CN114657596A - Electro-catalytic nitrate radical reduction catalyst Fe-CoS2Preparation method of/CC - Google Patents
Electro-catalytic nitrate radical reduction catalyst Fe-CoS2Preparation method of/CC Download PDFInfo
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- CN114657596A CN114657596A CN202210226480.8A CN202210226480A CN114657596A CN 114657596 A CN114657596 A CN 114657596A CN 202210226480 A CN202210226480 A CN 202210226480A CN 114657596 A CN114657596 A CN 114657596A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 230000009467 reduction Effects 0.000 title claims abstract description 26
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 18
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
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- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
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- LOUWOZBMDAQCRT-UHFFFAOYSA-N cobalt sulfanylideneiron Chemical compound [S].[Fe].[Co] LOUWOZBMDAQCRT-UHFFFAOYSA-N 0.000 claims abstract 2
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- 238000002360 preparation method Methods 0.000 claims description 11
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
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- 238000005406 washing Methods 0.000 claims description 6
- 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 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
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- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims 1
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- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 239000002064 nanoplatelet Substances 0.000 claims 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 70
- 229910021529 ammonia Inorganic materials 0.000 abstract description 32
- 229910002651 NO3 Inorganic materials 0.000 abstract description 25
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 25
- 238000011161 development Methods 0.000 abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
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- 229910052723 transition metal Inorganic materials 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/27—Ammonia
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/056—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of textile or non-woven fabric
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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Abstract
With the development of modern industry, the ammonia synthesis technology becomes more and more the Mingmen of industrial development, and the catalyst for producing non-noble metal is used for the electrocatalytic decomposition of Nitrate (NO)3 ‑) The saturated electrolyte has attracted much attention to the research of reducing nitrate radical to prepare ammonia, and the saturated electrolyte is the most popular in the energy field in recent years, and the invention provides a method for preparing ammonia by reducing nitrate radicalElectro-catalytic nitrate radical reduction catalyst Fe-CoS2Firstly, adding iron and cobalt reagents with specific proportion into a special reaction solution, adding a pre-reaction solution and carbon cloth into a reaction kettle for heating by a hydrothermal synthesis method, reacting to obtain an iron-cobalt precursor, then placing the iron-cobalt precursor into a tubular furnace with specific nitrogen flow rate for vulcanization treatment, and finally obtaining the iron-cobalt sulfide hybrid Fe-CoS2/CC, the Fe-CoS2Method for electrocatalytic nitrate reduction (NO) by using CC catalyst3 ‑RR) area shows excellent catalytic activity, and the ammonia yield reaches 17.2 x 10 relative to the standard hydrogen electrode‑2 mmol h‑1 cm‑2The Faraday efficiency reaches 88.92%.
Description
Technical Field
The invention relates to the field of preparation and application of inorganic nano materials, in particular to a method for preparing Fe doped CoS based on a hydrothermal method2Nano-sheet and loaded on carbon cloth (Fe-CoS)2/CC) catalyst material and application in the field of electrocatalysis nitrate reduction.
Background
Energy is an important support for the development of foundation stones and social progress of human beings, the main energy of the modern society is fossil fuels such as coal, petroleum and natural gas, but the fossil fuels not only face the problems of low reserves, non-regeneration and the like, but also cause environmental pollution and harm to human health due to combustion products of the fossil fuels, so that the development of efficient and sustainable energy is a problem to be solved urgently in the development of the modern society and the human progress.
Ammonia gas (NH)3) The ammonia gas is one of the largest chemicals produced in the world, is a basic chemical raw material for chemical production, is particularly important for the production of nitrogen fertilizers such as ammonium nitrate, urea and the like and various nitrogen-containing compound fertilizers, is a novel energy carrier, contains 17.6 percent of hydrogen and 12.5 percent of methanol, and is a promising candidate for the hydrogen energy economy in the future, so the ammonia gas occupies an indispensable position in the future population development, statistically, more than 1.4 million tons of ammonia gas are industrially produced every year, and the demand is continuously increased; today, the large demand for ammonia gas has developed into an imminent social problem, which has stimulated intensive research into the large-scale production technology of artificial ammonia gas, but the only currently available industrial synthesis method for ammonia is the development by Haber and Bosch of German chemists in the early 20 th century in the gas phase of N2And H2However, the Haber-Bosch process for synthesizing ammonia has the problems of harsh conditions, high requirement on equipment, high energy consumption (consuming 2% of energy supply worldwide every year), low conversion rate and the like, and is not more and more in line with the development requirements of the economic society, so that the search for a process capable of realizing high ammonia yield, high current efficiency and low energy consumption, and low-cost and large-scale ammonia production is the key point of future research.
In recent years, electrochemical nitrate reduction (NO)3 -RR) is of great interest, NO compares to the traditional Haber-Bosch process3 -RR has the following advantages: mild working conditions, N = O bond (204 kJ mol)-1) Relative N = N bond (941 kJ mol)-1) The low dissociation energy, the simplified equipment and the extremely small carbon emission, but the nitrate electrocatalyst with high efficiency is needed, in addition, the nitrate in water can generate adverse effects on human beings and the environment, and drinking the water containing the nitrate can cause methemoglobinemia, cause human fatigue, shortness of breath, cerebral anoxia and even death, so that the nitrate with harm in the environment is needed to be efficiently converted into useful ammonia, thereby relieving the production pressure of industrial nitrogen fixation synthetic ammonia and controlling the nitrate pollution in the water body.
In recent years, transition metals have been widely used in electrocatalyst design, among which transition metal sulfides are promising electrocatalysts due to their high conductivity and easy preparation process, and in addition, metal element doping can improve the catalytic performance of electrocatalysts by optimizing hydrogen adsorption energy and improving electron conductivity2the/CC application is a highly efficient electrocatalytic nitrate reduction catalyst.
Disclosure of Invention
One of the objects of the present invention is a Fe-CoS2Novel preparation method of/CC nitrate radical reduction catalyst.
Another object of the present invention is to synthesize Fe-CoS2the/CC catalyst is applied to an electrocatalytic nitrate reduction system.
The invention also aims to design a brand-new single-chamber membrane electrode nitrate radical reduction electrocatalysis test system by repeated test processing.
Drawings
FIG. 1 is a schematic structural diagram of a self-designed single-chamber membrane electrode nitrate radical reduction electrocatalysis test system provided by the invention. As shown in fig. 1, (1) an insulating layer; (2) a fixed base; (3) an ammonia solution storage tank; (4) the sodium sulfate-sodium nitrate mixed electrolyte is prepared; (5) a water outlet; (6) a water inlet; (7) a liquid inlet; (8) a counter electrode; (9) a reference electrode; (10) working electrode (Fe-CoS)2/CC）。
The technical scheme of the invention is as follows:
1. Fe-CoS2The novel preparation method of the/CC nitrate radical reduction catalyst is characterized by comprising the following preparation steps:
(1) adding iron and cobalt reagents with a fixed ratio of 10: 1-1: 1 into a specific reaction solution, namely an aqueous solution of urea to prepare a pre-reaction solution, adding the pre-reaction solution and carbon cloth with a certain size into a reaction kettle by using a hydrothermal synthesis method, heating for a certain time at a certain temperature, naturally cooling, washing, drying and collecting the obtained iron and cobalt precursor, wherein in the process, the use of the aqueous solution of urea can effectively regulate the morphology of the nano material, effectively regulate the pH of the solution, promote the generation of nano sheets and enable the generated iron and cobalt precursor to present a very thin physical structure;
(2) placing an iron-cobalt precursor in a tube furnace, fixing the nitrogen flow rate at 10-60 mL/min and the calcination temperature at 200oC ~ 600 oAnd C, adding sublimed sulfur as a vulcanizing agent to perform a vulcanizing reaction, wherein the mass ratio of the vulcanizing agent to the iron-cobalt precursor is 1: 10-1: 100, and the vulcanizing temperature is 200oC ~ 600 oC, vulcanizing for 1-6 h at a heating rate of 0.5oC/min to obtain Fe-CoS2CC, in the present process sublimed sulphur as a sulphurising agent for Fe-CoS2The generation of/CC is greatly promoted, and the generated Fe-CoS2the/CC has a plurality of exposed catalytic active sites, which is beneficial to the subsequent electrocatalytic process.
2. Fe-CoS2The preparation method of the/CC nitrate radical reduction catalyst is characterized in that a single-chamber membrane electrode nitrate radical reduction electrocatalysis performance test is adopted, and the steps are as follows:
by Fe-CoS2The method is characterized in that the/CC is used as a working electrode, the graphite electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, 0.1-2 mol/L sodium sulfate-sodium nitrate mixed solution is used as electrolyte, the electrocatalytic nitrate reduction process is carried out, the sodium sulfate-sodium nitrate mixed solution is used as electrolyte in the process, the reaction selectivity is improved, the hydrogen evolution reaction can be effectively inhibited, the nitrate reduction reaction is promoted, the mixed solution of the sodium sulfate and the sodium nitrate is applied to a nitrate reduction electrocatalytic test, and the result shows that the effect is excellent.
3. Nitrate reduction electrocatalytic test system using a novel single chamber membrane electrode, in which Fe-CoS2The method comprises the following steps of taking/CC as a working electrode, taking a graphite electrode as a counter electrode, taking an Ag/AgCl electrode as a reference electrode, electrolyzing a sodium sulfate-sodium nitrate mixed solution, and filling water with a certain temperature into a water inlet so as to keep a constant temperature state in a catalysis process, so that the catalysis process is effectively carried out, the nitrate reduction reaction is promoted, the excessive consumption of a catalyst is prevented, and the Faraday efficiency of the reaction can be effectively improved.
4. For Fe-CoS2The performance of the/CC nano-sheet and the ammonia yield of the electrocatalytic nitrate reduction reaction reach 17.2 multiplied by 10-2 mmol h-1 cm-2The Faraday efficiency is as high as 88.92%, and the ammonia yield and the Faraday efficiency are better.
The specific implementation scheme is as follows:
for a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and to the accompanying drawings, which are included to further illustrate features and advantages of the invention, and not to limit the scope of the invention as claimed.
Example 1
The first step is as follows: adding 60 mL of deionized water into a beaker, adding urea (0.6006 g, 10 mmol), stirring for 30 min to form a clear transparent solution, sequentially adding cobalt nitrate hexahydrate (0.5821 g, 2 mmol) and ferric nitrate nonahydrate (0.0808 g, 0.2 mmol) under continuous stirring, stirring for 30 min, and transferring 40 mL of the solution and carbon cloth into a polytetrafluoroethylene inner container; and sealing the hydrothermal high-pressure kettle, placing the hydrothermal high-pressure kettle in a drying oven at the temperature of 120 ℃ for heat preservation for 12 hours, naturally cooling, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the iron-cobalt precursor.
The second step: putting an iron-cobalt precursor and 1 g of sublimed sulfur into a tube furnace under the nitrogen atmosphere for 300 goCalcining C for 1 h at a temperature rise rate of 0.5oC/min and nitrogen flow rate of 10 mL/min to obtain Fe-CoS2/CC。
The third step: Fe-CoS2Application of/CC electrolytic nitrate radical
1. Using Fe-CoS2And the/CC is a working electrode, the graphite electrode is a counter electrode, the Ag/AgCl electrode is used as a reference electrode, 0.1-2 mol/L sodium sulfate-sodium nitrate mixed solution is used as electrolyte, the electrocatalytic nitrate reduction process is carried out, the cyclic voltammetry voltage interval is-0.6-1.6V, the highest potential is-0.6V, the lowest potential is-1.6V, the starting potential is-0.6V, the ending potential is-1.6V, the scanning rate is 0.05V/s, the sampling interval is 0.001V, the standing time is 2 s, and the number of scanning sections is 500.
2. And performing linear voltage scanning test, wherein the voltage interval is-0.6-1.6V, the initial potential is-0.6V, the final potential is-1.6V, the scanning rate is 5 mV/s, the sampling interval is 0.001V, and the standing time is 2 s.
3. By Fe-CoS2the/CC is a working electrode, the catalyst is subjected to a long-time nitrate radical reduction test, and the potential is respectively set to-0.7V, -0.8V, -0.9V, -1.0V and-1.1V, and the running time is 7200 s.
The fourth step: ammonia production test
1. Drawing a working curve: by NH4Cl is standard reagent in 0.1 mol/L sodium sulfate-sodium nitrate mixed solution to prepare 0.0, 0.5, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0 mu g/mL standard solution respectively and carry out chromogenic reaction to test absorbance, 50 mu L oxidant (containing 75 wt% NaOH and 75 wt% NaClO), 500 mu L colorant (containing 40 wt% sodium salicylate and 32 wt% NaOH), and 50 mu L catalyst (5 wt% Na) are added to 4 mL standard solution in sequence2[Fe(NO)(CN)5] ·2H2O), standing in a dark place at room temperature for color development for 1 h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording the absorbance value at 660 nm and the concentration to obtain a standard curve by plotting.
2. And (3) testing the yield of ammonia: mu.L of the electrolyte after 1-hour operation at each potential was taken and diluted to 4.0 ml, and 50. mu.L of an oxidizing agent (containing 75 wt% NaOH and 75 wt% NaClO), 500. mu.L of a coloring agent (containing 40 wt% sodium salicylate and 32 wt% NaOH), and 50. mu.L of a catalyst (5 wt% Na) were sequentially added2[Fe(NO)(CN)5] ·2H2O), standing in a dark place at room temperature for color development for 1 h, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording an absorbance value at 660 nm, finally obtaining the concentration of ammonia, and performing data processing and calculation on the ammonia to obtain Fe-CoS2Application of/CC to NO3 -The RR effect is excellent, and the ammonia yield reaches 17.2 multiplied by 10 under-0.9V (relative to a standard hydrogen electrode)-2 mmol h-1 cm-2The Faraday efficiency is up to 88.92%.
Example 2
The first step is as follows: adding 100 mL of deionized water into a beaker, adding urea (0.781 g, 13 mmol), stirring for 30 min to form a clear transparent solution, continuously stirring, sequentially adding cobalt nitrate hexahydrate (0.5821 g, 2 mmol) and ferrous sulfate heptahydrate (0.056 g, 0.2 mmol), stirring for 30 min, transferring 40 mL of the solution and carbon cloth into a polytetrafluoroethylene inner container, sealing a hydrothermal autoclave, placing the hydrothermal autoclave in an oven at 120 ℃ for heat preservation for 12 h, naturally cooling, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain an iron-cobalt precursor.
The second step is that: putting an iron-cobalt precursor and 1 g of sublimed sulfur into a tube furnace under the nitrogen atmosphere for 300 goCalcining C for 1 h at a temperature rise rate of 0.5oC/min and nitrogen flow rate of 10 mL/min to obtain the nano-sheet Fe-CoS2/CC。
The third step: Fe-CoS2Application of/CC electrolytic nitrate radical
1. With Fe-CoS2the/CC is a working electrode, the graphite electrode is a counter electrode, and Ag/A is usedgCl electrode is a reference electrode, 0.1-2 mol/L sodium sulfate-sodium nitrate mixed solution is used as electrolyte, electrocatalysis nitrate radical reduction process is carried out, cyclic voltammetry test voltage interval is-0.6 to-1.6V, highest potential is-0.6V, lowest potential is-1.6V, starting potential is-0.6V, end potential is-1.6V, scanning speed is 0.05V/s, sampling interval is 0.001V, standing time is 2 s, and scanning section number is 500.
2. Carrying out linear voltage scanning test, wherein the voltage interval is-0.6 to-1.6V, the initial potential is-0.6V, the final potential is-1.6V, the scanning rate is 5 mV/s, the sampling interval is 0.001V, the standing time is 2 s, firstly, introducing argon into the electrolyte for 30 min, and carrying out the first linear voltage scanning test after the argon is saturated; and then introducing nitrogen into the electrolyte for 30 min, and carrying out a second linear voltage scanning test after the nitrogen is saturated.
3. By Fe-CoS2the/CC is a working electrode, the catalyst is subjected to a long-time nitrate radical reduction test, the potential is respectively set to-0.7V, -0.8V, -0.9V, -1.0V, -1.1V, and the running time is 7200 s.
The fourth step: ammonia production test
1. Drawing a working curve: by NH4Cl is standard reagent in 0.1 mol/L sodium sulfate-sodium nitrate mixed solution to prepare 0.0, 0.5, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0 mu g/mL standard solution respectively and carry out chromogenic reaction to test absorbance, 50 mu L oxidant (containing 75 wt% NaOH and 75 wt% NaClO), 500 mu L colorant (containing 40 wt% sodium salicylate and 32 wt% NaOH), and 50 mu L catalyst (5 wt% Na) are added to 4 mL standard solution in sequence2[Fe(NO)(CN)5] ·2H2O), standing in a dark place at room temperature for color development for 1 h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording the absorbance value at 660 nm and the concentration to obtain a standard curve by plotting.
2. And (3) testing the yield of ammonia: mu.L of the electrolyte after running for 1 h at each potential was taken and diluted to 4 mL, and 50. mu.L of an oxidizing agent (containing 75 wt% of NaOH and 75 wt% of NaClO) and 500. mu.L of a coloring agent (containing 40 wt% of salicylic acid) were added in this orderSodium and 32 wt% NaOH), 50. mu.L of catalyst (5 wt% Na)2[Fe(NO)(CN)5] ·2H2O), standing in a dark place at room temperature for color development for 1 h, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording an absorbance value at 660 nm, finally obtaining the concentration of ammonia, and performing data processing and calculation on the ammonia to obtain Fe-CoS2Application of/CC to NO3 -The RR effect is excellent, the ammonia yield reaches 17.1 x 10 under-0.9V (relative to standard hydrogen electrode)-2 mmol h-1 cm-2The Faraday efficiency is up to 88.92%.
Embodiment 3
The first step is as follows: adding 100 mL of deionized water into a beaker, adding urea (0.901 g, 15 mmol), stirring for 30 min to form a clear transparent solution, continuously stirring, sequentially adding cobalt chloride hexahydrate (0.2597 g, 2 mmol) and ferric nitrate nonahydrate (0.0808 g, 0.2 mmol), stirring for 30 min, transferring 40 mL of the solution and carbon cloth into a polytetrafluoroethylene inner container, sealing a hydrothermal high-pressure autoclave, placing the autoclave in a drying oven at 120 ℃ for heat preservation for 12 h, naturally cooling, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain an iron-cobalt precursor.
The second step is that: putting an iron-cobalt precursor and 1 g of sublimed sulfur into a tube furnace under the nitrogen atmosphere for 300 goCalcining C for 1 h at a temperature rise rate of 0.5oC/min and nitrogen flow of 10 mL/min to obtain the nanosheet Fe-CoS2/CC。
The third step: Fe-CoS2CC electrolyzed water application.
1. By Fe-CoS2And the/CC is a working electrode, the graphite electrode is a counter electrode, the Ag/AgCl electrode is used as a reference electrode, 0.1-2 mol/L sodium sulfate-sodium nitrate mixed solution is used as electrolyte, the electrocatalytic nitrate reduction process is carried out, the cyclic voltammetry voltage interval is-0.6 to-1.6V, the highest potential is-0.6V, the lowest potential is-1.6V, the starting potential is-0.6V, the ending potential is-1.6V, the scanning rate is 0.05V/s, the sampling interval is 0.001V, the standing time is 2 s, and the number of scanning sections is 500.
2. And performing a linear voltage scanning test, wherein the voltage interval is-0.6 to-1.6V. The initial potential was-0.6V, the end potential was-1.6V, the scan rate was 5 mV/s, the sampling interval was 0.001V, and the rest time was 2 s.
3. With Fe-CoS2the/CC is a working electrode, the catalyst is subjected to a long-time nitrate radical reduction test, and the potential is respectively set to-0.7V, -0.8V, -0.9V, -1.0V and-1.1V, and the running time is 7200 s.
The fourth step: ammonia production test
1. Drawing a working curve: by NH4Cl is standard reagent in 0.1 mol/L sodium sulfate-sodium nitrate mixed solution to prepare 0.0, 0.5, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 6.0 mu g/mL standard solution respectively and carry out chromogenic reaction to test absorbance, 50 mu L oxidant (containing 75 wt% NaOH and 75 wt% NaClO), 500 mu L colorant (containing 40 wt% sodium salicylate and 32 wt% NaOH), and 50 mu L catalyst (5 wt% Na) are added to 4 mL standard solution in sequence2[Fe(NO)(CN)5] ·2H2O), standing in a dark place at room temperature for 1 h for color development, performing spectral scanning by using an ultraviolet-visible spectrophotometer within the wavelength range of 550 nm-800 nm, and recording the absorbance value at 660 nm and the concentration for plotting to obtain a standard curve.
2. And (3) testing the yield of ammonia: mu.L of the electrolyte solution after 1-hour operation at each potential was taken and diluted to 4 mL, and 50. mu.L of an oxidizing agent (containing 75 wt% NaOH and 75 wt% NaClO), 500. mu.L of a coloring agent (containing 40 wt% sodium salicylate and 32 wt% NaOH), and 50. mu.L of a catalyst (5 wt% Na) were sequentially added2[Fe(NO)(CN)5] ·2H2O), standing in a dark place at room temperature for color development for 1 h, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording an absorbance value at 660 nm, finally obtaining the concentration of ammonia, and performing data processing and calculation on the ammonia to obtain Fe-CoS2Application of/CC to NO3 -The RR effect is excellent, and the ammonia yield reaches 17.2 multiplied by 10 under 0.9V (relative to a standard hydrogen electrode)-2 mmol h-1 cm-2The Faraday efficiency is up to 88.90%.
Example 4
The first step is as follows: adding 100 mL of deionized water into a beaker, adding urea (1.051 g, 17.5 mmol), stirring for 30 min to form a clear transparent solution, continuously stirring, sequentially adding cobalt nitrate hexahydrate (1.164 g, 4 mmol) and ferric nitrate nonahydrate (0.1616 g, 0.4 mmol), stirring for 30 min, transferring 40 mL of the solution and carbon cloth into a polytetrafluoroethylene inner container, sealing a hydrothermal autoclave, placing the hydrothermal autoclave in a 120-DEG C oven for heat preservation for 12 h, naturally cooling, washing with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain an iron-cobalt precursor.
The second step: putting an iron-cobalt precursor and 1 g of sublimed sulfur into a tube furnace under the nitrogen atmosphere for 300 goCalcining C for 1 h at a temperature rise rate of 0.5oC/min and nitrogen flow rate of 10 mL/min to obtain Fe-CoS2/CC。
The third step: nanosheet Fe-CoS2CC electrolyzed water application.
1. By Fe-CoS2And the/CC is a working electrode, the graphite electrode is a counter electrode, the Ag/AgCl electrode is used as a reference electrode, 0.1-2 mol/L sodium sulfate-sodium nitrate mixed solution is used as electrolyte, the electrocatalytic nitrate reduction process is carried out, the cyclic voltammetry voltage interval is-0.6 to-1.6V, the highest potential is-0.6V, the lowest potential is-1.6V, the starting potential is-0.6V, the ending potential is-1.6V, the scanning rate is 0.05V/s, the sampling interval is 0.001V, the standing time is 2 s, and the number of scanning sections is 500.
2. And performing linear voltage scanning test, wherein the voltage interval is-0.6 to-1.6V, the initial potential is-0.6V, the final potential is-1.6V, the scanning rate is 5 mV/s, the sampling interval is 0.001V, and the standing time is 2 s.
3. By Fe-CoS2the/CC is a working electrode, the catalyst is subjected to a long-time nitrate radical reduction test, and the potential is respectively set to-0.7V, -0.8V, -0.9V, -1.0V and-1.1V, and the running time is 7200 s.
The fourth step: ammonia production test
1. Drawing a working curve: by NH4Cl is used as a standard reagent, 0.0, 0.5, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 and 6.0 mu g/mL standard solutions are respectively prepared in 0.1 mol/L sodium sulfate-sodium nitrate mixed solution and are subjected to color reaction to test absorbance, and 50 mu L of standard solution is taken and added into 4 mL of standard solution in sequenceOxidizing agent (containing 75 wt% NaOH and 75 wt% NaClO), 500. mu.L colorant (containing 40 wt% sodium salicylate and 32 wt% NaOH), 50. mu.L catalyst (5 wt% Na)2[Fe(NO)(CN)5] ·2H2O), standing in a dark place at room temperature for color development for 1 h, performing spectral scanning in a wavelength range of 550 nm-800 nm by using an ultraviolet visible spectrophotometer, and recording the absorbance value at 660 nm and the concentration to obtain a standard curve by plotting.
2. And (3) testing the yield of ammonia: mu.L of the electrolyte solution after 1-hour operation at each potential was taken and diluted to 4 mL, and 50. mu.L of an oxidizing agent (containing 75 wt% NaOH and 75 wt% NaClO), 500. mu.L of a coloring agent (containing 40 wt% sodium salicylate and 32 wt% NaOH), and 50. mu.L of a catalyst (5 wt% Na) were sequentially added2[Fe(NO)(CN)5] ·2H2O), standing in a dark place at room temperature for color development for 1 h, performing spectral scanning in a wavelength range of 550-800 nm by using an ultraviolet visible spectrophotometer, recording an absorbance value at 660 nm, finally obtaining the concentration of ammonia, and performing data processing and calculation on the ammonia to obtain Fe-CoS2Application of/CC to NO3 -The RR effect is excellent, and the ammonia yield reaches 17.1 multiplied by 10 under 0.9V (relative to a standard hydrogen electrode)-2 mmol h-1 cm-2The Faraday efficiency is up to 88.93%.
Claims (4)
1. Fe-CoS2The preparation method of the/CC nitrate radical reduction catalyst is characterized by comprising the following preparation steps:
(1) adding cobalt and iron reagents with a fixed proportion into a specific reaction solution to prepare a pre-reaction solution, adding the pre-reaction solution and carbon cloth with a certain size into a reaction kettle by a hydrothermal synthesis method, heating for a certain time at a certain temperature, naturally cooling, washing, drying and collecting the obtained iron-cobalt precursor;
(2) putting the iron-cobalt precursor into a tube furnace, fixing nitrogen flow rate and calcining temperature, and adding a certain amount of sulfur powder as a vulcanizing reagent to carry out vulcanization reaction to obtain the catalyst material iron-cobalt sulfide hybrid Fe-CoS2/CC。
2. The nanoplatelet Fe-CoS of claim 12The preparation method of the/CC nitrate radical reduction catalyst is characterized in that:
in the step (1), the specific reaction solution is an aqueous solution of urea; the cobalt source reagent is one or more of cobalt nitrate hexahydrate, cobalt chloride, cobalt acetylacetonate, cobalt sulfate and cobalt acetate tetrahydrate, and the concentration of the cobalt source solution is 0.001-0.02 mol/L; the iron source is one or more of ferric nitrate nonahydrate, ferric trichloride hexahydrate, ferrous sulfate heptahydrate and ferric sulfate, and the concentration of the iron source solution is 0.0002-0.002 mol/L; the molar ratio of the cobalt source to the iron source is 10: 1-1: 1; the reaction temperature of the iron-cobalt pre-reaction liquid is 100 DEG oC ~ 180 oC, the reaction time is 6-14 h;
in the step (2), the nitrogen flow rate is 10-50 mL/min; the used sulfuration reagent is sublimed sulfur, wherein the mass ratio of the sulfuration reagent to the iron-cobalt precursor is 1: 10-1: 100; the sulfurization temperature of the iron-cobalt precursor in the tube furnace is 300 DEGoC ~ 600 oC, vulcanizing for 1-6 h at a heating rate of 0.5oC/min。
3. Fe-CoS2The preparation method of the/CC nitrate radical reduction catalyst is characterized in that a single-chamber membrane electrode nitrate radical reduction electrocatalysis performance test is adopted, and the steps are as follows: the electrocatalysis nitrate radical reduction process adopts a three-electrode system and adopts Fe-CoS through a self-designed electrolytic cell2the/CC is used as a working electrode, the graphite electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, and the 0.1-2 mol/L sodium sulfate-sodium nitrate mixed solution is used as an electrolyte.
4. Fe-CoS2The preparation method of the/CC nitrate radical reduction catalyst is characterized in that the single-chamber membrane electrode nitrate radical reduction electrocatalysis test system is shown in figure 1, and (1) an insulating layer is arranged; (2) a fixed base; (3) an ammonia solution storage tank; (4) the sodium sulfate-sodium nitrate mixed electrolyte is prepared; (5) a water outlet; (6) a water inlet; (7) a liquid inlet; (8) a counter electrode; (9) a reference electrode; (10) working electricityPole (Fe-CoS)2/CC）。
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