CN115094438B - One-dimensional molybdenum diselenide/molybdenum-MOF composite nanomaterial and preparation method and application thereof - Google Patents
One-dimensional molybdenum diselenide/molybdenum-MOF composite nanomaterial and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a molybdenum diselenide/molybdenum-MOF composite nanomaterial with a one-dimensional structure, a preparation method and application thereof, wherein a molybdenum source and imidazole are uniformly mixed in water, and the obtained solution is subjected to heating reaction to obtain the Mo-MOF with the one-dimensional nanostructure; dissolving a selenium source in hydrazine hydrate, adding the obtained hydrazine hydrate solution of the selenium source into absolute ethyl alcohol, adding one-dimensional nano-structure Mo-MOF, stirring uniformly, and heating for reaction to obtain the one-dimensional molybdenum diselenide/molybdenum-MOF composite nano-material, wherein the appearance is MoSe of which the two-dimensional structure grows on the surface of the one-dimensional nano-structure Mo-MOF 2 The nano-sheet has the advantages of easily available materials, low cost, simple experimental equipment and operation, controllable reaction and easy repetition. MoSe prepared by the invention 2 The composite nano material of the/Mo-MOF is used as an electrocatalyst for hydrogen evolution reaction, has excellent performance and low price, is applicable to both acidic and alkaline environments, and has good practical application value.
Description
Technical Field
The invention belongs to the field of material preparation, and in particular relates to a one-dimensional MoSe structure 2 The preparation process of composite nanometer Mo-MOF material and its application as hydrogen separating catalyst in both acid and alkali environment.
Background
With the ever-increasing consumption of fossil fuels worldwide, very serious environmental problems are presented to people. The ever-warming global climate is also a consequence of the long-term and massive use of fossil fuels. In addition, fossil fuels such as coal, natural gas, and petroleum are difficult to regenerate in a short period of time, and thus suffer from exhaustion. Development of efficient, clean and renewable energy sources is urgent. Hydrogen is one of the most promising candidates for replacing conventional fossil fuels in various sustainable energy sources, and is a very excellent clean energy source because it has a very high combustion heating value, has a high energy density, and generates only water after combustion. However, the use of hydrogen also requires a number of problems to be solved, wherein how to produce hydrogen efficiently is a bottleneck.
The water is electrolyzed by utilizing electric energy generated by renewable energy sources such as solar energy, wind energy and the like, and hydrogen is prepared by hydrogen evolution reaction generated by the cathode, so that pure hydrogen can be generated at the cathode. The preparation conditions are simple and mild, and the raw materials are easy to obtain, so that great attention is paid to the preparation. However, high-efficiency electrocatalyst is needed for hydrogen evolution reaction in preparing hydrogen by electrolyzing water to reduce cathode overpotential and improve energy utilization efficiency, and high-efficiency and rapid hydrogen evolution reaction is realized. The commonly used catalyst is noble metal (such as Pt and Pd) with high price and limited reserves, which restricts the large-scale application of the water electrolysis hydrogen production process to industrial production. Therefore, there is a need to develop materials which have high catalytic ability and are inexpensive and readily available as catalysts for the electrolytic water hydrogen evolution reaction.
Scientists in recent years have found that transition metal selenide MoSe with two-dimensional lamellar structure 2 The combination energy of the lamellar edge object and hydrogen is similar to that of noble metal, so that the lamellar edge object and hydrogen can replace noble metal to be used as a hydrogen evolution reaction catalyst. But MoSe 2 The basal plane of the lamellar has no catalytic activity and the lamellar structure is characterized in that MoSe 2 Is easy to agglomerate and aggregate, reduces the quantity of the catalytic active edges and reduces the catalytic performance of the catalyst. And MoSe 2 The performance of catalyzing hydrogen evolution reaction in alkaline environment is very weak, and the practical use effect is also hindered.
Disclosure of Invention
The invention aims to solve at least one technical problem and provides a one-dimensional molybdenum diselenide/molybdenum-MOF composite nanomaterial and a preparation method thereof, wherein MoSe with a two-dimensional structure grows on the surface of Mo-MOF with a one-dimensional nanostructure 2 The nano sheet has simple raw materials and process equipment adopted in the synthesis process,The cost is low.
The invention also aims to provide a molybdenum diselenide/molybdenum-MOF composite nanomaterial with a one-dimensional structure, which is used as a catalytic material for electrolytic water hydrogen evolution reaction, has high catalytic performance and good catalytic electrolytic water hydrogen evolution reaction activity in both acidic and alkaline environments.
The specific technical scheme of the invention is as follows:
a preparation method of a one-dimensional molybdenum diselenide/molybdenum-MOF composite nanomaterial comprises the following steps:
A. uniformly mixing a molybdenum source and imidazole in water, and performing a heating reaction on the obtained solution to obtain a one-dimensional nano-structure Mo-MOF;
B. and D, dissolving a selenium source in hydrazine hydrate, adding the obtained selenium source hydrazine hydrate solution into absolute ethyl alcohol, adding the product obtained in the step A, uniformly stirring, and heating for reaction to obtain the molybdenum diselenide/molybdenum-MOF composite nanomaterial with a one-dimensional structure.
The mass ratio of the molybdenum source to the imidazole in the step A is 1: 1-2: 1, a step of;
the molybdenum source in step A is selected from molybdenum trioxide (MoO) 3 )；
In the step A, the dosage ratio of the molybdenum source to the water is 1:50-100g/ml;
the water in the step A is deionized water;
the heating reaction in the step A refers to: reacting for 10-14 hours at the temperature of 90-120 ℃;
preferably, the heating reaction in the step A is as follows: transferring the obtained solution into a polytetrafluoroethylene-lined reaction kettle, sealing the reaction kettle, putting the reaction kettle into a constant-temperature air blowing box, heating for reaction, centrifugally collecting after the reaction is finished, and cleaning and drying the product obtained in the reaction kettle; the obtained product is a metal organic framework compound (MOF) Mo-MOF with a one-dimensional nano structure formed by molybdenum ions and organic ligand imidazole.
The selenium source in the step B is selenium powder, selenium dioxide or sodium selenite; preferably, the selenium source is selenium powder;
in the step B, the selenium source is dissolved in hydrazine hydrate, and the concentration is 0.06-0.1 mol/L; the mass fraction concentration of the hydrazine hydrate is more than or equal to 85%;
in the step B, the volume ratio of the selenium source hydrazine hydrate solution to the absolute ethyl alcohol is 1:10 to 1:14;
in the step B, the ratio of the mass of the product obtained in the step A to the volume of the absolute ethyl alcohol is 1:1-2g/L;
the heating reaction in the step B refers to: reacting for 10-14 hours at 200-240 ℃.
The heating reaction in the step B is specifically as follows: and transferring the obtained solution into a polytetrafluoroethylene-lined reaction kettle, sealing the reaction kettle, putting the reaction kettle into a constant-temperature air blowing box, heating for reaction, centrifugally collecting the product obtained in the reaction kettle after the reaction is finished, and further cleaning and drying to obtain the final product.
The preparation method of the one-dimensional molybdenum diselenide/molybdenum-MOF composite nanomaterial provided by the invention is adopted to prepare the one-dimensional molybdenum diselenide/molybdenum-MOF composite nanomaterial, and MoSe with a two-dimensional structure grows on the surface of the one-dimensional Mo-MOF composite nanomaterial 2 Nanoplatelets, the final product is MoSe 2 MoSe with one-dimensional structure compounded with Mo-MOF 2 A composite nano material of Mo-MOF. The prepared one-dimensional MoSe 2 The diameter of the composite nano material of the Mo-MOF is 400-900 nm, the length is 10-20 microns, and the MoSe on the surface of the composite material 2 The thickness of the nano-sheet is 4-5 nm.
The application of the one-dimensional molybdenum diselenide/molybdenum-MOF composite nano material provided by the invention is used as an electrocatalyst for electrolytic water hydrogen evolution reaction, and can be used for catalyzing electrolytic water hydrogen evolution reaction in acidic and alkaline environments.
In recent years, various hydrogen evolution reaction catalysts based on non-noble metals such as transition metal chalcogenides, nitrides, carbides, and phosphides have been investigated as potential alternatives to platinum group metals. Among them, the transition metal selenide is considered as a promising hydrogen evolution reaction catalyst because of its wide resource distribution on earth and good physical and chemical properties. MoSe 2 The transition metal selenide is a two-dimensional lamellar structure, and two-dimensional lamellar layers are connected together through Van der Waals interaction. Theoretical calculations indicate MoSe 2 The edges of the two-dimensional sheet are living with catalytic hydrogen evolution reactionsSex position. But due to the structural characteristics of the two-dimensional lamellar, moSe 2 The sheets are easy to agglomerate and aggregate, the number of exposed two-dimensional sheet catalytic activity edges is reduced, the basal planes of the two-dimensional sheets are catalytic inert, and thus MoSe is weakened 2 Catalytic performance for hydrogen evolution reactions. Therefore, how to design and prepare the specific structure, effectively avoid MoSe 2 The agglomeration of the sheets and the increase of the exposure of the catalytic active sites of hydrogen evolution reaction at the edges of the sheets are the preparation of MoSe 2 The hydrogen evolution reaction catalyst needs to solve the problem. Furthermore, moSe 2 The catalyst can show remarkable catalytic hydrogen evolution reaction performance in an acidic environment, but has weak catalytic performance in an alkaline environment. This is because the reaction mechanism of the electrolyzed water hydrogen evolution reaction is different in the acidic and alkaline environments. H present in acidic environment, free H + The ion and hydrogen evolution reaction steps mainly comprise a catalyst and H + Interactions between ions due to MoSe 2 The two-dimensional lamellar edge has good free energy of hydrogen adsorption, so that the two-dimensional lamellar edge can show remarkable catalytic hydrogen evolution reaction performance in an acidic environment. In alkaline environment, the hydrogen evolution reaction process is closely related to the adsorption/dissociation process of the catalyst to water, due to MoSe 2 The adsorption/dissociation process of water is slow, so that the catalytic hydrogen evolution reaction activity is low in alkaline environment. Therefore, how to increase MoSe 2 The catalytic hydrogen evolution reaction performance under alkaline environment is one of the key problems to be solved in practical application of the electrolytic water hydrogen production process.
MOF (Metal Organic Frameworks, metal organic framework) materials are a class of porous coordination polymer materials formed by coordination bonds between transition metal ions and organic ligands. The MOF material has various excellent properties such as high porosity, large specific surface area, adjustable pore size and the like, and has been applied to the fields of gas adsorption and separation, ion transportation, drug carriers and the like. Due to the porous structural characteristics, the MOF material has good adsorption performance on water molecules. However, the catalytic performance of most MOF materials is severely limited by the lack of proper adsorption/desorption energy for electrocatalytic hydrogen evolution reaction intermediates, making them unusable as hydrogen evolution reaction catalysts.
The invention creatively uses MoSe with hydrogen evolution reaction catalytic activity 2 Combined with MOF material with water molecule adsorption property to prepare one-dimensional MoSe 2 A composite nano material of Mo-MOF.
In the liquid phase preparation process of the micro-nano MOF material, the change of the reaction solvent, the reaction temperature and time, the pH value and the molar ratio of metal to ligand has great influence on the structure, the size and the morphology of the synthesized MOF material. The reason is that the polarity of different solvents, the pH value of the solution and the difference of the solubility of the solvents to metal and organic ligands can lead to different bridging coordination modes of central metal ions and organic ligands, and the nucleation rate, the oriented growth and the self-assembly process of the MOF material can be influenced, so that different space geometric structures are formed, and the MOF products with different structures and morphologies are obtained. As reported in researches (Chemical Communications,2018, 54, 252), five MOF materials with special morphology and size can be prepared by regulating nucleation and growth rate of crystals with the aid of coordination regulating agent by using solvent with proper polarity and solubility.
Under the proper synthesis conditions and schemes provided by the invention, metal Mo and methylimidazole are matched and then grow in one-dimensional direction, and the prepared Mo-MOF material is a uniform nano material with one-dimensional structure, and is not a granular or block structure which is usually presented by MOF materials. If the Mo-MOF synthesis scheme of the invention is changed, the obtained Mo-MOF is not a one-dimensional structure of the invention. Further, selenizing the synthesized one-dimensional Mo-MOF nano material. And (3) taking absolute ethyl alcohol as a solvent, and reacting the one-dimensional Mo-MOF nano material with a hydrazine hydrate solution of selenium powder. The hydrazine hydrate solution of the selenium powder can react with Mo element in Mo-MOF to generate MoSe 2 。MoSe 2 Is of a two-dimensional lamellar structure, if the selenization reaction is too rapid, a large amount of MoSe is generated in the reaction system 2 ，MoSe 2 The sheets are easy to agglomerate to form flower-like or sphere-like structure, which reduces MoSe with catalytic activity of hydrogen evolution reaction 2 The number of the edges of the sheet weakens the catalytic performance of the material. The invention takes absolute ethyl alcohol as solvent, can effectively slow down the hydrazine hydrate solution of selenium powder and one dimensionRate of selenization reaction of Mo-MOF nanomaterial. Thus controlling the selenization reaction of the selenium source with the Mo-MOF to occur only from the surface of the Mo-MOF. Furthermore, at relatively high selenization temperatures, mo-MOF is still stable in absolute ethanol, with one-dimensional structure not destroyed.
Under the proper liquid phase system and synthesis condition obtained by the research, the one-dimensional Mo-MOF nano material is only selenized on the surface, the internal Mo-MOF is still present, the one-dimensional nano structure is still preserved, and the one-dimensional MoSe is prepared 2 A composite nano material of Mo-MOF. The invention creatively utilizes the composition and structural characteristics of Mo-MOF, rather than taking Mo-MOF as Mo source to participate in selenization reaction. The reaction system can effectively control the selenization reaction of the one-dimensional Mo-MOF nano material, and successfully prepare the MoSe with a one-dimensional structure 2 A composite nano material of Mo-MOF. If the synthesis scheme of the invention is changed, moSe with one-dimensional structure cannot be obtained 2 The composite nano material of the/Mo-MOF only forms single MoSe with flower-like structure formed by agglomeration of nano sheets with conventional two-dimensional structure 2 A material.
In the composite material prepared by the invention, the existence of Mo-MOF is beneficial to the adsorption of the material on water molecules in an alkaline environment. MoSe with catalytic activity for hydrogen evolution reaction 2 The nano-sheet grows on the surface of the one-dimensional Mo-MOF, so that the nano-sheet can be fully contacted with the solution, and the mass transfer process in the hydrogen evolution reaction process is facilitated. Furthermore MoSe 2 The nano-sheets grow on the surface of the one-dimensional Mo-MOF, so that agglomeration and accumulation of sheets can be avoided, and MoSe is enabled to be formed 2 The active edges of the nanoplatelets are fully exposed, thereby effectively increasing the catalytic hydrogen evolution reaction active sites of the material. Thus, the one-dimensional MoSe prepared 2 The composite nano material of the/Mo-MOF can show good catalytic performance of hydrogen evolution reaction in both acidic and alkaline environments.
Compared with the prior art, the method prepares MoSe by a liquid phase method 2 The material needed in the preparation process of the composite nano material of the/Mo-MOF is easy to obtain, the cost is low, experimental equipment and operation are simple, the reaction is controllable, and the repetition is easy. MoSe prepared by the invention 2 /Mo-MOThe F composite nano material is used as the hydrogen evolution reaction electrocatalyst, has excellent performance and low price, is applicable to both acidic and alkaline environments, and has good practical application value.
Drawings
Specific embodiments of the present invention will be further described below with reference to the accompanying drawings;
FIG. 1 is a scanning electron microscope image of a Mo-MOF nanomaterial of one-dimensional structure obtained in example 1;
FIG. 2 shows a one-dimensional MoSe of example 1 2 Scanning electron microscope images of the composite nano material of the/Mo-MOF;
FIG. 3 shows a one-dimensional MoSe of example 1 2 X-ray powder diffraction pattern spectrogram of the Mo-MOF composite nano material;
FIG. 4 shows a one-dimensional MoSe of example 1 2 Thermogravimetric analysis graphs of the composite nano material of/Mo-MOF and the nano material of one-dimensional structure Mo-MOF;
FIG. 5 shows a one-dimensional MoSe of example 2 2 Transmission electron microscope image of the composite nano material of the/Mo-MOF;
FIG. 6 shows a one-dimensional MoSe of example 3 2 Scanning electron microscope images of the composite nano material of the/Mo-MOF;
FIG. 7 shows a one-dimensional MoSe of example 4 2 Scanning electron microscope images of the composite nano material of the/Mo-MOF;
FIG. 8 shows a one-dimensional MoSe of example 5 2 Scanning electron microscope images of the composite nano material of the/Mo-MOF;
FIG. 9 is a Scanning Electron Microscope (SEM) image of the bulk structure Mo-MOF obtained in example 6;
FIG. 10 shows the flower-like MoSe of example 7 2 Scanning electron microscope images of (2);
FIG. 11 shows the flower-like MoSe obtained in example 7 2 A thermogravimetric analysis graph of (a);
FIG. 12 is one-dimensional MoSe obtained in example 1 2 Composite nanomaterial of Mo-MOF and one-dimensional Mo-MOF nanomaterial, flower-like MoSe obtained in example 7 2 At 0.5mol/L H 2 SO 4 Polarization curve graph of catalytic hydrogen evolution reaction in solution;
FIG. 13 is one-dimensional Mo obtained in example 1Se 2 Composite nanomaterial of Mo-MOF and one-dimensional Mo-MOF nanomaterial, flower-like MoSe obtained in example 7 2 Polarization curve of catalytic hydrogen evolution reaction in 1mol/L KOH solution.
Detailed Description
Example 1
One-dimensional MoSe structure 2 The preparation method of the composite nano material of the/Mo-MOF comprises the following steps:
1) 0.4g of molybdenum trioxide (MoO) was weighed out 3 ) Powder and 0.332g of imidazole (C 3 H 4 N 2 ) Sequentially adding the solution into 30mL of deionized water, and stirring until the solution and the deionized water are completely dissolved to obtain a uniform white solution.
2) Transferring the solution obtained in the step 1) into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, sealing the reaction kettle, and then placing the reaction kettle in a constant-temperature air blowing box, and heating at a constant temperature of 110 ℃ for reaction for 12 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, and products in the kettle are centrifugally collected and washed with deionized water and absolute ethyl alcohol for 5 times. And drying the product in a vacuum drying oven at 60 ℃ for 6 hours to obtain the white one-dimensional Mo-MOF nanomaterial.
3) 0.2mmol of selenium powder is weighed and 2.5mL of hydrazine hydrate (N) with the mass fraction of 85 percent is added 2 H 4 ·H 2 And O) in the solution, stirring until the selenium powder is completely dissolved, and obtaining the selenium powder hydrazine hydrate solution. The solution is added into 30mL of absolute ethyl alcohol drop by drop, after the two solutions are stirred to be mixed uniformly, 0.03g of the one-dimensional Mo-MOF nano material synthesized in the step 2) is added into the solution, and the solution is stirred for 30min, so that the one-dimensional Mo-MOF nano material is uniformly dispersed in the solution.
4) Transferring the solution obtained in the step 3) into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, sealing the reaction kettle, and then placing the reaction kettle into a constant-temperature air blowing box for reaction for 12 hours at the constant temperature of 220 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally collecting the product in the kettle, washing with deionized water and absolute ethyl alcohol for 5 times, and finally drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain the one-dimensional MoSe 2 A composite nano material of Mo-MOF.
FIG. 1 is a scanning electron microscope image of the product Mo-MOF obtained in step 2) of example 1, showing that the product is in the form ofThe one-dimensional rod-shaped structure has a smooth surface, the diameter of the one-dimensional rod-shaped structure is about 500 nm-900 nm, and the length is about 10-20 microns. FIG. 2 is a scanning electron microscope image of the product obtained in step 4) of example 1, and it can be seen that the product has a one-dimensional structure. But different from the smooth surface of the one-dimensional rod-shaped structure Mo-MOF, the surface of the one-dimensional structure product is formed by nano sheets, the diameter of the one-dimensional structure product is about 500nm, and the thickness of the nano sheets on the surface is about 4-5 nm. FIG. 3 shows the product MoSe obtained in step 4) of example 1 2 X-ray powder diffraction pattern spectrum of/Mo-MOF composite nano material, and the position of main diffraction peak and hexagonal crystal form MoSe 2 Is consistent with the standard card JCPDS No. 29-0914. FIG. 4 shows the product Mo-MOF material obtained in step 2) of example 1 and the MoSe obtained in step 4) 2 Thermogravimetric analysis graph of the Mo-MOF composite nanomaterial. Thermogravimetric analysis curve shows Mo-MOF material and MoSe 2 The Mo-MOF composite nanomaterial each exhibits a large weight loss stage between 300 ℃ and 420 ℃, which corresponds to the temperature range at which the ligands constituting the Mo-MOF material decompose at high temperatures. The X-ray powder diffraction pattern spectrogram and thermogravimetric analysis curve show that after selenization reaction, the one-dimensional Mo-MOF material surface generates MoSe with two-dimensional structure 2 The internal Mo-MOF structure of the nano-sheet still exists, and the product obtained in the step 4) of the example 1 is MoSe with one-dimensional structure 2 A composite nano material of Mo-MOF.
Example 2
One-dimensional MoSe structure 2 The preparation method of the composite nano material of the/Mo-MOF comprises the following steps:
1) 0.5g of molybdenum trioxide (MoO) was weighed out 3 ) Powder and 0.432g of imidazole (C 3 H 4 N 2 ) Sequentially adding the solution into 30mL of deionized water, and stirring until the solution and the deionized water are completely dissolved to obtain a uniform white solution.
2) The solution is transferred into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, the reaction kettle is sealed and then placed in a constant-temperature air blowing box, and the reaction is carried out at a constant temperature of 100 ℃ for 14h. After the reaction is finished, the reaction kettle is cooled to room temperature, products in the kettle are centrifugally collected, and the products are washed by deionized water and absolute ethyl alcohol for 6 times. And drying the product in a vacuum drying oven at 60 ℃ for 6 hours to obtain the white one-dimensional Mo-MOF nanomaterial.
3) 0.2mmol of selenium powder is weighed and 2.5mL of hydrazine hydrate (N) with the mass fraction of 85 percent is added 2 H 4 ·H 2 And O) in the solution, stirring until the selenium powder is completely dissolved, and obtaining the selenium powder hydrazine hydrate solution. The solution is added into 30mL of absolute ethyl alcohol drop by drop, after the two solutions are stirred to be mixed uniformly, 0.025g of the one-dimensional Mo-MOF nano material synthesized in the step 2) is added into the solution, and the solution is stirred for 30min, so that the one-dimensional Mo-MOF nano material is uniformly dispersed in the solution.
4) Transferring the solution obtained in the step 3) into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, sealing the reaction kettle, and then placing the reaction kettle into a constant-temperature air blowing box for constant-temperature heating reaction for 12 hours at 220 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally collecting the product in the kettle, washing with deionized water and absolute ethyl alcohol for 6 times, and finally drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain the MoSe with one-dimensional structure 2 A composite nano material of Mo-MOF.
Fig. 5 is a transmission electron microscope image of the product obtained in step 4) of example 2, which shows that the product is a one-dimensional nanostructure, the surface of which is a nanosheet and the interior of which is a solid structure. The transmission electron microscope image shows that Mo-MOF of one-dimensional nano rod structure generates MoSe of two-dimensional structure through selenizing reaction on the surface of nano rod in the selenizing process 2 The inside of the nanometer sheet is kept as a solid Mo-MOF nanometer rod to form a one-dimensional MoSe structure 2 A composite nano material of Mo-MOF.
Example 3
One-dimensional MoSe structure 2 The preparation method of the composite nano material of the/Mo-MOF comprises the following steps:
1) 0.4g of molybdenum trioxide (MoO) was weighed out 3 ) Powder and 0.382g of imidazole (C 3 H 4 N 2 ) Sequentially adding the solution into 30mL of deionized water, and stirring until the solution and the deionized water are completely dissolved to obtain a uniform white solution.
2) The solution is transferred into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, the reaction kettle is sealed and then placed in a constant-temperature air blowing box, and the reaction is carried out at a constant temperature of 110 ℃ for 12 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, and products in the kettle are centrifugally collected and washed with deionized water and absolute ethyl alcohol for 5 times. And drying the product in a vacuum drying oven at 60 ℃ for 6 hours to obtain the white one-dimensional Mo-MOF nanomaterial.
3) 0.2mmol of selenium powder is weighed and 2.5mL of hydrazine hydrate (N) with the mass fraction of 85 percent is added 2 H 4 ·H 2 And O) in the solution, stirring until the selenium powder is completely dissolved, and obtaining the selenium powder hydrazine hydrate solution. And (3) dropwise adding the solution into 30mL of absolute ethyl alcohol, stirring until the two solutions are uniformly mixed, adding 0.02g of the one-dimensional Mo-MOF nanomaterial synthesized in the step (2) into the solution, and stirring for 30min to uniformly disperse the one-dimensional Mo-MOF nanomaterial in the solution.
4) Transferring the solution obtained in the step 3) into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, sealing the reaction kettle, putting the reaction kettle into a constant-temperature air blowing box, and heating the reaction kettle at a constant temperature of 200 ℃ for 14h. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally collecting the product in the kettle, washing with deionized water and absolute ethyl alcohol for 5 times, and finally drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain black one-dimensional MoSe 2 A composite nano material of Mo-MOF.
FIG. 6 shows MoSe obtained in step 4) of example 3 2 The Mo-MOF composite nanomaterial is used for scanning electron microscope images, the material is of a one-dimensional structure, and the surface of the one-dimensional structure material is composed of nanosheets.
Example 4
One-dimensional MoSe structure 2 The preparation method of the composite nano material of the/Mo-MOF comprises the following steps:
1) 0.3g of molybdenum trioxide (MoO) was weighed out 3 ) Powder and 0.252g of imidazole (C 3 H 4 N 2 ) Sequentially adding the solution into 30mL of deionized water, and stirring until the solution and the deionized water are completely dissolved to obtain a uniform white solution.
2) The solution is transferred into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, the reaction kettle is sealed and then placed in a constant-temperature air blowing box, and the reaction is carried out at the constant temperature of 120 ℃ for 10 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, and products in the kettle are centrifugally collected and washed with deionized water and absolute ethyl alcohol for 5 times. And drying the product in a vacuum drying oven at 60 ℃ for 6 hours to obtain the white one-dimensional Mo-MOF nanomaterial.
3) 0.2mmol of selenium powder is weighed and 2.5mL of hydrazine hydrate (N) with the mass fraction of 85 percent is added 2 H 4 ·H 2 And O) in the solution, stirring until the selenium powder is completely dissolved, and obtaining the selenium powder hydrazine hydrate solution. The solution is added into 30mL of absolute ethyl alcohol drop by drop, after the two solutions are stirred to be mixed uniformly, 0.03g of the one-dimensional Mo-MOF nano material synthesized in the step 2) is added into the solution, and the solution is stirred for 30min, so that the one-dimensional Mo-MOF nano material is uniformly dispersed in the solution.
4) Transferring the solution obtained in the step 3) into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, sealing the reaction kettle, and then placing the reaction kettle into a constant-temperature air blowing box for constant-temperature heating reaction for 10 hours at 240 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally collecting the product in the kettle, washing with deionized water and absolute ethyl alcohol for 6 times, and finally drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain black one-dimensional MoSe 2 A composite nano material of Mo-MOF.
FIG. 7 shows MoSe obtained in step 4) of example 4 2 The scanning electron microscope image of the composite nano material of the/Mo-MOF shows that the material is of a one-dimensional structure, and the surface of the material of the one-dimensional structure is formed by nano-sheets.
Example 5
One-dimensional MoSe structure 2 The preparation method of the composite nano material of the/Mo-MOF comprises the following steps:
1) 0.4g of molybdenum trioxide (MoO) was weighed out 3 ) Powder and 0.282g of imidazole (C 3 H 4 N 2 ) Sequentially adding the solution into 30mL of deionized water, and stirring until the solution and the deionized water are completely dissolved to obtain a uniform white solution.
2) And transferring the solution into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50mL, sealing the reaction kettle, placing the reaction kettle in a constant-temperature air blowing box, and heating the reaction kettle at a constant temperature of 100 ℃ for 14h. After the reaction is finished, the reaction kettle is cooled to room temperature, and products in the kettle are centrifugally collected and washed with deionized water and absolute ethyl alcohol for 5 times. And drying the product in a vacuum drying oven at 60 ℃ for 6 hours to obtain the white one-dimensional Mo-MOF nanomaterial.
3) 0.25mmol of selenium powder is weighed out,3mL of hydrazine hydrate (N) with a mass fraction of 85% was added 2 H 4 ·H 2 And O) in the solution, stirring until the selenium powder is completely dissolved, and obtaining the selenium powder hydrazine hydrate solution. The solution is added into 30mL of absolute ethyl alcohol drop by drop, and after the two solutions are stirred until being mixed uniformly, 0.03g of the one-dimensional Mo-MOF nano material synthesized in the step 2) is added into the solution. Stirring for 30min to uniformly disperse the one-dimensional Mo-MOF nano material in the solution.
4) Transferring the solution obtained in the step 3) into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, sealing the reaction kettle, putting the reaction kettle into a constant-temperature air blowing box, and heating the reaction kettle at a constant temperature of 200 ℃ for 14h. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally collecting the product in the kettle, washing the product with deionized water and absolute ethyl alcohol for several times, and finally drying the product in a vacuum drying oven at 60 ℃ for 10 hours to obtain black one-dimensional MoSe 2 A composite nano material of Mo-MOF.
FIG. 8 shows MoSe obtained in step 4) of example 5 2 The scanning electron microscope image of the composite nano material of the/Mo-MOF shows that the material is of a one-dimensional structure, and the surface of the material of the one-dimensional structure is formed by nano-sheets.
Example 6 (as a comparison)
A preparation method of Mo-MOF with a block structure comprises the following steps:
1) 0.4g of molybdenum trioxide (MoO) was weighed out 3 ) Powder and 0.282g of imidazole (C 3 H 4 N 2 ) Sequentially adding the solution into 30mL of ethanol, and stirring until the solution and the ethanol are completely dissolved to obtain a uniform white solution.
2) And transferring the solution into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50mL, sealing the reaction kettle, placing the reaction kettle in a constant-temperature air blowing box, and heating the reaction kettle at a constant temperature of 100 ℃ for 14h. After the reaction is finished, the reaction kettle is cooled to room temperature, and products in the kettle are centrifugally collected and washed with deionized water and absolute ethyl alcohol for 5 times. And drying the product in a vacuum drying oven at 60 ℃ for 6 hours to obtain the white blocky Mo-MOF nanomaterial.
FIG. 9 is a scanning electron microscope image of the Mo-MOF material obtained in step 2) of example 6, and it can be seen that the obtained Mo-MOF material is particles with a block structure, and the particle size is between 0.6 and 1.5 μm. This shows that the synthesis scheme of example 6 cannot prepare Mo-MOF nanomaterial with one-dimensional structure.
Example 7 (as a comparison)
Flower-shaped MoSe 2 The preparation method of the material comprises the following steps:
1) 0.4g of molybdenum trioxide (MoO) was weighed out 3 ) Powder and 0.332g of imidazole (C 3 H 4 N 2 ) Sequentially adding the solution into 30mL of deionized water, and stirring until the solution and the deionized water are completely dissolved to obtain a uniform white solution.
2) The solution is transferred into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, the reaction kettle is sealed and then placed in a constant-temperature air blowing box, and the reaction is carried out at a constant temperature of 110 ℃ for 12 hours. After the reaction is finished, the reaction kettle is cooled to room temperature, and products in the kettle are centrifugally collected and washed with deionized water and absolute ethyl alcohol for 5 times. And drying the product in a vacuum drying oven at 60 ℃ for 6 hours to obtain the white one-dimensional Mo-MOF nanomaterial.
3) 0.2mmol of selenium powder is weighed and 2.5mL of hydrazine hydrate (N) with the mass fraction of 85 percent is added 2 H 4 ·H 2 And O) in the solution, stirring until the selenium powder is completely dissolved, and obtaining the selenium powder hydrazine hydrate solution. The solution is added into 30mL of deionized water drop by drop, and after the two solutions are stirred to be mixed uniformly, 0.03g of the one-dimensional Mo-MOF nanomaterial synthesized in the step 2) is added into the solution. Stirring for 30min to uniformly disperse the one-dimensional Mo-MOF nano material in the solution.
4) Transferring the solution obtained in the step 3) into a polytetrafluoroethylene lining of a reaction kettle with the volume of 50m L, sealing the reaction kettle, and then placing the reaction kettle into a constant-temperature air blowing box for constant-temperature heating reaction for 12 hours at 220 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, centrifugally collecting the product in the kettle, washing with deionized water and absolute ethyl alcohol for 6 times, and finally drying in a vacuum drying oven at 60 ℃ for 10 hours to obtain the flower-like structure MoSe 2 A material.
FIG. 10 shows MoSe obtained in step 4) of example 7 2 The scanning electron microscope image of the material can show that the material is in a flower-like structure formed by aggregation of a large number of nano sheets, which indicates that the original one-dimensional structure of the Mo-MOF cannot be reserved by adopting the selenizing scheme of the embodiment 7. FIG. 11 shows MoSe obtained in step 4) of example 7 2 Thermogravimetric analysis of nanomaterial. Thermogravimetric analysis showed that the material did not exhibit a significant loss of weight phase between 300 ℃ and 420 ℃ corresponding to the temperature phase of decomposition of the ligands constituting the Mo-MOF material at high temperatures, indicating that the selenization scheme of example 7 was used, not MoSe 2 Mose composite material with single flower-like structure 2 A material.
Example 8
One-dimensional MoSe structure 2 The application of the/Mo-MOF composite nano material in the field of catalytic water electrolysis hydrogen production comprises the following specific application methods:
the one-dimensional MoSe obtained in example 1 2 The composite nano material of/Mo-MOF is used as a catalyst to test the hydrogen evolution reaction performance of catalytic electrolyzed water in acidic and alkaline environments. The performance test of the hydrogen evolution reaction of the catalytic electrolysis water is that 0.5. 0.5M H is respectively used at room temperature 2 SO 4 Solution 1M KOH solution was used as the electrolyte solution in the acidic, alkaline environment of the test, using a standard three electrode system. Graphite rod as counter electrode, silver/silver chloride (Ag/AgCl) electrode as reference electrode, one-dimensional MoSe obtained in example 1 was prepared by Nafion reagent 2 Composite nanomaterial of/Mo-MOF, one-dimensional Mo-MOF nanomaterial, and flower-like MoSe obtained in example 7 2 The catalyst is fixed on the surface of a glassy carbon electrode and used as a working electrode, and the performance test of the catalytic hydrogen evolution reaction is carried out by adopting a linear sweep voltammetry.
FIG. 12 is a one-dimensional MoSe 2 Composite nano material of/Mo-MOF, nano material of one-dimensional Mo-MOF, flower-like MoSe 2 At 0.5mol/L H 2 SO 4 Polarization curve graph of catalytic hydrogen evolution reaction in solution. The test results show that in an acidic environment, compared with the one-dimensional Mo-MOF nano material, the one-dimensional MoSe 2 The composite nano material of the/Mo-MOF shows obvious catalytic hydrogen evolution reaction performance and is matched with flower-shaped MoSe 2 Compared with the catalyst, the catalytic hydrogen evolution reaction performance is further improved.
FIG. 13 is a one-dimensional MoSe 2 Composite nano material of/Mo-MOF, nano material of one-dimensional Mo-MOF, flower-like MoSe 2 Polarization curve of catalytic hydrogen evolution reaction in 1mol/L KOH solution. Test resultsShows that in alkaline environment, the nano material is matched with one-dimensional Mo-MOF nano material and flower-shaped MoSe 2 Compared with nano material, one-dimensional MoSe 2 The composite nano material of the/Mo-MOF has better catalytic hydrogen evolution reaction performance.
Claims (8)
1. The preparation method of the molybdenum diselenide/molybdenum-MOF composite nanomaterial with a one-dimensional structure is characterized by comprising the following steps of:
A. uniformly mixing a molybdenum source and imidazole in water, and performing a heating reaction on the obtained solution to obtain a one-dimensional nano-structure Mo-MOF;
B. dissolving a selenium source in hydrazine hydrate, adding the obtained hydrazine hydrate solution of the selenium source into absolute ethyl alcohol, adding the product obtained in the step A, uniformly stirring, and heating for reaction to obtain a molybdenum diselenide/molybdenum-MOF composite nanomaterial with a one-dimensional structure;
the mass ratio of the molybdenum source to the imidazole in the step A is 1: 1-2: 1, a step of;
the heating reaction in the step A refers to: reacting for 10-14 hours at the temperature of 90-120 ℃;
the morphology of the one-dimensional molybdenum diselenide/molybdenum-MOF composite nano material is as follows: moSe with two-dimensional structure grows on the surface of Mo-MOF with one-dimensional nano structure 2 Nanosheets, one-dimensional MoSe structure 2 The diameter of the composite nano material of the Mo-MOF is 400-900 nm, the length is 10-20 microns, and the MoSe on the surface of the composite material 2 The thickness of the nano-sheet is 4-5 nm.
2. The method of claim 1, wherein the molybdenum source in step a is selected from molybdenum trioxide.
3. The method of claim 1 or 2, wherein in step a, the molybdenum source and water are used in a ratio of 1:50 to 100g/ml.
4. The method according to claim 1, wherein the volume ratio of the selenium source hydrazine hydrate solution to the absolute ethanol in the step B is 1:10 to 1:14.
5. the method according to claim 1 or 4, wherein the ratio of the mass of the product obtained in step A to the volume of absolute ethanol in step B is 1:1-2g/L.
6. The method according to claim 1, wherein the heating reaction in step B means: reacting for 10-14 hours at 200-240 ℃.
7. A one-dimensional molybdenum diselenide/molybdenum-MOF composite nanomaterial prepared by the preparation method of any one of claims 1 to 6, characterized in that the one-dimensional molybdenum diselenide/molybdenum-MOF composite nanomaterial has the morphology of: moSe with two-dimensional structure grows on the surface of Mo-MOF with one-dimensional nano structure 2 Nanosheets, one-dimensional MoSe structure 2 The diameter of the composite nano material of the Mo-MOF is 400-900 nm, the length is 10-20 microns, and the MoSe on the surface of the composite material 2 The thickness of the nano-sheet is 4-5 nm.
8. Use of a one-dimensional molybdenum diselenide/molybdenum-MOF composite nanomaterial according to claim 7 for electrolytic water hydrogen evolution reactions.
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