CN106430445A - Modified carbon fiber particle electrode capable of removing benzoquinone by electro-catalysis and preparation method of modified carbon fiber particle electrode capable of removing benzoquinone by electro-catalysis - Google Patents

Modified carbon fiber particle electrode capable of removing benzoquinone by electro-catalysis and preparation method of modified carbon fiber particle electrode capable of removing benzoquinone by electro-catalysis Download PDF

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CN106430445A
CN106430445A CN201611050532.1A CN201611050532A CN106430445A CN 106430445 A CN106430445 A CN 106430445A CN 201611050532 A CN201611050532 A CN 201611050532A CN 106430445 A CN106430445 A CN 106430445A
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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
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen

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  • Chemical Kinetics & Catalysis (AREA)
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  • General Chemical & Material Sciences (AREA)
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  • Hydrology & Water Resources (AREA)
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Abstract

The invention discloses a modified carbon fiber particle electrode capable of removing benzoquinone by electro-catalysis and a preparation method of the modified carbon fiber particle electrode capable of removing the benzoquinone by electro-catalysis. The preparation method includes preparing a substance A from carbon fibers, trichloromethane and ethyl alcohol; using the substance A for modifying mixed liquid prepared from silver nitrate, platinum nitrate, diethyl ether and Ce(NO3)3 so as to obtain a substance E; using the substance E for modifying mixed liquid prepared from Pd(NO3)2, ethyl alcohol, AlCl3, PtCl4, ZnCl2 and CuCl2 so as to obtain a substance H; using the substance H for modifying mixed liquid prepared from lauryl sodium sulfate, normal hexane, n-butyl alcohol, ammonium metavanadate, sodium citrate, ZnCl2 and CuCl2 so as to obtain a substance K; using the substance K for modifying mixed liquid prepared from polyvinyl alcohol and HAuCl4 so as to obtain the modified carbon fiber particle electrode capable of removing benzoquinone by electro-catalysis.

Description

There is modified carbon fiber granule electrode and the preparation method that electro-catalysis removes benzoquinone 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 carbon fiber granule electrode removing benzoquinone 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, conductivity 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 lacking 1,4-benzoquinone specific pollutants has efficient electric catalytic elimination function at present Electrode material and preparation method.
Content of the invention
It is an object of the invention to provide a kind of have modified carbon fiber granule electrode and the system that electro-catalysis removes benzoquinone function Preparation Method, the comprising the following steps that of its preparation method：
(1) the 122g carbon fiber particles 1000mL deionized water wash being 4～6mm by particle diameter, is then placed in 500mL tri- Soak 8h in chloromethanes, after taking-up, use 1000mL deionized water wash, then the second being 95% with 1000mL mass percent concentration Place 1.5h in 85 DEG C of drying baker after alcohol washing, obtain substance A 1；
(2) 7.68 grams of platinum nitrates and 800mL deionized water being added to volume is in 1000mL conical flask, in 1000r/ Stir 3 minutes under the conditions of min, add 15mL concentrated nitric acid, after shaking up, be divided into 4 parts of equivalent, obtain mixed liquor K1, mixed liquor K2, mix Close liquid K3, mixed liquor K4；
(3) by 719 milligrams of Ce (NO3)3It is the AgNO of 0.39mol/L with 40mL 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A 3；
(5) by 739 milligrams of Ce (NO3)3It is the AgNO of 0.59mol/L with 50mL 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A 5；
(7) by 759 milligrams of Ce (NO3)3It is the AgNO of 0.79mol/L with 60mL 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A 7；
(9) by 779 milligrams of Ce (NO3)3It is the AgNO of 0.99mol/L with 70mL 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A；
(11) by 4.66 grams of AgNO3Being added to volume with 850mL ether is in 1000mL conical flask, in 1000r/min bar Stir 3 minutes under part, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor M1, mixed liquor M2, mixed liquor M3, mixed liquor M4, mixing Liquid M5；
(12) by 217 milligrams of AgNO3It is the Ce (NO of 0.85mol/L with 90mL molar concentration3)3Solution is added to mixed liquor In M1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N1；
(13) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance B 1；
(14) by 247 milligrams of AgNO3It is the Ce (NO of 0.75mol/L with 80mL molar concentration3)3Solution is added to mixed liquor In M2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N2；
(15) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance B 3；
(16) by 277 milligrams of AgNO3It is the Ce (NO of 0.65mol/L with 70mL molar concentration3)3Solution is added to mixed liquor In M3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N3；
(17) substance B 3 is added in mixed liquor N3, 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 4, substance B 4 is after the washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance B 5；
(18) by 307 milligrams of AgNO3It is the Ce (NO of 0.55mol/L with 60mL molar concentration3)3Solution is added to mixed liquor In M4, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N4；
(19) substance B 5 is added in mixed liquor N4, 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 6, substance B 6 is after the washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance C；
(20) by 236 milligrams of AgNO3It is the Ce (NO of 0.56mol/L with 78mL molar concentration3)3Solution is added to mixed liquor In M5, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N5；
(21) substance C is added in mixed liquor N5, 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material E；
(22) by 6.99 grams of Pd (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 concentrated nitric acid, 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；
(23) AlCl for 0.88mol/L by 85mL molar concentration3Solution is added in mixed liquor P1, in 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Q1；
(24) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F2；
(25) Pd (NO for 0.74mol/L by 80mL molar concentration3)2Solution is added in mixed liquor P2, in 1000r/ Stir 3 minutes under the conditions of min, obtain mixed liquor Q2；
(26) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F4；
(27) AlCl for 0.54mol/L by 65mL molar concentration3Solution is added in mixed liquor P3, in 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Q3；
(28) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F6；
(29) Pd (NO for 0.54mol/L by 60mL molar concentration3)2Solution is added in mixed liquor P4, in 1000r/ Stir 3 minutes under the conditions of min, obtain mixed liquor Q4；
(30) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F8；
(31) AlCl for 0.48mol/L by 45mL molar concentration3Solution and 40mL molar concentration are the Pd of 0.34mol/L (NO3)2Solution is added in mixed liquor P5, stirs 3 minutes, obtain mixed liquor Q5 under the conditions of 1000r/min；
(32) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F；
(33) by 5.26g 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；
(34) ZnCl for 0.49mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.77mol/L's CuCl2Solution is added in mixed liquor R1, stirs 3 minutes, obtain mixed liquor S1 under the conditions of 1000r/min；
(35) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material H1；
(36) ZnCl for 0.69mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.57mol/L's CuCl2Solution is added in mixed liquor R2, stirs 3 minutes, obtain mixed liquor S2 under the conditions of 1000r/min；
(37) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material H2；
(38) ZnCl for 0.89mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.37mol/L's CuCl2Solution is added in mixed liquor R3, stirs 3 minutes, obtain mixed liquor S3 under the conditions of 1000r/min；
(39) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material H；
(40) 3.18g sodium lauryl sulphate, 40mL normal hexane, 20 milliliters of n-butyl alcohol are added sequentially to volume and are In 250mL conical flask, add 6.94g ammonium 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 Washing with alcohol for 95%, obtains material I；
(41) 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；
(42) ZnCl for 0.28mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.91mol/L's CuCl2Solution is added in mixed liquor T1, stirs 3 minutes, obtain mixed liquor U1 under the conditions of 1000r/min；
(43) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K1；
(44) ZnCl for 0.38mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.81mol/L's CuCl2Solution is added in mixed liquor T2, stirs 3 minutes, obtain mixed liquor U2 under the conditions of 1000r/min；
(45) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K2；
(46) ZnCl for 0.48mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.71mol/L's CuCl2Solution is added in mixed liquor T3, stirs 3 minutes, obtain mixed liquor U3 under the conditions of 1000r/min；
(47) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K3；
(48) ZnCl for 0.58mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.61mol/L's CuCl2Solution is added in mixed liquor T4, stirs 3 minutes, obtain mixed liquor U4 under the conditions of 1000r/min；
(49) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K4；
(50) ZnCl for 0.68mol/L by 70mL molar concentration2Solution and 30mL molar concentration are 0.51mol/L's CuCl2Solution is added in mixed liquor T5, stirs 3 minutes, obtain mixed liquor U5 under the conditions of 1000r/min；
(51) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K；
(52) 9.44g polyvinyl alcohol and 900mL deionized water being added to volume is in 1000mL conical flask, in 1000r/ Stir 3 minutes under the conditions of min, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor V1, mixed liquor V2, mixed liquor V3；
(53) HAuCl for 0.82mol/L by 90mL molar concentration4Solution is added in mixed liquor V1, in 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor W1；
(54) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material Z1；
(55) HAuCl for 0.62mol/L by 70mL molar concentration4Solution is added in mixed liquor V2, in 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor W2；
(56) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material Z2；
(57) HAuCl for 0.42mol/L by 50mL molar concentration4Solution is added in mixed liquor V3, in 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor W3；
(58) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, the material obtaining is Remove the modified carbon fiber granule electrode of benzoquinone function for having electro-catalysis.
The invention has the beneficial effects as follows, prepared has the modified carbon fiber granule electrode tool that electro-catalysis removes benzoquinone function There is the features such as current efficiency is high, stability is strong, electrode life length, 1,4-benzoquinone removal efficiency are high.
Specific embodiment
The present invention provides a kind of modified carbon fiber granule electrode with electro-catalysis removal benzoquinone function and preparation method, under Face illustrates in fact to apply process by an example.
Embodiment 1.
(1) the 122g carbon fiber particles 1000mL deionized water wash being 4～6mm by particle diameter, is then placed in 500mL tri- Soak 8h in chloromethanes, after taking-up, use 1000mL deionized water wash, then the second being 95% with 1000mL mass percent concentration Place 1.5h in 85 DEG C of drying baker after alcohol washing, obtain substance A 1；
(2) 7.68 grams of platinum nitrates and 800mL deionized water being added to volume is in 1000mL conical flask, in 1000r/ Stir 3 minutes under the conditions of min, add 15mL concentrated nitric acid, after shaking up, be divided into 4 parts of equivalent, obtain mixed liquor K1, mixed liquor K2, mix Close liquid K3, mixed liquor K4；
(3) by 719 milligrams of Ce (NO3)3It is the AgNO of 0.39mol/L with 40mL 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A 3；
(5) by 739 milligrams of Ce (NO3)3It is the AgNO of 0.59mol/L with 50mL 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A 5；
(7) by 759 milligrams of Ce (NO3)3It is the AgNO of 0.79mol/L with 60mL 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A 7；
(9) by 779 milligrams of Ce (NO3)3It is the AgNO of 0.99mol/L with 70mL 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A；
(11) by 4.66 grams of AgNO3Being added to volume with 850mL ether is in 1000mL conical flask, in 1000r/min bar Stir 3 minutes under part, be divided into 5 parts of equivalent after shaking up, obtain mixed liquor M1, mixed liquor M2, mixed liquor M3, mixed liquor M4, mixing Liquid M5；
(12) by 217 milligrams of AgNO3It is the Ce (NO of 0.85mol/L with 90mL molar concentration3)3Solution is added to mixed liquor In M1, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N1；
(13) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance B 1；
(14) by 247 milligrams of AgNO3It is the Ce (NO of 0.75mol/L with 80mL molar concentration3)3Solution is added to mixed liquor In M2, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N2；
(15) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance B 3；
(16) by 277 milligrams of AgNO3It is the Ce (NO of 0.65mol/L with 70mL molar concentration3)3Solution is added to mixed liquor In M3, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N3；
(17) substance B 3 is added in mixed liquor N3, 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 4, substance B 4 is after the washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance B 5；
(18) by 307 milligrams of AgNO3It is the Ce (NO of 0.55mol/L with 60mL molar concentration3)3Solution is added to mixed liquor In M4, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N4；
(19) substance B 5 is added in mixed liquor N4, 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 6, substance B 6 is after the washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance C；
(20) by 236 milligrams of AgNO3It is the Ce (NO of 0.56mol/L with 78mL molar concentration3)3Solution is added to mixed liquor In M5, stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N5；
(21) substance C is added in mixed liquor N5, 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material E；
(22) by 6.99 grams of Pd (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 concentrated nitric acid, 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；
(23) AlCl for 0.88mol/L by 85mL molar concentration3Solution is added in mixed liquor P1, in 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Q1；
(24) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F2；
(25) Pd (NO for 0.74mol/L by 80mL molar concentration3)2Solution is added in mixed liquor P2, in 1000r/ Stir 3 minutes under the conditions of min, obtain mixed liquor Q2；
(26) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F4；
(27) AlCl for 0.54mol/L by 65mL molar concentration3Solution is added in mixed liquor P3, in 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor Q3；
(28) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F6；
(29) Pd (NO for 0.54mol/L by 60mL molar concentration3)2Solution is added in mixed liquor P4, in 1000r/ Stir 3 minutes under the conditions of min, obtain mixed liquor Q4；
(30) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F8；
(31) AlCl for 0.48mol/L by 45mL molar concentration3Solution and 40mL molar concentration are the Pd of 0.34mol/L (NO3)2Solution is added in mixed liquor P5, stirs 3 minutes, obtain mixed liquor Q5 under the conditions of 1000r/min；
(32) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F；
(33) by 5.26g 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；
(34) ZnCl for 0.49mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.77mol/L's CuCl2Solution is added in mixed liquor R1, stirs 3 minutes, obtain mixed liquor S1 under the conditions of 1000r/min；
(35) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material H1；
(36) ZnCl for 0.69mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.57mol/L's CuCl2Solution is added in mixed liquor R2, stirs 3 minutes, obtain mixed liquor S2 under the conditions of 1000r/min；
(37) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material H2；
(38) ZnCl for 0.89mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.37mol/L's CuCl2Solution is added in mixed liquor R3, stirs 3 minutes, obtain mixed liquor S3 under the conditions of 1000r/min；
(39) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material H；
(40) 3.18g sodium lauryl sulphate, 40mL normal hexane, 20 milliliters of n-butyl alcohol are added sequentially to volume and are In 250mL conical flask, add 6.94g ammonium 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 Washing with alcohol for 95%, obtains material I；
(41) 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；
(42) ZnCl for 0.28mol/L by 30mL molar concentration2Solution and 70mL molar concentration are 0.91mol/L's CuCl2Solution is added in mixed liquor T1, stirs 3 minutes, obtain mixed liquor U1 under the conditions of 1000r/min；
(43) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K1；
(44) ZnCl for 0.38mol/L by 40mL molar concentration2Solution and 60mL molar concentration are 0.81mol/L's CuCl2Solution is added in mixed liquor T2, stirs 3 minutes, obtain mixed liquor U2 under the conditions of 1000r/min；
(45) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K2；
(46) ZnCl for 0.48mol/L by 50mL molar concentration2Solution and 50mL molar concentration are 0.71mol/L's CuCl2Solution is added in mixed liquor T3, stirs 3 minutes, obtain mixed liquor U3 under the conditions of 1000r/min；
(47) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K3；
(48) ZnCl for 0.58mol/L by 60mL molar concentration2Solution and 40mL molar concentration are 0.61mol/L's CuCl2Solution is added in mixed liquor T4, stirs 3 minutes, obtain mixed liquor U4 under the conditions of 1000r/min；
(49) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K4；
(50) ZnCl for 0.68mol/L by 70mL molar concentration2Solution and 30mL molar concentration are 0.51mol/L's CuCl2Solution is added in mixed liquor T5, stirs 3 minutes, obtain mixed liquor U5 under the conditions of 1000r/min；
(51) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K；
(52) 9.44g polyvinyl alcohol and 900mL deionized water being added to volume is in 1000mL conical flask, in 1000r/ Stir 3 minutes under the conditions of min, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor V1, mixed liquor V2, mixed liquor V3；
(53) HAuCl for 0.82mol/L by 90mL molar concentration4Solution is added in mixed liquor V1, in 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor W1；
(54) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material Z1；
(55) HAuCl for 0.62mol/L by 70mL molar concentration4Solution is added in mixed liquor V2, in 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor W2；
(56) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material Z2；
(57) HAuCl for 0.42mol/L by 50mL molar concentration4Solution is added in mixed liquor V3, in 1000r/min Under the conditions of stir 3 minutes, obtain mixed liquor W3；
(58) 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 washing with alcohol that 100mL mass percent concentration is 87% 75 DEG C drying baker in place 140 minutes, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, the material obtaining is Remove the modified carbon fiber granule electrode of benzoquinone function for having electro-catalysis.
It is presented herein below, with what the inventive method was obtained, there is the modified carbon fiber granule electrode that electro-catalysis removes benzoquinone function In electric catalysis reactor, Electro-catalytic Oxidation Process test is carried out to the waste water containing benzoquinone, further illustrated the present invention.
The modified carbon fiber granule electrode with electro-catalysis removal benzoquinone function that the inventive method is obtained is seated in electricity In catalytic reactor, Degrading experiment is carried out to the waste water containing benzoquinone, result shows the electrocatalytic reaction being loaded by this electrode Device can efficiently remove the benzoquinone in waste water, when the benzoquinone concentration in waste water is 44.9mg/L, is 5.0 in pH, voltage is 14V, under the conditions of process time is 45min, the benzoquinone concentration in water outlet after process is reduced to 1.8mg/L, and treatment effeciency reaches 95.99%.

Claims (1)

1. a kind of preparation method of the modified carbon fiber granule electrode with electro-catalysis removal benzoquinone function is it is characterised in that be somebody's turn to do The comprising the following steps that of method：
(1) the 122g carbon fiber particles 1000mL deionized water wash being 4～6mm by particle diameter, is then placed in 500mL tri- chloromethane Soak 8h in alkane, use 1000mL deionized water wash after taking-up, then washed with the ethanol that 1000mL mass percent concentration is 95% Place 1.5h in 85 DEG C of drying baker after washing, obtain substance A 1；
(2) 7.68 grams of platinum nitrates and 800mL deionized water being added to volume is in 1000mL conical flask, in 1000r/min bar Stir 3 minutes under part, add 15mL concentrated nitric acid, be divided into 4 parts of equivalent after shaking up, obtain mixed liquor K1, mixed liquor K2, mixed liquor K3, mixed liquor K4；
(3) by 719 milligrams of Ce (NO3)3It is the AgNO of 0.39mol/L with 40mL 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 75 DEG C after the washing with alcohol that 100mL mass percent concentration is 87% Place 140 minutes in dry case, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A 3；
(5) by 739 milligrams of Ce (NO3)3It is the AgNO of 0.59mol/L with 50mL 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 75 DEG C after the washing with alcohol that 100mL mass percent concentration is 87% Place 140 minutes in dry case, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A 5；
(7) by 759 milligrams of Ce (NO3)3It is the AgNO of 0.79mol/L with 60mL 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 75 DEG C after the washing with alcohol that 100mL mass percent concentration is 87% Place 140 minutes in dry case, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A 7；
(9) by 779 milligrams of Ce (NO3)3It is the AgNO of 0.99mol/L with 70mL 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance A；
(11) by 4.66 grams of AgNO3Being added to volume with 850mL ether is in 1000mL conical flask, stirs under the conditions of 1000r/min Mix 3 minutes, after shaking up, be divided into 5 parts of equivalent, obtain mixed liquor M1, mixed liquor M2, mixed liquor M3, mixed liquor M4, mixed liquor M5；
(12) by 217 milligrams of AgNO3It is the Ce (NO of 0.85mol/L with 90mL molar concentration3)3Solution is added in mixed liquor M1, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N1；
(13) 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 washing with alcohol that 100mL mass percent concentration is 87% in 75 DEG C of drying Place 140 minutes in case, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance B 1；
(14) by 247 milligrams of AgNO3It is the Ce (NO of 0.75mol/L with 80mL molar concentration3)3Solution is added in mixed liquor M2, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N2；
(15) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance B 3；
(16) by 277 milligrams of AgNO3It is the Ce (NO of 0.65mol/L with 70mL molar concentration3)3Solution is added in mixed liquor M3, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N3；
(17) substance B 3 is added in mixed liquor N3, 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 4, substance B 4 is after the washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance B 5；
(18) by 307 milligrams of AgNO3It is the Ce (NO of 0.55mol/L with 60mL molar concentration3)3Solution is added in mixed liquor M4, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N4；
(19) substance B 5 is added in mixed liquor N4, 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 6, substance B 6 is after the washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain substance C；
(20) by 236 milligrams of AgNO3It is the Ce (NO of 0.56mol/L with 78mL molar concentration3)3Solution is added in mixed liquor M5, Stir 3 minutes under the conditions of 1000r/min, obtain mixed liquor N5；
(21) substance C is added in mixed liquor N5, 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 washing with alcohol that 100mL mass percent concentration is 87% in 75 DEG C of drying Place 140 minutes in case, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material E；
(22) by 6.99 grams of Pd (NO3)2Being added to volume with 850mL ethanol is in 1000mL conical flask, in 1000r/min condition Lower stirring 3 minutes, adds 5mL concentrated nitric acid, 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；
(23) AlCl for 0.88mol/L by 85mL molar concentration3Solution is added in mixed liquor P1, under the conditions of 1000r/min Stirring 3 minutes, obtains mixed liquor Q1；
(24) 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 75 DEG C after the washing with alcohol that 100mL mass percent concentration is 87% Place 140 minutes in dry case, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F2；
(25) Pd (NO for 0.74mol/L by 80mL molar concentration3)2Solution is added in mixed liquor P2, in 1000r/min bar Stir 3 minutes under part, obtain mixed liquor Q2；
(26) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F4；
(27) AlCl for 0.54mol/L by 65mL molar concentration3Solution is added in mixed liquor P3, under the conditions of 1000r/min Stirring 3 minutes, obtains mixed liquor Q3；
(28) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F6；
(29) Pd (NO for 0.54mol/L by 60mL molar concentration3)2Solution is added in mixed liquor P4, in 1000r/min bar Stir 3 minutes under part, obtain mixed liquor Q4；
(30) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F8；
(31) AlCl for 0.48mol/L by 45mL molar concentration3Solution and 40mL molar concentration are the Pd of 0.34mol/L (NO3)2Solution is added in mixed liquor P5, stirs 3 minutes, obtain mixed liquor Q5 under the conditions of 1000r/min；
(32) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material F；
(33) by 5.26g 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；
(34) ZnCl for 0.49mol/L by 40mL molar concentration2Solution and 60mL molar concentration are the CuCl of 0.77mol/L2Molten Liquid is added in mixed liquor R1, stirs 3 minutes, obtain mixed liquor S1 under the conditions of 1000r/min；
(35) 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 75 DEG C after the washing with alcohol that 100mL mass percent concentration is 87% Place 140 minutes in dry case, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material H1；
(36) ZnCl for 0.69mol/L by 50mL molar concentration2Solution and 50mL molar concentration are the CuCl of 0.57mol/L2Molten Liquid is added in mixed liquor R2, stirs 3 minutes, obtain mixed liquor S2 under the conditions of 1000r/min；
(37) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material H2；
(38) ZnCl for 0.89mol/L by 60mL molar concentration2Solution and 40mL molar concentration are the CuCl of 0.37mol/L2Molten Liquid is added in mixed liquor R3, stirs 3 minutes, obtain mixed liquor S3 under the conditions of 1000r/min；
(39) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material H；
(40) 3.18g sodium lauryl sulphate, 40mL normal hexane, 20 milliliters of n-butyl alcohol are added sequentially to volume and bore for 250mL In shape bottle, add 6.94g ammonium 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 Washing with alcohol, obtains material I；
(41) 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；
(42) ZnCl for 0.28mol/L by 30mL molar concentration2Solution and 70mL molar concentration are the CuCl of 0.91mol/L2Molten Liquid is added in mixed liquor T1, stirs 3 minutes, obtain mixed liquor U1 under the conditions of 1000r/min；
(43) 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 75 DEG C after the washing with alcohol that 100mL mass percent concentration is 87% Place 140 minutes in dry case, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K1；
(44) ZnCl for 0.38mol/L by 40mL molar concentration2Solution and 60mL molar concentration are the CuCl of 0.81mol/L2Molten Liquid is added in mixed liquor T2, stirs 3 minutes, obtain mixed liquor U2 under the conditions of 1000r/min；
(45) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K2；
(46) ZnCl for 0.48mol/L by 50mL molar concentration2Solution and 50mL molar concentration are the CuCl of 0.71mol/L2Molten Liquid is added in mixed liquor T3, stirs 3 minutes, obtain mixed liquor U3 under the conditions of 1000r/min；
(47) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K3；
(48) ZnCl for 0.58mol/L by 60mL molar concentration2Solution and 40mL molar concentration are the CuCl of 0.61mol/L2Molten Liquid is added in mixed liquor T4, stirs 3 minutes, obtain mixed liquor U4 under the conditions of 1000r/min；
(49) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K4；
(50) ZnCl for 0.68mol/L by 70mL molar concentration2Solution and 30mL molar concentration are the CuCl of 0.51mol/L2Molten Liquid is added in mixed liquor T5, stirs 3 minutes, obtain mixed liquor U5 under the conditions of 1000r/min；
(51) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material K；
(52) 9.44g polyvinyl alcohol and 900mL deionized water being added to volume is in 1000mL conical flask, in 1000r/min Under the conditions of stir 3 minutes, be divided into 3 parts of equivalent after shaking up, obtain mixed liquor V1, mixed liquor V2, mixed liquor V3；
(53) HAuCl for 0.82mol/L by 90mL molar concentration4Solution is added in mixed liquor V1, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor W1；
(54) 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 75 DEG C after the washing with alcohol that 100mL mass percent concentration is 87% Place 140 minutes in dry case, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material Z1；
(55) HAuCl for 0.62mol/L by 70mL molar concentration4Solution is added in mixed liquor V2, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor W2；
(56) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, obtain material Z2；
(57) HAuCl for 0.42mol/L by 50mL molar concentration4Solution is added in mixed liquor V3, in 1000r/min condition Lower stirring 3 minutes, obtains mixed liquor W3；
(58) 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 washing with alcohol that 100mL mass percent concentration is 87% at 75 DEG C Place 140 minutes in drying baker, be subsequently placed in Muffle furnace roasting 63 minutes under the conditions of 512 DEG C, the material obtaining is to be had Electro-catalysis is had to remove the modified carbon fiber granule electrode of benzoquinone function.
CN201611050532.1A 2016-11-21 2016-11-21 Modified carbon fiber particle electrode capable of removing benzoquinone by electro-catalysis and preparation method of modified carbon fiber particle electrode capable of removing benzoquinone by electro-catalysis Withdrawn CN106430445A (en)

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Citations (2)

* 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
CN106076338A (en) * 2016-07-15 2016-11-09 武汉钢铁股份有限公司 A kind of method preparing catalyst

Patent Citations (2)

* 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
CN106076338A (en) * 2016-07-15 2016-11-09 武汉钢铁股份有限公司 A kind of method preparing catalyst

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