CN108889337B - Photocatalyst for dye wastewater treatment by using L-phenylalanine Schiff base derivative and preparation and application methods thereof - Google Patents
Photocatalyst for dye wastewater treatment by using L-phenylalanine Schiff base derivative and preparation and application methods thereof Download PDFInfo
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- -1 L-phenylalanine Schiff base Chemical class 0.000 title claims abstract description 52
- 239000002262 Schiff base Substances 0.000 title claims abstract description 41
- 229960005190 phenylalanine Drugs 0.000 title claims abstract description 33
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 33
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-Phenylalanine Natural products OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000004065 wastewater treatment Methods 0.000 title claims description 10
- 229940024606 amino acid Drugs 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002351 wastewater Substances 0.000 claims abstract description 18
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 9
- 150000001413 amino acids Chemical class 0.000 claims abstract description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910052603 melanterite Inorganic materials 0.000 claims abstract description 7
- WQRWNOKNRHCLHV-TWGQIWQCSA-N (z)-2-bromo-3-phenylprop-2-enal Chemical compound O=CC(/Br)=C/C1=CC=CC=C1 WQRWNOKNRHCLHV-TWGQIWQCSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002835 absorbance Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 5
- 239000006228 supernatant Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 16
- 238000006731 degradation reaction Methods 0.000 claims description 10
- 230000015556 catabolic process Effects 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 6
- FNDRXBYGDCDXLQ-MDZDMXLPSA-N 1-bromo-4-[(e)-2-(4-butylphenyl)ethenyl]benzene Chemical compound C1=CC(CCCC)=CC=C1\C=C\C1=CC=C(Br)C=C1 FNDRXBYGDCDXLQ-MDZDMXLPSA-N 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000000593 degrading effect Effects 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- 239000010919 dye waste Substances 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 21
- 235000001014 amino acid Nutrition 0.000 description 17
- 230000001699 photocatalysis Effects 0.000 description 11
- 239000011701 zinc Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 6
- 150000004753 Schiff bases Chemical class 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/39—
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
A photocatalyst of L-phenylalanine Schiff base derivative for treating dye waste water is prepared from phenylalanine and alpha-bromocinnamaldehyde through synthesizing chiral amino acid Schiff base ligand, and mixing it with FeSO4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·2H2Performing complex reaction on O to obtain three amino acid metal complexes C for treating dye wastewater18H19BrFe2+NO4、C18H19BrNi2+NO4And C18H19BrZn2+NO4I.e., three photocatalysts. When the method is applied, under the condition of visible light, the three amino acid metal complexes are irradiated and then catalytically degraded with RhB, and the degraded solution is filtered, and the supernatant is taken to measure the absorbance. The invention has wide raw material source, simple preparation, simple and convenient operation and reliable performance, and can be effectively used for treating dye wastewater.
Description
Technical Field
The invention belongs to the field of photocatalytic degradation of dye wastewater, and particularly relates to a photocatalyst for treating dye wastewater by using an L-phenylalanine Schiff base derivative, and a preparation method and an application method thereof, which provide a new solution for treating industrial wastewater.
Background
The dye wastewater has the characteristics of complex components, high concentration, high chromaticity and more difficultly-degraded substances, contains various organic matters with biotoxicity or 'three-cause' performance, and is difficult to treat by adopting a conventional treatment method, so the treatment of the industrial wastewater is the focus of attention of the chemical and environmental protection industry. The photocatalytic oxidation method is the most common dye pollution treatment method at present, the most important thing is to select the most appropriate photocatalytic material, the quantum efficiency of many photocatalysts is relatively low at present, the photocatalytic activity of many photocatalysts is limited to a certain extent, and the visible sunlight cannot be effectively utilized. In addition, the waste is easy to cause loss in the using process and is difficult to recover. Therefore, it is a difficult point and hot point to solve the photocatalytic technology at present to develop a new, efficient and environment-friendly photocatalytic material.
TiO2ZnO is a common photocatalyst at present, and ZnO and TiO have the characteristics of high chemical stability, deeper valence band energy level, light corrosion resistance, no toxicity and the like2The photocatalyst is widely applied to dye wastewater treatment. But ZnO, TiO2The quantum efficiency of (a) is relatively low, and therefore the photocatalytic activity thereof is limited to a certain extent, and visible sunlight cannot be effectively utilized. The photocatalytic light source used by the existing catalyst has high energy consumption and low utilization rate. If visible light or sunlight can be used as a light source, the operation cost of the photocatalysis technology can be greatly reduced; in addition, in the aspects of economy and technology, the nano ZnO and the nano TiO are used2The particle radius is small, the loss is easy to cause in the using process, and the recovery is difficult. Therefore, the development of a novel, efficient, environment-friendly and recyclable photocatalytic material is a problem of solving the difficulties and hot spots in the photocatalytic technology at present.
Schiff bases and their derivatives have been of great interest to scientists in the 21 st century as industrial catalysts, active agents in the biological field, chelating agents, analytical chemicals and stabilizers. In addition, the Schiff base ligand containing multifunctional groups and the metal complex thereof play an important role in the fields of stereochemistry, structure science, magnetism, spectroscopy, dynamics, reaction mechanism, coordination reaction, analytical chemistry, catalysis, stabilizer dyes and pigments, photography, electro-optical display, agriculture and the like.
However, no amino acid schiff base metal complex has been reported as a photocatalyst.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the photocatalyst for treating the dye wastewater by using the L-phenylalanine Schiff base derivative, and the preparation and application methods thereof, wherein the photocatalyst has the advantages of wide raw material source, simple preparation, simple and convenient operation and reliable performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
the chemical structural formula of the photocatalyst of the L-phenylalanine Schiff base derivative for treating the dye wastewater is as follows:
m in the chemical structural formula is any one of Fe, Ni and Zn.
The invention relates to a preparation method of a photocatalyst for treating dye wastewater by using L-phenylalanine Schiff base derivatives, which comprises the following steps: taking phenylalanine and alpha-bromocinnamaldehyde as raw materials, firstly synthesizing an amino acid Schiff base ligand with chirality, and then carrying out complex reaction on the amino acid Schiff base ligand and metal salt to obtain an amino acid metal complex, namely a photocatalyst, for treating dye wastewater.
The metal salt is FeSO4·7H2O、NiCl2·6H2O or (CH)3COO)2Zn·2H2O, the amino acid metal complex obtained is C18H19BrFe2+NO4、C18H19BrNi2+NO4Or C18H19Br Zn2+NO4。
The synthesis method of the amino acid Schiff base ligand comprises the following steps: firstly, respectively adding 0.5-1 mmol of phenylalanine, 0.5-1 mmol of potassium hydroxide and 5-10 mL of methanol, heating and stirring, dropwise adding 3-5 mL of 0.5-1 mmol of alpha-bromo-cinnamaldehyde methanol solution when the solution becomes colorless and transparent, and carrying out reflux reaction for 2-3h after dropwise adding is finished; then, the solvent is evaporated under reduced pressure, and the crude product is recrystallized by water to obtain a solid with earthy yellow color, namely the amino acid Schiff base ligand.
When phenylalanine and potassium hydroxide are added, n (C) is added9H11NO2):n(KOH)＝1:1。
When the amino acid Schiff base ligand and the metal salt are subjected to complex reaction, the amino acid Schiff base ligand is dissolved in methanol, and FeSO is respectively added4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·2H2O and stirring, heating to 60-70 ℃, reacting for 2-3h at constant temperature, filtering after the reaction is finished, recrystallizing by using ethanol to obtain black solid, light green solid and black solid respectively, and correspondingly obtaining three amino acid metal complexes C18H19BrFe2+NO4、C18H19BrNi2+NO4And C18H19BrZn2+NO4。
The application method of the L-phenylalanine Schiff base derivative used for the photocatalyst for dye wastewater treatment comprises the following steps: under visible light conditions, three amino acid metal complexes C18H19BrFe2+NO4、C18H19BrNi2+NO4And C18H19BrZn2+NO4And (3) catalyzing and degrading RhB after illumination, filtering the solution after degradation, taking supernatant liquid, measuring absorbance, and finishing degradation when the absorbance is stable.
The illumination time for catalyzing and degrading RhB is 60-120min, and a needle filter is adopted when the solution is filtered.
Before illumination, the amino acid metal complex is ultrasonically vibrated in an ultrasonic instrument for 1-2min to uniformly disperse the solid powder.
Compared with the prior art, the invention firstly takes the phenylalanine and the alpha-bromocinnamaldehyde as the raw materials to synthesize the chiral aminoAcid Schiff base ligand, and then the amino acid Schiff base ligand is respectively reacted with metal salt FeSO4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·2H2Performing a complexing reaction on O to obtain three novel amino acid metal complexes, characterizing the structures of the amino acid metal complexes by using an infrared spectrometer, a fluorescence spectrophotometer, an ultraviolet-visible spectrophotometer, an element analyzer and the like, testing the photocatalytic properties of the amino acid metal complexes by using an ultraviolet diffuse reflection spectrum, and investigating 3 metal coordination compounds C under the irradiation of visible light18H19BrFe2+NO4、C18H19BrNi2+NO4、C18H19Br Zn2+NO4Degradation performance on RhB. The experimental result shows that the catalysts have degradation performance on RhB, wherein C18H19Br Zn2+NO4Has the strongest degradation capability.
Drawings
FIG. 1 is a line graph of the degradation rate of three photocatalysts on RhB;
in the figure: 1 is C18H19BrFe2+NO42 is C18H19BrNi2+NO4And 3 is C18H19BrZn2+NO4。
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The synthetic route of the photocatalyst for treating dye wastewater by using the L-phenylalanine Schiff base derivative is as follows:
m in the chemical formula is different metals and can be any one of Fe, Ni and Zn.
Example 1
The invention relates to a preparation method of a photocatalyst for treating dye wastewater by using L-phenylalanine Schiff base derivatives, which comprises the following steps:
(1) synthesizing a phenylalanine Schiff base ligand;
adding 1mmol of phenylalanine, 1mmol of potassium hydroxide and 10mL of methanol into a three-neck flask, heating and stirring, slowly dropwise adding 5mL of 1mmol of alpha-bromocinnamaldehyde methanol solution when the solution becomes colorless and transparent, and after dropwise adding, carrying out reflux reaction for about 3h (TCL tracking). The solvent was evaporated off under reduced pressure and the crude product was recrystallized from water to give 0.27g of a yellowish brown solid. Yield: 75%, IR (KBr, cm)-1)υ:1674(stretch C＝O),1635(stretch C＝N),2919(stretch CH2),2949(stretch CH),3098(stretch OH),1595(stretch Ph),1498(stretch Ph).1H NMR(400MHz,DMSO,ppm)δ:2.50(2H,d,CH2),3.70(1H,t,CH),6.71-7.24(10H,m,Ar-H),7.19(1H,s,C＝CH),7.79(1H,s,N＝CH),9.45(1H,s,COOH)ppm.LC-MS(M+1)Calcd for C18H16BrNO2:357.04found 357.00.Anal.Calcd(％)For C18H16BrNO2:C,60.35；H,4.50；N,3.91；Found:C,60.30；H,4.53；N,3.89。
(2) Synthesizing a phenylalanine Schiff base metal complex;
1mmol of Schiff base ligand and 10mL of methanol are added into a three-neck flask, heated and stirred to be completely dissolved, and 1mmol of metal salt (FeSO) is respectively added4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·2H2O), reacting for 2-3h at constant temperature of 60 ℃. Filtering, and recrystallizing with ethanol to obtain black solid, light green solid, and black solid.
Phenylalanine schiff base iron metal complex (1): yellow crystals 0.34g, yield: 60-75%,; IR (KBr); v 3380,1602,521,424cm-1；Anal.calcd for C18H19BrFe2+NO4:C,48.14；H,4.26；N,3.12；found C,48.12；H,4.23；N,3.18。
Phenylalanine schiff base nickel metal complex (2): pale yellow crystals 0.38g, yield: 79-85 percent; IR (KBr); v 3357,1600,523,473cm-1；Anal.calcd for C18H19BrNi2+NO4:C,47.84；H,4.24；N,3.10；found C,47.80；H,4.26；N,3.12。
0.32g of yellow-green needle-shaped crystals of the phenylalanine Schiff base zinc complex (3), yield: 65-70%,; IR (KBr), v 3406, 1601, 598, 480cm-1；Anal.calcd for C18H19Br Zn2+NO4:C,47.14；H,4.18；N,3.05；found C,47.15；H,4.20；N,3.01。
Example 2
The invention relates to a preparation method of a photocatalyst for treating dye wastewater by using L-phenylalanine Schiff base derivatives, which comprises the following steps:
adding 0.5mmol of phenylalanine, 0.5mmol of potassium hydroxide and 5mL of methanol into a three-neck flask, heating and stirring, slowly dropwise adding 2mL of methanol solution of 0.5mmol of alpha-bromo-cinnamaldehyde when the solution becomes colorless and transparent, and after dropwise adding, carrying out reflux reaction for about 2-3 h. The solvent is evaporated under reduced pressure, and the crude product is recrystallized by water to obtain a solid of earthy yellow.
Then the obtained ligand is respectively reacted with metal salt FeSO4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·2H2And performing complex reaction on the O to obtain three photocatalysts for treating the dye wastewater. The photocatalyst is reacted by means of a homogeneous reactor during preparation, the dye wastewater is prepared for a laboratory, and the drying mode is drying by a blast drying oven.
Example 3
The invention relates to a preparation method of a photocatalyst for treating dye wastewater by using L-phenylalanine Schiff base derivatives, which comprises the following steps:
adding 0.75mmol of phenylalanine, 0.75mmol of potassium hydroxide and 7mL of methanol into a three-neck flask, heating and stirring, slowly dropwise adding 3mL of methanol solution of 0.75mmol of alpha-bromo-cinnamaldehyde when the solution becomes colorless and transparent, and after dropwise adding, carrying out reflux reaction for about 2-3 h. The solvent is evaporated under reduced pressure, and the crude product is recrystallized by water to obtain a solid of earthy yellow.
Then the obtained ligand is respectively reacted with metal salt FeSO4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·2H2And performing complex reaction on the O to obtain three photocatalysts for treating the dye wastewater. The photocatalyst is prepared by means of a homogeneous reactor for reaction,the dye wastewater is prepared in a laboratory, and the drying mode is drying by a blast drying oven.
Referring to fig. 1, the application method of the L-phenylalanine schiff base derivative of the invention used as the photocatalyst for dye wastewater treatment comprises the following steps:
the degradation performance of 3 metal coordination compounds on RhB under visible light irradiation is examined. Adding 0.02g of catalyst, controlling the reaction temperature at 25-45 ℃, the light irradiation time at 60-120min, and preparing the concentration of model pollutant RhB at 1 x 10-7-1×10-5mol/L. The experimental results show that the degradation rates of the three photocatalysts to RhB are respectively 54.1%, 63.9% and 72.7%.
Thereby predicting that the method has better application prospect in the fields of sewage treatment and the like.
Claims (7)
1. A photocatalyst of L-phenylalanine Schiff base derivatives for dye wastewater treatment is characterized in that:
the chemical structural formula is as follows:
m in the chemical structural formula is any one of Fe, Ni and Zn.
2. A method for preparing a photocatalyst for dye wastewater treatment using the L-phenylalanine schiff base derivative as described in claim 1, wherein: taking phenylalanine and alpha-bromocinnamaldehyde as raw materials, firstly synthesizing an amino acid Schiff base ligand with chirality, and then carrying out complex reaction on the amino acid Schiff base ligand and metal salt to obtain an amino acid metal complex, namely a photocatalyst, for treating dye wastewater; the metal salt is FeSO4·7H2O、NiCl2·6H2O or (CH)3COO)2Zn·2H2O, the amino acid metal complex obtained is C18H19BrFe2+NO4、C18H19BrNi2+NO4Or C18H19Br Zn2+NO4(ii) a Dissolving amino acid Schiff base ligand in methanol, and respectively adding FeSO4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·2H2O and stirring, heating to 60-70 ℃, reacting for 2-3h at constant temperature, filtering after the reaction is finished, recrystallizing by using ethanol to obtain black solid, light green solid and black solid respectively, and correspondingly obtaining three amino acid metal complexes C18H19BrFe2+NO4、C18H19BrNi2+NO4And C18H19BrZn2+NO4。
3. The method for preparing the photocatalyst for dye wastewater treatment by using the L-phenylalanine Schiff base derivative as claimed in claim 2, wherein the synthesis method of the amino acid Schiff base ligand comprises the following steps: firstly, respectively adding 0.5-1 mmol of phenylalanine, 0.5-1 mmol of potassium hydroxide and 5-10 mL of methanol, heating and stirring, dropwise adding 3-5 mL of 0.5-1 mmol of alpha-bromo-cinnamaldehyde methanol solution when the solution becomes colorless and transparent, and carrying out reflux reaction for 2-3h after dropwise adding is finished; then, the solvent is evaporated under reduced pressure, and the crude product is recrystallized by water to obtain a solid with earthy yellow color, namely the amino acid Schiff base ligand.
4. The method for preparing a photocatalyst for dye wastewater treatment from the derivatives of L-phenylalanine Schiff base according to claim 3, wherein the method comprises the following steps: when phenylalanine and potassium hydroxide are added, n (C) is added9H11NO2):n(KOH)＝1:1。
5. An application method of the amino acid metal complex prepared by the preparation method of the photocatalyst of the L-phenylalanine Schiff base derivative in the dye wastewater treatment of claim 3, which is characterized in that: under visible light conditions, three amino acid metal complexes C18H19BrFe2+NO4、C18H19BrNi2+NO4And C18H19BrZn2+NO4And (3) catalyzing and degrading RhB after illumination, filtering the solution after degradation, taking supernatant liquid, measuring absorbance, and finishing degradation when the absorbance is stable.
6. The method for using an amino acid metal complex according to claim 5, wherein: the illumination time for catalyzing and degrading RhB is 60-120min, and a needle filter is adopted when the solution is filtered.
7. The method for using an amino acid metal complex according to claim 5, wherein: before illumination, the amino acid metal complex is ultrasonically vibrated in an ultrasonic instrument for 1-2min to uniformly disperse the solid powder.
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