CN108499529B - Active coke supported nano gold catalyst and preparation method and application thereof - Google Patents

Active coke supported nano gold catalyst and preparation method and application thereof Download PDF

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CN108499529B
CN108499529B CN201810273936.XA CN201810273936A CN108499529B CN 108499529 B CN108499529 B CN 108499529B CN 201810273936 A CN201810273936 A CN 201810273936A CN 108499529 B CN108499529 B CN 108499529B
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active coke
mixed solution
catalyst
solution
sodium borohydride
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CN108499529A (en
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符玉葵
陈畅亚
曾光明
赖萃
秦蕾
黄丹莲
易欢
何江凡
李必胜
黄芳龙
李玲
李敏芳
张明明
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Hunan University
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Abstract

The invention discloses an active coke-supported nano-gold catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: mixing the active coke with water, mixing with a chloroauric acid solution, and performing ultrasonic treatment to obtain a mixed solution of the active coke and the chloroauric acid; and mixing the obtained mixed solution with an ascorbic acid solution for reduction reaction to obtain the active coke-supported nano gold catalyst. The active coke-loaded nano-gold catalyst has the advantages of good dispersibility, high loading rate, good adsorption performance, good catalytic performance and the like, the preparation method has the advantages of simple preparation process, simple and convenient operation, high production efficiency, short production period, low cost, high product yield and the like, and the active coke-loaded nano-gold catalyst can be prepared in a large scale under the normal temperature condition without adding an active agent and a protective agent and is beneficial to industrial utilization. The catalyst can rapidly and thoroughly catalyze and reduce the nitroaromatic compound, and has good use value and application prospect.

Description

Active coke supported nano gold catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of nano metal catalysts, and relates to an active coke-loaded nano gold catalyst, and a preparation method and application thereof.
Background
The nitroaromatic compound is a common industrial pollutant and has the characteristics of high toxicity, biological degradation resistance and the like. The reduction product arylamine is an important intermediate product for industrial production and application, and is used for synthesizing fine chemicals such as pesticides, medicines, synthetic resins, surfactants and the like. At present, the development of new catalysts for this reaction is a research hotspot. With the development of nano science and technology, the nano gold catalyst with high specific surface area is used for catalyzing and reducing nitro compounds and electrochemically reducing CO2And low-temperature catalytic oxidation of CO, etc. have led extensive researchers. However, the nanogold catalyst has large surface energy and small particle size, is easily agglomerated during the reaction to cause reduction of catalytic activity, and the limited metal resources lead to an urgent need for development of a highly active, recyclable catalytic material. Based on the above problems, in order to fully exert the performance of the metal catalyst, loading the nano gold particles on the carrier is a good solution. In recent years, many studies have been reported in which nanogold particles are supported on silica, metal oxide, zeolite, or the like as a carrier. However, these carriers are not stable enough, and especially in strong acid and strong base environments, the material properties are easy to change, and it is difficult to uniformly distribute the nano-gold on the surface. In order to improve the stability of the catalyst, it is very important to find a novel material with good stability for loading the nano-gold.
At present, mesoporous carbon, graphene (graphene oxide), carbon nanofibers and the like are often used as carriers for loading nanogold. However, the existing nanogold catalyst has the following problems: for example, Hequanping et al (CN 101805256) prepared a mesoporous carbon supported gold catalyst for oxidation of glucose only; the mesoporous carbon supported nano gold catalyst prepared by people of Reunion et al (CN 102553583A) and the like by utilizing a template method can be used for hydrogenation reaction of nitrobenzene compounds, but the hydrogenation reaction needs heating and pressurizing, so that the energy consumption is increased; the preparation method comprises the following steps of preparing an Au/mesoporous carbon catalyst by using Au/SAB-15 as a template and cane sugar as a carbon source, wherein the Au/mesoporous carbon catalyst is inferior to Au/SAB-15 in catalytic activity; zhang Peng and the like adopt the traditional electrospinning technology and an in-situ chemical reduction method to prepare the CNFs @ Au catalyst, the catalytic effect is good, but the preparation method is complex. In addition, carbon material carriers such as graphene, carbon nanotubes, carbon nanofibers, fullerenes, and the like are expensive and costly, and are not suitable for large-scale processing of nitroaromatic compounds. Actually, the activated coke is often used for desulfurization and denitrification, mercury removal, adsorption of organic pollutants in wastewater, etc., however, reports of gold-supported catalysts using the activated coke as a carrier have been rare so far, and there is almost no research on supporting nanogold on the activated coke as a carrier.
Among the methods for preparing the supported catalyst, the chemical reduction method is a simple and practical preparation method. However, most of the existing chemical reduction methods utilize hydrazine, sodium citrate and sodium borohydride as reducing agents, and the reducing agents have certain toxicity and are easy to explode. Therefore, the adoption of a non-toxic, harmless and environment-friendly reducing agent is advocated by green chemistry. In addition, the existing preparation method of the nanogold catalyst still has the following problems: (1) the protective agent is added in the preparation process and is difficult to remove by a common water washing method; (2) some manufacturing processes must be carried out under the condition of high temperature, the reaction is violent, and the energy consumption is increased; (3) the preparation steps are complex, and the used chemical reagents are too many, thus being easy to cause secondary pollution to the environment. In addition, the existing nano gold catalyst is adopted to catalyze and reduce the nitroaromatic compound, the catalytic effect is not ideal, and the time for completely catalyzing and reducing the nitroaromatic compound is long. Therefore, the simple method which can uniformly load the nano-gold on the active coke under the normal temperature condition without adding a surfactant and a protective agent is obtained, and the method has important guiding significance for applying the material to the actual treatment of the wastewater containing the nitroaromatic compound.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art, provide an active coke-supported nano-gold catalyst with good dispersibility, high loading rate, good adsorption performance and good catalytic performance, and also provide a preparation method of the active coke-supported nano-gold catalyst with simple preparation process, simple and convenient operation, high production efficiency, short production period and high product yield, and application of the active coke-supported nano-gold catalyst in catalytic reduction of nitroaromatic compounds.
In order to solve the technical problems, the invention adopts the following technical scheme:
an active coke-supported nano-gold catalyst, which takes active coke as a carrier; the surface of the active coke is loaded with nano gold particles.
The active coke loaded nano-gold catalyst is further improved, and the particle size of the nano-gold particles is 5-35 nm; the content of the nano-gold particles in the active coke-supported nano-gold catalyst is 3.25 wt% -12.78 wt%.
As a general technical concept, the present invention also provides a preparation method of the above active coke-supported nanogold catalyst, comprising the steps of:
s1, mixing the active coke with water to obtain an active coke mixed solution;
s2, mixing the active coke mixed solution obtained in the step S1 with a chloroauric acid solution, and performing ultrasonic treatment to obtain a mixed solution of active coke and chloroauric acid;
and S3, mixing the mixed solution of the active coke and the chloroauric acid obtained in the step S2 with an ascorbic acid solution for reduction reaction to obtain the active coke-supported nano gold catalyst.
In the above preparation method, further improvement is provided, in the step S1, the mass-to-volume ratio of the activated coke powder to the water is 0.2 g-0.6 g: 200 mL.
In the above preparation method, a further improvement is that in the step S2, the volume ratio of the activated coke mixed solution to the chloroauric acid solution is 200: 1-3; the concentration of the chloroauric acid solution is 24.3 mmol/L.
In the above preparation method, a further improvement is that in step S3, the volume ratio of the mixed solution of the active coke and the chloroauric acid to the ascorbic acid solution is 201-203: 10; the concentration of the ascorbic acid is 0.01 mol/L-0.1 mol/L.
In the above preparation method, further improvement is provided, in the step S2, the time of the ultrasonic treatment is 10min to 30 min.
In a further improvement of the above preparation method, in step S3, the reduction reaction is performed under stirring conditions; the time of the reduction reaction is 12-24 h.
In the above preparation method, further improvement is that the reduction reaction further comprises the following steps: filtering and washing the product obtained after the reduction reaction, and drying for 12-24 h in vacuum at 15-45 ℃.
In a further improvement of the above preparation method, in step S1, the activated coke further includes the following steps before use: cleaning, drying, ball milling and sieving the active coke; ultrapure water is adopted for cleaning; the rotation speed of the ball milling is 50 r/h-200 r/h; the ball milling time is 1-2 h; the sieving is 200 mesh sieving.
As a general technical concept, the invention also provides an application of the active coke-supported nano-gold catalyst or the active coke-supported nano-gold catalyst prepared by the preparation method in catalytic reduction of nitroaromatic compounds.
The application is further improved, and comprises the following steps: mixing the active coke-supported nano gold catalyst with a mixed solution containing a nitroaromatic compound and sodium borohydride for catalytic reduction reaction to complete the treatment of the nitroaromatic compound; the mass-volume ratio of the active coke-supported nano gold catalyst to the mixed solution containing the nitroaromatic compound and the sodium borohydride is 1 mg-15 mg: 3 mL.
In the application, the mixed solution containing the nitroaromatic compound and the sodium borohydride is further improved and prepared from a nitroaromatic compound solution and a sodium borohydride solution; the molar ratio of the nitroaromatic compound to the sodium borohydride in the mixed solution containing the nitroaromatic compound and the sodium borohydride is 1: 25-350; the nitroaromatic compound solution is a 4-nitrophenol solution, a2, 4-dinitrophenol solution or a mixed solution thereof; the concentration of the nitroaromatic compound solution is 0.2 mmol/L; the concentration of the sodium borohydride is 0.01-0.14 mol/L.
In the above application, further improvement, the catalytic reduction reaction is carried out under stirring conditions; the time of the catalytic reduction reaction is 0-40 s.
Compared with the prior art, the invention has the advantages that:
1. the invention provides an active coke supported nano-gold catalyst, which takes active coke as a carrier, and nano-gold particles are supported on the surface of the active coke. The method takes the activated coke as a carrier, has the advantages of low cost, good acid and alkali resistance, high mechanical strength, high porosity, large specific surface area, good conductivity and the like, loads the gold nanoparticles on the surface of the activated coke, can interact with gold precursor substances due to a large number of oxygen-containing groups (such as hydroxyl) on the surface of the activated coke, and has reducibility, so that the oxygen-containing groups can reduce part of the gold precursors to form gold nanoparticles, so as to obtain more reduction active sites, thus not only stably fixing the gold nanoparticles to improve the loading capacity of the gold nanoparticles, but also preventing the gold nanoparticles from agglomerating to improve the dispersibility thereof, and further obtaining better catalytic activity. In addition, the active coke has larger porosity and specific surface area, so that when the nano-gold particles are loaded on the surface of the active coke, the carrier material can be well prevented from being blocked by the nano-gold particles, thereby ensuring better adsorption performance, being beneficial to promoting the contact of pollutants and active sites and accelerating the reaction. The active coke-supported nano gold catalyst has the advantages of good dispersibility, high loading rate, good adsorption performance, good catalytic performance and the like, can rapidly and thoroughly catalyze and reduce nitroaromatic compounds, and has good use value and application prospect.
2. In the active coke-supported nano gold catalyst, the active coke is used as a carrier, compared with other carbon materials, the active coke has low cost, and the catalyst obtained by using the active coke as the carrier has better catalytic performance.
3. The invention also provides a preparation method of the active coke-supported nano gold catalyst, which comprises the steps of taking the active coke as a carrier, a chloroauric acid solution as a gold precursor and ascorbic acid as a reducing agent, and loading the nano gold particles on the surface of the active coke through a reduction reaction, so that the active coke-supported nano gold catalyst with high activity is obtained. In the invention, ascorbic acid is used as a green and mild reducing agent, and is dehydrogenated and oxidized in the process of reducing chloroauric acid, and gold ions are reduced at the same time to generate clusters firstly and continue to nucleate and grow. In addition, a large number of oxygen-containing groups exist on the surface of the active coke, the oxygen-containing groups can interact with gold precursors, the oxygen-containing groups also have reducibility, the oxygen-containing groups can reduce part of chloroauric acid to form nano Au cores, and the nano Au cores also provide active sites for the subsequent reduction of the chloroauric acid and can play a role in fixing nano gold particles and preventing the nano gold particles from agglomerating. The preparation method has the advantages of simple preparation process, simple and convenient operation, high production efficiency, short production period, low cost, high product yield and the like, does not add an active agent and a protective agent, can realize large-scale preparation at normal temperature, and is beneficial to industrial utilization.
4. The invention also provides the application of the active coke-supported nano gold catalyst in catalytic reduction of nitroaromatic compounds, the nitroaromatic compound solution and the sodium borohydride solution are mixed and then subjected to catalytic reduction reaction to realize the rapid and thorough conversion of the nitroaromatic compounds into other substances, and the method has the advantages of simple process, convenience in operation, low cost, mild reaction conditions, high reaction efficiency, good catalytic reduction effect and the like, can be applied to the actual treatment of nitroaromatic compound wastewater on a large scale, and has very high application value and commercial value.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a transmission electron microscope image of the active coke-supported nanogold catalyst prepared in example 3 of the invention.
Fig. 2 is a particle size distribution diagram of the active coke-supported nanogold catalyst prepared in example 3 of the invention.
Fig. 3 is a high-power transmission electron microscope image of the activated coke-supported nano-gold catalyst prepared in example 3 of the present invention.
FIG. 4 is an X-ray diffraction pattern of the activated coke-supported nanogold catalyst prepared in example 3 of the invention.
FIG. 5 shows that ln (C) is generated in the reaction process of reducing 4-nitrophenol by the catalysis of the active coke supported nano-gold catalyst in example 4 of the present inventiont/C0) Graph with reaction time t.
FIG. 6 is a graph showing the UV spectrum of the reaction solution of the active coke-supported nano gold catalyst (Au/AC-3) in the catalytic reduction process in example 4 of the present invention as a function of reaction time.
FIG. 7 is a graph showing the reaction rate constants of p-4-nitrophenol catalyzed at different catalyst loadings in example 5 of the present invention.
FIG. 8 is a graph showing the reaction rate constants of 4-nitrophenol catalyzed at different sodium borohydride concentrations in example 6 of the present invention.
FIG. 9 is a graph showing the UV spectrum of the reaction solution during the catalytic reduction reaction of the active coke-supported nano-gold catalyst (Au/AC-3) in example 7 of the present invention as a function of reaction time.
FIG. 10 is a graph showing the UV spectrum of the reaction solution during the catalytic reduction reaction of the active coke-supported nano-gold catalyst (Au/AC-3) in example 8 of the present invention as a function of reaction time.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the following examples, unless otherwise specified, the data obtained are the average of three or more repeated experiments.
Example 1
An active coke-supported nano-gold catalyst takes active coke as a carrier, and nano-gold particles are supported on the surface of the active coke.
In this example, the particle size of the gold nanoparticles is 5nm to 35 nm.
In this example, the content of the gold nanoparticles in the activated coke-supported gold nanoparticle catalyst was 3.25 wt%.
A preparation method of the active coke-supported nano-gold catalyst of the embodiment,
(1) pretreatment of active coke:
washing the active coke for many times by using ultrapure water, and drying in a vacuum drying oven; ball-milling the dried active coke for 2 hours at the ball-milling rotating speed of 200 r/h; and sieving the powder subjected to ball milling to obtain active coke powder with a sieve mesh of 200 meshes.
(2) Preparing an active coke-supported nano gold catalyst:
(2.1) 0.4g of the activated coke powder prepared in the step (1) is weighed and placed in a 300mL round-bottom flask, 200mL of ultrapure water is added, and the mixture is uniformly mixed to obtain an activated coke mixed solution.
And (2.2) adding 1mL of chloroauric acid solution with the concentration of 24.3mmol/L into the activated coke mixed solution obtained in the step (2.1), and carrying out ultrasonic treatment for 30min to obtain a mixed solution of activated coke and chloroauric acid.
And (2.3) placing the mixed solution of the active coke and the chloroauric acid obtained in the step (2.2) on a magnetic stirrer for stirring, dropwise adding 10mL of 0.1M ascorbic acid solution, carrying out reduction reaction for 24h under the stirring condition, filtering and washing the product solution after the reaction is finished, and carrying out vacuum drying for 24h under the condition that the temperature is 45 ℃ to obtain the active coke supported nano gold catalyst, wherein the serial number is Au/AC-1.
Example 2:
an active coke-supported nanogold catalyst, which is substantially the same as the active coke-supported nanogold catalyst in example 1, except that: in example 2, the content of the gold nanoparticles in the active coke-supported gold nanoparticle catalyst was 6.97 wt%.
A method for preparing the activated coke-supported nano-gold catalyst of the embodiment is substantially the same as the method for preparing the activated coke-supported nano-gold catalyst of the embodiment 1, except that: the amount of the chloroauric acid solution added in the preparation method of example 2 was 2 mL.
The active coke prepared in example 2 supports a nanogold catalyst, and the number of the catalyst is Au/AC-2.
Example 3:
an active coke-supported nanogold catalyst, which is substantially the same as the active coke-supported nanogold catalyst in example 1, except that: the content of the nano gold particles in the active coke-supported nano gold catalyst in example 3 was 12.78 wt%.
A method for preparing the activated coke-supported nano-gold catalyst of the embodiment is substantially the same as the method for preparing the activated coke-supported nano-gold catalyst of the embodiment 1, except that: the amount of the chloroauric acid solution added in the preparation method of example 3 was 3 mL.
The active coke prepared in example 3 supported the nanogold catalyst, numbered as Au/AC-3.
Fig. 1 is a transmission electron microscope image of the active coke-supported nanogold catalyst prepared in example 3 of the invention. As shown in fig. 1, in the activated coke-supported nanogold catalyst prepared in example 3 of the invention, a layer of nanogold particles is uniformly distributed on a carrier, and the catalyst has good dispersibility and high loading capacity.
Fig. 2 is a particle size distribution diagram of the active coke-supported nanogold catalyst prepared in example 3 of the invention. As shown in fig. 2, in the activated coke-supported nano-gold catalyst prepared in example 3 of the present invention, the particle size distribution of the nano-gold particles is between 5nm and 35 nm.
Fig. 3 is a high-power transmission electron microscope image of the activated coke-supported nano-gold catalyst prepared in example 3 of the present invention. As can be seen from fig. 3, the high power transmission electron microscope (HRTEM) image shows clear lattice fringes with interplanar spacings of 0.235nm and 0.205nm, respectively, corresponding to the (111) and (200) facets of the simple Au simple substance of face-centered cubic (fcc) structure.
To further examine the lattice structure of nanogold supported on the surface of the active coke, the catalyst was characterized using X-ray diffraction analysis, as shown in fig. 4. FIG. 4 is an X-ray diffraction pattern of the activated coke-supported nanogold catalyst prepared in example 3 of the invention. As can be seen from fig. 4, the X-ray diffraction pattern (XRD) clearly shows four diffraction peaks at 38.18 °, 44.38 °, 64.52 ° and 77.54 °, corresponding to the (111), (200), (311) and (222) crystal planes of Au, respectively, which are in good agreement with the standard diffraction peak of the simple substance Au of face-centered-cubic (fcc) structure (JCPDS No. 04-0784).
Example 4:
an application of an active coke-supported nano gold catalyst in catalytic reduction of a nitroaromatic compound, wherein the nitroaromatic compound is specifically 4-nitrophenol (4-NP), comprises the following steps:
(1) preparing a 4-nitrophenol solution with the concentration of 0.2mM and a sodium borohydride solution with the concentration of 0.10M by using ultrapure water; and mixing 2mL of 4-nitrophenol solution with 1mL of sodium borohydride solution to obtain a mixed solution containing 4-nitrophenol and sodium borohydride.
(2) Catalytic reduction of 4-nitrophenol by using active coke loaded nano-gold catalyst
A first group: 9mg of the active coke-supported nanogold catalyst (Au/AC-1) prepared in example 1 was weighed, and added to 3mL of the mixed solution containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and a catalytic reduction reaction was performed at room temperature, thereby completing the treatment of 4-nitrophenol. In the course of the catalytic reduction reaction, at reaction times of 0, 10s, 18s, 25s, 35s, the absorbance of the reaction solution was sampled and measured, thereby obtaining the effect of Au/AC-1 on the removal of 4-nitrophenol under different reaction time conditions, as shown in FIG. 4.
Second group: 9mg of the active coke-supported nanogold catalyst (Au/AC-2) prepared in example 2 was weighed, and added to 3mL of the mixed solution containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and a catalytic reduction reaction was performed at room temperature, thereby completing the treatment of 4-nitrophenol. In the course of the catalytic reduction reaction, at reaction times of 0, 5s, 10s, 20s, 25s, the absorbance of the reaction solution was sampled and measured, thereby obtaining the effect of Au/AC-2 on the removal of 4-nitrophenol under different reaction time conditions, as shown in FIG. 4.
Third group: 9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, and added to 3mL of the mixed solution containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and a catalytic reduction reaction was performed at room temperature, thereby completing the treatment of 4-nitrophenol. In the process of the catalytic reduction reaction, when the reaction time is 0, 5s, 10s, 13s, 16s and 20s, the absorbance of the reaction solution is sampled and measured, so that the removal effect of Au/AC-3 on 4-nitrophenol under different reaction time conditions is obtained, as shown in FIG. 4.
In the invention, the concentration of the sodium borohydride is far greater than that of the nitroaromatic compound, so that the catalytic reduction reaction can be regarded as a quasi-first-order reaction, namely, the reaction rate is in direct proportion to the concentration of the nitroaromatic compound. In addition, the concentration of nitroaromatics is directly proportional to the absorbance and can therefore be expressed by the following relationship: ln (A)t/A0)＝ln(Ct/C0) -kt, wherein k is the reaction rate constant; a. thetDenotes the absorbance at 400nm at a reaction time t, A0Represents the absorbance at 400nm at a reaction time of 0; ctDenotes the concentration at reaction time t, C0The concentration at which the reaction time was 0 is shown.
FIG. 5 shows that ln (C) is generated in the reaction process of reducing 4-nitrophenol by the catalysis of the active coke supported nano-gold catalyst in example 4 of the present inventiont/C0) Graph with reaction time t. The reaction rate constant (k) corresponding to the catalytic reduction of 4-nitrophenol by using the active coke supported nano-gold catalyst in the embodiment 4 of the inventionapp) And the time corresponding to complete catalytic reduction of 4-nitrophenol, as shown in table 1. As can be seen from FIG. 5, when the active coke-supported nanogold catalyst is used for catalytic reduction of 4-nitrophenol, samples all show a better linear relationship, and the reaction conforms to first-order kinetic characteristics. As can be seen from FIG. 5 and Table 1, the reaction rate constant (A) increases with the amount of the chloroauric acid solution addedkapp) The value is correspondingly increased, and the reaction rate constant k corresponding to the active coke supported nano gold catalyst (Au/AC-1, Au/AC-2 and Au/AC-3) is correspondingly increasedappThe values are respectively 0.073s-1、0.1347s-1、0.1916s-1(ii) a Meanwhile, with the increase of the adding amount of the chloroauric acid solution, the time corresponding to the complete catalytic reduction of 4-nitrophenol is reduced, and the time corresponding to the complete catalytic reduction of 4-nitrophenol by the active coke-supported nanogold catalyst (Au/AC-1, Au/AC-2 and Au/AC-3) is respectively 35s, 25s and 20s, which shows that the catalytic activity of the active coke-supported nanogold catalyst is enhanced with the increase of the adding amount of the chloroauric acid (the time for completely catalytic reduction of 4-nitrophenol is shorter and the reaction rate constant is higher).
TABLE 1 reaction rate constant k corresponding to the catalytic reduction of 4-nitrophenol with the activated-coke-supported-nanogold catalyst in example 4 of the inventionappAnd the time corresponding to the complete catalytic reduction of 4-nitrophenol
Figure BDA0001613215980000071
Figure BDA0001613215980000081
FIG. 6 is a graph showing the UV spectrum of the reaction solution of the active coke-supported nano gold catalyst (Au/AC-3) in the catalytic reduction process in example 4 of the present invention as a function of reaction time. As can be seen from fig. 6: in a 4-nitrophenol/sodium borohydride reduction system, a mixed solution of 4-nitrophenol and sodium borohydride is bright yellow, and an absorption peak at 400nm is a characteristic absorption peak of 4-nitrophenol in an alkaline solution. Once the active coke-supported nano gold catalyst is introduced into the mixed solution, the characteristic absorption peak of 4-nitrophenol gradually decreases with time until disappears, and simultaneously, a new absorption peak is generated at 300nm and gradually rises, and the solution gradually becomes colorless, which indicates that 4-nitrophenol is completely converted into 4-aminophenol, namely, the active coke-supported nano gold catalyst (Au/AC-3) can completely and rapidly catalyze sodium borohydride to reduce 4-nitrophenol within 20 s.
Example 5:
an application of an active coke-supported nano gold catalyst in catalytic reduction of a nitroaromatic compound, wherein the nitroaromatic compound is specifically 4-nitrophenol (4-NP), comprises the following steps:
(1) preparing a 4-nitrophenol solution with the concentration of 0.2mM and a sodium borohydride solution with the concentration of 0.10M by using ultrapure water; and mixing 2mL of 4-nitrophenol solution with 1mL of sodium borohydride solution to obtain a mixed solution containing 4-nitrophenol and sodium borohydride.
(2) Catalytic reduction of 4-nitrophenol by using active coke loaded nano-gold catalyst
A first group: 1mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and subjected to catalytic reduction reaction at room temperature for 10min, thereby completing the treatment of 4-nitrophenol.
Second group: 2mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and subjected to catalytic reduction reaction at room temperature for 5min, thereby completing the treatment of 4-nitrophenol.
Third group: 3mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and subjected to catalytic reduction reaction at room temperature for 3min, thereby completing the treatment of 4-nitrophenol.
And a fourth group: 6mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and subjected to catalytic reduction reaction at room temperature for 45 seconds, thereby completing the treatment of 4-nitrophenol.
And a fifth group: 9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and subjected to catalytic reduction reaction at room temperature for 20 seconds, thereby completing the treatment of 4-nitrophenol.
A sixth group: 12mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and subjected to catalytic reduction reaction at room temperature for 20 seconds, thereby completing the treatment of 4-nitrophenol.
A seventh group: 15mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and subjected to catalytic reduction reaction at room temperature for 20 seconds, thereby completing the treatment of 4-nitrophenol.
FIG. 7 is a graph showing the reaction rate constants for 4-nitrophenol catalyzed at different catalyst loadings in example 5 of the present invention. As can be seen from FIG. 7, the reaction rate constant increased with the increase of the amount of the catalyst, and then became substantially stable when the amount of the catalyst reached 9mg, because the reaction rate constant became substantially stable when the amount of the catalyst reached 9mg due to the limited content of 4-nitrophenol in the solution. Thus, an optimum catalyst dosage of 9mg was selected. Therefore, the degradation efficiency of the active coke-supported nano gold catalyst prepared by the method disclosed by the invention on 4-nitrophenol has a great relationship with the dosage of the active coke-supported nano gold catalyst.
Example 6:
an application of an active coke-supported nano gold catalyst in catalytic reduction of a nitroaromatic compound, wherein the nitroaromatic compound is specifically 4-nitrophenol (4-NP), comprises the following steps:
(1) a4-nitrophenol solution was prepared with ultrapure water at a concentration of 0.2mM, and sodium borohydride solutions were prepared at concentrations of 0.02M, 0.04M, 0.06M, 0.08M, 0.10M, 0.12M, 0.14M.
And mixing 7 parts by volume of 2mL of 4-nitrophenol solution with 1mL of sodium borohydride solution with the concentration of 0.02M, 0.04M, 0.06M, 0.08M, 0.10M, 0.12M and 0.14M respectively to obtain mixed solutions containing 4-nitrophenol and sodium borohydride with different concentrations, which are numbered as A1, A2, A3, A4, A5, A6 and A7 in sequence.
(2) Catalytic reduction of 4-nitrophenol by using active coke loaded nano-gold catalyst
A first group: 9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution (a1) containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 50), and subjected to catalytic reduction reaction at room temperature for 10min, thereby completing the treatment of 4-nitrophenol.
Second group: 9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution (a2) containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 100), and subjected to catalytic reduction reaction at room temperature for 3min, thereby completing the treatment of 4-nitrophenol.
Third group: 9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to the mixed solution (a3) containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 150), and subjected to catalytic reduction reaction at room temperature for 2min, thereby completing the treatment of 4-nitrophenol.
And a fourth group: 9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution (a4) containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 200), and subjected to catalytic reduction reaction at room temperature for 1min to complete the treatment of 4-nitrophenol.
And a fifth group: 9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution (a5) containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and subjected to catalytic reduction reaction at room temperature for 20 seconds, thereby completing the treatment of 4-nitrophenol.
A sixth group: 9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution (a6) containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 300), and subjected to catalytic reduction reaction at room temperature for 20 seconds, thereby completing the treatment of 4-nitrophenol.
A seventh group: 9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, added to 3mL of the mixed solution (a7) containing 4-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 4-nitrophenol to sodium borohydride in the mixed solution was 1: 350), and subjected to catalytic reduction reaction at room temperature for 20 seconds, thereby completing the treatment of 4-nitrophenol.
FIG. 8 is a graph showing the reaction rate constants of 4-nitrophenol catalyzed at different sodium borohydride concentrations in example 6 of the present invention. As can be seen from FIG. 8, the reaction rate constant increased with the increase of the concentration of sodium borohydride, and then became substantially stable when the concentration of sodium borohydride reached 0.10M, which is attributed to the fact that 4-nitrophenol had been completely reduced at this concentration and the reaction rate constant had reached the maximum. Thus, the optimum concentration was selected to be 0.10M in sodium borohydride solution. Therefore, the degradation efficiency of the active coke-supported nano gold catalyst prepared by the method disclosed by the invention on 4-nitrophenol has a great relationship with the concentration of a sodium borohydride solution.
Example 7:
an application of an active coke-supported nano gold catalyst in catalytic reduction of a nitroaromatic compound, wherein the nitroaromatic compound is specifically 2-nitrophenol, comprises the following steps:
(1) preparing a 2-nitrophenol solution with the concentration of 0.2mM and a sodium borohydride solution with the concentration of 0.10M by using ultrapure water; and mixing 2mL of 2-nitrophenol solution with 1mL of sodium borohydride solution to obtain a mixed solution containing 2-nitrophenol and sodium borohydride.
(2) Catalytic reduction of 2-nitrophenol by using active coke loaded nano-gold catalyst
9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, and added to 3mL of the mixed solution containing 2-nitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 2-nitrophenol to sodium borohydride in the mixed solution was 1: 250), and a catalytic reduction reaction was performed at room temperature, thereby completing the treatment of 2-nitrophenol. In the course of the catalytic reduction reaction, at reaction times of 5s, 8s, 10s, 12s, 20s, and 40s, the absorbance of the reaction solution was sampled and measured, thereby obtaining ultraviolet spectra for the reaction solution under different reaction time conditions, as shown in fig. 7.
FIG. 9 is a graph showing the UV spectrum of the reaction solution during the catalytic reduction reaction of the active coke-supported nano-gold catalyst (Au/AC-3) in example 7 of the present invention as a function of reaction time. As can be seen from FIG. 7, in the 2-nitrophenol/sodium borohydride reduction system, the absorption peak at 415nm is the characteristic absorption peak of 2-nitrophenol in the alkaline solution. Once the active coke-supported nano-gold catalyst is introduced into the mixed solution, the characteristic absorption peak of 2-nitrophenol gradually decreases with time until disappearance, and simultaneously, a new absorption peak is generated at 283nm and gradually rises, and the solution gradually becomes colorless, which indicates that the 2-nitrophenol is completely reduced in a catalytic manner within 40 s.
Example 8:
an application of an active coke-supported nano gold catalyst in catalytic reduction of a nitroaromatic compound, wherein the nitroaromatic compound is specifically 2, 4-dinitrophenol, comprises the following steps:
(1) preparing a2, 4-dinitrophenol solution with the concentration of 0.2mM and a sodium borohydride solution with the concentration of 0.10M by using ultrapure water; 2mL of 2, 4-dinitrophenol solution and 1mL of sodium borohydride solution are mixed to obtain a mixed solution containing 2, 4-dinitrophenol and sodium borohydride.
(2) 2, 4-dinitrophenol is catalytically reduced by utilizing active coke supported nano gold catalyst
9mg of the active coke-supported nanogold catalyst (Au/AC-3) prepared in example 3 was weighed, and added to 3mL of the mixed solution containing 2, 4-dinitrophenol and sodium borohydride prepared in step (1) (the molar ratio of 2, 4-dinitrophenol to sodium borohydride in the mixed solution was 1: 250), and catalytic reduction was performed at room temperature to complete the treatment of 2, 4-dinitrophenol. In the course of the catalytic reduction reaction, at reaction times of 5s, 8s, 10s, 20s, 30s, and 40s, the absorbance of the reaction solution was sampled and measured, thereby obtaining ultraviolet spectra of the reaction solution under different reaction time conditions, as shown in fig. 8.
FIG. 10 is a graph showing the UV spectrum of the reaction solution during the catalytic reduction reaction of the active coke-supported nano-gold catalyst (Au/AC-3) in example 8 of the present invention as a function of reaction time. As can be seen from FIG. 8, the absorption peak at 359nm in the 2, 4-dinitrophenol/sodium borohydride reduction system is the characteristic absorption peak of 2, 4-dinitrophenol in an alkaline solution. Once the active coke-supported nano-gold catalyst is introduced into the mixed solution, the characteristic absorption peak of the 2, 4-dinitrophenol gradually decreases with time until the absorption peak disappears, and the solution gradually becomes colorless, which indicates that the 2, 4-dinitrophenol is completely reduced in a catalytic manner within 40 s.
In the invention, the active coke-supported nano gold catalyst can completely catalyze the nitroaromatic compound in a short time, because when the nano gold is supported on the surface of the active coke, the concentration of the nitroaromatic compound near the active site nano gold is increased due to the larger specific surface area of the active coke, so that more nitroaromatic compounds are contacted with the active site. When the active site adsorbs nitroaromatic compound, sodium borohydride is used as hydrogen source, and-NO in nitroaromatic compound2The rapid transfer of electrons with the surface of the nano gold leads the nitro aromatic compound to be rapidly reduced.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.

Claims (6)

1. The application of the active coke-supported nano gold catalyst in catalytic reduction of nitroaromatic compounds is characterized by comprising the following steps: mixing the active coke-supported nano gold catalyst with a mixed solution containing a nitroaromatic compound and sodium borohydride for catalytic reduction reaction to complete the treatment of the nitroaromatic compound; the mass-volume ratio of the active coke-supported nano gold catalyst to the mixed solution containing the nitroaromatic compound and the sodium borohydride is 9-15 mg: 3 mL;
the mixed solution containing the nitroaromatic compound and the sodium borohydride is prepared from a nitroaromatic compound solution and a sodium borohydride solution; the molar ratio of the nitroaromatic compound to the sodium borohydride in the mixed solution containing the nitroaromatic compound and the sodium borohydride is 1: 250-350;
the catalytic reduction reaction is carried out under the condition of stirring; the time of the catalytic reduction reaction is 5-40 s;
the active coke-supported nano gold catalyst takes active coke as a carrier; the surface of the active coke is loaded with nano gold particles; the content of the nano-gold particles in the active coke-supported nano-gold catalyst is 6.97wt% -12.78 wt%.
2. The use according to claim 1, wherein the nitroaromatic compound solution is a 4-nitrophenol solution, a2, 4-dinitrophenol solution or a mixed solution thereof; the concentration of the nitroaromatic compound solution is 0.2 mmol/L; the concentration of the sodium borohydride is 0.01-0.14 mol/L.
3. The use according to claim 1, wherein the gold nanoparticles have a particle size of 5nm to 35 nm.
4. The use according to claim 1 or 3, wherein the preparation method of the active coke-supported nanogold catalyst comprises the following steps:
s1, mixing the active coke with water to obtain an active coke mixed solution; the mass volume ratio of the active coke powder to the water is 0.2-0.6 g: 200 mL;
s2, mixing the active coke mixed solution obtained in the step S1 with a chloroauric acid solution, and performing ultrasonic treatment to obtain a mixed solution of active coke and chloroauric acid; the volume ratio of the active coke mixed solution to the chloroauric acid solution is 200: 1-3; the concentration of the chloroauric acid solution is 24.3 mmol/L;
s3, mixing the mixed solution of the active coke and the chloroauric acid obtained in the step S2 with an ascorbic acid solution for reduction reaction to obtain an active coke-loaded nano gold catalyst; the volume ratio of the mixed solution of the active coke and the chloroauric acid to the ascorbic acid solution is 201-203: 10; the concentration of the ascorbic acid is 0.01 mol/L-0.1 mol/L.
5. The use according to claim 4, wherein in the step S2, the time of the ultrasonic treatment is 10-30 min;
in the step S3, the reduction reaction is performed under stirring conditions; the time of the reduction reaction is 12-24 h; the reduction reaction also comprises the following treatment steps: filtering and washing the product obtained after the reduction reaction, and drying for 12-24 h in vacuum at 15-45 ℃.
6. The use according to claim 4, wherein in the step S1, the active coke further comprises the following processes before use: cleaning, drying, ball milling and sieving the active coke; ultrapure water is adopted for cleaning; the rotation speed of the ball milling is 50 r/h-200 r/h; the ball milling time is 1-2 h; the sieving is 200 mesh sieving.
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