CN108889337A - L-phenylalanine Schiff base derivatives are used for the photochemical catalyst and its preparation and application method of dye wastewater treatment - Google Patents
L-phenylalanine Schiff base derivatives are used for the photochemical catalyst and its preparation and application method of dye wastewater treatment Download PDFInfo
- Publication number
- CN108889337A CN108889337A CN201810549626.6A CN201810549626A CN108889337A CN 108889337 A CN108889337 A CN 108889337A CN 201810549626 A CN201810549626 A CN 201810549626A CN 108889337 A CN108889337 A CN 108889337A
- Authority
- CN
- China
- Prior art keywords
- schiff base
- phenylalanine
- wastewater treatment
- dye wastewater
- photochemical catalyst
- 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.)
- Granted
Links
- -1 L-phenylalanine Schiff base Chemical class 0.000 title claims abstract description 57
- 239000002262 Schiff base Substances 0.000 title claims abstract description 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 229960005190 phenylalanine Drugs 0.000 title claims abstract description 36
- 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 31
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 16
- 229940024606 amino acid Drugs 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006731 degradation reaction Methods 0.000 claims abstract description 14
- 230000015556 catabolic process Effects 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims abstract description 9
- 229910052603 melanterite Inorganic materials 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
- 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 8
- 238000005286 illumination Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 238000002835 absorbance Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 239000006228 supernatant Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 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
- 239000000126 substance Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003756 stirring 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
- 150000001413 amino acids Chemical class 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000004753 Schiff bases Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000000975 dye Substances 0.000 description 21
- 235000001014 amino acid Nutrition 0.000 description 14
- 239000011701 zinc Substances 0.000 description 9
- 230000001699 photocatalysis Effects 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 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
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 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
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- 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 kind of L-phenylalanine Schiff base derivatives are used for the photochemical catalyst and its preparation and application method of dye wastewater treatment, using phenylalanine and alpha-bromo-cinnamaldehyde as raw material when preparation, first synthesis has a chiral amino-acid schiff base ligand, then by amino-acid schiff base ligand respectively with metal salt FeSO4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·2H2O carries out complex reaction, obtains three kinds of amino acids metal complex C for dye wastewater treatment18H19BrFe2+NO4、C18H19BrNi2+NO4And C18H19BrZn2+NO4, i.e. three kinds of photochemical catalysts.Using when under visible light conditions, by three kinds of amino acids metal complex catalytic degradation RhB after illumination, filtering solution takes supernatant to measure absorbance after degradation.Raw material sources of the present invention are wide, prepare simple, easy to operate and reliable performance, can be effective for dye wastewater treatment.
Description
Technical field
The invention belongs to waste water from dyestuff photocatalytic degradation fields, and in particular to a kind of L-phenylalanine Schiff base derivatives use
In the photochemical catalyst and its preparation and application method of dye wastewater treatment, new solution route is provided for the improvement of industrial wastewater.
Background technique
Waste water from dyestuff has the characteristics that complicated component, high concentration, high chroma, hard-degraded substance are more, and containing there are many have
The organic matter of bio-toxicity or " three cause " performance, it is difficult to be administered using conventional administering method, so industrial wastewater is controlled
Reason is chemical industry environmental protection industry focus of attention.And photocatalytic oxidation is most common dye discoloration processing method, it is most
It is important to choose most suitable catalysis material, current many photochemical catalyst quantum efficiencies compare lower, photocatalysis
Activity is restricted to a certain extent, cannot efficiently use visible sunlight.In addition, loss is easily caused in use process, it is difficult
With recycling.Therefore, a kind of novel, efficient and environmentally friendly catalysis material is developed, is the current difficult point solved in photocatalysis technology
And hot spot.
TiO2, ZnO be common photochemical catalyst at present, since it is high with chemical stability, valence-band level is deeper, fast light
The features such as burn into is nontoxic, ZnO, TiO2It is widely used in dye wastewater treatment as photochemical catalyst.But ZnO, TiO2Amount
Sub- efficiency compares lower, therefore its photocatalytic activity is restricted to a certain extent, cannot efficiently use visible sunlight.
The photocatalysis light source energy consumption that catalyst uses at present is very big, and utilization rate is low.It, can if can be using visible light or sunlight as light source
To substantially reduce the operating cost of photocatalysis technology；In addition, in terms of economic and technical, due to nano-ZnO, TiO2Particle radius
It is smaller, loss is easily caused in use process, it is difficult to be recycled.Therefore, a kind of novel, efficient, environmentally friendly, recoverable light is developed
Catalysis material is the current difficult point and hot spot solved in photocatalysis technology.
In 21 century, schiff bases and its derivative as industrial catalyst, the active agent of biological field, chelating agent, point
Chemical reagent and stabilizer are analysed by scientific worker's extensive concern.In addition, schiff base ligand and its metal containing multifunctional groups are matched
Object is closed in spatial chemistry, structure, magnetics, spectrum, hydro bromic acid, complexation reaction, analytical chemistry, catalysis, stabilization
Agent dyestuff and pigment, photography, electric light are shown and the fields such as agricultural suffer from important role.
But the report not yet about amino-acid schiff base metal complex as photochemical catalyst.
Summary of the invention
The present invention is directed to above-mentioned the problems of the prior art, provides a kind of L-phenylalanine Schiff base derivatives for dyestuff
The photochemical catalyst and its preparation and application method of wastewater treatment, raw material sources are wide, prepare simple, easy to operate and reliable performance.
To achieve the goals above, the technical solution adopted by the present invention is：
L-phenylalanine Schiff base derivatives are for the photochemical catalyst chemical structural formula of dye wastewater treatment：
M in chemical structural formula is any one in Fe, Ni and Zn.
Preparation method of the L-phenylalanine Schiff base derivatives of the present invention for the photochemical catalyst of dye wastewater treatment：With benzene
Alanine and alpha-bromo-cinnamaldehyde are raw material, and synthesis first has a chiral amino-acid schiff base ligand, then by amino acid Schiff
Aar ligand and metal salt carry out complex reaction, obtain the amino acids metal complex for dye wastewater treatment, i.e. photochemical catalyst.
The metal salt is FeSO4·7H2O、NiCl2·6H2O or (CH3COO)2Zn·2H2O, obtained amino acid gold
Metal complex is C18H19BrFe2+NO4、C18H19BrNi2+NO4Or C18H19Br Zn2+NO4。
The synthetic method of amino-acid schiff base ligand is：Firstly, it is separately added into 0.5~1mmol phenylalanine, 0.5~
The potassium hydroxide of 1mmol and the methanol of 5~10mL, heating stirring wait solution when becoming colorless transparent, then it is added dropwise 0.5~
Alpha-bromo-cinnamaldehyde 3~5mL of methanol solution of 1mmol, drop finish, 2~3h of back flow reaction；Then evaporating solvent under reduced pressure, by crude product
Khaki solid, i.e. amino-acid schiff base ligand are recrystallized to obtain with water.
Phenylalanine and potassium hydroxide make n (C when being added9H11NO2):N (KOH)=1:1.
When amino-acid schiff base ligand and metal salt carry out complex reaction, amino-acid schiff base ligand is dissolved in methanol, point
It Jia Ru not FeSO4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·2H2O is simultaneously stirred, and is heated to 60~70 DEG C, at a constant temperature instead
2~3h is answered, is filtered after reaction, obtains black solid, light green solid, black solid respectively using ethyl alcohol recrystallization,
Corresponding to obtaining three kinds of amino acids metal complex C18H19BrFe2+NO4、C18H19BrNi2+NO4And C18H19BrZn2+NO4。
Application method of the L-phenylalanine Schiff base derivatives of the present invention for the photochemical catalyst of dye wastewater treatment：Can
Under the conditions of light-exposed, by three kinds of amino acids metal complex C18H19BrFe2+NO4、C18H19BrNi2+NO4And C18H19BrZn2+NO4,
The catalytic degradation RhB after illumination, filtering solution takes supernatant to measure absorbance after degradation, and absorbance steadily completes drop
Solution.
The light application time of catalytic degradation RhB is 60-120min, and syringe filter is used when filtering solution.
By amino acids metal complex, ultrasonic vibration 1-2min keeps solid powder evenly dispersed in Ultrasound Instrument before illumination.
Compared with prior art, the present invention is for the first time using phenylalanine and alpha-bromo-cinnamaldehyde as raw material, and synthesis has first
Chiral amino Schiff base ligand, then by amino Schiff base ligand respectively with metal salt FeSO4·7H2O、NiCl2·
6H2O、(CH3COO)2Zn·2H2O carries out complex reaction, three kinds of novel amino acids metal complexs is obtained, by amino acids metal
Complex infrared spectrometer, sepectrophotofluorometer, ultraviolet-uisible spectrophotometer and elemental analyser etc. characterize its structure,
And its photocatalysis property is tested with UV Diffuse Reflectance Spectroscopy, under visible light illumination, investigate 3 kinds of metal complexes
C18H19BrFe2+NO4、C18H19BrNi2+NO4、C18H19Br Zn2+NO4To the degradation property of RhB.The experimental results showed that catalyst
There is degradation property to RhB, wherein C18H19Br Zn2+NO4Degradation capability it is most strong.
Detailed description of the invention
Degradation rate line chart of the tri- kinds of photochemical catalysts of Fig. 1 to RhB；
In figure：1 is C18H19BrFe2+NO4, 2 be C18H19BrNi2+NO4, 3 be C18H19BrZn2+NO4。
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and embodiments.
Synthetic route of the L-phenylalanine Schiff base derivatives of the present invention for the photochemical catalyst of dye wastewater treatment is as follows：
M in chemical formula is different metal, can be any one in Fe, Ni and Zn.
Embodiment 1
Preparation method of the L-phenylalanine Schiff base derivatives of the present invention for the photochemical catalyst of dye wastewater treatment：
(1) synthesis of phenylalanine Schiff base ligand；
Phenylalanine 1mmol, potassium hydroxide 1mmol and 10mL methanol are added in three-neck flask, heating stirring waits molten
When liquid bleach is transparent, be slowly added dropwise 1mmol alpha-bromo-cinnamaldehyde methanol solution 5mL, drop finishes, back flow reaction about 3h (TCL with
Track).Evaporating solvent under reduced pressure, crude product recrystallize to obtain khaki solid 0.27g with water.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) synthesis of phenylalanine Schiff base metal complexes；
In three-neck flask be added Schiff base ligand 1mmol and 10mL methanol, heating stirring make its all dissolve, respectively plus
Enter 1mmol metal salt (FeSO4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·2H2O), 2-3h is reacted at 60 DEG C of constant temperature.It crosses
Filter obtains black solid, light green solid, black solid with ethyl alcohol recrystallization respectively.
Phenylalanine schiff bases ferrous metal complex (1)：The crystal 0.34g of yellow, yield：60-75%,；IR(KBr),
ν: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 bases nickel metal complex (2)：Flaxen crystal 0.38g, yield：79-85%,；IR
(KBr),ν: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.
Phenylalanine schiff bases zinc metal complex (3) acicular crystal 0.32g of yellow green, yield：65-70%,；IR
(KBr), ν: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.
Embodiment 2
Preparation method of the L-phenylalanine Schiff base derivatives of the present invention for the photochemical catalyst of dye wastewater treatment：
The addition phenylalanine 0.5mmol, potassium hydroxide 0.5mmol and 5mL methanol in three-neck flask, heating stirring, etc.
When solution bleach is transparent, the methanol solution 2mL of 0.5mmol alpha-bromo-cinnamaldehyde is slowly added dropwise, drop finishes, back flow reaction about 2-
3h.Evaporating solvent under reduced pressure, crude product recrystallize to obtain khaki solid with water.
Then by obtained ligand respectively at metal salt FeSO4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·
2H2O carries out complex reaction, obtains three kinds of photochemical catalysts for dye wastewater treatment.Photochemical catalyst is in the preparation by homogeneous
Reactor is reacted, and waste water from dyestuff is laboratory configuration, and drying mode is air dry oven drying.
Embodiment 3
Preparation method of the L-phenylalanine Schiff base derivatives of the present invention for the photochemical catalyst of dye wastewater treatment：
The addition phenylalanine 0.75mmol, potassium hydroxide 0.75mmol and 7mL methanol in three-neck flask, heating stirring,
When waiting solution bleach transparent, the methanol solution 3mL of 0.75mmol alpha-bromo-cinnamaldehyde is slowly added dropwise, drop finishes, back flow reaction
About 2-3h.Evaporating solvent under reduced pressure, crude product recrystallize to obtain khaki solid with water.
Then by obtained ligand respectively at metal salt FeSO4·7H2O、NiCl2·6H2O、(CH3COO)2Zn·
2H2O carries out complex reaction, obtains three kinds of photochemical catalysts for dye wastewater treatment.Photochemical catalyst is in the preparation by homogeneous
Reactor is reacted, and waste water from dyestuff is laboratory configuration, and drying mode is air dry oven drying.
Referring to Fig. 1, application of the L-phenylalanine Schiff base derivatives of the present invention for the photochemical catalyst of dye wastewater treatment
Method：
Under visible light illumination, 3 kinds of metal complexes are investigated to the degradation property of RhB.Catalyst quality, which is added, is
0.02g, control reaction temperature is at 25-45 DEG C, and light irradiation time is 60-120min, the concentration of preparation model pollutant RhB is 1
×10-7-1×10-5mol/L.The experimental results showed that three kinds of photochemical catalysts are respectively 54.1%, 63.9% and to the degradation rate of RhB
72.7%.
To predict that it will have preferable application prospect in fields such as sewage treatments.
Claims (10)
1. the photochemical catalyst that a kind of L-phenylalanine Schiff base derivatives are used for dye wastewater treatment, it is characterised in that：
Chemical structural formula is：
2. L-phenylalanine Schiff base derivatives are used for the photochemical catalyst of dye wastewater treatment according to claim 1, special
Sign is：M in chemical structural formula is any one in Fe, Ni and Zn.
3. a kind of preparation method of L-phenylalanine Schiff base derivatives for the photochemical catalyst of dye wastewater treatment, feature exist
In：Using phenylalanine and alpha-bromo-cinnamaldehyde as raw material, synthesis first has a chiral amino-acid schiff base ligand, then by amino
Sour schiff base ligand and metal salt carry out complex reaction, obtain the amino acids metal complex for dye wastewater treatment, i.e. light
Catalyst.
4. preparation of the L-phenylalanine Schiff base derivatives for the photochemical catalyst of dye wastewater treatment according to claim 3
Method, it is characterised in that：The metal salt is FeSO4·7H2O、NiCl2·6H2O or (CH3COO)2Zn·2H2O is obtained
Amino acids metal complex is C18H19BrFe2+NO4、C18H19BrNi2+NO4Or C18H19Br Zn2+NO4。
5. preparation of the L-phenylalanine Schiff base derivatives for the photochemical catalyst of dye wastewater treatment according to claim 3
Method, which is characterized in that the synthetic method of amino-acid schiff base ligand is：Firstly, it is separately added into 0.5~1mmol phenylalanine,
The potassium hydroxide of 0.5~1mmol and the methanol of 5~10mL, heating stirring when solution being waited to become colorless transparent, then are added dropwise
Alpha-bromo-cinnamaldehyde 3~5mL of methanol solution of 0.5~1mmol, drop finish, 2~3h of back flow reaction；Then evaporating solvent under reduced pressure, will
Crude product recrystallizes to obtain khaki solid, i.e. amino-acid schiff base ligand with water.
6. preparation of the L-phenylalanine Schiff base derivatives for the photochemical catalyst of dye wastewater treatment according to claim 5
Method, it is characterised in that：Phenylalanine and potassium hydroxide make n (C when being added9H11NO2):N (KOH)=1:1.
7. being used for the photochemical catalyst of dye wastewater treatment according to the L-phenylalanine Schiff base derivatives of claim 3 or 5
Preparation method, it is characterised in that：Amino-acid schiff base ligand is dissolved in methanol, is separately added into FeSO4·7H2O、NiCl2·
6H2O、(CH3COO)2Zn·2H2O is simultaneously stirred, and is heated to 60~70 DEG C, is reacted 2~3h at a constant temperature, was carried out after reaction
Filter, using ethyl alcohol recrystallization respectively black solid, light green solid, black solid, corresponding to obtaining three kinds of amino acids metals
Complex C18H19BrFe2+NO4、C18H19BrNi2+NO4And C18H19BrZn2+NO4。
8. a kind of system of L-phenylalanine Schiff base derivatives as described in claim 7 for the photochemical catalyst of dye wastewater treatment
The application method for three kinds of amino acids metal complexs that Preparation Method is prepared, it is characterised in that：Under visible light conditions, by three
Kind amino acids metal complex C18H19BrFe2+NO4、C18H19BrNi2+NO4And C18H19BrZn2+NO4, drop is catalyzed after illumination
RhB is solved, filtering solution takes supernatant to measure absorbance after degradation, and absorbance steadily completes degradation.
9. the application method of three kinds of amino acids metal complexs according to claim 8, it is characterised in that：Catalytic degradation RhB
Light application time be 60-120min, syringe filter is used when filtering solution.
10. the application method of three kinds of amino acids metal complexs according to claim 8, it is characterised in that：It will before illumination
Amino acids metal complex ultrasonic vibration 1-2min in Ultrasound Instrument keeps solid powder evenly dispersed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810549626.6A CN108889337B (en) | 2018-05-31 | 2018-05-31 | Photocatalyst for dye wastewater treatment by using L-phenylalanine Schiff base derivative and preparation and application methods thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810549626.6A CN108889337B (en) | 2018-05-31 | 2018-05-31 | Photocatalyst for dye wastewater treatment by using L-phenylalanine Schiff base derivative and preparation and application methods thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108889337A true CN108889337A (en) | 2018-11-27 |
| CN108889337B CN108889337B (en) | 2021-07-23 |
Family
ID=64343686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810549626.6A Active CN108889337B (en) | 2018-05-31 | 2018-05-31 | Photocatalyst for dye wastewater treatment by using L-phenylalanine Schiff base derivative and preparation and application methods thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108889337B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303441A (en) * | 2020-02-17 | 2020-06-19 | 忻州师范学院 | Proline and proline derivative functionalized chiral metal organic framework material and synthesis method thereof |
| CN111393395A (en) * | 2020-04-02 | 2020-07-10 | 太原理工大学 | Method for transferring C = N double bond by chlorella |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8476437B2 (en) * | 2008-08-27 | 2013-07-02 | Cadila Healthcare Limited | Process for preparation of (2R)-4-oxo-4-[3-(trifluoromethyl)-5,6-dihydro [1,2,4]-triazolo[4,3-a]pyrazin-7(8H)-yl]-l-(2,4,5-trifluorophenyl)butan-2-amine and new impurities in preparation thereof |
| CN106272789A (en) * | 2015-06-04 | 2017-01-04 | 东北林业大学 | A kind of water ballast type cinnamic aldehyde protectant preparation method of sill material |
| CN107960533A (en) * | 2016-10-20 | 2018-04-27 | 湖南晶天科技实业有限公司 | A kind of amino acid aldehyde schiff bases feed addictive and a kind of feed |
| CN108273557A (en) * | 2018-02-09 | 2018-07-13 | 长江水利委员会长江科学院 | A kind of iron schiff bases compound photochemical catalyst and preparation method thereof |
-
2018
- 2018-05-31 CN CN201810549626.6A patent/CN108889337B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8476437B2 (en) * | 2008-08-27 | 2013-07-02 | Cadila Healthcare Limited | Process for preparation of (2R)-4-oxo-4-[3-(trifluoromethyl)-5,6-dihydro [1,2,4]-triazolo[4,3-a]pyrazin-7(8H)-yl]-l-(2,4,5-trifluorophenyl)butan-2-amine and new impurities in preparation thereof |
| CN106272789A (en) * | 2015-06-04 | 2017-01-04 | 东北林业大学 | A kind of water ballast type cinnamic aldehyde protectant preparation method of sill material |
| CN107960533A (en) * | 2016-10-20 | 2018-04-27 | 湖南晶天科技实业有限公司 | A kind of amino acid aldehyde schiff bases feed addictive and a kind of feed |
| CN108273557A (en) * | 2018-02-09 | 2018-07-13 | 长江水利委员会长江科学院 | A kind of iron schiff bases compound photochemical catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HUI WANG等: "Synthesis, antimicrobial activity of Schiff base compounds of cinnamaldehyde and amino acids", 《BIOORGANIC & MEDICINAL CHEMISTRY LETTERS》 * |
| NAJLA H. TAHER等: "Synthesis and Characterization of Some Cinnamaldehyde Schiff Base Complexes", 《RAF. JOUR. SCI.》 * |
| QUAN SONG等: "Degradation of organic pollutants in waters by a water-insolubleiron(III) Schiff base complex", 《APPLIED CATALYSIS A: GENERAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111303441A (en) * | 2020-02-17 | 2020-06-19 | 忻州师范学院 | Proline and proline derivative functionalized chiral metal organic framework material and synthesis method thereof |
| CN111393395A (en) * | 2020-04-02 | 2020-07-10 | 太原理工大学 | Method for transferring C = N double bond by chlorella |
| CN111393395B (en) * | 2020-04-02 | 2022-12-27 | 太原理工大学 | Method for transferring C = N double bond of chlorella |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108889337B (en) | 2021-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Visible light photocatalysis of dye-sensitized TiO2: The selective aerobic oxidation of amines to imines | |
| Wang et al. | Visible-light-induced tandem reaction of o-aminothiophenols and alcohols to benzothiazoles over Fe-based MOFs: Influence of the structure elucidated by transient absorption spectroscopy | |
| CN105524007B (en) | A kind of preparation method and application of nanometer of Cu organic coordination compound crystal | |
| CN103657686B (en) | A kind of low-temperature co-precipitation method prepares the method for indium sulfide tin photochemical catalyst | |
| Singh et al. | New benzimidazolium-based chiral ionic liquids: synthesis and application in enantioselective sodium borohydride reductions in water | |
| Bai et al. | Flower-like Bi2O2CO3-mediated selective oxidative coupling processes of amines under visible light irradiation | |
| CN104478759A (en) | Preparation method for synthesizing imine through photo-catalytic oxidation of amine | |
| CN104324762A (en) | Preparation method and applications of ternary composite material | |
| CN108889337A (en) | L-phenylalanine Schiff base derivatives are used for the photochemical catalyst and its preparation and application method of dye wastewater treatment | |
| CN110483585A (en) | A kind of preparation method and applications of the organic cage compound of metal of adjustable high-efficient selective catalytic reduction nitrobenzaldehyde | |
| CN102580784A (en) | In-situ synthesis method of metal porphyrin sensitized titanium dioxide photocatalyst | |
| Baran et al. | Photocatalytic oxidation of volatile pollutants of air driven by visible light | |
| CN107814760A (en) | A kind of preparation method and applications for being used to be catalyzed the organic cage compound of metal of reduction nitrobenzene aniline | |
| CN107715873A (en) | A kind of preparation method and application using metal-organic framework materials as the carrier loaded La Pt base catalyst being modified | |
| Zhu et al. | The synthesis, light-harvesting, and photocatalysis of naphthylporphyrin-functionalized platinum nanocomposites | |
| Miyagawa et al. | Photochemical reduction of Cr (VI) compounds by amino acid Schiff base copper complexes with a hydroxyl group and titanium oxide composites in aqueous solutions | |
| Wei et al. | Highly selective photocatalytic oxidation of alcohols under the application of novel metal organic frameworks (MOFs) based catalytic system | |
| CN104785270A (en) | Visible light catalysts used for treatment of methylene blue dye waste water and a preparing method thereof | |
| Li et al. | Synergistic catalytic effect of N-hydroxyphthalimide/cobalt tetraamide phthalocyanine and its application for aerobic oxidation of hydrocarbons and alcohols | |
| CN103709061A (en) | Photochemistry method for synthesizing imine or oxime by using alcohol and amine in one pot | |
| Zeng et al. | Bismuth vanadate: A versatile heterogeneous catalyst for photocatalytic functionalization of C (sp2)–H bonds | |
| Malav et al. | Carbon-carbon cross coupling reactions assisted by Schiff base complexes of Palladium, cobalt and copper: A brief overview | |
| Shanmugapriya et al. | A suitable modified palladium immobilized on imidazolium supported ionic liquid catalysed transfer hydrogenation of nitroarenes | |
| CN113444071A (en) | Cell membrane targeted singlet oxygen generator and preparation method and application thereof | |
| CN108786922A (en) | A kind of preparation method of coupling reaction nickel, palladium modification nano silicon dioxide |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |