CN108906041B - Preparation method of single-layer gold film for photocatalytic degradation of 4-nitrophenol - Google Patents
Preparation method of single-layer gold film for photocatalytic degradation of 4-nitrophenol Download PDFInfo
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Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J35/59—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a preparation method of a single-layer gold film for photocatalytic degradation of 4-nitrophenol, which specifically comprises the following steps: firstly, preparing a glass ball with positive electricity on the surface and gold nanoparticle sol; soaking the glass ball in gold nanoparticle sol for electrostatic self-assembly; then taking out the glass ball, placing the glass ball in the fiveleaf akebia fruit extracting solution, and adding chloroauric acid aqueous solution to soak the glass ball to prepare a single-layer gold film; according to the invention, the glass ball with positive electricity and the gold nanoparticles with negative electricity are mutually attracted, so that the gold nanoparticles are attached to the surface of the glass ball to form gold seeds; the single-layer gold film is prepared by using the non-toxic fiveleaf akebia fruit extracting solution which is convenient and easy to obtain, low in price and easy to store to replace conventional toxic hydroxylamine hydrochloride as a reducing agent, the prepared single-layer gold film is stable in performance, strong in adhesion capacity, uniform in film thickness and capable of being recycled, a new synthesis way is provided for preparation of other single-layer metal films, and the defects that tiny particles are easy to run off and difficult to recover in the using process are overcome.
Description
Technical Field
The invention relates to a preparation method of a single-layer gold film for photocatalytic degradation of 4-nitrophenol, belonging to the technical field of preparation of nano-particle catalysts.
Background
P-nitrophenol (p-nitrophenol) is also known as 4-nitrophenol (4-nitrophenol), and the nitrophenol has three isomers in total, namely, o-, m-, and p-nitrophenol. The p-nitrophenol is colorless or yellowish crystal at normal temperature, can be dissolved in hot water, ethanol and ether, is easily soluble in caustic alkali and is yellow in carbonate solution of alkali metal. It is easy to oxidize in air, and the color becomes dark. Unstable at high temperatures and begin to decompose when heated to 273 ℃. P-nitrophenol is flammable, toxic and can cause allergy when absorbed through skin. The toxic effects on humans are not fully understood. Animal experiment results: has stimulating and inhibiting effects on central nerve and vagus nerve terminal, and can also cause hyperpigmentation and dyspnea. Toxicity strength sequence of nitrophenol: alignment > spacer > neighbor. Commonly used as intermediates of fine chemicals such as pesticides, medicines, dyes and the like; also useful as a manufacturing agent for phenacetin, paracetamol, a pesticide 1605, a developer mitol, paranitrophenol sulphurized grass green GN, sulphurized vat black CL, sulphurized vat black CLB, sulphurized vat blue RNX, sulphurized red brown B3R, as a leather fungicide and as an acid number indicator. Para-nitrophenol is an organic pollutant, has high stability, solubility and accumulation effect, is easy to cause serious pollution to the environment and is difficult to remove.
The photocatalytic degradation method is a more effective method for treating 4-nitrophenol in sewage, and the degradation efficiency depends on the performance of a photocatalyst used. Gold nanoparticles are of great interest because of their high photocatalytic efficiency. However, in practical applications, gold nanoparticles are difficult to recover, which increases the cost and limits further applications of photocatalytic degradation methods.
At present, gold is loaded on a substrate to prepare a gold film, which is an effective way for realizing gold recycling and reducing the cost of photocatalytic degradation reaction. Heretofore, there have been mainly physical and chemical methods for producing gold films. The physical methods include pulsed laser deposition, vacuum evaporation, magnetron sputtering, and the like. The method has simple operation flow, but has higher requirement on equipment and high cost. The chemical method includes a chemical vapor deposition method, a laser chemical decomposition method, an electrostatic self-assembly method, and the like. Among them, the electrostatic self-assembly method is attracting attention because of its simple method, low cost, good controllability, and the prepared film has the advantages of stable quality, strong adhesion, uniform film thickness, etc. In the film formation process, hydroxylamine hydrochloride is generally used as a reducing agent to achieve rapid reduction of gold ions. However, hydroxylamine hydrochloride is toxic and easily causes environmental pollution. The method utilizes the green plant extract to replace hydroxylamine hydrochloride to realize the rapid preparation of the single-layer gold film, and provides a new idea for the selection of a reducing agent in the preparation process of the metal film. Based on the invention, the cost for preparing the gold film is low, the preparation process is pollution-free, the structure of the gold film is uniform, the photocatalytic activity is high, the gold film can be repeatedly utilized, and a foundation is laid for the practical application of the technology for degrading 4-nitrophenol by photocatalysis.
Disclosure of Invention
Aiming at the problems and the requirements in the prior art, the invention aims to provide a preparation method of a single-layer gold film for photocatalytic degradation of 4-nitrophenol, which utilizes green plant fiveleaf akebia fruit extracting solution to replace hydroxylamine hydrochloride to realize rapid preparation of the single-layer gold film and overcomes the defects that micro particles are easy to run off and difficult to recover in the using process.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a single-layer gold film for photocatalytic degradation of 4-nitrophenol is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) soaking the glass ball by using a mixed solution of 3-aminopropyltriethoxysilane and absolute ethyl alcohol, and standing for 24 hours to positively charge the surface of the glass ball;
(2) mixing deionized water and a chloroauric acid aqueous solution, heating to boil, and then injecting a sodium citrate aqueous solution to obtain gold nanoparticle sol;
(3) soaking the positively charged glass spheres in the step (1) in the gold nanoparticle sol prepared in the step (2) to perform electrostatic self-assembly;
(4) and (4) taking out the glass ball which is subjected to the electrostatic self-assembly in the step (3), placing the glass ball into the fiveleaf akebia fruit extracting solution, adding a chloroauric acid aqueous solution, and soaking to obtain the single-layer gold film.
Preferably, the diameter of the glass ball is 2.5 mm-5.5 mm.
Preferably, the 3-aminopropyltriethoxysilane and the absolute ethanol in the step (1) are mixed according to a volume ratio of 1: 100.
Preferably, the electrostatic self-assembly time in step (3) is controlled to be 1 to 2 hours.
Preferably, the amount of the aqueous chloroauric acid solution added in step (4) is 20 to 80 μ L, and the immersion treatment time in step (4) is 1 to 2 hours.
Preferably, the glass spheres in step (1) are treated by the following steps before the experiment: and (3) putting the glass balls into a vessel, cleaning for 3 times, each time for 10min, and naturally drying for later use after cleaning.
Preferably, in the preparation process of the fiveleaf akebia fruit extract, the mixing ratio of the fiveleaf akebia fruit to deionized water is 1 g: (75-150) mL.
Preferably, the preparation of the fiveleaf akebia fruit extract comprises the following steps:
s1: mixing the akebia trifoliata koidz with deionized water according to the mixing ratio of 1 g: (75-150) mL, heating to boiling, and keeping the boiling state for 10-30 minutes;
s2: and (5) after the liquid in the step S1 is naturally cooled, centrifuging at 10000rpm for 10min, and preparing a supernatant, namely the fiveleaf akebia fruit extracting solution.
As a preferred scheme, the preparation of the gold nanoparticle sol comprises the following steps: mixing 100mL of deionized water with 290uL0.1mol/L chloroauric acid aqueous solution, heating to boil, reacting for 10min, injecting 3mL of 1wt% sodium citrate aqueous solution, continuing to keep the boiling state, reacting for 15min, cooling the liquid, and centrifuging to obtain the gold nanoparticle sol.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the glass ball is soaked in the mixed solution of 3-aminopropyltriethoxysilane and absolute ethyl alcohol to be positively charged, and the positively charged glass ball and the negatively charged gold nanoparticles are mutually attracted through electrostatic interaction, so that the gold nanoparticles are attached to the surface of the glass ball to form gold seeds; non-toxic fiveleaf akebia fruit extracting solution is used for replacing toxic hydroxylamine hydrochloride to serve as a reducing agent, gold seeds are used as an active center, and chloroauric acid is continuously reduced at normal temperature; the reduced gold is deposited and grows on the surface of the gold seed to form a film, and the prepared single-layer gold film has stable performance, strong adhesive capacity and uniform film thickness and can be repeatedly used; the single-layer gold film is prepared by replacing conventional toxic hydroxylamine hydrochloride with the non-toxic fiveleaf akebia fruit extracting solution which is convenient and easy to obtain, low in price and easy to store as a reducing agent, so that the single-layer gold film is low in preparation cost and free of any environmental pollution, and a new synthetic approach is provided for preparation of other single-layer metal films; in addition, the preparation method has simple process, the prepared single-layer gold film has uniform structure and good reusability, the raw material fiveleaf akebia fruit is convenient and easy to obtain, and the photocatalytic activity of the single-layer gold film is equivalent to that of gold nanoparticles; overcomes the defects that the micro particles are easy to lose and difficult to recover in the using process, and effectively promotes the development of the technology for degrading the 4-nitrophenol by photocatalysis.
Drawings
FIG. 1 is a scanning electron micrograph of gold nanoparticles prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction pattern of gold nanoparticles prepared in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of gold nanoparticles prepared in example 2 of the present invention;
FIG. 4 is an X-ray diffraction pattern of gold nanoparticles prepared in example 2 of the present invention;
FIG. 5 is a scanning electron micrograph of gold nanoparticles prepared in example 3 of the present invention;
FIG. 6 is an X-ray diffraction pattern of gold nanoparticles prepared in example 3 of the present invention.
Detailed description of the preferred embodiments
The technical solution of the present invention is further described in detail below with reference to the accompanying drawings and examples.
The extract of fiveleaf akebia fruit used in the following examples was prepared by extracting:
s1: mixing akebia trifoliata koidz (g) with deionized water (mL) according to a mixing ratio of 1 g: (75-150) mL, heating to boiling, and keeping the boiling state for 10-30 minutes;
s2: and (5) after the liquid in the step S1 is naturally cooled, centrifuging at 10000rpm for 10min, and preparing a supernatant, namely the fiveleaf akebia fruit extracting solution.
The gold nanoparticle sol used in each of the following examples was prepared by extraction through the following steps:
preparing gold nanoparticles by using a 1wt% sodium citrate aqueous solution as a reducing agent, mixing 100mL of deionized water with 290uL of 0.1mol/L chloroauric acid aqueous solution, heating to 100 ℃ to boil, carrying out boiling reaction for 10min, adding 3mL of 1wt% sodium citrate aqueous solution, continuing to keep the boiling state for reaction for 15min, cooling the liquid, and centrifuging to obtain the gold nanoparticle sol.
Example 1
The preparation method of the single-layer gold film for photocatalytic degradation of 4-nitrophenol, provided by the embodiment, specifically comprises the following steps:
(1) putting glass balls with the diameter of 2.5mm into a utensil, cleaning for 3 times, each time for 10min, and naturally drying for later use after cleaning;
(2) soaking the glass ball prepared in the step (1) by using a mixed solution of 3-aminopropyltriethoxysilane and absolute ethanol according to the volume ratio of 1:100, and standing for 24 hours to positively charge the surface of the glass ball;
(3) cleaning the positively charged glass spheres with 20mL of absolute ethanol by resonance for 3 times, removing redundant 3-aminopropyl triethoxysilane by resonance cleaning for 10min each time, and naturally drying;
(4) soaking the glass ball prepared in the step (3) in the gold nanoparticle sol for 1 hour, and carrying out electrostatic self-assembly to enable the surface of the glass ball to uniformly adsorb gold seeds;
(5) and (3) taking out the glass balls subjected to electrostatic self-assembly in the step (4), and placing the glass balls into the akebia fruit extracting solution, wherein the akebia fruit extracting solution is prepared by adding 75mL of deionized water into 1g of akebia fruit and mixing, then adding 20 mu L of chloroauric acid aqueous solution, and performing soaking treatment and standing for 1 hour to obtain the single-layer gold film.
The surface of the gold film prepared by the method is subjected to morphology analysis by adopting a field emission scanning electron microscope of a Japan NERCN-TC-006 model, as shown in figure 1; as can be seen from FIG. 1, the prepared gold film has a single-layer structure and is uniform in film formation.
The composition of the gold film prepared by the above method was analyzed by X-ray diffractometer model D/max-2600PC from Japan, as shown in FIG. 2; fig. 2 shows that the X-ray diffraction pattern of the gold film is consistent with the standard pattern of elemental gold, which indicates that the prepared gold film contains elemental gold and no other impurities.
Example 2
The preparation method of the single-layer gold film for photocatalytic degradation of 4-nitrophenol, provided by the embodiment, specifically comprises the following steps:
(1) putting glass balls with the diameter of 4mm into a vessel, cleaning for 3 times, each time for 10min, and naturally drying for later use after cleaning;
(2) soaking the glass ball prepared in the step (1) by using a mixed solution of 3-aminopropyltriethoxysilane and absolute ethanol according to the volume ratio of 1:100, and standing for 24 hours to positively charge the surface of the glass ball;
(3) cleaning the positively charged glass spheres with 20mL of absolute ethanol by resonance for 3 times, removing redundant 3-aminopropyl triethoxysilane by resonance cleaning for 10min each time, and naturally drying;
(4) soaking the glass ball prepared in the step (3) in the gold nanoparticle sol for 1.5 hours, and carrying out electrostatic self-assembly to enable the surface of the glass ball to uniformly adsorb gold seeds;
(5) and (3) taking out the glass balls subjected to electrostatic self-assembly in the step (4), and placing the glass balls into the akebia fruit extracting solution, wherein the akebia fruit extracting solution is prepared by adding 110mL of deionized water into 1g of akebia fruit and mixing, then adding 50 mu L of chloroauric acid aqueous solution, and performing soaking treatment and standing for 1.5 hours to obtain the single-layer gold film.
The surface of the gold film prepared by the method is subjected to morphology analysis by using a field emission scanning electron microscope of a Japan NERCN-TC-006 model, as shown in FIG. 3; as can be seen from FIG. 3, the prepared gold film has a single-layer structure and is uniform in film formation.
The composition of the gold film prepared by the above method was analyzed by X-ray diffractometer model D/max-2600PC from Japan, as shown in FIG. 4; fig. 4 shows that the X-ray diffraction pattern of the gold film is consistent with the standard pattern of elemental gold, which indicates that the prepared gold film contains elemental gold and no other impurities.
Example 3
The preparation method of the single-layer gold film for photocatalytic degradation of 4-nitrophenol, provided by the embodiment, specifically comprises the following steps:
(1) putting glass balls with the diameter of 5.5mm into a utensil, cleaning for 3 times, each time for 10min, and naturally drying for later use after cleaning;
(2) soaking the glass ball prepared in the step (1) by using a mixed solution of 3-aminopropyltriethoxysilane and absolute ethanol according to the volume ratio of 1:100, and standing for 24 hours to positively charge the surface of the glass ball;
(3) cleaning the positively charged glass spheres with 20mL of absolute ethanol by resonance for 3 times, removing redundant 3-aminopropyl triethoxysilane by resonance cleaning for 10min each time, and naturally drying;
(4) soaking the glass ball prepared in the step (3) in the gold nanoparticle sol for 2 hours, and carrying out electrostatic self-assembly to enable the surface of the glass ball to uniformly adsorb gold seeds;
(5) and (3) taking out the glass balls subjected to electrostatic self-assembly in the step (4), and placing the glass balls into the akebia fruit extracting solution, wherein the akebia fruit extracting solution is prepared by adding 150mL of deionized water into 1g of akebia fruit and mixing, then adding 80 mu L of chloroauric acid aqueous solution, and performing soaking treatment and standing for 2 hours to obtain the single-layer gold film.
The surface of the gold film prepared by the method is subjected to morphology analysis by using a field emission scanning electron microscope of a Japanese NERCN-TC-006 model, as shown in FIG. 5; FIG. 5 shows that the prepared gold film has a single-layer structure and is uniform in film formation.
The composition of the gold film prepared by the above method was analyzed by X-ray diffractometer model D/max-2600PC from Japan, as shown in FIG. 6; fig. 6 shows that the X-ray diffraction pattern of the gold film is consistent with the standard pattern of elemental gold, indicating that the prepared gold film contains elemental gold and no other impurities.
In summary, it can be seen that: according to the invention, the glass ball is soaked in the mixed solution of 3-aminopropyltriethoxysilane and absolute ethyl alcohol to be positively charged, and the positively charged glass ball and the negatively charged gold nanoparticles are mutually attracted through electrostatic interaction, so that the gold nanoparticles are attached to the surface of the glass ball to form gold seeds; the method comprises the steps of replacing toxic hydroxylamine hydrochloride with non-toxic green plant akebia fruit extracting solution to serve as a reducing agent, controlling the ratio of akebia fruit (g) to deionized water (mL) to be 1 (75-150), adding 20-80 muL of chloroauric acid aqueous solution, controlling the soaking time to be 1-2 hours, taking gold seeds as active centers, and continuously reducing chloroauric acid at normal temperature; the reduced gold is deposited and grows on the surface of the gold seed to form a film, and the prepared single-layer gold film has stable performance, strong adhesive capacity and uniform film thickness and can be repeatedly used; the single-layer gold film is prepared by replacing conventional toxic hydroxylamine hydrochloride with the non-toxic fiveleaf akebia fruit extracting solution which is convenient and easy to obtain, low in price and easy to store as a reducing agent, so that the single-layer gold film is low in preparation cost and free of any environmental pollution, and a new synthetic approach is provided for preparation of other single-layer metal films; in addition, the preparation method has simple process, the prepared single-layer gold film has uniform structure and good reusability, the raw material fiveleaf akebia fruit is convenient and easy to obtain, and the photocatalytic activity of the single-layer gold film is equivalent to that of gold nanoparticles; overcomes the defects that the micro particles are easy to lose and difficult to recover in the using process, and effectively promotes the development of the technology for degrading the 4-nitrophenol by photocatalysis.
Although the above examples only exemplify reactions on a laboratory scale, it will be understood by those skilled in the art that the present invention is not limited to the degradation of 4-nitrophenol, but may also be used for other organic contaminants such as 2-nitrophenol, 3-nitrophenol, 2-nitroresorcinol, methyl red, methyl orange, and the like.
It is finally necessary to point out here: the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (9)
1. A preparation method of a single-layer gold film for photocatalytic degradation of 4-nitrophenol is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) soaking the glass ball by using a mixed solution of 3-aminopropyltriethoxysilane and absolute ethyl alcohol, and standing for 24 hours to positively charge the surface of the glass ball;
(2) mixing deionized water and a chloroauric acid aqueous solution, heating to boil, and then injecting a sodium citrate aqueous solution to obtain gold nanoparticle sol;
(3) soaking the positively charged glass spheres in the step (1) in the gold nanoparticle sol prepared in the step (2) to perform electrostatic self-assembly;
(4) taking out the glass ball subjected to the electrostatic self-assembly in the step (3), placing the glass ball in the fiveleaf akebia fruit extracting solution, adding a chloroauric acid aqueous solution, and soaking to obtain a single-layer gold film;
the diameter of the glass ball is 2.5 mm-5.5 mm;
and (2) mixing the 3-aminopropyltriethoxysilane and the absolute ethanol in the step (1) according to a volume ratio of 1: 100.
2. The method for producing a single-layer gold film according to claim 1, characterized in that: and (4) controlling the electrostatic self-assembly time in the step (3) to be 1-2 hours.
3. The method for producing a single-layer gold film according to claim 1, characterized in that: the amount of the aqueous chloroauric acid solution added in the step (4) is 20-80 muL.
4. The method for producing a single-layer gold film according to claim 1, characterized in that: the soaking treatment time in the step (4) is 1-2 hours.
5. The method for producing a single-layer gold film according to claim 1, characterized in that: the glass spheres in step (1) were treated before the experiment by the following steps: and (3) putting the glass balls into a vessel, cleaning for 3 times, each time for 10min, and naturally drying for later use after cleaning.
6. The method for producing a single-layer gold film according to claim 1, characterized in that: in the preparation process of the fiveleaf akebia fruit extracting solution, the mixing proportion of the dosage of the fiveleaf akebia fruit and the deionized water is 1 g: (75-150) mL.
7. The method for producing a single-layer gold film according to any one of claims 1 to 6, characterized in that: the preparation method of the fiveleaf akebia fruit extracting solution comprises the following steps:
s1: mixing the akebia trifoliata koidz with deionized water according to the mixing ratio of 1 g: (75-150) mL, heating to boiling, and keeping the boiling state for 10-30 minutes;
s2: and (5) after the liquid in the step S1 is naturally cooled, centrifuging at 10000rpm for 10min, and preparing a supernatant, namely the fiveleaf akebia fruit extracting solution.
8. The method for producing a single-layer gold film according to any one of claims 1 to 6, characterized in that: the preparation of the gold nanoparticle sol comprises the following steps: and (3) mixing 100mL of deionized water with 290 mu L of 0.1mol/L chloroauric acid aqueous solution, heating to boil, reacting for 10min, injecting 3mL of 1wt% sodium citrate aqueous solution, continuously keeping the boiling state, reacting for 15min, cooling the liquid, and centrifuging to obtain the gold nanoparticle sol.
9. The method for producing a single-layer gold film according to claim 7, characterized in that: the preparation of the gold nanoparticle sol comprises the following steps: and (3) mixing 100mL of deionized water with 290 mu L of 0.1mol/L chloroauric acid aqueous solution, heating to boil, reacting for 10min, injecting 3mL of 1wt% sodium citrate aqueous solution, continuously keeping the boiling state, reacting for 15min, cooling the liquid, and centrifuging to obtain the gold nanoparticle sol.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306099A (en) * | 2000-11-14 | 2001-08-01 | 中国科学院长春应用化学研究所 | Process for preparing surface plasma resonance response chip by wet chemical method |
| CN1683074A (en) * | 2005-03-11 | 2005-10-19 | 南京大学 | Process for preparing visible light responding photo catalytic film layer |
| CN101811044A (en) * | 2010-04-23 | 2010-08-25 | 华东理工大学 | Potassium niobate nanotube photocatalyst and preparation method and application thereof |
| CN102126703A (en) * | 2010-01-15 | 2011-07-20 | 中国科学院合肥物质科学研究院 | Two-dimensional multi-shell hollow sphere ordered structure array and preparation method thereof |
| CN102408124A (en) * | 2011-09-14 | 2012-04-11 | 上海理工大学 | Method for preparing zinc oxide nanometer sheet based on zinc oxide nanometer rod array |
| CN102512991A (en) * | 2011-12-23 | 2012-06-27 | 天津工业大学 | Polymer catalytic membrane containing palladium metal activity functional layer and preparation method thereof |
| CN103861479A (en) * | 2012-12-18 | 2014-06-18 | 天津工业大学 | Polyvinylidene fluoride/gold nanoparticle hybrid hollow fiber membrane and preparation method thereof |
| CN104034773A (en) * | 2014-06-20 | 2014-09-10 | 首都师范大学 | Gold film microelectrode array and manufacture method thereof |
| CN104831261A (en) * | 2015-04-03 | 2015-08-12 | 首都师范大学 | Microring electrode and production method thereof |
| CN107900378A (en) * | 2017-12-18 | 2018-04-13 | 上海理工大学 | A kind of method that silver nano-grain is prepared using fiveleaf akebia fruit extracting solution |
-
2018
- 2018-07-24 CN CN201810816809.XA patent/CN108906041B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306099A (en) * | 2000-11-14 | 2001-08-01 | 中国科学院长春应用化学研究所 | Process for preparing surface plasma resonance response chip by wet chemical method |
| CN1683074A (en) * | 2005-03-11 | 2005-10-19 | 南京大学 | Process for preparing visible light responding photo catalytic film layer |
| CN102126703A (en) * | 2010-01-15 | 2011-07-20 | 中国科学院合肥物质科学研究院 | Two-dimensional multi-shell hollow sphere ordered structure array and preparation method thereof |
| CN101811044A (en) * | 2010-04-23 | 2010-08-25 | 华东理工大学 | Potassium niobate nanotube photocatalyst and preparation method and application thereof |
| CN102408124A (en) * | 2011-09-14 | 2012-04-11 | 上海理工大学 | Method for preparing zinc oxide nanometer sheet based on zinc oxide nanometer rod array |
| CN102512991A (en) * | 2011-12-23 | 2012-06-27 | 天津工业大学 | Polymer catalytic membrane containing palladium metal activity functional layer and preparation method thereof |
| CN103861479A (en) * | 2012-12-18 | 2014-06-18 | 天津工业大学 | Polyvinylidene fluoride/gold nanoparticle hybrid hollow fiber membrane and preparation method thereof |
| CN104034773A (en) * | 2014-06-20 | 2014-09-10 | 首都师范大学 | Gold film microelectrode array and manufacture method thereof |
| CN104831261A (en) * | 2015-04-03 | 2015-08-12 | 首都师范大学 | Microring electrode and production method thereof |
| CN107900378A (en) * | 2017-12-18 | 2018-04-13 | 上海理工大学 | A kind of method that silver nano-grain is prepared using fiveleaf akebia fruit extracting solution |
Non-Patent Citations (1)
| Title |
|---|
| "Catalytic reduction of 4-nitrophenol and photo inhibition of Pseudomonas aeruginosa using gold nanoparticles as photocatalyst";Khan Shafiullah et al;《JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY B-BIOLOGY》;20170413;第170卷;参见第182页第2.3-2.4节，第186页第4节 * |
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