CN112266056A - Solid-state electrode and preparation method and application thereof - Google Patents
Solid-state electrode and preparation method and application thereof Download PDFInfo
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- CN112266056A CN112266056A CN202011154130.2A CN202011154130A CN112266056A CN 112266056 A CN112266056 A CN 112266056A CN 202011154130 A CN202011154130 A CN 202011154130A CN 112266056 A CN112266056 A CN 112266056A
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- metal oxide
- urea
- layered double
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 124
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000004202 carbamide Substances 0.000 claims abstract description 65
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 59
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 29
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 11
- 239000006260 foam Substances 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- SWCIQHXIXUMHKA-UHFFFAOYSA-N aluminum;trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SWCIQHXIXUMHKA-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 238000002848 electrochemical method Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims 1
- 229940044175 cobalt sulfate Drugs 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 20
- 238000007599 discharging Methods 0.000 abstract description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 abstract description 10
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 abstract description 8
- 235000013877 carbamide Nutrition 0.000 description 59
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 9
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002798 spectrophotometry method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical group [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Chemical group 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical group [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 210000003456 pulmonary alveoli Anatomy 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
Abstract
The invention provides a solid electrode and a preparation method and application thereof, wherein the solid electrode comprises foamed nickel and a composite material layer positioned on the surface of the foamed nickel, the composite material layer is a composite material layer containing layered double-metal oxide, and the layered double-metal oxide is a layered double-metal oxide containing nickel and cobalt at the same time or a layered double-metal oxide containing nickel and aluminum at the same time; the composite material layer is a layered double-metal oxide containing nickel and cobalt or a layered double-metal oxide containing nickel and aluminum, so that the solid-state electrode has good circulation stability, can be charged and discharged for many times in alkali liquor, and can keep high electric quantity; when the three-electrode system prepared by the solid electrode is used for treating wastewater containing urea, the urea can be degraded to generate nitrogen and carbon dioxide without generating ammonia, and the three-electrode system can be repeatedly charged and discharged, so that the urea in the wastewater can be degraded to a greater extent through repeated charging and discharging.
Description
Technical Field
The invention belongs to the field of electrochemistry, and relates to a solid electrode and a preparation method and application thereof.
Background
Urea, also known as carbamide (carbomide), is an organic compound composed of carbon, nitrogen, oxygen, and hydrogen. Urea is readily soluble in water and can decompose in water to form ammonia, which can be harmful to humans and the environment when the concentration of ammonia is too high.
In addition, urea is a pollutant, and due to the characteristic of being easily soluble in water, the urea can permeate into soil along with industrial wastewater to pollute underground water, and if the underground water with the urea is drunk by a human body living object and exceeds an absorbable standard, the underground water can damage organs such as liver, kidney, alveolus and the like of a human body, so that the health of the human body is threatened.
CN108474281A provides a reducing agent supply system and a control method thereof, which can control a heating system to convert urea into nitrogen oxide, thereby achieving the effect of decomposing urea, but the effect needs to be performed at a higher temperature, and byproducts are easily generated, which is not beneficial for industrial application.
In addition, in the prior art, urea degradation is carried out by other methods, such as a biodegradation method, urea is removed by nitrification or denitrification of microorganisms, but the method has high requirements on environment, large influence factors of the environment and poor repeatability.
Therefore, it is necessary to provide a method for removing urea from water, which is environmentally friendly and stable.
Disclosure of Invention
The invention aims to provide a solid electrode and a preparation method and application thereof, wherein the solid electrode comprises foamed nickel and a composite material layer positioned on the surface of the foamed nickel, and the composite material layer is a layered double-metal oxide containing nickel and cobalt or a layered double-metal oxide containing nickel and aluminum at the same time, so that the solid electrode has better circulation stability, can be charged and discharged in alkali liquor for multiple times and can keep higher electric quantity; when the three-electrode system prepared by the solid electrode is used for treating wastewater containing urea, the urea can be degraded to generate nitrogen and carbon dioxide without generating ammonia, and the three-electrode system can be repeatedly charged and discharged, so that the urea in the wastewater can be degraded to a greater extent through repeated charging and discharging.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide a solid-state electrode comprising nickel foam and a composite material layer on the surface of the nickel foam, wherein the composite material layer is a composite material layer comprising a layered double oxide, and the layered double oxide is a layered double oxide containing both nickel and cobalt or a layered double oxide containing both nickel and aluminum.
The solid electrode comprises foamed nickel and a composite material layer positioned on the surface of the foamed nickel, wherein the composite material layer is a layered double-metal oxide containing nickel and cobalt simultaneously or a layered double-metal oxide containing nickel and aluminum simultaneously, so that the solid electrode has better circulation stability, can be charged and discharged for many times in alkali liquor, and can keep higher electric quantity.
When the three-electrode system is used for treating wastewater containing urea, the urea can be degraded to generate nitrogen and carbon dioxide without generating ammonia, and the three-electrode system can be repeatedly charged and discharged, and is expected to degrade the urea in the wastewater to a greater extent through repeated charging and discharging.
In the present invention, the composite material layer further includes a conductive agent and a binder.
The conductive agent plays a role in conducting electricity, and the binder plays a role in binding, so that the composite material layer formed by mixing the conductive agent, the binder and the layered metal oxide is fixed on the surface of the foamed nickel, and the composite material layer has high electrochemical activity.
The specific types of the conductive agent and the binder are not limited, and can be adjusted by a person skilled in the art according to actual needs, wherein the conductive agent is preferably acetylene black, and the binder is preferably polyvinylidene fluoride.
Preferably, the conductive agent is added in an amount of 1.5 to 3g (e.g., 1.5g, 1.8g, 2g, 2.2g, 2.5g, 2.8g, 3g, etc.) and the binder is added in an amount of 0.8 to 1.2g (e.g., 0.8g, 0.85g, 0.9g, 0.95g, 1g, 1.05g, 1.1g, 1.15g, 1.2g, etc.) based on the amount of the layered metal oxide added being 6 to 8g (e.g., 6g, 6.2g, 6.5g, 6.7g, 7g, 7.2g, 7.5g, 7.7g, 8g, etc.).
It is a second object of the present invention to provide a method for producing a solid-state electrode according to the first object, the method comprising: and (2) placing the layered bimetal oxide, the conductive agent and the binder into a solvent, mixing to obtain slurry, then coating the slurry on the surface of the nickel foam, and curing to obtain the solid electrode.
In the invention, the preparation method of the solid electrode is simple, the raw materials are easy to obtain, the price is low, and the method is easy to realize.
In the present invention, the preparation method of the layered metal oxide comprises: adding the mixed solution of the nickel source and the metal source into alkali liquor, mixing, separating to obtain a precipitate, and freeze-drying the precipitate to obtain the layered double-metal oxide.
Preferably, the total concentration of nickel ions and metal ions in the mixed solution is 1-1.5M, such as 1M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M, etc.
Preferably, the nickel source comprises any one of nickel nitrate hexahydrate, nickel nitrate, nickel chloride, nickel sulfate or nickel acetate or a combination of at least two of them.
Preferably, the metal source comprises a cobalt source or an aluminum source.
Preferably, the cobalt source comprises any one of cobalt nitrate hexahydrate, cobalt nitrate, cobalt sulphate or cobalt acetate or a combination of at least two of the foregoing.
Preferably, the aluminium source comprises any one or a combination of at least two of aluminium nitrate nonahydrate, aluminium nitrate or aluminium chloride.
Preferably, the lye comprises a sodium hydroxide solution and/or a potassium hydroxide solution.
Preferably, the concentration of the lye is 1-3M, such as 1M, 1.2M, 1.5M, 1.7M, 2M, 2.2M, 2.5M, 2.7M, 3M and the like.
Preferably, the means of separation is centrifugation.
The centrifugation is adopted in the invention only for separation, the specific speed and time of the centrifugation are not specifically limited, and the skilled person can adjust the centrifugation according to actual needs, wherein the higher centrifugation speed corresponds to shorter centrifugation time, and the lower centrifugation speed corresponds to longer centrifugation time.
Preferably, the preparation method further comprises washing the separated precipitate with ultrapure water for 3-5 times, such as 3 times, 4 times or 5 times.
Preferably, the temperature of the freeze drying is-40 to-10 ℃, such as-40 ℃, -35 ℃, -30 ℃, -25 ℃, -20 ℃, -15 ℃, -10 ℃ and the like, and the time of the freeze drying is 18 to 24 hours, such as 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours and the like.
Preferably, the solvent comprises azomethylpyrrolidone.
Preferably, the mixing is performed under stirring for a period of time of 5-10min, e.g. 5min, 6min, 7min, 8min, 9min, 10min, etc.
Preferably, the curing mode is natural airing.
Preferably, the preparation method further comprises the step of drying the cured product obtained after curing in vacuum.
Preferably, the vacuum degree of the vacuum drying is-0.2 to-0.1 MPa (for example, -0.2MPa, -0.19MPa, -0.18MPa, -0.17MPa, -0.16MPa, -0.15MPa, -0.14MPa, -0.13MPa, -0.12MPa, -0.11MPa, -0.1MPa, etc.), the temperature of the vacuum drying is 60 to 80 ℃ (for example, 60 ℃, 62 ℃, 65 ℃, 67 ℃, 70 ℃, 72 ℃, 75 ℃, 77 ℃, 80 ℃, etc.), and the time of the vacuum drying is 12 to 24 hours (for example, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, etc.).
A third object of the present invention is to provide a three-electrode system comprising a working electrode, a reference electrode and a counter electrode, the working electrode being the solid-state electrode of one of the objects.
Preferably, the reference electrode is an Ag/AgCl electrode.
Preferably, the counter electrode is foamed nickel, and the size of the foamed nickel is the same as that of the foamed nickel in the working electrode.
It is a fourth object of the present invention to provide an electrochemical sensor comprising the three-electrode system described in the third object.
The fifth purpose of the invention is to provide the application of the electrochemical sensor in the fourth purpose in treating the urea-containing wastewater.
Preferably, the application comprises: the working electrode is charged to reach a constant potential by adopting an electrochemical method, and then is placed in the urea solution for natural discharge, thereby achieving the effect of degrading urea.
Compared with the prior art, the invention has the following beneficial effects:
the solid electrode comprises foamed nickel and a composite material layer positioned on the surface of the foamed nickel, wherein the composite material layer is a layered double-metal oxide containing nickel and cobalt simultaneously or a layered double-metal oxide containing nickel and aluminum simultaneously, so that the solid electrode has better circulation stability, can be charged and discharged for many times in alkali liquor, and can keep higher electric quantity; when the three-electrode system prepared by the solid electrode is used for treating wastewater containing urea, the urea can be degraded to generate nitrogen and carbon dioxide without generating ammonia, and the three-electrode system can be repeatedly charged and discharged, so that the urea in the wastewater can be degraded to a greater extent through repeated charging and discharging.
Drawings
FIG. 1 is a transmission electron micrograph of a layered bimetallic oxide containing nickel and cobalt prepared according to example 1;
fig. 2 is an enlarged view of fig. 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a solid-state electrode, which comprises the following steps:
(1) mixing Ni (NO) and Co at a molar ratio of 1:13)2·6H2O and Co (NO)3)2·6H2Dissolving O in ultrapure water to form 50mL of solution with the total metal ion concentration of 1.2M, adding 50mL of 2M KOH solution into the solution, violently mixing for 1h, centrifuging to obtain a precipitate, centrifuging and washing the precipitate for 5 times, and freeze-drying at-30 ℃ for 18h to obtain a layered double metal oxide containing nickel and cobalt;
(2) mixing the layered double-metal oxide containing nickel and cobalt obtained in the step (1), acetylene black and polyvinylidene fluoride (purchased from Arkema France) according to the mass ratio of 7:2:1, and then adding N-methyl pyrrolidone for mixing to form slurry;
(3) and (3) coating the slurry obtained in the step (2) on 5 cm-1.6 mm nickel foam (purchased from Kagay electronics Co., Ltd., Kun mountain) for natural drying, then placing the dried slurry in a roller press for compressing to 200 micrometers, and then placing the pressed slurry in a vacuum drying oven for drying at 70 ℃ for 12 hours to obtain the solid electrode.
The prepared solid electrode is used as a working electrode, the reference electrode is an Ag/AgCl electrode, the counter electrode is foamed nickel with the same size as nickel foam adopted by the solid electrode, and the electrolyte is potassium hydroxide solution with the concentration of 1M to form a three-electrode system.
Charging the assembled three-electrode system to a constant voltage, then placing the three-electrode system in 50mL of 0.1M urea solution to enable the three-electrode system to naturally discharge, observing that a large number of bubbles exist on the surface of the three-electrode system, and taking the three-electrode system out of the urea solution when the bubbles are not observed any more to finish one-time charging and discharging; the charging and discharging process is repeated for 9 times, the concentration of nitrogen in the urea solution is detected, and the result shows that the degradation rate of the urea is 12.27 percent when the concentration of the nitrogen in the urea solution is reduced from 261.18mg/L to 229.13 mg/L.
And (3) testing the ammonia nitrogen concentration before and after the urea solution is decomposed by adopting a nano reagent spectrophotometry, and finding that no ammonia nitrogen is generated, which indicates that the urea is not hydrolyzed.
The gas generated in the charging and discharging process of 10 microliter is absorbed by an injector and detected by gas chromatography, and the detection result shows that the generated gas is nitrogen and carbon dioxide, which indicates that ammonia is not generated in the degradation process of urea.
Fig. 1 is a transmission electron microscope of the layered double oxide containing nickel and cobalt prepared in step (1), and fig. 2 is an enlarged view of fig. 1, and it can be seen from fig. 1 and 2 that the double oxide has a layered structure.
Example 2
The embodiment provides a preparation method of a solid-state electrode, which comprises the following steps:
(1) mixing Ni (NO) and Co at a molar ratio of 1:13)2·6H2O and Co (NO)3)2·6H2Dissolving O in ultrapure water to form 60mL of solution with the total metal ion concentration of 1M, adding 100mL of 1M KOH solution into the solution, violently mixing for 3h, centrifuging to obtain a precipitate, centrifuging and washing the precipitate for 3 times, and freeze-drying at-30 ℃ for 24h to obtain a layered double-metal oxide containing nickel and cobalt;
(2) mixing the layered double-metal oxide containing nickel and cobalt obtained in the step (1), acetylene black and polyvinylidene fluoride (purchased from Arkema France) according to the mass ratio of 6:3:0.8, and then adding N-methyl pyrrolidone for mixing to form slurry;
(3) and (3) coating the slurry obtained in the step (2) on 5 cm-1.6 mm nickel foam (purchased from Kagay electronics Co., Ltd., Kun mountain) for natural drying, then placing the dried slurry in a roller press for compressing to 200 micrometers, and then placing the pressed slurry in a vacuum drying oven for drying at 60 ℃ for 24 hours to obtain the solid electrode.
The prepared solid electrode is used as a working electrode, the reference electrode is an Ag/AgCl electrode, the counter electrode is foamed nickel with the same size as nickel foam adopted by the solid electrode, and the electrolyte is potassium hydroxide solution with the concentration of 1M to form a three-electrode system.
Charging the assembled three-electrode system to a constant voltage, then placing the three-electrode system in 50mL of 0.1M urea solution to enable the three-electrode system to naturally discharge, observing that a large number of bubbles exist on the surface of the three-electrode system, and taking the three-electrode system out of the urea solution when the bubbles are not observed any more to finish one-time charging and discharging; the charging and discharging process is repeated for 9 times, the concentration of nitrogen in the urea solution is detected, and the result shows that the degradation rate of the urea is 13.81 percent when the concentration of the nitrogen in the urea solution is reduced from 261.18mg/L to 225.11 mg/L.
And (3) testing the ammonia nitrogen concentration before and after the urea solution is decomposed by adopting a nano reagent spectrophotometry, and finding that no ammonia nitrogen is generated, which indicates that the urea is not hydrolyzed.
The gas generated in the charging and discharging process of 10 microliter is absorbed by an injector and detected by gas chromatography, and the detection result shows that the generated gas is nitrogen and carbon dioxide, which indicates that ammonia is not generated in the degradation process of urea.
Example 3
The embodiment provides a preparation method of a solid-state electrode, which comprises the following steps:
(1) mixing Ni (NO) and Co at a molar ratio of 1:13)2·6H2O and Co (NO)3)2·6H2Dissolving O in ultrapure water to form 40mL of solution with the total metal ion concentration of 1.5M, adding 50mL of 3M KOH solution into the solution, violently mixing for 5h, centrifuging to obtain a precipitate, centrifuging and washing the precipitate for 4 times, and freeze-drying at-40 ℃ for 18h to obtain a layered double metal oxide containing nickel and cobalt;
(2) mixing the layered double metal oxide containing nickel and cobalt obtained in the step (1), acetylene black and polyvinylidene fluoride (purchased from Arkema France) according to the mass ratio of 8:1.5:1.2, and then adding N-methyl pyrrolidone for mixing to form slurry;
(3) and (3) coating the slurry obtained in the step (2) on 5 cm-1.6 mm nickel foam (purchased from Kagay electronics Co., Ltd., Kun mountain) for natural drying, then placing the dried slurry in a roller press for compressing to 200 micrometers, and then placing the pressed slurry in a vacuum drying oven for drying at 80 ℃ for 12 hours to obtain the solid electrode.
The prepared solid electrode is used as a working electrode, the reference electrode is an Ag/AgCl electrode, the counter electrode is foamed nickel with the same size as nickel foam adopted by the solid electrode, and the electrolyte is potassium hydroxide solution with the concentration of 1M to form a three-electrode system.
Charging the assembled three-electrode system to a constant voltage, then placing the three-electrode system in 50mL of 0.1M urea solution to enable the three-electrode system to naturally discharge, observing that a large number of bubbles exist on the surface of the three-electrode system, and taking the three-electrode system out of the urea solution when the bubbles are not observed any more to finish one-time charging and discharging; the charging and discharging process is repeated for 9 times, the concentration of nitrogen in the urea solution is detected, and the result shows that the degradation rate of the urea is 10.59 percent when the concentration of the nitrogen in the urea solution is reduced from 261.18mg/L to 233.66 mg/L.
And (3) testing the ammonia nitrogen concentration before and after the urea solution is decomposed by adopting a nano reagent spectrophotometry, and finding that no ammonia nitrogen is generated, which indicates that the urea is not hydrolyzed.
The gas generated in the charging and discharging process of 10 microliter is absorbed by an injector and detected by gas chromatography, and the detection result shows that the generated gas is nitrogen and carbon dioxide, which indicates that ammonia is not generated in the degradation process of urea.
Example 4
The only difference from example 1 is that the cobalt source was replaced with an equivalent number of moles of aluminum source, and the composition and preparation method were the same as those of example 1.
The bimetallic oxide containing nickel and aluminum layers obtained in this example was subjected to transmission electron microscopy and found to have a layered structure as well.
The prepared solid electrode is used as a working electrode, the reference electrode is an Ag/AgCl electrode, the counter electrode is foamed nickel with the same size as nickel foam adopted by the solid electrode, and the electrolyte is potassium hydroxide solution with the concentration of 1M to form a three-electrode system.
Charging the assembled three-electrode system to a constant voltage, then placing the three-electrode system in 50mL of 0.1M urea solution to enable the three-electrode system to naturally discharge, observing that a large number of bubbles exist on the surface of the three-electrode system, and taking the three-electrode system out of the urea solution when the bubbles are not observed any more to finish one-time charging and discharging; the charging and discharging process is repeated for 9 times, the concentration of nitrogen in the urea solution is detected, and the result shows that the degradation rate of the urea is 8.44 percent when the concentration of the nitrogen in the urea solution is reduced from 261.18mg/L to 239.13 mg/L.
And (3) testing the ammonia nitrogen concentration before and after the urea solution is decomposed by adopting a nano reagent spectrophotometry, and finding that no ammonia nitrogen is generated, which indicates that the urea is not hydrolyzed.
The gas generated in the charging and discharging process of 10 microliter is absorbed by an injector and detected by gas chromatography, and the detection result shows that the generated gas is nitrogen and carbon dioxide, which indicates that ammonia is not generated in the degradation process of urea.
Comparative example 1
The only difference from example 1 is that the layered double oxide of example 1 was replaced with nickel hydroxide and cobalt hydroxide of equal mass in a 1:1 molar ratio, and the remaining composition and preparation method were the same as in example 1.
The three-electrode system was placed in the urea solution in the manner of example 1, and subjected to the same charging and discharging processes, and it was found that the nitrogen concentration in the urea solution did not substantially change before and after charging and discharging.
Comparative example 2
The only difference from example 4 is that the layered double oxide of example 4 was replaced with nickel hydroxide and aluminum hydroxide of equal mass in a molar ratio of 1:1, and the remaining composition and preparation method were the same as in example 1.
The three-electrode system was placed in the urea solution in the manner of example 4, and subjected to the same charging and discharging processes, and it was found that the nitrogen concentration in the urea solution did not substantially change before and after charging and discharging.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The solid electrode is characterized by comprising foamed nickel and a composite material layer positioned on the surface of the foamed nickel, wherein the composite material layer is a composite material layer containing layered double-metal oxide, and the layered double-metal oxide is a layered double-metal oxide containing nickel and cobalt simultaneously or a layered double-metal oxide containing nickel and aluminum simultaneously.
2. The solid state electrode of claim 1, wherein the composite layer further comprises a conductive agent and a binder;
preferably, the conductive agent comprises acetylene black;
preferably, the binder comprises polyvinylidene fluoride;
preferably, the addition amount of the conductive agent is 1.5-3g and the addition amount of the binder is 0.8-1.2g, based on the addition amount of the layered metal oxide being 6-8 g.
3. The method for producing a solid-state electrode according to claim 1 or 2, characterized by comprising: and (2) placing the layered bimetal oxide, the conductive agent and the binder into a solvent, mixing to obtain slurry, then coating the slurry on the surface of the nickel foam, and curing to obtain the solid electrode.
4. The production method according to claim 3, wherein the production method of the layered metal oxide comprises: adding a mixed solution of a nickel source and a metal source into an alkali liquor, mixing, separating to obtain a precipitate, and freeze-drying the precipitate to obtain the layered double-metal oxide;
preferably, the total concentration of nickel ions and metal ions in the mixed solution is 1-1.5M;
preferably, the nickel source comprises any one of nickel nitrate hexahydrate, nickel nitrate, nickel chloride, nickel sulfate or nickel acetate or a combination of at least two of the above;
preferably, the metal source comprises a cobalt source or an aluminum source;
preferably, the cobalt source comprises any one of cobalt nitrate hexahydrate, cobalt nitrate, cobalt sulfate or cobalt acetate or a combination of at least two of the foregoing;
preferably, the aluminium source comprises any one or a combination of at least two of aluminium nitrate nonahydrate, aluminium nitrate or aluminium chloride;
preferably, the lye comprises a sodium hydroxide solution and/or a potassium hydroxide solution;
preferably, the concentration of the alkali liquor is 1-3M;
preferably, the separation is by centrifugation;
preferably, the preparation method further comprises the steps of cleaning the precipitate obtained after separation for 3-5 times by adopting ultrapure water;
preferably, the temperature of the freeze drying is-40 to-10 ℃, and the time of the freeze drying is 18 to 24 hours.
5. The method of claim 3, wherein the solvent comprises N-methylpyrrolidone;
preferably, the mixing is carried out under stirring conditions, and the mixing time is 5-10 min;
preferably, the curing mode is natural airing;
preferably, the preparation method further comprises the steps of drying the cured product obtained after curing in vacuum;
preferably, the vacuum degree of the vacuum drying is-0.2 to-0.1 MPa, the temperature of the vacuum drying is 60 to 80 ℃, and the time of the vacuum drying is 12 to 24 hours.
6. A three-electrode system comprising a working electrode, a reference electrode, and a counter electrode, wherein the working electrode is the solid-state electrode of claim 1 or 2.
7. A three-electrode system according to claim 6, wherein the reference electrode is an Ag/AgCl electrode;
preferably, the counter electrode is foamed nickel, and the size of the foamed nickel is the same as that of the foamed nickel in the working electrode.
8. An electrochemical sensor comprising a three-electrode system according to claim 6 or 7.
9. Use of an electrochemical sensor according to claim 8 for the treatment of urea-containing wastewater.
10. The application according to claim 9, wherein the application comprises: the working electrode is charged to reach a constant potential by adopting an electrochemical method, and then is placed in the urea solution for natural discharge, thereby achieving the effect of degrading urea.
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