CN116639788A - Water treatment method for enhancing oxidation of high-valence metal by carbon quantum dots - Google Patents
Water treatment method for enhancing oxidation of high-valence metal by carbon quantum dots Download PDFInfo
- Publication number
- CN116639788A CN116639788A CN202310749960.7A CN202310749960A CN116639788A CN 116639788 A CN116639788 A CN 116639788A CN 202310749960 A CN202310749960 A CN 202310749960A CN 116639788 A CN116639788 A CN 116639788A
- Authority
- CN
- China
- Prior art keywords
- carbon quantum
- quantum dots
- concentration
- treatment method
- water treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 185
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 15
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 64
- 239000000243 solution Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 6
- 231100000719 pollutant Toxicity 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 51
- 239000000126 substance Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000003014 reinforcing effect Effects 0.000 claims description 7
- 238000001308 synthesis method Methods 0.000 claims description 6
- 238000006056 electrooxidation reaction Methods 0.000 claims description 4
- 238000010891 electric arc Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 238000000608 laser ablation Methods 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 2
- 229940088710 antibiotic agent Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 50
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 14
- 239000007800 oxidant agent Substances 0.000 abstract description 13
- 230000001590 oxidative effect Effects 0.000 abstract description 7
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 59
- DCOPUUMXTXDBNB-UHFFFAOYSA-N diclofenac Chemical compound OC(=O)CC1=CC=CC=C1NC1=C(Cl)C=CC=C1Cl DCOPUUMXTXDBNB-UHFFFAOYSA-N 0.000 description 42
- 229960001259 diclofenac Drugs 0.000 description 42
- 239000002351 wastewater Substances 0.000 description 41
- 239000007853 buffer solution Substances 0.000 description 32
- 239000012452 mother liquor Substances 0.000 description 24
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 18
- 239000000356 contaminant Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- 239000011572 manganese Substances 0.000 description 12
- -1 ferrates Chemical compound 0.000 description 10
- 239000010413 mother solution Substances 0.000 description 10
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 9
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 9
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 9
- 239000004021 humic acid Substances 0.000 description 9
- 229960001680 ibuprofen Drugs 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 8
- 229910001424 calcium ion Inorganic materials 0.000 description 8
- 229910001425 magnesium ion Inorganic materials 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 7
- RULKYXXCCZZKDZ-UHFFFAOYSA-N 2,3,4,5-tetrachlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C(Cl)=C1Cl RULKYXXCCZZKDZ-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 6
- 229910021397 glassy carbon Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229960005404 sulfamethoxazole Drugs 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- YKJOVEVYXKEPGB-UHFFFAOYSA-N 1,2-oxazol-3-ylmethanesulfonic acid Chemical compound OS(=O)(=O)CC=1C=CON=1 YKJOVEVYXKEPGB-UHFFFAOYSA-N 0.000 description 2
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229960003742 phenol Drugs 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229960003500 triclosan Drugs 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C02F2101/345—Phenols
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
A water treatment method for enhancing oxidation of high-valence metal by carbon quantum dots belongs to the technical field of water treatment and solves the problems existing in the prior art. The method comprises the following steps: adding the carbon quantum dot solution and potassium permanganate or potassium ferrate into the polluted water to be treated in sequence, and treating for 10-60 min under the stirring condition to obtain the water. The invention has excellent pollutant removal effect in the pH range of 4-8, excellent oxidation efficiency and faster reaction rate; under complex water quality, good efficiency is maintained, and the method is beneficial to application in actual engineering. In the potassium ferrate/carbon quantum dot system, the removal effect of organic pollutants is improved by 10-40%, and the oxidation reaction rate is improved by 1.1-22.8 times. In the potassium permanganate/carbon quantum dot system, the removal effect of organic pollutants is improved by 0.1 to 6.4 times; the electron transfer efficiency is enhanced, the utilization efficiency of the oxidant is improved, and the pollutant degradation effect is enhanced. The invention is suitable for water treatment.
Description
Technical Field
The invention belongs to the technical field of water treatment; in particular to a water treatment method for enhancing oxidation of high-valence metal by using carbon quantum dots.
Background
With the continuous progress of society, human activities have led to more and more environmental pollutionThe pollution problem, especially the organic matters with high risk and potential threat to ecological safety are discharged into the water body, so that serious water environment pollution is caused. Advanced oxidation technology is a chemical technology for highly treating organic matters with high efficiency, and commonly used oxidants comprise ozone, persulfates, fenton systems, fenton-like systems, high-valence metals and the like. Among them, the high valence metal oxides represented by ferrate and permanganate are considered as a green, multifunctional and efficient oxidant because of their high oxidation-reduction potential and their good adsorption capacity of the reduced products. Although high valence metal oxidants can oxidatively degrade many types of organic contaminants, their effectiveness is not high in some reactions. Since iron in the intermediate valence state (tetravalent iron Fe (IV), pentavalent iron Fe (V)) and manganese in the intermediate valence state (trivalent manganese Mn (III), tetravalent manganese Mn (IV), pentavalent manganese Mn (V), hexavalent manganese Mn (VI)) have higher reactivity, a great deal of research has focused on the excitation of high valence metal oxidants with reducing substances to produce intermediate valence active species, such as metals (divalent manganese Mn (II), divalent iron Fe (II), divalent cobalt Co (II)), nonmetallic species (sulfite SO 3 2- Thiosulfate S 2 O 3 2- Hydroxylamine NH 2 OH) and carbonaceous materials (carbon nanotubes, graphene, biochar, hydrothermal carbon). In recent years, with the advancement of the two-carbon policy, recycling of carbon represented by a carbon-based catalyst has been actively progressed. Carbonaceous materials can be classified into zero dimension (e.g., carbon quantum dots), one dimension (e.g., carbon nanotubes), two dimension (e.g., graphene), and three dimension (e.g., biochar) according to dimensions. Although characterization experiments and probe compound experiments prove that carbonyl c=o functional groups on one-dimensional, two-dimensional and three-dimensional carbon materials are active sites for exciting high-valence metal oxidants to generate intermediate-state active species, the carbon materials are excited to generate intermediate-state oxidation active species to consume oxidants, and meanwhile, in an actual water body, a complex water body environment consumes oxidants, so that the oxidant utilization efficiency is low. Therefore, it is necessary to seek more efficient sustainable and green carbon materials to strengthen higher valence metal oxidants.
Disclosure of Invention
The invention aims to solve the technical problems and provides a water treatment method for reinforcing oxidation of high-valence metal by using carbon quantum dots.
The water treatment method for reinforcing high-valence metal oxidation by using the carbon quantum dots is realized according to the following processes:
and sequentially adding the carbon quantum dot solution and potassium permanganate or potassium ferrate into the polluted water to be treated, and treating for 10-60 min under the stirring condition to finish the water treatment method.
Further, the concentration of the carbon quantum dot solution in the polluted water to be treated is 2-20 mg/L.
Further, the concentration of the potassium permanganate or the potassium ferrate in the polluted water to be treated is 30-100 mu mol/L.
Further, the pH value of the polluted water to be treated is 4-9.
Further, the preparation method of the carbon quantum dot solution comprises the following steps: the preparation method is carried out by adopting the existing microwave synthesis method, thermal decomposition method, hydrothermal treatment method, template path method, plasma treatment method, arc discharge treatment method, laser ablation method, electrochemical oxidation method, chemical oxidation method or ultrasonic synthesis method.
The principle of the invention is mainly as follows:
the sulfoxide probe experiment proves that in the ferrate/carbon quantum dot system, intermediate states Fe (IV) and Fe (V) are one of active species, but are not the reasons for causing the strengthening effect. The open circuit voltage experiment proves that the oxidation-reduction potential of the glassy carbon electrode coated with the carbon quantum dot is higher than that of an uncoated glassy carbon electrode, and the experiment shows that the voltage of a reaction system is reduced along with the sequential addition of potassium ferrate and organic pollutants (phenol) respectively, so that the organic matters consume the oxidant. In addition, an open-circuit current experiment also proves that in a three-electrode reaction system which takes a glassy carbon electrode coated with carbon quantum dots as a working electrode, potassium ferrate is added to cause the current to drop instantaneously; the subsequent addition of organic contaminants, the current is further significantly reduced, indicating that electrons on the organic species can be transferred to potassium ferrate via carbon quantum dots, mediating direct electron transfer. The carbon quantum dots have conductivity, and can generate a new direct electron transfer mechanism after being combined with the potassium ferrate, thereby promoting the utilization efficiency of electrons and improving the oxidation efficiency of organic matters.
The invention proves that the intermediate manganese is not an active species with strengthening effect in a permanganate/carbon quantum dot system through sulfoxide probe experiments and ultraviolet-visible spectrum experiments. The open circuit voltage experiment proves that the oxidation-reduction potential of the glassy carbon electrode coated with the carbon quantum dot is higher than that of an uncoated glassy carbon electrode, and the experiment shows that the voltage of a reaction system is reduced along with the sequential addition of potassium permanganate and organic pollutants (diclofenac) respectively, so that the organic matters consume the oxidant. In addition, an open-circuit current experiment also proves that in a three-electrode reaction system which takes a glassy carbon electrode coated with carbon quantum dots as a working electrode, potassium permanganate is added to cause the current to drop instantaneously; and then adding an organic substance, and further obviously reducing the current, which indicates that electrons on the organic substance can be transferred to potassium permanganate through carbon quantum dots, and direct electron transfer is mediated. The carbon quantum dots have conductivity, and after the carbon quantum dots are combined with the potassium permanganate, a new direct electron transfer mechanism can be generated, so that the electron utilization efficiency is promoted, and the oxidation efficiency of organic matters is improved.
The invention has the beneficial effects that:
1. the invention takes phenols (phenol), bisphenol A (BPA), tetrachlorophenol (4-CP), p-hydroxybenzoic acid (p-HBA), antibiotics (sulfamethoxazole (SMX), ibuprofen (IBP), and Diclofenac (DCF)) as examples, experiments prove that the effect of removing organic pollutants by 10-40% is improved by carbon quantum dot enhanced potassium ferrate (Fe (VI) +CQDs), the reaction rate is improved by 1.1-22.8 times, the effect of removing organic pollutants by 0.1-6.4 times by carbon quantum dot enhanced potassium permanganate is improved by 1.1-6.8 times, and simultaneously, the iron-manganese oxide generated after oxidation of high-valence metal is coupled with the carbon quantum dot, thereby being beneficial to realizing solid-liquid separation without secondary pollution - Hydrogen phosphate ion H 2 PO 4 - Sulfate radical SO 4 2- Bicarbonate ion HCO 3 - Ca ion Ca 2+ Mg of magnesium ion 2+ The humic acid HA and the actual water body), the water treatment method for enhancing the oxidation of the high-valence metal by the carbon quantum dots is found to have good water-change interference resistance, and the carbon quantum dots enhance the reaction rate by enhancing the potassium ferrate/potassium permanganate, thereby being beneficial to the application of the method in the actual engineering.
2. Experiments prove that the water treatment method for reinforcing the oxidation of the high-valence metal by the carbon quantum dots has wide pH application range and excellent removal effect in the pH range of 4-8.
According to the water treatment method for enhancing oxidation of high-valence metal by using carbon quantum dots, for a potassium ferrate system, the optimal pH value range of polluted water to be treated is 4-8, and the treatment effect is nearly consistent in the range; for the potassium permanganate system, the optimal pH value of the polluted water to be treated is 4, the treatment effect is basically stable along with the gradual increase of the pH value, and only the reaction rate is reduced.
3. Experiments prove that the water treatment method for reinforcing the oxidation of the high-valence metal by the carbon quantum dots has excellent oxidation efficiency and higher reaction rate. In the potassium ferrate/carbon quantum dot system, the removal effect of organic pollutants is improved by 10-40%, and the oxidation reaction rate is improved by 1.1-22.8 times. In the potassium permanganate/carbon quantum dot system, the removal effect of organic pollutants is improved by 0.1 to 6.4 times.
4. The invention has good water quality change interference resistance, and under different water quality backgrounds (chloride ions, hydrogen phosphate ions, hydrogen carbonate ions, calcium ions, magnesium ions, humic acid and actual water bodies), the removal efficiency of the potassium ferrate/carbon quantum dot system is obviously improved compared with that of a non-reinforced system; for the potassium permanganate/carbon quantum dot system, the removal effect is not affected by background factors basically, and even in the presence of hydrogen phosphate ions, the removal effect is further enhanced. Experiments in practical water bodies also prove that the potassium ferrate/carbon quantum dot system is superior to a potassium ferrate system alone; the potassium permanganate/carbon quantum dot system is superior to the potassium permanganate system alone. The effect proves that the water treatment method for reinforcing the oxidation of the high-valence metal by the carbon quantum dots is beneficial to the application in practical engineering.
5. The invention strengthens the electron transfer efficiency, improves the utilization efficiency of the oxidant, enhances the degradation effect on organic pollutants in water, and improves the reaction rate.
The invention is suitable for water treatment.
Drawings
FIG. 1 is a bar graph of the results of the test of carbon quantum dots, ferrates, and carbon quantum dot-enhanced ferrate systems of examples 2, 3, and 4 for the removal of 7 typical contaminating organics;
FIG. 2 is a bar graph of the results of the test of the carbon quantum dot, permanganate and carbon quantum dot enhanced permanganate systems of examples 2, 3 and 4 to remove 7 typical contaminant organics;
FIG. 3 is a kinetic test result of ferrate and carbon quantum dot enhanced ferrate system of example 4 for removal of 7 typical contaminating organics;
FIG. 4 is a graph of a kinetic fit of the carbon quantum dot enhanced ferrate system of example 5 to phenol oxidation in a simulated contaminated water body at pH=5, pH=6, pH=7;
FIG. 5 is a graph of a kinetic fit of the carbon quantum dot enhanced ferrate system of example 5 to phenol oxidation in a simulated contaminated water body at pH=8 and pH=9;
FIG. 6 is a graph of the phenol removal effect of the carbon quantum dot enhanced ferrate system of example 5 on a simulated contaminated water body with pH=5, pH=6, and pH=7;
FIG. 7 is a graph of the effect of the carbon quantum dot enhanced ferrate system of example 5 on phenol removal from a simulated contaminated water body at pH=8 and pH=9;
FIG. 8 is a graph of the removal of DCF from a simulated contaminated water body of pH=4 and pH=5 using the carbon quantum dot enhanced permanganate system of example 6;
FIG. 9 is a graph of the removal of DCF from a simulated contaminated water body of pH=6 and pH=7 using the carbon quantum dot enhanced permanganate system of example 6;
FIG. 10 is a graph of the removal of DCF from a simulated contaminated water body of pH=8 and pH=9 using the carbon quantum dot enhanced permanganate system of example 6;
FIG. 11 is a graph of test results of the effect of different water quality background influencing factors on the phenol removal effect of the carbon quantum dot enhanced ferrate system in example 7;
FIG. 12 is a graph of test results of the effect of different water quality background influencing factors on the phenol removal effect of the carbon quantum dot enhanced ferrate system in example 7;
FIG. 13 is a graph of test results of the effect of different water quality background influencing factors on the phenol removal effect of the carbon quantum dot enhanced ferrate system in example 7;
FIG. 14 is a graph showing the results of the test of the change in open circuit voltage and current for potassium ferrate and phenol addition in example 7;
FIG. 15 is a graph of test results of the effect of different water quality background influencing factors on DCF removal by the carbon quantum dot reinforced permanganate system in example 8;
FIG. 16 is a graph of test results of the effect of different water quality background influencing factors on DCF removal by the carbon quantum dot reinforced permanganate system in example 8;
FIG. 17 is a graph of test results of the effect of different water quality background influencing factors on DCF removal by the carbon quantum dot reinforced permanganate system in example 8;
FIG. 18 is a graph of test results of the effect of different water quality background influencing factors on DCF removal by the carbon quantum dot reinforced permanganate system in example 8;
FIG. 19 is a graph showing the results of the test of the open circuit voltage and current changes by adding potassium permanganate and DCF in example 8.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.
The first embodiment is as follows: in the embodiment, the water treatment method for strengthening the oxidation of the high-valence metal by the carbon quantum dots is realized according to the following process:
and sequentially adding the carbon quantum dot solution and potassium permanganate or potassium ferrate into the polluted water to be treated, and treating for 10-60 min under the stirring condition to finish the water treatment method.
The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the concentration of the carbon quantum dot solution in the polluted water to be treated is 2-20 mg/L. Other steps and parameters are the same as in the first embodiment.
And a third specific embodiment: the difference between the present embodiment and the second embodiment is that the concentration of the carbon quantum dot solution in the polluted water to be treated is 4mg/L. Other steps and parameters are the same as in the second embodiment.
The specific embodiment IV is as follows: the difference between the present embodiment and the second embodiment is that the concentration of the carbon quantum dot solution in the polluted water to be treated is 8mg/L. Other steps and parameters are the same as in the second embodiment.
Fifth embodiment: the present embodiment differs from the first embodiment in that the concentration of potassium permanganate or ferrate in the contaminated water to be treated is 30 to 100. Mu. Mol/L. Other steps and parameters are the same as in the first embodiment.
Specific embodiment six: this embodiment differs from the fifth embodiment in that the concentration of potassium permanganate or ferrate in the contaminated water to be treated is 50. Mu. Mol/L. Other steps and parameters are the same as in the fifth embodiment.
Seventh embodiment: the first difference between this embodiment and the specific embodiment is that the pH of the contaminated water to be treated is 4 to 9. Other steps and parameters are the same as in the first embodiment.
Eighth embodiment: the seventh difference between this embodiment and the specific embodiment is that the pH of the contaminated water to be treated is 5 to 8. Other steps and parameters are the same as in embodiment seven.
Detailed description nine: the first difference between this embodiment and the specific embodiment is that the contaminants in the contaminated water to be treated are phenolic contaminants and antibiotic substances. Other steps and parameters are the same as in the first embodiment.
Detailed description ten: this embodiment differs from the specific embodiment in that the treatment is performed for 50 minutes under the stirring condition. Other steps and parameters are the same as in the first embodiment.
Eleventh embodiment: the first difference between this embodiment and the specific embodiment is that the preparation method of the carbon quantum dot solution includes: the preparation method is carried out by adopting the existing microwave synthesis method, thermal decomposition method, hydrothermal treatment method, template path method, plasma treatment method, arc discharge treatment method, laser ablation method, electrochemical oxidation method, chemical oxidation method or ultrasonic synthesis method. Other steps and parameters are the same as in the first embodiment.
The beneficial effects of the invention are verified by the following examples:
example 1:
in this embodiment, the preparation of the carbon quantum dot solution is performed by the existing electrochemical oxidation method, and the process is as follows:
1. inserting two graphite electrodes into ultrapure water electrolyte with pH=5, wherein the electrode distance is 7cm, the applied voltage is 30V, and electrolyzing for 72-96 hours until the solution turns into deep yellow;
2. filtering the solution with a polytetrafluoroethylene filter membrane with the diameter of 0.22 mu m to obtain a filtered solution;
3. transferring the filtered solution to a centrifuge, centrifuging at 10000r/min for 40min, and taking supernatant to obtain the prepared carbon quantum dot solution.
Example 2:
in this example, the carbon quantum dots of example 1 were examined for their ability to adsorb phenolic substances (phenol, bisphenol a, tetrachlorophenol, parahydroxybenzoic acid) and antibiotic substances (sulfamethoxazole, ibuprofen, diclofenac) in simulated wastewater.
The organic contaminant mother liquor was added to a buffer solution at pH 7 so that its concentration was 6 μm as a simulated wastewater. The carbon quantum dot solution prepared in example 1 was added to the simulated wastewater and reacted for 60 minutes under stirring. During the reaction, samples were taken at intervals of 5 to 10 minutes, filtered through a 0.22 μm polytetrafluoroethylene filter, and the concentration C of the target contaminant was measured. Will eachThe initial concentration of the self-targeted contaminant is designated C 0 Calculate C/C 0 Variation with reaction time.
In the embodiment, 7 groups of experiments are arranged, and the concentration of the added carbon quantum dots is controlled to be 4mg/L or 8mg/L respectively. Various organic pollutants C/C 0 As shown in figures 1 and 2, the carbon quantum dots have limited adsorption effect on organic pollutants, and the removal rate is below 10%.
Example 3:
in this example, the effect of potassium ferrate or potassium permanganate on the oxidative removal of the 7 contaminants was examined.
In this example, 14 experiments were set up and the organic contaminant mother liquor was added to a buffer solution at pH 7 to a concentration of 6. Mu.M as simulated wastewater. To the simulated wastewater, potassium permanganate or potassium ferrate was added at a concentration of 30. Mu.M, and reacted under stirring for 60 minutes. During the reaction, samples were taken at intervals of 5 to 10 minutes, filtered through a 0.22 μm polytetrafluoroethylene filter, and the concentration C of the target contaminant was measured. The initial concentration of each target contaminant was designated C 0 Calculate C/C 0 Variation with reaction time.
In each set of experiments, organic pollutant C/C 0 The removal rates of potassium ferrate to phenol, bisphenol A, tetrachlorophenol, parahydroxybenzoic acid, sulfamethoxazole, ibuprofen and diclofenac were about 52%, 86%, 64%, 45%, 73%, 17% and 83%, respectively, as shown in FIGS. 1 and 2. The removal rates for potassium permanganate were approximately 51.9%, 88.7%, 67.2%, 12.5%, 1.8%, 26.6% and 28%, respectively. The potassium ferrate or potassium permanganate alone has certain limitations in the removal of organic contaminants.
Example 4:
in this example, the oxidation removal effect of the 7 pollutants described above was examined for a potassium ferrate/carbon quantum dot system and a potassium permanganate/carbon quantum dot system.
In this example, 14 experiments were set up and the organic contaminant mother liquor was added to a buffer solution at pH 7 to a concentration of 6. Mu.M as simulated wastewater. Adding 4mg/L and 8mg/L carbon quantum dots into the simulated wastewater, and respectively adding potassium ferrate and potassium permanganate to make the concentration of the carbon quantum dots be 30 mu M, wherein the method comprises the following steps of:
first set of experiments: the phenol mother liquor was added to a buffer solution at pH 7 so that its concentration was 6. Mu.M. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 4mg/L. Finally, potassium ferrate solution was added to a concentration of 30. Mu.M.
Second set of experiments: the bisphenol A mother liquor was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 4mg/L. Finally, potassium ferrate solution was added to a concentration of 30. Mu.M.
Third set of experiments: the tetrachlorofene mother liquor was added to a buffer solution at pH 7 to give a concentration of 6 μm. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 4mg/L. Finally, potassium ferrate solution was added to a concentration of 30. Mu.M.
Fourth set of experiments: the parahydroxybenzoic acid mother liquor was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 4mg/L. Finally, potassium ferrate solution was added to a concentration of 30. Mu.M.
Fifth set of experiments: sulfomethylisoxazole mother liquor was added to a buffer solution at pH 7 so that its concentration was 6. Mu.M. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 4mg/L. Finally, potassium ferrate solution was added to a concentration of 30. Mu.M.
Sixth set of experiments: the ibuprofen mother liquor was added to a buffer solution at pH 7 so that its concentration was 6. Mu.M. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 4mg/L. Finally, potassium ferrate solution was added to a concentration of 30. Mu.M.
Seventh set of experiments: the diclofenac mother solution was added to a buffer solution at pH 7 so that its concentration was 6 μm. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 4mg/L. Finally, potassium ferrate solution was added to a concentration of 30. Mu.M.
Eighth set of experiments: the phenol mother liquor was added to a buffer solution at pH 7 so that its concentration was 6. Mu.M. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 8mg/L. Finally, potassium permanganate solution was added to a concentration of 30 μm.
Ninth set of experiments: the bisphenol A mother liquor was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 8mg/L. Finally, potassium permanganate solution was added to a concentration of 30 μm.
Tenth set of experiments: the tetrachlorofene mother liquor was added to a buffer solution at pH 7 to give a concentration of 6 μm. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 8mg/L. Finally, potassium permanganate solution was added to a concentration of 30 μm.
Eleventh set of experiments: the parahydroxybenzoic acid mother liquor was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 8mg/L. Finally, potassium permanganate solution was added to a concentration of 30 μm.
Twelfth set of experiments: sulfomethylisoxazole mother liquor was added to a buffer solution at pH 7 so that its concentration was 6. Mu.M. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 8mg/L. Finally, potassium permanganate solution was added to a concentration of 30 μm.
Thirteenth set of experiments: the ibuprofen mother liquor was added to a buffer solution at pH 7 so that its concentration was 6. Mu.M. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 8mg/L. Finally, potassium permanganate solution was added to a concentration of 30 μm.
Fourteenth set of experiments: the diclofenac mother solution was added to a buffer solution at pH 7 so that its concentration was 6 μm. Then adding carbon quantum dots to make the concentration of the carbon quantum dots 8mg/L. Finally, potassium permanganate solution was added to a concentration of 30 μm.
The reaction was carried out for 60 minutes with stirring. During the reaction, samples were taken at intervals of 5 to 10 minutes, filtered through a 0.22 μm polytetrafluoroethylene filter, and the concentration C of the target contaminant was measured. The initial concentration of each target contaminant was designated C 0 Calculate C/C 0 Variation with reaction time.
In each set of experiments, organic pollutant C/C 0 The change after the reaction is finished is shown in figures 1 and 2, and the potassium ferrate/carbon quantum dot system comprises p-phenol, bisphenol A, tetrachlorophenol, p-hydroxybenzoic acid, sulfamethoxazole, ibuprofen and diclofenacThe removal rates of (a) are about 87%, 98%, 88%, 66%, 80%, 57% and 99%, respectively. The removal rates for the potassium permanganate/carbon quantum dot system were approximately 100%, 96%, 85.4%, 37.1%, 13.8%, 40% and 100%, respectively. The potassium ferrate/carbon quantum dot system or the potassium permanganate/carbon quantum dot system is obviously superior to the separate systems for removing organic pollutants.
As shown in FIG. 3, the apparent rate constants of potassium ferrate alone, for bisphenol A, diclofenac, sulfamethoxazole, tetrachlorophenol, phenol, parahydroxybenzoic acid, and ibuprofen, were 539.87, 187.5, 276.28, 166.33, 75.65, 113.43, and 160.37M, respectively -1 s -1 . In the carbon quantum dot enhanced potassium ferrate system, apparent rate constants of bisphenol A, diclofenac, sulfamethylisoxazole, tetrachlorophenol, phenol, parahydroxybenzoic acid, and ibuprofen are respectively increased to 1189.40, 4270.70, 285.78, 890.32, 478.83, 300.90 and 291.43M -1 s -1 。
Example 5:
in this example, the effect of pH change on phenol oxidation efficiency of potassium ferrate/carbon quantum dot system was examined.
In this example, a total of 5 experiments were set up, and phenol mother liquor was added to buffer solutions having pH values of 5, 6, 7, 8, and 9, respectively, so that the concentrations thereof were 6. Mu.M, as simulated wastewater. 4mg/L carbon quantum dots are added into the simulated wastewater, and then potassium ferrate is added to make the concentration of the carbon quantum dots be 30 mu M.
The reaction was carried out for 60 minutes with stirring. During the reaction, samples were taken at 5 to 10 minute intervals, filtered through a 0.22 μm polytetrafluoroethylene filter, and the phenol concentration C was measured. The initial concentration of phenol was designated C 0 Calculate C/C 0 Variation with reaction time.
In each group of experiments, the simulation situation of the kinetics of degrading phenol by the potassium ferrate or the potassium ferrate/carbon quantum dot system is shown in figures 4-5, and the phenol C/C 0 The change with the reaction time is shown in FIGS. 6 to 7. The potassium ferrate/carbon quantum dot system has the best effect under the acidic and neutral conditionsThe next time under alkaline conditions. The removal rates are 73% and 81% respectively under the conditions of pH value of 5 and pH value of 6, and the removal rates are improved by 15% and 19% compared with a potassium ferrate system. The removal rate is 87% under the condition of pH value of 7, and the removal rate is improved by 36% compared with a potassium ferrate system. The removal rates were 46% and 30% at pH 8 and 9, respectively. Although the performance of the potassium ferrate/carbon quantum dot system decreases with increasing pH, the removal effect is better than that of potassium ferrate alone at various pH conditions.
Example 6:
in this example, the effect of pH change on the oxidation of diclofenac by the potassium permanganate/carbon quantum dot system was examined.
In this example, 6 experiments were set up and diclofenac mother solutions were added to buffer solutions having pH of 4, 5, 6, 7, 8, 9, respectively, so that their concentrations were 6 μm, as simulated wastewater. Adding 8mg/L carbon quantum dots into the simulated wastewater, and then adding potassium permanganate to make the concentration of the carbon quantum dots be 30 mu M.
The reaction was carried out for 60 minutes with stirring. During the reaction, samples were taken at intervals of 5 to 10 minutes, and the concentration C of diclofenac was measured by filtration through a 0.22 μm polytetrafluoroethylene filter. The initial concentration of diclofenac was designated as C 0 Calculate C/C 0 Variation with reaction time.
In each set of experiments, diclofenac C/C 0 As shown in figures 8-10, the reaction rate of the potassium permanganate/carbon quantum dot system is fastest under the acidic condition, and the removal effect can reach nearly 100% under various pH conditions, which is superior to that of potassium permanganate alone.
Example 7:
in the embodiment, the effect of the water quality background ion change and the actual water body on phenol oxidation effect of the potassium ferrate/carbon quantum dot system is examined.
In this example, a total of 7 experiments were set up, as follows:
first set of experiments: the phenol mother liquor was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by adding chloride ions so that its concentration was 1mM, 3mM and 5mM, respectively, as a simulated wastewater. 4mg/L carbon quantum dots are added into the simulated wastewater, and then potassium ferrate is added to make the concentration of the carbon quantum dots be 30 mu M.
Second set of experiments: the phenol mother liquor was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of hydrogen phosphate ions so that their concentrations were 1mM, 3mM and 5mM, respectively, as a simulated wastewater. 4mg/L carbon quantum dots are added into the simulated wastewater, and then potassium ferrate is added to make the concentration of the carbon quantum dots be 30 mu M.
Third set of experiments: the phenol mother liquor was added to a buffer solution at pH 7 so as to have a concentration of 6. Mu.M, followed by addition of bicarbonate ions so as to have concentrations of 1mM, 3mM and 5mM, respectively, as a simulated wastewater. 4mg/L carbon quantum dots are added into the simulated wastewater, and then potassium ferrate is added to make the concentration of the carbon quantum dots be 30 mu M.
Fourth set of experiments: the phenol mother liquor was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of calcium ions so that its concentration was 1mM, 3mM and 5mM, respectively, as a simulated wastewater. 4mg/L carbon quantum dots are added into the simulated wastewater, and then potassium ferrate is added to make the concentration of the carbon quantum dots be 30 mu M.
Fifth set of experiments: the phenol mother liquor was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of magnesium ions so that its concentration was 1mM, 3mM and 5mM, respectively, as a simulated wastewater. 4mg/L carbon quantum dots are added into the simulated wastewater, and then potassium ferrate is added to make the concentration of the carbon quantum dots be 30 mu M.
Sixth set of experiments: the phenol mother liquor was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of humic acid so that its concentration was 2mg/L, 5mg/L and 10mg/L, respectively, as simulated wastewater. 4mg/L carbon quantum dots are added into the simulated wastewater, and then potassium ferrate is added to make the concentration of the carbon quantum dots be 30 mu M.
Seventh set of experiments: the phenol mother liquor was added to a conical flask containing 100mL of river water so that its concentration was 6. Mu.M, as actual wastewater. Adding 4mg/L carbon quantum dots into the actual wastewater, and then adding potassium ferrate to make the concentration of the potassium ferrate be 30 mu M.
The reaction was carried out for 60 minutes with stirring. During the reaction, samples were taken at 5 to 10 minute intervals, filtered through a 0.22 μm polytetrafluoroethylene filter, and the phenol concentration C was measured. The initial concentration of phenol was recorded asC 0 Calculate C/C 0 Variation with reaction time.
In each set of experiments, phenol C/C 0 As shown in FIGS. 11-13, the potassium ferrate/carbon quantum dot system is not interfered by chloride ions, and the removal rate is about 87%. Phosphate has a certain inhibition effect on the potassium ferrate/carbon quantum dot system, and the removal efficiency of phenol is reduced from 50% to 40% as the concentration of phosphate is increased from 1mM to 5mM, but the removal effect on phenol is still close to that of the potassium ferrate system alone. Similarly, bicarbonate has some inhibitory effect on the potassium ferrate/carbon quantum dot system, and as the bicarbonate concentration increases from 1mM to 3mM, the phenol removal efficiency decreases from 82% to 64% and 44%. Under the condition of low concentration of bicarbonate, the removal effect of the potassium ferrate/carbon quantum dot system on phenol is higher than that of a potassium ferrate system alone, and the removal rate is 54%.
The calcium ion, the magnesium ion and the humic acid have certain inhibition effect on the potassium ferrate/carbon quantum dot system, and as the concentration of the calcium ion and the magnesium ion is increased from 1mM to 5mM, the removal efficiency of phenol is respectively reduced from 72% to 65% and 78% to 73%, and the removal effect on phenol is inhibited but is superior to that of the potassium ferrate system alone. 2mg/L humic acid has no influence on the removal of phenol by a potassium ferrate/carbon quantum dot system, and the system has better humic acid resistance; the effect of removing pollutants is better than that of a potassium ferrate system alone in the presence of 10mg/L humic acid. In an actual water body, the effect of removing phenol by the potassium ferrate/carbon quantum dot system is better than that of the potassium ferrate system, 61% of phenol is removed by the potassium ferrate/carbon quantum dot system when the reaction is carried out for 10 minutes, and compared with the situation that only 41% of phenol is removed by a single high-iron system in the actual water body.
The test results of the open circuit voltage and current changes with potassium ferrate and phenol are shown in FIG. 14. The open-circuit voltage of the carbon quantum dot electrode is +0.84V, and the voltage is reduced to +0.80V along with the addition of potassium ferrate. With further addition of phenol, the carbon quantum dot electrode voltage was reduced to +0.50V, demonstrating the transfer of electrons from phenol to the potassium ferrate/carbon quantum dot system. The timing current experiment result shows that with the addition of potassium ferrate and phenol respectively, the current also has a tendency of remarkably reducing, and further proves that electrons in the system are transferred from phenol to potassium ferrate, and the carbon quantum dots play a role of an electron shuttle.
Example 8:
in the embodiment, the effect of water quality background ion change and actual water body on the oxidation of diclofenac by a potassium permanganate/carbon quantum dot system is examined.
In this example, 8 experiments were set up, specifically as follows:
first set of experiments: the diclofenac mother solution was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of chloride ions so that its concentration was 1mM, 3mM and 5mM, respectively, as a simulated wastewater. Adding 8mg/L carbon quantum dots into the simulated wastewater, and then adding potassium permanganate to make the concentration of the carbon quantum dots be 30 mu M.
Second set of experiments: the diclofenac mother solution was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of sulfate ions so that its concentration was 1mM, 3mM and 5mM, respectively, as a simulated wastewater. Adding 8mg/L carbon quantum dots into the simulated wastewater, and then adding potassium permanganate to make the concentration of the carbon quantum dots be 30 mu M.
Third set of experiments: the diclofenac mother solution was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of bicarbonate ions so that its concentration was 1mM, 3mM and 5mM, respectively, as a simulated wastewater. Adding 8mg/L carbon quantum dots into the simulated wastewater, and then adding potassium permanganate to make the concentration of the carbon quantum dots be 30 mu M.
Fourth set of experiments: the diclofenac mother solution was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of hydrogen phosphate ions so that their concentrations were 1mM, 3mM and 5mM, respectively, as simulated wastewater. Adding 8mg/L carbon quantum dots into the simulated wastewater, and then adding potassium permanganate to make the concentration of the carbon quantum dots be 30 mu M.
Fifth set of experiments: the diclofenac mother solution was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of calcium ions so that its concentration was 1mM, 3mM and 5mM, respectively, as a simulated wastewater. Adding 8mg/L carbon quantum dots into the simulated wastewater, and then adding potassium permanganate to make the concentration of the carbon quantum dots be 30 mu M.
Sixth set of experiments: the diclofenac mother solution was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of magnesium ions so that its concentration was 1mM, 3mM and 5mM, respectively, as a simulated wastewater. Adding 8mg/L carbon quantum dots into the simulated wastewater, and then adding potassium permanganate to make the concentration of the carbon quantum dots be 30 mu M.
Seventh set of experiments: the diclofenac mother solution was added to a buffer solution having a pH of 7 so that its concentration was 6. Mu.M, followed by addition of humic acid so that its concentration was 2mg/L, 5mg/L and 10mg/L, respectively, as simulated wastewater. Adding 8mg/L carbon quantum dots into the simulated wastewater, and then adding potassium permanganate to make the concentration of the carbon quantum dots be 30 mu M.
Eighth set of experiments: the diclofenac mother liquor was added to an Erlenmeyer flask containing 100mL of river water so that its concentration was 6 μm as actual wastewater. Adding 8mg/L carbon quantum dots into the actual wastewater, and then adding potassium permanganate to make the concentration of the carbon quantum dots be 30 mu M.
The reaction was carried out for 60 minutes with stirring. During the reaction, samples were taken at intervals of 5 to 10 minutes, and the concentration C of diclofenac was measured by filtration through a 0.22 μm polytetrafluoroethylene filter. The initial concentration of diclofenac was designated as C 0 Calculate C/C 0 Variation with reaction time.
In each set of experiments, diclofenac C/C 0 As shown in figures 15-18, the potassium permanganate/carbon quantum dot system is not interfered by chloride ions, sulfate radicals, bicarbonate radicals and humic acid. The phosphate radical has obvious promoting effect on the potassium permanganate/carbon quantum dot system, and when the reaction is carried out for 10 minutes, the removal rate of diclofenac is increased from 55% to 100% along with the increase of the concentration of the phosphate radical from 1mM to 5 mM. The calcium ions have a certain inhibition effect on the potassium permanganate/carbon quantum dot system, and the removal rate of the diclofenac is reduced from 86% to 80% along with the increase of the concentration of the calcium ions from 1mM to 5 mM. The magnesium ion has a certain promoting effect on the potassium permanganate/carbon quantum dot system, and 1mM magnesium ion can enable the potassium permanganate/carbon quantum dot system to remove diclofenac by 100% within 20 minutes. In the actual water body, the potassium permanganate/carbon quantum dot system has the effect of removing diclofenacThe method is obviously superior to a potassium permanganate system, only 27% of triclosan can be removed by potassium permanganate alone, and compared with the potassium permanganate/carbon quantum dot system, 74% of triclosan can be removed, and the performance is improved by 47%.
The test results of the open circuit voltage and current changes with potassium permanganate and DCF are shown in fig. 19. The open-circuit voltage of the carbon quantum dot electrode is +1.00V, and the voltage is reduced to +0.94V along with the addition of potassium permanganate. With further addition of DCF, the open circuit voltage was reduced to +0.78v, demonstrating the transfer of electrons from DCF to the potassium permanganate/carbon quantum dot system. The timing current experiment result shows that the current also has a tendency of obviously reducing when potassium permanganate and DCF are respectively added, and the current is reduced from-0.37 mu A to-0.43 mu A, so that the electron transfer from DCF to potassium permanganate in the system is further proved, and the carbon quantum dots play a role in transferring electrons.
Claims (10)
1. A water treatment method for reinforcing oxidation of high-valence metal by using carbon quantum dots is characterized by comprising the following steps:
and sequentially adding the carbon quantum dot solution and potassium permanganate or potassium ferrate into the polluted water to be treated, and treating for 10-60 min under the stirring condition to finish the water treatment method.
2. The water treatment method for reinforcing oxidation of high-valence metal by using carbon quantum dots according to claim 1, wherein the concentration of the carbon quantum dot solution in polluted water to be treated is 2-20 mg/L.
3. The water treatment method for enhancing oxidation of high-valence metal by using carbon quantum dots according to claim 2, wherein the concentration of the carbon quantum dot solution in polluted water to be treated is 4mg/L.
4. The water treatment method for enhancing oxidation of high-valence metal by using carbon quantum dots according to claim 2, wherein the concentration of the carbon quantum dot solution in polluted water to be treated is 8mg/L.
5. The water treatment method for enhancing oxidation of high-valence metal by using carbon quantum dots according to claim 1, wherein the concentration of potassium permanganate or potassium ferrate in polluted water to be treated is 30-100 mu mol/L.
6. The water treatment method for enhancing oxidation of high-valence metal by using carbon quantum dots according to claim 5, wherein the concentration of potassium permanganate or potassium ferrate in the polluted water to be treated is 50 mu mol/L.
7. The water treatment method for enhancing oxidation of high-valence metal by using carbon quantum dots according to claim 1, wherein the pH value of the polluted water to be treated is 4-9.
8. The water treatment method for enhancing oxidation of high-valence metal by using carbon quantum dots according to claim 7, wherein the pollutants in the polluted water to be treated are phenolic pollutants and antibiotics.
9. The water treatment method for enhancing oxidation of high-valence metal by using carbon quantum dots according to claim 1, wherein the water treatment method is characterized in that the water treatment is carried out for 50min under the stirring condition.
10. The water treatment method for enhancing oxidation of high-valence metal by using carbon quantum dots according to claim 1, wherein the preparation method of the carbon quantum dot solution is characterized by comprising the following steps: the preparation method is carried out by adopting the existing microwave synthesis method, thermal decomposition method, hydrothermal treatment method, template path method, plasma treatment method, arc discharge treatment method, laser ablation method, electrochemical oxidation method, chemical oxidation method or ultrasonic synthesis method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310749960.7A CN116639788A (en) | 2023-06-25 | 2023-06-25 | Water treatment method for enhancing oxidation of high-valence metal by carbon quantum dots |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310749960.7A CN116639788A (en) | 2023-06-25 | 2023-06-25 | Water treatment method for enhancing oxidation of high-valence metal by carbon quantum dots |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116639788A true CN116639788A (en) | 2023-08-25 |
Family
ID=87615505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310749960.7A Pending CN116639788A (en) | 2023-06-25 | 2023-06-25 | Water treatment method for enhancing oxidation of high-valence metal by carbon quantum dots |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116639788A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117566847A (en) * | 2024-01-15 | 2024-02-20 | 南京信息工程大学 | Method for degrading organic pollutants based on photocatalytic activation ferrate |
-
2023
- 2023-06-25 CN CN202310749960.7A patent/CN116639788A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117566847A (en) * | 2024-01-15 | 2024-02-20 | 南京信息工程大学 | Method for degrading organic pollutants based on photocatalytic activation ferrate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ahmadi et al. | Organic dye degradation through peroxymonosulfate catalyzed by reusable graphite felt/ferriferrous oxide: Mechanism and identification of intermediates | |
| Aziz et al. | Heavy metal pollution in the aquatic environment: efficient and low-cost removal approaches to eliminate their toxicity: a review | |
| Rajoria et al. | Treatment of electroplating industry wastewater: a review on the various techniques | |
| Yang et al. | A bimetallic Fe–Mn oxide-activated oxone for in situ chemical oxidation (ISCO) of trichloroethylene in groundwater: efficiency, sustained activity, and mechanism investigation | |
| Ghosh et al. | Reduction of COD and removal of Zn2+ from rayon industry wastewater by combined electro-Fenton treatment and chemical precipitation | |
| Xu et al. | Activation of peroxymonosulfate by MnFe2O4@ BC composite for bisphenol A degradation: the coexisting of free-radical and non-radical pathways | |
| Can et al. | Effect of some operational parameters on the arsenic removal by electrocoagulation using iron electrodes | |
| CN108928890B (en) | Method for treating refractory wastewater by three-dimensional electrode coupling oxidant | |
| Baek et al. | Electrochemical removal of selenate from aqueous solutions | |
| US20090261042A1 (en) | Method for adsorption of fluid contaminants and regeneration of the adsorbent | |
| JP2008284520A (en) | Supported catalyst-type magnetic adsorbent and method for treating peroxide-containing wastewater | |
| KR101966784B1 (en) | The generating device for contiuous hydrogen peroxide | |
| Zhu et al. | Oxygen vacancies-rich α@ δ-MnO2 mediated activation of peroxymonosulfate for the degradation of CIP: The role of electron transfer process on the surface | |
| Liu et al. | Ozone catalytic oxidation of biologically pretreated semi-coking wastewater (BPSCW) by spinel-type MnFe2O4 magnetic nanoparticles | |
| Yu et al. | Research progress on the removal, recovery and direct high-value materialization of valuable metal elements in electroplating/electroless plating waste solution | |
| CN116639788A (en) | Water treatment method for enhancing oxidation of high-valence metal by carbon quantum dots | |
| Zeng et al. | Activity and mechanism of vanadium sulfide for organic contaminants oxidation with peroxymonosulfate | |
| Guo et al. | Singlet oxygen-mediated electrochemical filter for selective and rapid degradation of organic compounds | |
| Zhang et al. | Enhanced degradation of metronidazole by cobalt doped TiO2/sulfite process under visible light | |
| Lu et al. | Sustainable decontamination of heavy metal in wastewater and soil with novel rectangular wave asymmetrical alternative current electrochemistry | |
| Li et al. | Intrinsic mechanisms of calcium sulfite activation by siderite for atrazine degradation | |
| Xie et al. | Mechanisms and pathways of ethidium bromide Fenton-like degradation by reusable magnetic nanocatalysts | |
| Li et al. | An efficient and robust flow-through electrochemical Ti4O7 membrane system for simultaneous Cr (VI) reduction and Cr immobilization with membrane cleaning by a periodic polarity reversal strategy | |
| CN113559840B (en) | Auto-oxidation catalyst, preparation method and method for removing organic matters in high-salinity wastewater | |
| Tung et al. | Hydrothermal synthesis of CuCoFe layered double hydroxide and its performance in the degradation of antibiotics: Influencing factors, degradation pathways, and reaction mechanism |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |