CN103539227A - Preparation Technology of Ag-doped MnO2-CeO2 Active Alumina Particle Electrode Containing CuO Interlayer - Google Patents

Abstract

The invention discloses a preparation process of an Ag-doped MnO ₂ -CeO ₂ active alumina particle electrode containing a CuO intermediate layer. Add _AgNO3 to isopropanol to obtain solution A, add treated _Al2O3 to solution A, _filter to obtain particle B and microemulsion X, and obtain particle D after washing with ethanol; add particle D to X Particle F was obtained after medium filtration. Solutions B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , C, D, E, F were prepared using Ce(NO ₃ ) ₂ , CuCl ₂ , MnCl ₂ . Particle F is treated with solutions B ₁ , B ₂ , B ₃ , B ₄ , and B ₅ in sequence to obtain particle I. Particle I was added to solution C, filtered, washed with ethanol and dried to obtain Particle K. Particle K was added to solution D, filtered, washed with ethanol and dried to obtain particle M. M was added to solution E, filtered, washed with ethanol and dried to obtain particle O. Add particles O to solution F, filter, wash with ethanol, dry and bake at 580°C for 4 hours to obtain an Ag-doped MnO ₂ -CeO ₂ active alumina particle electrode containing a CuO interlayer.

Description

Preparation Technology of Ag-doped MnO2-CeO2 Active Alumina Particle Electrode Containing CuO Interlayer

technical field

The invention belongs to the technical field of chemically modified electrodes for treating wastewater by an electrocatalytic oxidation method, and in particular relates to a preparation process of an Ag-doped MnO ₂ -CeO ₂ active alumina particle electrode containing a CuO intermediate layer.

Background technique

Electrocatalytic oxidation technology degrades organic pollutants in wastewater by generating strong oxidizing active groups such as hydroxyl radicals. It has no secondary pollution, low cost, strong applicability, and high efficiency in treating high-concentration, biodegradable wastewater. Advanced features, in which three-dimensional electrocatalytic oxidation technology, by adding a catalytically active particle electrode between the anode and cathode of the two-dimensional electrode, the surface of the filled granular electrode is charged in a certain way, and the effective area of the two-dimensional electrode is improved. Small, poor mass transfer effect, low current efficiency and other defects, it is suitable for various concentrations of wastewater, even for wastewater with low pollutant concentration, it has a good treatment effect, and it is a kind of electrocatalytic oxidation water treatment that has been studied more at present. technology. The application of the three-dimensional electrode method to wastewater treatment is not only closely related to the performance of the main electrode, but also closely related to the performance of the particle electrode. Therefore, how to improve the catalytic performance of the particle electrode has become a research hotspot in recent years.

Commonly used particle electrode materials mainly include metal conductors, metal oxides, glass or plastic balls coated with metal layers, graphite particles, activated alumina particles, carbon fiber materials, and activated carbon particles. The large resistance and low conductivity of traditional electrodes make it low current efficiency, insufficient stability, short life, high cost of electrode materials in wastewater treatment, and the electrode preparation process is complicated, which limits the development of particle electrode materials. Therefore, the new The research on particle electrode materials still needs to be further strengthened. In recent years, the preparation of supported particle electrodes by impregnation-thermal decomposition has attracted more and more attention from scholars, but there are disadvantages such as poor reusability and low electrode efficiency, and there is still a lack of research on the preparation process of particle electrodes.

Contents of the invention

The object of the present invention is to provide a preparation process of an Ag-doped MnO ₂ -CeO ₂ active alumina particle electrode containing a CuO intermediate layer. The specific steps are as follows:

(1) Wash 300g of γ-Al ₂ O ₃ balls with a particle size of 3-5mm with 500ml of deionized water, repeat the washing 3 times, then soak in 200ml of absolute ethanol for 10h, and wash once with 500ml of deionized water Afterwards, drying at 80°C for 10 hours to obtain granular substance A;

(2) _Add 50ml of AgNO with a concentration of 0.5mol/L into 150ml of isopropanol to obtain solution A;

(3) Add the granular substance A obtained in step (1) to the solution A obtained in step (2), and shake it in a shaker for 3h, filter to obtain granular substance B and microemulsion X, and use 100mL of 95% mass concentration Wash the granular substance B with ethanol, repeat the washing twice, and then dry at 80°C for 10 hours to obtain granular substance C;

(4) The granular substance C obtained in step (3) is placed in a muffle furnace and roasted at 500° C. for 4 hours to obtain the granular substance D;

(5) Add the granular substance D obtained in step (4) to the microemulsion X obtained in step (3), and shake it in a shaker for 3h, filter and remove the liquid to obtain granular substance E, and use 100mL of ethanol with a mass concentration of 95% Washing the granular substance E, repeating the washing twice, then drying at 80°C for 10 hours, and then roasting in a muffle furnace at 500°C for 4 hours to obtain granular substance F;

(6) 10ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 100ml concentration is 0.5mol/L CuCl ₂ solution joins in 120ml isopropanol and 5ml concentrated hydrochloric acid, then adds 10ml concentration and is 0.5mol /L MnCl ₂ solution, shake well and divide into 5 equal parts to obtain solution B ₁ , solution B ₂ , solution B ₃ , solution B ₄ , and solution B ₅ ;

(7) Add the granular substance F obtained in step (5) to the solution B ₁ obtained in step (6), shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G1, and use 100mL of ethanol with a mass concentration of 95% washing the granular substance G1, repeating the washing twice, and then drying at 80° C. for 10 hours to obtain the granular substance H ₁ ;

(8) Add the granular substance H ₁ obtained in step (7) to the solution B ₂ obtained in step (6), shake it in a shaker for 3 hours, remove the liquid by filtration to obtain granular substance G2, and use 100 mL of washing the granular substance G2 with ethanol, repeating the washing twice, and then drying at 80°C for 10 hours to obtain the granular substance H ₂ ;

(9) Add the granular substance _H2 obtained in step (8) to the solution _B3 obtained in step (6), shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G3, and use 100mL of 95% mass concentration washing the granular substance G3 with ethanol, repeating the washing twice, and then drying at 80° C. for 10 hours to obtain the granular substance H ₃ ;

(10) Add the granular substance _H3 obtained in step (9) to the solution _B4 obtained in step (6), and shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G4, and use 100mL of washing the granular substance G4 with ethanol, repeating the washing twice, and then drying at 80°C for 10 hours to obtain the granular substance H ₄ ;

(11) Add the granular substance _H4 obtained in step (10) to the solution _B5 obtained in step (6), and shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G5, and use 100mL of Wash the granular substance G5 with ethanol, repeat the washing twice, and then dry at 80°C for 10 hours to obtain granular substance _H5 ; place _H5 in a muffle furnace and roast at 580°C for 4 hours to obtain granular substance I;

(12) 20ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 80ml concentration is 0.5mol/L CuCl ₂ solution joins in 120ml isopropanol and 5ml concentrated hydrochloric acid, then adds 20ml concentration is 0.5mol /L of MnCl _solution to obtain solution C;

(13) Add the granular substance I obtained in step (11) to the solution C obtained in step (12), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain granular substance J, wash with 100 mL of ethanol with a mass concentration of 95% For granular substance J, repeat washing twice, and then dry at 80°C for 10 hours to obtain granular substance K;

(14) 40ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 40ml concentration is 0.5mol/L CuCl ₂ solution is added in 120ml isopropanol and 5ml concentrated hydrochloric acid, then add 40ml concentration is 0.5mol /L of MnCl _solution to obtain solution D;

(15) Add the granular substance K obtained in step (13) to the solution D obtained in step (14), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain granular substance L, wash with 100 mL of ethanol with a mass concentration of 95% The granular substance L was repeatedly washed twice, and then dried at 80°C for 10 hours to obtain the granular substance M;

(16) 45ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 15ml concentration is 0.5mol/L CuCl ₂ solution joins in 120ml isopropanol and 5ml concentrated hydrochloric acid, then adds 60ml concentration and is 0.5mol /L of MnCl _solution to obtain solution E;

(17) Add the particulate matter M obtained in step (15) to the solution E obtained in step (16), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain particulate matter N, wash with 100 mL of ethanol with a mass concentration of 95% For granular substance N, repeat washing twice, and then dry at 80°C for 10 hours to obtain granular substance O;

(18) 15ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 5ml concentration is 0.5mol/L CuCl ₂ solution joins in 120ml isopropanol and 5ml concentrated hydrochloric acid, then adds 100ml concentration is 0.5mol /L of MnCl _solution to obtain solution F;

(19) Add the particulate substance O obtained in step (17) to the solution F obtained in step (18), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain particulate substance P, wash with 100 mL of ethanol with a mass concentration of 95% The granular substance P was repeatedly washed twice, and then dried at 80°C for 10 hours to obtain the granular substance Q, which was placed in a muffle furnace and roasted at 580°C for 4 hours, and the obtained granular substance was the CuO-containing interlayer. Loading Ag-doped MnO ₂ -CeO ₂ active alumina particle electrode.

The beneficial effect of the invention is that the prepared Ag-doped MnO ₂ -CeO ₂ activated alumina particle electrode containing the CuO intermediate layer has the characteristics of high current efficiency, strong stability, long electrode life and the like.

Detailed ways

The invention provides a preparation process of an Ag-doped MnO ₂ -CeO ₂ active alumina particle electrode containing a CuO intermediate layer, and an example is used to illustrate the implementation process.

Example 1.

Wash 300g of γ-Al ₂ O ₃ spheres with a particle size of 3-5mm with 500ml of deionized water, repeat the washing 3 times, then soak in 200ml of absolute ethanol for 10h, wash once with 500ml of deionized water, and then Dry at 80° C. for 10 h to obtain granular substance A.

Add 50ml of _AgNO3 with a concentration of 0.5mol/L into 150ml of isopropanol to obtain solution A. Add granular substance A to solution A, shake in a shaker for 3 h, filter to obtain granular substance B and microemulsion X, wash granular substance B with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then wash at 80 Dry at ℃ for 10 hours to obtain granular substance C; put granular substance C in a muffle furnace and roast at 500°C for 4 hours to obtain granular substance D; add granular substance D to microemulsion X, and Shake for 3 hours, remove the liquid by filtration to obtain particulate matter E, wash E with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, then dry at 80 °C for 10 h, and then place it in a muffle furnace for roasting at 500 °C 4h, the particulate matter F was obtained.

Add 10ml of Ce(NO ₃ ) solution with _a concentration of 0.5mol/L and _100ml of a CuCl solution with a concentration of 0.5mol/L into 120ml of isopropanol and 5ml of concentrated hydrochloric acid, and then add 10ml of a solution with a concentration of 0.5mol/L The MnCl ₂ solution was shaken and divided into 5 equal parts to obtain solution B ₁ , solution B ₂ , solution B ₃ , solution B ₄ , and solution B ₅ ;

Add granular substance F to solution B1, shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G1, wash granular substance G1 with 100 mL of ethanol with a mass concentration of 95%, repeat the washing 2 times, and then place it at 80°C Dry at 95°C for 10 hours to obtain granular substance _H1 ; add granular substance _H1 to solution _B2 , and shake in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G2, and wash the granular substance with 100 mL of ethanol with a mass concentration of 95% G2, repeat washing twice, and then dry at 80°C for 10 hours to obtain granular substance _H2 ; add granular substance _H2 to solution _B3 , shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G3, Wash the granular substance G3 with 100mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then dry it at 80°C for 10h to obtain the granular substance _H3 ; add the granular substance _H3 to the solution _B4 , and shake Shake in medium for 3 hours, remove the liquid by filtration to obtain granular substance G4, wash granular substance G4 with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then dry at 80°C for 10 hours to obtain granular substance _H4 ; ₄ was added to solution _B5 , and shaken in a shaker for 3 hours, filtered to remove the liquid to obtain granular substance G5, washed with 100mL of ethanol with a mass concentration of 95%, repeated washing twice, and then dried at 80°C After 10 hours, granular substance H ₅ was obtained; H ₅ was calcined in a muffle furnace at 580° C. for 4 hours to obtain granular substance I.

Add 20ml of Ce(NO ₃ ) solution with _a concentration of 0.5mol/L and _80ml of CuCl solution with a concentration of 0.5mol/L into 120ml of isopropanol and 5ml of concentrated hydrochloric acid, and then add 20ml of a solution with a concentration of 0.5mol/L MnCl ₂ solution to obtain solution C.

Add granular substance I to solution C, and shake it in a shaker for 3 hours; filter and remove the liquid to obtain granular substance J, wash granular substance J with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then store the granular substance at 80°C Under drying for 10 h, granular material K was obtained.

Add 40ml of Ce(NO ₃ ) solution with _a concentration of 0.5mol/L and _40ml of CuCl solution with a concentration of 0.5mol/L into 120ml of isopropanol and 5ml of concentrated hydrochloric acid, and then add 40ml of a concentration of 0.5mol/L with MnCl ₂ solution to obtain solution D.

Add granular substance K to solution D, and shake it in a shaker for 3 hours; filter and remove the liquid to obtain granular substance L, wash granular substance L with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then store it at 80°C Under drying for 10h, the granular material M was obtained.

Add 45ml of Ce(NO ₃ ) ₂ solution with a concentration of 0.5mol/L and 15ml of CuCl ₂ solution with a concentration of 0.5mol/L into 120ml of isopropanol and 5ml of concentrated hydrochloric acid, and then add 60ml of 0.5mol/L with a concentration of MnCl ₂ solution to obtain solution E.

Add the particulate matter M to the solution E, and shake it in a shaker for 3 hours; remove the liquid by filtration to obtain the particulate matter N, wash the granular matter N with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then store it at 80°C Under drying for 10h, granular material O was obtained.

Add 15ml of Ce(NO ₃ ) ₂ solution with a concentration of 0.5mol/L and 5ml of CuCl ₂ solution with a concentration of 0.5mol/L into 120ml of isopropanol and 5ml of concentrated hydrochloric acid, and then add 100ml of 0.5mol/L MnCl ₂ solution to obtain solution F.

Add the particulate matter O to the solution F and shake it in a shaker for 3 hours; remove the liquid by filtration to obtain the particulate matter P, wash the particulate matter P with 100 mL of ethanol with a mass concentration of 95%, repeat the washing twice, and then store it at 80°C Drying for 10 hours under the hood to obtain granular material Q, put Q in a muffle furnace and bake at 580°C for 4 hours, and the obtained granular material is the Ag-doped MnO ₂ -CeO ₂ activated alumina particle electrode containing CuO interlayer .

In the following, the Ag-doped MnO ₂ -CeO ₂ active alumina particle electrode containing a CuO intermediate layer prepared by the method of the present invention was used to conduct a degradation test on coal chemical industry wastewater in a three-dimensional electrode reactor to further illustrate the present invention.

The Ag-doped MnO ₂ -CeO ₂ activated alumina particle electrode containing the CuO intermediate layer prepared by the method of the present invention is packed in a three-dimensional electrode reactor, and a degradation test is carried out on coal chemical industry wastewater, and the results show that the electrode can be efficiently treated For COD in coking wastewater, when the influent COD is 512mg/L, the Ag-doped MnO ₂ -CeO ₂ activated alumina particles containing the CuO intermediate layer are used as the third pole, the pH is 4.5, the voltage is 12V, and the treatment time After 60 minutes, the COD in the effluent after treatment was reduced to 44mg/L, and the treatment efficiency reached 91.41%.

Claims (1)

1. a loading Ag-doped MnO ₂ -CeO ₂ preparation technology containing CuO interlayer active alumina particle electrode, it is characterized in that, the concrete steps of this technology are as follows: (1) Wash 300g of γ-Al ₂ O ₃ balls with a particle size of 3-5mm with 500ml of deionized water, repeat the washing 3 times, then soak in 200ml of absolute ethanol for 10h, and wash once with 500ml of deionized water Afterwards, drying at 80°C for 10 hours to obtain granular substance A; (2) _Add 50ml of AgNO with a concentration of 0.5mol/L into 150ml of isopropanol to obtain solution A; (3) Add the granular substance A obtained in step (1) to the solution A obtained in step (2), and shake it in a shaker for 3h, filter to obtain granular substance B and microemulsion X, and use 100mL of 95% mass concentration Wash the granular substance B with ethanol, repeat the washing twice, and then dry at 80°C for 10 hours to obtain granular substance C; (4) The granular substance C obtained in step (3) is placed in a muffle furnace and roasted at 500° C. for 4 hours to obtain the granular substance D; (5) Add the granular substance D obtained in step (4) to the microemulsion X obtained in step (3), and shake it in a shaker for 3h, filter and remove the liquid to obtain granular substance E, and use 100mL of ethanol with a mass concentration of 95% Washing the granular substance E, repeating the washing twice, then drying at 80°C for 10 hours, and then roasting in a muffle furnace at 500°C for 4 hours to obtain granular substance F; (6) 10ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 100ml concentration is 0.5mol/L CuCl ₂ solution joins in 120ml isopropanol and 5ml concentrated hydrochloric acid, then adds 10ml concentration and is 0.5mol /L MnCl ₂ solution, shake well and divide into 5 equal parts to obtain solution B ₁ , solution B ₂ , solution B ₃ , solution B ₄ , and solution B ₅ ; (7) Add the granular substance F obtained in step (5) to the solution B ₁ obtained in step (6), shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G1, and use 100mL of ethanol with a mass concentration of 95% washing the granular substance G1, repeating the washing twice, and then drying at 80°C for 10 hours to obtain the granular substance H1; (8) Add the granular substance H ₁ obtained in step (7) to the solution B ₂ obtained in step (6), shake it in a shaker for 3 hours, remove the liquid by filtration to obtain granular substance G2, and use 100 mL of washing the granular substance G2 with ethanol, repeating the washing twice, and then drying at 80°C for 10 hours to obtain the granular substance H ₂ ; (9) Add the granular substance _H2 obtained in step (8) to the solution B3 obtained in step (6), and shake it in a shaker for 3h, filter and remove the liquid to obtain granular substance G3, and use 100mL of ethanol with a mass concentration of 95% washing the granular substance G3, repeating the washing twice, and then drying at 80°C for 10 hours to obtain the granular substance H ₃ ; (10) Add the granular substance _H3 obtained in step (9) to the solution _B4 obtained in step (6), and shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G4, and use 100mL of washing the granular substance G4 with ethanol, repeating the washing twice, and then drying at 80°C for 10 hours to obtain the granular substance H ₄ ; (11) Add the granular substance _H4 obtained in step (10) to the solution _B5 obtained in step (6), and shake it in a shaker for 3 hours, filter and remove the liquid to obtain granular substance G5, and use 100mL of Wash the granular substance G5 with ethanol, repeat the washing twice, and then dry at 80°C for 10 hours to obtain granular substance H5; place H5 in a muffle furnace and roast at 580°C for 4 hours to obtain granular substance I; (12) 20ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 80ml concentration is 0.5mol/L CuCl ₂ solution joins in 120ml isopropanol and 5ml concentrated hydrochloric acid, then adds 20ml concentration is 0.5mol /L of MnCl _solution to obtain solution C; (13) Add the granular substance I obtained in step (11) to the solution C obtained in step (12), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain granular substance J, wash with 100 mL of ethanol with a mass concentration of 95% For granular substance J, repeat washing twice, and then dry at 80°C for 10 hours to obtain granular substance K; (14) 40ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 40ml concentration is 0.5mol/L CuCl ₂ solution is added in 120ml isopropanol and 5ml concentrated hydrochloric acid, then add 40ml concentration is 0.5mol /L of MnCl _solution to obtain solution D; (15) Add the granular substance K obtained in step (13) to the solution D obtained in step (14), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain granular substance L, wash with 100 mL of ethanol with a mass concentration of 95% The granular substance L was repeatedly washed twice, and then dried at 80°C for 10 hours to obtain the granular substance M; (16) 45ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 15ml concentration is 0.5mol/L CuCl ₂ solution joins in 120ml isopropanol and 5ml concentrated hydrochloric acid, then adds 60ml concentration and is 0.5mol /L of MnCl _solution to obtain solution E; (17) Add the particulate matter M obtained in step (15) to the solution E obtained in step (16), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain particulate matter N, wash with 100 mL of ethanol with a mass concentration of 95% For granular substance N, repeat washing twice, and then dry at 80°C for 10 hours to obtain granular substance O; (18) 15ml concentration is 0.5mol/L Ce(NO ₃ ) ₂ solution and 5ml concentration is 0.5mol/L CuCl ₂ solution joins in 120ml isopropanol and 5ml concentrated hydrochloric acid, then adds 100ml concentration is 0.5mol /L of MnCl _solution to obtain solution F; (19) Add the particulate substance O obtained in step (17) to the solution F obtained in step (18), and shake it in a shaker for 3 hours; filter and remove the liquid to obtain particulate substance P, wash with 100 mL of ethanol with a mass concentration of 95% The granular substance P was repeatedly washed twice, and then dried at 80°C for 10 hours to obtain the granular substance Q, which was placed in a muffle furnace and roasted at 580°C for 4 hours, and the obtained granular substance was the CuO-containing interlayer. Loading Ag-doped MnO ₂ -CeO ₂ activated alumina particles as electrodes.