CN115845901A - Carbon quantum dot with phase transfer effect and preparation method and application thereof - Google Patents
Carbon quantum dot with phase transfer effect and preparation method and application thereof Download PDFInfo
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- CN115845901A CN115845901A CN202211563383.4A CN202211563383A CN115845901A CN 115845901 A CN115845901 A CN 115845901A CN 202211563383 A CN202211563383 A CN 202211563383A CN 115845901 A CN115845901 A CN 115845901A
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- carbon quantum
- quantum dot
- phase transfer
- transfer effect
- naphthenic acid
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 230000000694 effects Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title description 16
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002202 Polyethylene glycol Chemical class 0.000 claims abstract description 30
- 229920001223 polyethylene glycol Chemical class 0.000 claims abstract description 30
- 239000002351 wastewater Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000006731 degradation reaction Methods 0.000 claims abstract description 21
- 230000015556 catabolic process Effects 0.000 claims abstract description 20
- -1 pyrrole compound Chemical class 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052751 metal Chemical class 0.000 claims abstract description 13
- 239000002184 metal Chemical class 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 230000000593 degrading effect Effects 0.000 claims abstract description 11
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- WRXNJTBODVGDRY-UHFFFAOYSA-N 2-pyrrolidin-1-ylethanamine Chemical compound NCCN1CCCC1 WRXNJTBODVGDRY-UHFFFAOYSA-N 0.000 claims description 9
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 5
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 5
- NGXSWUFDCSEIOO-UHFFFAOYSA-N pyrrolidin-3-amine Chemical compound NC1CCNC1 NGXSWUFDCSEIOO-UHFFFAOYSA-N 0.000 claims description 5
- JHHZLHWJQPUNKB-UHFFFAOYSA-N pyrrolidin-3-ol Chemical compound OC1CCNC1 JHHZLHWJQPUNKB-UHFFFAOYSA-N 0.000 claims description 5
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001510 metal chloride Inorganic materials 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 125000005608 naphthenic acid group Chemical group 0.000 claims 2
- 229960003280 cupric chloride Drugs 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 abstract description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 abstract description 8
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000001721 carbon Chemical class 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 44
- 239000000203 mixture Substances 0.000 description 14
- 239000012074 organic phase Substances 0.000 description 9
- 238000002798 spectrophotometry method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
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- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002358 oil sand bitumen Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention relates to the field of wastewater degradation treatment, and particularly discloses application of carbon quantum dots with a phase transfer effect in catalytic degradation of naphthenic acid and a method for degrading naphthenic acid. The carbon quantum dots are prepared by combining a pyrrole compound, polyethylene glycol and a metal salt through a coordination bond effect to obtain a coordination compound and then performing a hydrothermal reaction. Wherein the pyrrole compound can form a carbon nucleus to improve the reaction activity of the reaction; the polyethylene glycol with a linear structure can complex metal ions and is combined with metal ions of persulfate; the transition metal salt may function to activate the persulfate. The carbon quantum dots generated by combining the three substances have uniform particle size and excellent morphology catalytic performance. The carbon quantum dots provided by the invention degrade naphthenic acid in wastewater by catalyzing sodium persulfate, the degradation rate can reach 96.7%, and the carbon quantum dots have the advantages of high catalytic efficiency, simple and convenient operation, low production cost and the like, and have wide application prospects in the fields of medicine, papermaking, tanning, pollution environment treatment and the like.
Description
Technical Field
The invention relates to the field of wastewater degradation treatment, in particular to a carbon quantum dot with a phase transfer effect and a preparation method and application thereof.
Background
With the increasing demand for energy and the increasing depletion of conventional energy sources, crude oil has become an important refinery feedstock. Naphthenic acid is an organic acid existing in crude oil, oil sand bitumen and tailing wastewater, and can cause serious corrosion problems to equipment, transportation pipelines and storage tanks, cause environmental pollution and poison to organisms. At present, naphthenic acid treatment technologies mainly comprise advanced oxidation technology, adsorption, coagulation, hydrogenation technology, microbial degradation and the like, and the treatment method generally has the problems of introduction of other impurity ions after treatment, large investment in equipment, low treatment efficiency, high toxicity and the like.
As a novel carbon material, the carbon quantum dot has the advantages of excellent biocompatibility, low toxicity and the like, and has a wide application prospect in many fields. In general, the organic phase and the aqueous phase can form a two-phase system, the oxidant is generally inorganic acid salt such as sodium persulfate and the like, is easy to dissolve in water, and has low solubility in the organic phase, so that the oxidant cannot effectively contact with naphthenic acid to be treated, and the naphthenic acid in the wastewater cannot be fully degraded. Therefore, the carbon quantum dot which is simple and convenient to operate, high in treatment efficiency and environment-friendly and has the phase transfer effect is developed and used for catalytically degrading naphthenic acid in wastewater, and the method has very important significance.
Disclosure of Invention
Aiming at the problems of poor treatment effect, high treatment cost and the like of a naphthenic acid catalytic oxidation degradation treatment method in the prior art, the invention provides a preparation method and application of a carbon quantum dot with a phase transfer effect.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the carbon quantum dot with the phase transfer function is prepared from a coordination compound prepared from a pyrrole compound, polyethylene glycol and a metal salt by a hydrothermal method.
Compared with the prior art, the coordination compound prepared from the pyrrole compound, the polyethylene glycol and the metal salt is combined through coordination bond action, in the prepared phase transfer action carbon quantum dot, the pyrrole compound can form a carbon core in the synthesis process of the carbon quantum dot, and meanwhile, nitrogen in the pyrrole can be doped into the carbon quantum dot as a hetero atom, so that the electronic structure of the carbon quantum dot is obviously changed, more active sites are provided for a reaction system, and the reaction activity of the reaction is improved; the polyethylene glycol with a linear structure can complex metal ions and is combined with metal ions of persulfate; the transition metal salt can activate persulfate, and SO with stronger oxidability than persulfate is generated by reaction 4 - And the oxidation capability of the naphthenic acid is enhanced. Polyethylene glycol is used as a carrier, metal ions in persulfate are firstly complexed, and then the metal ions are combined with persulfate to form ion pairs, so that the ion pairs can enter an organic phase, and the persulfate which is difficult to enter the organic phase is brought into organic phase to degrade naphthenic acid. In the organic phase, the complexation is weakened, the persulfate is combined with the naphthenic acid to achieve the purpose of oxidizing and degrading the naphthenic acid, the metal ions slowly separate from the polyethylene glycol and return to the water phase, the polyethylene glycol returns to a linear structure, and the metal ions return to the water phase, so that the reversible transfer of carbon quantum dots in the organic phase and the water phase is realized, and the degradation efficiency of the persulfate on the naphthenic acid is improved.
Preferably, the pyrrole compound is at least one of 1- (2-aminoethyl) pyrrolidine, 3-aminopyrrolidine, or 3-pyrrolidinol.
Preferably, the polyethylene glycol is at least one of PEG200, PEG300, PEG400 or PEG 600.
Preferably, the metal salt is at least one of metal chloride or metal nitrate.
More preferably, the metal salt is at least one of zinc chloride, aluminum chloride, ferric chloride, copper chloride, cobalt chloride, nickel chloride, molybdenum chloride, lanthanum nitrate, calcium nitrate, lead nitrate, strontium nitrate, and cerium nitrate.
Preferably, the molar ratio of the pyrrole compound, the polyethylene glycol and the metal salt is 1-2.
Preferably, the preparation method of the coordination compound comprises the following steps: and mixing and stirring the pyrrole compound, the polyethylene glycol and the metal salt uniformly, heating to 50-110 ℃, and reacting for 1-3h to obtain the coordination compound.
Preferably, the preparation method of the phase transfer carbon quantum dot comprises the following steps: and adding 30-40mL of deionized water into the coordination compound, placing the coordination compound in a reaction kettle, placing the reaction kettle in an oven, and reacting for 10-15h at the hydrothermal temperature of 180-220 ℃ to obtain the phase transfer carbon quantum dot.
The invention also provides a method for catalyzing and degrading naphthenic acid by using the carbon quantum dots with the phase transfer effect, which comprises the following steps:
adding the carbon quantum dots with the phase transfer effect into wastewater containing naphthenic acid for catalytic degradation treatment.
In combination with the above, the addition amount of the carbon quantum dots with phase transfer effect can be changed or adjusted in a wide range, and is obtained by performing routine adjustment according to the concentration of naphthenic acid in the wastewater, specific components of the wastewater and other conditions.
Preferably, when the carbon quantum dots with the phase transfer effect prepared by the method are used for treating naphthenic acid in wastewater, the mass ratio of the phase transfer carbon quantum dots to the sodium persulfate oxidant to the naphthenic acid-containing wastewater is 1.
Specifically, the method for catalytically degrading naphthenic acid in wastewater based on carbon quantum dots with phase transfer effect comprises the following steps:
adding the prepared carbon quantum dots with the phase transfer effect into naphthenic acid wastewater with different concentrations according to a certain proportion, and carrying out magnetic stirring reaction for 10-60min at the temperature of 30-80 ℃. And (3) determining the concentration of the non-oxidized naphthenic acid in the reacted solution by using an ultraviolet spectrophotometry, and evaluating the catalytic degradation condition of the naphthenic acid in the wastewater.
Naphthenic acid is carboxylic acid with the general structural formula C n H 2n+Z O 2 And almost insoluble in water, naphthenic acid reacts with metal to generate naphthenate. Sodium persulfate as the oxidant has low solubility in the organic phase and is readily soluble in water. The polyethylene glycol can capture Na + And S 2 O 8 2- Form ion pairs to thereby form S 2 O 8 2- Also substituted into the organic phase; s 2 O 8 2- Stable at room temperature, can be activated into sulfate radicals by heating, and the effect of the degradation reaction is that the secondary free radicals (equations 1 and 2) generated by the sulfate free radical reaction gradually degrade naphthenic acid into a water phase. Thereby achieving the purpose of catalyzing and degrading naphthenic acid.
SO 4 -· +H 2 O→SO 4 2- +OH·+H + 1
SO 4 -· +OH - →SO 4 2- +OH· 2
Compared with other methods for treating naphthenic acid in wastewater, the method for catalytically degrading naphthenic acid in wastewater by using carbon quantum dots with phase transfer effect provided by the invention monitors the concentration of naphthenic acid which is not oxidized by using an ultraviolet spectrophotometer, is simple and convenient to operate, simple in preparation method, higher in efficiency of catalytically degrading naphthenic acid, and has a great application prospect in the aspect of organic wastewater treatment.
Drawings
FIG. 1 is a transmission electron micrograph of a carbon quantum dot prepared according to example 2 of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment of the invention provides a carbon quantum dot with a phase transfer effect, and a preparation method of the carbon quantum dot comprises the following steps:
0.01mol (0.86 g) of 3-aminopyrrolidine, 0.12mol (83.6 g) of polyethylene glycol (PEG 400) and 0.007mol (1.11 g) of ferric chloride are mixed and then added into a 100mL three-neck flask, the mixture is placed in an oil bath pot, and the mixture is heated and stirred to 50 ℃ from room temperature for 1.5h to obtain the 3-aminopyrrolidine/polyethylene glycol/ferric chloride coordination compound.
Adding 1g of 3-aminopyrrolidine/polyethylene glycol/ferric chloride coordination compound into 30mL of deionized water, and carrying out hydrothermal reaction for 11h at 180 ℃ to obtain the carbon quantum dot with the phase transfer effect.
0.1g of the prepared carbon quantum dots with the phase transfer effect and 0.1g of sodium persulfate oxidant are added into 1g of naphthenic acid wastewater with the concentration of 10mmol/L, and the mixture is magnetically stirred for 30min at the temperature of 40 ℃. The concentration of the non-oxidized naphthenic acid in the solution after the reaction is determined to be 0.24mmol/L by an ultraviolet spectrophotometry, and the catalytic degradation rate of the naphthenic acid is 90.3 percent.
Example 2
The embodiment of the invention provides a carbon quantum dot with a phase transfer effect, and the preparation method specifically comprises the following steps:
0.01mol (1.14 g) of 1- (2-aminoethyl) pyrrolidine, 0.1mol (69.7 g) of polyethylene glycol (PEG 200) and 0.006mol (1.63 g) of molybdenum chloride were mixed, added to a 100mL three-necked flask, placed in an oil bath, and heated from room temperature with stirring to 100 ℃ for about 3 hours to give a 1- (2-aminoethyl) pyrrolidine/polyethylene glycol/molybdenum chloride complex.
Adding 1g of 1- (2-aminoethyl) pyrrolidine/polyethylene glycol/molybdenum chloride coordination compound into 35mL of deionized water, and carrying out hydrothermal reaction at 220 ℃ for 14h to obtain the carbon quantum dot with the phase transfer effect.
0.1g of the prepared carbon quantum dots with the phase transfer effect and 0.1g of sodium persulfate oxidant are added into 1g of naphthenic acid wastewater with the concentration of 10mmol/L, and the mixture is magnetically stirred for 50min at the temperature of 70 ℃. The concentration of the non-oxidized naphthenic acid in the solution after the reaction is determined to be 0.13mmol/L by an ultraviolet spectrophotometry, and the catalytic degradation rate of the naphthenic acid is 96.7 percent.
Example 3
The embodiment of the invention provides a carbon quantum dot with a phase transfer effect, and a preparation method of the carbon quantum dot comprises the following steps:
0.015mol (1.71 g) of 1- (2-aminoethyl) pyrrolidine, 0.15mol (104.5 g) of polyethylene glycol (PEG 400) and 0.005mol (1.22 g) of lanthanum chloride are mixed, added into a 100mL three-neck flask, placed in an oil bath pot, heated and stirred to 70 ℃ from room temperature, and heated for 2 hours to obtain the 1- (2-aminoethyl) pyrrolidine/polyethylene glycol/lanthanum chloride coordination compound.
Adding 1g of 1- (2-aminoethyl) pyrrolidine/polyethylene glycol/lanthanum chloride coordination compound into 30mL of deionized water, and carrying out hydrothermal reaction at 200 ℃ for 12h to obtain the carbon quantum dot with the phase transfer effect.
0.1g of the prepared carbon quantum dot with the phase transfer effect and 0.1g of sodium persulfate oxidant are added into 1g of naphthenic acid wastewater with the concentration of 10mmol/L, and the mixture is magnetically stirred for 40min at the temperature of 50 ℃. The concentration of the non-oxidized naphthenic acid in the solution after the reaction is determined to be 0.32mmol/L by an ultraviolet spectrophotometry, and the catalytic degradation rate of the naphthenic acid is 86.2 percent.
Example 4
The embodiment of the invention provides a carbon quantum dot with a phase transfer effect, and the preparation method specifically comprises the following steps:
0.016mol (1.39 g) of 3-pyrrolidinol, 0.08mol (55.8 g) of polyethylene glycol (PEG 300) and 0.006mol (1.98 g) of lead nitrate are mixed and then added into a 100mL three-neck flask, the mixture is placed in an oil bath pot, and the mixture is heated and stirred from room temperature to 90 ℃ for 2.5h to obtain the 3-pyrrolidinol/polyethylene glycol/lead nitrate coordination compound.
And adding 1g of 3-pyrrolidinol/polyethylene glycol/lead nitrate coordination compound into 30mL of deionized water, and carrying out hydrothermal reaction at 210 ℃ for 12h to obtain the carbon quantum dot with the phase transfer effect.
0.1g of the prepared carbon quantum dots with the phase transfer effect and 0.1g of sodium persulfate oxidant are added into 1g of naphthenic acid wastewater with the concentration of 10mmol/L, and the mixture is magnetically stirred for 50min at the temperature of 60 ℃. The concentration of the non-oxidized naphthenic acid in the solution after the reaction is determined to be 0.29mmol/L by an ultraviolet spectrophotometry, and the catalytic degradation rate of the naphthenic acid is 87.8 percent.
Comparative example 1
The invention provides a carbon quantum dot with phase transfer effect, and the preparation method specifically comprises the following steps:
0.01mol (1.14 g) of 1- (2-aminoethyl) pyrrolidine, 0.08mol (55.8 g) of polyethylene glycol (PEG 200) and 0.001mol (0.053 g) of ammonium chloride are mixed and added into a 100mL three-neck flask, the mixture is placed in an oil bath pot, the mixture is heated and stirred to 80 ℃ from room temperature, and the mixture is heated for 2 hours, so that a coordination compound cannot be obtained, and even if the temperature is raised to 120 ℃, the reaction time is prolonged to 5 hours, the corresponding coordination compound cannot be synthesized, and a subsequent carbon quantum dot with a phase transfer effect cannot be prepared.
Comparative example 2
The invention provides a carbon quantum dot with phase transfer effect, and the preparation method comprises the following steps:
0.01mol (1.08 g) of p-phenylenediamine, 0.08mol (55.8 g) of polyethylene glycol (PEG 400) and 0.001mol (0.164 g) of calcium nitrate are mixed and added into a 100mL three-neck flask, the mixture is placed in an oil bath pot, heating and stirring are carried out from room temperature to 100 ℃, heating is carried out for 1.5h, no coordination compound can be obtained, even if the temperature is raised to 130 ℃, the reaction time is prolonged to 5h, the corresponding coordination compound can not be synthesized, and the subsequent carbon quantum dot with the phase transfer effect can not be prepared.
Comparative example 3
The comparative example provides a ZSM-5 molecular sieve for degrading naphthenic acid wastewater, and the preparation method specifically comprises the following steps:
0.1g of ZSM-5 and 0.1g of sodium persulfate oxidant are added into 1g of naphthenic acid wastewater with the concentration of 10mmol/L, and the mixture is magnetically stirred for 40min at the temperature of 50 ℃. The concentration of the non-oxidized naphthenic acid in the reacted solution is 1.62mmol/L by using an ultraviolet spectrophotometry, and the catalytic degradation rate of the naphthenic acid is only 32.1 percent.
The ZSM-5 molecular sieve is purchased from an alatin reagent official website. The molecular sieve specifications were as follows:
comparative example 4
The comparative example provides a dual-phase catalyst for degrading naphthenic acid wastewater, and the preparation method comprises the following steps:
the hydrophilic phase was 0.03mol (9.67 g) tetrabutylammonium bromide and 0.01mol (2.7) FeCl 3 ·6H 2 O, and the hydrophobic phase is a eutectic solvent consisting of 0.1mol (56.1 g) of ammonium tetraphenylborate and 0.01mol (1.72 g) of capric acid. And uniformly mixing the hydrophilic phase and the hydrophobic phase to obtain the two-phase catalyst. 30mL of the prepared biphase catalyst and 0.1g of sodium persulfate oxidant are added into 1g of 10mmol/L naphthenic acid wastewater, and the mixture is magnetically stirred for 40min at the temperature of 60 ℃. The solution after the reaction is measured by ultraviolet spectrophotometry to be not oxidized with the concentration of 1.53mmol/L and the naphthenic acid is catalyzed and degradedThe ratio was 38.1%.
In conclusion, the preparation method of the carbon quantum dots with the phase transfer effect is simple, the prepared carbon quantum dots have the advantages of uniform dispersion, simplicity in operation, high efficiency of catalytic degradation of naphthenic acid in wastewater and the like, the degradation method is simple, a sample does not need to be pretreated, the treatment process is simple, the degradation efficiency is high, and the carbon quantum dots have wide application value.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The carbon quantum dot with the phase transfer effect is characterized in that the carbon quantum dot is prepared from a coordination compound prepared from a pyrrole compound, polyethylene glycol and metal salts through a hydrothermal method.
2. The phase transfer carbon quantum dot of claim 1, wherein the azole compound is at least one of 1- (2-aminoethyl) pyrrolidine, 3-aminopyrrolidine, or 3-pyrrolidinol.
3. The carbon quantum dot with phase transfer effect of claim 1, wherein the polyethylene glycol is at least one of PEG200, PEG300, PEG400, or PEG 600.
4. The phase-transfer carbon quantum dot according to claim 1, wherein the metal salt is at least one of a metal chloride or a metal nitrate.
5. The phase-transfer carbon quantum dot according to claim 4, wherein the metal salt is at least one of zinc chloride, aluminum chloride, ferric chloride, cupric chloride, cobalt chloride, nickel chloride, molybdenum chloride, lanthanum nitrate, calcium nitrate, lead nitrate, strontium nitrate, or cerium nitrate.
6. The phase transfer carbon quantum dot according to any one of claims 1 to 5, wherein the molar ratio of the pyrrole compound, polyethylene glycol and metal salt is 1 to 2.
7. The method for producing a phase-transfer carbon quantum dot according to any one of claims 1 to 6, characterized by comprising the steps of:
step one, uniformly mixing the pyrrole compound, polyethylene glycol and metal salt, and reacting at 50-110 ℃ for 1-3h to obtain a coordination compound;
and step two, adding 30-40mL of deionized water into the coordination compound, and reacting for 10-15h at 180-220 ℃ to obtain the carbon quantum dot with the phase transfer effect.
8. Use of the carbon quantum dots with phase transfer effect according to any one of claims 1 to 7 for catalytic degradation of naphthenic acids.
9. The method for catalytically degrading naphthenic acid by using the carbon quantum dot with phase transfer effect according to any one of claims 1 to 8, wherein the carbon quantum dot with phase transfer effect and an oxidizing agent are added into wastewater containing naphthenic acid for catalytic degradation.
10. The method for the catalytic degradation of naphthenic acids by carbon quantum dots with phase transfer effect of claim 9, wherein the oxidant is soluble persulfate.
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