CN115646548A - Cu-based bipyridine double-ligand electrocatalyst for removing nitrate in wastewater and preparation method thereof - Google Patents
Cu-based bipyridine double-ligand electrocatalyst for removing nitrate in wastewater and preparation method thereof Download PDFInfo
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Abstract
The invention provides a Cu-based bipyridine double-ligand electrocatalyst for removing nitrate in wastewater and a preparation method thereof. The catalyst has the nitrate conversion rate of over 75 percent under the voltage of-1.2V (taking Ag/AgCl as a reference electrode), and the preparation method has the characteristics of lower cost, simpler synthesis and industrialized scale-up application, and has industrial production prospect.
Description
Technical Field
The invention belongs to the technical field of electrocatalysts for water treatment, and relates to a Cu-based bipyridyl double-ligand electrocatalyst for removing nitrate in wastewater and a preparation method thereof.
Background
Due to the continuous development of industry, commerce and agriculture, the nitrogen content in industrial sewage and domestic sewage is continuously increased. Among them, the pollution of nitrate nitrogen is the most serious, and the control of nitrate pollution in water has attracted more and more attention. NO 3 - As stable nitrogen oxide in water, the existence of the nitrogen oxide can cause eutrophication of water, and the nitrogen oxide is easily reduced into nitrite after being taken into human bodies, and has huge toxicity so as to interfere the functions of the human bodies. Meanwhile, nitrate itself has the problems of difficult degradation, more secondary pollutants and the like, so that the search for a clean and efficient nitrate wastewater treatment mode is becoming a problem for researchers.
The traditional methods for treating nitrate pollution include physical methods (ion exchange method, electrodialysis method and reverse osmosis method), chemical methods (metal reduction method and catalytic reduction method) and biological methods (denitrification and reactor method), however, the physical methods and the chemical methods are expensive in cost and easy to generate secondary pollutants, the most widely used biological denitrification and denitrification methods at present require additional carbon sources besides harsh reaction conditions (having requirements on temperature, pH and the like), and CO is generated in the reaction process 2 And the greenhouse gases are equal, and meanwhile, the production amount of activated sludge is large, and the post-treatment is complex. With the emergence of the electrochemical technology in the field of sewage treatment, the removal of nitrate pollutants in wastewater by electrocatalysis is favored by researchers. Due to excellent nitrate removal rates and mild reaction conditions, selective electrocatalytic nitrate reduction (ENRR) technology, which can be driven by renewable energy, is considered as an effective alternative to traditional methods.
At present, the catalysts for electrocatalytic reduction of nitrate mainly include non-metal-based (GF, BDD), metal-based (Pd, ni, fe, etc.), bimetallic-based (Cu/Ni, co/Fe, etc.) and composite-based (Cu/rGO/GP) electrocatalysts. Among them, metal-based electrocatalysts have been developed as many single metal-based electrocatalysts, such as Cu, fe, al, ni, zn, ag, au, pt and Pd, due to their relatively high catalytic activity, but these metal-based electrocatalysts currently exist only in the laboratory research stage, among which, the Cu-based electrocatalysts, which are relatively reasonable in cost, have been the focus of research on the electrocatalysis reduction of nitrate due to their relatively high activity, and are widely regarded as having good practical application prospects.
Therefore, an electrocatalyst with good electrocatalytic performance to remove nitrate pollutants in water, relatively simple and reasonable preparation process, and suitability for industrial production and application is needed at present.
Disclosure of Invention
The invention aims to solve the problems in the background art and provides a Cu-based bipyridyl dual-ligand electrocatalyst for removing nitrate in wastewater and a preparation method thereof, wherein the electrocatalyst is a modified Cu-bipy-MOF catalyst, the nitrate conversion rate of the catalyst under-1.2V voltage (Ag/AgCl is used as a reference electrode) can reach more than 75%, and the preparation method has the characteristics of low cost, simple synthesis and industrialized scale-up application, and has an industrial production prospect.
In order to achieve the purpose, the invention adopts the technical scheme formed by the following technical measures.
A Cu-based bipyridyl double-ligand electrocatalyst for removing nitrate in wastewater is prepared by the following steps:
(1) Copper salt and MOF ligand are selected and weighed, and are mixed with 2,2' -bipyridine (bipy) and sodium hydroxide (NaOH) according to the molar ratio of Cu: bipy: MOF: naOH = (2 to 3): 2:3:6, uniformly mixing to obtain a mixture for later use;
wherein the MOF ligand is trimesic acid or isophthalic acid;
(2) Measuring distilled water as solution A;
(3) Adding the solution A into the mixture obtained in the step (1), adding 10-11 mg of 2,2' -bipyridyl into per ml of the solution A, and fully and uniformly mixing to obtain solution B;
(4) Reacting the solution B obtained in the step (3) at the temperature of 155-165 ℃ for at least 72h; and after the reaction time is up, filtering, washing and drying to obtain an indigo catalyst powder crystal, namely the modified Cu-bipy-MOF catalyst.
The modified Cu-bipy-MOF catalyst prepared by the preparation method can be used for removing nitrate in water body through electrocatalysis, especially nitrate nitrogen pollutants.
Generally, the copper salt in step (1) is a copper salt conventionally used in the art for preparing a copper ion solution, and includes, but is not limited to, hydrated copper nitrate, hydrated copper acetate, and hydrated copper chloride; in order to simplify the experimental operation and design a control experimental scheme, the copper salt selected by the technical scheme is copper acetate monohydrate (CH) 3 (COO)·H 2 O), it will be clear to the skilled person that the copper salt in step (1) is mainly to provide copper ions, the choice of the specific anionic group of which will not generally have an impact on the technical effect achieved by the present invention.
In step (1), the molar ratio is Cu: bipy: MOF: naOH = (2 to 3): 2:3:6, in order to confirm the maximum product yield ratio range through experiments, if the molar ratio of the copper salt to the double ligand exceeds the range, the synthesis morphology and the performance of the modified Cu-bipy-MOF catalyst are obviously influenced. The inventor of the invention finds that in the experimental exploration stage, when the proportion of the electrocatalyst of the same type as the electrocatalyst of the invention is excessively changed based on the electrocatalyst of a dual-ligand system formed by bip and MOF ligands during the preparation of the electrocatalyst based on metal copper ions, the color of the modified Cu-bip-MOF catalyst prepared by the method is remarkably changed (the crystal is changed from normal blue to purple), and the purity of the modified Cu-bip-MOF catalyst prepared by the method is proved to be remarkably reduced; similarly, it is presumed that the modified Cu-bipy-MOF catalyst provided by the present invention has a greatly reduced purity even if the ratio is excessively changed during the preparation, and thus it is difficult to obtain an electrocatalyst with catalytic performance consistent with that of the present invention.
It should be noted that the most obvious sign of successful synthesis is that the final preparation of fine indigo powder is uniform, and when the adjustment is carried out within the range of the mixture ratio defined in the present invention (small change of the molar ratio of Cu), the crystal particles and morphology after synthesis will change, but the catalyst performance will not be significantly affected. In the above mixture ratio, cu represents the molar amount of copper element in the copper salt, bipy represents the molar amount of 2,2' -bipyridine, MOF represents the molar amount of MOF ligand, and NaOH represents the molar amount of sodium hydroxide.
Generally, the mixture in step (3) is fully mixed uniformly, and under laboratory conditions, in order to avoid the influence of ratio change on a control experiment, an ultrasonic treatment mode can be selected, specifically, the mixture is placed in an ultrasonic container for ultrasonic treatment for at least 5min, until solid particles are completely dissolved, and a clear solution is observed. Based on the technical purpose of thorough mixing and uniform mixing, the skilled person can select a proper thorough mixing means according to the existing experimental conditions or industrial conditions.
It should be noted that, in the actual industrial scale-up production, when the ultrasonic treatment is performed in an ultrasonic container having a large volume (more than 1L), a slight aggregation phenomenon is observed in the mixed liquid, and therefore, it is recommended to perform mechanical stirring during the ultrasonic treatment.
And (3) reacting the solution B obtained in the step (3) at 155-165 ℃ for at least 72 hours in the step (4), wherein the solution B can be selectively placed in a closed container for reaction in order to avoid the change of the mixture ratio caused by the evaporation phenomenon.
Generally, the temperature environment of 155-165 ℃ in the step (4), the heating and heat preservation modes thereof, and a person skilled in the art can select a suitable process mode according to the existing experimental conditions or industrial conditions. Under laboratory conditions, the solvent thermal method is preferably matched with a closed container, and specifically the solvent thermal method is placed in a hydrothermal constant temperature box for solvent thermal reaction.
Typically, the filtration washing and drying in step (4) is a conventional process in the art, preferably by centrifugation with an organic reagent (e.g., alcohol); preferably by vacuum drying.
It should be noted that, in practical experiments, the inventor finds that, in the step (4), the liquid B obtained in the step (3) is reacted for at least 72 hours in an environment with a temperature of 155-165 ℃, and after the reaction time is up, the obtained liquid B is mixed with light-weight blue flocculent precipitate besides the indigo crystal powder (i.e. the modified Cu-bipy-MOF catalyst). When the precipitate is washed and stood by water, the indigo crystals of the modified Cu-bipy-MOF catalyst are settled at the bottom of a washing container firstly due to higher density, and the blue flocculent precipitate with lighter weight is settled at a lower speed, so that most of the blue flocculent precipitate can be separated when the catalyst is settled and the blue flocculent precipitate is not settled or a small part of the blue flocculent precipitate is settled. And then when organic reagent (such as alcohol) is used for washing, placing the washing container into an ultrasonic cleaning instrument for ultrasonic oscillation, wherein in the ultrasonic process, a small part of unseparated blue flocculent precipitate can be dissolved in the organic reagent under the ultrasonic action, and the modified Cu-bipy-MOF catalyst cannot be dissolved, so that pure indigo crystal powder after washing, namely the modified Cu-bipy-MOF catalyst, is obtained.
The modified Cu-based dual-ligand catalyst (modified Cu-bipy-MOF catalyst) is finally prepared by the technical scheme, and the electrolyte is 50mM/L electrolyte solution Na 2 SO 4 Under the condition of constant voltage of-1.2V, the conversion rate of 70mg/L-N of the simulated nitrate wastewater can reach more than 75 percent; in 50mM electrolyte solution Na 2 SO 4 Under the condition of constant voltage of-1.4V, the conversion rate of 70mg/L-N of the simulated nitrate wastewater can reach more than 65 percent; in the electrolyte of 50mM/L electrolyte solution Na 2 SO 4 Under the condition of constant voltage of-1.0V, the conversion rate of 70mg/L-N of the simulated nitrate wastewater can reach more than 60 percent; in 50mM electrolyte solution Na 2 SO 4 、1.0mMNa 2 CO 3 Under the constant voltage condition of-1.2V, the conversion rate of 70mg/L-N of the simulated wastewater can reach more than 70 percent; in the electrolyte of 50mM/L electrolyte solution Na 2 SO 4 、2.0mM Ca 2 SO 4 Under the constant voltage condition of-1.2V, the conversion rate of 70mg/L-N of the simulated wastewater can reach over 75 percent.
The invention is based on the principle that a Metal Organic Framework (MOF) has the characteristics of both organic polymers and inorganic compounds and is a novel porous material which is developed quickly in the field of coordination chemistry. Has the advantages of good physical and chemical properties, various types, ordered and well-regulated structure, high porosity, large specific surface area and the like. The metal center of the MOF material can be almost all selected metals, and Zn, cu and Fe are more applied metal centers. The invention proves that the copper-based MOFs electrocatalyst formed by the double ligands and the copper ions is selected through practical experiments, and the copper-based MOFs electrocatalyst has excellent performance of reducing nitrate in water by an electrocatalytic cathode through practical tests.
Through search and query, the MOFs-based electrocatalyst formed by copper ions and ligands is only slightly found in relevant electrochemical theoretical research in the prior art literature, and the specific application and technical effect of the MOFs-based electrocatalyst are not reported in the literature.
The inventor of the present invention found that the mono-ligand Cu-based MOFs electrocatalyst has a defect of very poor water stability in the actual preparation and application processes of the MOFs-based electrocatalyst, and thus also demonstrated the reason why the application thereof to the water treatment related field is not seen.
Experimental observation shows that the prepared single-ligand Cu-based MOFs electrocatalyst is placed in water for 30min, the catalyst is changed into an agglomerated block from a powder state, and meanwhile, experiments prove that the activity of the catalyst is reduced by about 10% every time a circulation experiment is carried out, which shows that the catalyst framework is damaged in the water and has great instability.
In order to solve the technical defects, the inventors of the present invention found through a large number of exploratory experiments that the modified Cu-bipy-MOF catalyst prepared by composing bipy and MOF ligands into a dual ligand system has very excellent water stability, and remains in the original powder form after 7 days in the water stability test. Meanwhile, a double-ligand system formed by bipy and MOF ligands is beneficial to further improving the performance of reducing nitrate in water by the electrocatalytic cathode. The reason is that the double-ligand structure and the Cu metal center form a stable 3D framework structure, and meanwhile, the Cu atom and the O atom in the metal center form a coordination bond which is more stable than the traditional hydrogen bond connection.
It should be noted that the MOF ligand selected in the present invention is limited to trimesic acid or isophthalic acid, and practical experiments prove that the MOF ligand selected above can form a stable MOF metal organic framework with copper ions. In fact, there is no systematic theoretical research to guide the selection of the combination relationship between MOF ligands and metal ions, so in the case of limiting copper ions, the selection of MOF ligands needs to actually verify whether the MOF metal organic framework can be successfully self-assembled through experiments, and on this basis, the technical scheme of the present invention adopts a dual-ligand design route, and the skilled person can not predict and speculate the appropriate MOF ligands under the dual-ligand system. The present invention is based on a large number of experimental searches, and finally determines that trimesic acid or isophthalic acid can successfully form a Cu-based electrocatalyst of a dual ligand system with bipy when used as a MOF ligand, so that the present invention is limited only by the selection of the MOF ligand in the spirit of the fact.
Since the modified Cu-bipy-MOF catalyst provided by the invention is an electrocatalyst, the modified Cu-bipy-MOF catalyst can be applied by persons skilled in the art based on the related prior art in the field of electrocatalytic water treatment, and can be applied to the preparation of electrodes of electrocatalytic water treatment equipment.
However, it should be noted that, because the modified Cu-bipy-MOF catalyst provided by the present invention is also a novel electrocatalyst, the process parameters in the application method thereof are significantly different from those of the existing electrocatalyst, in order to better illustrate the present invention, a reference application method is provided:
the preparation method of the electrode applying the modified Cu-bipy-MOF catalyst mainly comprises the following steps:
weighing a modified Cu-bipy-MOF catalyst and carbon conductive powder, wherein the mass ratio of the modified Cu-bipy-MOF catalyst to the carbon conductive powder is (1-1.5): 1;
(II) preparing an organic solvent as a solution A;
(III) adding a binder into the solution A, wherein the addition amount of the binder is 1% of the volume of the solution A to obtain solution B;
adding the modified Cu-bipy-MOF catalyst and the carbon conductive powder weighed in the step (I) into the liquid B for mixing, adding 2-2.5 mg of the modified Cu-bipy-MOF catalyst into 1mL of the liquid B, uniformly mixing, and fully dispersing to obtain a mixed suspension;
(V) uniformly dripping the mixed suspension obtained in the step (IV) on two surfaces of a cathode plateWhen the solvent is completely volatilized, the electrode loaded with the modified Cu-bipy-MOF catalyst is obtained; wherein the area of the cathode sheet is controlled to be 1cm 2 0.33-1.33 mg of modified Cu-bipy-MOF catalyst needs to be loaded.
Generally, the carbon-based conductive powder in step (i) is a conductive powder conventionally used in the field of electrocatalytic water treatment, and serves to improve the conductivity of the electrocatalyst after mixing with the electrocatalyst. One skilled in the art can select suitable carbon-based conductive powders according to the existing literature or actual process conditions, including but not limited to any one or more of conductive carbon black powder, conductive graphite powder, chopped carbon fiber powder, carbon nanotube powder, and graphene powder.
Generally, the organic solvent in step (ii) is an organic solvent conventionally used in the field of electrocatalytic water treatment, and one skilled in the art can select a suitable organic solvent according to the existing literature or actual process conditions, including but not limited to any one of ethanol, isopropanol and methanol.
Preferably, in the step (ii), the organic solvent is a mixed solution of isopropanol and ethanol, wherein the volume ratio of isopropanol to ethanol is (1-1.2): 4.
typically, the binder used in step (iii) is a binder conventionally used in the field of electrocatalytic water treatment, and those skilled in the art can select a suitable binder according to the existing literature or actual process conditions, including a conventional commercially available binder or some conventional organic binder (e.g. chitosan).
And (3) obtaining a mixed suspension after uniformly mixing and fully dispersing in the step (IV), wherein the obtained liquid is the mixed suspension, and preferably performing the dispersing treatment in an ultrasonic treatment mode for ensuring the fully dispersing treatment.
Typically, the cathode sheet in step (v) is a cathode sheet conventionally used in the field of electrocatalytic water treatment, and one skilled in the art can select a suitable cathode sheet according to the existing literature or actual process conditions, including but not limited to any one of carbon paper cathode sheet, carbon felt cathode sheet and carbon cloth cathode sheet.
In step (v), the solvent to be volatilized completely can be promoted by one skilled in the art directly or indirectly according to the technical conditions recorded in the existing literature or actual process conditions, for example, a heating device can be placed under the cathode sheet to increase the temperature to promote the solvent volatilization.
It should be noted that, in order to better ensure the loading effect of the modified Cu-bipy-MOF catalyst, the cathode sheet in step (5) may be selected according to its specific material, and is pretreated with reference to the prior art literature in the art or directly purchased as a pretreated cathode sheet. For example, when the cathode sheet is selected to be a carbon paper cathode sheet, the carbon paper cathode sheet needs to be subjected to hydrophilic treatment, specifically, the carbon paper cathode sheet is subjected to hydrophilic treatment in concentrated nitric acid at 80 ℃ for at least 6 hours.
It should be noted that in order to ensure the accurate loading of the modified Cu-bipy-MOF catalyst on the cathode plate, the quantitative loss caused by the overflow or dripping of the liquid should be prevented during the dripping; in the dropping process, the mixed suspension needs to be ensured to be in a dispersed suspension state as much as possible so as to ensure that the modified Cu-bipy-MOF catalyst is uniformly dispersed on the surface of the electrode as much as possible.
The invention has the following beneficial effects:
1. the modified Cu-bipy-MOF catalyst provided by the invention has relatively low voltage (-1.0 to-1.2V), and the reference electrode is Ag/AgCl), and relatively high nitrate concentration (70 mg/L NO) 3 - -N), the electro-catalytic conversion rate of the nitrate is more than 75%, and the method is particularly suitable for electro-catalytic treatment for removing nitrate nitrogen in drinking water.
2. The modified Cu-bipy-MOF catalyst provided by the invention has excellent water stability by forming a double-ligand system by bipy and MOF ligands, and is suitable for long-term electro-catalysis removal treatment of nitrate nitrogen in water.
3. The modified Cu-bipy-MOF catalyst provided by the invention does not use noble metals and rare earth metals in the preparation process, only uses common copper salts and organic ligands on the market, and other used reagents are conventional chemical reagents, so that the overall cost of raw materials is greatly reduced compared with that of the noble metal catalyst on the market, and the modified Cu-bipy-MOF catalyst has better catalytic effect and lower cost and has excellent market application prospect compared with non-noble metal catalysts on the market.
4. The preparation method has the characteristics of low cost and suitability for continuous production of process steps, and has an industrial production prospect.
Drawings
FIG. 1 is a plot of nitrate removal rate at-0.8V voltage for nitrate removal for the modified Cu-bipy-MOF catalyst prepared in example 1.
FIG. 2 is a plot of the nitrate removal rate at-1.0V for the modified Cu-bipy-MOF catalyst prepared in example 1.
FIG. 3 is a plot of the nitrate removal rate at-1.2V for the modified Cu-bipy-MOF catalyst prepared in example 1.
FIG. 4 is a plot of the nitrate removal rate at-1.4V for the modified Cu-bipy-MOF catalyst prepared in example 1.
FIG. 5 is a graph comparing the nitrate removal rate at different voltages for nitrate removal for the modified Cu-bipy-MOF catalyst prepared in example 1.
FIG. 6 is a graph of the removal rate of the modified Cu-bipy-MOF catalyst prepared in example 1 when nitrite removal was performed.
FIG. 7 is an electron microscope scanning image of the modified Cu-bipy-MOF catalyst prepared in example 1, which shows that the surface of the prepared material is smooth, the material is a sheet structure, and the characteristics of the MOFs material are described.
FIG. 8 is a photograph of a sample of the modified Cu-bipy-MOF catalyst prepared in example 1 after vacuum drying.
FIG. 9 is a plot of nitrate nitrogen removal at-1.2V voltage for the modified Cu-bipy-MOF catalyst prepared in example 1.
FIG. 10 is a plot of nitrate nitrogen removal at-1.2V voltage for the modified Cu-bipy-MOF catalyst prepared in example 1.
FIG. 11 is a comparison of the-1.2V voltage nitrate removal rate curves for nitrate removal for the modified Cu-bipy-MOF catalysts prepared in examples 1-3.
FIG. 12 is an XRD pattern of the modified Cu-bipy-MOF catalyst prepared in example 1. Diffraction peaks are obvious in the ranges of 10-15 degrees and 20-25 degrees, and the successful synthesis and preparation of the modified Cu-bipy-MOF catalyst are proved.
FIG. 13 is an SEM image of the Cu-bipy-BTC catalyst prepared in example 4. Example 4 changes the addition of Cu salt (by reducing the molar ratio by 10%), and it can be seen that changing the compounding ratio within a suitable range has an obvious effect on the particle size and morphology of the catalyst, which is visually reflected as the particle size, but has no obvious effect on the performance of the catalyst.
FIG. 14 is an SEM image of the modified Cu-MOF catalyst prepared in comparative example 1 after being dispersed in a water body and stirred for 3h, wherein the Cu-MOF structure is destroyed in the water, and the MOF structure is scattered.
FIG. 15 is SEM image of sample of modified Cu-MOF catalyst prepared in comparative example 1 after being filtered and vacuum dried, and the structure of the MOFs material is obvious.
Detailed Description
The invention is further illustrated by the following examples in connection with the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
The electro-catalyst is used for testing the nitrate-removing wastewater through a Chenghua CHI660e electrochemical workstation, an H-type double-chamber electrolytic cell reactor with the single-chamber volume of 250mL is used for performance testing, the catalytic conversion of the nitrate-removing wastewater is simulated under different voltages, and a three-nitrogen rapid detector is used for detecting nitrate nitrogen, ammonia nitrogen and nitrite in the reaction process and calculating the removal rate.
In the following examples, the reagents used were: analytical grade sodium hydroxide (NaOH), sodium nitrate (NaNO) 3 ) Sodium nitrite (NaNO) 2 ) Copper acetate monohydrate (Cu (CH) 3 COO) 2 ·H 2 O), sodium sulfate (Na) 2 SO 4 ) Purchased from Shanghai wheat Lin Shenghua, inc. Trimesic acidAcid (H) 3 BTC) was purchased from shanghai teng technologies ltd. 2,2' -bipyridine (bipy) was purchased from Bidepharmam. Nafion 117 solution (5% wt%) was purchased from Sigma Aldrich. Carbon black (Vulcan XC 72R) was purchased from Cabot.
All the above chemicals were used directly without further purification. Dongli 090 carbon paper is selected as the substrate of the working electrode and is subjected to HNO before use 3 Boiling the solution.
Example 1
Example 1 is a modified Cu-bipy-MOF catalyst, which is prepared by a process comprising the steps of:
(1) Weighing 0.199g of copper acetate monohydrate, 0.141g of trimesic acid, 0.156g of 2,2' -bipyridyl and 0.080g of sodium hydroxide small particles, and uniformly mixing to obtain mixed powder for later use;
(2) Measuring 15mL of distilled water for later use as solution A;
(3) Slowly adding the A liquid drops into the mixed powder obtained in the step (1) at room temperature, and fully and uniformly mixing to obtain a B liquid;
(4) Transferring the solution B obtained in the step (3) into a 25mL reaction kettle liner, screwing a reaction kettle cover, and then reacting in a constant temperature box at 160 ℃ for 72 hours; and after the reaction time is up, filtering, washing and drying to obtain an indigo catalyst powder crystal, namely the modified Cu-bipy-MOF catalyst.
The modified Cu-bipy-MOF catalyst prepared by the method is subjected to vacuum drying and then is tested for nitrate reduction activity in an electrochemical activity evaluation device.
The preparation method of the electrode comprises the following steps: 8mg of modified Cu-bipy-MOF catalyst, 8mg of conductive carbon black powder, 3.2mL of ethanol and 0.8mL of isopropanol, adding 40uL of adhesive Nafion 117 into the mixed solution, slowly dripping the mixture on two sides of carbon paper (3 x 2cm specification) in a solution dispersion state, and obtaining the electrode loaded with the modified Cu-bipy-MOF catalyst after the solvent is completely volatilized.
The test conditions were: the electrolyte solution was 50mM Na 2 SO 4 The nitrate concentration is 70mg/L, the voltage is-0.8V, the anode adopts a Pt electrode, the reference electrode is an Ag/AgCl electrode, and the prepared catalyst electrode is a working electrode. Nitrate removalThe rate is shown in the attached figure 1 of the specification.
The test conditions were: the electrolyte solution was 50mM Na 2 SO 4 The nitrate concentration is 70mg/L, the voltage is-1.0V, the anode adopts a Pt electrode, the reference electrode is an Ag/AgCl electrode, and the prepared catalyst electrode is a working electrode. The nitrate removal rate is shown in the attached figure 2 of the specification.
The test conditions were: the electrolyte solution was 50mM Na 2 SO 4 The nitrate concentration is 70mg/L, the voltage is-1.2V, the anode adopts a Pt electrode, the reference electrode is an Ag/AgCl electrode, and the prepared catalyst electrode is a working electrode. The nitrate removal rate is shown in figure 3 of the specification.
The test conditions were: the electrolyte solution was 50mM Na 2 SO 4 The nitrate concentration is 70mg/L, the voltage is-1.4V, the anode adopts a Pt electrode, the reference electrode is an Ag/AgCl electrode, and the prepared catalyst electrode is a working electrode. The nitrate removal rate is shown in figure 4 in the specification.
The test conditions were: the electrolyte solution was 50mM Na 2 SO 4 The nitrite concentration is 70mg/L, the voltage is-1.2V, the anode adopts a Pt electrode, the reference electrode is an Ag/AgCl electrode, and the prepared catalyst electrode is a working electrode. The nitrite removal rate is shown in figure 6 in the specification.
The test conditions were: the electrolyte solution was 50mM Na 2 SO 4 Nitrate concentration of 70mg/L, CO 3 2- The concentration is 1.0mM, and the voltage of the anode and the cathode is-1.2V. Nitrate removal rate and N 2 The selectivity is shown in figure 9 of the specification.
The test conditions were: the electrolyte solution was 50mM Na 2 SO 4 Nitrate concentration of 70mg/L, ca 2+ The concentration is 2.0mM, and the voltage of the anode and the cathode is-1.2V. Nitrate removal rate and N 2 The selectivity is shown in the attached figure 10 of the specification.
Example 2
Example 2 only 4mg of the modified Cu-bipy-MOF catalyst was added to the electrode preparation method, and the preparation of the modified Cu-bipy-MOF catalyst and other conditions in the electrode preparation method were consistent with example 1.
Example 3
Example 3 the electrode preparation method was performed with the addition of 16mg of the modified Cu-bipy-MOF catalyst, and the preparation of the modified Cu-bipy-MOF catalyst and other conditions in the electrode preparation method were the same as in example 1.
The electrodes obtained from examples 1 to 3 were subjected to comparative tests:
the test conditions were: the electrolyte solution was 50mM Na 2 SO 4 The nitrate concentration is 70mg/L, the voltage is-1.2V, the anode adopts a Pt electrode, the reference electrode is an Ag/AgCl electrode, and the prepared catalyst electrode is a working electrode. The nitrate removal rate is compared with that of the nitrate removal rate shown in the attached figure 11 in the specification.
From the results of comparative experiments, it is quite unexpected that the electrocatalytic performance of the electrode loaded modified Cu-bipy-MOF catalyst does not have a trend of increasing or decreasing with the increase of the amount of the electrode loaded modified Cu-bipy-MOF catalyst, and the electrocatalytic performance of the electrode loaded modified Cu-bipy-MOF catalyst has a completely different effect trend with the same type of modified Cu-bip-MOF catalyst. By comparison, it is clear that the concentration of the compound is 1cm 2 The electrode piece is loaded with 0.33mg of the modified Cu-bipy-MOF catalyst, so that the best effect can be achieved, and the preparation cost is greatly saved.
Comparative example 1
The comparative example is a modified Cu-MOF catalyst, and the preparation method comprises the following steps:
(1) Weighing 1g of copper nitrate monohydrate and 0.5g of trimesic acid, and uniformly mixing to obtain mixed powder for later use;
(2) Weighing 16.6ml of DMF and ethanol, mixing, and enabling the volume ratio of the two to be 1:1 as solution A;
(3) Slowly adding the A liquid drops into the mixed powder obtained in the step (1) at room temperature, and fully and uniformly mixing to obtain a B liquid;
(4) Transferring the solution B obtained in the step (3) into a 50mL reaction kettle lining, screwing a reaction kettle cover, and reacting in an 85 ℃ thermostat for 12 hours; and after the reaction time is up, filtering, washing and drying to obtain light blue catalyst powder crystals, namely the modified Cu-MOF catalyst.
The modified Cu-MOF catalyst prepared by the method is dispersed in a water body and stands for 3 hours, and obvious sheet-shaped precipitates appear, so that the structure of the modified Cu-MOF catalyst is damaged.
In contrast, the modified Cu-bipy-MOF catalyst prepared in example 1 was dispersed in water and left to stand, and no precipitate appeared in the water after 7 days at normal temperature, which proves that the modified Cu-bipy-MOF catalyst has good water stability.
Example 4
Example 4 is a modified Cu-bipy-MOF catalyst, which is prepared by a process comprising the steps of:
(1) Weighing 0.179g of copper acetate monohydrate, 0.141g of trimesic acid, 0.156g of 2,2' -bipyridyl and 0.080g of sodium hydroxide small particles, and uniformly mixing to obtain mixed powder for later use;
(2) Measuring 15mL of distilled water for later use as solution A;
(3) Slowly adding the A liquid drops into the mixed powder obtained in the step (1) at room temperature, and fully and uniformly mixing to obtain a B liquid;
(4) Transferring the solution B obtained in the step (3) into a 25mL reaction kettle liner, screwing a reaction kettle cover, and then reacting in a constant temperature box at 160 ℃ for 72 hours; and after the reaction time is up, filtering, washing and drying to obtain an indigo catalyst powder crystal, namely the modified Cu-bipy-MOF catalyst.
Example 5
The embodiment provides a Cu-based bipyridyl double-ligand electrocatalyst for removing nitrate in wastewater, and a preparation method thereof comprises the following steps:
(1) Copper salt (cupric chloride) and MOF ligand were selected and weighed to be in a molar ratio of Cu to 2,2' -bipyridine (bipy) and sodium hydroxide (NaOH): bipy: MOF: naOH =2:2:3:6, uniformly mixing to obtain a mixture for later use;
wherein the MOF ligand is trimesic acid;
(2) Measuring distilled water as solution A;
(3) Adding the solution A into the mixture obtained in the step (1), adding 10mg of 2,2' -bipyridine into each ml of the solution A, and fully and uniformly mixing to obtain solution B;
(4) Reacting the solution B obtained in the step (3) for 84h at the temperature of 155 ℃; and after the reaction time is up, filtering, washing and drying to obtain an indigo catalyst powder crystal, namely the modified Cu-bipy-MOF catalyst.
The preparation method of the electrode using the modified Cu-bipy-MOF catalyst prepared by the embodiment mainly comprises the following steps:
weighing a modified Cu-bipy-MOF catalyst and carbon conductive powder, wherein the mass ratio of the modified Cu-bipy-MOF catalyst to the carbon conductive powder is 1.5:1;
(II) preparing ethanol as solution A;
(III) adding a bonding agent (chitosan) into the solution A, wherein the addition amount of the bonding agent is 1% of the volume of the solution A to be used as a solution B;
adding the modified Cu-bipy-MOF catalyst and the carbon conductive powder weighed in the step (I) into the liquid B for mixing, adding 2.5mg of the modified Cu-bipy-MOF catalyst into 1mL of the liquid B, uniformly mixing, and fully dispersing to obtain a mixed suspension;
(V) uniformly dripping the mixed suspension obtained in the step (IV) on two surfaces of a cathode sheet, and obtaining an electrode loaded with the modified Cu-bipy-MOF catalyst after the solvent is completely volatilized; wherein the area of the cathode sheet is controlled to be 1cm 2 1mg of modified Cu-bipy-MOF catalyst was loaded.
Example 6
The embodiment provides a Cu-based bipyridyl double-ligand electrocatalyst for removing nitrate in wastewater, and a preparation method thereof comprises the following steps:
(1) Copper salt (copper nitrate) and MOF ligand were selected and weighed to be mixed with 2,2' -bipyridine (bipy) and sodium hydroxide (NaOH) in a molar ratio of Cu: bipy: MOF: naOH =3:2:3:6, uniformly mixing to obtain a mixture for later use;
wherein the MOF ligand is isophthalic acid;
(2) Measuring distilled water as solution A;
(3) Adding the solution A into the mixture obtained in the step (1), adding 10mg of 2,2' -bipyridine into each ml of the solution A, and fully and uniformly mixing to obtain solution B;
(4) Reacting the solution B obtained in the step (3) for 72 hours at the temperature of 160 ℃; and after the reaction time is up, filtering, washing and drying to obtain an indigo catalyst powder crystal, namely the modified Cu-bipy-MOF catalyst.
The preparation method of the electrode using the modified Cu-bipy-MOF catalyst prepared by the embodiment mainly comprises the following steps:
weighing a modified Cu-bipy-MOF catalyst and carbon conductive powder, wherein the mass ratio of the modified Cu-bipy-MOF catalyst to the carbon conductive powder is 1:1;
(II) preparing methanol as solution A;
(III) adding a bonding agent (Nafion 117 5wt% solution) into the liquid A, wherein the adding amount of the bonding agent is 1% of the volume of the liquid A to obtain a liquid B;
adding the modified Cu-bipy-MOF catalyst and the carbon conductive powder weighed in the step (I) into the liquid B for mixing, adding 2mg of the modified Cu-bipy-MOF catalyst into 1mL of the liquid B, uniformly mixing, and fully dispersing to obtain a mixed suspension;
(V) uniformly dripping the mixed suspension obtained in the step (IV) on two surfaces of a cathode sheet, and obtaining an electrode loaded with the modified Cu-bipy-MOF catalyst after the solvent is completely volatilized; wherein the area of the cathode plate is controlled to be 1cm 2 0.8mg of the modified Cu-bipy-MOF catalyst was loaded.
Example 7
The embodiment provides a Cu-based bipyridyl double-ligand electrocatalyst for removing nitrate in wastewater, and a preparation method thereof comprises the following steps:
(1) Copper acetate monohydrate and MOF ligand were selected and weighed to match the molar ratio of 2,2' -bipyridine (bipy) and sodium hydroxide (NaOH) to Cu: bipy: MOF: naOH =2:2:3:6, uniformly mixing to obtain a mixture for later use;
wherein the MOF ligand is isophthalic acid;
(2) Measuring distilled water as solution A;
(3) Adding the solution A into the mixture obtained in the step (1), adding 11mg of 2,2' -bipyridine into each ml of the solution A, and fully and uniformly mixing to obtain solution B;
(4) Reacting the solution B obtained in the step (3) for 72 hours at the temperature of 165 ℃; and after the reaction time is up, filtering, washing and drying to obtain an indigo catalyst powder crystal, namely the modified Cu-bipy-MOF catalyst.
The preparation method of the electrode using the modified Cu-bipy-MOF catalyst prepared by the embodiment mainly comprises the following steps:
weighing a modified Cu-bipy-MOF catalyst and carbon conductive powder, wherein the mass ratio of the modified Cu-bipy-MOF catalyst to the carbon conductive powder is 1.5:1;
(II) preparing a mixed solution of isopropanol and ethanol as a solution A; wherein the volume ratio of the isopropanol to the ethanol is 1.2:4;
(III) adding a binder into the solution A, wherein the addition amount of the binder is 1% of the volume of the solution A to obtain solution B;
adding the modified Cu-bipy-MOF catalyst and the carbon conductive powder weighed in the step (I) into the liquid B for mixing, adding 2.2mg of the modified Cu-bipy-MOF catalyst into 1mL of the liquid B, uniformly mixing, and fully dispersing to obtain a mixed suspension;
(V) uniformly dripping the mixed suspension obtained in the step (IV) on two surfaces of a cathode sheet, and obtaining an electrode loaded with the modified Cu-bipy-MOF catalyst after the solvent is completely volatilized; wherein the area of the cathode sheet is controlled to be 1cm 2 0.67mg of the modified Cu-bipy-MOF catalyst was loaded.
Claims (10)
1. A preparation method of a Cu-based bipyridyl double-ligand electrocatalyst for removing nitrate in wastewater is characterized by comprising the following steps:
(1) Copper salt and MOF ligand are selected and weighed, and are mixed with 2,2' -bipyridine and sodium hydroxide according to the molar ratio of Cu: bipy: MOF: naOH = (2 to 3): 2:3:6, uniformly mixing to obtain a mixture for later use;
wherein the MOF ligand is trimesic acid or isophthalic acid;
(2) Measuring distilled water as solution A;
(3) Adding the solution A into the mixture obtained in the step (1), adding 10-11 mg of 2,2' -bipyridyl into per ml of the solution A, and fully and uniformly mixing to obtain solution B;
(4) Reacting the solution B obtained in the step (3) at the temperature of 155-165 ℃ for at least 72h; and after the reaction time is up, filtering, washing and drying to obtain an indigo catalyst powder crystal, namely the modified Cu-bipy-MOF catalyst.
2. The method of claim 1, wherein: the copper salt in the step (1) comprises any one of hydrated copper nitrate, hydrated copper acetate and hydrated copper chloride.
3. The method of claim 1, wherein: and (4) reacting the solution B obtained in the step (3) at the temperature of 155-165 ℃ for at least 72h, namely placing the solution B in a closed container for reaction.
4. A method for preparing a Cu-based bipyridine double ligand electrocatalyst for removing nitrate from wastewater as claimed in any one of claims 1 to 3, the resulting modified Cu-bipy-MOF catalyst is prepared.
5. The modified Cu-bipy-MOF catalyst of claim 4 is applied to the technical field of electrocatalysis for water treatment.
6. A preparation method of an electrode applying the modified Cu-bipy-MOF catalyst of claim 4, which is characterized by mainly comprising the following steps:
weighing a modified Cu-bipy-MOF catalyst and carbon conductive powder, wherein the mass ratio of the modified Cu-bipy-MOF catalyst to the carbon conductive powder is (1-1.5): 1;
(II) preparing an organic solvent as solution A;
(III) adding a binder into the solution A, wherein the addition amount of the binder is 1% of the volume of the solution A to obtain solution B;
adding the modified Cu-bipy-MOF catalyst and the carbon conductive powder weighed in the step (I) into the liquid B for mixing, adding 2-2.5 mg of the modified Cu-bipy-MOF catalyst into 1mL of the liquid B, uniformly mixing, and fully dispersing to obtain a mixed suspension;
(V) uniformly dripping the mixed suspension obtained in the step (IV) on two surfaces of a cathode sheet, and obtaining an electrode loaded with the modified Cu-bipy-MOF catalyst after the solvent is completely volatilized; wherein the area of the cathode sheet is controlled to be 1cm 2 0.33-1.33 mg of modified Cu-bipy-MOF catalyst needs to be loaded.
7. The method according to claim 6, wherein: the carbon-based conductive powder in the step (I) comprises any one or more of conductive carbon black powder, conductive graphite powder, chopped carbon fiber powder, carbon nanotube powder and graphene powder.
8. The method according to claim 6, wherein: in the step (II), the organic solvent comprises any one of ethanol, isopropanol and methanol.
9. The method of claim 8, wherein: in the step (II), the organic solvent is a mixed solution of isopropanol and ethanol, wherein the volume ratio of the isopropanol to the ethanol is (1-1.2): 4.
10. the method according to claim 6, wherein: and (V) the cathode plate comprises any one of a carbon paper cathode plate, a carbon felt material cathode plate and a carbon cloth material cathode plate.
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