CN115121244A - Method for preparing graphene-loaded gold cluster nanocomposite through in-situ reduction of sodium borohydride and application of graphene-loaded gold cluster nanocomposite - Google Patents
Method for preparing graphene-loaded gold cluster nanocomposite through in-situ reduction of sodium borohydride and application of graphene-loaded gold cluster nanocomposite Download PDFInfo
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- ZFMRLFXUPVQYAU-UHFFFAOYSA-N sodium 5-[[4-[4-[(7-amino-1-hydroxy-3-sulfonaphthalen-2-yl)diazenyl]phenyl]phenyl]diazenyl]-2-hydroxybenzoic acid Chemical compound C1=CC(=CC=C1C2=CC=C(C=C2)N=NC3=C(C=C4C=CC(=CC4=C3O)N)S(=O)(=O)O)N=NC5=CC(=C(C=C5)O)C(=O)O.[Na+] ZFMRLFXUPVQYAU-UHFFFAOYSA-N 0.000 claims description 16
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- 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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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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Abstract
The invention discloses a method for preparing a graphene-loaded gold cluster nanocomposite through in-situ reduction of sodium borohydride and application thereof, wherein the method comprises the following steps: graphene pretreatment: activating carboxyl on graphene by adopting EDC and NHS; loading a gold cluster on graphene: and (2) carrying out reduction reaction on chloroauric acid by adopting NIBC and TCEP, adding graphene with activated carboxyl for continuous reaction after full reaction, adding sodium borohydride for reduction reaction after full reaction, and purifying after the reaction is finished to obtain the graphene-loaded gold cluster nanocomposite. The method adopts a sodium borohydride in-situ reduction method to prepare the uniform graphene-loaded gold cluster nanocomposite with small particle size distribution. The graphene-loaded gold cluster nanocomposite prepared by the method has high efficiency on the catalytic degradation of azo dyes, does not reduce the catalytic degradation capability of the material after multiple times of catalysis, and has cycle stability.
Description
Technical Field
The invention belongs to the field of preparing and synthesizing functional nano materials, and particularly relates to a method for preparing a graphene-loaded gold cluster nano composite material by sodium borohydride in-situ reduction and application of the graphene-loaded gold cluster nano composite material.
Background
Gold clusters are composed of several to several hundred gold atoms, typically 1-3nm in size. The size of the nano-composite material is equivalent to the Fermi wavelength of electrons, so that the nano-composite material has the properties of a semiconductor, has optical properties, catalytic activity and the like which are greatly different from bulk gold, has a high electron density, an easily functionalized nano interface and good biocompatibility, and is widely applied to the fields of catalysis, fluorescence imaging, targeted therapy, drug carriers and the like at present. However, the specific surface area is large, spontaneous aggregation is very likely to occur in a solution system, and although the prior art has more mature ligand modification technology for stabilizing the ligand, the ligand modification technology still cannot achieve good effect.
Loading the gold clusters on a two-dimensional lamellar structure is an effective way for solving the problem, and the graphene has the advantages of large specific surface area, high mechanical strength and large heat conductivity coefficient, so that the method is widely researched in various fields. Meanwhile, graphene has an important property of containing boundary groups and plane defects. This enables the graphene surface to be functionalized, thereby supporting the gold clusters.
At present, a lot of work researches the preparation method of the graphene-loaded gold cluster nanocomposite, and Song et al (Song et al, Journal of Materials Chemistry A,2017,5(1):230) uses glutathione as a ligand of a gold cluster and loads the gold cluster on a graphene sheet layer by an in-situ hydrothermal reduction method. The prepared graphene-loaded gold cluster nanocomposite is small and uniform in particle size. The hydrothermal reduction method is a mild and slow method, which can prepare nano materials with uniform particle size, but the conditions are harsh, and the crystal growth process and principle cannot be monitored, so that the method is not suitable for mass production. For the synthesis of gold clusters, Brust et al (Mathias Brust et al, Journal of the Chemical Society, Chemical Communications,1994,7:801) prepared gold clusters of uniform particle size using sodium borohydride as a reducing agent. Yu et al (Yu et al, Chemical Engineering Journal,2018,335(1):176) prepared gold clusters with uniform particle size distribution by the Brust method and then connected to graphene with EDC-NHS. The method belongs to an ex-situ method, and the preparation steps are relatively complex.
In addition, the gold cluster has discrete electronic states and structural characteristics similar to molecules due to the fact that the size of the gold cluster is equivalent to the Fermi wavelength of electrons, and the unique physical and chemical properties of the gold cluster cause the gold cluster to have extremely high potential in the field of catalysis. However, the specific surface area is large, spontaneous aggregation is extremely likely to occur in a solution system, and although the ligand modification technology is well established at present for stabilizing the ligand. And in the catalysis process, as the catalytic active sites are positioned on the surface of gold atoms, the aggregation of the gold atoms can be accelerated, so that the circulation stability of the catalyst is reduced. Therefore, the development of a high-activity and high-stability dye degradation catalyst becomes the focus of attention of the current academia.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides sodium borohydride (NaBH) 4 ) The method for preparing the graphene-loaded gold cluster nanocomposite through in-situ reduction adopts a brust method to prepare the uniform graphene-loaded gold cluster nanocomposite with small particle size distribution in situ.
The invention also aims to provide application of the graphene-loaded gold cluster nanocomposite.
In order to realize the purpose, the invention is realized by the following technical scheme:
on one hand, the invention provides a method for preparing a graphene-loaded gold cluster nanocomposite through in-situ reduction of sodium borohydride, which comprises the following steps:
graphene pretreatment:
activating carboxyl on graphene by adopting 1-ethyl- (3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide;
loading a gold cluster on graphene:
carrying out reduction reaction on chloroauric acid by adopting N-isobutyryl-L-cysteine and tris (2-carboxyethyl) phosphine, adding graphene with activated carboxyl for continuous reaction after full reaction, adding sodium borohydride for reduction reaction after full reaction, and purifying after the reaction is finished to obtain the graphene-loaded gold cluster nanocomposite material.
Preferably, the graphene pretreatment comprises the following specific steps: preparing graphene aqueous slurry by adopting a dispersing agent, dissolving the graphene aqueous slurry in methanol, weighing 1-ethyl- (3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide, adding the 1-ethyl- (3-dimethylaminopropyl) carbodiimide and the N-hydroxysuccinimide into the methanol, carrying out ultrasonic dispersion together, and then storing at a low temperature. Because the dispersibility of the graphene in water is not good, the graphene material with good dispersibility in water is obtained by adopting the dispersing agent, and the subsequent synthesis and application are facilitated. Among them, the dispersant may be selected conventionally in the art.
Further preferably, the graphene content in the graphene aqueous slurry is 1-1.5 wt%.
It is further preferred that the molar ratio of 1-ethyl- (3-dimethylaminopropyl) carbodiimide to N-hydroxysuccinimide is 1: 1.
Preferably, the graphene-supported gold cluster specifically comprises the following steps: weighing N-isobutyryl-L-cysteine and tris (2-carboxyethyl) phosphine, dissolving in methanol, adding a chloroauric acid solution and acetic acid, stirring at a low temperature and a normal pressure for reaction, adding a pretreated graphene solution into the solution system after full reaction, continuing to react at the low temperature and the normal pressure, adding a sodium borohydride solution into the solution system after full reaction, stirring at the low temperature and the normal pressure for reaction, and after the reaction is finished, settling, centrifuging, dialyzing, and freeze-drying to obtain solid powder, namely the graphene-loaded gold cluster nanocomposite.
Further preferably, the mass ratio of N-isobutyryl-L-cysteine to tris (2-carboxyethyl) phosphine is 19: 1.
More preferably, the molar ratio of chloroauric acid to N-isobutyryl-L-cysteine is 1 (2-4).
Further preferably, the molar ratio of the chloroauric acid to the sodium borohydride is 1 (10-30).
On the other hand, the invention provides an application of the graphene-loaded gold cluster nanocomposite in catalytic degradation of azo dyes.
Preferably, the azo dye comprises congo red, direct dark brown M.
Compared with the prior art, the invention has the following beneficial effects:
the existing technologies for preparing graphene-loaded gold clusters mainly fall into two categories: ex-situ and in-situ hydrothermal reduction. The main idea of the ex-situ method is to prepare a gold cluster first, and then connect the gold cluster to a graphene sheet layer by, for example, an EDC-NHS method, thereby obtaining the graphene-loaded gold cluster nanocomposite. The method requires two steps for synthesis, which is troublesome. And the gold cluster has larger steric hindrance and is difficult to be connected to the graphene sheet layer. The main ideas of the in-situ hydrothermal reduction method are as follows: firstly, a ligand is connected to a graphene sheet layer through a chemical bond method, then chloroauric acid is added to serve as a gold source, and the graphene-loaded gold cluster nanocomposite is obtained through long-time hydrothermal reduction under the high-temperature condition. Although the method is mild, the process is too energy-consuming and takes too long. According to the invention, an in-situ sodium borohydride reduction method is adopted, so that the graphene-loaded gold cluster nanocomposite with uniform particle size distribution can be rapidly prepared. The main idea is as follows: the ligand is blended with chloroauric acid, and trivalent gold is reduced into a monovalent gold complex (Au-SR) through sulfydryl on the ligand. And then adding the activated carboxyl graphene lamella into the mixed system, so that Au-SR connects gold to the graphene lamella through the chemical bond action between the ligand and graphene. Inspired by the brust method, sodium borohydride is added to rapidly reduce the monovalent gold complex into the gold cluster, and thus the graphene-loaded gold cluster nano composite material is prepared.
The preparation method provided by the invention adopts the method that the univalent gold complex is connected with the graphene to form an amido bond, so that the defect of overlarge steric hindrance of gold clusters can be avoided compared with an ex-situ method, and compared with a method of connecting the ligand to the graphene in advance, the method can effectively improve the effective collision between the chloroauric acid and the ligand and improve the reaction efficiency. The sodium borohydride reduction method is simple and convenient to operate and simple in process compared with a hydrothermal method, and the obtained graphene-loaded gold cluster nanocomposite is small and uniform in particle size.
The graphene-loaded gold cluster nanocomposite prepared by the method has high efficiency on the catalytic degradation of azo dyes, does not reduce the catalytic degradation capability of the material after multiple times of catalysis, and has cycle stability.
Drawings
Fig. 1 is a STEM image of a graphene-supported gold cluster nanocomposite material according to example 1 of the present invention.
Fig. 2 is EDS mapping of sulfur of graphene-supported gold cluster nanocomposite according to example 1 of the present invention.
Fig. 3 is EDS mapping of gold of graphene-supported gold cluster nanocomposite according to example 1 of the present invention.
Fig. 4 is EDS mapping of gold and sulfur of graphene-supported gold cluster nanocomposite according to example 1 of the present invention.
Fig. 5 is a large-scale Transmission Electron Microscope (TEM) image of the graphene-supported gold cluster nanocomposite material according to example 1 of the present invention.
Fig. 6 is a small-scale Transmission Electron Microscope (TEM) image of the graphene-supported gold cluster nanocomposite material according to example 1 of the present invention.
Fig. 7 is a statistical chart of the particle size distribution of the graphene-supported gold cluster nanocomposite in example 1 of the present invention.
Fig. 8 is an X-ray photoelectron spectroscopy (XPS) full spectrum of the graphene-supported gold cluster nanocomposite according to example 1 of the present invention.
Fig. 9 is a gold fine-distribution spectrum of X-ray photoelectron spectroscopy (XPS) of the graphene-supported gold cluster nanocomposite material according to example 1 of the present invention.
Fig. 10 is a graph showing the conversion rate of graphene-supported gold cluster catalytic congo red according to experimental example 1 of the present invention as a function of time.
Fig. 11 is a graph of the cycle performance of graphene-supported gold cluster catalytic congo red according to experimental example 1 of the present invention.
Fig. 12 is a graph showing the conversion of graphene-supported gold cluster-catalyzed direct deep brown M according to experimental example 2 of the present invention as a function of time.
Fig. 13 is a cycle performance diagram of graphene-supported gold cluster catalyzed direct deep brown M in experimental example 2 of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with the specific examples, but the present invention should not be construed as being limited thereto, and only by way of example.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are either commercially available from conventional sources or are prepared in conventional manners.
Example 1
The embodiment provides a preparation method of a graphene-loaded gold cluster nanocomposite, which comprises the following steps:
step one, graphene pretreatment:
0.3 to 0.7mL of graphene aqueous slurry (1 wt%) was dissolved in 1mL of methanol, and 10mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) and 10mg of N-hydroxysuccinimide (NHS) were weighed and added thereto, and collectively ultrasonically dispersed for 10 minutes, and then left at 0 ℃ for use. EDC is used for activating carboxyl on a graphene sheet layer in the step, but the carboxyl activated by EDC is easy to hydrolyze, NHS is added to form a stable active ester intermediate, and the stable carboxyl is not hydrolyzed and reacts with imino in a ligand to generate a C-N bond.
Step two, loading a gold cluster on graphene:
50.35mg of N-isobutyryl-L-cysteine (NIBC) and 2.65mg of tris (2-carboxyethyl) phosphine (TCEP) were weighed out and dissolved in 1mL of methanol, and 0.62mL of chloroauric acid solution (2% in methanol), 2.31mL of methanol, and 0.57mL of acetic acid were added thereto, and the reaction was stirred at 0 ℃ under normal pressure for 0.5 hour. After full reaction, adding the pretreated graphene solution into the solution system, and continuously reacting for 0.5h at 0 ℃ under normal pressure. After the reaction was completed, 2mL of an ethanol-dispersed sodium borohydride solution (71mg) was added to the above solution system, and the mixture was stirred at 0 ℃ under normal pressure for 0.5 h. After the reaction is finished, adding acetone as a settling agent, centrifuging for 5 minutes at the speed of 5000 r/min, discarding the supernatant, adding 10mL of water to dissolve the precipitate, transferring the precipitate into a dialysis bag with the molecular weight cutoff of 50kDa, dialyzing for 2 days, and freeze-drying by using a freeze dryer to obtain a solid powder sample.
Example 2
The embodiment provides a preparation method of a graphene-loaded gold cluster nanocomposite, which comprises the following steps:
0.3 to 0.7mL of an aqueous slurry of graphene (1.5 wt%) was dissolved in 1mL of methanol, and 10mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) and 10mg of N-hydroxysuccinimide (NHS) were weighed and added thereto, and collectively ultrasonically dispersed for 10 minutes, and then left at 0 ℃ for use.
Step two, loading a gold cluster on graphene:
50.35mg of N-isobutyryl-L-cysteine (NIBC) and 2.65mg of tris (2-carboxyethyl) phosphine (TCEP) were weighed out and dissolved in 1mL of methanol, and 0.93mL of chloroauric acid solution (2% in methanol), 2.31mL of methanol, and 0.57mL of acetic acid were added thereto, and the reaction was stirred at 0 ℃ under normal pressure for 0.5 hour. After full reaction, adding the pretreated graphene solution into the solution system, and continuously reacting for 0.5h at 0 ℃ under normal pressure. After the reaction was complete, 3mL of an ethanol-dispersed sodium borohydride solution (106.5mg) was added to the above solution system, and the mixture was stirred at 0 ℃ under normal pressure for 0.5 h. After the reaction is finished, adding acetone as a settling agent, centrifuging for 5 minutes at the speed of 5000 r/min, discarding the supernatant, adding 10mL of water to dissolve the precipitate, transferring the precipitate into a dialysis bag with the molecular weight cutoff of 50kDa, dialyzing for 2 days, and freeze-drying by using a freeze dryer to obtain a solid powder sample.
Example 3
The embodiment provides a preparation method of a graphene-loaded gold cluster nanocomposite, which comprises the following steps:
0.3 to 0.7mL of an aqueous slurry of graphene (1.5 wt%) was dissolved in 1mL of methanol, and 10mg of 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC) and 10mg of N-hydroxysuccinimide (NHS) were weighed and added thereto, and collectively ultrasonically dispersed for 10 minutes, and then left at 0 ℃ for use.
Step two, loading a gold cluster on graphene:
50.35mg of N-isobutyryl-L-cysteine (NIBC) and 2.65mg of tris (2-carboxyethyl) phosphine (TCEP) were weighed out and dissolved in 1mL of methanol, and 1.24mL of chloroauric acid solution (2% in methanol), 2.31mL of methanol, and 0.57mL of acetic acid were added thereto, and the reaction was stirred at 0 ℃ under normal pressure for 0.5 hour. After full reaction, adding the pretreated graphene solution into the solution system, and continuously reacting for 0.5h at 0 ℃ under normal pressure. After the reaction was completed, 4mL of an ethanol-dispersed sodium borohydride solution (142mg) was added to the above solution system, and the mixture was stirred at 0 ℃ under normal pressure for 0.5 h. After the reaction is finished, adding acetone as a settling agent, centrifuging for 5 minutes at the speed of 5000 r/min, discarding the supernatant, adding 10mL of water to dissolve the precipitate, transferring the precipitate into a dialysis bag with the molecular weight cutoff of 50kDa, dialyzing for 2 days, and freeze-drying by using a freeze dryer to obtain a solid powder sample.
The invention takes the graphene-supported gold cluster nanocomposite material prepared in example 1 as an example, and the characterization of the synthetic result is described as follows:
fig. 1 is a STEM image of a graphene-supported gold cluster nanocomposite. This image demonstrates the uniform distribution of gold clusters over the graphene sheet layer.
Fig. 2 is an EDS mapping image of sulfur of the graphene-supported gold cluster nanocomposite. This image shows the distribution of elemental sulfur in figure 1.
Fig. 3 is an EDS mapping image of gold of the graphene-supported gold cluster nanocomposite. This image shows the distribution of gold elements in fig. 1.
Fig. 4 is an EDS mapping image of sulfur and gold of the graphene-supported gold cluster nanocomposite. This image shows that the gold and sulfur are closely located and are located substantially at the high contrast in fig. 1.
Fig. 5 is a large-scale TEM image of the graphene-supported gold cluster nanocomposite. The figure demonstrates that the high-contrast gold clusters on the graphene sheet layer are uniformly distributed, and no large amount of aggregation occurs on the submicron scale.
Fig. 6 is a small-scale TEM image of the graphene-supported gold cluster nanocomposite. The figure also demonstrates that the gold clusters with high contrast on the graphene sheet layer are uniformly distributed, no aggregation phenomenon occurs on the nanoscale, and the particle size of the gold clusters is uniform.
Fig. 7 is a statistical diagram of the particle size distribution of the graphene-supported gold cluster nanocomposite. This figure is a statistical analysis of the particle size by selecting 200 gold clusters from fig. 5 and 6. The particle size of the light emitting clusters is about 1.6nm according to the Gaussian distribution.
Fig. 8 is an XPS full spectrum of the graphene-supported gold cluster nanocomposite. This figure demonstrates that the material contains C, N, O, S, Au elements.
Fig. 9 is an XPS Au 4f fine spectrum of the graphene-supported gold cluster nanocomposite. The peak separation of the spectrogram shows that the material contains 0-valent gold and 1-valent gold simultaneously, and conforms to the structure of gold clusters, which indicates that the gold clusters with high contrast in the electron microscope images in FIGS. 1-6.
In order to more conveniently illustrate that the graphene-loaded gold cluster nanocomposite can be successfully prepared by adopting the technical scheme of the invention, the preferred embodiment 1 of the invention is illustrated as an example, and both the embodiment 2 and the embodiment 3 are successfully synthesized, which is not described in detail herein.
Experimental example 1
In this experimental example, the graphene-supported gold cluster nanocomposite material prepared in example 1 is used to verify the application effect of the graphene-supported gold cluster nanocomposite material in congo red:
(1) catalytic congo red degradation experiment: preparing 0.1mmol/L Congo red aqueous solution, 0.1mol/L sodium borohydride aqueous solution and 0.1mg/mL graphene-loaded gold cluster aqueous solution. 2mL of Congo red solution, 0.2mL of sodium borohydride solution and 0.02mL of graphene-loaded gold cluster solution are uniformly mixed, and the ultraviolet data (the test wavelength range is 300-600nm) is measured every 1 minute. The absorbance of the UV absorption is proportional to the concentration of the substance according to Lambert-beer's law, and thus the concentration can be replaced by the absorbance. Congo red has a characteristic absorption wavelength of 503nm and is converted (A-A) according to the formula% 0 )/A 0 "(A is the current absorbance, A 0 Initial absorbance) can be calculated as a curve of conversion over time.
(2) Congo red cyclic catalysis experiment: the method comprises the steps of testing the cycle performance of Congo red by adopting a step-by-step liquid adding method, uniformly mixing 2mL of Congo red solution, 0.2mL of sodium borohydride solution and 0.02mL of graphene-loaded gold cluster solution, and recording the time required by catalysis until the conversion rate is greater than 90%. And (3) supplementing 2mL of Congo red solution and 0.2mL of sodium borohydride solution into the residual solution of the catalyst, and recording the time required for the catalyst to reach a conversion rate of more than 90%. Then 2mL of Congo red solution and 0.2mL of sodium borohydride solution are supplemented to the residual solution of the catalyst, and the time required for the catalyst to reach a conversion rate of more than 90% is recorded. The principle of the method is as follows: the reaction substrate and the reducing agent are replenished after the first degradation is finished, which is equivalent to simultaneously diluting the reaction substrate, the reducing agent and the catalyst by one time, so that the time required for degradation should be consistent theoretically.
Fig. 10 is a graph of conversion rate of catalytic degradation of congo red by graphene-supported gold clusters over time. It can be found that the time required for the conversion rate to reach 95% is about 13 minutes, and the material has high efficiency on the catalytic degradation of azo dyes. Fig. 11 shows the cycle stability of catalytic degradation of congo red by graphene-supported gold clusters. It can be seen from the figure that 3 times of catalysis does not reduce the catalytic degradation capability of the material.
Experimental example 2
In this experimental example, the graphene-supported gold cluster nanocomposite prepared in example 1 is used to verify the application effect of the graphene-supported gold cluster nanocomposite in direct dark brown M:
(1) direct dark brown M degradation experiment: preparing 0.3mmol/L direct dark brown M aqueous solution, 0.1mol/L sodium borohydride aqueous solution and 0.1mg/mL graphene-loaded gold cluster aqueous solution. 2mL of the direct dark brown M solution, 0.2mL of the sodium borohydride solution and 0.02mL of the graphene-loaded gold cluster solution are uniformly mixed, and the ultraviolet data (the test wavelength range is 200-750nm) of the mixture is measured every 1 minute. The absorbance of the UV absorption is proportional to the concentration of the substance according to Lambert-beer's law, and thus the concentration can be replaced by the absorbance. The characteristic absorption wavelength of direct deep brown M is 513nm, according to the formula "conversion (%) - (A-A) 0 )/A 0 "(A is the current absorbance, A 0 Initial absorbance) can be calculated as a curve of conversion over time.
(2) Direct dark brown M cycle catalysis experiment: the cycle performance of the direct dark brown M is tested by adopting a step-by-step liquid adding method, firstly, 2mL of direct dark brown M solution, 0.2mL of sodium borohydride solution and 0.02mL of graphene-loaded gold cluster solution are uniformly mixed, and the time required for catalyzing until the conversion rate is more than 90% is recorded. Supplementing 2mL of direct dark brown M solution and 0.2mL of sodium borohydride solution into the residual solution of the catalyst, and recording the time required for the catalyst to reach a conversion rate of more than 90%. Then 2mL of direct dark brown M solution and 0.2mL of sodium borohydride solution are supplemented to the residual solution of the catalyst, and the time required for the catalyst to reach a conversion rate of more than 90% is recorded.
Fig. 12 is a graph of the conversion rate of graphene-supported gold cluster catalytic degradation direct deep brown M over time. It can be found that the time required for the conversion rate to reach 95% is about 13 minutes, and the material has high efficiency on the catalytic degradation of azo dyes. Fig. 13 shows the cycling stability of graphene-supported gold cluster catalytic degradation direct dark brown M. It can be seen from the figure that 3 times of catalysis does not reduce the catalytic degradation capability of the material.
In order to more conveniently illustrate that the graphene-loaded gold cluster nanocomposite prepared by the technical scheme of the present invention can catalyze and degrade azo dyes, preferred embodiment 1 of the present invention is described as an example, and the degradation effects of embodiment 2 and embodiment 3 are substantially the same as those of embodiment 1, which is not described in detail herein.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. A method for preparing a graphene-loaded gold cluster nanocomposite through in-situ reduction of sodium borohydride is characterized by comprising the following steps:
graphene pretreatment:
activating carboxyl on graphene by adopting 1-ethyl- (3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide;
loading a gold cluster on graphene:
carrying out reduction reaction on chloroauric acid by adopting N-isobutyryl-L-cysteine and tris (2-carboxyethyl) phosphine, adding graphene with activated carboxyl for continuous reaction after full reaction, adding sodium borohydride for reduction reaction after full reaction, and purifying after the reaction is finished to obtain the graphene-loaded gold cluster nanocomposite material.
2. The method for preparing a graphene-supported gold cluster nanocomposite through in-situ reduction of sodium borohydride according to claim 1, wherein the graphene pretreatment specifically comprises the following steps: preparing graphene aqueous slurry by adopting a dispersing agent, dissolving the graphene aqueous slurry in methanol, weighing 1-ethyl- (3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide, adding the 1-ethyl- (3-dimethylaminopropyl) carbodiimide and the N-hydroxysuccinimide into the methanol, carrying out ultrasonic dispersion together, and then storing at a low temperature.
3. The method for preparing a graphene-supported gold cluster nanocomposite through in-situ reduction of sodium borohydride according to claim 2, wherein the graphene content in the graphene aqueous slurry is 1-1.5 wt%.
4. The method for preparing graphene-supported gold cluster nanocomposite through in-situ reduction of sodium borohydride according to claim 2, wherein the molar ratio of 1-ethyl- (3-dimethylaminopropyl) carbodiimide to N-hydroxysuccinimide is 1: 1.
5. The method for preparing the graphene-supported gold cluster nanocomposite through in-situ reduction of sodium borohydride according to claim 1, wherein the specific steps of the graphene-supported gold cluster are as follows: weighing N-isobutyryl-L-cysteine and tris (2-carboxyethyl) phosphine, dissolving in methanol, adding a chloroauric acid solution and acetic acid, stirring at a low temperature and a normal pressure for reaction, adding a pretreated graphene solution into the solution system after full reaction, continuing to react at the low temperature and the normal pressure, adding a sodium borohydride solution into the solution system after full reaction, stirring at the low temperature and the normal pressure for reaction, and after the reaction is finished, settling, centrifuging, dialyzing, and freeze-drying to obtain solid powder, namely the graphene-loaded gold cluster nanocomposite.
6. The method for preparing the graphene-supported gold cluster nanocomposite through in-situ reduction of sodium borohydride according to claim 5, wherein the mass ratio of N-isobutyryl-L-cysteine to tris (2-carboxyethyl) phosphine is 19: 1.
7. The method for preparing the graphene-supported gold cluster nanocomposite through in-situ reduction of sodium borohydride according to claim 5, wherein the molar ratio of chloroauric acid to N-isobutyryl-L-cysteine is 1 (2-4).
8. The method for preparing the graphene-supported gold cluster nanocomposite through in-situ reduction of sodium borohydride according to claim 5, wherein the molar ratio of chloroauric acid to sodium borohydride is 1 (10-30).
9. The graphene-supported gold cluster nanocomposite prepared by the preparation method according to any one of claims 1 to 8, and application of the graphene-supported gold cluster nanocomposite in catalytic degradation of azo dyes.
10. The use of the graphene-supported gold cluster nanocomposite material according to claim 9 in catalytic degradation of azo dyes, wherein the azo dyes include congo red, direct dark brown M.
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