CN106379965A - Modified ceramic particle electrode with function of removing thiophene through electro-catalysis, and preparation method - Google Patents
Modified ceramic particle electrode with function of removing thiophene through electro-catalysis, and preparation method Download PDFInfo
- Publication number
- CN106379965A CN106379965A CN201611039120.8A CN201611039120A CN106379965A CN 106379965 A CN106379965 A CN 106379965A CN 201611039120 A CN201611039120 A CN 201611039120A CN 106379965 A CN106379965 A CN 106379965A
- Authority
- CN
- China
- Prior art keywords
- mixed liquor
- minutes
- added
- conditions
- substance
- 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.)
- Withdrawn
Links
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
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
-
- 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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a modified ceramic particle electrode with a function of removing thiophene through electro-catalysis, and a preparation method. The preparation method comprises the following steps: preparing a substance A from ceramic, trichloromethane and ethanol; modifying mixed liquid prepared from silver nitrate, platinum nitrate, ethyl ether and Bi(NO3)3 by the substance A to prepare a substance E; modifying mixed liquid prepared from Mg(NO3)2, ethanol, CeCl3, ZrCl4, MnCl2 and ZnCl2 by the substance E to prepare a substance H; modifying mixed liquid prepared from lauryl sodium sulfate, normal hexane, normal butanol, ammonium metavanadate, sodium citrate, MnCl2 and ZnCl2 by the substance H to prepare a substance K; and modifying mixed liquid prepared from polyvinylpyrrolidone and HAuCl4 by the substance K to obtain a substance, namely the modified ceramic particle electrode with the function of removing the thiophene through electro-catalysis.
Description
Technical field
The invention belongs to organic wastewater with difficult degradation thereby Electrocatalytic Oxidation processing technology field, particularly to one kind, there is electricity and urge
Change the modified ceramic granule electrode removing thiophene function and preparation method.
Background technology
Electro-catalytic oxidation technology is the very promising water technology of the one kind gradually growing up in recent years, mainly
The active group by producing hydroxyl radical free radical etc. with strong oxidizing property carries out oxidative degradation to the organic pollution in waste water, can
So that hardly degraded organic substance or bio-toxicity pollutant be converted into biodegradable or innocuous substance, that improves waste water can be biochemical
Property, thus beneficial to follow-up biological treatment.Therefore, electrocatalytic oxidation water technology is processing high concentration, bio-refractory work
Industry waste water aspect has the features such as non-secondary pollution, low cost, strong applicability, efficiency high.Electrode material is electrocatalytic oxidation skill
The core component of art, its performance has decisive influence for the treatment effeciency of electro-catalytic oxidation technology and operating cost, because
This exploration and the electrocatalysis material preparing good combination property are the research emphasis of current electro-catalytic oxidation technology.But traditional electrode
The resistance of material is larger, conductance is low so that its current efficiency is low in the treatment of waste water, stability not, short life, electrode material
Material is relatively costly, limits popularization and application in water process for the electro-catalytic oxidation technology and development, so new electrode materials
Research also needs to strengthen further with preparation.Also lack at present and there is to thiophene specific pollutants efficient electric catalytic elimination function
Electrode material and preparation method.
Content of the invention
It is an object of the invention to provide a kind of have modified ceramic granule electrode and the preparation that electro-catalysis removes thiophene function
Method, the comprising the following steps that of its preparation method:
(1) the 94g ceramic particle that particle diameter is 4~6mm is washed with 1000mL deionized water, be then placed in 500mL trichlorine
Soak 8h in methane, washed with 1000mL deionized water after taking-up, then the ethanol being 95% with 1000mL mass percent concentration
Place 1.5h in 85 DEG C of drying box after washing, obtain substance A 1;
(2) 7.6 grams of platinum nitrates and 850mL deionized water being added to volume is in 1000mL conical flask, in 1000r/min
Under the conditions of stir 3 minutes, add 15mL red fuming nitric acid (RFNA), be divided into 5 parts of equivalent after shaking up, obtain mixed liquor K1, mixed liquor K2, mixed liquor
K3, mixed liquor K4, mixed liquor K5;
(3) by 469 milligrams of Bi (NO3)3It is the AgNO of 0.57mol/L with 148mL molar concentration3Solution is added to mixed liquor
In K1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L1;
(4) substance A 1 is added in mixed liquor L1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain substance A 2, substance A 2 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 3;
(5) by 489 milligrams of Bi (NO3)3It is the AgNO of 0.67mol/L with 158mL molar concentration3Solution is added to mixed liquor
In K2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L2;
(6) substance A 3 is added in mixed liquor L2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain substance A 4, substance A 4 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 5;
(7) by 509 milligrams of Bi (NO3)3It is the AgNO of 0.77mol/L with 168mL molar concentration3Solution is added to mixed liquor
In K3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L3;
(8) substance A 5 is added in mixed liquor L3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain substance A 6, substance A 6 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 7;
(9) by 529 milligrams of Bi (NO3)3It is the AgNO of 0.87mol/L with 178mL molar concentration3Solution is added to mixed liquor
In K4, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L4;
(10) substance A 7 is added in mixed liquor L4, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains substance A 8, substance A 8 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 9;
(11) by 549 milligrams of Bi (NO3)3It is the AgNO of 0.97mol/L with 188mL molar concentration3Solution is added to mixed liquor
In K5, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L5;
(12) substance A 9 is added in mixed liquor L5, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
Be filtered to remove liquid and obtain substance A 10 after temperature, substance A 10 after the ethanol washing that 100mL mass percent concentration is 93%
Place 126 minutes in 86 DEG C of drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A;
(13) by 6.38 grams of AgNO3Being added to volume with 750mL ether is in 1000mL conical flask, in 1000r/min bar
Stir 3 minutes under part, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor M1, mixed liquor M2, mixed liquor M3;
(14) by 314 milligrams of AgNO3It is the Bi (NO of 0.51mol/L with 76mL molar concentration3)3Solution is added to mixed liquor
In M1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N1;
(15) substance A is added in mixed liquor N1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain substance B, substance B is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance B 1;
(16) by 309 milligrams of AgNO3It is the Bi (NO of 0.61mol/L with 86mL molar concentration3)3Solution is added to mixed liquor
In M2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N2;
(17) substance B 1 is added in mixed liquor N2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains substance B 2, substance B 2 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance C;
(18) by 304 milligrams of AgNO3It is the Bi (NO of 0.71mol/L with 96mL molar concentration3)3Solution is added to mixed liquor
In M3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N3;
(19) substance C is added in mixed liquor N3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material D, material D is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material E;
(20) by 6.38 grams of Mg (NO3)2Being added to volume with 850mL ethanol is in 1000mL conical flask, in 1000r/min
Under the conditions of stir 3 minutes, add 5mL red fuming nitric acid (RFNA), be divided into 5 parts of equivalent after shaking up, obtain mixed liquor P1, mixed liquor P2, mixed liquor
P3, mixed liquor P4, mixed liquor P5;
(21) CeCl for 0.69mol/L by 88mL molar concentration3Solution is added in mixed liquor P1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q1;
(22) material E is added in mixed liquor Q1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material F1, material F1 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F2;
(23) Mg (NO for 0.63mol/L by 74mL molar concentration3)2Solution is added in mixed liquor P2, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor Q2;
(24) material F2 is added in mixed liquor Q2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material F3, material F3 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F4;
(25) CeCl for 0.59mol/L by 78mL molar concentration3Solution is added in mixed liquor P3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q3;
(26) material F4 is added in mixed liquor Q3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material F5, material F5 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F6;
(27) Mg (NO for 0.53mol/L by 64mL molar concentration3)2Solution is added in mixed liquor P4, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor Q4;
(28) material F6 is added in mixed liquor Q4, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material F7, material F7 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F8;
(29) CeCl for 0.43mol/L by 68mL molar concentration3Solution and 54mL molar concentration are the Mg of 0.49mol/L
(NO3)2Solution is added in mixed liquor P5, stirs 3 minutes, obtain mixed liquor Q5 under the conditions of 1000r/min;
(30) material F8 is added in mixed liquor Q5, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material F9, material F9 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F;
(31) by 6.31g ZrCl4It is added to volume with the sodium citrate solution that 750mL mass percent concentration is 10%
For, in 1000mL conical flask, stirring 3 minutes under the conditions of 1000r/min, being divided into 3 parts of equivalent after shaking up, obtain mixed liquor R1, mix
Close liquid R2, mixed liquor R3;
(32) MnCl for 0.55mol/L by 41mL molar concentration2Solution and 59mL molar concentration are 0.58mol/L's
ZnCl2Solution is added in mixed liquor R1, stirs 3 minutes, obtain mixed liquor S1 under the conditions of 1000r/min;
(33) material F is added in mixed liquor S1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material G1, material G1 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material H1;
(34) MnCl for 0.6mol/L by 51mL molar concentration2Solution and 49mL molar concentration are 0.48mol/L's
ZnCl2Solution is added in mixed liquor R2, stirs 3 minutes, obtain mixed liquor S2 under the conditions of 1000r/min;
(35) material H1 is added in mixed liquor S2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material G2, material G2 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material H2;
(36) MnCl for 0.75mol/L by 61mL molar concentration2Solution and 39mL molar concentration are 0.38mol/L's
ZnCl2Solution is added in mixed liquor R3, stirs 3 minutes, obtain mixed liquor S3 under the conditions of 1000r/min;
(37) material H2 is added in mixed liquor S3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material G3, material G3 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material H;
(38) 2.69g lauryl sodium sulfate, 40mL n-hexane, 20 milliliters of n-butanols are added sequentially to volume and are
In 250mL conical flask, add 5.37g sodium metavanadate and 150mL deionized water, be placed in 70 DEG C of water-baths in 1000r/min bar
Under part stir 1h, be subsequently adding 25mL molar concentration be 2.40mol/L hydrochloric acid solution, temperature be 45 DEG C shaking table in shake
0.5h, is centrifuged 15min under the conditions of 7500r/min after being cooled to room temperature, removes supernatant, use 500mL mass percent concentration
Ethanol washing for 95%, obtains material I;
(39) material I and sodium citrate solution that 850mL mass percent concentration is 15% being added to volume is
In 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor T1, mixing
Liquid T2, mixed liquor T3, mixed liquor T4, mixed liquor T5;
(40) MnCl for 0.82mol/L by 46mL molar concentration2Solution and 54mL molar concentration are 0.93mol/L's
ZnCl2Solution is added in mixed liquor T1, stirs 3 minutes, obtain mixed liquor U1 under the conditions of 1000r/min;
(41) material H is added in mixed liquor U1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material J1, material J1 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K1;
(42) MnCl for 0.78mol/L by 41mL molar concentration2Solution and 49mL molar concentration are 0.90mol/L's
ZnCl2Solution is added in mixed liquor T2, stirs 3 minutes, obtain mixed liquor U2 under the conditions of 1000r/min;
(43) material K1 is added in mixed liquor U2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material J2, material J2 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K2;
(44) MnCl for 0.74mol/L by 36mL molar concentration2Solution and 54mL molar concentration are 0.87mol/L's
ZnCl2Solution is added in mixed liquor T3, stirs 3 minutes, obtain mixed liquor U3 under the conditions of 1000r/min;
(45) material K2 is added in mixed liquor U3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material J3, material J3 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K3;
(46) MnCl for 0.70mol/L by 31mL molar concentration2Solution and 69mL molar concentration are 0.84mol/L's
ZnCl2Solution is added in mixed liquor T4, stirs 3 minutes, obtain mixed liquor U4 under the conditions of 1000r/min;
(47) material K3 is added in mixed liquor U4, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material J4, material J4 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K4;
(48) MnCl for 0.66mol/L by 26mL molar concentration2Solution and 74mL molar concentration are 0.83mol/L's
ZnCl2Solution is added in mixed liquor T5, stirs 3 minutes, obtain mixed liquor U5 under the conditions of 1000r/min;
(49) material K4 is added in mixed liquor U5, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material J5, material J5 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K;
(50) 8.11g polyvinylpyrrolidone and 900mL deionized water being added to volume is in 1000mL conical flask,
Stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor V1, mixed liquor V2, mixed liquor V3, mix
Close liquid V4, mixed liquor V5;
(51) HAuCl for 0.63mol/L by 49mL molar concentration4Solution is added in mixed liquor V1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor W1;
(52) material K is added in mixed liquor W1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material L1, material L1 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z1;
(53) HAuCl for 0.69mol/L by 54mL molar concentration4Solution is added in mixed liquor V2, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor W2;
(54) material Z1 is added in mixed liquor W2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material L2, material L2 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z2;
(55) HAuCl for 0.75mol/L by 59mL molar concentration4Solution is added in mixed liquor V3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor W3;
(56) material Z2 is added in mixed liquor W3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material L3, material L3 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z3;
(57) HAuCl for 0.81mol/L by 64mL molar concentration4Solution is added in mixed liquor V4, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor W4;
(58) material Z3 is added in mixed liquor W4, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material L4, material L4 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z4;
(59) HAuCl for 0.87mol/L by 69mL molar concentration4Solution is added in mixed liquor V5, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor W5;
(60) material Z4 is added in mixed liquor W5, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material L5, material L5 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, the material obtaining is
Remove the modified ceramic granule electrode of thiophene function for having electro-catalysis.
The invention has the beneficial effects as follows, the prepared modified ceramic granule electrode with electro-catalysis removal thiophene function has
Current efficiency is high, stability is strong, electrode life length, high to thiophene removal efficiency the features such as.
Specific embodiment
The present invention provides a kind of modified ceramic granule electrode with electro-catalysis removal thiophene function and preparation method, below
Illustrate in fact to apply process by an example.
Embodiment 1.
(1) the 94g ceramic particle that particle diameter is 4~6mm is washed with 1000mL deionized water, be then placed in 500mL trichlorine
Soak 8h in methane, washed with 1000mL deionized water after taking-up, then the ethanol being 95% with 1000mL mass percent concentration
Place 1.5h in 85 DEG C of drying box after washing, obtain substance A 1;
(2) 7.6 grams of platinum nitrates and 850mL deionized water being added to volume is in 1000mL conical flask, in 1000r/min
Under the conditions of stir 3 minutes, add 15mL red fuming nitric acid (RFNA), be divided into 5 parts of equivalent after shaking up, obtain mixed liquor K1, mixed liquor K2, mixed liquor
K3, mixed liquor K4, mixed liquor K5;
(3) by 469 milligrams of Bi (NO3)3It is the AgNO of 0.57mol/L with 148mL molar concentration3Solution is added to mixed liquor
In K1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L1;
(4) substance A 1 is added in mixed liquor L1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain substance A 2, substance A 2 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 3;
(5) by 489 milligrams of Bi (NO3)3It is the AgNO of 0.67mol/L with 158mL molar concentration3Solution is added to mixed liquor
In K2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L2;
(6) substance A 3 is added in mixed liquor L2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain substance A 4, substance A 4 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 5;
(7) by 509 milligrams of Bi (NO3)3It is the AgNO of 0.77mol/L with 168mL molar concentration3Solution is added to mixed liquor
In K3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L3;
(8) substance A 5 is added in mixed liquor L3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain substance A 6, substance A 6 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 7;
(9) by 529 milligrams of Bi (NO3)3It is the AgNO of 0.87mol/L with 178mL molar concentration3Solution is added to mixed liquor
In K4, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L4;
(10) substance A 7 is added in mixed liquor L4, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains substance A 8, substance A 8 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 9;
(11) by 549 milligrams of Bi (NO3)3It is the AgNO of 0.97mol/L with 188mL molar concentration3Solution is added to mixed liquor
In K5, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L5;
(12) substance A 9 is added in mixed liquor L5, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
Be filtered to remove liquid and obtain substance A 10 after temperature, substance A 10 after the ethanol washing that 100mL mass percent concentration is 93%
Place 126 minutes in 86 DEG C of drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A;
(13) by 6.38 grams of AgNO3Being added to volume with 750mL ether is in 1000mL conical flask, in 1000r/min bar
Stir 3 minutes under part, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor M1, mixed liquor M2, mixed liquor M3;
(14) by 314 milligrams of AgNO3It is the Bi (NO of 0.51mol/L with 76mL molar concentration3)3Solution is added to mixed liquor
In M1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N1;
(15) substance A is added in mixed liquor N1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain substance B, substance B is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance B 1;
(16) by 309 milligrams of AgNO3It is the Bi (NO of 0.61mol/L with 86mL molar concentration3)3Solution is added to mixed liquor
In M2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N2;
(17) substance B 1 is added in mixed liquor N2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains substance B 2, substance B 2 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance C;
(18) by 304 milligrams of AgNO3It is the Bi (NO of 0.71mol/L with 96mL molar concentration3)3Solution is added to mixed liquor
In M3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N3;
(19) substance C is added in mixed liquor N3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material D, material D is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material E;
(20) by 6.38 grams of Mg (NO3)2Being added to volume with 850mL ethanol is in 1000mL conical flask, in 1000r/min
Under the conditions of stir 3 minutes, add 5mL red fuming nitric acid (RFNA), be divided into 5 parts of equivalent after shaking up, obtain mixed liquor P1, mixed liquor P2, mixed liquor
P3, mixed liquor P4, mixed liquor P5;
(21) CeCl for 0.69mol/L by 88mL molar concentration3Solution is added in mixed liquor P1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q1;
(22) material E is added in mixed liquor Q1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material F1, material F1 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F2;
(23) Mg (NO for 0.63mol/L by 74mL molar concentration3)2Solution is added in mixed liquor P2, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor Q2;
(24) material F2 is added in mixed liquor Q2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material F3, material F3 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F4;
(25) CeCl for 0.59mol/L by 78mL molar concentration3Solution is added in mixed liquor P3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q3;
(26) material F4 is added in mixed liquor Q3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material F5, material F5 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F6;
(27) Mg (NO for 0.53mol/L by 64mL molar concentration3)2Solution is added in mixed liquor P4, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor Q4;
(28) material F6 is added in mixed liquor Q4, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material F7, material F7 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F8;
(29) CeCl for 0.43mol/L by 68mL molar concentration3Solution and 54mL molar concentration are the Mg of 0.49mol/L
(NO3)2Solution is added in mixed liquor P5, stirs 3 minutes, obtain mixed liquor Q5 under the conditions of 1000r/min;
(30) material F8 is added in mixed liquor Q5, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material F9, material F9 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F;
(31) by 6.31g ZrCl4It is added to volume with the sodium citrate solution that 750mL mass percent concentration is 10%
For, in 1000mL conical flask, stirring 3 minutes under the conditions of 1000r/min, being divided into 3 parts of equivalent after shaking up, obtain mixed liquor R1, mix
Close liquid R2, mixed liquor R3;
(32) MnCl for 0.55mol/L by 41mL molar concentration2Solution and 59mL molar concentration are 0.58mol/L's
ZnCl2Solution is added in mixed liquor R1, stirs 3 minutes, obtain mixed liquor S1 under the conditions of 1000r/min;
(33) material F is added in mixed liquor S1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material G1, material G1 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material H1;
(34) MnCl for 0.6mol/L by 51mL molar concentration2Solution and 49mL molar concentration are 0.48mol/L's
ZnCl2Solution is added in mixed liquor R2, stirs 3 minutes, obtain mixed liquor S2 under the conditions of 1000r/min;
(35) material H1 is added in mixed liquor S2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material G2, material G2 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material H2;
(36) MnCl for 0.75mol/L by 61mL molar concentration2Solution and 39mL molar concentration are 0.38mol/L's
ZnCl2Solution is added in mixed liquor R3, stirs 3 minutes, obtain mixed liquor S3 under the conditions of 1000r/min;
(37) material H2 is added in mixed liquor S3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material G3, material G3 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material H;
(38) 2.69g lauryl sodium sulfate, 40mL n-hexane, 20 milliliters of n-butanols are added sequentially to volume and are
In 250mL conical flask, add 5.37g sodium metavanadate and 150mL deionized water, be placed in 70 DEG C of water-baths in 1000r/min bar
Under part stir 1h, be subsequently adding 25mL molar concentration be 2.40mol/L hydrochloric acid solution, temperature be 45 DEG C shaking table in shake
0.5h, is centrifuged 15min under the conditions of 7500r/min after being cooled to room temperature, removes supernatant, use 500mL mass percent concentration
Ethanol washing for 95%, obtains material I;
(39) material I and sodium citrate solution that 850mL mass percent concentration is 15% being added to volume is
In 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor T1, mixing
Liquid T2, mixed liquor T3, mixed liquor T4, mixed liquor T5;
(40) MnCl for 0.82mol/L by 46mL molar concentration2Solution and 54mL molar concentration are 0.93mol/L's
ZnCl2Solution is added in mixed liquor T1, stirs 3 minutes, obtain mixed liquor U1 under the conditions of 1000r/min;
(41) material H is added in mixed liquor U1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material J1, material J1 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K1;
(42) MnCl for 0.78mol/L by 41mL molar concentration2Solution and 49mL molar concentration are 0.90mol/L's
ZnCl2Solution is added in mixed liquor T2, stirs 3 minutes, obtain mixed liquor U2 under the conditions of 1000r/min;
(43) material K1 is added in mixed liquor U2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material J2, material J2 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K2;
(44) MnCl for 0.74mol/L by 36mL molar concentration2Solution and 54mL molar concentration are 0.87mol/L's
ZnCl2Solution is added in mixed liquor T3, stirs 3 minutes, obtain mixed liquor U3 under the conditions of 1000r/min;
(45) material K2 is added in mixed liquor U3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material J3, material J3 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K3;
(46) MnCl for 0.70mol/L by 31mL molar concentration2Solution and 69mL molar concentration are 0.84mol/L's
ZnCl2Solution is added in mixed liquor T4, stirs 3 minutes, obtain mixed liquor U4 under the conditions of 1000r/min;
(47) material K3 is added in mixed liquor U4, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material J4, material J4 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K4;
(48) MnCl for 0.66mol/L by 26mL molar concentration2Solution and 74mL molar concentration are 0.83mol/L's
ZnCl2Solution is added in mixed liquor T5, stirs 3 minutes, obtain mixed liquor U5 under the conditions of 1000r/min;
(49) material K4 is added in mixed liquor U5, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material J5, material J5 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K;
(50) 8.11g polyvinylpyrrolidone and 900mL deionized water being added to volume is in 1000mL conical flask,
Stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor V1, mixed liquor V2, mixed liquor V3, mix
Close liquid V4, mixed liquor V5;
(51) HAuCl for 0.63mol/L by 49mL molar concentration4Solution is added in mixed liquor V1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor W1;
(52) material K is added in mixed liquor W1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room temperature
After be filtered to remove liquid and obtain material L1, material L1 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z1;
(53) HAuCl for 0.69mol/L by 54mL molar concentration4Solution is added in mixed liquor V2, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor W2;
(54) material Z1 is added in mixed liquor W2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material L2, material L2 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z2;
(55) HAuCl for 0.75mol/L by 59mL molar concentration4Solution is added in mixed liquor V3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor W3;
(56) material Z2 is added in mixed liquor W3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material L3, material L3 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z3;
(57) HAuCl for 0.81mol/L by 64mL molar concentration4Solution is added in mixed liquor V4, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor W4;
(58) material Z3 is added in mixed liquor W4, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material L4, material L4 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z4;
(59) HAuCl for 0.87mol/L by 69mL molar concentration4Solution is added in mixed liquor V5, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor W5;
(60) material Z4 is added in mixed liquor W5, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to room
It is filtered to remove liquid after temperature and obtains material L5, material L5 is after the ethanol washing that 100mL mass percent concentration is 93% 86
DEG C drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, the material obtaining is
Remove the modified ceramic granule electrode of thiophene function for having electro-catalysis.
It is presented herein below and exist with the modified ceramic granule electrode with electro-catalysis removal thiophene function that the inventive method is obtained
In electric catalysis reactor, Electro-catalytic Oxidation Process test is carried out to the waste water containing thiophene, further illustrated the present invention.
The modified ceramic granule electrode with electro-catalysis removal thiophene function that the inventive method is obtained is seated in electricity and urges
Change in reactor, Degrading experiment has been carried out to the waste water containing thiophene, result shows the electric catalysis reactor being loaded by this electrode
The thiophene in waste water can efficiently be removed, when the thiophene concentration in waste water is 52.3mg/L, be 5.0 in pH, voltage is 14V,
Under the conditions of process time is 45min, the thiophene concentration in water outlet after process is reduced to 2.8mg/L, and treatment effeciency reaches
94.65%.
Claims (1)
1. a kind of have electro-catalysis remove thiophene function modified ceramic granule electrode preparation method it is characterised in that the party
The comprising the following steps that of method:
(1) the 94g ceramic particle that particle diameter is 4~6mm is washed with 1000mL deionized water, be then placed in 500mL chloroform
Middle immersion 8h, is washed with 1000mL deionized water after taking-up, then is washed with the ethanol that 1000mL mass percent concentration is 95%
Place 1.5h in 85 DEG C of drying box afterwards, obtain substance A 1;
(2) 7.6 grams of platinum nitrates and 850mL deionized water being added to volume is in 1000mL conical flask, in 1000r/min condition
Lower stirring 3 minutes, add 15mL red fuming nitric acid (RFNA), be divided into 5 parts of equivalent after shaking up, obtain mixed liquor K1, mixed liquor K2, mixed liquor K3,
Mixed liquor K4, mixed liquor K5;
(3) by 469 milligrams of Bi (NO3)3It is the AgNO of 0.57mol/L with 148mL molar concentration3Solution is added in mixed liquor K1,
Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L1;
(4) substance A 1 is added in mixed liquor L1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain substance A 2, substance A 2 is dry at 86 DEG C after the ethanol washing that 100mL mass percent concentration is 93%
Place 126 minutes in dry case, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 3;
(5) by 489 milligrams of Bi (NO3)3It is the AgNO of 0.67mol/L with 158mL molar concentration3Solution is added in mixed liquor K2,
Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L2;
(6) substance A 3 is added in mixed liquor L2, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain substance A 4, substance A 4 is dry at 86 DEG C after the ethanol washing that 100mL mass percent concentration is 93%
Place 126 minutes in dry case, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 5;
(7) by 509 milligrams of Bi (NO3)3It is the AgNO of 0.77mol/L with 168mL molar concentration3Solution is added in mixed liquor K3,
Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L3;
(8) substance A 5 is added in mixed liquor L3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain substance A 6, substance A 6 is dry at 86 DEG C after the ethanol washing that 100mL mass percent concentration is 93%
Place 126 minutes in dry case, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 7;
(9) by 529 milligrams of Bi (NO3)3It is the AgNO of 0.87mol/L with 178mL molar concentration3Solution is added in mixed liquor K4,
Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L4;
(10) substance A 7 is added in mixed liquor L4, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains substance A 8, substance A 8 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A 9;
(11) by 549 milligrams of Bi (NO3)3It is the AgNO of 0.97mol/L with 188mL molar concentration3Solution is added to mixed liquor K5
In, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L5;
(12) substance A 9 is added in mixed liquor L5, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains substance A 10, substance A 10 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Drying box in place 126 minutes, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance A;
(13) by 6.38 grams of AgNO3Being added to volume with 750mL ether is in 1000mL conical flask, stirs under the conditions of 1000r/min
Mix 3 minutes, after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor M1, mixed liquor M2, mixed liquor M3;
(14) by 314 milligrams of AgNO3It is the Bi (NO of 0.51mol/L with 76mL molar concentration3)3Solution is added in mixed liquor M1,
Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N1;
(15) substance A is added in mixed liquor N1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain substance B, substance B is after the ethanol washing that 100mL mass percent concentration is 93% in 86 DEG C of drying
Place 126 minutes in case, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance B 1;
(16) by 309 milligrams of AgNO3It is the Bi (NO of 0.61mol/L with 86mL molar concentration3)3Solution is added in mixed liquor M2,
Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N2;
(17) substance B 1 is added in mixed liquor N2, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains substance B 2, substance B 2 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain substance C;
(18) by 304 milligrams of AgNO3It is the Bi (NO of 0.71mol/L with 96mL molar concentration3)3Solution is added in mixed liquor M3,
Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N3;
(19) substance C is added in mixed liquor N3, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material D, material D is after the ethanol washing that 100mL mass percent concentration is 93% in 86 DEG C of drying
Place 126 minutes in case, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material E;
(20) by 6.38 grams of Mg (NO3)2Being added to volume with 850mL ethanol is in 1000mL conical flask, in 1000r/min condition
Lower stirring 3 minutes, adds 5mL red fuming nitric acid (RFNA), is divided into 5 parts of equivalent after shaking up, and obtains mixed liquor P1, mixed liquor P2, mixed liquor P3, mixes
Close liquid P4, mixed liquor P5;
(21) CeCl for 0.69mol/L by 88mL molar concentration3Solution is added in mixed liquor P1, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Q1;
(22) material E is added in mixed liquor Q1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material F1, material F1 is dry at 86 DEG C after the ethanol washing that 100mL mass percent concentration is 93%
Place 126 minutes in dry case, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F2;
(23) Mg (NO for 0.63mol/L by 74mL molar concentration3)2Solution is added in mixed liquor P2, in 1000r/min bar
Stir 3 minutes under part, obtain mixed liquor Q2;
(24) material F2 is added in mixed liquor Q2, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material F3, material F3 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F4;
(25) CeCl for 0.59mol/L by 78mL molar concentration3Solution is added in mixed liquor P3, under the conditions of 1000r/min
Stirring 3 minutes, obtains mixed liquor Q3;
(26) material F4 is added in mixed liquor Q3, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material F5, material F5 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F6;
(27) Mg (NO for 0.53mol/L by 64mL molar concentration3)2Solution is added in mixed liquor P4, in 1000r/min bar
Stir 3 minutes under part, obtain mixed liquor Q4;
(28) material F6 is added in mixed liquor Q4, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material F7, material F7 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F8;
(29) CeCl for 0.43mol/L by 68mL molar concentration3Solution and 54mL molar concentration are the Mg of 0.49mol/L
(NO3)2Solution is added in mixed liquor P5, stirs 3 minutes, obtain mixed liquor Q5 under the conditions of 1000r/min;
(30) material F8 is added in mixed liquor Q5, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material F9, material F9 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material F;
(31) by 6.31g ZrCl4Being added to volume with the sodium citrate solution that 750mL mass percent concentration is 10% is
In 1000mL conical flask, stir 3 minutes under the conditions of 1000r/min, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor R1, mixing
Liquid R2, mixed liquor R3;
(32) MnCl for 0.55mol/L by 41mL molar concentration2Solution and 59mL molar concentration are the ZnCl of 0.58mol/L2Molten
Liquid is added in mixed liquor R1, stirs 3 minutes, obtain mixed liquor S1 under the conditions of 1000r/min;
(33) material F is added in mixed liquor S1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material G1, material G1 is dry at 86 DEG C after the ethanol washing that 100mL mass percent concentration is 93%
Place 126 minutes in dry case, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material H1;
(34) MnCl for 0.6mol/L by 51mL molar concentration2Solution and 49mL molar concentration are the ZnCl of 0.48mol/L2Molten
Liquid is added in mixed liquor R2, stirs 3 minutes, obtain mixed liquor S2 under the conditions of 1000r/min;
(35) material H1 is added in mixed liquor S2, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material G2, material G2 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material H2;
(36) MnCl for 0.75mol/L by 61mL molar concentration2Solution and 39mL molar concentration are the ZnCl of 0.38mol/L2Molten
Liquid is added in mixed liquor R3, stirs 3 minutes, obtain mixed liquor S3 under the conditions of 1000r/min;
(37) material H2 is added in mixed liquor S3, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material G3, material G3 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material H;
(38) 2.69g lauryl sodium sulfate, 40mL n-hexane, 20 milliliters of n-butanols are added sequentially to volume and bore for 250mL
In shape bottle, add 5.37g sodium metavanadate and 150mL deionized water, be placed in 70 DEG C of water-baths and stir under the conditions of 1000r/min
1h, be subsequently adding 25mL molar concentration be 2.40mol/L hydrochloric acid solution, temperature be 45 DEG C shaking table in shake 0.5h, cold
But it is centrifuged 15min under the conditions of 7500r/min to after room temperature, remove supernatant, be 95% with 500mL mass percent concentration
Ethanol washs, and obtains material I;
(39) material I and sodium citrate solution that 850mL mass percent concentration is 15% are added to volume to bore for 1000mL
In shape bottle, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor T1, mixed liquor T2, mix
Close liquid T3, mixed liquor T4, mixed liquor T5;
(40) MnCl for 0.82mol/L by 46mL molar concentration2Solution and 54mL molar concentration are the ZnCl of 0.93mol/L2Molten
Liquid is added in mixed liquor T1, stirs 3 minutes, obtain mixed liquor U1 under the conditions of 1000r/min;
(41) material H is added in mixed liquor U1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material J1, material J1 is dry at 86 DEG C after the ethanol washing that 100mL mass percent concentration is 93%
Place 126 minutes in dry case, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K1;
(42) MnCl for 0.78mol/L by 41mL molar concentration2Solution and 49mL molar concentration are the ZnCl of 0.90mol/L2Molten
Liquid is added in mixed liquor T2, stirs 3 minutes, obtain mixed liquor U2 under the conditions of 1000r/min;
(43) material K1 is added in mixed liquor U2, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material J2, material J2 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K2;
(44) MnCl for 0.74mol/L by 36mL molar concentration2Solution and 54mL molar concentration are the ZnCl of 0.87mol/L2Molten
Liquid is added in mixed liquor T3, stirs 3 minutes, obtain mixed liquor U3 under the conditions of 1000r/min;
(45) material K2 is added in mixed liquor U3, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material J3, material J3 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K3;
(46) MnCl for 0.70mol/L by 31mL molar concentration2Solution and 69mL molar concentration are the ZnCl of 0.84mol/L2Molten
Liquid is added in mixed liquor T4, stirs 3 minutes, obtain mixed liquor U4 under the conditions of 1000r/min;
(47) material K3 is added in mixed liquor U4, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material J4, material J4 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K4;
(48) MnCl for 0.66mol/L by 26mL molar concentration2Solution and 74mL molar concentration are the ZnCl of 0.83mol/L2Molten
Liquid is added in mixed liquor T5, stirs 3 minutes, obtain mixed liquor U5 under the conditions of 1000r/min;
(49) material K4 is added in mixed liquor U5, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material J5, material J5 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material K;
(50) 8.11g polyvinylpyrrolidone and 900mL deionized water being added to volume is in 1000mL conical flask,
Stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor V1, mixed liquor V2, mixed liquor V3, mix
Close liquid V4, mixed liquor V5;
(51) HAuCl for 0.63mol/L by 49mL molar concentration4Solution is added in mixed liquor V1, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor W1;
(52) material K is added in mixed liquor W1, temperature be 45 DEG C shaking table in shake 15 minutes, be cooled to mistake after room temperature
Filter liquid and obtain material L1, material L1 is dry at 86 DEG C after the ethanol washing that 100mL mass percent concentration is 93%
Place 126 minutes in dry case, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z1;
(53) HAuCl for 0.69mol/L by 54mL molar concentration4Solution is added in mixed liquor V2, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor W2;
(54) material Z1 is added in mixed liquor W2, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material L2, material L2 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z2;
(55) HAuCl for 0.75mol/L by 59mL molar concentration4Solution is added in mixed liquor V3, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor W3;
(56) material Z2 is added in mixed liquor W3, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material L3, material L3 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z3;
(57) HAuCl for 0.81mol/L by 64mL molar concentration4Solution is added in mixed liquor V4, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor W4;
(58) material Z3 is added in mixed liquor W4, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material L4, material L4 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, obtain material Z4;
(59) HAuCl for 0.87mol/L by 69mL molar concentration4Solution is added in mixed liquor V5, in 1000r/min condition
Lower stirring 3 minutes, obtains mixed liquor W5;
(60) material Z4 is added in mixed liquor W5, temperature be 45 DEG C shaking table in shake 15 minutes, after being cooled to room temperature
It is filtered to remove liquid and obtains material L5, material L5 is after the ethanol washing that 100mL mass percent concentration is 93% at 86 DEG C
Place 126 minutes in drying box, be subsequently placed in Muffle furnace roasting 75 minutes under the conditions of 482 DEG C, the material obtaining is to be had
Electro-catalysis is had to remove the modified ceramic granule electrode of thiophene function.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611039120.8A CN106379965A (en) | 2016-11-21 | 2016-11-21 | Modified ceramic particle electrode with function of removing thiophene through electro-catalysis, and preparation method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201611039120.8A CN106379965A (en) | 2016-11-21 | 2016-11-21 | Modified ceramic particle electrode with function of removing thiophene through electro-catalysis, and preparation method |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106379965A true CN106379965A (en) | 2017-02-08 |
Family
ID=57959254
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201611039120.8A Withdrawn CN106379965A (en) | 2016-11-21 | 2016-11-21 | Modified ceramic particle electrode with function of removing thiophene through electro-catalysis, and preparation method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106379965A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102099301A (en) * | 2008-07-15 | 2011-06-15 | 德诺拉工业有限公司 | Method for treating industrial wastewaters |
CN103539229A (en) * | 2013-10-30 | 2014-01-29 | 北京师范大学 | Particle electrode for efficiently removing various organic compounds and preparation method thereof |
-
2016
- 2016-11-21 CN CN201611039120.8A patent/CN106379965A/en not_active Withdrawn
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102099301A (en) * | 2008-07-15 | 2011-06-15 | 德诺拉工业有限公司 | Method for treating industrial wastewaters |
CN103539229A (en) * | 2013-10-30 | 2014-01-29 | 北京师范大学 | Particle electrode for efficiently removing various organic compounds and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106379965A (en) | Modified ceramic particle electrode with function of removing thiophene through electro-catalysis, and preparation method | |
CN106430456A (en) | Modified activated carbon particle electrode with function using electro-catalysis to remove chlorophenol and preparation method | |
CN106365268A (en) | Modified active carbon particle electrode having function of removing phenol through electro-catalysis and manufacturing method | |
CN106430460A (en) | Modified graphite particle electrode with function of electro-catalytically removing thiophene and preparation method | |
CN106396011A (en) | Modified graphite particle electrode with electrocatalytic carbazole removal function and preparation method | |
CN106430442A (en) | Modified ferroferric oxide particle electrode capable of removing furan by electro-catalysis and preparation method of ferroferric oxide particle electrode capable of removing furan by electro-catalysis | |
CN106517435A (en) | Modified graphite particle electrode with function of electro-catalytically removing phenol and preparation method | |
CN106348404A (en) | Modified quartz particle electrode with function of removing thiofuran through electrocatalysis and preparation method thereof | |
CN106365265A (en) | Modified zeolite particle electrode with function of removing phenol through electrocatalysis and preparation method | |
CN106517438A (en) | Modified ferroferric oxide particle electrode with function of electrocatalytically removing thiophene and preparation method | |
CN106396006A (en) | Modified activated carbon particle electrode with electrocatalytic aniline removal function and preparation method thereof | |
CN106430436A (en) | Modified zeolite particle electrode with electro-catalytic pyridine removal function and method for preparing modified zeolite particle electrode | |
CN106396019A (en) | Modified zeolite particle electrode with electrocatalytic thiophene removal function and preparation method thereof | |
CN106396017A (en) | Modified ceramic particle electrode with electro-catalysis pyridine removal function and preparation method | |
CN106517429A (en) | Modified ceramic particle electrode with function of removing furan through electro-catalysis and preparation method | |
CN106517436A (en) | Modified activated carbon particle electrode with electrocatalytic nitrobenzene removal function and preparation method thereof | |
CN106430457A (en) | Modified zeolite particle electrode with function of electrocatalytically removing aniline and preparation method of modified zeolite particle electrode | |
CN106495281A (en) | There is electro-catalysis to remove modified activated carbon granule electrode and the preparation method of carbazole function | |
CN106430461A (en) | Modified graphite particle electrode with electro-catalytic pyridine removal function and method for preparing modified graphite particle electrode | |
CN106396021A (en) | Modified quartz particle electrode with electrocatalytic aniline removal function and preparation method | |
CN106379966A (en) | Modified ceramic particle electrode with function of removing phenol through electro-catalysis and preparation method thereof | |
CN106365271A (en) | Modified active carbon particle electrode having function of removing furan through electro-catalysis and manufacturing method | |
CN106517437A (en) | Modified carbon fiber particle electrode with electrocatalytic thiophene removal function and preparation method thereof | |
CN106396024A (en) | Modified quartz particle electrode with electrocatalytic pyridine removal function, and production method thereof | |
CN106477685A (en) | Modified graphite granule electrode and the preparation method of aniline function is removed with electro-catalysis |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WW01 | Invention patent application withdrawn after publication | ||
WW01 | Invention patent application withdrawn after publication |
Application publication date: 20170208 |