CN113089000B - Molybdenum-based catalyst with in-plane defects and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a molybdenum-based catalyst with in-plane defects and a preparation method and application thereof. The molybdenum disulfide electrocatalyst prepared by the invention has rich in-plane defects, can effectively adsorb and activate dinitrogen molecules, has good stability, large specific surface area and good electrocatalytic performance, and simultaneously keeps high thermal stability and the like.
Description
Technical Field
The invention relates to a preparation method and application of a molybdenum-based catalyst with in-plane defects, belonging to the technical fields of material synthesis, electrocatalysis and fine chemical engineering.
Background
The synthetic ammonia is one of the most important inventions in the 20 th century, and makes a great contribution to the promotion of the progress of the human society. Ammonia is one of the most important basic chemical products, and the yield is the first of various chemical products. Currently, the global ammonia yield is about 5 hundred million tons, and the method has a quite important position in the aspects of food and energy chemistry; among them, 90% of ammonia is used in the fertilizer industry, and the emergence and development of the fertilizer industry have greatly improved crop yield, thereby solving the problem of grains caused by the rapid growth of population.
The Haber-Bosch process (Haber-Bosch process) is widely used for industrial synthesis of ammonia, i.e. synthesis of ammonia from nitrogen and hydrogen under high temperature and high pressure conditions and under the action of iron-based catalyst, and synthesis of ammonia by Haber process requires high pressure>700bar), high temperature (>673K) The process has high energy consumption and serious pollution, the energy consumption of the whole process accounts for 1 to 2 percent of the annual energy consumption of the world, the used high-purity hydrogen is derived from the natural gas reforming of fossil fuel, and annual CO2The discharge amount is up to 4.5 hundred million tons. In contrast to the industrial synthesis of ammonia, biological nitrogen fixation is a process in which plants and bacteria convert nitrogen in the atmosphere into ammonia at normal temperature and pressure by using nitrogenase, but the ammonia obtained by biological nitrogen fixation cannot meet the requirements of human beings. Therefore, the search for a non-noble metal catalyst with high performance and low cost to synthesize ammonia under mild conditions is an important research topic in the field of catalysis.
In recent years, catalytic nitrogen fixation at normal temperature and pressure by using renewable energy electric energy has attracted extensive attention of researchers on the global scale, and is considered to be one of the most promising technologies for replacing industrial synthetic ammonia. In the past few years, the development of NRR has relied primarily on transition metal-based electrocatalysts. However, in practical applications, the catalytic efficiency still needs to be improved, mainly due to the following points: first, most transition metals that bind too weakly to nitrogen are not sufficient for N2Activating; second, the d-orbital electron in the transition metal also contributes to the formation of a metal-H bond in the Hydrogen Evolution Reaction (HER), resulting in a reduction in faraday efficiency; third, although some transition metals block HER at appropriate potentials, there is a pressing need for a viable alternative mechanism to obtain reasonable NRR performance. Thus, the evolution of electrocatalytic NRR conversion can be driven not only from the development of an entirely new class of catalysts, but also by modifying the catalyst to obtain an effective N2A new mechanism of activation.
Molybdenum disulfide (MoS)2) The molybdenum disulfide is a common graphene-like two-dimensional material, is widely applied to the fields of photoelectrocatalysis, petrochemical catalysis, hydrogen storage materials, solar cells and the like, and can be divided into a stable 2H semiconductor state and a metastable 1T metal state according to different phase structures. MoS2The d-orbital of Mo is favorable for receiving nitrogenThe lone pair of atoms and the donation of electrons to the pi-orbital of N.ident.N to weaken the N.ident.N bond, favour the activation of nitrogen and take into account the natural N.ident.N2The fixation is realized by nitrogen fixation enzyme produced by plant bacteria, and the active center of the nitrogen fixation enzyme is of a Mo-based structure and contains Mo and S elements. Thus, MoS2Has great potential development prospect in the aspect of electro-catalysis nitrogen reduction, and simultaneously MoS2Has the advantages of high stability, high catalytic activity and the like, and is hopeful to be a substitute of nitrogen-fixing noble metal catalysts such as ruthenium and the like. Currently prepared MoS2There are many morphologies, among them, patent application No. 201611027687.3 discloses a method for preparing monolayer molybdenum disulfide, patent application No. 201611078868.9 discloses a method for preparing hollow spherical molybdenum disulfide, and patent application No. 201610417377.6 discloses a method for preparing jelly-fungus molybdenum disulfide with edge crimp, however, MoS, which is an important two-dimensional planar material and has wide application in catalysis, electrochemistry and electronic devices2The material, which is proved to be only positioned at the boundary of the material through experiments and theoretical calculation, has the advantages that the catalytic active sites are only positioned at the boundary of the material, the high-activity edge structure is less exposed, and a large number of surface sites are catalytically inert, so that MoS is severely restricted2The large-scale practical application of the nano material as a new generation nitrogen fixation reaction catalyst adopts defect engineering in MoS2The surface defect is manufactured to expose more edge active sites, and simultaneously, the property of the inert plane area is changed to be the active sites, so that the capability of the catalyst for adsorbing and activating nitrogen can be enhanced, and the performance of the electro-catalytic synthesis of ammonia is improved.
The patent with the application number of 202010405604.X discloses a molybdenum disulfide catalyst rich in a defect 1T-2H mixed phase and a preparation method and application thereof, and particularly discloses a preparation method for synthesizing the molybdenum disulfide catalyst rich in the defect 1T-2H mixed phase by a hydrothermal synthesis method, a mixed solvent of water and ethanol and an organic acid as a regulating agent, but the molybdenum disulfide synthesized in the patent is a mixed phase, a large number of defect sites are concentrated on the edge of crystals, and defects in a basal plane are lacking.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a molybdenum-based catalyst with in-plane defects and a preparation method thereof.
The technical scheme of the invention is as follows:
the invention discloses a molybdenum-based catalyst with in-plane defects, which is MoS2The nano-flake is in a dispersed single-layer nano-flake thickness of 2nm, and stable in-plane defects consisting of three adjacent S vacancies exist in the plane of the nano-flake.
The invention also discloses a preparation method of the molybdenum-based catalyst with in-plane defects, which uses molybdenum pentachloride as a molybdenum source, thiourea as a sulfur source and a sulfur position end capping agent, and prepares molybdenum disulfide two-dimensional nanosheets with rich in-plane defects by utilizing coordination complexation of the molybdenum pentachloride and the thiourea and adopting a bottom-up method.
Further, the preparation method of the molybdenum-based catalyst with the in-plane defects specifically comprises the following steps:
(1) dissolving molybdenum pentachloride and thiourea in 60-70 mL of absolute ethanol, and stirring for 60-70 min to form MoS2Nano-crystallites;
(2) mixing MoS2Drying the nano microcrystal, and then placing the dried nano microcrystal in a ball mill for high-energy grinding;
(3) the MoS subjected to high-energy grinding2Pouring the nano microcrystalline powder into a polytetrafluoroethylene reaction kettle, adding absolute ethyl alcohol with the same volume as that in the step (1), adding a steel sleeve, and carrying out hydrothermal reaction;
(4) after the reaction is finished and the reaction product is cooled to room temperature, centrifugal separation is carried out, precipitates are respectively washed by distilled water and absolute ethyl alcohol, and vacuum drying is carried out at the temperature of 60-70 ℃ to obtain MoS rich in-plane defects2Two-dimensional nanosheets.
Further, the concentration of the molybdenum pentachloride in the step (1) is 14mmol, and the concentration of the thiourea is 28-70 mmol; the molar ratio of the molybdenum pentachloride to the thiourea is 1: 2-5.
Further, the ball milling time of the sample in the step (2) is 60-120 min, and the rotating speed is 200-300 r/min.
Further, the temperature of the hydrothermal reaction in the step (3) is 160-220 ℃, and the time of the hydrothermal reaction is 12-36 hours.
The invention also discloses application of the molybdenum-based catalyst with the in-plane defects in the electrochemical ammonia synthesis reaction.
Further, the molybdenum-based catalyst with the in-plane defects is dispersed in a dispersion liquid containing ethanol, water and Nafion, and is dripped on hydrophobic carbon paper after ultrasonic treatment to prepare a working electrode, and a three-electrode system is utilized to carry out electrocatalysis ammonia synthesis reaction.
Further, the volume ratio of ethanol, water and Nafion solution in the dispersion liquid is 12:12: 1.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the preparation method provided by the invention, molybdenum pentachloride and thiourea are respectively used as Mo and S element sources and are dispersed in absolute ethyl alcohol, and the process can realize Mo5+Cation and CH4N2Coordination and complexation between S, and ball milling the obtained powder after drying the formed mixture, wherein the ball milling process effectively enhances Mo5+And CH4N2Interaction of S, thereby MoS is formed2Nanocrystallites, to which an excess of CH is added during the subsequent hydrothermal reaction4N2S, reacting part of thiourea with molybdenum pentachloride to form MoS2The other part of thiourea in the nanocrystal is taken as an S-site blocking agent to be adsorbed on MoS2Nanocrystalline surface, oriented prevention of MoS2The growth of the nano crystal can generate abundant in-plane defects with three adjacent S vacancies, so that the molybdenum-based catalyst prepared by the method is different from the edge defects in the conventional molybdenum disulfide; the molybdenum-based catalyst prepared by the method has rich in-plane defects, changes the property of the molybdenum disulfide inert plane area, exposes more in-plane active sites, and greatly enhances the nitrogen adsorption and activation energy of the catalystThe performance of the electro-catalytic synthesis of ammonia is effectively improved.
(2) The preparation method provided by the invention is simple and easy to control, the production process is green and environment-friendly, the energy consumption is low, the yield is high, the cost is low, the actual production needs are met, and the large-scale popularization is facilitated.
(3) The molybdenum-based catalyst prepared by the method has strong stability and reproducibility in an electrocatalysis reaction system, high repeated utilization rate and very high practical value and application prospect.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of a molybdenum-based catalyst having in-plane defects prepared according to example 1 of the present invention;
FIG. 2 is a schematic view of a spherical aberration transmission electron microscope (HAADF-STEM) of a molybdenum-based catalyst having in-plane defects prepared in example 1 according to the present invention;
FIG. 3 is a graph showing a comparison of nitrogen temperature programmed desorption of molybdenum-based catalysts having in-plane defects and molybdenum-based catalysts having no defects, obtained in example 1 of the present invention (N)2-TPD)；
Fig. 4 is a graph comparing the electrocatalytic nitrogen fixation activity of the molybdenum-based electrocatalyst with in-plane defects and the molybdenum-based electrocatalyst without defects prepared in example 1 according to the present invention.
Detailed Description
In order to facilitate understanding of the present invention, the technical solutions of the present invention will be further described with reference to the following detailed description and the accompanying drawings, but the present invention is not limited thereto.
Example 1
A molybdenum-based catalyst having in-plane defects, said molybdenum-based catalyst being in the form of MoS2The nano-flake is in a dispersed single-layer nano-flake thickness of 2nm, and stable in-plane defects consisting of three adjacent S vacancies exist in the plane of the nano-flake.
The preparation method of the molybdenum-based catalyst with the in-plane defects comprises the following steps of preparing molybdenum disulfide two-dimensional nanosheets with rich in-plane defects by using molybdenum pentachloride as a molybdenum source, thiourea as a sulfur source and a sulfur site blocking agent and utilizing coordination and complexation of the molybdenum pentachloride and the thiourea, wherein the method comprises the following steps:
(1) dissolving 14mmol of molybdenum pentachloride and 60mmol of thiourea in 70mL of absolute ethanol, stirring for 60min to form MoS2Nano-crystallites; the molar ratio of the molybdenum pentachloride to the thiourea is 7: 30;
(2) mixing MoS2Drying the nano microcrystal, and then placing the dried nano microcrystal in a ball mill for high-energy grinding for 60min at the rotating speed of 200 r/min;
(3) the MoS subjected to high-energy grinding2Pouring the nano microcrystalline powder into a polytetrafluoroethylene reaction kettle, adding 70mL of absolute ethyl alcohol, adding a steel sleeve, and carrying out hydrothermal reaction; the temperature of the hydrothermal reaction is 220 ℃, and the time of the hydrothermal reaction is 18 h;
(4) after the reaction is finished and the temperature is cooled to room temperature, centrifugal separation is carried out, precipitates are respectively washed by distilled water and absolute ethyl alcohol, and vacuum drying is carried out at the temperature of 60 ℃ to obtain MoS rich in-plane defects2Two-dimensional nanosheets.
Example 2
A molybdenum-based catalyst having in-plane defects, said molybdenum-based catalyst being in the form of MoS2The nano-flake is in a dispersed single-layer nano-flake thickness of 2nm, and stable in-plane defects consisting of three adjacent S vacancies exist in the plane of the nano-flake.
The preparation method of the molybdenum-based catalyst with the in-plane defects comprises the following steps of preparing molybdenum disulfide two-dimensional nanosheets with rich in-plane defects by using molybdenum pentachloride as a molybdenum source, thiourea as a sulfur source and a sulfur site blocking agent and utilizing coordination and complexation of the molybdenum pentachloride and the thiourea, wherein the method comprises the following steps:
(1) dissolving 14mmol of molybdenum pentachloride and 28mmol of thiourea in 70mL of absolute ethanol, stirring for 60min to form MoS2Nano-crystallites; the molar ratio of the molybdenum pentachloride to the thiourea is 1: 2;
(2) mixing MoS2Drying the nano microcrystal, and then placing the dried nano microcrystal in a ball mill for high-energy grinding for 80min at the rotating speed of 250 r/min;
(3) the MoS subjected to high-energy grinding2Pouring the nano microcrystalline powder into a polytetrafluoroethylene reaction kettle, adding 70mL of absolute ethyl alcohol, and addingCarrying out hydrothermal reaction after steel sleeve mounting; the temperature of the hydrothermal reaction is 160 ℃, and the time of the hydrothermal reaction is 12 hours;
(4) after the reaction is finished and the reaction product is cooled to room temperature, centrifugal separation is carried out, precipitates are respectively washed by distilled water and absolute ethyl alcohol, and the precipitates are dried in vacuum at the temperature of 70 ℃ to obtain MoS rich in surface defects2Two-dimensional nanosheets.
Example 3
A molybdenum-based catalyst having in-plane defects, said molybdenum-based catalyst being in the form of MoS2The nano-flake is in a dispersed single-layer nano-flake thickness of 2nm, and stable in-plane defects consisting of three adjacent S vacancies exist in the plane of the nano-flake.
The preparation method of the molybdenum disulfide catalyst with the in-plane defects comprises the following steps of taking molybdenum pentachloride as a molybdenum source, thiourea as a sulfur source and a sulfur site blocking agent, and preparing the molybdenum disulfide two-dimensional nanosheet with rich in-plane defects by utilizing coordination and complexation of the molybdenum pentachloride and the thiourea, wherein the method comprises the following steps:
(1) dissolving molybdenum pentachloride with the mass of 14mmol and thiourea with the mass of 40mmol in 60mL of absolute ethyl alcohol, stirring for 60min to form MoS2Nano-crystallites; the molar ratio of the molybdenum pentachloride to the thiourea is 7: 20;
(2) mixing MoS2Drying the nano microcrystal, and then placing the dried nano microcrystal in a ball mill for high-energy grinding for 120min at the rotating speed of 200 r/min;
(3) the MoS subjected to high-energy grinding2Pouring the nano microcrystalline powder into a polytetrafluoroethylene reaction kettle, adding 60mL of absolute ethyl alcohol, adding a steel sleeve, and carrying out hydrothermal reaction; the temperature of the hydrothermal reaction is 180 ℃, and the time of the hydrothermal reaction is 16 h;
(4) after the reaction is finished and the reaction product is cooled to room temperature, centrifugal separation is carried out, precipitates are respectively washed by distilled water and absolute ethyl alcohol, and the precipitates are dried in vacuum at the temperature of 60 ℃ to obtain MoS rich in surface defects2Two-dimensional nanosheets.
Example 4
A molybdenum-based catalyst having in-plane defects, said molybdenum-based catalyst being in the form of MoS2The nano-flake is in the form of nano-flake, the thickness of dispersed single-layer nano-flake is 2nm, and the nano-flake exists in the surface of the nano-flakeA stable in-plane defect consisting of three adjacent S vacancies.
The preparation method of the molybdenum-based catalyst with the in-plane defects comprises the following steps of preparing molybdenum disulfide two-dimensional nanosheets with rich in-plane defects by using molybdenum pentachloride as a molybdenum source, thiourea as a sulfur source and a sulfur site blocking agent and utilizing coordination and complexation of the molybdenum pentachloride and the thiourea, wherein the method comprises the following steps:
(1) dissolving 14mmol of molybdenum pentachloride and 70mmol of thiourea in 65mL of absolute ethanol, stirring for 60min to form MoS2Nano-crystallites; the molar ratio of the molybdenum pentachloride to the thiourea is 1: 5;
(2) mixing MoS2Drying the nano microcrystal, and then placing the dried nano microcrystal in a ball mill for high-energy grinding for 120min at the rotating speed of 300 r/min;
(3) the MoS subjected to high-energy grinding2Pouring the nano microcrystalline powder into a polytetrafluoroethylene reaction kettle, adding 65mL of absolute ethyl alcohol, adding a steel sleeve, and carrying out hydrothermal reaction; the temperature of the hydrothermal reaction is 200 ℃, and the time of the hydrothermal reaction is 36 h;
(4) after the reaction is finished and the reaction product is cooled to room temperature, centrifugal separation is carried out, precipitates are respectively washed by distilled water and absolute ethyl alcohol, and vacuum drying is carried out at 65 ℃ to obtain MoS rich in surface defects2Two-dimensional nanosheets.
Example 5
An application of molybdenum-based catalyst with in-plane defects in electrochemical ammonia synthesis reaction is characterized in that 5mg of prepared molybdenum disulfide catalyst with in-plane defects is dispersed in a dispersion liquid comprising 240 mu L of ethanol, 240 mu L of water and 20 mu L of N in an emulsion, and is dripped on hydrophobic carbon paper after being subjected to ultrasonic treatment for 1h to prepare a working electrode, and a three-electrode system is utilized for the electrocatalytic ammonia synthesis reaction.
Performance testing
The performance test of the molybdenum-based catalyst having in-plane defects prepared according to the preparation method provided in example 1 of the present invention is as follows:
FIG. 1 is an X-ray powder diffraction pattern of a molybdenum-based catalyst having in-plane defects prepared according to the method of example 1 of the present invention, and it can be seen from FIG. 1 that the characteristic peaks detected by XRD are consistent with those of a molybdenum disulfide standard card, indicating that a molybdenum-based catalyst was successfully prepared by the method of the present invention;
FIG. 2 is a schematic diagram of a spherical aberration transmission electron microscope of a molybdenum-based catalyst having in-plane defects prepared according to the preparation method provided in example 1 of the present invention, and it can be seen from FIG. 2 that the molybdenum-based catalyst prepared by the method of the present invention is rich in-plane defects;
fig. 3 is a comparison graph of nitrogen temperature programmed desorption of molybdenum-based catalysts with in-plane defects and molybdenum-based catalysts without defects prepared by the preparation method provided in example 1 of the present invention, and it can be seen from fig. 3 that the center of nitrogen desorption of the molybdenum-based catalyst rich in-plane defects is 313 ℃, the center of nitrogen desorption of the molybdenum-based catalysts without defects is 306 ℃, the nitrogen desorption temperature of the molybdenum-based catalysts with in-plane defects is higher, and the nitrogen desorption amount is larger, which indicates that the molybdenum-based catalysts rich in-plane defects and nitrogen have stronger chemical bonding force;
FIG. 4 is a graph showing a comparison of electrocatalytic nitrogen fixation activity of a molybdenum-based catalyst having in-plane defects and a molybdenum-based catalyst having no defects prepared according to the preparation method provided in example 1 of the present invention, in which a three-electrode system was used in an electrocatalytic experiment, the prepared molybdenum-based catalyst was dropped on carbon paper as a working electrode, platinum as a counter electrode, silver/silver chloride as a reference electrode, and a certain amount of electrolyte K was added to the system as shown in example 52SO4Before testing, blowing nitrogen into the electrolyte for 1h, and applying a certain bias voltage to react when the nitrogen in the electrolyte is saturated, wherein all potentials are relative to a standard hydrogen electrode; as can be seen from FIG. 4, the molybdenum-based catalyst rich in surface defects prepared by the present invention has more excellent activity for synthesizing ammonia by electrocatalytic nitrogen fixation, and when the bias is-0.3V vs. RHE, the ammonia synthesis yield is 43.4 mu g h at most-1mgcat. -1The Faraday efficiency can reach 16.8%.
The above description is only an embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are also included in the scope of the present invention.
Claims (8)
1. A method for preparing a molybdenum-based catalyst having in-plane defects, comprising: the molybdenum-based catalyst is MoS2The nano-flake is in a dispersed single-layer nano-flake thickness of 2nm, and stable in-plane defects consisting of three adjacent S vacancies exist in the surface of the nano-flake; the preparation of the molybdenum-based catalyst takes molybdenum pentachloride as a molybdenum source, thiourea as a sulfur source and a sulfur site end capping agent, and prepares the molybdenum disulfide two-dimensional nanosheet with rich in-plane defects by utilizing coordination and complexation of the molybdenum pentachloride and the thiourea and adopting a bottom-up method, and specifically comprises the following steps:
(1) dissolving molybdenum pentachloride and thiourea in 60-70 mL of absolute ethanol, and stirring for 60-70 min to form MoS2Nano-crystallites; wherein the molar ratio of the molybdenum pentachloride to the thiourea is 1: 2-5;
(2) mixing MoS2Drying the nano microcrystal and then placing the dried nano microcrystal in a ball mill for high-energy grinding;
(3) the MoS subjected to high-energy grinding2Pouring the nano microcrystalline powder into a polytetrafluoroethylene reaction kettle, adding absolute ethyl alcohol with the same volume as that in the step (1), adding a steel sleeve, and carrying out hydrothermal reaction;
(4) after the reaction is finished and the reaction product is cooled to room temperature, centrifugal separation is carried out, precipitates are respectively washed by distilled water and absolute ethyl alcohol, and vacuum drying is carried out at the temperature of 60-70 ℃ to obtain MoS rich in-plane defects2Two-dimensional nanosheets.
2. A method of making a molybdenum disulfide catalyst having in-plane defects according to claim 1, wherein: the concentration of the molybdenum pentachloride in the step (1) is 14mmol, and the concentration of the thiourea is 28-70 mmol.
3. The method of preparing a molybdenum-based catalyst having in-plane defects according to claim 1, wherein: the ball milling time of the sample in the step (2) is 60-120 min, and the rotating speed is 200-300 r/min.
4. A method of making a molybdenum disulfide catalyst having in-plane defects according to claim 1, wherein: the temperature of the hydrothermal reaction in the step (3) is 160-220 ℃, and the time of the hydrothermal reaction is 12-36 h.
5. A molybdenum-based catalyst having in-plane defects, characterized by: the method according to any one of claims 1 to 4, wherein the molybdenum-based catalyst is MoS2The nano-flake is in a dispersed single-layer nano-flake thickness of 2nm, and stable in-plane defects consisting of three adjacent S vacancies exist in the plane of the nano-flake.
6. Use of the molybdenum-based catalyst having in-plane defects according to claim 5 in the electrochemical synthesis of ammonia.
7. Use of a molybdenum-based catalyst with in-plane defects according to claim 6 in the reaction of electrochemical synthesis of ammonia, characterized in that: the molybdenum disulfide catalyst with in-plane defects is dispersed in dispersion liquid comprising ethanol, water and Nafion solution, and is dripped on hydrophobic carbon paper after ultrasonic treatment to prepare a working electrode, and a three-electrode system is utilized to carry out electrocatalytic ammonia synthesis reaction.
8. Use of a molybdenum disulphide catalyst with in-plane defects according to claim 7 in the reaction for the electrochemical synthesis of ammonia, characterized in that: the volume ratio of ethanol, water and Nafion solution in the dispersion liquid is 12:12: 1.
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