CN108163931A - The graphite electrode modified based on CeO-ZrO-NiO and pyrazine - Google Patents
The graphite electrode modified based on CeO-ZrO-NiO and pyrazine Download PDFInfo
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- CN108163931A CN108163931A CN201711459365.0A CN201711459365A CN108163931A CN 108163931 A CN108163931 A CN 108163931A CN 201711459365 A CN201711459365 A CN 201711459365A CN 108163931 A CN108163931 A CN 108163931A
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- mixed liquor
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- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 21
- 239000010439 graphite Substances 0.000 title claims abstract description 21
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 139
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- NHVGHXUOFWEOSN-UHFFFAOYSA-N 3,5-dibromo-1h-pyrazin-2-one Chemical compound BrC1=CNC(=O)C(Br)=N1 NHVGHXUOFWEOSN-UHFFFAOYSA-N 0.000 claims abstract description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 15
- WNZURIDUDWMEKQ-UHFFFAOYSA-N 3,5-dibromo-2-chloropyrazine Chemical compound ClC1=NC=C(Br)N=C1Br WNZURIDUDWMEKQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- JVSDZAGCHKCSGR-UHFFFAOYSA-N 2,5-dichloropyrazine Chemical class ClC1=CN=C(Cl)C=N1 JVSDZAGCHKCSGR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 36
- OMOVVBIIQSXZSZ-UHFFFAOYSA-N [6-(4-acetyloxy-5,9a-dimethyl-2,7-dioxo-4,5a,6,9-tetrahydro-3h-pyrano[3,4-b]oxepin-5-yl)-5-formyloxy-3-(furan-3-yl)-3a-methyl-7-methylidene-1a,2,3,4,5,6-hexahydroindeno[1,7a-b]oxiren-4-yl] 2-hydroxy-3-methylpentanoate Chemical compound CC12C(OC(=O)C(O)C(C)CC)C(OC=O)C(C3(C)C(CC(=O)OC4(C)COC(=O)CC43)OC(C)=O)C(=C)C32OC3CC1C=1C=COC=1 OMOVVBIIQSXZSZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- AEVSSZHXGJAPIE-UHFFFAOYSA-N 3-chloropyrazin-2-amine Chemical compound NC1=NC=CN=C1Cl AEVSSZHXGJAPIE-UHFFFAOYSA-N 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003643 water by type Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- ITTXBHQAWOFJAI-UHFFFAOYSA-N 5-bromo-1h-pyrazin-2-one Chemical class BrC1=CNC(=O)C=N1 ITTXBHQAWOFJAI-UHFFFAOYSA-N 0.000 claims description 3
- 244000137852 Petrea volubilis Species 0.000 claims description 3
- 241000165940 Houjia Species 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 5
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 abstract 1
- WGFCNCNTGOFBBF-UHFFFAOYSA-N 2-bromopyrazine Chemical compound BrC1=CN=CC=N1 WGFCNCNTGOFBBF-UHFFFAOYSA-N 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- VGKOARVVEXZTPU-UHFFFAOYSA-N n-methylpyrazin-2-amine Chemical class CNC1=CN=CC=N1 VGKOARVVEXZTPU-UHFFFAOYSA-N 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000593 degrading effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a kind of graphite electrodes modified based on CeO ZrO NiO and pyrazine.Graphite rod after cleaning is through Ce (NO3)2, obtain substance C after the mixed liquor processing for preparing of 2,5 dichloropyrazines, n-butanol, isopropanol, methanol and 3,5 dibromo, 2 chloropyrazine.Substance C is through Zr (NO3)2, obtain substance D after the mixed liquor processing for preparing of 2 methylamino pyrazines, n-butanol, isopropanol, methanol and 2 amino, 3 chloropyrazine.Substance D is through Ni (NO3)2, the substance that obtains after the mixed liquor processing for preparing of 2 hydroxyl, 5 bromo-pyrazine, n-butanol, isopropanol, methanol and 3,5 dibromo, 2 hydroxypyrazine be the graphite electrode modified based on CeO ZrO NiO and pyrazine.The invention has the advantages that the features such as graphite electrode obtained modified based on CeO ZrO NiO and pyrazine active high, adaptable, long lifespan.
Description
Technical field
The invention belongs to the chemically modified electrode technical fields of electrochemical treatment of wastewater, more particularly to a kind of to be based on CeO-
ZrO-NiO and the graphite electrode of pyrazine modification.
Background technology
Electro-catalytic oxidation technology is by generating the active group of the strong oxidizing properties such as hydroxyl radical free radical come having in degrading waste water
Machine pollutant has the characteristics that non-secondary pollution, at low cost, strong applicability, efficient, in processing high concentration, bio-refractory
There is application potential in terms of waste water.Electrochemical reaction is usually what is carried out near electrode surface, therefore electrode surface performance is such as
What is most important, selects suitable electrode material and it is modified, to improve the surface catalysis performance of electrode, become electrochemistry
The new issue of worker's research.How to improve the hydrogen reduction catalytic performance of electrode becomes the hot spot of research, there is many research collection
In in modified electrode material to improve its hydrogen reduction catalytic performance.The surface microstructure and state of electro catalytic electrode are to influence electricity
An important factor for catalytic performance, also lacks high, adaptable, long lifespan the electrode of activity at present.
Invention content
The object of the present invention is to provide a kind of graphite electrodes modified based on CeO-ZrO-NiO and pyrazine.Prepare the graphite
Electrode method is as follows：
(1) it is to be put into the burning equipped with 250mL ethyl alcohol after 4cm graphite rods are polished by a diameter of 1cm, length with 1000 mesh sand paper
It is impregnated 30 minutes in cup, takes out and obtain substance A 1 after rinsing with ruinning water with 500mL；Substance A 1 is put into 250mL percents by volume
It is impregnated 30 minutes in a concentration of 50% sulfuric acid solution, takes out and obtain substance A 2 after rinsing with ruinning water with 500mL；Substance A 2 is put
Enter and impregnated 30 minutes in the NaOH solution that 250mL mass percent concentrations are 10%, take out and obtained after rinsing with ruinning water with 500mL
Substance A 3；Substance A is obtained after substance A 3 is dried；
(2) by 3.33 grams of Ce (NO3)2It is added in 900mL deionized waters, stirs 3 minutes under the conditions of 1000r/min, so
1.5mL concentrated nitric acids are added in afterwards, and 5 parts of equivalent is divided into after shaking up, obtains mixed liquor H1, mixed liquor H2, mixed liquor H3；
(3) by 0.61 gram of 2,5- dichloropyrazine, 10mL n-butanols, 10mL isopropanols and 10mL methanol be added to 150mL without
In water-ethanol, stirred 3 minutes under the conditions of 1000r/min, 3 parts of equivalent be divided into after shaking up, obtain mixed liquor J1, mixed liquor J2,
Mixed liquor J3；
(4) mixed liquor J1 and 0.19 gram of 3,5-, bis- bromo- 2- chloropyrazine are added in mixed liquor H1, in 1000r/min items
It is stirred 3 minutes under part, obtains mixed liquor K1；
(5) substance A is added in mixed liquor K1, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Substance B 1 is obtained, substance B 1 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance B 2；
(6) mixed liquor J2 and 0.17 gram of 3,5-, bis- bromo- 2- chloropyrazine are added in mixed liquor H2, in 1000r/min items
It is stirred 3 minutes under part, obtains mixed liquor K2；
(7) substance B 2 is added in mixed liquor K2, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Substance B 3 is obtained, substance B 3 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance B 4；
(8) mixed liquor J3 and 0.15 gram of 3,5-, bis- bromo- 2- chloropyrazine are added in mixed liquor H3, in 1000r/min items
It is stirred 3 minutes under part, obtains mixed liquor K3；
(9) substance B 4 is added in mixed liquor K3, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Substance B 5 is obtained, substance B 5 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C；
(10) by 1.89 grams of Zr (NO3)2It is added in 1200mL deionized waters, is stirred 3 minutes under the conditions of 1000r/min,
Then 1.5mL concentrated nitric acids are added in, 4 parts of equivalent is divided into after shaking up, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor
L4；
(11) by 1.08 grams of 2- methylaminos pyrazines, 15mL n-butanols, 25mL isopropanols and 10mL methanol be added to 150mL without
In water-ethanol, stirred 3 minutes under the conditions of 1000r/min, 4 parts of equivalent be divided into after shaking up, obtain mixed liquor M1, mixed liquor M2,
Mixed liquor M3, mixed liquor M4；
(12) mixed liquor M1 and 0.23 gram of 2- amino -3- chloropyrazine are added in mixed liquor L1, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor N1；
(13) substance C is added in mixed liquor N1, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Substance C 1 is obtained, substance C 1 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C 2；
(14) mixed liquor M2 and 0.24 gram of 2- amino -3- chloropyrazine are added in mixed liquor L2, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor N2；
(15) substance C 2 is added in mixed liquor N2, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance C 3, and substance C 3 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C 4；
(16) mixed liquor M3 and 0.25 gram of 2- amino -3- chloropyrazine are added in mixed liquor L3, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor N3；
(17) substance C 4 is added in mixed liquor N3, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance C 5, and substance C 5 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C 6；
(18) mixed liquor M4 and 0.26 gram of 2- amino -3- chloropyrazine are added in mixed liquor L4, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor N4；
(19) substance C 6 is added in mixed liquor N4, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance C 7, and substance C 7 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D；
(20) by 1.47 grams of Ni (NO3)2It is added in 1500mL deionized waters, is stirred 3 minutes under the conditions of 1000r/min,
Then add in 15mL concentrated nitric acids, 5 parts of equivalent is divided into after shaking up, obtain mixed liquor O1, mixed liquor O2, mixed liquor O3, mixed liquor O4,
Mixed liquor O5；
(21) 1.04 grams of 2- hydroxyl -5- bromo-pyrazines, 15mL n-butanols, 25mL isopropanols and 10mL methanol are added to
It in 150mL absolute ethyl alcohols, is stirred 3 minutes under the conditions of 1000r/min, 5 parts of equivalent is divided into after shaking up, obtained mixed liquor P1, mix
Close liquid P2, mixed liquor P3, mixed liquor P4, mixed liquor P5；
(22) mixed liquor P1 and 0.11 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q1；
(23) substance D is added in mixed liquor Q1, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Substance D1 is obtained, substance D1 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D2；
(24) mixed liquor P2 and 0.13 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O2, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q2；
(25) substance D2 is added in mixed liquor Q2, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance D3, and substance D3 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D4；
(26) mixed liquor P3 and 0.15 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q3；
(27) substance D4 is added in mixed liquor Q3, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance D5, and substance D5 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D6；
(28) mixed liquor P4 and 0.17 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O4, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q4；
(29) substance D6 is added in mixed liquor Q4, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance D7, and substance D7 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D8；
(30) mixed liquor P5 and 0.19 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O5, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q5；
(31) substance D8 is added in mixed liquor Q5, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance D9, substance D9 is placed 300 minutes in drying box of the temperature for 75 DEG C, obtained substance is based on CeO-
ZrO-NiO and the graphite electrode of pyrazine modification.
The invention has the advantages that the graphite electrode obtained modified based on CeO-ZrO-NiO and pyrazine is active
The features such as high, adaptable, long lifespan.
Specific embodiment
The present invention provides the graphite electrode modified based on CeO-ZrO-NiO and pyrazine, illustrates below by an example
Its implementation process.
Embodiment 1.
(1) it is to be put into the burning equipped with 250mL ethyl alcohol after 4cm graphite rods are polished by a diameter of 1cm, length with 1000 mesh sand paper
It is impregnated 30 minutes in cup, takes out and obtain substance A 1 after rinsing with ruinning water with 500mL；Substance A 1 is put into 250mL percents by volume
It is impregnated 30 minutes in a concentration of 50% sulfuric acid solution, takes out and obtain substance A 2 after rinsing with ruinning water with 500mL；Substance A 2 is put
Enter and impregnated 30 minutes in the NaOH solution that 250mL mass percent concentrations are 10%, take out and obtained after rinsing with ruinning water with 500mL
Substance A 3；Substance A is obtained after substance A 3 is dried；
(2) by 3.33 grams of Ce (NO3)2It is added in 900mL deionized waters, stirs 3 minutes under the conditions of 1000r/min, so
1.5mL concentrated nitric acids are added in afterwards, and 5 parts of equivalent is divided into after shaking up, obtains mixed liquor H1, mixed liquor H2, mixed liquor H3；
(3) by 0.61 gram of 2,5- dichloropyrazine, 10mL n-butanols, 10mL isopropanols and 10mL methanol be added to 150mL without
In water-ethanol, stirred 3 minutes under the conditions of 1000r/min, 3 parts of equivalent be divided into after shaking up, obtain mixed liquor J1, mixed liquor J2,
Mixed liquor J3；
(4) mixed liquor J1 and 0.19 gram of 3,5-, bis- bromo- 2- chloropyrazine are added in mixed liquor H1, in 1000r/min items
It is stirred 3 minutes under part, obtains mixed liquor K1；
(5) substance A is added in mixed liquor K1, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Substance B 1 is obtained, substance B 1 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance B 2；
(6) mixed liquor J2 and 0.17 gram of 3,5-, bis- bromo- 2- chloropyrazine are added in mixed liquor H2, in 1000r/min items
It is stirred 3 minutes under part, obtains mixed liquor K2；
(7) substance B 2 is added in mixed liquor K2, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Substance B 3 is obtained, substance B 3 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance B 4；
(8) mixed liquor J3 and 0.15 gram of 3,5-, bis- bromo- 2- chloropyrazine are added in mixed liquor H3, in 1000r/min items
It is stirred 3 minutes under part, obtains mixed liquor K3；
(9) substance B 4 is added in mixed liquor K3, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Substance B 5 is obtained, substance B 5 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C；
(10) by 1.89 grams of Zr (NO3)2It is added in 1200mL deionized waters, is stirred 3 minutes under the conditions of 1000r/min,
Then 1.5mL concentrated nitric acids are added in, 4 parts of equivalent is divided into after shaking up, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor
L4；
(11) by 1.08 grams of 2- methylaminos pyrazines, 15mL n-butanols, 25mL isopropanols and 10mL methanol be added to 150mL without
In water-ethanol, stirred 3 minutes under the conditions of 1000r/min, 4 parts of equivalent be divided into after shaking up, obtain mixed liquor M1, mixed liquor M2,
Mixed liquor M3, mixed liquor M4；
(12) mixed liquor M1 and 0.23 gram of 2- amino -3- chloropyrazine are added in mixed liquor L1, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor N1；
(13) substance C is added in mixed liquor N1, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Substance C 1 is obtained, substance C 1 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C 2；
(14) mixed liquor M2 and 0.24 gram of 2- amino -3- chloropyrazine are added in mixed liquor L2, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor N2；
(15) substance C 2 is added in mixed liquor N2, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance C 3, and substance C 3 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C 4；
(16) mixed liquor M3 and 0.25 gram of 2- amino -3- chloropyrazine are added in mixed liquor L3, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor N3；
(17) substance C 4 is added in mixed liquor N3, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance C 5, and substance C 5 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C 6；
(18) mixed liquor M4 and 0.26 gram of 2- amino -3- chloropyrazine are added in mixed liquor L4, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor N4；
(19) substance C 6 is added in mixed liquor N4, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance C 7, and substance C 7 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D；
(20) by 1.47 grams of Ni (NO3)2It is added in 1500mL deionized waters, is stirred 3 minutes under the conditions of 1000r/min,
Then 1.5mL concentrated nitric acids are added in, 5 parts of equivalent is divided into after shaking up, obtains mixed liquor O1, mixed liquor O2, mixed liquor O3, mixed liquor
O4, mixed liquor O5；
(21) 1.04 grams of 2- hydroxyl -5- bromo-pyrazines, 15mL n-butanols, 25mL isopropanols and 10mL methanol are added to
It in 150mL absolute ethyl alcohols, is stirred 3 minutes under the conditions of 1000r/min, 5 parts of equivalent is divided into after shaking up, obtained mixed liquor P1, mix
Close liquid P2, mixed liquor P3, mixed liquor P4, mixed liquor P5；
(22) mixed liquor P1 and 0.11 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q1；
(23) substance D is added in mixed liquor Q1, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Substance D1 is obtained, substance D1 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D2；
(24) mixed liquor P2 and 0.13 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O2, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q2；
(25) substance D2 is added in mixed liquor Q2, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance D3, and substance D3 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D4；
(26) mixed liquor P3 and 0.15 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q3；
(27) substance D4 is added in mixed liquor Q3, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance D5, and substance D5 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D6；
(28) mixed liquor P4 and 0.17 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O4, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q4；
(29) substance D6 is added in mixed liquor Q4, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance D7, and substance D7 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D8；
(30) mixed liquor P5 and 0.19 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O5, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q5；
(31) substance D8 is added in mixed liquor Q5, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid
Body obtains substance D9, substance D9 is placed 300 minutes in drying box of the temperature for 75 DEG C, obtained substance is based on CeO-
ZrO-NiO and the graphite electrode of pyrazine modification.
Here is to be seated in two with the method for the present invention graphite electrode obtained modified based on CeO-ZrO-NiO and pyrazine
Degrading experiment has been carried out to pharmacy waste water in dimension electrode reactor, has been further illustrated the present invention.
Two-dimentional electricity will be seated in the graphite electrode modified made from the method for the present invention based on CeO-ZrO-NiO and pyrazine
In the reactor of pole, Degrading experiment is carried out to pharmacy waste water, the results showed that the two-dimensional electrode reactor for being filled with the electrode can
COD in efficient process pharmacy waste water, when influent COD is 1144mg/L, the COD in being discharged after processing is reduced to 70mg/L.
Claims (1)
1. a kind of graphite electrode modified based on CeO-ZrO-NiO and pyrazine, which is characterized in that prepare the graphite electrode method
It is as follows：
(1) it is to be put into the beaker equipped with 250mL ethyl alcohol after 4cm graphite rods are polished by a diameter of 1cm, length with 1000 mesh sand paper
It impregnates 30 minutes, takes out and obtain substance A 1 after rinsing with ruinning water with 500mL；Substance A 1 is put into 250mL concentration of volume percent
To be impregnated 30 minutes in 50% sulfuric acid solution, take out and obtain substance A 2 after rinsing with ruinning water with 500mL；Substance A 2 is put into
250mL mass percent concentrations are to be impregnated 30 minutes in 10% NaOH solution, take out and obtain object after rinsing with ruinning water with 500mL
Matter A3；Substance A is obtained after substance A 3 is dried；
(2) by 3.33 grams of Ce (NO3)2It is added in 900mL deionized waters, is stirred 3 minutes under the conditions of 1000r/min, Ran Houjia
Enter 1.5mL concentrated nitric acids, 5 parts of equivalent is divided into after shaking up, obtain mixed liquor H1, mixed liquor H2, mixed liquor H3；
(3) 0.61 gram of 2,5- dichloropyrazine, 10mL n-butanols, 10mL isopropanols and 10mL methanol are added to the anhydrous second of 150mL
It in alcohol, is stirred 3 minutes under the conditions of 1000r/min, 3 parts of equivalent is divided into after shaking up, obtain mixed liquor J1, mixed liquor J2, mixing
Liquid J3；
(4) mixed liquor J1 and 0.19 gram of 3,5-, bis- bromo- 2- chloropyrazine are added in mixed liquor H1, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor K1；
(5) substance A is added in mixed liquor K1, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
Substance B 1 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance B 2 by substance B 1；
(6) mixed liquor J2 and 0.17 gram of 3,5-, bis- bromo- 2- chloropyrazine are added in mixed liquor H2, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor K2；
(7) substance B 2 is added in mixed liquor K2, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
Substance B 3 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance B 4 by substance B 3；
(8) mixed liquor J3 and 0.15 gram of 3,5-, bis- bromo- 2- chloropyrazine are added in mixed liquor H3, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor K3；
(9) substance B 4 is added in mixed liquor K3, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
Substance B 5 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C by substance B 5；
(10) by 1.89 grams of Zr (NO3)2It is added in 1200mL deionized waters, stirs 3 minutes under the conditions of 1000r/min, then
1.5mL concentrated nitric acids are added in, 4 parts of equivalent is divided into after shaking up, obtains mixed liquor L1, mixed liquor L2, mixed liquor L3, mixed liquor L4；
(11) 1.08 grams of 2- methylaminos pyrazines, 15mL n-butanols, 25mL isopropanols and 10mL methanol are added to the anhydrous second of 150mL
It in alcohol, is stirred 3 minutes under the conditions of 1000r/min, 4 parts of equivalent is divided into after shaking up, obtain mixed liquor M1, mixed liquor M2, mixing
Liquid M3, mixed liquor M4；
(12) mixed liquor M1 and 0.23 gram of 2- amino -3- chloropyrazine are added in mixed liquor L1, are stirred under the conditions of 1000r/min
It mixes 3 minutes, obtains mixed liquor N1；
(13) substance C is added in mixed liquor N1, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
Substance C 1 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C 2 by substance C 1；
(14) mixed liquor M2 and 0.24 gram of 2- amino -3- chloropyrazine are added in mixed liquor L2, are stirred under the conditions of 1000r/min
It mixes 3 minutes, obtains mixed liquor N2；
(15) substance C 2 is added in mixed liquor N2, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
To substance C 3, substance C 3 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C 4；
(16) mixed liquor M3 and 0.25 gram of 2- amino -3- chloropyrazine are added in mixed liquor L3, are stirred under the conditions of 1000r/min
It mixes 3 minutes, obtains mixed liquor N3；
(17) substance C 4 is added in mixed liquor N3, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
To substance C 5, substance C 5 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance C 6；
(18) mixed liquor M4 and 0.26 gram of 2- amino -3- chloropyrazine are added in mixed liquor L4, are stirred under the conditions of 1000r/min
It mixes 3 minutes, obtains mixed liquor N4；
(19) substance C 6 is added in mixed liquor N4, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
To substance C 7, substance C 7 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D；
(20) by 1.47 grams of Ni (NO3)2It is added in 1500mL deionized waters, stirs 3 minutes under the conditions of 1000r/min, then
1.5mL concentrated nitric acids are added in, 5 parts of equivalent is divided into after shaking up, mixed liquor O1 is obtained, mixed liquor O2, mixed liquor O3, mixed liquor O4, mixes
Close liquid O5；
(21) by 1.04 grams of 2- hydroxyl -5- bromo-pyrazines, 15mL n-butanols, 25mL isopropanols and 10mL methanol be added to 150mL without
In water-ethanol, stirred 3 minutes under the conditions of 1000r/min, 5 parts of equivalent be divided into after shaking up, obtain mixed liquor P1, mixed liquor P2,
Mixed liquor P3, mixed liquor P4, mixed liquor P5；
(22) mixed liquor P1 and 0.11 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O1, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor Q1；
(23) substance D is added in mixed liquor Q1, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
Substance D1 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D2 by substance D1；
(24) mixed liquor P2 and 0.13 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O2, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor Q2；
(25) substance D2 is added in mixed liquor Q2, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
To substance D3, substance D3 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D4；
(26) mixed liquor P3 and 0.15 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O3, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor Q3；
(27) substance D4 is added in mixed liquor Q3, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
To substance D5, substance D5 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D6；
(28) mixed liquor P4 and 0.17 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O4, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor Q4；
(29) substance D6 is added in mixed liquor Q4, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
To substance D7, substance D7 in drying box of the temperature for 75 DEG C is placed 300 minutes, obtains substance D8；
(30) mixed liquor P5 and 0.19 gram of 3,5-, bis- bromo- 2- hydroxypyrazine are added in mixed liquor O5, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor Q5；
(31) substance D8 is added in mixed liquor Q5, is shaken 90 minutes in the shaking table for being 50 DEG C in temperature, be filtered to remove liquid and obtain
To substance D9, substance D9 is placed 300 minutes in drying box of the temperature for 75 DEG C, obtained substance is based on CeO-ZrO-
NiO and the graphite electrode of pyrazine modification.
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