is ultrasonically treated to 10 points at room temperature
Clock is then transferred into 50mlTeflon lining and heats 72 hours at 150 DEG C；Finally, obtained by being collected by centrifugation
Yellow powder is washed with DMF and MeOH respectively, and is dried in vacuo at 60 DEG C；
S2. Au@NH is synthesized by ultrasonic method2-MIL-125
Firstly, under ultrasonic wave effect, by 5mgNH2- MIL-125 is dissolved in 5.76ml water, secondly, being added concentration 1wt%'s
120μLHAuCl4, and kept for 5 minutes under ultrasound；Finally, 360 μ L trisodium citrates are rapidly joined in solution and at ultrasound
Product is collected by centrifugation until the color of solution becomes stable darkviolet in reason 20 minutes, for several times with methanol and water washing.
7. a kind of composite Nano enzyme catalyst, which is characterized in that including using Au@NH described in claim 12- MIL-125 receives
Acceptable auxiliary material in rice enzyme catalyst and catalyst.
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| CN111534505A (en) * | 2020-04-30 | 2020-08-14 | 辽宁大学 | Immobilized laccase and preparation method and application thereof |
| CN114471727A (en) * | 2022-02-10 | 2022-05-13 | 重庆工商大学 | Au @ NH2-MIL-125(Cu/Ti) photocatalyst and preparation method and application thereof |
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Cited By (5)
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| CN111534505A (en) * | 2020-04-30 | 2020-08-14 | 辽宁大学 | Immobilized laccase and preparation method and application thereof |
| CN114471727A (en) * | 2022-02-10 | 2022-05-13 | 重庆工商大学 | Au @ NH2-MIL-125(Cu/Ti) photocatalyst and preparation method and application thereof |
| CN114471727B (en) * | 2022-02-10 | 2023-11-17 | 重庆工商大学 | Au@NH 2 MIL-125 (Cu/Ti) photocatalyst, and preparation method and application thereof |
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Application publication date: 20190702 |