CN111151250A - Preparation method of fluorescent copper nanocluster-carbon composite catalyst - Google Patents
Preparation method of fluorescent copper nanocluster-carbon composite catalyst Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 48
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
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- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
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- 235000013878 L-cysteine Nutrition 0.000 claims abstract description 12
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- 150000001879 copper Chemical class 0.000 claims abstract description 5
- 238000004108 freeze drying Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 16
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- 239000000843 powder Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001431 copper ion Inorganic materials 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 8
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021392 nanocarbon Inorganic materials 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 29
- 238000006731 degradation reaction Methods 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 14
- 239000000243 solution Substances 0.000 description 27
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
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- 238000005424 photoluminescence Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- -1 Hydroxyl Chemical group 0.000 description 1
- 241001146210 Senecio scandens Species 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/40—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- 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
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention provides a fluorescent copper nanocluster-carbon composite catalyst and a preparation method thereof, wherein a soluble copper salt is dissolved in an L-cysteine solution, a carbon material is added, after uniform stirring, a sodium hydroxide solution is added, stirring reaction is carried out at the reaction temperature of 50-60 ℃, and after the reaction is finished, freeze drying is carried out, so as to obtain the copper nanocluster-carbon composite catalyst. The copper nanocluster-carbon composite catalyst prepared by the invention has the characteristics of strong fluorescence and high catalytic efficiency, and a Fenton-like catalytic degradation system formed by the copper nanocluster-carbon composite catalyst and hydrogen peroxide not only has the advantages of the traditional Fenton system, but also widens the pH range of Fenton reaction, accelerates the reaction rate, and is low in cost and environment-friendly in material.
Description
Technical Field
The invention relates to the field of composite catalysts, in particular to a copper nanocluster-carbon composite catalyst with fluorescence characteristics and a preparation method thereof.
Background
With ferrous catalyst/H2O2The Fenton advanced oxidation technology represented by a system is a common method for removing organic pollutants difficult to biodegrade in wastewater, and the reaction mechanism of the Fenton method is to utilize Fe2+Catalysis of H under acidic conditions2O2Hydroxyl free radicals with strong oxidizing property are generated, but the pH range of the traditional Fenton reaction is narrow (the pH value is between 2 and 4), and a large amount of iron-containing sludge, H, is generated2O2The utilization rate is not high, the degradation efficiency of pollutants is unstable, the cost is high and the like, and the application of the organic pollutants in the wastewater is limited.
The metal nanoclusters are relatively stable nanostructures composed of several to dozens of metal atoms (generally gold, silver and the like), the size of the metal nanoclusters is generally several nanometers, and the size effect and surface ligands supplement each other, so that the material has special optical properties and 'molecular-like properties' such as catalytic activity, and the physical properties of the metal nanoclusters with the core size in the sub-nanometer range are obviously different from those of large nanoparticles and bulk metals of the metal nanoclusters. Nanoclusters have unique properties depending on size, such as catalytic, electrochemical, and fluorescence characteristics, and particularly for gold and silver nanoclusters, have received increasing attention. Copper is widely used due to its low cost, similar characteristics to silver and gold, and high conductivity, but research on copper nanoclusters is relatively limited compared to widely researched gold and silver nanoclusters.
As a novel photoluminescence and nanometer catalytic material, copper nanoclusters are receiving more and more attention in various fields such as photoluminescence analysis, biological probe imaging and catalysis, can be used for manufacturing a fluorescent probe for detecting various analytes in cell imaging, including pH, small molecules, biomolecules and metal ions, and also have application in the aspect of antibiosis, and have high catalytic activity for hydrogenation of carbonyl and olefin groups in water, electroreduction of oxygen and selective hydrogenation of acetylene.
Disclosure of Invention
Aiming at the problems, the invention provides a copper nanocluster-carbon composite catalyst with fluorescence characteristics and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
a fluorescent copper nanocluster-carbon composite catalyst is a carbon material doped copper nanocluster.
The second objective of the present invention is to provide a preparation method of the fluorescent copper nanocluster-carbon composite catalyst, which comprises the following specific steps:
dissolving soluble copper salt in an L-cysteine solution, adding carbon material powder, uniformly stirring, adding a sodium hydroxide solution, stirring for reaction at the reaction temperature of 50-60 ℃, and freeze-drying to obtain the copper nanocluster-carbon composite catalyst after the reaction is finished.
As a further optimized embodiment of the invention, the soluble copper salt is one or more of copper chloride, copper nitrate and copper sulfate.
As a further optimized embodiment of the invention, the concentration of copper ions in the reaction system is 0.1-0.3 mmol/L.
As a further optimized embodiment of the invention, the concentration of the L-cysteine solution is 0.1-0.5 mol/L.
In a further preferred embodiment of the present invention, the carbon material is one or more of biochar, carbon nanotubes, carbon nanofibers or carbon nanospheres, and the amount of the carbon material added is 0.02 to 0.1 g/L.
As a further optimized embodiment of the invention, the concentration of the sodium hydroxide solution is 1.0mol/L, and the stirring reaction time is 2-8 h.
The invention also aims to provide an application method of the fluorescent copper nanocluster-carbon composite catalyst, which is used for catalyzing hydrogen peroxide to generate hydroxyl radicals.
The catalyst is used for catalyzing Fenton-like reaction as a further optimized embodiment of the invention.
The invention has the beneficial effects that:
(1) the template-based synthesis technology is an effective synthesis method for preparing copper nanoclusters (CuNCs), templates with different cavity sizes can control the size distribution and the core size of metal nanoparticles, the templates and a reducing agent are generally separated during preparation, the templates promote the formation of a nanoscale space structure, and the reducing agent promotes Cu2+Production of Cu by ion reduction0And Cu+The invention relates to an ionic polymer, which uses L-cysteine (L-Cys) as a template method and a reducing agent to synchronously form a nano-scale spatial structure and promote Cu2+Production of Cu by ion reduction0And Cu+The ionic polymer is used for preparing the copper nanocluster through one-step reaction, and the method has the advantages of low cost and environment-friendly materials.
(2) The carbon material is doped into the copper nanocluster, the obtained copper nanocluster-carbon catalyst is high in stability and can be used as a non-iron composite catalyst for Fenton-like oxidative degradation of organic pollutants in water treatment, and a Fenton-like catalytic degradation system formed by the copper nanocluster-carbon catalyst and hydrogen peroxide not only has the advantages of a traditional Fenton system, but also widens the pH range of the reaction and accelerates the reaction rate.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, other drawings can be obtained on the basis of the following drawings without inventive effort.
FIG. 1 is a schematic view of a process for preparing the copper nanocluster-carbon composite catalyst;
fig. 2 is a schematic diagram of a mechanism of the copper nanocluster-carbon composite catalyst for catalytically degrading an organic substance;
FIG. 3 shows the degradation effect of different catalytic systems on amino black 10B;
FIG. 4 is the effect of different initial pH on the degradation of aminoblack 10B by the catalytic system;
fig. 5 is a reuse performance of the copper nanocluster-carbon composite catalyst.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
2.0mmol of CuSO4·7H2Dissolving O in 25mL of 0.25mol/L L-Cys solution, adding 0.5g of straw-fired biochar material, stirring for 5min, adding 0.4mL of 1.0mol/LNaOH solution, stirring and reacting for 4.5h in a constant-temperature water bath kettle at 55 ℃ to obtain copper nanocluster-carbon mixed solution, and finally drying by a freeze dryer to obtain dark gray powder, namely the copper nanocluster-carbon catalyst material.
Example 2
Picking up biomass materials, firstly carbonizing the biomass materials at 200 ℃ for 1h by using a muffle furnace, then transferring the biomass materials into a high-temperature tubular furnace, firing the biomass materials at 900 ℃ for 1h under the protection of nitrogen, finally grinding the fired carbon into powder, and drying the powder for later use;
2.0mmol of CuCl2·2H2Dissolving O in 25mL of 0.25mol/L L-Cys solution, adding 0.5g of a biological carbon material fired by red senecio scandens, stirring for 5min, adding 0.4mL of 1.0mol/LNaOH solution, stirring and reacting for 4.5h in a constant-temperature water bath kettle at 55 ℃ to obtain a copper nano-cluster-carbon mixed solution, and finally drying by using a freeze dryer to obtain dark gray powder, namely the copper nano-cluster-carbon catalyst material.
Example 3
2.0mmol of CuSO4·7H2Dissolving O in 25mL of 0.25mol/L L-Cys solution, adding 0.5g of graphene carbon material, stirring for 5min, adding 0.4mL of 1.0mol/LNaOH solution, stirring and reacting for 4.5h in a constant-temperature water bath kettle at 55 ℃ to obtain copper nano-cluster-carbon mixed solution, and finally drying by using a freeze dryer to obtain dark gray powder, namely the copper nano-cluster-carbon catalyst material.
Example 4
2.0mmol of CuSO4·7H2Dissolving O in 25mL of 0.25mol/L L-Cys solution, adding 0.5g of carbon nanofiber, stirring for 5min, adding 0.4mL of 1.0mol/LNaOH solution, stirring and reacting for 4.5h in a constant-temperature water bath kettle at 55 ℃ to obtain a copper nanocluster-carbon mixed solution, and finally drying by using a freeze dryer to obtain dark gray powder, namely the copper nanocluster-carbon catalyst material.
Example 5
2.0mmol of CuSO4·7H2Dissolving O in 25mL of 0.25mol/L L-Cys solution, adding 0.5g of carbon nano tube, stirring for 5min, adding 0.4mL of 1.0mol/LNaOH solution, stirring and reacting for 4.5h in a constant-temperature water bath kettle at 55 ℃ to obtain a copper nano cluster-carbon mixed solution, and finally drying by using a freeze dryer to obtain dark gray powder, namely the copper nano cluster-carbon catalyst material.
Experimental example 1
Degradation efficiency of different catalytic systems on amino black 10B
Are respectively represented by H2O2、CuNCs/C、CuSO4+H2O2、CuNCs+H2O2、CuNCs/C(2:1)+H2O2、CuNCs/C(1:1)+H2O2、CuNCs/C(1:2)+H2O2Degrading amino black 10B by 7 different catalytic systems under the same reaction condition, wherein the reaction temperature is 25 ℃; the dosage of the catalyst is 0.06 g/L; h2O225 mmol/L; initial pH was 6.0, pH was not adjusted; the original concentration of amino black 10B was 10 mg/L.
The results of the degradation rates of 7 different systems on amino black 10B are shown in FIG. 3, and independent H is obtained under the same reaction conditions2O2The degradation rate of the system to the amino black 10B is very low, only about 5 percent, which shows that H2O2Has an oxidizing power of less than-OH; in the CuNCs/C system, the degradation efficiency is below 5%, and the reason that the removal rate is low is that: the system mainly depends on adsorption to remove the amino black 10B, but the specific surface areas of CuNCs and C are smaller, while the amino black 10B is a hydrophilic organic dye, and the surfaces of CuNCs and C are hydrophobic; in CuSO4+H2O2In the system, the degradation efficiency is lower than 10 percent, which is much lower than that of the traditional Fenton-like system; in CuNCs + H2O2The degradation rate in the system at 30min is 63.1%, and the degradation rate at 180min reaches 87.2%, but the observation shows that the color of the amino black 10B solution is changed from dark blue to light purple, and the colorless and transparent effect can not be achieved; the CuNCs/C composite materials prepared by different CuNCs/C ratios have different catalytic performances, and the degradation rate is increased along with the increase of the carbon ratio as shown in figure 3In addition, the catalytic action of CuNCs is easy to generate agglomeration and a large amount of precipitation of copper ions, but the CuNCs/C composite system prevents the agglomeration of CuNCs and reduces the precipitation of copper ions, which may cause the CuNCs/C + H2O2The degradation efficiency of the amino black 10B in the formed Fenton system is higher, when CuNCs and C are 1:2, the degradation rate reaches 98.6% after 180 minutes, the agglomeration of the CuNCs is reduced due to the increase of the carbon content, and the degradation efficiency of the specific surface area is improved.
Experimental example 2
Effect of different initial pH values on catalytic degradation
The pH is an important factor influencing the generation of OH in the Fenton reaction, the initial pH values of the solution are set to be 2.0, 4.0, 6.0, 8.0 and 10.0 respectively in the experiment, the degradation efficiency of the amino black 10B under different pH values is investigated, wherein the pH value of the amino black 10B solution is about 6 under natural conditions, and the amino black 10B solution is degraded at normal temperature; the dosage of the catalyst is 0.06 g/L; h2O225 mmol/L; the original concentration of amino black 10B was 10 mg/L. The results are shown in FIG. 4.
As can be seen from fig. 4, as the pH of the initial solution increased, the degradation rate of aminoblack 10B increased first and then decreased, and reached a maximum of 94.7% at pH 6.0, but the degradation rate was also excellent at pH 4.0 and pH 8.0, and the degradation rates were 92.6% and 91.9%, respectively, indicating CuNCs/C + H2O2The system has wide applicable pH range and good degradation effect, and the reason is that the CuNCs/C catalyst has acidity, so that an acidic medium is provided for the reaction, and the CuNCs/C catalyst still has high catalytic activity under an alkaline condition. And when the pH is 2.0, the copper ions in the solution are [ Cu (H) ]2O)4]2+The copper ions in the form (a) exist, and the reaction rate of the copper ions and hydrogen peroxide is slow, so the degradation rate is low. When the pH reached 10.0, the generation of hydroxyl radicals was inhibited at the CuNCs/C surface, while the pH of the solution was adjusted>At 6.0, the amount of copper ions consumed by the formation of precipitates is reduced, and the degradation effect is deteriorated. Because the CuNCs/C catalyst is an acidic system and the pH of the amino black 10B solution is about 6 in a natural state, the amino black 10B is degraded by the reaction without adjusting the pH.
Experimental example 3
Repeated use performance
The experiment simulates the treatment process of the amino black 10B dye wastewater, a 250mL beaker is used for simulating a reaction tank, 200mL of 10mg/L amino black 10B organic dye is contained in the reaction tank, and 0.06g/L of CuNCs/C and 25mmol/LH are added2O2After the reaction time is 360min, the supernatant is poured off (discharge after simulated wastewater treatment), the reaction bottom mud (mainly CuNCs/C) is reserved, and then 10mg/L aminoblack 10B solution is added to 200mL (simulated water intake) and 25mmol/L H2O2And absorbance was measured at 30, 120 and 360min, and the first recycling rate of CuNCs/C was calculated, followed by repetition up to the sixth. The results are shown in FIG. 5.
As can be seen from FIG. 5, after 6 times of recycling, the degradation rate of the amino black 10B in 30min is reduced from 61.3% to 51.7%, the degradation rate of 120min is reduced from 79.8% to 70.1%, and the degradation rate of 360min is reduced from 94.5% to 83.1%, so that the average removal rate of the CuNCs/C after 6 times of recycling to the amino black 10B is reduced by less than 10%, and the average degradation rate after 360min is 87.8%, which indicates that the CuNCs/C catalyst has good reusability and better application prospect. After 6 times of repeated use, the small reduction of the degradation rate of the amino black 10B is probably because a small amount of Cu is precipitated in the reaction process of the CuNCs/C catalyst2+And is lost with the discharge of the solution.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. A fluorescent copper nanocluster-carbon composite catalyst is characterized in that the catalyst is a carbon material doped copper nanocluster.
2. The method of using the fluorescent copper nanocluster-carbon composite catalyst as recited in claim 1, wherein the method is used for catalyzing hydrogen peroxide to generate hydroxyl radicals.
3. The method of use according to claim 2, wherein the method is used for catalytic Fenton-like reactions.
4. The method for preparing the fluorescent copper nanocluster-carbon composite catalyst as recited in claim 1, wherein the copper nanocluster-carbon composite catalyst is prepared by dissolving a soluble copper salt in an L-cysteine solution, adding a carbon material powder, stirring uniformly, adding a sodium hydroxide solution, stirring for reaction at a reaction temperature of 50-60 ℃, and freeze-drying after the reaction is completed.
5. The method for preparing the fluorescent copper nanocluster-carbon composite catalyst as recited in claim 4, wherein the soluble copper salt is one or more of copper chloride, copper nitrate and copper sulfate.
6. The method for preparing the fluorescent copper nanocluster-carbon composite catalyst according to claim 4, wherein the concentration of copper ions in a reaction system is 0.1 to 0.3 mmol/L.
7. The method for preparing the fluorescent copper nanocluster-carbon composite catalyst according to claim 4, wherein the concentration of the L-cysteine solution is 0.1-0.5 mol/L.
8. The method for preparing the fluorescent copper nanocluster-carbon composite catalyst as recited in claim 4, wherein the carbon material is one or more of biochar, carbon nanotube, carbon nanofiber or nanocarbon sphere, and the addition amount is 0.02-0.1 g/L.
9. The method for preparing the fluorescent copper nanocluster-carbon composite catalyst according to claim 4, wherein the concentration of the sodium hydroxide solution is 1.0mol/L, and the stirring reaction time is 2-8 h.
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