CN106517438A - Modified ferroferric oxide particle electrode with function of electrocatalytically removing thiophene and preparation method - Google Patents
Modified ferroferric oxide particle electrode with function of electrocatalytically removing thiophene and preparation method Download PDFInfo
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- 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
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- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
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- C02F2001/46133—Electrodes characterised by the material
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention discloses a modified ferroferric oxide particle electrode with the function of electrocatalytically removing thiophene and a preparation method. The method comprises the steps: preparing a substance A from ferroferric oxide, trichloromethane and ethanol; modifying a mixed solution prepared from silver nitrate, platinum nitrate, diethyl ether and Bi(NO3)3 by the substance A, so as to prepare a substance E; modifying a mixed solution prepared from Co(NO3)2, ethanol, InCl3, SnCl4, ZnCl2 and MnCl2 by the substance E, so as to prepare a substance H; modifying a mixed solution prepared from sodium lauryl sulfate, n-hexane, n-butanol, sodium metavanadate, sodium citrate, ZnCl2 and MnCl2 by the substance H, so as to prepare a substance K; and modifying a mixed solution prepared from polyvinyl pyrrolidone and HAuCl4 by the substance K, thereby obtaining a substance, i.e., the modified ferroferric oxide particle electrode with the function of electrocatalytically removing the thiophene.
Description
Technical field
The invention belongs to organic wastewater with difficult degradation thereby Electrocatalytic Oxidation processing technology field, more particularly to one kind are urged with electricity
Change the improved ferroferric oxide granule electrode and preparation method for removing thiophene function.
Background technology
Electro-catalytic oxidation technology is a kind of very promising water technology for gradually growing up in recent years, mainly
Oxidative degradation is carried out to the organic pollution in waste water by producing the active groups with strong oxidizing property such as hydroxyl radical free radical, 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, so as to be beneficial to follow-up biological treatment.Therefore, electrocatalytic oxidation water technology is processing high concentration, bio-refractory work
The features such as there is non-secondary pollution, low cost, strong applicability, efficiency high in terms of industry waste water.Electrode material is electrocatalytic oxidation skill
The core component of art, its performance have decisive influence for the treatment effeciency and operating cost of electro-catalytic oxidation technology, because
This electrocatalysis material for exploring and preparing good combination property is 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 enough, short life, electrode material
Material is relatively costly, limits popularization and application of the electro-catalytic oxidation technology in water process and development, so new electrode materials
Research also needs to further strengthen with preparation.Also lack at present and there is to thiophene specific pollutants efficient electric catalytic elimination function
Electrode material and preparation method.
The content of the invention
It is an object of the invention to provide a kind of improved ferroferric oxide granule electrode that thiophene function is removed with electro-catalysis
And preparation method, its preparation method comprises the following steps that：
(1) the 76g ferriferrous oxide particles that particle diameter is 4～6mm are washed with 1000mL deionized waters, is then placed in
8h is soaked in 500mL chloroforms, is washed with 1000mL deionized waters after taking-up, then with 1000mL mass percent concentrations be
1.5h is placed in 85 DEG C of drying box after 95% ethanol washing, substance A 1 is obtained；
(2) 3.48 grams of platinum nitrates and 850mL deionized waters are added to into volume in 1000mL conical flasks, in 1000r/
Stir 3 minutes under the conditions of min, add 15mL red fuming nitric acid (RFNA)s, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor K1, mixed liquor K2, mix
Close liquid K3, mixed liquor K4, mixed liquor K5；
(3) by 597 milligrams of Bi (NO3)3With the AgNO that 69mL molar concentrations are 0.62mol/L3Solution is added to mixed liquor K1
In, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L1；
(4) substance A 1 is added in mixed liquor L1, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain substance A 2, substance A 2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 3；
(5) by 587 milligrams of Bi (NO3)3With the AgNO that 74mL molar concentrations are 0.67mol/L3Solution is added to mixed liquor K2
In, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L2；
(6) substance A 3 is added in mixed liquor L2, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain substance A 4, substance A 4 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 5；
(7) by 577 milligrams of Bi (NO3)3With the AgNO that 79mL molar concentrations are 0.72mol/L3Solution is added to mixed liquor K3
In, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L3；
(8) substance A 5 is added in mixed liquor L3, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain substance A 6, substance A 6 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 7；
(9) by 567 milligrams of Bi (NO3)3With the AgNO that 84mL molar concentrations are 0.77mol/L3Solution is added to mixed liquor K4
In, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L4；
(10) substance A 7 is added in mixed liquor L4, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains substance A 8, substance A 8 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 9；
(11) by 557 milligrams of Bi (NO3)3With the AgNO that 89mL molar concentrations are 0.82mol/L3Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains substance A 10, substance A 10 Jing after the ethanol washing that 100mL mass percent concentrations are 88%
Place 136 minutes in 78 DEG C of drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A；
(13) by 3.26 grams of AgNO3Volume is added to in 1000mL conical flasks with 750mL ether, in 1000r/min bars
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 312 milligrams of AgNO3With the Bi (NO that 74mL molar concentrations are 0.51mol/L3)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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain substance B, substance B is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance B 1；
(16) by 322 milligrams of AgNO3With the Bi (NO that 79mL molar concentrations are 0.61mol/L3)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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains substance B 2, substance B 2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance C；
(18) by 332 milligrams of AgNO3With the Bi (NO that 84mL molar concentrations are 0.71mol/L3)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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain material D, material D is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material E；
(20) by 5.39 grams of Co (NO3)2Volume is added to in 1000mL conical flasks with 850mL ethanol, in 1000r/min
Under the conditions of stir 3 minutes, add 5mL red fuming nitric acid (RFNA)s, 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) by 62mL molar concentrations for 0.94mol/L InCl3Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain material F1, material F1 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F2；
(23) by 48mL molar concentrations for 0.91mol/L Co (NO3)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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material F3, material F3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F4；
(25) by 52mL molar concentrations for 0.84mol/L InCl3Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material F5, material F5 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F6；
(27) by 38mL molar concentrations for 0.81mol/L Co (NO3)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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material F7, material F7 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F8；
(29) by 42mL molar concentrations for 0.74mol/L InCl3Solution and the Co that 28mL molar concentrations are 0.71mol/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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material F9, material F9 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F；
(31) by 5.68g SnCl4Volume is added to the sodium citrate solution that 750mL mass percent concentrations are 10%
In for 1000mL conical flasks, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor R1, mix
Close liquid R2, mixed liquor R3；
(32) by 46mL molar concentrations for 0.66mol/L ZnCl2Solution and 54mL molar concentrations are for 0.69mol/L's
MnCl2Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain material G1, material G1 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material H1；
(34) by 41mL molar concentrations for 0.76mol/L ZnCl2Solution and 59mL molar concentrations are for 0.79mol/L's
MnCl2Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material G2, material G2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material H2；
(36) by 36mL molar concentrations for 0.86mol/L ZnCl2Solution and 64mL molar concentrations are for 0.89mol/L's
MnCl2Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material G3, material G3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material H；
(38) 3.37g lauryl sodium sulfate, 40mL n-hexanes, 20 milliliters of n-butanols are added sequentially to volume and are
In 250mL conical flasks, 6.38g sodium metavanadates and 150mL deionized waters are added, be placed in 70 DEG C of water-baths in 1000r/min bars
1h is stirred under part, the hydrochloric acid solution that 25mL molar concentrations are 2.40mol/L is subsequently adding, is shaken in the shaking table that temperature is 45 DEG C
0.5h, under the conditions of 7500r/min is centrifuged 15min after being cooled to room temperature, removes supernatant, use 500mL mass percent concentrations
Ethanol for 95% is washed, and obtains material I；
(39) sodium citrate solution that material I and 850mL mass percent concentration is 15% is added to volume is
In 1000mL conical flasks, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor T1, mixing
Liquid T2, mixed liquor T3, mixed liquor T4, mixed liquor T5；
(40) by 48mL molar concentrations for 0.86mol/L ZnCl2Solution and 52mL molar concentrations are for 0.52mol/L's
MnCl2Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain material J1, material J1 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K1；
(42) by 44mL molar concentrations for 0.81mol/L ZnCl2Solution and 56mL molar concentrations are for 0.57mol/L's
MnCl2Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material J2, material J2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K2；
(44) by 40mL molar concentrations for 0.76mol/L ZnCl2Solution and 60mL molar concentrations are for 0.62mol/L's
MnCl2Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material J3, material J3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K3；
(46) by 36mL molar concentrations for 0.71mol/L ZnCl2Solution and 64mL molar concentrations are for 0.67mol/L's
MnCl2Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material J4, material J4 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K4；
(48) by 32mL molar concentrations for 0.66mol/L ZnCl2Solution and 68mL molar concentrations are for 0.72mol/L's
MnCl2Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material J5, material J5 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K；
(50) 7.26g polyvinylpyrrolidones and 900mL deionized waters are added to into volume in 1000mL conical flasks,
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, mixed
Close liquid V4, mixed liquor V5；
(51) by 83mL molar concentrations for 0.82mol/L HAuCl4Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain material L1, material L1 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z1；
(53) by 73mL molar concentrations for 0.78mol/L HAuCl4Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material L2, material L2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z2；
(55) by 63mL molar concentrations for 0.74mol/L HAuCl4Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material L3, material L3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z3；
(57) by 53mL molar concentrations for 0.70mol/L HAuCl4Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material L4, material L4 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z4；
(59) by 43mL molar concentrations for 0.66mol/L HAuCl4Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material L5, material L5 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, the material for obtaining is i.e.
It is the improved ferroferric oxide granule electrode that thiophene function is removed with electro-catalysis.
The invention has the beneficial effects as follows, the obtained improved ferroferric oxide particle electricity that thiophene function is removed with electro-catalysis
Have that current efficiency is high, stability is strong, electrode life length, it is high to thiophene removal efficiency the features such as.
Specific embodiment
The present invention provides a kind of improved ferroferric oxide granule electrode and preparation side that thiophene function is removed with electro-catalysis
Method, illustrates to apply in fact process below by an example.
Embodiment 1.
(61) the 76g ferriferrous oxide particles that particle diameter is 4～6mm are washed with 1000mL deionized waters, is then placed in
8h is soaked in 500mL chloroforms, is washed with 1000mL deionized waters after taking-up, then with 1000mL mass percent concentrations be
1.5h is placed in 85 DEG C of drying box after 95% ethanol washing, substance A 1 is obtained；
(62) 3.48 grams of platinum nitrates and 850mL deionized waters are added to into volume in 1000mL conical flasks, in 1000r/
Stir 3 minutes under the conditions of min, add 15mL red fuming nitric acid (RFNA)s, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor K1, mixed liquor K2, mix
Close liquid K3, mixed liquor K4, mixed liquor K5；
(63) by 597 milligrams of Bi (NO3)3With the AgNO that 69mL molar concentrations are 0.62mol/L3Solution is added to mixed liquor
In K1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L1；
(64) substance A 1 is added in mixed liquor L1, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains substance A 2, substance A 2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 3；
(65) by 587 milligrams of Bi (NO3)3With the AgNO that 74mL molar concentrations are 0.67mol/L3Solution is added to mixed liquor
In K2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L2；
(66) substance A 3 is added in mixed liquor L2, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains substance A 4, substance A 4 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 5；
(67) by 577 milligrams of Bi (NO3)3With the AgNO that 79mL molar concentrations are 0.72mol/L3Solution is added to mixed liquor
In K3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L3；
(68) substance A 5 is added in mixed liquor L3, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains substance A 6, substance A 6 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 7；
(69) by 567 milligrams of Bi (NO3)3With the AgNO that 84mL molar concentrations are 0.77mol/L3Solution is added to mixed liquor
In K4, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L4；
(70) substance A 7 is added in mixed liquor L4, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains substance A 8, substance A 8 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 9；
(71) by 557 milligrams of Bi (NO3)3With the AgNO that 89mL molar concentrations are 0.82mol/L3Solution is added to mixed liquor
In K5, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L5；
(72) substance A 9 is added in mixed liquor L5, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains substance A 10, substance A 10 Jing after the ethanol washing that 100mL mass percent concentrations are 88%
Place 136 minutes in 78 DEG C of drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A；
(73) by 3.26 grams of AgNO3Volume is added to in 1000mL conical flasks with 750mL ether, in 1000r/min bars
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；
(74) by 312 milligrams of AgNO3With the Bi (NO that 74mL molar concentrations are 0.51mol/L3)3Solution is added to mixed liquor
In M1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N1；
(75) substance A is added in mixed liquor N1, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain substance B, substance B is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance B 1；
(76) by 322 milligrams of AgNO3With the Bi (NO that 79mL molar concentrations are 0.61mol/L3)3Solution is added to mixed liquor
In M2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N2；
(77) substance B 1 is added in mixed liquor N2, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains substance B 2, substance B 2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance C；
(78) by 332 milligrams of AgNO3With the Bi (NO that 84mL molar concentrations are 0.71mol/L3)3Solution is added to mixed liquor
In M3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N3；
(79) substance C is added in mixed liquor N3, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain material D, material D is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material E；
(80) by 5.39 grams of Co (NO3)2Volume is added to in 1000mL conical flasks with 850mL ethanol, in 1000r/min
Under the conditions of stir 3 minutes, add 5mL red fuming nitric acid (RFNA)s, 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；
(81) by 62mL molar concentrations for 0.94mol/L InCl3Solution is added in mixed liquor P1, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q1；
(82) material E is added in mixed liquor Q1, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain material F1, material F1 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F2；
(83) by 48mL molar concentrations for 0.91mol/L Co (NO3)2Solution is added in mixed liquor P2, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor Q2；
(84) material F2 is added in mixed liquor Q2, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material F3, material F3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F4；
(85) by 52mL molar concentrations for 0.84mol/L InCl3Solution is added in mixed liquor P3, in 1000r/min
Under the conditions of stir 3 minutes, obtain mixed liquor Q3；
(86) material F4 is added in mixed liquor Q3, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material F5, material F5 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F6；
(87) by 38mL molar concentrations for 0.81mol/L Co (NO3)2Solution is added in mixed liquor P4, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor Q4；
(88) material F6 is added in mixed liquor Q4, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material F7, material F7 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F8；
(89) by 42mL molar concentrations for 0.74mol/L InCl3Solution and the Co that 28mL molar concentrations are 0.71mol/L
(NO3)2Solution is added in mixed liquor P5, stirs 3 minutes, obtain mixed liquor Q5 under the conditions of 1000r/min；
(90) material F8 is added in mixed liquor Q5, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material F9, material F9 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F；
(91) by 5.68g SnCl4Volume is added to the sodium citrate solution that 750mL mass percent concentrations are 10%
In for 1000mL conical flasks, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor R1, mix
Close liquid R2, mixed liquor R3；
(92) by 46mL molar concentrations for 0.66mol/L ZnCl2Solution and 54mL molar concentrations are for 0.69mol/L's
MnCl2Solution is added in mixed liquor R1, stirs 3 minutes, obtain mixed liquor S1 under the conditions of 1000r/min；
(93) material F is added in mixed liquor S1, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room temperature
After be filtered to remove liquid and obtain material G1, material G1 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material H1；
(94) by 41mL molar concentrations for 0.76mol/L ZnCl2Solution and 59mL molar concentrations are for 0.79mol/L's
MnCl2Solution is added in mixed liquor R2, stirs 3 minutes, obtain mixed liquor S2 under the conditions of 1000r/min；
(95) material H1 is added in mixed liquor S2, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material G2, material G2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material H2；
(96) by 36mL molar concentrations for 0.86mol/L ZnCl2Solution and 64mL molar concentrations are for 0.89mol/L's
MnCl2Solution is added in mixed liquor R3, stirs 3 minutes, obtain mixed liquor S3 under the conditions of 1000r/min；
(97) material H2 is added in mixed liquor S3, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material G3, material G3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material H；
(98) 3.37g lauryl sodium sulfate, 40mL n-hexanes, 20 milliliters of n-butanols are added sequentially to volume and are
In 250mL conical flasks, 6.38g sodium metavanadates and 150mL deionized waters are added, be placed in 70 DEG C of water-baths in 1000r/min bars
1h is stirred under part, the hydrochloric acid solution that 25mL molar concentrations are 2.40mol/L is subsequently adding, is shaken in the shaking table that temperature is 45 DEG C
0.5h, under the conditions of 7500r/min is centrifuged 15min after being cooled to room temperature, removes supernatant, use 500mL mass percent concentrations
Ethanol for 95% is washed, and obtains material I；
(99) sodium citrate solution that material I and 850mL mass percent concentration is 15% is added to volume is
In 1000mL conical flasks, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor T1, mixing
Liquid T2, mixed liquor T3, mixed liquor T4, mixed liquor T5；
(100) by 48mL molar concentrations for 0.86mol/L ZnCl2Solution and 52mL molar concentrations are for 0.52mol/L's
MnCl2Solution is added in mixed liquor T1, stirs 3 minutes, obtain mixed liquor U1 under the conditions of 1000r/min；
(101) material H is added in mixed liquor U1, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material J1, material J1 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K1；
(102) by 44mL molar concentrations for 0.81mol/L ZnCl2Solution and 56mL molar concentrations are for 0.57mol/L's
MnCl2Solution is added in mixed liquor T2, stirs 3 minutes, obtain mixed liquor U2 under the conditions of 1000r/min；
(103) material K1 is added in mixed liquor U2, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material J2, material J2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K2；
(104) by 40mL molar concentrations for 0.76mol/L ZnCl2Solution and 60mL molar concentrations are for 0.62mol/L's
MnCl2Solution is added in mixed liquor T3, stirs 3 minutes, obtain mixed liquor U3 under the conditions of 1000r/min；
(105) material K2 is added in mixed liquor U3, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material J3, material J3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K3；
(106) by 36mL molar concentrations for 0.71mol/L ZnCl2Solution and 64mL molar concentrations are for 0.67mol/L's
MnCl2Solution is added in mixed liquor T4, stirs 3 minutes, obtain mixed liquor U4 under the conditions of 1000r/min；
(107) material K3 is added in mixed liquor U4, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material J4, material J4 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K4；
(108) by 32mL molar concentrations for 0.66mol/L ZnCl2Solution and 68mL molar concentrations are for 0.72mol/L's
MnCl2Solution is added in mixed liquor T5, stirs 3 minutes, obtain mixed liquor U5 under the conditions of 1000r/min；
(109) material K4 is added in mixed liquor U5, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material J5, material J5 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K；
(110) 7.26g polyvinylpyrrolidones and 900mL deionized waters are added to into volume in 1000mL conical flasks,
Under the conditions of 1000r/min stir 3 minutes, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor V1, mixed liquor V2, mixed liquor V3,
Mixed liquor V4, mixed liquor V5；
(111) by 83mL molar concentrations for 0.82mol/L HAuCl4Solution is added in mixed liquor V1, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor W1；
(112) material K is added in mixed liquor W1, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material L1, material L1 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z1；
(113) by 73mL molar concentrations for 0.78mol/L HAuCl4Solution is added in mixed liquor V2, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor W2；
(114) material Z1 is added in mixed liquor W2, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material L2, material L2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z2；
(115) by 63mL molar concentrations for 0.74mol/L HAuCl4Solution is added in mixed liquor V3, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor W3；
(116) material Z2 is added in mixed liquor W3, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material L3, material L3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z3；
(117) by 53mL molar concentrations for 0.70mol/L HAuCl4Solution is added in mixed liquor V4, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor W4；
(118) material Z3 is added in mixed liquor W4, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material L4, material L4 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z4；
(119) by 43mL molar concentrations for 0.66mol/L HAuCl4Solution is added in mixed liquor V5, in 1000r/
Stir 3 minutes under the conditions of min, obtain mixed liquor W5；
(120) material Z4 is added in mixed liquor W5, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to room
Liquid is filtered to remove after temperature and obtains material L5, material L5 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% 78
DEG C drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, the material for obtaining is i.e.
It is the improved ferroferric oxide granule electrode that thiophene function is removed with electro-catalysis.
It is presented herein below with the improved ferroferric oxide particle obtained in the inventive method with electro-catalysis removal thiophene function
Electrode has carried out Electro-catalytic Oxidation Process test to the waste water containing thiophene in electric catalysis reactor, further illustrates this
It is bright.
By the improved ferroferric oxide granule electrode filling that there is obtained in the inventive method electro-catalysis to remove thiophene function
In electric catalysis reactor, Degrading experiment is carried out to the waste water containing thiophene, as a result shown the electro-catalysis loaded by the electrode
Reactor can efficiently remove the thiophene in waste water, when the thiophene concentration in waste water is 52.3mg/L, be 5.0 in pH, voltage
For 14V, under the conditions of process time is 45min, the thiophene concentration after process in water outlet is reduced to 3.1mg/L, and treatment effeciency reaches
94.07%.
Claims (1)
1. a kind of preparation method of the improved ferroferric oxide granule electrode that thiophene function is removed with electro-catalysis, its feature exists
In comprising the following steps that for, the method：
(1) the 76g ferriferrous oxide particles that particle diameter is 4～6mm are washed with 1000mL deionized waters, is then placed in 500mL tri-
8h is soaked in chloromethanes, is washed with 1000mL deionized waters after taking-up, then with the second that 1000mL mass percent concentrations are 95%
1.5h is placed in 85 DEG C of drying box after alcohol washing, substance A 1 is obtained；
(2) 3.48 grams of platinum nitrates and 850mL deionized waters are added to into volume in 1000mL conical flasks, in 1000r/min bars
Stir 3 minutes under part, add 15mL red fuming nitric acid (RFNA)s, 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 597 milligrams of Bi (NO3)3With the AgNO that 69mL molar concentrations are 0.62mol/L3Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature
Filter liquid and obtain substance A 2, substance A 2 is dry at 78 DEG C Jing after the ethanol washing that 100mL mass percent concentrations are 88%
Place 136 minutes in dry case, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 3；
(5) by 587 milligrams of Bi (NO3)3With the AgNO that 74mL molar concentrations are 0.67mol/L3Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature
Filter liquid and obtain substance A 4, substance A 4 is dry at 78 DEG C Jing after the ethanol washing that 100mL mass percent concentrations are 88%
Place 136 minutes in dry case, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 5；
(7) by 577 milligrams of Bi (NO3)3With the AgNO that 79mL molar concentrations are 0.72mol/L3Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature
Filter liquid and obtain substance A 6, substance A 6 is dry at 78 DEG C Jing after the ethanol washing that 100mL mass percent concentrations are 88%
Place 136 minutes in dry case, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 7；
(9) by 567 milligrams of Bi (NO3)3With the AgNO that 84mL molar concentrations are 0.77mol/L3Solution 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, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains substance A 8, substance A 8 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A 9；
(11) by 557 milligrams of Bi (NO3)3With the AgNO that 89mL molar concentrations are 0.82mol/L3Solution is added in mixed liquor K5,
Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor L5；
(12) substance A 9 is added in mixed liquor L5, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains substance A 10, substance A 10 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Drying box in place 136 minutes, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance A；
(13) by 3.26 grams of AgNO3Volume is added to, in 1000mL conical flasks, to stir under the conditions of 1000r/min with 750mL ether
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 312 milligrams of AgNO3With the Bi (NO that 74mL molar concentrations are 0.51mol/L3)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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature
Filter liquid and obtain substance B, substance B is Jing after the ethanol washing that 100mL mass percent concentrations are 88% in 78 DEG C of drying
Place 136 minutes in case, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance B 1；
(16) by 322 milligrams of AgNO3With the Bi (NO that 79mL molar concentrations are 0.61mol/L3)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, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains substance B 2, substance B 2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain substance C；
(18) by 332 milligrams of AgNO3With the Bi (NO that 84mL molar concentrations are 0.71mol/L3)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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature
Filter liquid and obtain material D, material D is Jing after the ethanol washing that 100mL mass percent concentrations are 88% in 78 DEG C of drying
Place 136 minutes in case, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material E；
(20) by 5.39 grams of Co (NO3)2Volume is added to in 1000mL conical flasks with 850mL ethanol, in 1000r/min conditions
Lower stirring 3 minutes, adds 5mL red fuming nitric acid (RFNA)s, is divided into 5 parts of equivalent after shaking up, and obtains mixed liquor P1, mixed liquor P2, mixed liquor P3, mixed
Close liquid P4, mixed liquor P5；
(21) by 62mL molar concentrations for 0.94mol/L InCl3Solution 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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature
Filter liquid and obtain material F1, material F1 is dry at 78 DEG C Jing after the ethanol washing that 100mL mass percent concentrations are 88%
Place 136 minutes in dry case, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F2；
(23) by 48mL molar concentrations for 0.91mol/L Co (NO3)2Solution is added in mixed liquor P2, in 1000r/min bars
Stir 3 minutes under part, obtain mixed liquor Q2；
(24) material F2 is added in mixed liquor Q2, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material F3, material F3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F4；
(25) by 52mL molar concentrations for 0.84mol/L InCl3Solution 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, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material F5, material F5 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F6；
(27) by 38mL molar concentrations for 0.81mol/L Co (NO3)2Solution is added in mixed liquor P4, in 1000r/min bars
Stir 3 minutes under part, obtain mixed liquor Q4；
(28) material F6 is added in mixed liquor Q4, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material F7, material F7 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F8；
(29) by 42mL molar concentrations for 0.74mol/L InCl3Solution and the Co that 28mL molar concentrations are 0.71mol/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, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material F9, material F9 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material F；
(31) by 5.68g SnCl4Volume is added to the sodium citrate solution that 750mL mass percent concentrations are 10% is
In 1000mL conical flasks, stir 3 minutes under the conditions of 1000r/min, after shaking up, be divided into 3 parts of equivalent, obtain mixed liquor R1, mixing
Liquid R2, mixed liquor R3；
(32) by 46mL molar concentrations for 0.66mol/L ZnCl2Solution and the MnCl that 54mL molar concentrations are 0.69mol/L2It is molten
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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature
Filter liquid and obtain material G1, material G1 is dry at 78 DEG C Jing after the ethanol washing that 100mL mass percent concentrations are 88%
Place 136 minutes in dry case, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material H1；
(34) by 41mL molar concentrations for 0.76mol/L ZnCl2Solution and the MnCl that 59mL molar concentrations are 0.79mol/L2It is molten
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, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material G2, material G2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material H2；
(36) by 36mL molar concentrations for 0.86mol/L ZnCl2Solution and the MnCl that 64mL molar concentrations are 0.89mol/L2It is molten
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, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material G3, material G3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material H；
(38) 3.37g lauryl sodium sulfate, 40mL n-hexanes, 20 milliliters of n-butanols are added sequentially to volume and are bored for 250mL
In shape bottle, 6.38g sodium metavanadates and 150mL deionized waters are added, be placed in 70 DEG C of water-baths and stir under the conditions of 1000r/min
1h, is subsequently adding the hydrochloric acid solution that 25mL molar concentrations are 2.40mol/L, shakes 0.5h in the shaking table that temperature is 45 DEG C, cold
But 15min is centrifuged under the conditions of 7500r/min to after room temperature, removes supernatant, be 95% with 500mL mass percent concentrations
Ethanol is washed, and obtains material I；
(39) sodium citrate solution that material I and 850mL mass percent concentration is 15% is 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) by 48mL molar concentrations for 0.86mol/L ZnCl2Solution and the MnCl that 52mL molar concentrations are 0.52mol/L2It is molten
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, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature
Filter liquid and obtain material J1, material J1 is dry at 78 DEG C Jing after the ethanol washing that 100mL mass percent concentrations are 88%
Place 136 minutes in dry case, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K1；
(42) by 44mL molar concentrations for 0.81mol/L ZnCl2Solution and the MnCl that 56mL molar concentrations are 0.57mol/L2It is molten
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, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material J2, material J2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K2；
(44) by 40mL molar concentrations for 0.76mol/L ZnCl2Solution and the MnCl that 60mL molar concentrations are 0.62mol/L2It is molten
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, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material J3, material J3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K3；
(46) by 36mL molar concentrations for 0.71mol/L ZnCl2Solution and the MnCl that 64mL molar concentrations are 0.67mol/L2It is molten
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, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material J4, material J4 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K4；
(48) by 32mL molar concentrations for 0.66mol/L ZnCl2Solution and the MnCl that 68mL molar concentrations are 0.72mol/L2It is molten
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, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material J5, material J5 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material K；
(50) 7.26g polyvinylpyrrolidones and 900mL deionized waters are added to into volume in 1000mL conical flasks,
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, mixed
Close liquid V4, mixed liquor V5；
(51) by 83mL molar concentrations for 0.82mol/L HAuCl4Solution is added in mixed liquor V1, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor W1；
(52) material K is added in mixed liquor W1, shakes 15 minutes in the shaking table that temperature is 45 DEG C, be cooled to mistake after room temperature
Filter liquid and obtain material L1, material L1 is dry at 78 DEG C Jing after the ethanol washing that 100mL mass percent concentrations are 88%
Place 136 minutes in dry case, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z1；
(53) by 73mL molar concentrations for 0.78mol/L HAuCl4Solution is added in mixed liquor V2, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor W2；
(54) material Z1 is added in mixed liquor W2, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material L2, material L2 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z2；
(55) by 63mL molar concentrations for 0.74mol/L HAuCl4Solution is added in mixed liquor V3, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor W3；
(56) material Z2 is added in mixed liquor W3, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material L3, material L3 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z3；
(57) by 53mL molar concentrations for 0.70mol/L HAuCl4Solution is added in mixed liquor V4, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor W4；
(58) material Z3 is added in mixed liquor W4, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material L4, material L4 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, obtain material Z4；
(59) by 43mL molar concentrations for 0.66mol/L HAuCl4Solution is added in mixed liquor V5, in 1000r/min conditions
Lower stirring 3 minutes, obtains mixed liquor W5；
(60) material Z4 is added in mixed liquor W5, is shaken 15 minutes in the shaking table that temperature is 45 DEG C, after being cooled to room temperature
It is filtered to remove liquid and obtains material L5, material L5 is Jing after the ethanol washing that 100mL mass percent concentrations are 88% at 78 DEG C
Place 136 minutes in drying box, be subsequently placed in Muffle furnace roasting 55 minutes under the conditions of 542 DEG C, the material for obtaining as has
There is electro-catalysis to remove the improved ferroferric oxide granule electrode of thiophene function.
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| 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 |
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