CN110963551A - Preparation method of graphene inorganic polymer composite electrode - Google Patents
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Abstract
The invention discloses a preparation method of a graphene inorganic polymer composite electrode, which comprises the steps of mixing and stirring fly ash, graphene, sodium silicate, potassium hydroxide and deionized water to form slurry, uniformly dip-coating the slurry on the surface of a pretreated steel substrate by adopting a dipping and pulling method, and preparing the graphene inorganic polymer composite electrode through a maintenance reaction process; wherein: the amount of the graphene, the sodium silicate, the potassium hydroxide and the deionized water is 0% -1%, 37%, 11.2% and 50% of the mass of the fly ash respectively, the graphene inorganic polymer composite electrode is used as an anode for electrocatalysis of organic dye wastewater degradation, and the electrocatalysis degradation rate of the indigo dye can reach 100%. Not only realizes the harmless utilization of the industrial solid waste fly ash, but also provides a new way for the treatment of dye wastewater.
Description
Technical Field
The invention belongs to the technical field of solid waste resource utilization, relates to preparation of an electrocatalysis electrode material, and particularly relates to a preparation method of a graphene inorganic polymer composite electrode and application of the graphene inorganic polymer composite electrode in dye wastewater degradation.
Background
The electrocatalytic oxidation treatment technology can be applied to the treatment of organic wastewater, the electrode material is the main carrier of the electrocatalytic oxidation technology, and the degradation of organic matters mainly occurs at the anode, so that the preparation of the anode material with good comprehensive performance is the key point of the electrocatalytic oxidation technology[1]。
The anode materials used by the prior electrocatalytic oxidation technology are mainly concentrated on carbon electrodes, metal oxide coating electrodes and diamond film electrodes[2]。
The carbon electrode material mainly comprises porous graphite, carbon fiber, carbon felt, carbon aerogel and the like. Kong et al[3]The graphite is used as the anode to degrade textile wastewater, and the degradation rate is good. However, the good adsorption of the carbon electrode can lead the reaction product to be diffused unfavorably, accumulated on the surface of the electrode and cover the active site, thus leading to the pollution of the electrode[4]。
The metal electrode usually uses simple substance metal as electrode material, and commonly used are noble metals such as Au, Ag, Pt, Pd, Ir, and alloys thereof. Jebraj et al[5]The oxidation effect of hydroxylamine on pH 7 by electrocatalytic oxidation of hydroxylamine compounds using Au electrodes was close to the theoretical simulation results. In addition, the noble metal coating also has higher catalytic activity, and common electrodes comprise Ti/Pt and Ti/Pd, Limeier and the like[6]The Pd/Ti electrode is prepared by electrodeposition in PdCl2 solution by taking Ti as a substrate electrode and is used for treating halogen-containing aromatic compounds. However, the precious metal is in short supply and expensive, which is not suitable for large-scale application in industry.
The metal oxide coating electrode is prepared by taking a conductive material such as titanium, platinum, iron and the like as a substrate and coating one or more metal oxides on the substrate, wherein the titanium-based coating electrode is the main form of the metal oxide electrode[7]. The electrode-supported metal oxide is mainly RuO2、IrO2、SnO2And PbO2For instance, Hanweiqing[8]The Chinese patent application (publication number: CN103395865A) discloses a titanium-based tubular ruthenium dioxide coatingA layer electrode and a preparation method thereof adopt a titanium filter tube as a substrate, a thin layer of uniformly dispersed and compact ruthenium dioxide is formed on the surface of the titanium filter tube by a thermal oxidation method, and an oxide film coating after thermal oxidation has a firm structure and good electrocatalysis performance. Lizheng[9]The Chinese patent application (publication number: CN104651895A) discloses a preparation method of a titanium-based lead dioxide electrode, which adopts a treated titanium plate as a substrate, and controls the electrodeposition current density to be 20-35mA/cm2To obtain PbO2The current efficiency of the electrodeposited coating remains unchanged during the catalytic organic degradation process. In addition, on the basis of a single metal oxide anode, the catalytic activity of the electrode can be improved by doping metal elements, doping other metal oxides, doping nano-particles or introducing an intermediate layer, such as Liunan and the like[10]Preparation of La-doped Ti/PbO by electrodeposition2The La electrode is used for treating nitrobenzene wastewater, and the removal rate is close to 100%. Shouazu et al[11]The Chinese application patent (publication number: CN109824123A) discloses a SnO2The preparation method of the-NiO oxide coating electrode comprises the steps of dissolving stannous chloride and nickel chloride in absolute ethyl alcohol, then mixing the obtained stannous chloride and nickel chloride solution on a titanium matrix according to a certain proportion for coating, and obtaining SnO by adopting a thermal decomposition method2The NiO oxide coating electrode has good application prospect in electrocatalytic degradation.
Xu et al[12]Hydroxyl multi-walled carbon nanotubes (MWCNTOH) are doped into PbO2In the preparation of anode Ti/SnO2-Sb/PbO2MWCNTOH improves the effective reaction area of the electrode. The Yuhong principle[13]Preparation of Ti/Mn/SnO by using Mn as intermediate layer2Electrode, ratio Ti/SnO2The service life of the electrode is obviously prolonged. The public security[14]The Chinese patent application (publication number: CN110040820A) discloses a titanium-based tin antimony oxide electrode modified by a titanium dioxide mesh structure, which comprises a titanium substrate, an intermediate layer and a catalyst layer, wherein the intermediate layer of the titanium dioxide mesh structure is formed on the surface of the titanium substrate after hydrothermal synthesis reaction, and then tin antimony oxide is formed on the intermediate layer of the mesh structure by a pulse electrodeposition method and a temperature programmed annealing activation methodThe catalyst layer and the prepared electrode have strong stability and electrocatalysis performance.
The doping elements in the diamond film electrode mainly comprise nitrogen, phosphorus, boron and the like, wherein the boron-doped diamond film (BDD) electrode is mainly used in the field of electrocatalysis. Bai et al15]The Si-based BDD electrode is successfully prepared by a microwave plasma chemical vapor deposition method, and the degradation effect of the BDD electrode on m-dinitrobenzene is researched. Xufeng, etc[16]The Chinese patent application (publication number: CN102242374A) discloses a preparation method of a titanium-based boron-doped diamond coating electrode, which is realized by sputtering a transition layer on a base material and then depositing a boron-doped diamond coating by a CVD method on the basis, wherein the base material is titanium, the transition layer is niobium or tantalum through magnetron sputtering, the boron-doped concentration used in the CVD process is 6000-10000ppm, and the prepared BBD electrode has high repeatability.
In conclusion, the applicant consults a large amount of domestic and foreign literature data and patents through a system, and does not find any relevant report about the preparation method of any graphene-fly ash-based inorganic polymer composite electrode and the application of the graphene-fly ash-based inorganic polymer composite electrode in the electrocatalysis of organic dye degradation.
The following are the main references relevant to the present invention:
[1] wenqing, preparation of electrocatalytic electrode materials and application to the study of wastewater treatment, Harbin engineering university, (2008).
[2] Research and application of catalytic electrode for treating wastewater, 32(12) (2006) 4-9.
[3]Kong Y，Wang Z L，Wang Y，et al，Degradation of Methyl Orange inArtificial Wastewater Through Electro chemical Oxidation Using ExfoliatedGraphite Electrode，New Carbon Materials，26(6)(2011)459-464。
[4] Shengyi, li guang, huhuikang, research progress of electrochemical oxidation anode material for organic wastewater, industrial water treatment, 26(3), (2006) 4-7.
[5]Jebaraj A J J,Kumsa D,Scherson D A，Oxidation of Hydroxylamine onGold Electrodes in Aqueous Electrolytes:Rota-ting Ring-disk and In SituInfrared Reflection Absorption Spectroscopy Studies，Journal of PhysicalChemistry C，116(12)(2012)6932-6942。
[6] Limeier, Machilus, Mashon, electrochemical dechlorination of m-chlorobenzoic acid on Pd/Ti electrodes, journal of chemistry, 69(23) (2011) 2762-2766.
[7] Quality of Zhayue, Wangde Jun, Zhao dynasty, research progress of electrode materials for electrocatalytic oxidation treatment of refractory wastewater, material guide, 33(07) (2019) 1125-1132.
[8] Korea Weiqing, Zhang Yonghao, Zhongyizhong, Sun Yunlong, Wang Lianjun, Sun Xiuyun, Li Jiansheng, Shenjinyou, titanium-based tubular ruthenium dioxide coating membrane electrode and a preparation method thereof, Chinese patent application (CN 103395865A).
[9] Li Zheng, a preparation method of titanium-based lead dioxide electrode, China patent application (CN 104651895A).
[10]Liu nan, Liu\28156, coke Xin, Ti/PbO2La electrode for treating nitrobenzene wastewater, advanced chemical journal, 32(6) (2011) 1266-.
[11]Showy group, yanbin, chenxin, mahongqiong, guo, von colloke, chenopodium hair, a SnO2NiO oxide coated electrodes, method of preparation and use thereof, Chinese patent application (CN 109824123A).
[12]Xu Z，Liu H，Niu J，Journal of Hazardous Materials，327(2017)144。
[13] The performance of the Cuiyihong, Fengyije, Liujunfeng, and the performance of the titanium-based stannic oxide electrocatalytic electrode containing the Mn intermediate layer, the materials research report, 19(1), (2005) 47-53.
[14] Schwann, schli and wann, titanium-based tin antimony oxide electrode modified by titanium dioxide net structure and a preparation method thereof, Chinese patent application (CN 110040820A).
[15]Bai H，He P，Pan J，Journal of Colloid and Interface Science，497(2017)422。
[16] Xufeng, Zuodun, Zheng Lin, xu Chun, Lu Wen Zhuang, Zhou Chun, Zhanxuhui, Ti-based boron-doped diamond coated electrode preparation method, Chinese patent application (CN 102242374A).
Disclosure of Invention
The invention aims to provide a preparation method of a graphene inorganic polymer composite electrode, so as to reveal the rule of influence of the doping amount of graphene in the graphene inorganic polymer composite electrode on the degradation rate of electro-catalytic organic dye wastewater.
In order to realize the task, the invention adopts the following technical solution:
a preparation method of a graphene inorganic polymer composite electrode is characterized in that fly ash, graphene, sodium silicate, potassium hydroxide and deionized water are mixed and stirred into slurry, the slurry is uniformly dip-coated on the surface of a pretreated steel sheet substrate by adopting a dipping and pulling method, and the graphene inorganic polymer composite electrode is prepared through a maintenance reaction process; wherein the amount of the graphene, the sodium silicate, the potassium hydroxide and the deionized water is 0-1%, 37%, 11.2% and 50% of the mass of the fly ash respectively.
The method specifically comprises the following steps:
(1) weighing the fly ash and the graphene according to the formula ratio, and fully mixing;
(2) weighing sodium silicate according to the formula amount;
(3) weighing solid potassium hydroxide according to the formula amount;
(4) weighing deionized water according to the formula ratio, and dissolving sodium silicate and solid potassium hydroxide into the deionized water;
(5) pouring the sodium silicate and the potassium hydroxide aqueous solution in the step (4) into the mixture of the fly ash and the graphene, and stirring to form uniformly mixed slurry;
(6) and dip-coating the slurry on the surface of the pretreated steel sheet substrate by adopting a pulling method, and placing the sample in a drying oven for curing reaction for 8 hours at the temperature of 80 ℃ under a sealed condition to obtain the graphene inorganic polymer composite electrode.
The research of the applicant finds that the graphene inorganic polymer composite electrode obtained by the method can be applied to indigo dye wastewater degradation.
The specific application comprises the following steps:
(1) the initial concentration C is prepared by a volumetric flaskoIn an aqueous solution of the indigo dye in an amount of 0.1 mol/ml is addedL sodium sulfate solution, using UV-visible spectrophotometer at lambdamaxInitial absorbance A was measured at 610nm0；
(2) Connecting the prepared graphene inorganic polymer composite electrode with the positive electrode of a direct-current stabilized power supply to be used as the anode of an electrocatalysis device, and connecting the pretreated steel sheet electrode with the negative electrode of the direct-current stabilized power supply to be used as the cathode of the electrocatalysis device;
(3) placing the anode and the cathode in parallel in a container with a certain volume and concentration of CoApplying a certain bias voltage to the graphene inorganic polymer composite electrode in the indigo dye aqueous solution, simulating sunlight irradiation for a certain time by using a xenon lamp at room temperature, placing the reaction solution in a cuvette, and using an ultraviolet-visible spectrophotometer at lambdamaxAbsorbance A at time t of 610nmtDye concentration of Ct；
(4) After the absorbance is measured, all the reaction liquid is put into the reactor again;
(5) repeating the step (3) and the step (4) until the absorbance of the indigo dye aqueous solution does not change with the change of time, and calculating the degradation rate of the indigo dye by adopting the following formula:
the preparation method of the graphene inorganic polymer composite electrode is characterized by comprising the following steps: the graphene inorganic polymer composite electrode which is not reported in the literature is prepared by adopting industrial wastes. The conductivity of the graphene inorganic polymer composite electrode is adjusted by controlling the doping amount of the graphene, so that the electro-catalysis controllability is achieved. Meanwhile, the harmless recycling of the solid waste fly ash is realized.
Drawings
FIG. 1 is a flow chart of a process for preparing a graphene inorganic polymer composite electrode and electrically catalyzing and degrading organic dye wastewater.
Fig. 2 is a photograph of a graphene inorganic polymer composite electrode.
FIG. 3 is a graph of the degradation rate of the graphene inorganic polymer composite electrode electrocatalytic degradation of indigo dye with different amounts of doped graphene along with time (the concentration of the indigo dye is 25mg/L, the volume is 50mL, and the bias voltage is 1V).
FIG. 4 is a graph of the degradation rate of the graphene inorganic polymer composite electrode electrocatalytic degradation of indigo dye with different amounts of doped graphene along with time (the concentration of the indigo dye is 15mg/L, the volume is 50mL, and the bias voltage is 0.5V).
The present invention will be described in further detail with reference to the following drawings and examples.
Detailed Description
It should be noted that the following examples are only for better illustrating the present invention, and the present invention is not limited to these examples.
The embodiment provides a preparation method of a graphene inorganic polymer composite electrode, which comprises the steps of selecting fly ash, graphene, sodium silicate, solid potassium hydroxide and deionized water as raw materials, mixing and stirring the raw materials to form slurry, uniformly dip-coating the slurry on the surface of a pretreated steel sheet substrate by adopting a dipping and pulling method, and carrying out a maintenance reaction process to obtain the graphene inorganic polymer composite electrode; wherein the doping amount of the graphene is 0-1% of the mass of the fly ash, the doping amount of the sodium silicate is 37% of the mass of the fly ash, the doping amount of the potassium hydroxide is 11.2% of the mass of the fly ash, and the using amount of the water is 50% of the mass of the fly ash.
The preparation method comprises the following steps:
(1) weighing the fly ash and the graphene according to the formula ratio, fully mixing and then placing into a beaker;
(2) weighing sodium silicate according to the formula amount;
(3) weighing solid potassium hydroxide according to the formula amount;
(4) weighing deionized water according to the formula ratio, and dissolving sodium silicate and solid potassium hydroxide into the deionized water;
(5) pouring the sodium silicate and the potassium hydroxide aqueous solution in the step (4) into the beaker filled with the mixture of the fly ash and the graphene in the step (1), and stirring to form uniformly mixed slurry;
(6) and dip-coating the slurry on the surface of the pretreated steel sheet substrate by adopting a pulling method, and placing the sample in a drying oven for curing reaction for 8 hours at the temperature of 80 ℃ under a sealed condition to obtain the graphene inorganic polymer composite electrode.
The raw material sources are as follows:
(1) graphene (Craphene, abbreviated as GR) was purchased from Nanjing Xiancheng nanomaterial science and technology Co., Ltd.
(2) Fly ash from an internal combustion power plant, wherein the main oxide composition (mass percent) of the fly ash is as follows: SiO 22(36.33％)，Al2O3(44.47％)，CaO(1.82％)，Na2O(0.088％)，MgO(0.264％)，K2O(0.402％)，Fe2O3(1.94％)，TiO2(1.92％)，P2O5(0.2％)，SO3(0.429％)。
(3) Sodium silicate, purchased from Yanghua chemical reagents, Inc., Tianjin, analytically pure reagent.
(4) Solid potassium hydroxide was purchased from a chemical reagent factory of Syngnathus, Denmark, and analyzed to obtain pure reagents.
(5) Deionized water, self-made in laboratories.
(6) The steel sheet substrate is a 304 type stainless steel sheet with the thickness of 15mm (length) multiplied by 15mm (width) multiplied by 0.2mm (thickness).
The pretreatment process of the 304 type stainless steel sheet comprises the steps of polishing the surface of the steel sheet by using sand paper, then placing the steel sheet in a sodium hydroxide solution with the mass fraction of 40%, carrying out water bath reaction for 1h at 80 ℃ under magnetic stirring, washing with deionized water after taking out, then placing the steel sheet in an oxalic acid solution with the mass fraction of 10%, carrying out water bath reaction for 30min at 95 ℃ under magnetic stirring, washing with deionized water after taking out, drying, and placing in absolute ethyl alcohol for storage and later use.
The following are specific examples given by the inventors.
Example 1:
accurately weighing 100g of fly ash, taking the weighed mass as a metering basis (100%), wherein the doping amount of sodium silicate is 37% of the mass of the fly ash, the doping amount of potassium hydroxide is 11.2% of the mass of the fly ash, and the dosage of deionized water is 50% of the mass of the fly ash.
Weighing sodium silicate, solid potassium hydroxide and deionized water, dissolving the sodium silicate and the solid potassium hydroxide in the deionized water, adding the aqueous solution of the sodium silicate and the potassium hydroxide into the fly ash, uniformly stirring, and carrying out chemical reaction to form uniformly mixed slurry; dipping and coating the slurry on the surface of a pretreated 304 type stainless steel sheet with the thickness of 15mm (length) × 15mm (width) × 0.2mm (thickness) by adopting a dipping and pulling method (the treatment process is shown in figure 1), wherein the thickness of the coating is about 100 micrometers, a sample is placed in a constant temperature box under the sealing condition and is cured for 8 hours at the temperature of 80 ℃, then the sample is taken out, the graphene inorganic polymer composite electrode which is not doped with graphene is obtained and is marked as 0GR, and a real photograph of the prepared graphene inorganic polymer composite electrode is shown in figure 2 a.
Example 2:
accurately weighing 100g of fly ash, taking the weighed amount as a metering basis (100%), taking the doping amount of graphene as 0.01% of the mass of the fly ash, uniformly mixing the materials in a vibration mill, and performing co-grinding, wherein the doping amount of sodium silicate is 37% of the mass of the fly ash, the doping amount of potassium hydroxide is 11.2% of the mass of the fly ash, and the using amount of deionized water is 50% of the mass of the fly ash. Weighing sodium silicate, solid potassium hydroxide and deionized water, dissolving the sodium silicate and the solid potassium hydroxide in the deionized water, adding an aqueous solution of the sodium silicate and the potassium hydroxide into a co-ground material of fly ash and graphene, uniformly stirring, and carrying out a chemical reaction to form uniformly mixed slurry; the slurry was dip-coated onto the surface of a pretreated 304 type stainless steel sheet (length: 15 mm: width: 0.2 mm) (see fig. 1) by dip-coating method, the thickness of the coating was about 100 μm, the sample was placed in a thermostat at 80 ℃ for 8 hours under a sealed condition, and a graphene inorganic polymer composite electrode with a doping amount of 0.01% was obtained and recorded as 0.01GR, and the photograph of the prepared graphene inorganic polymer composite electrode was shown in fig. 2 b.
In the following examples, applicants give examples of applications of graphene inorganic polymer composite electrodes in organic dye degradation.
In the following examples, the electrochemical performance (cyclic voltammetry, linear sweep voltammetry, impedance) of the graphene inorganic polymer composite electrode with different amounts of doped graphene is tested at an electrochemical workstation, which indicates that the graphene inorganic polymer composite electrode can be applied to electrocatalytic degradation of dyes.
Example 3:
the graphene inorganic polymer composite electrode (0GR) obtained in example 1 was connected to the positive electrode of a dc stabilized voltage power supply, and used as the anode of an electrocatalytic device; connecting a steel sheet electrode with the same size as the anode with the negative electrode of a direct current stabilized voltage power supply to be used as the cathode of the electro-catalysis device; putting the anode and the cathode in parallel into 50mL of 25mg/L indigo dye solution (containing 0.1mol/L of sodium sulfate electrolyte) with the electrode spacing of 2 cm; the DC stabilized voltage supply provides 1V bias voltage for the electrode, and a xenon lamp is used for simulating sunlight to irradiate the anode at a distance of 15 cm; centrifuging every 10min, transferring supernatant in centrifuge tube into cuvette, and measuring maximum absorption wavelength (lambda) of indigo dye with ultraviolet-visible spectrophotometermax610nm), the indigo dye degradation rate was calculated using the following formula (1):
the degradation rate of the indigo dye is shown in table 1 and fig. 3, and the highest degradation rate at 100min was 98%.
Table 1: degradation rate of 0GR graphene inorganic polymer composite electrode on indigo dye wastewater
| Time (min) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 | 100 | 110 |
| Degradation Rate (%) | 0 | 69 | 79 | 82 | 86 | 89 | 91 | 94 | 96 | 97 | 98 | 98 |
Example 4:
the graphene inorganic polymer composite electrode (0.01GR) obtained in example 2 was connected to the positive electrode of a dc stabilized voltage power supply, and used as the anode of an electrocatalysis device; connecting a steel sheet electrode with the same size as the anode with the negative electrode of a direct current stabilized voltage power supply to be used as the cathode of the electro-catalysis device; putting the anode and the cathode in parallel into 50mL of 25mg/L indigo dye solution (containing 0.1mol/L of sodium sulfate electrolyte) with the electrode spacing of 2 cm; the DC regulated power supply provides 1V bias voltage for the electrode, and the xenon lamp simulates sunlight to irradiate the sunPolar, distance 15 cm; centrifuging every 10min, transferring supernatant in centrifuge tube into cuvette, and measuring maximum absorption wavelength (lambda) of indigo dye with ultraviolet-visible spectrophotometermax610nm), the degradation rate of the indigo dye was calculated using formula (1) in example 3, as shown in table 2 and fig. 3, and the highest degradation rate at 100min was 100%.
Table 2: degradation rate of 0.01GR graphene inorganic polymer composite electrode on indigo dye wastewater
| Time (min) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 | 90 | 100 | 110 |
| Degradation Rate (%) | 0 | 70 | 81 | 88 | 92 | 94 | 96 | 97 | 98 | 99 | 100 | 100 |
Example 5:
the graphene inorganic polymer composite electrode (0GR) in example 1 was connected to the positive electrode of a dc stabilized voltage power supply, and used as the anode of an electrocatalytic device; connecting a steel sheet electrode with the same size as the anode with the negative electrode of a direct current stabilized voltage power supply to be used as the cathode of the electro-catalysis device; putting the anode and the cathode in parallel into 50mL of 15mg/L indigo dye solution (containing 0.1mol/L sodium sulfate electrolyte) with the electrode spacing of 2 cm; the DC stabilized voltage supply provides 0.5V bias voltage for the electrode, and a xenon lamp is used for simulating sunlight to irradiate the anode at a distance of 15 cm; centrifuging every 10min, transferring supernatant in centrifuge tube into cuvette, and measuring maximum absorption wavelength (lambda) of indigo dye with ultraviolet-visible spectrophotometermax610nm), the degradation rate of the indigo dye was calculated using formula (1) in example 3, and the degradation rate of the indigo dye is shown in table 3 and fig. 4. The highest degradation rate at 80min was 100%.
Table 3: degradation rate of 0GR graphene inorganic polymer composite electrode on indigo dye wastewater
| Time (min) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 | 80 |
| Degradation Rate (%) | 0 | 47 | 66 | 80 | 87 | 93 | 97 | 99 | 100 |
Example 6:
the graphene inorganic polymer composite electrode (0.01GR) in example 2 was connected to the positive electrode of a dc regulated power supply, and used as the anode of an electrocatalytic device; connecting a steel sheet electrode with the same size as the anode with the cathode of a DC stabilized power supplyThen, as the cathode of the electrocatalytic device; putting the anode and the cathode in parallel into 50mL of 15mg/L indigo dye solution (containing 0.1mol/L sodium sulfate electrolyte) with the electrode spacing of 2 cm; the DC stabilized voltage supply provides 0.5V bias voltage for the electrode, and a xenon lamp is used for simulating sunlight to irradiate the anode at a distance of 15 cm; centrifuging every 10min, transferring supernatant in centrifuge tube into cuvette, and measuring maximum absorption wavelength (lambda) of indigo dye with ultraviolet-visible spectrophotometermax610nm), the degradation rate of the indigo dye was calculated using formula (1) in example 3, as shown in table 4 and fig. 4, and the highest degradation rate at 50min was 100%.
Table 4: degradation rate of 0.01GR graphene inorganic polymer composite electrode on indigo dye wastewater
| Time (min) | 0 | 10 | 20 | 30 | 40 | 50 | 60 | 70 |
| Degradation Rate (%) | 0 | 59 | 80 | 92 | 97 | 100 | 100 | 100 |
As can be seen from fig. 3 and 4, under the same condition, the inorganic polymer composite electrode doped with graphene has a higher degradation rate for dyes, and thus, by adjusting the doping amount of graphene, different graphene inorganic polymer composite electrodes can be prepared and used as efficient catalysts for degrading indigo organic dyes.
Comparative experimental examples are given below:
comparative experimental example 1:
accurately weighing 100g of fly ash, taking the weighed amount as a metering basis (100%), wherein the doping amount of graphene is 1% of the mass of the fly ash, the doping amount of sodium silicate is 37% of the mass of the fly ash, the doping amount of potassium hydroxide is 11.2% of the mass of the fly ash, and the dosage of deionized water is 50% of the mass of the fly ash. Weighing sodium silicate, solid potassium hydroxide and deionized water, dissolving the sodium silicate and the solid potassium hydroxide in the deionized water, adding graphene into an aqueous solution of the sodium silicate and the potassium hydroxide, and ultrasonically dispersing for 2 hours, wherein the graphene is not uniformly dispersed, and the graphene inorganic polymer composite electrode cannot be prepared.
Comparative experiment example 2:
accurately weighing 100g of fly ash, taking the weighed amount as a metering basis (100%), taking the doping amount of graphene as 0.1% of the mass of the fly ash, uniformly mixing the materials in a vibration mill, and performing co-grinding, wherein the doping amount of sodium silicate is 37% of the mass of the fly ash, the doping amount of potassium hydroxide is 11.2% of the mass of the fly ash, and the using amount of water is 50% of the mass of the fly ash. Weighing sodium silicate, solid potassium hydroxide and deionized water, dissolving the sodium silicate and the solid potassium hydroxide in the deionized water, adding an aqueous solution of the sodium silicate and the potassium hydroxide into a co-ground material of fly ash and graphene, uniformly stirring, and carrying out a chemical reaction to form uniformly mixed slurry; the slurry is coated on the surface of a pretreated 304 type stainless steel sheet (the treatment process is shown in figure 1) with the thickness of 15mm (length) multiplied by 15mm (width) multiplied by 0.2mm (thickness) by dipping and pulling method, the thickness of the coating is about 100 mu m, a sample is placed in a sealing bag and is placed in a drying box to be maintained for 16h at the temperature of 80 ℃, and cracks appear on the surface of the prepared graphene inorganic polymer composite electrode.
Comparative experiment example 3:
connecting the graphene inorganic polymer composite electrode prepared in comparative experiment example 2 with the positive electrode of a direct-current stabilized power supply to serve as the anode of an electro-catalytic device; connecting a steel sheet electrode with the same size as the anode with the negative electrode of a direct current stabilized voltage power supply to be used as the cathode of the electro-catalysis device; putting the anode and the cathode in parallel into 50mL of 25mg/L indigo dye solution (containing 0.1mol/L of sodium sulfate electrolyte) with the electrode spacing of 2 cm; the DC stabilized voltage supply provides 1V bias voltage for the electrode, and a xenon lamp is used for simulating sunlight to irradiate the anode at a distance of 15 cm; centrifuging every 10min, transferring supernatant in centrifuge tube into cuvette, and measuring maximum absorption wavelength (lambda) of indigo dye with ultraviolet-visible spectrophotometermax610nm), the indigo dye degradation rate was calculated still using the formula (1) in example 3.
However, in the experimental process, it is found that the graphene inorganic polymer composite electrode prepared in comparative experiment example 2 has bubbles on the surface in the degradation process of the indigo organic dye, and the coating falls off in a large area, so that the degradation experiment of the indigo organic dye is forced to be interrupted.
The experiment proves that the graphene inorganic polymer composite electrode prepared in comparative experiment example 2 is difficult to be selected as a catalyst for degrading the indigo organic dye.
Claims (7)
1. A preparation method of a graphene inorganic polymer composite electrode is characterized in that fly ash, graphene, sodium silicate, potassium hydroxide and deionized water are mixed and stirred into slurry, the slurry is uniformly dip-coated on the surface of a pretreated steel sheet substrate by adopting a dipping and pulling method, and the graphene inorganic polymer composite electrode is prepared through a maintenance reaction process; wherein the amount of the graphene, the sodium silicate, the potassium hydroxide and the deionized water is 0-1%, 37%, 11.2% and 50% of the mass of the fly ash respectively.
2. The method according to claim 1, comprising in particular the steps of:
(1) weighing the fly ash and the graphene according to the formula ratio, and fully mixing;
(2) weighing sodium silicate according to the formula amount;
(3) weighing solid potassium hydroxide according to the formula amount;
(4) weighing deionized water according to the formula ratio, and dissolving sodium silicate and solid potassium hydroxide into the deionized water;
(5) pouring the sodium silicate and the potassium hydroxide aqueous solution in the step (4) into the mixture of the fly ash and the graphene, and stirring to form uniformly mixed slurry;
(6) and dip-coating the slurry on the surface of the pretreated steel sheet substrate by adopting a pulling method, and placing the pretreated steel sheet substrate in a drying oven for curing reaction for 8 hours at the temperature of 80 ℃ under a sealed condition to obtain the graphene inorganic polymer composite electrode material.
3. The method according to claim 1, wherein the stainless steel sheet is pretreated by polishing the surface of the stainless steel sheet with sand paper, then placing the steel sheet in a sodium hydroxide solution with a mass fraction of 40%, performing a water bath reaction at 80 ℃ for 1h under magnetic stirring, taking out and washing with deionized water, then placing the steel sheet in an oxalic acid solution with a mass fraction of 10%, performing a water bath reaction at 95 ℃ for 30min under magnetic stirring, taking out and washing with deionized water and drying, and placing in absolute ethyl alcohol for storage.
4. The method of claim 1, wherein the fly ash comprises the following major oxides in percent by mass: SiO 22：36.33％，Al2O3：44.47％，CaO：1.82％，Na2O：0.088％，MgO：0.264％，K2O：0.402％，Fe2O3：1.94％，TiO2：1.92％，P2O5：0.2％，SO3：0.429％。
5. A graphene inorganic polymer composite electrode prepared by the method according to any one of claims 1 to 4.
6. The graphene inorganic polymer composite electrode according to any one of claims 1 to 5 for indigo organic dye degradation applications.
7. The use according to claim 6, comprising in particular the following steps:
(1) the initial concentration C is prepared by a volumetric flaskoAdding 0.1mol/L sodium sulfate solution into the indigo dye aqueous solution, and using an ultraviolet-visible spectrophotometer at lambdamaxInitial absorbance A was measured at 610nm0；
(2) Connecting the prepared graphene inorganic polymer composite electrode with the positive electrode of a direct-current stabilized power supply to be used as the anode of an electrocatalysis device, and connecting the pretreated steel sheet electrode with the negative electrode of the direct-current stabilized power supply to be used as the cathode of the electrocatalysis device;
(3) placing the anode and the cathode in parallel in a container with a certain volume and concentration of CoApplying a certain bias voltage to the graphene inorganic polymer composite electrode material in the indigo dye aqueous solution, simulating sunlight irradiation for a certain time by using a xenon lamp at room temperature, placing the reaction solution in a cuvette, and using an ultraviolet-visible spectrophotometer at lambdamaxAbsorbance A at time t of 610nmtDye concentration of Ct；
(4) After the absorbance is measured, all the reaction liquid is put into the reactor again;
(5) repeating the step (3) and the step (4) until the absorbance of the indigo dye aqueous solution does not change with the change of time, and calculating the degradation rate of the indigo dye by adopting the following formula:
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