CN111229251A - Ag/Cu2O composite material and preparation method and application thereof - Google Patents
Ag/Cu2O composite material and preparation method and application thereof Download PDFInfo
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- CN111229251A CN111229251A CN202010115081.5A CN202010115081A CN111229251A CN 111229251 A CN111229251 A CN 111229251A CN 202010115081 A CN202010115081 A CN 202010115081A CN 111229251 A CN111229251 A CN 111229251A
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 21
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000004098 Tetracycline Substances 0.000 claims abstract description 16
- 229960002180 tetracycline Drugs 0.000 claims abstract description 16
- 229930101283 tetracycline Natural products 0.000 claims abstract description 16
- 235000019364 tetracycline Nutrition 0.000 claims abstract description 16
- 150000003522 tetracyclines Chemical class 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 98
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 16
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000007853 buffer solution Substances 0.000 claims description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 11
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 11
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 239000012265 solid product Substances 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 230000003115 biocidal effect Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 229960003638 dopamine Drugs 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000005447 environmental material Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 15
- 230000004913 activation Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 241000237536 Mytilus edulis Species 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003640 drug residue Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention belongs to the technical field of preparation of environmental materials, and particularly relates to Ag/Cu2O composite material and its preparation method and application. The invention takes dopamine as a connecting agent and a reducing agent to cover the PDA in-situ growth on Cu2Surface of OAg by utilizing abundant groups on the surface of PDA+Adsorption on Cu2O surface, and finally the self-reducing ability of PDA to convert Ag+Reducing into Ag nano particles to realize Ag/Cu2And preparing the O composite material and removing the antibiotic residues in the water body. Ag/Cu prepared by the invention2The O composite material effectively activates PS to generate free radicals with strong oxidizing capability, thereby showing good tetracycline removing capability of the catalyst and realizing water purification. The preparation method disclosed by the invention expands the application of the Cu (I) -based material in activating PS to degrade pollutants; the used material is a biological derivative material, is nontoxic and environment-friendly, is simple and convenient to operate, has a good antibiotic removal effect, and is a safe and efficient treatment technology.
Description
Technical Field
The invention belongs to the technical field of preparation of environmental materials, and particularly relates to Ag/Cu2O composite material and its preparation method and application.
Background
Tetracycline (TC) is a drug residue widely existing in water environment, and poses serious threat to human health, and is particularly important and urgent for removing antibiotic pollutants in the water environment. In recent years, Advanced Oxidation technology (Advanced Oxidation Process) based on sulfate radicals has received a wide attention due to its good ability to degrade environmental pollutants. The main activation method is that Peroxymonosulfate (PMS) or Peroxydisulfate (PS) is activated by heat, ultraviolet or ultrasonic wave and then can be converted into sulfate radical (SO)4 .-). Compared to these activation methods, the activation of persulfate salts with transition metals is of more interest because of the lower energy consumption required. Among them, copper is considered to be one of the most effective metals, and it occurs mainly in the copper (cu (ii)) oxidation state, because cu (i) is unstable and is easily oxidized by some oxidizing agents. However, Cu (II) has poor activation performance for PMS/PS, since Cu (II) only acts as an electron acceptor, while Cu (I) has the potential to activate PMS/PS and induce SO4 .-And ‧ OH formation. Although Cu (I) can be used as a good activator for PMS/PS, the system has certain limitations, such as instability of Cu (I), which can reduce the oxidation rate. Whether the copper can be utilized to activate PS to generate sulfate radicals for treating wastewater pollutants or not is not reported in relevant researches at present.
Disclosure of Invention
In view of the above, the object of the present invention is to provide an Ag/Cu alloy2O composite material and its preparation method and application. The Ag/Cu2The O composite material takes dopamine (PDA) as reductionDepositing Ag nano particles and modifying Cu2O is used for activating PS to generate sulfate radicals for treating wastewater pollutants, and is particularly applied to treating antibiotics in water environment.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides Ag/Cu2The preparation method of the O composite material specifically comprises the following steps:
（1）Cu2preparation of O material: adding a copper nitrate trihydrate solution, dropwise adding a sodium hydroxide solution and glucose, reacting in a water bath for a period of time, washing an obtained solid product, and drying in vacuum to obtain Cu2O powder;
（2）PDA/Cu2preparation of O: mixing the Cu prepared in the step (1)2Dispersing O in deionized water by ultrasonic, adding dopamine hydrochloride, mixing uniformly, adding Tris-HCl buffer solution, continuing stirring, centrifuging, washing and drying in vacuum to obtain PDA/Cu2O；
(3) Ag/Cu excited by PDA2Preparing an O composite material: the PDA/Cu prepared in the step (2)2O ultrasonic dispersion is carried out, silver nitrate solution is added into deionized water, the product is centrifuged after stirring reaction, the deionized water and ethanol are washed, and the Ag/Cu is obtained after vacuum drying2And (3) an O composite material.
The concentration of the copper nitrate trihydrate solution in the step (1) is 83.33-125 mmol/L.
In the step (1), the dosage relationship of the copper nitrate trihydrate, the sodium hydroxide solution and the glucose is 1.208 g: 10 mL of: 0.8-1.5 g; the concentration of the sodium hydroxide solution is 3-4 mol/L.
The temperature of the water bath reaction in the step (1) is 50-70 ℃; the period of time is 30-40 min; the temperature of vacuum drying is 60-80 ℃.
The deionized water in the step (2) is used in an amount capable of effectively dispersing Cu2O; the addition amount of dopamine hydrochloride and Cu2The mass ratio of O is 1-2: 2.
the concentration of the Tris-HCl buffer solution in the step (2) is 5 mmol/L; the dosage of the Tris-HCl buffer solution is 80-100 mL of the Tris-HCl buffer solution added in every 100 mg of dopamine hydrochloride.
The continuous stirring time in the step (2) is 10-14 hours, and the vacuum drying temperature is 60-80 ℃.
Dispersing PDA/Cu in step (3)2The deionized water of O is used in an amount capable of being uniformly dispersed; PDA/Cu in step (3)2The mass ratio of O to silver nitrate is 25: 1 to 10.
The stirring reaction time in the step (3) is 20-40 min; the temperature of the vacuum drying is 60-80 ℃.
The invention also provides Ag/Cu prepared by the preparation method2O composite material, said Ag/Cu2O composite material in Cu2The surface of O is covered with a PDA layer in situ, Ag particles are deposited on Cu2And (4) surface O.
The invention also provides Ag/Cu prepared by the preparation method2The application of the O composite material in degrading antibiotics in wastewater is further characterized in that tetracycline in a water body is degraded.
Further, the application is Ag/Cu2The O composite material and the PS jointly degrade the tetracycline.
The invention has the beneficial effects that:
the invention is inspired by the composition of mussel and shellfish bioadhesive protein, takes dopamine (PDA) with environmental protection and biocompatibility as a connecting agent and a reducing agent, and firstly covers the PDA in situ in Cu through autopolymerization2Surface of O, then use rich groups of PDA surface to convert Ag+Adsorption on Cu2O surface, and finally the self-reducing ability of PDA to convert Ag+Reducing into Ag nano particles to realize Ag/Cu2And preparing the O composite material and removing the antibiotic residues in the water body. Ag/Cu prepared by the invention2The O composite material is added with zero-valent silver to induce and activate continuous production, and the Cu (I) is regenerated from the Cu (II), so that PS is effectively activated to generate free radicals with strong oxidation capacity, thereby showing the good removal capacity of the catalyst on tetracycline and realizing water purification. The preparation method disclosed by the invention expandsThe Cu (I) based material activates PS to degrade pollutants; the used material is a biological derivative material, is nontoxic and environment-friendly, is simple and convenient to operate, has a good antibiotic removal effect, and is a safe and efficient treatment technology.
Drawings
FIG. 1 is an XRD pattern of the prepared material demonstrating the crystalline structure of the material;
FIG. 2 is an SEM photograph of the material, and Cu can be seen2The morphology of O and the successful deposition of Ag nanoparticles;
fig. 3 is a graph of PS activation degradation of the resulting material, showing that the performance of the composite material is improved.
Detailed Description
The present invention will be further described by the following examples, however, the scope of the present invention is not limited to the following examples. The present invention has been described generally and/or specifically with respect to materials used in testing and testing methods. The following examples are examples of experimental methods not indicating specific conditions, and the detection is usually carried out according to conventional conditions or according to the conditions recommended by the manufacturers. The reagents used in the following examples were commercially available, dopamine hydrochloride in the present invention was purchased from Aladdin reagent, Inc., and Tris-HCl buffer, copper nitrate trihydrate, sodium hydroxide, glucose, tetracycline, ethanol were purchased from pharmaceutical Chemicals, Inc.
Evaluation of catalytic activity of the catalyst prepared in the present invention: the method comprises the following steps of (1) carrying out in a beaker, adding 100 mL of tetracycline simulation wastewater into the beaker under a dark condition, measuring an initial value of the tetracycline simulation wastewater, then adding the prepared catalyst and PS, carrying out magnetic stirring to keep the catalyst in a suspension or floating state, sampling and analyzing every 5 min, carrying out centrifugal separation, taking supernatant, measuring absorbance by using a spectrophotometer, and carrying out a formula: ƞ = [ (1-C)t/C0)]x100% to calculate the degradation rate, where C0Absorbance of the tetracycline solution to reach adsorption equilibrium, CtThe absorbance of the tetracycline solution was determined for the timed samples.
Example 1:
（1）Cu2o materialThe preparation of (1):
1.208 g of copper nitrate trihydrate is dissolved in 60 mL of deionized water, 10 mL of sodium hydroxide (3 mol/L) solution is dripped, 0.8g of glucose is added as a reducing agent, after the reaction in water bath at 50 ℃ for 40min, the obtained solid product is washed for a plurality of times by deionized water and ethanol, and the Cu is obtained after the vacuum drying at 60 ℃2O powder;
（2）PDA/Cu2preparation of O:
taking 200 mg of Cu prepared in the step (1)2Dispersing O in 30 mL deionized water by ultrasonic, adding 200 mg dopamine hydrochloride, stirring uniformly, adding 160 mL Tris-HCl buffer solution (5 mmol/L), stirring continuously at room temperature for 10 hours, centrifuging and washing the product, and drying in vacuum at 80 ℃ to obtain PDA/Cu2O；
(3) Ag/Cu excited by PDA2Preparing an O composite material:
taking 100 mg of PDA/Cu prepared in the step (2)2Dispersing O in 10 mL deionized water by ultrasonic, adding 2 mL silver nitrate solution (2 mg/mL), stirring at room temperature for reaction for 20min, centrifuging, washing with deionized water and ethanol, and vacuum drying at 80 deg.C to obtain Ag/Cu excited by PDA2And (3) an O composite material.
Prepared Ag/Cu2The O composite material is put into a photochemical reactor for a photocatalytic degradation test, and the total removal rate of the composite material to the tetracycline reaches 80 percent in 30 minutes.
Example 2:
（1）Cu2preparation of O material:
1.208 g of copper nitrate trihydrate is dissolved in 40 mL of deionized water, 10 mL of sodium hydroxide (4 mol/L) solution is added dropwise, 1.2 g of glucose is added as a reducing agent, after the mixture reacts in water bath at the temperature of 60 ℃ for half an hour, the obtained solid is washed for a plurality of times by deionized water and ethanol, and the Cu is obtained after vacuum drying at the temperature of 60 DEG2O powder;
（2）PDA/Cu2preparation of O:
taking 200 mg of Cu prepared in the step (1)2Dispersing O in 30 mL deionized water by ultrasonic, adding 100 mg dopamine hydrochloride, stirring uniformly, adding 80 mL Tris-HCl buffer solution (5 mm)ol/L), continuously stirring and reacting for 14 hours at room temperature, centrifuging, washing, and then drying in vacuum at 60 ℃ to obtain PDA/Cu2O；
(3) Ag/Cu excited by PDA2Preparing an O composite material:
taking 100 mg of PDA/Cu prepared in the step (2)2Dispersing O in 10 mL deionized water by ultrasonic, adding 2 mL silver nitrate solution (5 mg/mL), stirring at room temperature for reaction for 30min, centrifuging, washing with deionized water and ethanol, and vacuum drying at 60 deg.C to obtain Ag/Cu2And (3) an O composite material.
Prepared Ag/Cu2The O composite material is put into a photochemical reactor for a photocatalytic degradation test, and the total removal rate of the composite material to the tetracycline reaches 87 percent in 30 minutes.
Example 3:
（1）Cu2preparation of O material:
1.208 g of copper nitrate trihydrate is dissolved in 60 mL of deionized water, 10 mL of sodium hydroxide (3 mol/L) solution is added dropwise, 1.5 g of glucose is added as a reducing agent, after the mixture reacts in 70 ℃ water bath for half an hour, the obtained solid is washed for a plurality of times by deionized water and ethanol, and the Cu is obtained after vacuum drying at 60 DEG2O powder;
（2）PDA/Cu2preparation of O:
taking 200 mg of Cu prepared in the step (1)2Dispersing O in 30 mL deionized water by ultrasonic, adding 100 mg dopamine hydrochloride, stirring uniformly, adding 80 mL Tris-HCl buffer solution (5 mmol/L), stirring at room temperature for reaction for 12 hours, centrifuging, washing, and vacuum drying at 60 ℃ to obtain PDA/Cu2O；
(3) Ag/Cu excited by PDA2Preparing an O composite material:
taking 100 mg of PDA/Cu prepared in the step (2)2Dispersing O in 10 mL deionized water by ultrasonic, adding 2 mL silver nitrate solution (10 mg/mL), stirring at room temperature for reaction for 30min, centrifuging, washing with deionized water and ethanol, and vacuum drying at 60 deg.C to obtain Ag/Cu2And (3) an O composite material.
Prepared Ag/Cu2The O composite material is put into a photochemical reactorAnd (3) carrying out a photocatalytic degradation test, and measuring that the total removal rate of the composite material to the tetracycline reaches 95% in 30 minutes.
FIG. 1 shows Cu prepared in this example2O and Ag/Cu2XRD pattern of O composite; as can be seen in FIG. 1, Cu2The XRD characteristic peak of O completely corresponds to that of a standard card, and Ag/Cu2Removing corresponding Cu from XRD pattern of O composite material2Besides the characteristic peak of O, the characteristic peak of Ag is also found, which indicates that PDA successfully reduces Ag+Preparation of Ag deposited Cu2And (3) an O composite material.
FIG. 2 shows Cu prepared in this example2O and Ag/Cu2SEM image of O composite; wherein a is Cu2O, b is Ag/Cu2An O composite material; as can be seen from FIG. 2, Cu2The O material is a polyhedron with smooth surface; Ag/Cu2After the O composite material deposits Ag, a plurality of silver particles are loaded on the surface, and the dopamine is proved to effectively attach and reduce Ag ions into Ag monomers in Cu2Surface of O.
Example 4:
（1）Cu2preparation of O material:
1.208 g of copper nitrate trihydrate is dissolved in 60 mL of deionized water, 10 mL of sodium hydroxide (3 mol/L) solution is added dropwise, 1.2 g of glucose is added as a reducing agent, after the mixture reacts in water bath at the temperature of 60 ℃ for half an hour, the obtained solid is washed for a plurality of times by the deionized water and ethanol, and the Cu is obtained after vacuum drying at the temperature of 60 DEG2O powder;
（2）PDA/Cu2preparation of O:
200 mg of Cu prepared in step (1)2Dispersing O in 30 mL deionized water by ultrasonic, adding 100 mg dopamine hydrochloride, stirring uniformly, adding 80 mL Tris-HCl buffer solution (5 mmol/L), stirring at room temperature for reaction for 12 hours, centrifuging, washing, and vacuum drying at 80 ℃ to obtain PDA/Cu2O；
(3) Ag/Cu excited by PDA2Preparing an O composite material:
taking 100 mg of PDA/Cu prepared in the step (2)2O is dispersed in 10 mL of deionized water by ultrasonic, then 2 mL of silver nitrate solution (20 mg/mL) is added, and the reaction is stirred at room temperature for 40miAfter n, centrifuging, washing with deionized water and ethanol, and drying in vacuum at 60 ℃ to obtain Ag/Cu2And (3) an O composite material.
Prepared Ag/Cu2The O composite material is put into a photochemical reactor for a photocatalytic degradation test, and the total removal rate of the composite material to tetracycline reaches 78 percent in 30 minutes.
FIG. 3 is Ag/Cu prepared in each example2A graph comparing the degradation rate curves of the O composite materials; atlas proves Cu2O has PS activation capacity, so that catalytic degradation is realized, more particularly, the deposition of Ag further strengthens the PS activation capacity, and shows higher catalytic degradation capacity.
While embodiments of the invention have been shown and described above, it is to be understood that the above embodiments are exemplary and not to be construed as limiting the invention, and that various embodiments or examples and features of various embodiments or examples described in this specification are capable of being combined and brought together by those skilled in the art without thereby conflicting with each other.
Claims (10)
1. Ag/Cu2The preparation method of the O composite material is characterized by comprising the following steps:
（1）Cu2preparation of O material: adding a copper nitrate trihydrate solution, dropwise adding a sodium hydroxide solution and glucose, reacting in a water bath for a period of time, washing an obtained solid product, and drying in vacuum to obtain Cu2O powder;
（2）PDA/Cu2preparation of O: mixing the Cu prepared in the step (1)2Dispersing O in deionized water by ultrasonic, adding dopamine hydrochloride, mixing uniformly, adding Tris-HCl buffer solution, continuing stirring, centrifuging, washing and drying in vacuum to obtain PDA/Cu2O；
(3) Ag/Cu excited by PDA2Preparing an O composite material: the PDA/Cu prepared in the step (2)2Dispersing O in deionized water by ultrasonic, adding silver nitrate solution, stirring, reacting, centrifuging, washing with deionized water and ethanol, and vacuum drying to obtain Ag/Cu2And (3) an O composite material.
2. Ag/Cu according to claim 12The preparation method of the O composite material is characterized in that the concentration of the copper nitrate trihydrate solution in the step (1) is 83.33-125 mmol/L.
3. Ag/Cu according to claim 12The preparation method of the O composite material is characterized in that the dosage relationship of the copper nitrate trihydrate, the sodium hydroxide solution and the glucose in the step (1) is 1.208 g: 10 mL of: 0.8-1.5 g; the concentration of the sodium hydroxide solution is 3-4 mol/L.
4. Ag/Cu according to claim 12The preparation method of the O composite material is characterized in that the temperature of the water bath reaction in the step (1) is 50-70 ℃; the time is 30-40 min; the temperature of vacuum drying is 60-80 ℃.
5. Ag/Cu according to claim 12The preparation method of the O composite material is characterized in that the deionized water in the step (2) is used in an amount capable of effectively dispersing Cu2O; the addition amount of dopamine hydrochloride and Cu2The mass ratio of O is 1-2: 2.
6. Ag/Cu according to claim 12The preparation method of the O composite material is characterized in that the concentration of the Tris-HCl buffer solution in the step (2) is 5 mmol/L; the dosage of the Tris-HCl buffer solution is 80-100 mL of the Tris-HCl buffer solution added in every 100 mg of dopamine hydrochloride.
7. Ag/Cu according to claim 12The preparation method of the O composite material is characterized in that the continuous stirring time in the step (2) is 10-14 hours, and the vacuum drying temperature is 60-80 ℃.
8. Ag/Cu according to claim 12The preparation method of the O composite material is characterized in thatIn step (3), PDA/Cu2The mass ratio of O to silver nitrate is 25: 1 to 10.
9. Ag/Cu according to claim 1 to 82Ag/Cu prepared by preparation method of O composite material2The O composite material is characterized in that the Ag/Cu2O composite material in Cu2The surface of O is covered with a PDA layer in situ, Ag particles are deposited on Cu2And (4) surface O.
10. Ag/Cu according to claim 92The application of the O composite material in degrading tetracycline in water.
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| CN114950509A (en) * | 2022-05-31 | 2022-08-30 | 齐齐哈尔大学 | Catalyst for microwave activation persulfate rapid oxidative degradation of PPCPs wastewater and preparation and application methods thereof |
| CN114950509B (en) * | 2022-05-31 | 2023-06-20 | 齐齐哈尔大学 | Microwave activated persulfate rapid oxidative degradation PPCPs wastewater catalyst and preparation and application methods thereof |
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