CN106430460A - Modified graphite particle electrode with function of electro-catalytically removing thiophene and preparation method - Google Patents

Modified graphite particle electrode with function of electro-catalytically removing thiophene and preparation method Download PDF

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CN106430460A
CN106430460A CN201611050122.7A CN201611050122A CN106430460A CN 106430460 A CN106430460 A CN 106430460A CN 201611050122 A CN201611050122 A CN 201611050122A CN 106430460 A CN106430460 A CN 106430460A
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mixed liquor
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不公告发明人
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Beijing Qingyuan Environmental Protection Technology Co Ltd
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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
    • C02F1/467—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
    • 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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Environmental & Geological Engineering (AREA)
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Abstract

The invention discloses a modified graphite particle electrode with a function of electro-catalytically removing thiophene and a preparation method. The preparation method comprises the following steps: preparing graphite, trichloromethane and ethyl alcohol into a matter A; modifying a mixed liquor prepared from silver nitrate, platinum nitrate, diethyl ether and Sb(NO3)3 with the matter A, thereby preparing a matter E; modifying the mixed liquor prepared from Cd(NO3)2, ethanol, AlCl3, PtCl4, MnCl2 and ZnCl2 with the matter E, thereby preparing a matter H; modifying the mixed liquor prepared from lauryl sodium sulfate, normal hexane, n-butyl alcohol, sodium metavanadate, sodium citrate, MnCl2 and ZnCl2 with the matter H, thereby preparing a matter K; modifying the mixed liquor prepared from polyvinylpyrrolidone and HAuCl4 with the matter K, thereby obtaining the modified graphite particle electrode with the function of electro-catalytically removing thiophene.

Description

There is modified graphite granule electrode and the preparation method that electro-catalysis removes thiophene function
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 graphite 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 graphite granule electrode and the preparation that electro-catalysis removes thiophene function Method, the comprising the following steps that of its preparation method：
(1) the 97g graphite granule 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) 4.29 grams of platinum nitrates and 850mL deionized water being added to volume is in 1000mL conical flask, in 1000r/ Stir 3 minutes under the conditions of min, add 15mL red fuming nitric acid (RFNA), 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 526 milligrams of Sb (NO3)3It is the AgNO of 0.82mol/L with 71mL molar concentration3Solution 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, 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 3；
(5) by 536 milligrams of Sb (NO3)3It is the AgNO of 0.87mol/L with 76mL molar concentration3Solution 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, 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 5；
(7) by 546 milligrams of Sb (NO3)3It is the AgNO of 0.92mol/L with 81mL molar concentration3Solution 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, 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 7；
(9) by 556 milligrams of Sb (NO3)3It is the AgNO of 0.97mol/L with 86mL molar concentration3Solution 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, 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 9；
(11) by 566 milligrams of Sb (NO3)3It is the AgNO of 1.02mol/L with 91mL 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 97% Place 141 minutes in 76 DEG C of drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A；
(13) by 4.02 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 329 milligrams of AgNO3It is the Sb (NO of 0.57mol/L with 77mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance B 1；
(16) by 339 milligrams of AgNO3It is the Sb (NO of 0.61mol/L with 87mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance C；
(18) by 349 milligrams of AgNO3It is the Sb (NO of 0.65mol/L with 97mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material E；
(20) by 6.29 grams of Cd (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) AlCl for 0.54mol/L by 83mL 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F2；
(23) Cd (NO for 0.51mol/L by 76mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F4；
(25) AlCl for 0.44mol/L by 73mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F6；
(27) Cd (NO for 0.41mol/L by 66mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F8；
(29) AlCl for 0.34mol/L by 63mL molar concentration3Solution and 56mL molar concentration are the Cd of 0.31mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F；
(31) by 3.98g PtCl4It 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 0.62mol/L by 43mL molar concentration2Solution and 57mL molar concentration are 0.73mol/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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material H1；
(34) MnCl for 0.82mol/L by 46mL molar concentration2Solution and 54mL molar concentration are 0.71mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material H2；
(36) MnCl for 1.02mol/L by 49mL molar concentration2Solution and 51mL molar concentration are 0.69mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material H；
(38) 3.62g lauryl sodium sulfate, 40mL n-hexane, 20 milliliters of n-butanols are added sequentially to volume and are In 250mL conical flask, add 6.49g 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 0.66mol/L by 49mL molar concentration2Solution and 51mL molar concentration are 0.86mol/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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K1；
(42) MnCl for 0.68mol/L by 54mL molar concentration2Solution and 46mL molar concentration are 0.84mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K2；
(44) MnCl for 0.70mol/L by 59mL molar concentration2Solution and 41mL molar concentration are 0.82mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K3；
(46) MnCl for 0.72mol/L by 64mL molar concentration2Solution and 36mL molar concentration are 0.80mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K4；
(48) MnCl for 0.74mol/L by 69mL molar concentration2Solution and 31mL molar concentration are 0.78mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K；
(50) 9.29g 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 0.67mol/L by 54mL 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z1；
(53) HAuCl for 0.62mol/L by 50mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z2；
(55) HAuCl for 0.57mol/L by 46mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z3；
(57) HAuCl for 0.52mol/L by 42mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z4；
(59) HAuCl for 0.47mol/L by 38mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, the material obtaining is Remove the modified graphite granule electrode of thiophene function for having electro-catalysis.
The invention has the beneficial effects as follows, the prepared modified graphite 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 graphite 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 97g graphite granule 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) 4.29 grams of platinum nitrates and 850mL deionized water being added to volume is in 1000mL conical flask, in 1000r/ Stir 3 minutes under the conditions of min, add 15mL red fuming nitric acid (RFNA), 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 526 milligrams of Sb (NO3)3It is the AgNO of 0.82mol/L with 71mL molar concentration3Solution 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, 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 3；
(5) by 536 milligrams of Sb (NO3)3It is the AgNO of 0.87mol/L with 76mL molar concentration3Solution 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, 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 5；
(7) by 546 milligrams of Sb (NO3)3It is the AgNO of 0.92mol/L with 81mL molar concentration3Solution 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, 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 7；
(9) by 556 milligrams of Sb (NO3)3It is the AgNO of 0.97mol/L with 86mL molar concentration3Solution 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, 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 9；
(11) by 566 milligrams of Sb (NO3)3It is the AgNO of 1.02mol/L with 91mL 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 97% Place 141 minutes in 76 DEG C of drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A；
(13) by 4.02 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 329 milligrams of AgNO3It is the Sb (NO of 0.57mol/L with 77mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance B 1；
(16) by 339 milligrams of AgNO3It is the Sb (NO of 0.61mol/L with 87mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance C；
(18) by 349 milligrams of AgNO3It is the Sb (NO of 0.65mol/L with 97mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material E；
(20) by 6.29 grams of Cd (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) AlCl for 0.54mol/L by 83mL 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F2；
(23) Cd (NO for 0.51mol/L by 76mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F4；
(25) AlCl for 0.44mol/L by 73mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F6；
(27) Cd (NO for 0.41mol/L by 66mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F8；
(29) AlCl for 0.34mol/L by 63mL molar concentration3Solution and 56mL molar concentration are the Cd of 0.31mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F；
(31) by 3.98g PtCl4It 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 0.62mol/L by 43mL molar concentration2Solution and 57mL molar concentration are 0.73mol/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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material H1；
(34) MnCl for 0.82mol/L by 46mL molar concentration2Solution and 54mL molar concentration are 0.71mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material H2；
(36) MnCl for 1.02mol/L by 49mL molar concentration2Solution and 51mL molar concentration are 0.69mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material H；
(38) 3.62g lauryl sodium sulfate, 40mL n-hexane, 20 milliliters of n-butanols are added sequentially to volume and are In 250mL conical flask, add 6.49g 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 0.66mol/L by 49mL molar concentration2Solution and 51mL molar concentration are 0.86mol/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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K1；
(42) MnCl for 0.68mol/L by 54mL molar concentration2Solution and 46mL molar concentration are 0.84mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K2；
(44) MnCl for 0.70mol/L by 59mL molar concentration2Solution and 41mL molar concentration are 0.82mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K3；
(46) MnCl for 0.72mol/L by 64mL molar concentration2Solution and 36mL molar concentration are 0.80mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K4；
(48) MnCl for 0.74mol/L by 69mL molar concentration2Solution and 31mL molar concentration are 0.78mol/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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K；
(50) 9.29g 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 0.67mol/L by 54mL 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z1；
(53) HAuCl for 0.62mol/L by 50mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z2；
(55) HAuCl for 0.57mol/L by 46mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z3；
(57) HAuCl for 0.52mol/L by 42mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z4；
(59) HAuCl for 0.47mol/L by 38mL 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 97% 76 DEG C drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, the material obtaining is Remove the modified graphite granule electrode of thiophene function for having electro-catalysis.
It is presented herein below and exist with the modified graphite 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 graphite 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 2.6mg/L, and treatment effeciency reaches 95.03%.

Claims (1)

1. a kind of have electro-catalysis remove thiophene function modified graphite granule electrode preparation method it is characterised in that the party The comprising the following steps that of method：
(1) the 97g graphite granule 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) 4.29 grams of platinum nitrates and 850mL deionized water being added to volume is in 1000mL conical flask, in 1000r/min bar Stir 3 minutes under part, 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 526 milligrams of Sb (NO3)3It is the AgNO of 0.82mol/L with 71mL 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 76 DEG C after the ethanol washing that 100mL mass percent concentration is 97% Place 141 minutes in dry case, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 3；
(5) by 536 milligrams of Sb (NO3)3It is the AgNO of 0.87mol/L with 76mL 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 76 DEG C after the ethanol washing that 100mL mass percent concentration is 97% Place 141 minutes in dry case, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 5；
(7) by 546 milligrams of Sb (NO3)3It is the AgNO of 0.92mol/L with 81mL 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 76 DEG C after the ethanol washing that 100mL mass percent concentration is 97% Place 141 minutes in dry case, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 7；
(9) by 556 milligrams of Sb (NO3)3It is the AgNO of 0.97mol/L with 86mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A 9；
(11) by 566 milligrams of Sb (NO3)3It is the AgNO of 1.02mol/L with 91mL molar concentration3Solution 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, 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 97% at 76 DEG C Drying box in place 141 minutes, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance A；
(13) by 4.02 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 329 milligrams of AgNO3It is the Sb (NO of 0.57mol/L with 77mL 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 97% in 76 DEG C of drying Place 141 minutes in case, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance B 1；
(16) by 339 milligrams of AgNO3It is the Sb (NO of 0.61mol/L with 87mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain substance C；
(18) by 349 milligrams of AgNO3It is the Sb (NO of 0.65mol/L with 97mL 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 97% in 76 DEG C of drying Place 141 minutes in case, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material E；
(20) by 6.29 grams of Cd (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) AlCl for 0.54mol/L by 83mL 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 76 DEG C after the ethanol washing that 100mL mass percent concentration is 97% Place 141 minutes in dry case, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F2；
(23) Cd (NO for 0.51mol/L by 76mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F4；
(25) AlCl for 0.44mol/L by 73mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F6；
(27) Cd (NO for 0.41mol/L by 66mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F8；
(29) AlCl for 0.34mol/L by 63mL molar concentration3Solution and 56mL molar concentration are the Cd of 0.31mol/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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material F；
(31) by 3.98g PtCl4Being 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 0.62mol/L by 43mL molar concentration2Solution and 57mL molar concentration are the ZnCl of 0.73mol/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 76 DEG C after the ethanol washing that 100mL mass percent concentration is 97% Place 141 minutes in dry case, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material H1；
(34) MnCl for 0.82mol/L by 46mL molar concentration2Solution and 54mL molar concentration are the ZnCl of 0.71mol/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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material H2；
(36) MnCl for 1.02mol/L by 49mL molar concentration2Solution and 51mL molar concentration are the ZnCl of 0.69mol/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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material H；
(38) 3.62g lauryl sodium sulfate, 40mL n-hexane, 20 milliliters of n-butanols are added sequentially to volume and bore for 250mL In shape bottle, add 6.49g 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 0.66mol/L by 49mL molar concentration2Solution and 51mL molar concentration are the ZnCl of 0.86mol/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 76 DEG C after the ethanol washing that 100mL mass percent concentration is 97% Place 141 minutes in dry case, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K1；
(42) MnCl for 0.68mol/L by 54mL molar concentration2Solution and 46mL molar concentration are the ZnCl of 0.84mol/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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K2；
(44) MnCl for 0.70mol/L by 59mL molar concentration2Solution and 41mL molar concentration are the ZnCl of 0.82mol/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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K3；
(46) MnCl for 0.72mol/L by 64mL molar concentration2Solution and 36mL molar concentration are the ZnCl of 0.80mol/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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K4；
(48) MnCl for 0.74mol/L by 69mL molar concentration2Solution and 31mL molar concentration are the ZnCl of 0.78mol/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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material K；
(50) 9.29g 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 0.67mol/L by 54mL 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 76 DEG C after the ethanol washing that 100mL mass percent concentration is 97% Place 141 minutes in dry case, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z1；
(53) HAuCl for 0.62mol/L by 50mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z2；
(55) HAuCl for 0.57mol/L by 46mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z3；
(57) HAuCl for 0.52mol/L by 42mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, obtain material Z4；
(59) HAuCl for 0.47mol/L by 38mL 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 97% at 76 DEG C Place 141 minutes in drying box, be subsequently placed in Muffle furnace roasting 72 minutes under the conditions of 488 DEG C, the material obtaining is to be had Electro-catalysis is had to remove the modified graphite granule electrode of thiophene function.
CN201611050122.7A 2016-11-21 2016-11-21 Modified graphite particle electrode with function of electro-catalytically removing thiophene and preparation method Withdrawn CN106430460A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107986431A (en) * 2017-12-04 2018-05-04 北京中科宇清环保有限公司 A kind of polyurethane catalytic filler for electric field-enhanced oxygen-enriching device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107986431A (en) * 2017-12-04 2018-05-04 北京中科宇清环保有限公司 A kind of polyurethane catalytic filler for electric field-enhanced oxygen-enriching device

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