CN114873708A - Method for electrocatalytic reduction of N-nitrosodimethylamine - Google Patents
Method for electrocatalytic reduction of N-nitrosodimethylamine Download PDFInfo
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- CN114873708A CN114873708A CN202210647082.3A CN202210647082A CN114873708A CN 114873708 A CN114873708 A CN 114873708A CN 202210647082 A CN202210647082 A CN 202210647082A CN 114873708 A CN114873708 A CN 114873708A
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- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 title claims abstract description 128
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- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 2
- WBNQDOYYEUMPFS-UHFFFAOYSA-N N-nitrosodiethylamine Chemical compound CCN(CC)N=O WBNQDOYYEUMPFS-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
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- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
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Images
Classifications
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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
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a method for treating N-nitrosodimethylamine by electrocatalytic reduction, which comprises the following steps: s1, synthesizing a supported metal catalyst, S2, preparing a composite electrode, S3, placing the composite electrode obtained from S2 as a working electrode in a cathode chamber, placing an electrode platinum wire in an anode chamber, separating the cathode chamber and the anode chamber by a Nafion-117 proton exchange membrane, and separating Na containing N-nitrosodimethylamine and Na not containing N-nitrosodimethylamine 2 SO 4 The solution is respectively placed in a cathode chamber and an anode chamber, and electrocatalytic reduction is carried out under direct current voltage. And the activity of the catalyst in electrochemically reducing N-nitrosodimethylamine was tested by a three-electrode reactor. The method has the characteristics of simple reaction mechanism, no secondary pollution in the reduction process, greenness, high efficiency and the like, and has good effect in the treatment of the typical disinfection by-product N-nitrosodimethylamineAnd the application prospect is good.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a method for electrocatalytic reduction of N-nitrosodimethylamine.
Background
Due to the widespread use of chloramine disinfection methods, N-Nitrosodimethylamine (NDMA) has become an emerging disinfection by-product. Toxicity testing results show that NDMA can cause damage to the liver, lungs and nervous system of an organism to varying degrees. NDMA has been classified as a possible human carcinogen by the international agency for research on cancer (IARC) due to its genotoxicity, cytotoxicity and carcinogenicity (group 2A). Therefore, it is desirable to explore efficient and environmentally friendly techniques for removing NDMA from water.
Currently, many methods for removing NDMA from water have been reported, including adsorption, Reverse Osmosis (RO), Advanced Oxidation Processes (AOPs), uv photolysis, chemical reduction, and biodegradation. However, these methods have certain limitations, such as higher running cost of RO, AOPs and uv photolysis, low reaction rate of ZVI reduction, and higher requirement for solution pH. Although liquid phase catalytic hydrogenation reduction of NDMA using metal catalysts (supported Pd, Ni, Ru-based catalysts, etc.) has proven to be an effective method, particularly Ru-based catalysts. However, hydrogen supply has become a potential obstacle to the application of this catalytic hydrogenation technology due to the greater safety risks involved in the transportation, storage and use of hydrogen.
The electrochemical reduction has the advantages of safety, mild reaction conditions and no additional secondary pollutants, and is a technology which is expected to be practically applied. The method mainly reduces pollutants by means of electrons and active hydrogen H to achieve the aim of eliminating toxicity. Electrochemical reduction methods have been shown to remove a variety of water pollutants, such as bromates, nitrates, halogenated organics, etc., but the use of electrochemical reduction methods for treating NDMA has been less studied. The currently reported method only adopts microorganisms as an anode and promotes the oxidation of NDMA by an electrochemical device, but the method needs to screen and domesticate floras, has long treatment time, is sensitive to the change of temperature and the like, is not easy to control, is easy to pollute a bioelectrode and needs a subsequent treatment process. Compared with a bioelectrode, the catalyst-electrode material composite electrode is directly adopted, the method has the characteristics of simplicity in operation, strong activity, high stability and the like, and the high-efficiency removal of the NDMA in water can be hopefully realized by adopting the catalyst for electrocatalytic reduction in consideration of the fact that the Ru-based catalyst has higher activity of liquid-phase catalytic hydrogenation reduction of the NDMA.
Disclosure of Invention
In view of the problems pointed out by the background art, the invention provides a method for electrocatalytic reduction of N-nitrosodimethylamine, which can be carried out under normal temperature and pressure, has mild conditions, simple operation and green and environment-friendly process, and provides a new solution for removal of N-nitrosodimethylamine in water.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method of electrocatalytic reduction of N-nitrosodimethylamine, comprising the steps of:
s1, synthesizing a supported metal catalyst:
loading metal on a carbon-based carrier by adopting a sodium borohydride chemical reduction method or an impregnation method to obtain a supported metal catalyst;
s2, preparing a composite electrode:
grinding the supported metal catalyst obtained in the step S1, and fixing the metal catalyst on the surface of an electrode material to form a composite electrode after ultrasonic dispersion through a perfluorinated sulfonic acid resin Nafion solution;
s3, electrocatalytic reduction:
placing the composite electrode obtained from S2 in the cathode chamber as the working electrode, placing platinum wire in the anode chamber, separating the cathode chamber and the anode chamber by Nafion-117 proton exchange membrane, and mixing Na containing N-nitrosodimethylamine with Na containing no N-nitrosodimethylamine 2 SO 4 The solution is respectively placed in a cathode chamber and an anode chamber, and electrocatalytic reduction is carried out under direct current voltage.
Further, in the above scheme, in step S1, a specific method for synthesizing the supported metal catalyst by using a chemical reduction method is as follows:
mixing and stirring a carbon-based carrier and a metal salt solution for 1-3 hours to obtain a mixed solution A, adding sodium borohydride into the mixed solution A under an ice bath condition, continuously stirring for 1-3 hours, cleaning, filtering, and drying in a vacuum oven at 30-60 ℃ to obtain a supported metal catalyst;
wherein the metal accounts for 0.5-5 wt% of the total mass of the catalyst; the molar ratio of the sodium borohydride to the metal is 5-10.
Further, In the above aspect, the metal is a platinum group metal selected from any one of Pd, Pt, Rh, and Ru, or a bimetal formed by combining a platinum group metal and a nonmetal selected from any one of Pd-In, Pd-Ni, and Ru-Cu.
Further, in the above scheme, the carbon-based support is selected from any one of carbon nanotubes, CMK-3, and graphene.
Further, in the above scheme, in step S2, a specific method for preparing the composite electrode is as follows:
and (2) taking 10-20 mg of the supported metal catalyst obtained in the step S1, grinding and sieving the supported metal catalyst, dispersing the ground supported metal catalyst into 1mL of ethanol water solution with the mass concentration of 20-50%, adding 20-100 mu L of perfluorinated sulfonic acid resin Nafion solution with the mass concentration of 5%, ultrasonically dispersing for 30-60 min to obtain a mixed solution B, uniformly coating the mixed solution B on the surface of carbon paper, and naturally airing at room temperature to obtain the composite electrode.
Further, in step S1, the method for synthesizing the supported metal catalyst by the impregnation method includes: mixing the metal salt solution with the carrier, fully stirring, evaporating to dryness in a water bath, and finally roasting and reducing to obtain the catalyst.
Further, in the above scheme, in the step S2, the size of the prepared composite electrode is 2-10 cm 2 。
Further, in the above scheme, in the step S3, Na containing and not containing N-nitrosodimethylamine 2 SO 4 After the solution is respectively placed in the cathode chamber and the anode chamber, N is introduced under the condition of stirring 2 To remove oxygen from the solution, followed by applying a constant voltage, electrocatalytic reduction in a three-electrode reactorAnd (4) carrying out primary reaction.
Further, in the above scheme, in the step S3, the Na 2 SO 4 The concentration of the solution is 2-10 mmoL/L.
Further, in the above scheme, in the step S3, the concentration of N-nitrosodimethylamine is 2-20 μmoL/L.
Further, in the above scheme, in the step S3, the Na 2 SO 4 The concentration of the solution is 2-10 mmoL/L; the concentration of the N-nitrosodimethylamine is 2-20 mu moL/L.
Further, in the above embodiment, in the step S3, the dc voltage for the electrocatalytic reduction is-0.7V to-1.1V.
Compared with the prior art, the beneficial effects of the invention are embodied in the following points:
first, the method for electrocatalytic reduction of N-nitrosodimethylamine has the advantages of simple reaction mechanism, no corrosion, no pollution, no passivation and the like of electrodes in the electrocatalytic reduction process of pollutants, and green and environmental protection.
Secondly, the method for electrocatalytic reduction of N-nitrosodimethylamine has the characteristics of high catalytic reduction efficiency of N-nitrosodimethylamine in water, short treatment time, high efficiency, high speed and the like.
Thirdly, the method for electrocatalytic reduction of N-nitrosodimethylamine is milder to the electrocatalytic reduction reaction of N-nitrosodimethylamine and has the characteristics of long-term effect and the like.
Drawings
FIG. 1 is a transmission electron micrograph of catalysts Ru/CNT, Pd/CNT, Pt/CNT, and Rh/CNT;
wherein (a) is Ru/CNT; (b) is Pd/CNT; (c) is Pt/CNT; (d) is Rh/CNT;
FIG. 2 is a graph of the reaction curves for different composite electrodes for electrocatalytic reduction of NDMA;
wherein, (a) is a reaction profile; (b) is an electrode and the corresponding initial activity;
FIG. 3 is a product analysis of an Ru/CNT composite electrode for electrocatalytic reduction of NDMA;
wherein (a) is carbon balance; (b) is nitrogen balance;
FIG. 4 is a graph of the reaction of an Ru/CNT composite electrode for the electrocatalytic reduction of NDMA;
wherein (a) is a different constant voltage; (b) is a graph of the relationship between constant voltage and initial activity of the reaction;
FIG. 5 is a graph of the reaction of an Ru/CNT composite electrode for the electrocatalytic reduction of NDMA;
wherein (a) is a reaction of different initial NDMA concentrations; (b) fitting graphs for an L-H model;
FIG. 6 is a graph of the reaction of an Ru/CNT composite electrode for the electrocatalytic reduction of NDMA;
wherein, (a) is a reaction under different pH conditions; (b) is a graph of the relationship between pH and initial activity of the reaction;
FIG. 7 is a graph of the reaction of an Ru/CNT composite electrode for the electrocatalytic reduction of NDMA;
wherein (a) is a reaction at different electrolyte concentrations; (b) is a graph of the relationship between the concentration of the electrolyte and the initial activity of the reaction;
FIG. 8 is a graph of the reaction of an Ru/CNT composite electrode for the electrocatalytic reduction of NDMA;
wherein, (a) is a cyclic reaction curve; (b) is a graph of the relationship between the cycle number and the initial activity of the reaction;
FIG. 9 is a graph of the reaction of electrocatalytic reduction of a Ru/CMK3 composite electrode and a Ru/CNT composite electrode NDMA;
FIG. 10 is a graph of the reaction of electrocatalytic reduction of a Ru/CNT-copper foam composite electrode and a Ru/CNT-carbon paper composite electrode NDMA;
FIG. 11 is a graph showing the electrocatalytic reduction reaction of Ru/CNT composite electrode with different N-nitrosamines.
Detailed Description
The technical solutions of the present invention are further illustrated by the following specific examples, but it should be noted that the following examples are only for describing the content of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
Preparation of composite electrode (Ru/CNT-carbon paper as an example):
(1) Ru/CNT: mixing and stirring CNT and ruthenium chloride solution for 1h, adding sodium borohydride solution into the mixture under the ice bath condition, wherein the molar ratio of sodium borohydride to Ru is 5, continuously stirring the mixture for 1h, cleaning and filtering the mixture, and drying the mixture in a vacuum oven at 60 ℃ to obtain the Ru/CNT catalyst, wherein the loading capacity of Ru is 2 wt.%. The transmission electron microscope image of Ru/CNT is shown in figure 1(a), and it can be seen that Ru is uniformly dispersed on the surface of CNT, and the average particle size is about 2.14nm (within 1-3 h and 50-60 ℃, the stirring time and the vacuum oven temperature are changed, and the obtained Ru/CNT has no obvious difference from the method);
(2) Ru/CNT-carbon paper: grinding and sieving 20mg Ru/CNT, dispersing into 1mL 30% ethanol water solution, adding 40 μ L5% perfluorosulfonic acid resin Nafion solution, ultrasonically dispersing for at least 30min, and uniformly coating the obtained mixed solution to 10cm 2 And (3) naturally airing the surface of the carbon paper to obtain the Ru/CNT-carbon paper composite electrode (the mass fraction of the ethanol water solution is changed to be 20-50%, the dosage of the Ru/CNT is changed to be 10-20 mg, and the dosage of the Nafion solution is changed to be 20-100 mu L, so that the Ru/CNT-carbon paper composite electrode is not greatly influenced in the preparation process of the Ru/CNT-carbon paper composite electrode).
According to the steps, different metal salt solutions are used to prepare the Pd/CNT-carbon paper, the Pt/CNT-carbon paper and the Rh/CNT-carbon paper composite electrode respectively, and as can be seen from a transmission electron microscope picture of figure 1, the average grain diameters of metal Pd, Pt and Rh in each catalyst are respectively 4.53 nm, 3.14 nm and 2.34 nm.
The composite electrode prepared by the method is used for carrying out electrocatalytic reduction reaction of N-nitrosodimethylamine in a three-electrode system. Wherein the initial concentration of NDMA is 10 μmoL/L, and the electrolyte Na 2 SO 4 The solution concentration was 5mmoL/L, the constant voltage applied was-0.9V, and the initial pH of the reaction was 6. The reaction curve is shown in fig. 2, and it can be seen that the Ru/CNT-carbon paper composite electrode has the best effect, and the removal rate of N-nitrosodimethylamine reaches 98% after reacting for 2h under a constant potential.
Example 2
The method of example 1 was used to increase the metal loading to 5 wt.% and the composite electrode area to 15cm, respectively 2 Two composite electrodes were prepared. Taking 10 mu moL/L as the initial concentration of NDMA and 5mmoL/L as the electrolyte Na 2 SO 4 Concentration of solutionApplying a constant voltage of-0.9V, carrying out electrocatalytic reduction on N-nitrosodimethylamine by adopting the composite electrode, wherein the reaction time is 2h, and the removal rate of NDMA is more than 99% after the reaction is finished.
Example 3
Taking 10 mu moL/L as the initial concentration of NDMA and 5mmoL/L as the electrolyte Na 2 SO 4 The solution concentration was adjusted to-0.9V, electrocatalytic reduction of N-nitrosodimethylamine was performed using the Ru/CNT-carbon paper composite electrode of example 1, and the reduced product was examined, as shown in FIG. 3. From the carbon and nitrogen balance results, it can be seen that the reduction products of NDMA are Dimethylamine (DMA) and ammonium.
Example 4
Using the Ru/CNT-carbon paper composite electrode of example 1 as a working electrode, the initial concentration of NDMA was 10. mu. moL/L, and the electrolyte Na 2 SO 4 The solution concentration is 5mmoL/L, the constant voltage is adjusted to-0.7 to-1.1V, and the N-nitrosodimethylamine is subjected to electrocatalytic reduction. As can be seen from fig. 4, as the voltage was adjusted from-0.7V to-0.9V, the electron and active H content gradually increased, so that the removal rate of NDMA gradually increased. However, when the working voltage is further increased, the removal rate of the NDMA is not changed greatly, mainly because a large amount of active H is converted into hydrogen through a Heyrovsky or Tafel process, and the adsorption of the NDMA on the surface of an electrode is blocked, so that-0.9V is selected as the optimal working voltage.
Example 5
The Ru/CNT-carbon paper composite electrode of example 1 was used as a working electrode, the constant voltage was-0.9V, and the electrolyte was Na 2 SO 4 The concentration of the solution is 5mmoL/L, the initial concentration of NDMA is adjusted to be 2-20 mu moL/L, and N-nitrosodimethylamine is subjected to electrocatalytic reduction. The relationship between the initial concentration of NDMA and the initial activity of the reaction is shown in FIG. 5(b), and it can be seen that there is a good linear relationship (R) between the reciprocal of the two 2 ＝0.99>0.96), consistent with the L-H model, indicates that the reaction of electrocatalytic reduction of NDMA is governed by the adsorption of contaminants on the electrode surface.
Example 6
Composite electricity using the Ru/CNT-carbon paper of example 1The electrode is a working electrode, the constant voltage is-0.9V, and the electrolyte Na 2 SO 4 The solution concentration was 5mmoL/L, the initial concentration of NDMA was 10. mu. moL/L, the initial pH was adjusted to 2, 7 and 12, and electrocatalytic reduction of N-nitrosodimethylamine was performed, and the results are shown in FIG. 6. It can be seen that the reactivity gradually decreased with increasing pH. Under acidic conditions, the solution contains a large amount of H + Promoting the production of active H, and NDMA is mainly in protonated form (CH) 3 ) 2 N-N＝OH + The catalyst is easier to be adsorbed on the surface of the cathode, thereby having higher reactivity. However, despite the unfavorable electrocatalytic reduction at high pH, the NDMA removal rate was still above 85% within 2h, indicating that electrocatalytic reduction of NDMA using Ru/CNT composite electrodes is feasible over a very wide pH range.
Example 7
The Ru/CNT-carbon paper composite electrode of example 1 was used as a working electrode, a constant voltage of-0.9V and an initial NDMA concentration of 10. mu. moL/L were used, and an electrolyte Na was adjusted 2 SO 4 The electrocatalytic reduction of N-nitrosodimethylamine was carried out at solution concentrations of 2, 5 and 10mmoL/L, and the results are shown in FIG. 7. It can be seen that Na is associated with the electrolyte 2 SO 4 The initial activity of the reaction is gradually enhanced when the concentration of the solution is increased from 2 to 10mmoL/L, because the higher the concentration of the electrolyte, the more free ions can be provided, and the conduction of electrons is more favorable. However, even under the condition of lower electrolyte concentration (2mmoL/L), the removal rate of the NDMA in 2h is still 90%, which shows that in the electrolyte concentration range of 2-10 mmoL/L, the Ru/CNT composite electrode has good activity on the electrocatalytic reduction of the NDMA.
Example 8
The cyclic reaction of electrocatalytic reduction of NDMA was performed using the Ru/CNT composite electrode of example 1, with a constant voltage of-0.9V and Na as electrolyte 2 SO 4 The solution concentration was 5mmoL/L and the initial concentration of NDMA was 10. mu. moL/L, and 5 cycles of reaction were carried out. As shown in FIG. 8, after 5 cycles of use, the Ru/CNT composite electrode still has high electrocatalytic reduction activity, and the removal rate of NDMA can be maintained above 95%, indicating that the electrodeThe stability is good, and the application of the composite material in degrading NDMA in a water body has certain feasibility.
Comparative example 1
A Ru/CMK-3-carbon paper composite electrode was prepared by exchanging the support CNT for CMK-3 according to the synthesis method of example 1, and the reaction for electrocatalytic reduction of NDMA was performed using each of the two electrodes. Wherein the constant voltage is-0.9V, and the electrolyte is Na 2 SO 4 The solution concentration was 5mmoL/L and the initial concentration of NDMA was 20. mu. moL/L. As can be seen from FIG. 9, the Ru/CMK-3 composite electrode also has a certain electrocatalytic activity.
Comparative example 2
According to the synthesis method in example 1, the electrode material carbon paper was changed to copper foam to prepare a Ru/CNT-copper foam composite electrode, and the two electrodes were used to perform the reaction of electrocatalytic reduction of NDMA, respectively. Wherein the constant voltage is-0.9V, and the electrolyte Na 2 SO 4 The solution concentration was 5mmoL/L and the initial concentration of NDMA was 20. mu. moL/L. As can be seen from FIG. 10, the Ru/CNT-copper foam composite electrode has better activity for electrocatalytic reduction of NDMA.
Comparative example 3
In order to further explore the universality of the method on various N-nitrosamines, N-dimethyl Nitrosamine (NDMA), N-diethyl Nitrosamine (NDEA), N-di-N-butyl Nitrosamine (NDBA), N-Nitrosomorpholine (NMOR) and N-nitrosodiphenylamine (NDPhA) are respectively selected to carry out electrocatalytic reduction reaction. Wherein the constant voltage is-0.9V, and the electrolyte is Na 2 SO 4 The solution concentration was 5mmoL/L and the initial concentration of N-nitrosamine was 10. mu. moL/L. The reaction curve is shown in FIG. 11, and the Ru/CNT electrode is found to be capable of removing various N-nitrosamines through electrocatalytic reduction and has better universality.
Claims (10)
1. A method for electrocatalytic reduction of N-nitrosodimethylamine, comprising the steps of:
s1, synthesizing a supported metal catalyst:
loading metal on a carbon-based carrier by adopting a sodium borohydride chemical reduction method or an impregnation method to obtain a supported metal catalyst;
s2, preparing a composite electrode:
grinding the supported metal catalyst obtained in the step S1, and fixing the metal catalyst on the surface of an electrode material to form a composite electrode after ultrasonic dispersion through a perfluorinated sulfonic acid resin Nafion solution;
s3, electrocatalytic reduction:
placing the composite electrode obtained from S2 in the cathode chamber as the working electrode, placing platinum wire in the anode chamber, separating the cathode chamber and the anode chamber by Nafion-117 proton exchange membrane, and mixing Na containing N-nitrosodimethylamine with Na containing no N-nitrosodimethylamine 2 SO 4 The solution is respectively placed in a cathode chamber and an anode chamber, and electrocatalytic reduction is carried out under direct current voltage.
2. The method for electrocatalytic reduction of N-nitrosodimethylamine according to claim 1, wherein said step S1, the supported metal catalyst is synthesized by chemical reduction method by the following specific methods:
mixing and stirring a carbon-based carrier and a metal salt solution for 1-3 hours to obtain a mixed solution A, adding sodium borohydride into the mixed solution A under an ice bath condition, continuously stirring for 1-3 hours, cleaning, filtering, and drying in a vacuum oven at 30-60 ℃ to obtain a supported metal catalyst;
wherein the metal accounts for 0.5-5 wt% of the total mass of the catalyst; the molar ratio of the sodium borohydride to the metal is 5-10.
3. An electrocatalytic reduction method of N-nitrosodimethylamine according to claim 2, wherein said metal is a platinum group metal or a bimetal formed by combining a platinum group metal and a nonmetal, said platinum group metal is selected from any one of Pd, Pt, Rh, Ru, and said bimetal formed by combining a platinum group metal and a nonmetal is selected from any one of Pd-In, Pd-Ni, Ru-Cu.
4. The method for electrocatalytic reduction of N-nitrosodimethylamine according to claim 2, wherein said carbon based support is selected from any of carbon nanotubes, CMK-3, graphene.
5. The method for electrocatalytic reduction of N-nitrosodimethylamine according to claim 1, wherein said step S2, the method for preparing the composite electrode comprises:
and (2) taking 10-20 mg of the supported metal catalyst obtained in the step S1, grinding and sieving the supported metal catalyst, dispersing the ground supported metal catalyst into 1mL of ethanol water solution with the mass concentration of 20-50%, adding 20-100 mu L of perfluorinated sulfonic acid resin Nafion solution with the mass concentration of 5%, ultrasonically dispersing for 30-60 min to obtain a mixed solution B, uniformly coating the mixed solution B on the surface of carbon paper, and naturally airing at room temperature to obtain the composite electrode.
6. The method of claim 1, wherein the size of the composite electrode prepared in step S2 is 5-15 cm 2 。
7. The method of claim 4, wherein in step S3, Na containing or not containing N-nitrosodimethylamine is added 2 SO 4 After the solution is respectively placed in the cathode chamber and the anode chamber, N is introduced under the condition of stirring 2 To remove oxygen from the solution, and then applying a constant voltage to perform an electrocatalytic reduction reaction in a three-electrode reactor.
8. The method for electrocatalytic reduction of N-nitrosodimethylamine according to claim 1, wherein said Na in step S3 2 SO 4 The concentration of the solution is 2-10 mmoL/L.
9. The method for electrocatalytic reduction of N-nitrosodimethylamine according to claim 1, wherein said concentration of N-nitrosodimethylamine in step S3 is 2-20 μmoL/L.
10. The method of claim 1, wherein the direct current voltage for electrocatalytic reduction in step S3 is-0.7V to-1.1V.
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