CN112473698B - Sulfur vacancy Cu-MoS 2 Process for preparing catalyst - Google Patents

Sulfur vacancy Cu-MoS 2 Process for preparing catalyst Download PDF

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CN112473698B
CN112473698B CN202011301601.8A CN202011301601A CN112473698B CN 112473698 B CN112473698 B CN 112473698B CN 202011301601 A CN202011301601 A CN 202011301601A CN 112473698 B CN112473698 B CN 112473698B
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CN112473698A (en
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叶伟
陶婷
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Hangzhou Normal University
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    • B01J35/50—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J35/33—
    • 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
    • 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
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
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    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to the field of catalytic materials, and discloses a sulfur vacancy Cu-MoS aiming at the problem of low catalytic activity of the existing electrocatalytic nitrogen fixation catalyst 2 A method of preparing a catalyst comprising: preparation of MoO 3 A nanoribbon; adding MoO 3 Dissolving the nanobelt in a first solvent, stirring until the nanobelt is dissolved, adding thiourea and a compound of cupric, stirring until the thiourea and the compound of cupric are dissolved, reacting in a reaction kettle, and centrifuging and washing to obtain Cu-doped MoS 2 A catalyst; MoS doping Cu 2 Calcining the catalyst under protective gas; MoS doping of calcined Cu 2 And carrying out plasma treatment. MoS prepared by the invention 2 The catalyst, Cu doping forms heteronuclear diatomic center, and simultaneously introduces sulfur vacancy, realizes the structural design of defect catalyst and heteronuclear diatomic, the invention prepares Cu-MoS 2 The catalyst shows excellent electrocatalytic nitrogen reduction activity, and the synthesis method has mild reaction conditions and high yield, and is suitable for large-scale production of the catalyst.

Description

Sulfur vacancy Cu-MoS 2 Process for preparing catalyst
Technical Field
The invention relates to the field of catalytic materials, in particular to a Cu-MoS with sulfur vacancy 2 A method for preparing the catalyst.
Background
NH 3 Is an important chemical substance for producing chemical fertilizers, dyes, explosives, resins and the like, and the most important application of the chemical fertilizer is to produce the chemical fertilizers, and the annual output is up to two hundred million tons. Therefore, the artificial nitrogen fixation is obviousThis is particularly important. Although N is 2 Is the most abundant molecule in the atmosphere, but its thermodynamic stability and non-polarity make it chemically inert, N 2 Reduction to NH 3 Is a very difficult challenge. The method for fixing nitrogen in industry adopts a haber-bosch method, namely a process of generating ammonia gas by reacting nitrogen and hydrogen at 400 ℃ and 200 atmospheric pressures. The reaction of the process needs high temperature and high pressure, and the reaction conditions are harsh and energy consumption is large. And its reactant hydrogen is derived from water gas reforming, the capture process aggravates CO 2 The emission of (2) not only consumes a large amount of energy, but also aggravates the greenhouse effect. Therefore, more and more people pay more attention to develop a more environment-friendly artificial nitrogen fixation method.
At present, the methods for fixing nitrogen artificially mainly comprise thermal catalysis, electrocatalysis, photocatalysis and the like. The electrocatalytic nitrogen fixation can greatly improve the nitrogen reduction activity because the electrode surface can provide a plurality of electrons with high activity, and the hydrogen gas is from the protons in the electrolyte, so the acquisition way is safer and more environment-friendly, thereby the electrocatalytic nitrogen fixation is widely concerned by scientists and researchers. Therefore, the research on the catalyst for improving the catalytic activity of the nitrogen fixation reaction has important significance.
The invention belongs to the technical field of semiconductor photocatalysis, and particularly relates to a sulfur indium zinc photocatalyst rich in a surface sulfur vacancy defect state structure (ZnIn) 2 S 4 ) A photocatalyst and a preparation method thereof. The invention provides a sulfur indium zinc photocatalyst rich in surface sulfur vacancy defect state structure and a preparation method thereof, and the preparation method is characterized in that: after high-temperature and high-pressure hydrogenation treatment, a large number of sulfur vacancy defect state structures exist on the surface of the sulfur indium zinc photocatalyst. Compared with an unmodified sulfur indium zinc photocatalyst, a sulfur indium zinc photocatalyst rich in surface sulfur vacancy defect state structure has a large number of sulfur vacancy defect state structures on the surface of the photocatalyst, and the surface sulfur vacancy defects can form photogenerated carrier capture traps, effectively promote the separation of photogenerated charges and reduce photogenerated electrons? Recombination of hole pairs, thereby largelyThe photocatalytic hydrogen production performance is improved.
The method has the disadvantages that the improvement of the catalytic activity of the catalyst only stays in the introduction of the sulfur vacancy defect, and the improvement capability of the catalytic activity is limited.
Disclosure of Invention
The invention provides a sulfur vacancy Cu-MoS for overcoming the problem of low catalytic activity of the existing electrocatalytic nitrogen fixation catalyst 2 The invention discloses a preparation method of a catalyst, and realizes the preparation of a sulfide sulfur vacancy catalyst and the prepared MoS 2 The catalyst presents a nanometer flower structure, Cu doping forms heteronuclear diatomic center, and simultaneously introduces sulfur vacancy, thus perfectly realizing the structural design of defect catalyst and heteronuclear diatomic 2 The catalyst shows excellent electrocatalytic nitrogen reduction activity, and the synthesis method has mild reaction conditions and high yield, and is suitable for large-scale production of the catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
sulfur vacancy Cu-MoS 2 The preparation method of the catalyst comprises the following steps:
(1) dissolving sodium molybdate in a first solvent, adding a second solvent, stirring, reacting in a reaction kettle, and centrifugally washing to obtain a MoO3 nanobelt;
(2) adding MoO 3 Dissolving the nanobelt in a first solvent, stirring until the nanobelt is dissolved, adding thiourea and a compound of cupric, stirring until the thiourea and the compound of cupric are dissolved, reacting in a reaction kettle, and centrifuging and washing to obtain Cu-doped MoS 2 A catalyst;
(3) MoS doping Cu 2 Calcining the catalyst under protective gas;
(4) calcining the Cu-doped MoS 2 And treating with plasma to obtain the product.
The heteronuclear diatoms have different electronegativities of the two atoms, so that nitrogen is converted into polar molecules from original nonpolar molecules by receiving different numbers of effective electrons when nitrogen molecules are adsorbed to metal atoms, thereby promoting the adsorption and activation of the nitrogen molecules on the surface of the catalyst, and promoting the self-activation of the nitrogen moleculesIn the world, molybdenum-dependent nitrogen fixation enzymes catalyze N through multiple proton and electron transfer steps 2 And (4) fixing. The molecular compound with molybdenum as the substrate is proved to be a good nitrogen fixing material, and for the electro-catalysis nitrogen fixing catalyst, vacancies are introduced into the material, so that the electron capture capacity can be improved, the energy band structure can be adjusted, the reaction path can be changed, and the catalytic activity of the nitrogen fixing reaction can be improved.
The invention provides a method for preparing Cu-doped MoS with sulfur vacancy 2 The method of the catalyst comprises the following steps of preparing the copper-doped MoS by a hydrothermal synthesis method by taking molybdenum oxide as a template 2 Under the bombardment of oxygen plasma, obtaining Cu-MoS with sulfur vacancy 2 Compared with the existing compound taking molybdenum as a substrate, the catalyst can realize Cu-doped MoS 2 And contains sulfur defects. The method has mild reaction conditions and provides a direction for artificial nitrogen fixation.
Preferably, in the step (1), the concentration of sodium molybdate is 0.1-1mol/L, the first solvent is water, and the second solvent is nitric acid.
Preferably, in the step (1), the volume ratio of the sodium molybdate to the first solvent to the second solvent is 0.5-0.8: 5-10: and 1, dropwise adding the second solvent.
Preferably, in the step (1), the reaction temperature is 150 ℃ and 250 ℃, and the reaction time is 16-20 h.
Only in the temperature and time range of synthesis, MoO with high structural stability and good catalytic activity can be prepared 3 Nanobelts to finally prepare sulfur vacancy Cu-MoS with excellent performance 2 The catalyst has strong promoting effect.
Preferably, in the step (2), the cupric compound is one of cupric chloride, cupric sulfate, cupric nitrate and cupric acetate.
Preferably, in the step (2), MoO 3 The molar ratio of the compound of the nanobelt, the thiourea and the divalent copper is 0.08: 1-1.1: 0.005-0.01.
Preferably, in the step (2), the reaction temperature is 100-200 ℃, and the reaction time is 10-14 h.
Preferably, in the step (3), the protective gas is one of argon and nitrogen, the calcination temperature is 350-500 ℃, and the calcination time is 180-320 min.
If the calcination temperature is too low, the catalytic activity cannot be effectively molded, and if the calcination temperature is too high, the structural stability and the catalytic activity in the catalyst can be damaged, so that the overall catalytic capability of the catalyst is reduced.
Preferably, in the step (4), the process gas for plasma treatment is one of oxygen and nitrogen.
Preferably, in the step (4), the plasma treatment time is 50-70 min.
Therefore, the invention has the following beneficial effects:
(1) firstly, the Cu-MoS obtained by the invention 2 A catalyst exhibiting a nanoflower structure;
(2) second, our resulting MoS 2 Has defects which can expose more active sites, and sulfur defects are increased along with the increase of the oxygen plasma treatment time, relative to the Cu-MoS without the defects 2 A catalyst, which has higher catalytic activity;
(3) moreover, the obtained catalyst has a Cu-Mo diatomic heteronuclear catalytic center, and the doping of copper can adjust the electronic structure of the catalyst;
(4) based on the structural advantages, the Cu-MoS of the invention 2 The catalyst can widely meet the requirements of catalysis, and shows higher catalytic activity in an acid electrolyte.
Drawings
FIG. 1 is a Cu-MoS alloy with sulfur vacancies of example 1 2 Scanning electron micrographs of the catalyst with a scale of 200 nm.
FIG. 2 is Cu-MoS having no S vacancies of comparative example 1 2 A transmission electron micrograph of the catalyst is taken at 100 nm.
Detailed Description
The invention is further described below with reference to specific embodiments.
General examples
Sulfur vacancy Cu-MoS 2 The preparation method of the catalyst comprises the following steps:
(1) dissolving sodium molybdate with the concentration of 0.1-1mol/L in water, then dropwise adding nitric acid and stirring, reacting for 16-20h in a reaction kettle at the temperature of 150- 3 A nanoribbon; the volume ratio of the sodium molybdate to the water to the nitric acid is 0.5-0.8: 5-10: 1
(2) Adding MoO 3 Dissolving the nanobelt in water, stirring until the nanobelt is dissolved, adding thiourea and a compound of divalent copper, stirring until the thiourea and the compound of divalent copper are dissolved, reacting for 10-14h at the temperature of 100 ℃ and 200 ℃ in a reaction kettle, and centrifuging and washing to obtain Cu-doped MoS 2 A catalyst; MoO 3 The molar ratio of the compound of the nanobelt, the thiourea and the divalent copper is 0.08: 1-1.1: 0.005-0.01; the cupric compound is one of cupric chloride, cupric sulfate, cupric nitrate and cupric acetate;
(3) MoS doping Cu 2 The catalyst is calcined at 500 ℃ under the protection gas (argon and nitrogen) for 180-320 min; (4) calcining the Cu-doped MoS 2 Treating with plasma for 50-70min to obtain product; the process gas for plasma treatment is one of oxygen and nitrogen.
Example 1
Sulfur vacancy Cu-MoS 2 The preparation method of the catalyst comprises the following steps:
(1) dissolving sodium molybdate with the concentration of 0.5mol/L in water, then dropwise adding nitric acid and stirring, reacting for 18h at the temperature of 200 ℃ in a reaction kettle, and centrifugally washing to obtain MoO 3 A nanoribbon; the volume ratio of sodium molybdate, water and nitric acid is 0.65: 8: 1
(2) Adding MoO 3 Dissolving the nanobelt in water, stirring until the nanobelt is dissolved, adding thiourea and a cupric compound, stirring until the thiourea and the cupric compound are dissolved, reacting in a reaction kettle at 150 ℃ for 12 hours, and centrifuging and washing to obtain Cu-doped MoS 2 A catalyst; MoO 3 The molar ratio of the compounds of the nanobelt, the thiourea and the divalent copper is 0.08: 1.05: 0.008; the compound of divalent copper is cupric chloride;
(3) MoS doping Cu 2 Calcining the catalyst for 250min at 430 ℃ under the protection gas nitrogen;
(4) will be calcinedPost-fired Cu doped MoS 2 Treating with plasma for 60min to obtain product; the process gas for plasma treatment is nitrogen.
Example 2
Sulfur vacancy Cu-MoS 2 The preparation method of the catalyst comprises the following steps:
(1) dissolving sodium molybdate with the concentration of 0.1mol/L in water, then dropwise adding nitric acid and stirring, reacting for 16-20h at 250 ℃ in a reaction kettle, and centrifuging and washing to obtain MoO 3 A nanoribbon; the volume ratio of sodium molybdate, water and nitric acid is 0.5: 10: 1
(2) Adding MoO 3 Dissolving the nanobelt in water, stirring until the nanobelt is dissolved, adding thiourea and a cupric compound, stirring until the thiourea and the cupric compound are dissolved, reacting in a reaction kettle at 100 ℃ for 14 hours, and centrifuging and washing to obtain Cu-doped MoS 2 A catalyst; MoO 3 The molar ratio of the compound of the nanobelt, the thiourea and the divalent copper is 0.08: 1: 0.01; the compound of bivalent copper is cupric chloride;
(3) MoS doping Cu 2 Calcining the catalyst for 320min at 350 ℃ under the protection gas argon;
(4) calcining the Cu-doped MoS 2 Treating with plasma for 50min to obtain product; the process gas for plasma treatment is oxygen.
Example 3
Sulfur vacancy Cu-MoS 2 The preparation method of the catalyst comprises the following steps:
(1) dissolving sodium molybdate with the concentration of 1mol/L in water, then dropwise adding nitric acid and stirring, reacting for 20 hours at the temperature of 150 ℃ in a reaction kettle, and centrifugally washing to obtain MoO 3 A nanoribbon; the volume ratio of sodium molybdate, water and nitric acid is 0.8: 5: 1
(2) Adding MoO 3 Dissolving the nanobelt in water, stirring to dissolve, adding thiourea and a cupric compound, stirring to dissolve, reacting in a reaction kettle at 200 ℃ for 10 hours, and centrifuging and washing to obtain Cu-doped MoS 2 A catalyst; MoO 3 The molar ratio of the compound of the nanobelt, the thiourea and the divalent copper is 0.08: 1.1: 0.005; the compound of bivalent copper is copper sulfate;
(3) MoS doping Cu 2 Catalyst retentionCalcining at 500 deg.C for 180min under protective gas nitrogen;
(4) calcining the Cu-doped MoS 2 Treating with plasma for 70min to obtain product; the process gas for plasma treatment is oxygen.
Example 4
Sulfur vacancy Cu-MoS 2 The preparation method of the catalyst comprises the following steps:
(1) dissolving sodium molybdate with the concentration of 0.4mol/L in water, then dropwise adding nitric acid and stirring, reacting for 17 hours at the temperature of 180 ℃ in a reaction kettle, and centrifugally washing to obtain MoO 3 A nanoribbon; the volume ratio of sodium molybdate, water and nitric acid is 0.6: 6: 1
(2) Adding MoO 3 Dissolving the nanobelt in water, stirring until the nanobelt is dissolved, adding thiourea and a cupric compound, stirring until the thiourea and the cupric compound are dissolved, reacting in a reaction kettle at 130 ℃ for 11 hours, and centrifuging and washing to obtain Cu-doped MoS 2 A catalyst; MoO 3 The molar ratio of the compounds of the nanobelt, the thiourea and the divalent copper is 0.08: 1.03: 0.007; the compound of bivalent copper is copper nitrate;
(3) MoS doping Cu 2 Calcining the catalyst at 400 ℃ for 200min under protective gas (argon and nitrogen);
(4) the calcined Cu-doped MoS 2 Treating with plasma for 55min to obtain product; the process gas for plasma treatment is one of oxygen and nitrogen.
Example 5
Sulfur vacancy Cu-MoS 2 The preparation method of the catalyst comprises the following steps:
(1) dissolving sodium molybdate with the concentration of 0.8mol/L in water, then dropwise adding nitric acid and stirring, reacting for 19 hours at 200 ℃ in a reaction kettle, and centrifuging and washing to obtain MoO 3 A nanoribbon; the volume ratio of sodium molybdate, water and nitric acid is 0.7: 9: 1
(2) Adding MoO 3 Dissolving the nanobelt in water, stirring until the nanobelt is dissolved, adding thiourea and a cupric compound, stirring until the thiourea and the cupric compound are dissolved, reacting for 13 hours at 180 ℃ in a reaction kettle, and centrifuging and washing to obtain Cu-doped MoS 2 A catalyst; MoO 3 The molar ratio of the compounds of the nanobelt, the thiourea and the divalent copper is 0.08: 1.08: 0.009; the compound of bivalent copper is copper acetate;
(3) MoS doping Cu 2 Calcining the catalyst for 300min at 450 ℃ under the protection of nitrogen gas;
(4) calcining the Cu-doped MoS 2 Treating with plasma for 65min to obtain product; the process gas for plasma treatment is one of oxygen and nitrogen.
Comparative example 1 (differing from example 1 in that Cu-MoS 2 The catalyst does not contain sulfur vacancies. )
Sulfur vacancy Cu-MoS 2 The preparation method of the catalyst comprises the following steps:
(1) dissolving sodium molybdate with the concentration of 0.5mol/L in water, then dropwise adding nitric acid and stirring, reacting for 18 hours at the temperature of 200 ℃ in a reaction kettle, and centrifugally washing to obtain MoO 3 A nanoribbon; the volume ratio of sodium molybdate, water and nitric acid is 0.65: 8: 1
(2) Adding MoO 3 Dissolving the nanobelt in water, stirring until the nanobelt is dissolved, adding thiourea and a cupric compound, stirring until the thiourea and the cupric compound are dissolved, reacting in a reaction kettle at 150 ℃ for 12 hours, and centrifuging and washing to obtain Cu-doped MoS 2 A catalyst; MoO 3 The molar ratio of the compound of the nanobelt, the thiourea and the divalent copper is 0.08: 1.05: 0.008; the compound of divalent copper is cupric chloride;
(3) MoS doping Cu 2 Calcining the catalyst for 250min at 430 ℃ under the protection of nitrogen gas;
comparative example 2 (differing from example 1 in that the catalyst was MoS containing only sulfur vacancies 2 A catalyst. )
Sulfur vacancy Cu-MoS 2 The preparation method of the catalyst comprises the following steps:
(1) dissolving sodium molybdate with the concentration of 0.5mol/L in water, then dropwise adding nitric acid and stirring, reacting for 18h at the temperature of 200 ℃ in a reaction kettle, and centrifugally washing to obtain MoO 3 A nanoribbon; the volume ratio of sodium molybdate, water and nitric acid is 0.65: 8: 1
(2) Adding MoO 3 Dissolving the nanobelt in water, stirring until the nanobelt is dissolved, adding thiourea, stirring until the thiourea is dissolved, reacting in a reaction kettle at 150 ℃ for 12 hours, and centrifuging and washing to obtain MoS 2 A catalyst; MoO 3 The compound molar ratio of the nanobelt to the thiourea is 0.08: 1.05; (3) MoS doping Cu 2 Calcining the catalyst for 250min at 430 ℃ under the protection gas nitrogen;
(4) the calcined MoS is treated 2 Treating with plasma for 60min to obtain product; the process gas for plasma treatment is one of nitrogen.
For the above examples and comparative examples, Cu-MoS with Sulfur vacancies 2 The catalyst is used for electrochemical nitrogen reduction reaction, and the catalytic reaction activity of the catalyst is evaluated by the following specific method:
Cu-MoS with sulfur vacancies 2 Catalyst for electrochemical nitrogen reduction reaction
1 mg of the Cu-MoS vacancy prepared in each item 2 The catalyst was dispersed in a mixed solution of 0.075 ml of distilled water, 0.025 ml of isopropyl alcohol and 0.02 ml of naphthol and sonicated for 30 minutes to obtain a catalyst slurry. And uniformly dripping 12 microliter of slurry on the surface of the ground electrode, wherein the area of the electrode is 0.19625 square centimeters. The electrochemical workstation used was Chenghua electrochemical workstation, and the rotating disk test system used was the equipment produced by Pine corporation, USA. The nitrogen reduction performance was then measured in a 0.05 mole per liter sulfuric acid solution saturated with nitrogen. Sulfur vacancy Cu-MoS prepared in detection project 2 Ammonia production and faraday efficiency of the catalyst under acidic conditions.
Table 1 evaluation of the effectiveness of the various items and of the Cu-MoS2 catalyst with respect to sulfur vacancies
Item Ammonia production (ug h) -1 mg -1 cat-1 ) Faraday efficiency (%)
Example 1 7.9 17.6
Example 2 18.4 22.1
Example 3 27.3 27.4
Example 4 14.7 21.3
Example 5 12.4 18.2
Comparative example 1 5.3 5.8
Comparative example 2 3.6 4.1
And (4) conclusion: as can be seen from examples 1 to 5, only within the parameter range of the production method of the present invention, a sulfur vacancy Cu-MoS having a large number of catalytic sites and high reactivity can be produced 2 A catalyst.
Comparative example 1 differs from example 1 in that Cu-MoS 2 The catalyst does not contain sulfur vacancy; the absence of sulfur vacancies reduced the catalyst reactivity and contact area, which resulted in a decrease in the overall catalytic activity of the catalyst, and therefore the corresponding data was all reduced.
Comparative example 2 differs from example 1 in that the catalyst was MoS containing only sulfur vacancies 2 A catalyst; the heteronuclear diatoms have different electronegativities of the two atoms, so that nitrogen is converted into polar molecules from original nonpolar molecules by receiving different numbers of effective electrons when nitrogen molecules are adsorbed to metal atoms, adsorption and activation of the nitrogen molecules on the surface of the catalyst are promoted, and the catalytic activity of the catalyst is remarkably reduced because the heteronuclear diatoms are not contained.
It can be seen from the data of examples 1-5 and comparative examples 1-2 that only the solution within the scope of the claims of the present invention can satisfy the above requirements in all aspects, and an optimized solution can be obtained, and an optimal Cu-MoS with sulfur vacancy can be obtained 2 A catalyst. The change of the mixture ratio, the replacement/addition/subtraction of raw materials or the change of the feeding sequence can bring corresponding negative effects.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.

Claims (10)

1. Sulfur vacancy Cu-MoS 2 The application of the catalyst in electrochemical nitrogen reduction reaction is characterized in that the sulfur vacancy Cu-MoS 2 The preparation method of the catalyst comprises the following steps:
(1) dissolving sodium molybdate in a first solvent, adding a second solvent, stirring, reacting in a reaction kettle, and centrifugally washing to obtain MoO 3 A nanoribbon;
(2) adding MoO 3 Dissolving the nanobelt in a first solvent, stirring until the nanobelt is dissolved, adding thiourea and a cupric compound, stirring until the thiourea and the cupric compound are dissolved, reacting in a reaction kettle, and centrifuging and washing to obtain Cu-doped MoS 2 A catalyst;
(3) MoS doping Cu 2 Calcining the catalyst under protective gas;
(4) the calcined Cu-doped MoS 2 And treating with plasma to obtain the product.
2. The Cu-MoS with sulfur vacancy of claim 1 2 The application of the catalyst in the electrochemical nitrogen reduction reaction is characterized in that in the step (1), the concentration of sodium molybdate is 0.1-1mol/L, the first solvent is water, and the second solvent is nitric acid.
3. The Cu-MoS with sulfur vacancy as claimed in claim 1 2 The application of the catalyst in the electrochemical nitrogen reduction reaction is characterized in that in the step (1), the volume ratio of sodium molybdate to the first solvent to the second solvent is 0.5-0.8: 5-10:and 1, dropwise adding the second solvent.
4. The Cu-MoS with sulfur vacancy as claimed in claim 1 2 The application of the catalyst in the electrochemical nitrogen reduction reaction is characterized in that in the step (1), the reaction temperature is 150-250 ℃, and the reaction time is 16-20 h.
5. The Cu-MoS with sulfur vacancy of claim 1 2 The application of the catalyst in the electrochemical nitrogen reduction reaction is characterized in that in the step (2), the compound of the bivalent copper is one of copper chloride, copper sulfate, copper nitrate and copper acetate.
6. The Cu-MoS with sulfur vacancy of claim 1 2 The application of the catalyst in the electrochemical nitrogen reduction reaction is characterized in that in the step (2), MoO 3 The molar ratio of the compounds of the nanobelt, the thiourea and the divalent copper is 0.08: 1-1.1: 0.005-0.01.
7. The Cu-MoS with sulfur vacancy of claim 1 2 The application of the catalyst in the electrochemical nitrogen reduction reaction is characterized in that in the step (2), the reaction temperature is 100-200 ℃, and the reaction time is 10-14 h.
8. The Cu-MoS with sulfur vacancy of claim 1 2 The application of the catalyst in the electrochemical nitrogen reduction reaction is characterized in that in the step (3), the protective gas is one of argon and nitrogen, the calcination temperature is 350-500 ℃, and the calcination time is 180-320 min.
9. The Cu-MoS with sulfur vacancy as claimed in claim 1 2 The application of the catalyst in the electrochemical nitrogen reduction reaction is characterized in that in the step (4), the process gas for plasma treatment is one of oxygen and nitrogen.
10. The Cu-MoS with sulfur vacancy of claim 1 2 The application of the catalyst in the electrochemical nitrogen reduction reaction is characterized in that in the step (4), the plasma treatment time is 50-70 min.
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