CN110980893B - Electrocatalytic oxidation anode material for preferentially removing nonyl phenol and treatment method - Google Patents

Electrocatalytic oxidation anode material for preferentially removing nonyl phenol and treatment method Download PDF

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CN110980893B
CN110980893B CN201911071197.7A CN201911071197A CN110980893B CN 110980893 B CN110980893 B CN 110980893B CN 201911071197 A CN201911071197 A CN 201911071197A CN 110980893 B CN110980893 B CN 110980893B
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phenol
tin dioxide
electrocatalytic oxidation
nonyl phenol
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CN110980893A (en
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赵国华
牛宝玲
蔡郡倬
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Tongji University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols

Abstract

The invention relates to an electrocatalytic oxidation anode material for preferentially removing nonyl phenol and a treatment method, wherein the electrocatalytic oxidation anode material is prepared by the following method: preparing 4- (9-amino nonyl) -phenol template molecules, modifying the template molecules on the surface of silicon dioxide through condensation reaction to form a kernel, growing high-index crystal face tin dioxide crystals on the surface of the kernel to obtain a molecular imprinting material precursor, and removing and fixing the kernel on a substrate electrode to obtain the imprinted high-index crystal face tin dioxide electrode. And taking the imprinted high-index crystal face tin dioxide electrode as a working anode for preferential electrocatalytic oxidation removal of nonyl phenol in a complex pollution system. Compared with the prior art, the electrode has excellent electrocatalytic activity and strong specificity recognition capability, can realize preferential electrocatalytic oxidation removal of nonyl phenol in a complex system, and the lowest concentration of nonyl phenol in treated effluent can reach 10 mu g L‑1The following.

Description

Electrocatalytic oxidation anode material for preferentially removing nonyl phenol and treatment method
Technical Field
The invention belongs to the field of water pollution control engineering, and particularly relates to an electrocatalytic oxidation anode material for preferentially removing nonyl phenol and a treatment method.
Background
Nonylphenol, denoted NP, is an alkylphenol contaminant. It has high toxicity, can simulate estrogen, influence normal reproduction and development of organism, and is classified as endocrine disruptor. And the NP molecule contains long alkyl chain, further increases the liposolubility, oxidation resistance and toxicity of the NP molecule, and has increasingly serious environmental problems along with the continuous accumulation of NP in water. However, because NP is difficult to be mineralized by microorganisms as a first carbon source due to competition of low concentration and high concentration of low-toxicity organic matters in the current municipal sewage treatment process, the preferential removal of NP in a water body is particularly necessary. Some conventional methods for removing NP, such as adsorption, do not fundamentally mineralize organic contaminants to harmless standards; the period of the microbial degradation of the pollutants is long, and many organic pollutants belong to biological non-degradable organic matters, so that the efficiency of the microbial degradation of the organic pollutants is low; the added large amount of chemical reagent has negative influence on microorganisms and environment; the electrochemical method has high efficiency of oxidizing organic pollutants, mild operation conditions and high automation degree. However, the conventional electrochemical oxidation method also has some disadvantages, such as indiscriminate mineralization of the contaminants, inability to achieve the goal of preferential removal of the target contaminants, and the like.
The reaction kinetics are related to mass transfer, which is closely related to the local concentration of the reaction mass. As one of the emerging specific recognition technologies, the molecular imprinting (denoted as MI) technology offers the possibility of enrichment of target contaminants, thereby favoring the kinetics of the target reaction. Conventional MI prepared from imprinted polymers has many limitations in electrocatalytic oxidation, such as autooxidation. In addition, some inorganic blots synthesized by sol-gel methods are not conducive to the oxidation of contaminants due to poor electron transfer.
Many studies have shown that tin dioxide (expressed as SnO)2) If the SnO is preferentially exposed to2The catalytic activity can be further enhanced by high energy crystal planes of the crystal, such as the high index crystal plane (denoted as HIF). The specific surface energy of the high-index crystal plane (221) is high (2.28J m)-2) And is favorable for the electron transfer process. The non-specific adsorption sites of the single crystal structure are few. However, it has no specific recognition ability, and cannot achieve the purpose of removing contaminants preferentially in a complex system.
The tannery wastewater is a typical complex pollution system, generally contains pollutants such as NP, tannin, lignin, protein, amino acid and the like, and has the characteristics of complex components, high chemical oxygen demand and difficult oxidation, so that the treatment of the tannery wastewater becomes a very important research subject in the field of sewage treatment at present.
Disclosure of Invention
The invention aims to solve the problems and provide an electrocatalytic oxidation anode material for preferentially removing nonyl phenol and a treatment method, wherein the anode material is imprinted with high-index crystal face tin dioxide (expressed as MI-SnO)2,HIF) The electrode has excellent electrocatalytic activity, and the method can realize high efficiency in a single systemIn addition to NP, preferential electrocatalytic oxidation removal of NP in complex systems is also achievable.
The purpose of the invention is realized by the following technical scheme:
an electrocatalytic oxidation anode material for preferentially removing nonyl phenol is an imprinted high-index crystal face tin dioxide electrode, and the imprinted high-index crystal face tin dioxide electrode is prepared by the following method: preparing 4- (9-amino nonyl) -phenol template molecules, modifying the template molecules on the surface of silicon dioxide through condensation reaction to form a kernel, growing high-index crystal face tin dioxide crystals on the surface of the kernel to obtain a molecular imprinting material precursor, and removing and fixing the kernel on a substrate electrode to obtain the MI-SnO2,HIFAnd an electrode.
The MI-SnO2,HIFThe electrode is prepared by the following method:
(a) adding palladium (II) acetate, triphenylphosphine and triethanolamine into a reactor in an inert gas atmosphere to obtain a mixed solution, adding 4-bromophenol and 9-bromo-1-nonene into the mixed solution, reacting to obtain a reaction mixture, adding palladium carbon, 4- (9-bromoacyl) -phenol and phthalimide into the reaction mixture in a hydrogen atmosphere to react, and purifying to obtain a 4- (9-aminononyl) -phenol template molecule, wherein the palladium (II) acetate is prepared from the following raw materials: triphenylphosphine: triethanolamine: 4-bromophenol: 9-bromo-1-nonene: palladium on carbon: 4- (9-bromoacyl) -phenol: the addition ratio of the phthalimide is (2-6): (3-12): (1-3):(1-3): (0.5-4):(0.2-2): (1-4): (1-4);
(b) weighing aminated silica, dissolving and dispersing in ethanol, adding succinic anhydride, stirring for 0.5-6h at room temperature, centrifuging and washing to obtain carboxylated silica, mixing the obtained carboxylated silica with the 4- (9-aminononyl) -phenol template molecule obtained in the step (a), and carrying out condensation reaction to obtain the inner core, wherein the aminated silica: the mass addition ratio of the succinic anhydride is (0.2-0.8): (0.3-1.0), the concentration of the 4- (9-aminononyl) -phenol template molecule is 10-150 mu mol L-1；
(c) Weighing tin tetrachloride, concentrated hydrochloric acid and ethanol, mixing, stirring for 1-6h at room temperature to obtain a tin dioxide sol, immersing the core obtained in the step (b) into the tin dioxide sol, growing a tin dioxide crystal on the surface of the core, calcining for 0.5-2h at the temperature of 100-: concentrated hydrochloric acid: ethanol: the adding proportion of the inner core is (2-8) g: (2-10) mL: (20-60) mL, the molecular imprinting material precursor which is not completely grown: tin tetrachloride: polyvinylpyrrolidone: concentrated hydrochloric acid: ethanol: the addition ratio of water is (0.5-3.0) g: (1-4) g: (2-5) g: (1-6) mL: (20-40) mL: (20-40) mL;
(d) etching the fully-grown molecular imprinting material precursor obtained in the step (c) by adopting hydrofluoric acid for 4-15h to remove silicon dioxide, then taking conductive glass as a substrate electrode, uniformly mixing the molecular imprinting material precursor with water, ethanol and an adhesive to obtain a coating solution, fixing the coating solution on the conductive glass, calcining at 200-500 ℃ for 0.5-2h to remove 4- (9-aminononyl) -phenol template molecules, and thus obtaining the MI-SnO2,HIFAn electrode, wherein the fully grown molecular imprinting material precursor: the addition ratio of hydrofluoric acid is (0.2-4.0) g: (10-30) mL, wherein the mass fraction of the hydrofluoric acid is 2-20 wt%, and the etching of the silicon dioxide molecularly imprinted material precursor is as follows: water: ethanol: the addition ratio of the adhesive is (2-30) mg: (0.5-5) mL: (0.2-1) mL: (0.5-2) mL.
A treatment method of an electrocatalytic oxidation anode material for preferentially removing nonyl phenol comprises the following steps: taking the imprinted high-index crystal face tin dioxide electrode as a working anode and a platinum sheet, stainless steel or a carbon rod as a counter electrode to form a two-electrode system for preferential electrocatalytic oxidation removal of nonyl phenol in a complex pollution system, wherein the range of the applied cell voltage of the two-electrode system is 2-20V;
or the imprinted high-index crystal face tin dioxide electrode is used as a working anode, a platinum sheet, stainless steel or a carbon rod is used as a counter electrode, saturated calomel is used as a reference electrode to form a three-electrode system for preferential electrocatalytic oxidation removal of nonyl phenol in a complex pollution system, and the bias range applied by the three-electrode system is 0.5-3V (relative to a standard hydrogen electrode);
the complex contamination system comprises nonylphenol and coexisting contaminants comprising one or more of alkylphenols, aromatic compounds, lignin, proteins, or pesticides, the nonylphenol concentration being in the range of 20-200 μ g L-1The concentration range of the coexisting pollutants is 0.4-380mg L-1。
The electrocatalytic oxidation treatment method can also be used for the efficient removal of NP in a single system, which is a mixed solution containing 0.05-8 mu mol L-1NP and 0.1-2mol L-1Na2SO4An electrolyte.
For MI-SnO in the invention2,HIFThe electrolyte composition, the process conditions (voltage, medicine adding amount and the like), the calcination process, the hydrothermal reaction process and the like in the preparation process of the electrode are specifically limited: the MI-SnO with good crystal form can be obtained through hydrothermal reaction treatment under the conditions of the voltage and the time2,HIFNano octahedron; for example, when the amount of hydrofluoric acid is too much during etching, waste is caused, and certain damage is caused to glass instruments; too little hydrofluoric acid will result in incomplete etching of the silicon dioxide and thus reduced interference rejection. In addition, the raw materials or processing techniques used are all conventional commercial products or conventional processing techniques in the art.
Aiming at selectively removing NP pollutant, the invention takes electrocatalytic oxidation and molecular imprinting technology as main technical means, namely, a high-index crystal face tin dioxide electrocatalyst with excellent electrocatalytic activity is combined with a molecular imprinting identification means with specific identification capability, and the preferential electrocatalytic oxidation removal of NP in a complex pollution system is successfully realized.
Compared with the prior art, the invention has the following advantages:
(1) the invention modifies the target moleculeThe 4- (9-amino nonyl) -phenol template molecule and the carboxylated silicon dioxide are fixed on the silicon dioxide microsphere through common condensation reaction, the template molecule is prevented from falling off in the process of growing the electrode material, and the MI-SnO2,HIFThe enrichment effect on NP is realized, and the NP comes from the construction of molecular imprinting of the electrode, so that the electrode can perform shape-selective recognition on pollutants in a complex system, the NP can be preferentially adsorbed on the surface of the electrode, and other interferents are not easily adsorbed on the surface of the electrode, thereby realizing the purpose of preferentially removing the NP in the complex system.
(2) The invention prepares MI-SnO by utilizing a simple hydrothermal method2,HIFAnode, MI-SnO2,HIFThe high-index crystal face {221} is exposed on the surface of the electrode, the exposed high-index crystal face has excellent electrocatalytic performance, the electrocatalytic activity of the catalyst is improved, and the preparation of the electrode adopts an inorganic imprinting method, so that the defect that organic imprinting is easy to oxidize is overcome, and the rapid transfer of electrons is facilitated.
(3) Utilization of MI-SnO in the present invention2,HIFThe electrode studies the effects of strong and weak anti-interference capability (large interference factor and poor anti-interference capability) of the electrode in the presence of interferents with different multiples and preferentially removing NP in an actual system. When the concentration ratio of NP to interferent is 1: at 1000 deg.c, the interference factor values of interference protein, amino acid, tannin and lignin (expressed as the current difference between complex system and NP: the current difference between NP and electrolyte solution) are below 0.10, proving its strong anti-interference ability. And in the presence of 10000 times of interferents, the interference factors are all below 0.151, which shows that the anti-interference capability is extremely strong.
(4) The method is used for preferential electrocatalytic oxidation removal of NP in a complex pollution system, and the lowest concentration of NP in treated effluent can reach 10 mu g L-1Hereinafter, i.e., MI-SnO2,HIFThe electrode still has good preferential removal capacity for NP in a complex pollution system.
(5) MI-SnO used in the present invention2,HIFThe anode is a solid electrode, the preparation method is simple, the manufacturing cost is low, the electrocatalytic activity is high, the chemical stability is good, the cyclic utilization can be realized, and the secondary pollution is not easy to causeThe method has potential application value in the environmental fields of preferentially removing low-concentration and high-toxicity pollutants and the like in a complex system.
Drawings
FIG. 1 is MI-SnO prepared in example 12,HIFScanning electron micrographs of the electrodes;
FIG. 2 is a graph of degradation of NP in a single system at 1.2V bias over time in example 2;
FIG. 3 is a graph of degradation of NP in a single system at 2.1V bias over time in example 4;
FIG. 4 is MI-SnO in example 52,HIFAn anti-interference capability test chart of the electrode pair NP;
FIG. 5 is a graph showing the degradation of NP over time in an actual system under a bias of 1.8V in example 8.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
An electrocatalytic oxidation anode material for preferentially removing nonyl phenol is an imprinted high-index crystal face tin dioxide electrode and is prepared by the following method: preparing 4- (9-amino nonyl) -phenol template molecules, modifying the template molecules on the surface of silicon dioxide through condensation reaction to form a kernel, growing high-index crystal face tin dioxide crystals on the surface of the kernel for multiple times to obtain a molecular imprinting material precursor, removing the kernel, and fixing the molecular imprinting material precursor on a substrate electrode to obtain MI-SnO2,HIFAnd an electrode.
MI-SnO2,HIFThe electrode is prepared by the following method:
(a) adding palladium (II) acetate, triphenylphosphine and triethanolamine into a reactor in an inert gas atmosphere to obtain a mixed solution, adding 4-bromophenol and 9-bromo-1-nonene into the mixed solution, reacting to obtain a reaction mixture, adding palladium carbon, 4- (9-bromoacyl) -phenol and phthalimide into the reaction mixture in a hydrogen atmosphere to react, and purifying to obtain a 4- (9-aminononyl) -phenol template molecule, wherein the palladium (II) acetate is prepared from the following raw materials: triphenylphosphine: triethanolamine: 4-bromophenol: 9-bromo-1-nonene: palladium on carbon: 4- (9-bromoacyl) -phenol: the addition ratio of the phthalimide is (2-6): (3-12): (1-3):(1-3): (0.5-4):(0.2-2): (1-4): (1-4);
(b) weighing aminated silica, dissolving and dispersing in ethanol, adding succinic anhydride, stirring for 0.5-6h at room temperature, centrifuging and washing to obtain carboxylated silica, mixing the obtained carboxylated silica with the 4- (9-aminononyl) -phenol template molecule obtained in the step (a), and carrying out condensation reaction to obtain the inner core, wherein the aminated silica: the mass addition ratio of the succinic anhydride is (0.2-0.8): (0.3-1.0), the concentration of the 4- (9-aminononyl) -phenol template molecule is 10-150 mu mol L-1；
(c) Weighing tin tetrachloride, concentrated hydrochloric acid and ethanol, mixing, stirring for 1-6h at room temperature to obtain a tin dioxide sol, immersing the core obtained in the step (b) into the tin dioxide sol, growing a tin dioxide crystal on the surface of the core, calcining for 0.5-2h at the temperature of 100-: concentrated hydrochloric acid: ethanol: the adding proportion of the inner core is (2-8) g: (2-10) mL: (20-60) mL, the molecular imprinting material precursor which is not completely grown: tin tetrachloride: polyvinylpyrrolidone: concentrated hydrochloric acid: ethanol: the addition ratio of water is (0.5-3.0) g: (1-4) g: (2-5) g: (1-6) mL: (20-40) mL: (20-40) mL;
(d) etching the fully grown molecular imprinting material precursor obtained in the step (c) by adopting hydrofluoric acid for 4-15h to remove silicon dioxide, then taking conductive glass as a substrate electrode, uniformly mixing the molecular imprinting material precursor with water, ethanol and an adhesive to obtain a coating solution, fixing the coating solution on the conductive glass, and calcining for 0.5-2h at the temperature of 200-: the addition ratio of hydrofluoric acid is (0.2-4.0) g: (10-30) mL, wherein the mass fraction of the hydrofluoric acid is 2-20 wt%, and the etching of the silicon dioxide molecularly imprinted material precursor is as follows: water: ethanol: the addition ratio of the adhesive is (2-30) mg: (0.5-5) mL: (0.2-1) mL: (0.5-2) mL. The finally obtained electrode material exhibits a nano-octahedral structure, as shown in fig. 1.
Example 2
A treatment method of an electrocatalytic oxidation anode material for preferentially removing nonyl phenol comprises the following steps: the NP solution to be degraded (concentration 4.5. mu. mol L)-1NP solution of (2), containing 0.1mol L-1Na2SO4Solution) was placed in a light-transmitting circular degradation cell with a single quartz surface, and the MI-SnO prepared in example 1 was taken2，HIFThe electrode is used as a working anode (the effective area of the electrode is 4.5 cm)2) The platinum sheet is used as a counter electrode, the saturated calomel electrode is used as a reference electrode to form a three-electrode system, 1.2V bias voltage is applied to the three-electrode system, and the volume of degradation liquid is 100 mL. The temperature of the reaction system was maintained at 25 ℃ by means of a super constant temperature water bath. The concentration at this time was defined as the initial concentration C of NP0. The sampling interval was 30min, and the samples were filtered through a 0.22 μm aqueous needle filter. The time-dependent trend of the concentration of NP in the solution during the electrocatalysis was determined by HPLC, as shown in FIG. 2, and the ordinate is the ratio of the present concentration of NP in the single system to the initial concentration, as shown in FIG. 2. The results show that the NP removal was 82.2% when the applied bias was 1.2V.
Example 3
A treatment method of an electrocatalytic oxidation anode material for preferentially removing nonyl phenol comprises the following steps: the NP solution to be degraded (concentration 8. mu. mol L)-1NP solution of (2), containing 0.8mol L-1Na2SO4Solution) was placed in a light-transmitting circular degradation cell with a single quartz surface, and the MI-SnO prepared in example 1 was taken2，HIFThe electrode is used as a working anode (the effective area of the electrode is 6 cm)2) And stainless steel is used as a counter electrode to form a two-electrode system, the tank voltage of the two-electrode system is 5V, and the volume of the degradation liquid is 100 mL. Making use of a super constant-temperature water tankThe temperature of the system should be maintained at 25 ℃. The concentration at this time was defined as the initial concentration C of NP0. The sampling interval was 30min, and the samples were filtered through a 0.22 μm aqueous needle filter. The time-dependent change trend of the concentration of NP in the solution during the electrocatalysis process was determined by high performance liquid chromatography. The results show that the NP removal was 77.4% at a cell voltage of 5V.
Example 4
A treatment method of an electrocatalytic oxidation anode material for preferentially removing nonyl phenol comprises the following steps: the NP solution to be degraded (concentration 5. mu. mol L)-1NP solution of (2), containing 0.3mol L-1Na2SO4Solution) was placed in a light-transmitting circular degradation cell with a single quartz surface, and the MI-SnO prepared in example 1 was taken2，HIFThe electrode is used as a working anode (the effective area of the electrode is 4.5 cm)2) The carbon rod is used as a counter electrode, the saturated calomel electrode is used as a reference electrode to form a three-electrode system, 2.1V bias voltage is applied to the three-electrode system, and the volume of degradation liquid is 100 mL. The temperature of the reaction system was maintained at 25 ℃ by means of a super constant temperature water bath. The concentration at this time was defined as the initial concentration C of NP0. The sampling interval was 30min, and the samples were filtered through a 0.22 μm aqueous needle filter. The time-dependent trend of the concentration of NP in the solution during the electrocatalysis was determined by HPLC, as shown in FIG. 3. The results showed that the NP removal was 96.8% when the applied bias was 2.1V.
Example 5
A treatment method of an electrocatalytic oxidation anode material for preferentially removing nonyl phenol comprises the following steps: MI-SnO prepared in example 12，HIFIs a working anode (the effective area of the electrode is 5 cm)2) The saturated calomel electrode is used as a reference electrode, the platinum sheet is used as a counter electrode to form a three-electrode system, and the three-electrode system contains 0.1mol L of mercury-1Na of (2)2SO4For the electrolyte, a bias of 1.8V was applied, and the current of the two-component solution to which the NP solution and the interfering substance at 1000-fold concentration were added was measured by the i-t curve method. The selected interfering substances are respectively protein, amino acid, lignin and tannin. The results show that when the concentration of interferents is 1000 times that of NP, it is dryThe interference factors are respectively 6.31%, 6.78%, 9.51% and 9.02%. Therefore, the molecular imprinting can specifically identify NP molecules, and the prepared MI-SnO2，HIFThe electrode showed higher selectivity in electrocatalytic oxidation of NPs in complex systems, as shown in figure 4.
Example 6
A treatment method of an electrocatalytic oxidation anode material for preferentially removing nonyl phenol comprises the following steps: taking a water sample of tannery wastewater, wherein the water sample of the tannery wastewater mainly comprises NP (120.4 mu g L)-1) Tannin (280mg L)-1) Lignin (110mg L)-1) Protein (78mg L)-1) And filtering by filter paper to remove particles and suspended matters contained in the water sample, and filtering for multiple times by using a filter membrane with the diameter of 0.22 mu m to further purify the water sample. Purifying the water sample to prepare MI-SnO2，HIFIs a working anode (the effective area of the electrode is 5 cm)2) The saturated calomel electrode is a reference electrode, the stainless steel is a counter electrode, a three-electrode system is formed, and a bias voltage of 1.2V is applied to the three-electrode system to perform electrocatalytic oxidation on the solution. The sampling interval was 30min, and the samples were filtered through a 0.22 μm aqueous needle filter. The trend of the NP concentration in the solution over time during the electrocatalysis was determined by high performance liquid chromatography. The results showed that the concentration of NP in the effluent was 18.9. mu. g L when the applied bias was 1.2V-1。
Example 7
A treatment method of an electrocatalytic oxidation anode material for preferentially removing nonyl phenol comprises the following steps: taking a water sample of tannery wastewater, wherein the water sample of the tannery wastewater mainly comprises NP (87.3 mu g L)-1) Tannin (147mg L)-1) Lignin (202mg L)-1) Protein (96mg L)-1) And filtering by filter paper to remove particles and suspended matters contained in the water sample, and filtering for multiple times by using a filter membrane with the diameter of 0.22 mu m to further purify the water sample. Purifying the water sample to prepare MI-SnO2，HIFIs a working anode (the effective area of the electrode is 4.5 cm)2) The saturated calomel electrode is used as a reference electrode, the carbon rod is used as a counter electrode to form a three-electrode system, and a bias voltage of 1.5V is applied to the three-electrode system to carry out solution treatmentElectrocatalytic oxidation. The sampling interval was 30min, and the samples were filtered through a 0.22 μm aqueous needle filter. The time-dependent change trend of the concentration of NP in the solution during the electrocatalysis process was determined by high performance liquid chromatography. The results showed that the concentration of NP in the effluent was 10.4. mu. g L when the applied bias was 1.5V-1。
Example 8
A treatment method of an electrocatalytic oxidation anode material for preferentially removing nonyl phenol comprises the following steps: taking a water sample of tannery wastewater, wherein the water sample of the tannery wastewater mainly comprises NP (67.2 mu g L)-1) Tannin (188mg L)-1) Lignin (191mg L)-1) Protein (82mg L)-1) And filtering by filter paper to remove particles and suspended matters contained in the water sample, and filtering for multiple times by using a filter membrane with the diameter of 0.22 mu m to further purify the water sample. Purifying the water sample to prepare MI-SnO2，HIFIs a working anode (the effective area of the electrode is 6 cm)2) The saturated calomel electrode is a reference electrode, the carbon rod is a counter electrode to form a three-electrode system, and a bias voltage of 1.8V is applied to the three-electrode system to perform electrocatalytic oxidation on the solution. The sampling interval was 30min, and the samples were filtered through a 0.22 μm aqueous needle filter. The time-dependent trend of the NP concentration in the solution during the electrocatalysis was determined by HPLC, as shown in FIG. 5. The results showed that the concentration of NP in the effluent was 8.6. mu. g L when the applied bias was 1.8V-1。
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (3)

1. The electrocatalytic oxidation anode material for preferentially removing nonyl phenol is characterized by being an imprinted high-index crystal face tin dioxide electrode, and the imprinted high-index crystal face tin dioxide electrode is prepared by the following method: preparing 4- (9-amino nonyl) -phenol template molecules, modifying the 4- (9-amino nonyl) -phenol template molecules on the surface of silicon dioxide to form a kernel, growing high-index crystal face tin dioxide crystals on the surface of the kernel to obtain a molecular imprinting material precursor, and removing the kernel from the molecular imprinting material precursor and fixing the molecular imprinting material precursor on a substrate electrode to obtain the imprinted high-index crystal face tin dioxide electrode.
2. The electrocatalytic oxidation anode material for preferentially removing nonyl phenol of claim 1, wherein the imprinted high-index crystal-face tin dioxide electrode is prepared by the following method:
(a) adding palladium (II) acetate, triphenylphosphine and triethanolamine into a reactor in an inert gas atmosphere to obtain a mixed solution, adding 4-bromophenol and 9-bromo-1-nonene into the mixed solution, reacting to obtain a reaction mixture, adding palladium carbon, 4- (9-bromoacyl) -phenol and phthalimide into the reaction mixture in a hydrogen atmosphere to react, and purifying to obtain a 4- (9-aminononyl) -phenol template molecule, wherein the palladium (II) acetate is prepared from the following raw materials: triphenylphosphine: triethanolamine: 4-bromophenol: 9-bromo-1-nonene: palladium on carbon: 4- (9-bromoacyl) -phenol: the addition ratio of the phthalimide is (2-6): (3-12): (1-3):(1-3): (0.5-4):(0.2-2): (1-4): (1-4);
(b) weighing aminated silica, dissolving and dispersing in ethanol, adding succinic anhydride, stirring for 0.5-6h at room temperature, centrifuging and washing to obtain carboxylated silica, mixing the obtained carboxylated silica with the 4- (9-aminononyl) -phenol template molecule obtained in the step (a), and carrying out condensation reaction to obtain the inner core, wherein the aminated silica: the mass addition ratio of the succinic anhydride is (0.2-0.8): (0.3-1.0), the concentration of the 4- (9-aminononyl) -phenol template molecule is 10-150 mu mol L-1；
(c) Weighing tin tetrachloride, concentrated hydrochloric acid and ethanol, mixing, stirring for 1-6h at room temperature to obtain a tin dioxide sol, immersing the core obtained in the step (b) into the tin dioxide sol, growing a tin dioxide crystal on the surface of the core, calcining for 0.5-2h at the temperature of 100-: concentrated hydrochloric acid: ethanol: the adding proportion of the inner core is (2-8) g: (2-10) mL: (20-60) mL, the molecular imprinting material precursor which is not completely grown: tin tetrachloride: polyvinylpyrrolidone: concentrated hydrochloric acid: ethanol: the addition ratio of water is (0.5-3.0) g: (1-4) g: (2-5) g: (1-6) mL: (20-40) mL: (20-40) mL;
(d) etching the fully grown molecular imprinting material precursor obtained in the step (c) by adopting hydrofluoric acid for 4-15h to remove silicon dioxide, then taking conductive glass as a substrate electrode, uniformly mixing the molecular imprinting material precursor with water, ethanol and an adhesive to obtain a coating solution, fixing the coating solution on the conductive glass, and calcining for 0.5-2h at the temperature of 200-: the addition ratio of hydrofluoric acid is (0.2-4.0) g: (10-30) mL, wherein the mass fraction of the hydrofluoric acid is 2-20 wt%, and the etching of the silicon dioxide molecularly imprinted material precursor is as follows: water: ethanol: the addition ratio of the adhesive is (2-30) mg: (0.5-5) mL: (0.2-1) mL: (0.5-2) mL.
3. A treatment process for the electrocatalytic oxidation anode material with preferential removal of nonyl phenol, as claimed in any one of claims 1 or 2, which is in particular: taking the imprinted high-index crystal face tin dioxide electrode as a working anode and a platinum sheet, stainless steel or a carbon rod as a counter electrode to form a two-electrode system for preferential electrocatalytic oxidation removal of nonyl phenol in a complex pollution system, wherein the range of the applied cell voltage of the two-electrode system is 2-20V; or the imprinted high-index crystal face tin dioxide electrode is used as a working anode, a platinum sheet, stainless steel or a carbon rod is used as a counter electrode, saturated calomel is used as a reference electrode to form a three-electrode system for preferential electrocatalytic oxidation removal of nonyl phenol in a complex pollution system, and the bias voltage applied by the three-electrode system is in the range of 0.5-3V;
the complex contamination system comprises nonylphenol and coexisting contaminants comprising one or more of alkylphenols, aromatic compounds, lignin, proteins, or pesticides, the nonylphenol concentration being in the range of 20-200 μ g L-1The concentration range of the coexisting pollutants is 0.4-380mg L-1。
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