CN112237927A - Catalyst for electrocatalytic reduction of nitrate and preparation method and application thereof - Google Patents
Catalyst for electrocatalytic reduction of nitrate and preparation method and application thereof Download PDFInfo
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- CN112237927A CN112237927A CN202011032642.1A CN202011032642A CN112237927A CN 112237927 A CN112237927 A CN 112237927A CN 202011032642 A CN202011032642 A CN 202011032642A CN 112237927 A CN112237927 A CN 112237927A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 41
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 230000009467 reduction Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 30
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 18
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 16
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 16
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 238000006722 reduction reaction Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 5
- 238000004502 linear sweep voltammetry Methods 0.000 claims description 5
- 150000002823 nitrates Chemical class 0.000 claims description 5
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000008030 elimination Effects 0.000 abstract description 6
- 238000003379 elimination reaction Methods 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- PCBMYXLJUKBODW-UHFFFAOYSA-N [Ru].ClOCl Chemical compound [Ru].ClOCl PCBMYXLJUKBODW-UHFFFAOYSA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a catalyst for electrocatalytic reduction of nitrate, which comprises the following steps: forming a nickel oxide layer on the surface of the foamed nickel by using the foamed nickel as a substrate to obtain a compound; and depositing ruthenium nano particles on the compound by adopting a ruthenium trichloride solution and an electrochemical cyclic voltammetry to obtain the Ni-Ru composite catalyst. The invention provides a preparation method of a catalyst for electrocatalytic reduction of nitrate, which has the advantages of simple preparation method process, low Ru loading amount of the catalyst and low catalyst cost; the invention also provides application of the catalyst for electrocatalytic reduction of nitrate, which has higher current density, current Faraday efficiency and nitrate elimination rate in ammonia synthesis in a wide voltage range.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a catalyst for electrocatalytic reduction of nitrate and a preparation method and application thereof.
Background
In industrial processes, most industries produce nitrates either directly or indirectly, for example: ammonia wastes discharged from factories such as food and fuel oil refining are biologically and chemically converted to form nitrates; a large amount of nitrogen oxides generated in the combustion process of a thermal power plant, an automobile, a ship and the like form nitrates through precipitation and leaching; the artificial fertilizer is rich in ammonium nitrate, calcium nitrate, potassium nitrate and sodium nitrate, and the textile fuel is rich in urea and the like; nitric acid generated in the processes of acid washing, deplating, etching and the like in the electroplating industry. Nitrates are very soluble in water and are stable and not prone to co-precipitation and adsorption, and therefore conventional water treatment techniques are not suitable for nitrate removal.
The conventional nitrate removal method mainly comprises a reverse osmosis method, an electrodialysis method, an ion exchange method, a catalytic denitrification method, a chemical denitrification method and a biological denitrification method. The reverse osmosis method, the electrodialysis method and the ion exchange method have the problem of high cost, and the biological denitrification method has the problem of low efficiency. The nitric acid is reduced and converted into ammonia under the catalysis of an electrochemical method, so that the nitric acid can be removed, and valuable ammonia can be generated. In the existing research of synthesizing ammonia by electrochemical catalytic reduction of nitric acid, the Ru-based catalyst has the highest performance. The preparation method comprises preparing amorphous material by modified sol-gel methodDropping the ruthenium oxychloride on a carbon paper substrate by a titration method, reducing the ruthenium oxychloride by electrochemical reduction, and finally adding hydrogen chloride in H2Heat-treating in the atmosphere for 6 h. It can be seen that this method has a problem that the preparation process is complicated. And because the catalyst adopts a dripping method, the bonding force between the catalyst and the carbon paper is poor, and the catalyst has the problem of insufficient stability after long-time operation. In addition, the carbon paper substrate is adopted, so that the substrate is low in conductivity, and the problems that the current collection effect is poor and the reaction cannot be carried out under large current for a long time exist. (Journalthe American chemical society, 2020.142(15): p.7036-7046.). Other catalysts include Cu-based, Ti-based, and Co-based catalysts, but all have lower catalytic performance than Ru. Further, since Ru is a noble metal, there is a problem that the cost of the catalyst is high.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a catalyst for electrocatalytic reduction of nitrate, which has the advantages of simple preparation method process, low Ru loading amount of the catalyst and low catalyst cost.
The invention also provides application of the catalyst for electrocatalytic reduction of nitrate, which has higher current density, current Faraday efficiency and nitrate elimination rate in ammonia synthesis in a wide voltage range.
The invention adopts the following technical scheme:
a preparation method of a catalyst for electrocatalytic reduction of nitrate comprises the following steps:
forming a nickel oxide layer on the surface of the foamed nickel by using the foamed nickel as a substrate to obtain a compound;
and depositing ruthenium nano particles on the compound by adopting a ruthenium trichloride solution and an electrochemical cyclic voltammetry to obtain the Ni-Ru composite catalyst.
The further improvement of the technical scheme is that in the step of obtaining the composite by using the foamed nickel as the substrate and forming a nickel oxide layer on the surface of the foamed nickel, the nickel oxide layer is obtained by performing heat treatment on the surface of the foamed nickel in the air.
The technical proposal is further improved in that the temperature of the heat treatment is room temperature to 700 ℃, and the atmosphere of the heat treatment is air atmosphere.
The technical scheme is further improved in that the content of the ruthenium trichloride is 0.01-5 g/L, and the pH range is 0-14.
The technical proposal is further improved in that in the step of adopting ruthenium trichloride solution and adopting electrochemical cyclic voltammetry to deposit ruthenium nano particles on the compound to obtain the Ni-Ru composite catalyst, the electrochemical cyclic voltammetry comprises the following steps:
a three-electrode electrochemical system is adopted, foamed nickel with a nickel oxidation layer is used as a working electrode, and cyclic voltammetry scanning is adopted on the working electrode.
The technical proposal is further improved in that in the step of adopting a three-electrode electrochemical system, foam nickel with a nickel oxide layer is used as a working electrode, and cyclic voltammetry scanning is adopted on the working electrode, the voltage range is-1.0V-0.1V (vs RHE).
The technical scheme is further improved in that in the step of adopting a three-electrode electrochemical system, taking foamed nickel with a nickel oxidation layer as a working electrode and adopting cyclic voltammetry scanning on the working electrode, the scanning speed is 1-100 mV/s.
The technical scheme is further improved in that a three-electrode electrochemical system is adopted, foamed nickel with a nickel oxidation layer is used as a working electrode, and in the step of adopting cyclic voltammetry scanning on the working electrode, the number of cyclic voltammetry scanning is 1-100, and the number of cyclic voltammetry scanning is controlled by an electrochemical workstation.
The catalyst for electrocatalytic reduction of nitrate is prepared by the preparation method.
An application of a catalyst for electrocatalytic reduction of nitrate in the aspect of synthesizing ammonia by electrochemically catalyzing and reducing nitrate.
The invention has the beneficial effects that:
in the first aspect, the preparation method of the invention has simple process, adopts foamed nickel as a substrate, provides high electrochemical active surface area for electrochemical reaction, and is used for solving the problems that the prior art has high cost and high electrochemical activityAn oxide layer is introduced on the surface of the foamed nickel, so that the catalytic performance of the catalyst on nitrate reduction is effectively improved; in the second aspect, the catalyst is deposited by adopting an electrochemical cyclic voltammetry, which is beneficial to synthesizing the catalyst with small-size nanometer particle size, and the content of deposited ruthenium and the content of ruthenium oxide can be regulated and controlled by regulating the cycle number in the electrochemical deposition process; in the third aspect, the amount of the Ru loaded on the catalyst can be as low as 0.15 wt%, so that the cost of the catalyst is effectively reduced; meanwhile, the catalyst has higher current density, current Faraday efficiency and nitrate elimination rate in ammonia synthesis in a wide voltage range, the obtained catalyst is directly used for electrochemical reduction of nitrate, and the catalyst can obtain the nitrate with the concentration of up to 110mAcm at low voltage-2The current and the synthesis efficiency of the ammonia are as high as 100 percent, and the yield is as high as 1.4x10-7mol-1s-1cm-1(ii) a In a wide voltage range, namely-1.0V-0V (vs RHE), the current efficiency of the ammonia synthesis can be maintained to be up to 100 percent, the ammonia yield and the nitrate radical elimination rate can reach 1.56x10-6mol-1s-1cm-1。
Drawings
FIG. 1 is a schematic diagram of the preparation principle of the method for preparing the catalyst for electrocatalytic reduction of nitrate and the synthesis of ammonia by catalytic reduction of nitric acid according to the present invention;
FIG. 2 is a current-voltage curve of an electrodeposition process of the method for preparing a catalyst for the electrocatalytic reduction of nitrate of FIG. 1;
FIG. 3 is an electron micrograph, Raman and XPS spectra of the electrocatalytic nitrate reduction catalyst of FIG. 1;
FIG. 4 is a graphical representation of the catalytic performance of the electrocatalytic nitrate reduction catalyst of FIG. 1;
FIG. 5 is a performance graph of an application of the electrocatalytic nitrate reduction catalyst of the present invention;
FIG. 6 is another performance diagram of the application of the electrocatalytic nitrate reduction catalyst of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.
As shown in fig. 1 to 6, a method for preparing a catalyst for electrocatalytic reduction of nitrate includes the steps of:
forming a nickel oxide layer on the surface of the foamed nickel by using the foamed nickel as a substrate to obtain a compound; and depositing ruthenium nano particles on the compound by adopting a ruthenium trichloride solution and an electrochemical cyclic voltammetry to obtain the Ni-Ru composite catalyst. Foam nickel is used as a substrate to provide a high electrochemical active surface area for electrochemical reaction; and an oxide layer is introduced on the surface of the foamed nickel, so that the catalytic performance of the catalyst on nitrate reduction is effectively improved.
In the step of forming a nickel oxide layer on the surface of foamed nickel by using the foamed nickel as a substrate to obtain a composite, the nickel oxide layer is obtained by carrying out heat treatment on the surface of the foamed nickel in the air; the temperature of the heat treatment is between room temperature and 700 ℃, and the atmosphere of the heat treatment is air atmosphere.
Preferably, the heat treatment temperature is room temperature to 300 ℃ and the heat treatment time is 30 minutes.
Adding ruthenium trichloride, wherein in the process of adopting an electrochemical deposition catalyst, the content of ruthenium trichloride is 0.01-5 g/L, and the pH range is 0-14.
Preferably, the ruthenium trichloride content is 2g/L and the pH is 0.
In the step of adopting ruthenium trichloride solution and adopting electrochemical cyclic voltammetry to deposit ruthenium nano particles on the compound to obtain the Ni-Ru composite catalyst, the electrochemical cyclic voltammetry comprises the following steps:
a three-electrode electrochemical system is adopted, foamed nickel with a nickel oxidation layer is used as a working electrode, and cyclic voltammetry scanning is adopted on the working electrode. The catalyst is deposited by adopting an electrochemical cyclic voltammetry method, which is beneficial to synthesizing the catalyst with small-size nanometer particle size.
In the step of adopting a three-electrode electrochemical system, using foamed nickel with a nickel oxide layer as a working electrode and adopting cyclic voltammetry scanning on the working electrode, the voltage range is-1.0V-0.1V (vs RHE).
Preferably, the voltage range of the electrochemical deposition cycle sweep is from-0.6V to 0.1V (vs RHE).
In the step of adopting a three-electrode electrochemical system, taking foamed nickel with a nickel oxidation layer as a working electrode and adopting cyclic voltammetry scanning on the working electrode, the scanning speed is 1-100 mV/s.
In the step of adopting a three-electrode electrochemical system, foamed nickel with a nickel oxide layer is taken as a working electrode, and cyclic voltammetry scanning is adopted on the working electrode, wherein the number of cyclic voltammetry scanning is 1-100, and the number of cyclic voltammetry scanning is controlled by an electrochemical workstation. The content of the deposited ruthenium and the content of the ruthenium oxide can be regulated and controlled by regulating the cycle number in the electrochemical deposition process.
The catalyst for electrocatalytic reduction of nitrate is prepared by the preparation method.
An application of a catalyst for electrocatalytic reduction of nitrate in the aspect of synthesizing ammonia by electrochemically catalyzing and reducing nitrate. Can obtain up to 110mAcm at low voltage-2The current and the synthesis efficiency of the ammonia are as high as 100 percent, and the yield is as high as 1.4x10-7mol-1s- 1cm-1(ii) a In a wide voltage range, namely-1.0V-0V (vs RHE), the current efficiency of the ammonia synthesis can be maintained to be up to 100 percent, the ammonia yield and the nitrate radical elimination rate can reach 1.56x10-6mol-1s-1cm-1。
As shown in the figures 1 to 6, the preparation method has simple process, the Ru loading amount of the catalyst can be as low as 0.15 wt%, the cost of the catalyst is effectively reduced, and simultaneously, the catalyst has higher current density, current conversion efficiency and nitrate elimination rate in ammonia synthesis in a wide voltage range.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of a catalyst for electrocatalytic reduction of nitrate is characterized by comprising the following steps:
forming a nickel oxide layer on the surface of the foamed nickel by using the foamed nickel as a substrate to obtain a compound;
and depositing ruthenium nano particles on the compound by adopting a ruthenium trichloride solution and an electrochemical cyclic voltammetry to obtain the Ni-Ru composite catalyst.
2. The method for preparing a catalyst for electrocatalytic reduction of nitrate according to claim 1, wherein in the step of forming a nickel oxide layer on the surface of the nickel foam using the nickel foam as a substrate to obtain a composite, the nickel oxide layer is obtained by heat-treating the surface of the nickel foam in air.
3. The method for preparing a catalyst for electrocatalytic reduction of nitrate according to claim 2, wherein the temperature of the heat treatment is room temperature to 700 ℃, and the atmosphere of the heat treatment is an air atmosphere.
4. The method for preparing a catalyst for electrocatalytic reduction of nitrate according to claim 1, wherein the ruthenium trichloride is contained in an amount of 0.01 to 5g/L and has a pH in a range of 0 to 14.
5. The method for preparing a catalyst for electrocatalytic reduction of nitrate according to claim 1, wherein in the step of obtaining the Ni-Ru composite catalyst by depositing ruthenium nanoparticles on the composite using a ruthenium trichloride solution using electrochemical cyclic voltammetry, the electrochemical cyclic voltammetry comprises the steps of:
a three-electrode electrochemical system is adopted, foamed nickel with a nickel oxidation layer is used as a working electrode, and cyclic voltammetry scanning is adopted on the working electrode.
6. The method of claim 5, wherein the step of scanning with cyclic voltammetry on the working electrode is performed using a three-electrode electrochemical system using foamed nickel with a nickel oxide layer as the working electrode, and the voltage is in the range of-1.0V to 0.1V (vs RHE).
7. The method for preparing a catalyst for electrocatalytic reduction of nitrate according to claim 6, wherein in the step of employing a three-electrode electrochemical system, using foamed nickel having a nickel oxide layer as a working electrode, and employing cyclic voltammetry scanning on the working electrode, the scanning rate is 1 to 100 mV/s.
8. The method for preparing a catalyst for electrocatalytic reduction of nitrate according to claim 7, wherein in the step of using a three-electrode electrochemical system, using foamed nickel with a nickel oxide layer as a working electrode, and using cyclic voltammetry scans on the working electrode, the number of cyclic voltammetry scans is 1-100, and the number of cyclic voltammetry scans is controlled by an electrochemical workstation.
9. A catalyst for electrocatalytic reduction of nitrates obtained by the preparation process according to any one of claims 1 to 8.
10. Use of the catalyst for electrocatalytic reduction of nitrate according to claim 9 for the electrochemical catalytic reduction of nitrate to ammonia.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112981451A (en) * | 2021-02-07 | 2021-06-18 | 安徽农业大学 | Preparation method of catalytic electrode for preparing ammonia by electrochemical reduction of nitrate or nitrite |
| CN113005469A (en) * | 2021-01-27 | 2021-06-22 | 浙江大学衢州研究院 | Ruthenium-loaded amorphous nickel hydroxide/nickel phosphide composite electrode and preparation method and application thereof |
| CN113403633A (en) * | 2021-05-10 | 2021-09-17 | 杭州师范大学 | Preparation method of Cu-C-N metal organic frame electrocatalyst for reducing nitrate into ammonia |
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| CN113668001A (en) * | 2021-07-27 | 2021-11-19 | 北京化工大学 | Method for synthesizing ammonia by electrocatalysis nitrate radical reduction using hydrogen evolution reaction catalyst |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105970265A (en) * | 2016-05-19 | 2016-09-28 | 陕西师范大学 | Preparation method of sulfur doped Ni-Fe hydroxide nano-film catalyst for decomposing water to produce oxygen |
| CN110438528A (en) * | 2019-08-15 | 2019-11-12 | 上海工程技术大学 | A kind of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode and preparation method thereof |
| CN110980892A (en) * | 2019-10-29 | 2020-04-10 | 东莞理工学院 | Method for removing nitrate nitrogen and nitrite nitrogen in water body by activated cathode nascent hydrogen rapid reduction |
-
2020
- 2020-09-27 CN CN202011032642.1A patent/CN112237927B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105970265A (en) * | 2016-05-19 | 2016-09-28 | 陕西师范大学 | Preparation method of sulfur doped Ni-Fe hydroxide nano-film catalyst for decomposing water to produce oxygen |
| CN110438528A (en) * | 2019-08-15 | 2019-11-12 | 上海工程技术大学 | A kind of modified nickel foam supported precious metal catalyst hydrogen-precipitating electrode and preparation method thereof |
| CN110980892A (en) * | 2019-10-29 | 2020-04-10 | 东莞理工学院 | Method for removing nitrate nitrogen and nitrite nitrogen in water body by activated cathode nascent hydrogen rapid reduction |
Non-Patent Citations (1)
| Title |
|---|
| YONGSHENG WEI等: "Highly efficient and reactivated electrocatalyst of ruthenium electrodeposited on nickel foam for hydrogen evolution from NaBH4 alkaline solution" * |
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| CN113005469B (en) * | 2021-01-27 | 2022-04-08 | 浙江大学衢州研究院 | Ruthenium-loaded amorphous nickel hydroxide/nickel phosphide composite electrode and preparation method and application thereof |
| CN112981451A (en) * | 2021-02-07 | 2021-06-18 | 安徽农业大学 | Preparation method of catalytic electrode for preparing ammonia by electrochemical reduction of nitrate or nitrite |
| CN112981451B (en) * | 2021-02-07 | 2022-02-18 | 安徽农业大学 | Preparation method of catalytic electrode for preparing ammonia by electrochemical reduction of nitrate or nitrite |
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