CN112237927B - Catalyst for electrocatalytic reduction of nitrate as well as preparation method and application thereof - Google Patents
Catalyst for electrocatalytic reduction of nitrate as well as preparation method and application thereof Download PDFInfo
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- CN112237927B CN112237927B CN202011032642.1A CN202011032642A CN112237927B CN 112237927 B CN112237927 B CN 112237927B CN 202011032642 A CN202011032642 A CN 202011032642A CN 112237927 B CN112237927 B CN 112237927B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 38
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 66
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 29
- 239000006260 foam Substances 0.000 claims abstract description 27
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 22
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 22
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 230000008030 elimination Effects 0.000 claims abstract description 7
- 238000003379 elimination reaction Methods 0.000 claims abstract description 7
- 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 6
- 238000006722 reduction reaction Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 5
- 238000004502 linear sweep voltammetry Methods 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 description 6
- 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
- PCBMYXLJUKBODW-UHFFFAOYSA-N [Ru].ClOCl Chemical compound [Ru].ClOCl PCBMYXLJUKBODW-UHFFFAOYSA-N 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 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
- 238000010586 diagram 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
- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000002245 particle Substances 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
- 238000003980 solgel method Methods 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
- 239000002699 waste material Substances 0.000 description 1
Classifications
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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
- 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
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- 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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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
- C02F2101/163—Nitrates
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Abstract
The invention relates to the technical field of catalyst preparation, in particular to a method for preparing a catalyst for electrocatalytic reduction of nitrate, which comprises the following steps: forming a nickel oxide layer on the surface of foam nickel by taking the foam nickel as a substrate to obtain a compound; and 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 invention provides a preparation method of a catalyst for electrocatalytic reduction of nitrate, which has the advantages of simple preparation method process, low Ru load 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 of synthetic ammonia 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 directly or indirectly, for example: ammonia waste discharged from factories such as foods, fuel oil refining and the like is biologically and chemically converted to form nitrate; a large amount of nitrogen oxides generated in the combustion process of a thermal power plant, an automobile, a ship and the like are leached by precipitation to form nitrate; ammonium nitrate, calcium nitrate, potassium nitrate, sodium nitrate and urea and the like which are rich in the artificial fertilizer and the fuel of textile industry; nitric acid generated in the processes of acid washing, deplating, etching and the like in the electroplating industry. Nitrate is very soluble in water and is relatively stable and less 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 problems of high cost and low efficiency of the biological denitrification method. By electrochemical means, the reduction of nitric acid to ammonia under catalysis not only removes nitric acid, but also generates valuable ammonia. In the research of synthesizing ammonia by electrochemical catalytic reduction of nitric acid, ru-based catalyst has the highest performance. The preparation method comprises the steps of firstly preparing amorphous ruthenium oxychloride by an improved sol-gel method, then dripping the amorphous ruthenium oxychloride on a carbon paper substrate by a titration method, reducing the ruthenium oxychloride by electrochemical reduction, and finally reducing the amorphous ruthenium oxychloride in H 2 And heat-treating in the atmosphere for 6h. It can be seen that the method has the problem of complicated preparation procedures. And because the catalyst adopts a dripping method, the binding force between the catalyst and the carbon paper is poor, and the catalyst can run for a long time, so that the problem of insufficient stability can occur. In addition, because the carbon paper substrate is adopted, the substrate conductivity is not high, and the problem that the current collection effect is poor and the reaction can not be carried out under high current for a long time exists. (journal of the 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 properties than Ru. In addition, ru is a noble metal, and there is a problem that the catalyst cost 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 of synthetic ammonia 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 foam nickel by taking the foam nickel as a substrate to obtain a compound;
and 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 technical scheme is further improved that in the step of forming a nickel oxide layer on the surface of the foam nickel by taking the foam nickel as a substrate to obtain a compound, the nickel oxide layer is obtained by performing heat treatment on the surface of the foam nickel in the air.
The technical scheme is further improved in that the temperature of the heat treatment is between room temperature and 700 ℃, and the atmosphere of the heat treatment is air atmosphere.
The technical scheme is further improved in that the content of ruthenium trichloride is 0.01-5 g/L, and the pH range is 0-14.
The technical scheme is further improved that in the step of adopting ruthenium trichloride solution to deposit ruthenium nano particles on a compound by adopting electrochemical cyclic voltammetry to obtain the Ni-Ru composite catalyst, the electrochemical cyclic voltammetry comprises the following steps:
a three-electrode electrochemical system is adopted, foam nickel with a nickel oxide layer is used as a working electrode, and cyclic voltammetry scanning is adopted on the working electrode.
The technical scheme is further improved that in the step of adopting a three-electrode electrochemical system and adopting 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).
The technical scheme is further improved that in the step of adopting a three-electrode electrochemical system, taking foam nickel with a nickel oxide 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 in the step of adopting a three-electrode electrochemical system and adopting foamed nickel with a nickel oxide layer as a working electrode and adopting cyclic voltammetry scanning on the working electrode, the number of times of cyclic voltammetry scanning is 1-100 times, and the number of times of cyclic voltammetry scanning is controlled by an electrochemical workstation.
The catalyst for electrocatalytic reduction of nitrate is prepared by the preparation method.
The application of a catalyst for electrocatalytic reduction of nitrate in synthesizing ammonia by electrochemical catalytic reduction of nitrate.
The beneficial effects of the invention are as follows:
in the first aspect, the preparation method has simple process, adopts foam nickel as a substrate, provides high electrochemical activity surface area for electrochemical reaction, introduces an oxide layer on the surface of the foam nickel, and effectively improves the catalytic performance of the catalyst on nitrate reduction; in the second aspect, an electrochemical cyclic voltammetry is adopted to deposit a catalyst, so that the catalyst with small-size nano particle size can be synthesized, and the content of deposited ruthenium and the content of ruthenium oxide can be regulated and controlled by regulating the circulation times in the electrochemical deposition process; in the third aspect, the Ru loading of the catalyst can be as low as 0.15wt%, so that the cost of the catalyst is effectively reduced; simultaneously has higher current density, current Faraday efficiency and ammonia synthesis elimination rate in a wide voltage range, and the obtained catalyst is directly used for electrochemical reduction of nitrate, and can obtain up to 110mAcm at low voltage -2 The ammonia synthesis efficiency is up to 100% and the yield is up to 1.4x10 -7 mol -1 s -1 cm -1 The method comprises the steps of carrying out a first treatment on the surface of the Over a wide voltage range, i.e. -1.0V-0V (vs RHE), the current efficiency of synthesizing ammonia can be maintained up to 100%, and the ammonia yield and nitrate radical elimination rate can be up to 1.56x10 -6 mol -1 s -1 cm -1 。
Drawings
FIG. 1 is a schematic diagram of the preparation principle of the method for preparing a catalyst for electrocatalytic reduction of nitrate and the synthesis of ammonia by catalytic reduction of nitric acid;
FIG. 2 is a plot of current versus voltage for the electrodeposition process of the catalyst preparation method of FIG. 1 for electrocatalytically reducing nitrates;
FIG. 3 is an electron micrograph, raman and XPS spectra of the catalyst of FIG. 1 for electrocatalytically reducing nitrates;
FIG. 4 is a schematic illustration of the catalytic performance of the catalyst of FIG. 1 for electrocatalytic reduction of nitrates;
FIG. 5 is a graph of performance of an application of the catalyst for electrocatalytic reduction of nitrates of the present invention;
FIG. 6 is another performance graph of an application of the catalyst of the present invention for electrocatalytically reducing nitrates.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in connection with the embodiments of the present invention.
As shown in fig. 1 to 6, a method for preparing a catalyst for electrocatalytically reducing nitrate, comprising the steps of:
forming a nickel oxide layer on the surface of foam nickel by taking the foam nickel as a substrate to obtain a compound; and 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 foam nickel is used as a substrate to provide high electrochemical activity surface area for electrochemical reaction; and an oxide layer is introduced on the surface of the foam nickel, so that the catalytic performance of the catalyst on nitrate reduction is effectively improved.
Forming a nickel oxide layer on the surface of foam nickel by taking the foam nickel as a substrate to obtain a compound, wherein the nickel oxide layer is obtained by performing heat treatment on the surface of the foam nickel in 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.
Ruthenium trichloride is added, and the content of the ruthenium trichloride is 0.01-5 g/L and the pH range is 0-14 in the process of adopting an electrochemical deposition catalyst.
Preferably, the ruthenium trichloride content is 2g/L and the pH is 0.
In the step of adopting ruthenium trichloride solution to deposit ruthenium nano particles on the compound by adopting electrochemical cyclic voltammetry to obtain the Ni-Ru composite catalyst, the electrochemical cyclic voltammetry comprises the following steps:
a three-electrode electrochemical system is adopted, foam nickel with a nickel oxide layer is used as a working electrode, and cyclic voltammetry scanning is adopted on the working electrode. The electrochemical cyclic voltammetry is adopted to deposit the catalyst, which is helpful for synthesizing the catalyst with small-sized nanometer particle size.
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 scanning on the working electrode, the voltage range is-1.0V-0.1V (vs RHE).
Preferably, the electrochemical deposition cycle scans a voltage in the range of-0.6V to 0.1V (vs RHE).
In the step of adopting a three-electrode electrochemical system and adopting foamed nickel with a nickel oxide 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 and adopting foamed nickel with a nickel oxide layer as a working electrode and adopting cyclic voltammetry scanning on the working electrode, the number of times of cyclic voltammetry scanning is 1-100 times, and the number of times of cyclic voltammetry scanning is controlled by an electrochemical workstation. The content of deposited ruthenium and the content of ruthenium oxide can be regulated and controlled by regulating the circulation times in the electrochemical deposition process.
The catalyst for electrocatalytic reduction of nitrate is prepared by the preparation method.
The application of a catalyst for electrocatalytic reduction of nitrate in synthesizing ammonia by electrochemical catalytic reduction of nitrate. Can obtain a voltage of up to 110mAcm at low voltage -2 The ammonia synthesis efficiency is up to 100% and the yield is up to 1.4x10 -7 mol -1 s - 1 cm -1 The method comprises the steps of carrying out a first treatment on the surface of the In a wide voltage range, i.e. -1.0V-0V (vs RHE), the current efficiency of synthesizing ammonia can be maintained up to 100%, and the ammonia yield and nitrate elimination rate can be up to 1.56x10 -6 mol -1 s -1 cm -1 。
As shown in figures 1 to 6, the preparation method of the invention has simple process, the Ru load of the catalyst can be as low as 0.15wt%, the cost of the catalyst is effectively reduced, and the catalyst has higher current density, current conversion efficiency and nitrate radical elimination rate of synthetic ammonia in a wide voltage range.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (6)
1. The application of the catalyst for electrocatalytic reduction of nitrate in the aspect of synthesizing ammonia by electrochemically catalyzing and reducing nitrate is characterized in that the preparation method of the catalyst for electrocatalytic reduction of nitrate comprises the following steps:
forming a nickel oxide layer on the surface of foam nickel by taking the foam nickel as a substrate to obtain a compound;
depositing ruthenium nano particles on the compound by adopting a ruthenium trichloride solution and adopting an electrochemical cyclic voltammetry to obtain a Ni-Ru composite catalyst;
the electrochemical cyclic voltammetry comprises the following steps:
adopting a three-electrode electrochemical system, taking foam nickel with a nickel oxide layer as a working electrode, and adopting cyclic voltammetry scanning on the working electrode;
in the step of adopting a three-electrode electrochemical system and adopting foam 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;
at low voltage up to 110mAcm -2 The ammonia synthesis efficiency is up to 100% and the yield is up to 1.4x10 -7 mol -1 s -1 cm -1 The method comprises the steps of carrying out a first treatment on the surface of the In a wide voltage range, namely-1.0V-0V vs RHE, the current efficiency of synthesizing ammonia can be maintained to be up to 100%, and the ammonia yield and nitrate elimination rate can be up to 1.56x10 -6 mol -1 s -1 cm -1 。
2. The use of the catalyst for electrocatalytic reduction of nitrate according to claim 1 for electrochemical catalytic reduction of nitrate synthesis ammonia, wherein in the step of forming a nickel oxide layer on the surface of the nickel foam with the nickel foam as a substrate to obtain a composite, the nickel oxide layer is obtained by heat-treating the air on the surface of the nickel foam.
3. The use of the 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 use of the catalyst for electrocatalytic reduction of nitrate according to claim 1, wherein the content of ruthenium trichloride is 0.01-5 g/L and the pH range is 0-14.
5. The use of the electrocatalytic reduction nitrate catalyst according to claim 1, wherein in the step of using a three-electrode electrochemical system, using foam nickel with a nickel oxide layer as a working electrode and using cyclic voltammetry scanning on the working electrode, the scanning speed is 1-100 mv/s.
6. The use of the catalyst for electrocatalytic reduction of nitrate according to claim 5, wherein in the step of using a three-electrode electrochemical system, foamed nickel with nickel oxide layer as a working electrode and 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.
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