CN112473716A - Nitrogen-doped mesoporous carbon-based nano material loaded with copper-nickel alloy particles and preparation method and application thereof - Google Patents
Nitrogen-doped mesoporous carbon-based nano material loaded with copper-nickel alloy particles and preparation method and application thereof Download PDFInfo
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- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 56
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 52
- 239000000956 alloy Substances 0.000 title claims abstract description 52
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000002245 particle Substances 0.000 title claims abstract description 51
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 46
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 24
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 22
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005011 phenolic resin Substances 0.000 claims abstract description 18
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 238000007790 scraping Methods 0.000 claims abstract description 6
- 239000002351 wastewater Substances 0.000 claims description 26
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000012691 Cu precursor Substances 0.000 claims description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 229910002482 Cu–Ni Inorganic materials 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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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
- C02F1/46104—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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
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Abstract
The invention provides a nitrogen-doped mesoporous carbon-based nano material loaded with copper-nickel alloy particles, and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing deionized water, ethanol, precursors of copper and nickel, and dicyandiamide; dripping a phenolic resin solution, and then mixing the obtained mixed solution with a template agent; spreading the obtained solution on a culture dish; scraping the dried material of the culture dish by using a blade, and roasting in a nitrogen atmosphere to obtain the nitrogen-doped mesoporous carbon-based material loaded with the copper-nickel alloy particles. The electrode module prepared by using the nitrogen-doped mesoporous carbon-based material loaded with the copper-nickel alloy particles as the catalyst and the Ir-Ru/Ti electrode have good catalysis and selectivity when the electrode module electrocatalysis is carried out on water containing nitrate. Even under a neutral condition, the catalyst can still keep higher degradation efficiency, can effectively remove nitrate in a water body at normal temperature and normal pressure, and has the advantages of high removal efficiency, strong stability, good selectivity and the like.
Description
Technical Field
The invention belongs to the technical field of preparation and application of catalysts for removing nitrate from nitrogen-containing wastewater, and particularly relates to a nitrogen-doped mesoporous carbon-based nano material loaded with copper-nickel alloy particles, and a preparation method and application thereof.
Background
Among the many environmental problems, the most troublesome is undoubtedly the rapid, stable, efficient, low-consumption removal and conversion of nitrate nitrogen from nitrogen-containing wastewater into harmless nitrogen gas. The traditional water body denitrification technology, such as microbial denitrification and chemical denitrification, has certain limitations when being used for water body denitrification, and is difficult to be used for the denitrification treatment of complex water bodies. In addition, a large amount of byproducts are easily generated in the process of removing the nitrate in the water body by the traditional denitrification technology, so that the treatment difficulty is improved, and the treatment cost is increased. As a novel water body denitrification technology, the electrocatalytic denitrification has the characteristics of simple operation, short treatment time, high removal efficiency, high product selectivity and the like. The copper-nickel bimetal has the characteristics of good corrosion resistance, low impedance, strong reducibility and the like. In an actual electrocatalytic denitrification test, the copper-nickel bimetallic electrocatalyst can selectively convert nitrate nitrogen in a water body into ammonia nitrogen in a short time, and finally realizes the harmlessness of nitrate in the water body by combining an anodic oxidation technology method. The nitrogen-doped mesoporous carbon-based material loaded with the copper-nickel alloy particles prepared by the soft template method can be used as a catalyst to effectively remove nitrate in water, wherein the nitrogen-doped mesoporous carbon-based skeleton is used as a carrier, and the copper-nickel alloy is used as a catalytic active component.
Disclosure of Invention
Aiming at the defects, the invention provides the nitrogen-doped mesoporous carbon-based material used as the catalyst for loading the copper-nickel alloy particles, which has high removal efficiency, strong removal capability and good selectivity on nitrate nitrogen in nitrogen-containing wastewater, and the preparation method and the application thereof.
The invention provides the following technical scheme: the preparation method of the nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles comprises the following steps of:
1) mixing a copper precursor, a nickel precursor and dicyandiamide according to a proportion, and dissolving the mixture in a certain amount of mixed solution of deionized water and ethanol; the copper precursor is CuSO4·5H2O, precursor of nickel is NiCl2·5H2O, the mass ratio of the copper precursor to the nickel precursor to the dicyandiamide is 0.024 g: 0.01 g: 0.001g to 0.168g, wherein the volume ratio of the deionized water to the ethanol in the mixed solution of the deionized water and the ethanol is 10ml to 8ml, and the mixed solution of the deionized water and the ethanol is 18 ml;
2) dropwise adding a low molecular weight phenolic resin solution serving as a carbon source into the mixed solution obtained in the step 1), keeping the temperature at 40 ℃ during mixing, stirring by using a magnetic stirrer, and keeping the rotating speed at 200-300 r/min until the mixture is uniformly mixed;
3) mixing 1g of surfactant F127 serving as a template agent with 12ml of ethanol, heating the obtained solution to 40 ℃ in a water bath heating mode, then dropwise adding the solution into the mixed solution obtained in the step 2), and keeping the rotating speed of a stirrer at 200-300 r/min and the temperature at 40 ℃ until the solution is uniformly stirred;
4) laying the solution obtained in the step 3) on a conventional culture dish, standing and drying;
5) scraping the material dried by the culture dish in the step 4) by using a blade, placing the material in a muffle furnace in a nitrogen atmosphere for calcining to obtain the nitrogen-doped mesoporous carbon-based material loaded with the copper-nickel alloy particles
Further, the mass fraction of the phenolic resin in the phenolic resin solution in the step 2) is 20%.
Further, the amount of the phenolic resin solution added dropwise in the step 2) was 5.0 g.
Further, the culture dish in the step 4) is kept still for 8 hours at room temperature, and the culture dish is dried for 24 hours in a constant-temperature drying oven at 100 ℃.
Further, the calcination condition in the step 5) is to control the temperature rise rate to be 1 ℃/min, heat the mixture to 600 ℃, keep the temperature for 5h, and purge the mixture with nitrogen for 1h before the calcination starts so as to discharge air in the pipe.
The application also provides the nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles, which is prepared by the preparation method, wherein the nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles has an obvious mesoporous morphology, the pore diameter of mesopores is 4-5 nm, and copper-nickel nano particles are uniformly dispersed on the mesoporous carrier.
The application also provides an application of the nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles in treating nitrate in nitrogen-containing wastewater, which comprises the following steps: grinding the obtained nitrogen-doped mesoporous carbon-based material loaded with the copper-nickel alloy particles into powder by using a quartz mortar, coating the ground nitrogen-doped mesoporous carbon-based nano material powder loaded with the copper-nickel alloy particles on foamed nickel of 3cm multiplied by 4cm to serve as a working electrode, taking an Ir-Ru/Ti electrode of 3cm multiplied by 4cm as an auxiliary electrode and taking a saturated calomel electrode as a reference electrode, jointly placing the electrode and the reference electrode in 150mL of nitrogen-containing wastewater containing nitrate to form a three-electrode system, and carrying out electrocatalytic denitrification reaction for 7 hours at room temperature to remove the nitrate in the nitrogen-containing wastewater.
Further, the method for coating the grinded nitrogen-doped mesoporous carbon-based nano material powder loaded with the copper-nickel alloy particles on the foamed nickel comprises the following steps:
s1: dissolving a certain amount of polyvinylidene fluoride into N-methyl pyrrolidone to prepare a polyvinylidene fluoride adhesive with the mass fraction of 10%;
s2: putting 48mg of the ground nitrogen-doped mesoporous carbon-based nano material powder loaded with copper-nickel alloy particles, 6mg of acetylene black and 600 μ L of the polyvinylidene fluoride binder prepared in the step S1 into a quartz mortar, mixing and grinding uniformly, and then coating the mixture on foamed nickel with the size of 3cm multiplied by 4 cm; placing the coated foamed nickel into a blast drying oven, and drying for 6h at 80 ℃; then transferring the mixture into a vacuum drying oven, and drying the mixture for 12 hours at 120 ℃;
s3: and tabletting the dried foamed nickel to obtain the working electrode serving as the cathode.
Further, the concentration of nitrate nitrogen in the nitrogen-containing wastewater is 30mg/L, and the pH value is kept to be 7 in the electrocatalytic denitrification reaction process.
Further, the voltage of the working electrode is-1.8V, and the content of NaCl in the nitrogen-containing wastewater solution is 1.0 g/L.
Drawings
The invention will be described in more detail hereinafter on the basis of embodiments and with reference to the accompanying drawings. Wherein:
FIG. 1 is a TEM photograph of the nitrogen-doped mesoporous carbon-based nanomaterial loaded with Cu-Ni alloy particles in example 1 of the present invention;
FIG. 2 is a TEM photograph of the nitrogen-doped mesoporous carbon-based nanomaterial loaded with the Cu-Ni alloy particles in example 2 of the present invention;
FIG. 3 is a TEM photograph of the nitrogen-doped mesoporous carbon-based nanomaterial loaded with the Cu-Ni alloy particles in example 3 of the present invention;
detailed description of the preferred embodiments
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a nitrogen-doped mesoporous carbon-based nano material loaded with copper-nickel alloy particles and a preparation method thereof, and the method of the embodiment comprises the following steps:
(1) collecting 0.024g of CuSO4·5H2O, 0.01g of NiCl2·5H2O and 0.001g of dicyandiamide are put into a beaker, 10ml of deionized water and 8ml of ethanol are added into the beaker, and the mixture is completely dissolved for later use;
(2) preparing 20 mass percent of phenolic resin, dropwise adding 5.0g of the prepared phenolic resin into the solution obtained in the step (1), keeping the temperature at 40 ℃ during mixing, stirring by using a magnetic stirrer, and keeping the rotating speed at 200r/min until the mixture is uniformly mixed. The specific operation of preparing 20% mass fraction of phenolic resin is as follows: first, 24g of phenol was added to a single-neck flask, and heated in a constant-temperature water bath at 42 ℃ until it was completely melted. Meanwhile, NaOH and deionized water are used for preparing a sodium hydroxide solution with the mass fraction of 20%. 5g of a 20 wt% NaOH solution were added to the liquid phenol while stirring at a constant temperature of 42 ℃. After stirring for 10min, 40.8g of 37% formalin solution was added dropwise and stirring was continued for 0.5 h. And then, raising the temperature of the water bath kettle to 72 ℃ for reaction for 1h, after the reaction is finished, removing the mixed solution out of the water bath kettle, and adjusting the pH value of the mixed solution to be neutral by using 2mol/L and 0.6mol/L hydrochloric acid solution after the mixed solution is naturally cooled to room temperature. Then, the mixed solution was subjected to rotary evaporation using a rotary evaporator for about 2 hours until the water was completely removed. And finally, adding a certain mass of absolute ethyl alcohol into the obtained mixed solution, preparing the absolute ethyl alcohol into a 20 wt% phenolic resin ethanol solution, and storing the solution at 0 ℃ in a dark place. (ii) a
(3) Putting 1g of surfactant F127 serving as a template agent into another beaker, adding 12ml of ethanol for dissolving, dropwise adding the obtained solution into the solution obtained in the step (2) at 40 ℃, keeping the rotating speed of a stirrer at 200r/min, and then stirring for 1 h;
(4) spreading the solution obtained in the step (3) on a culture dish, placing the culture dish for 8 hours at room temperature, and then placing the culture dish in a constant-temperature drying oven for drying for 24 hours at 100 ℃;
(5) scraping the dried material of the culture dish in the step (4) by using a blade, placing the material in a muffle furnace in nitrogen atmosphere for calcining, heating the material at a heating rate of 1 ℃/min to 600 ℃, and keeping the temperature for 5 hours to obtain the nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles shown in the figure 1, wherein the obtained nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles has an obvious mesoporous morphology, the pore diameter of the mesopores is 4nm, and the copper-nickel nano particles are uniformly dispersed on a mesoporous carrier.
The embodiment also provides an application of the obtained nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles in treatment of nitrate in nitrogen-containing wastewater, which comprises the following steps:
s1: dissolving a certain amount of polyvinylidene fluoride into N-methyl pyrrolidone to prepare a polyvinylidene fluoride adhesive with the mass fraction of 10%;
s2: putting 48mg of the nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles obtained in the step (5), 6mg of acetylene black and 600L of the polyvinylidene fluoride binder prepared in the step S1 into a quartz mortar, mixing and grinding uniformly, and then coating the mixture on foamed nickel with the size of 3cm multiplied by 4 cm; placing the coated foamed nickel into a blast drying oven, and drying for 6h at 80 ℃; then transferring the mixture into a vacuum drying oven, and drying the mixture for 12 hours at 120 ℃;
s3: tabletting the dried foamed nickel to obtain a working electrode serving as a cathode; an Ir-Ru/Ti electrode is taken as an auxiliary electrode, a saturated calomel electrode is taken as a reference electrode, and the Ir-Ru/Ti electrode and the saturated calomel electrode are placed together in nitrate nitrogen NO with the volume of 150ml and the concentration of 30mg/L3 -In the nitrogen-containing wastewater containing-N, the NaCl content in the nitrogen-containing wastewater solution was 1.0g/L, a voltage of-1.8V was applied to the working electrode, the reaction was carried out for 7 hours, and then the nitrate removal rate was measured, and the results are shown in Table 1.
Example 2
The embodiment provides a nitrogen-doped mesoporous carbon-based nano material loaded with copper-nickel alloy particles and a preparation method thereof, and the method of the embodiment comprises the following steps:
(1) 0.024g of CuSO is taken4·5H2O、0.01gNiCl2·5H2O and 0.084g of dicyandiamide are put into a beaker, 10ml of deionized water and 8ml of ethanol are added into the beaker, and the mixture is completely dissolved for later use;
(2) preparing 20 wt% of phenolic resin, dropwise adding 5.0g of the prepared phenolic resin into the solution obtained in the step (1), keeping the temperature at 40 ℃ during mixing, stirring by using a magnetic stirrer, and keeping the rotating speed at 250r/min until the mixture is uniformly mixed;
(3) putting 1g of surfactant F127 serving as a template agent into another beaker, adding 12ml of ethanol for dissolving, dropwise adding the obtained solution into the solution obtained in the step (2) at 40 ℃, keeping the rotating speed of a stirrer at 250r/min, and then stirring for 1 h;
(4) spreading the solution obtained in the step (3) on a culture dish, placing the culture dish for 8 hours at room temperature, and then placing the culture dish in a constant-temperature drying oven for drying for 24 hours at 100 ℃;
(5) scraping the dried material of the culture dish in the step (4) by using a blade, placing the material in a muffle furnace in nitrogen atmosphere for calcining, heating the material at a heating rate of 1 ℃/min to 600 ℃, and keeping the temperature for 5 hours to obtain the nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles shown in the figure 2, wherein the obtained nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles has an obvious mesoporous morphology, the pore diameter of the mesopores is 4.5nm, and the copper-nickel nano particles are uniformly dispersed on a mesoporous carrier.
The embodiment also provides an application of the obtained nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles in the treatment of nitrate in nitrogen-containing wastewater, the same method as that in embodiment 1 is adopted to coat the nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles obtained in the embodiment on foamed nickel with the size of 3cm × 4cm to obtain a working electrode serving as a cathode, an Ir-Ru/Ti electrode is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and the three electrodes are placed in a nitrogen NO state containing nitrate with the concentration of 30mg/L and the volume of 150ml3 -In the nitrogen-containing wastewater containing-N, the NaCl content in the nitrogen-containing wastewater solution was 1.0g/L, a voltage of-1.8V was applied to the working electrode, the reaction was carried out for 7 hours, and then the nitrate removal rate was measured, and the results are shown in Table 1.
Example 3
The embodiment provides a nitrogen-doped mesoporous carbon-based nano material loaded with copper-nickel alloy particles and a preparation method thereof, and the method of the embodiment comprises the following steps:
(1) 0.024g of CuSO is taken4·5H2O、0.01gNiCl2·5H2O and 0.168g of cyanamide are put into a beaker, 10ml of deionized water and 8ml of ethanol are added into the beaker, and the mixture is completely dissolved for later use;
(2) preparing a phenolic resin solution with the mass fraction of 20% of phenolic resin, dropwise adding 5.0g of the prepared phenolic resin solution into the solution obtained in the step (1), keeping the temperature at 40 ℃ during mixing, stirring by using a magnetic stirrer, and keeping the rotating speed at 300r/min until the mixture is uniformly mixed;
(3) putting 1g of surfactant F127 serving as a template agent into another beaker, adding 12ml of ethanol for dissolving, dropwise adding the obtained solution into the solution obtained in the step (2) at 40 ℃, keeping the rotating speed of a stirrer at 300r/min, and then stirring for 1 h;
(4) spreading the solution obtained in the step (3) on a culture dish, placing the culture dish for 8 hours at room temperature, and then placing the culture dish in a constant-temperature drying oven for drying for 24 hours at 100 ℃;
(5) scraping the dried material of the culture dish in the step (4) by using a blade, placing the material in a muffle furnace in nitrogen atmosphere for calcining, heating the material at a heating rate of 1 ℃/min to 600 ℃, and keeping the temperature for 5 hours to obtain the nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles shown in the figure 3, wherein the obtained nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles has an obvious mesoporous morphology, the pore diameter of the mesopores is 5nm, and the copper-nickel nano particles are uniformly dispersed on a mesoporous carrier.
The embodiment also provides an application of the obtained nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles in the treatment of nitrate in nitrogen-containing wastewater, the same method as that in embodiment 1 is adopted to coat the nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles obtained in the embodiment on foamed nickel with the size of 3cm × 4cm to obtain a working electrode serving as a cathode, an Ir-Ru/Ti electrode is used as an auxiliary electrode, a saturated calomel electrode is used as a reference electrode, and the three electrodes are placed in a nitrogen NO state containing nitrate with the concentration of 30mg/L and the volume of 150ml3 -In the nitrogen-containing wastewater containing-N, the NaCl content in the nitrogen-containing wastewater solution was 1.0g/L, a voltage of-1.8V was applied to the working electrode, the reaction was carried out for 7 hours, and then the nitrate removal rate was measured, and the results are shown in Table 1.
Table 1 materials prepared in examples 1-3 and nitrate removal rates in wastewater containing nitrate nitrogen
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. The preparation method of the nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles is characterized by comprising the following steps of:
1) mixing a copper precursor, a nickel precursor and dicyandiamide according to a proportion, and dissolving the mixture in a certain amount of mixed solution of deionized water and ethanol; the copper precursor is CuSO4·5H2O, precursor of nickel is NiCl2·5H2O, the mass ratio of the copper precursor to the nickel precursor to the dicyandiamide is 0.024 g: 0.01 g: 0.001g to 0.168g, wherein the volume ratio of the deionized water to the ethanol in the mixed solution of the deionized water and the ethanol is 10ml to 8ml, and the mixed solution of the deionized water and the ethanol is 18 ml;
2) dropwise adding a low molecular weight phenolic resin solution serving as a carbon source into the mixed solution obtained in the step 1), keeping the temperature at 40 ℃ during mixing, stirring by using a magnetic stirrer, and keeping the rotating speed at 200-300 r/min until the mixture is uniformly mixed;
3) mixing 1g of surfactant F127 serving as a template agent with 12ml of ethanol, heating the obtained solution to 40 ℃ in a water bath heating mode, then dropwise adding the solution into the mixed solution obtained in the step 2), and keeping the rotating speed of a stirrer at 200-300 r/min and the temperature at 40 ℃ until the solution is uniformly stirred;
4) laying the solution obtained in the step 3) on a conventional culture dish, standing and drying;
5) scraping the material dried by the culture dish in the step 4) by using a blade, and calcining the material in a muffle furnace in nitrogen atmosphere to obtain the nitrogen-doped mesoporous carbon-based material loaded with the copper-nickel alloy particles.
2. The method for preparing the nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles according to claim 1, wherein the mass fraction of the phenolic resin in the phenolic resin solution in the step 2) is 20%.
3. The method for preparing the nitrogen-doped mesoporous carbon-based nanomaterial carrying copper-nickel alloy particles according to claim 1, wherein the dripping amount of the phenolic resin solution in the step 2) is 5.0 g.
4. The method for preparing the nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles according to claim 1, wherein the culture dish in the step 4) is kept still for 8 hours at room temperature, and the culture dish is dried in a constant-temperature drying oven at 100 ℃ for 24 hours.
5. The method for preparing the nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles according to claim 1, wherein the calcination conditions in the step 5) are that the temperature rise rate is controlled to be 1 ℃/min, the temperature is raised to 600 ℃, the temperature is kept for 5h, and nitrogen is used for purging for 1h before the calcination starts so as to exhaust air in the tube.
6. The nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles obtained by the preparation method according to any one of claims 1 to 5, wherein the nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles has an obvious mesoporous morphology, the pore diameter of the mesopores is 4nm to 5nm, and copper-nickel nanoparticles are uniformly dispersed on the mesoporous carrier.
7. The application of the nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles according to claim 6 in treatment of nitrate in nitrogen-containing wastewater is characterized by comprising the following steps: grinding the obtained nitrogen-doped mesoporous carbon-based material loaded with the copper-nickel alloy particles into powder by using a quartz mortar, coating the ground nitrogen-doped mesoporous carbon-based nano material powder loaded with the copper-nickel alloy particles on foamed nickel of 3cm multiplied by 4cm to serve as a working electrode, taking an Ir-Ru/Ti electrode of 3cm multiplied by 4cm as an auxiliary electrode and taking a saturated calomel electrode as a reference electrode, jointly placing the electrode and the reference electrode in 150mL of nitrogen-containing wastewater containing nitrate to form a three-electrode system, and carrying out electrocatalytic denitrification reaction for 7 hours at room temperature to remove the nitrate in the nitrogen-containing wastewater.
8. The application of the nitrogen-doped mesoporous carbon-based nano material loaded with the copper-nickel alloy particles in treating nitrate in nitrogen-containing wastewater according to claim 7, wherein the method for coating the grinded nitrogen-doped mesoporous carbon-based nano material powder loaded with the copper-nickel alloy particles on foamed nickel comprises the following steps:
s1: dissolving a certain amount of polyvinylidene fluoride into N-methyl pyrrolidone to prepare a polyvinylidene fluoride adhesive with the mass fraction of 10%;
s2: putting 48mg of the ground nitrogen-doped mesoporous carbon-based nano material powder loaded with copper-nickel alloy particles, 6mg of acetylene black and 600 μ L of the polyvinylidene fluoride binder prepared in the step S1 into a quartz mortar, mixing and grinding uniformly, and then coating the mixture on foamed nickel with the size of 3cm multiplied by 4 cm; placing the coated foamed nickel into a blast drying oven, and drying for 6h at 80 ℃; then transferring the mixture into a vacuum drying oven, and drying the mixture for 12 hours at 120 ℃;
s3: and tabletting the dried foamed nickel to obtain the working electrode serving as the cathode.
9. The application of the nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles of claim 7 in treatment of nitrate in nitrogen-containing wastewater, wherein the concentration of nitrate-form nitrogen in the nitrogen-containing wastewater is 30mg/L, and the pH is kept at 7 during the electrocatalytic denitrification reaction.
10. The application of the nitrogen-doped mesoporous carbon-based nanomaterial loaded with copper-nickel alloy particles of claim 7 to treatment of nitrate in nitrogen-containing wastewater, wherein the voltage of the working electrode is-1.8V, and the content of NaCl in the nitrogen-containing wastewater solution is 1.0 g/L.
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