阅读说明：本技术 一种负载二硫化钼纳米花的多孔碳电催化析氢材料及制法 (Molybdenum disulfide nanoflower-loaded porous carbon electrocatalytic hydrogen evolution material and preparation method thereof ) 是由 周伟 于 2020-12-10 设计创作，主要内容包括：本发明涉及电催化析氢技术领域,且公开了一种负载二硫化钼纳米花的多孔碳电催化析氢材料,丙烯腈单体和甲基丙烯酸酯基烷氧基磷酸酯在引发剂的作用下共聚,通过煅烧,得到氮磷共掺杂多孔碳材料,由于氮原子的电负性和碳接近,提高了多孔碳材料的电化学性质和电化学催化活性,磷原子的存在提高了多孔碳的比表面积,以多孔碳材料为载体,合成具有独特形貌的纳米花状二硫化钼,由于多孔碳材料具有纳米尺寸的孔道,可以将二硫化钼纳米花均匀分布在其孔隙内,形成复合催化材料,同时,导电性优异的氮磷共掺杂多孔碳材料可以提高催化剂的电子传递速率和导电性能,表现出更低的析氢过电位和优异的电解水析氢活性。(The invention relates to the technical field of electrocatalysis hydrogen evolution, and discloses a porous carbon electrocatalysis hydrogen evolution material loaded with molybdenum disulfide nanoflowers, acrylonitrile monomers and methacrylate alkoxy phosphate are copolymerized under the action of an initiator, and the copolymerization is carried out through calcination to obtain a nitrogen-phosphorus co-doped porous carbon material, because the electronegativity of nitrogen atoms is close to carbon, the electrochemical property and the electrochemical catalytic activity of the porous carbon material are improved, the specific surface area of the porous carbon is improved due to the existence of the phosphorus atoms, the porous carbon material is taken as a carrier to synthesize the nanoflower-shaped molybdenum disulfide with unique morphology, because the porous carbon material has nanometer-sized pore channels, the molybdenum disulfide nanoflowers can be uniformly distributed in pores of the porous carbon material to form a composite catalytic material, and meanwhile, the nitrogen-phosphorus co-doped porous carbon material with excellent conductivity can improve the electron transfer rate and the conductivity of a catalyst, exhibits lower hydrogen evolution overpotential and excellent hydrogen evolution activity of electrolyzed water.)

1. A porous carbon electrocatalytic hydrogen evolution material loaded with molybdenum disulfide nanoflowers is characterized in that: the preparation method of the porous carbon electrocatalytic hydrogen evolution material loaded with the molybdenum disulfide nanoflowers comprises the following steps:

(1) adding methacrylate-based alkoxy phosphate, acrylonitrile, divinyl benzene, hexadecane and azobisisobutyronitrile into a reactor, mixing to obtain an oil phase, mixing sodium dodecyl sulfate, sodium nitrite and distilled water to obtain a water phase, slowly adding the oil phase into the water phase, uniformly stirring, heating to 60-80 ℃ in a nitrogen atmosphere, and reacting for 6-10 hours to obtain phosphorus-containing polyacrylonitrile;

(2) adding distilled water, phosphorus-containing polyacrylonitrile and zinc chloride into a reactor, uniformly stirring, carrying out vacuum drying to remove moisture, placing the dried product into a tubular furnace, pre-oxidizing for 1-3h at 300 ℃ in an air atmosphere at 260-;

(3) adding a nitrogen-phosphorus co-doped porous carbon material, sodium molybdate, tetrabutylammonium bromide, sodium fluoride and thiourea into a distilled water solvent, adding dilute hydrochloric acid to adjust the pH value of the solution to 5-6, uniformly stirring, transferring to a reaction kettle, reacting at 180-220 ℃ for 20-30h, centrifuging, washing and drying the product, placing the product in a tubular furnace, annealing at 700-750 ℃ for 1-2h under the nitrogen atmosphere, and obtaining the porous carbon electrocatalytic hydrogen evolution material loaded with the molybdenum disulfide nanoflowers.

2. The porous carbon electrocatalytic hydrogen evolution material loaded with molybdenum disulfide nanoflowers according to claim 1, wherein the porous carbon electrocatalytic hydrogen evolution material is characterized in that: the mass ratio of the methacrylate alkoxy phosphate, the acrylonitrile, the divinylbenzene, the hexadecane, the azobisisobutyronitrile, the sodium dodecyl sulfate and the sodium nitrite in the step (1) is 10-25:100:0.8-1.2:4.5-6.5:1.5-2.5:1-1.8: 0.3-0.4.

3. The porous carbon electrocatalytic hydrogen evolution material loaded with molybdenum disulfide nanoflowers according to claim 1, wherein the porous carbon electrocatalytic hydrogen evolution material is characterized in that: the tubular furnace device in the step (2) comprises a motor, the motor is fixedly connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating wheel, the rotating wheel is movably connected with a sliding plate, the sliding plate is fixedly connected with a furnace body, the furnace body is fixedly connected with a furnace tube, and a display is arranged on the surface of the tubular furnace device.

4. The porous carbon electrocatalytic hydrogen evolution material loaded with molybdenum disulfide nanoflowers according to claim 1, wherein the porous carbon electrocatalytic hydrogen evolution material is characterized in that: the mass ratio of the phosphorus-containing polyacrylonitrile to the zinc chloride in the step (2) is 100: 120-160.

5. The porous carbon electrocatalytic hydrogen evolution material loaded with molybdenum disulfide nanoflowers according to claim 1, wherein the porous carbon electrocatalytic hydrogen evolution material is characterized in that: the mass ratio of the nitrogen and phosphorus co-doped porous carbon material, the sodium molybdate, the tetrabutylammonium bromide, the sodium fluoride and the thiourea in the step (3) is 100:380-420:15-20: 75-82.

Technical Field

The invention relates to the technical field of electrocatalytic hydrogen evolution, in particular to a porous carbon electrocatalytic hydrogen evolution material loaded with molybdenum disulfide nanoflowers and a preparation method thereof.

Background

The nano porous carbon is a nano material with a unique porous morphology, and has excellent performances such as a large specific surface area, rich electrochemical active sites, a large internal space and the like, can effectively prevent stacking, has a high mass transfer rate and a high charge transfer rate, and can shorten an ion transmission distance, so the nano porous carbon is widely researched in the fields of adsorbents, energy storage, super capacitors and the like, and compared with common porous carbon, the hetero atom doped porous carbon has better surface performance and conductivity, so that an aqueous solution can be easily diffused into the active sites of reaction, rich channels for transferring reactant water and product hydrogen are provided, excellent conditions can be provided for the application of the porous carbon in the field of hydrogen evolution by water electrolysis catalysis, and the hetero atom doped porous carbon is also widely researched.

Molybdenum disulfide as one of transition metal dichalcogenides shows excellent performance in the fields of fuel cells, capacitors and the like, and meanwhile, the free energy of hydrogen bond combination of molybdenum disulfide is very close to noble metal platinum, so that extensive research is carried out in the field of electrolytic water catalytic hydrogen evolution, as the electrocatalytic active sites of molybdenum disulfide are positioned at the edge positions, the number of the active sites is limited, and the electrolytic water catalytic hydrogen evolution performance is limited to a greater extent due to the reasons that molybdenum disulfide has poor self conductivity, molybdenum disulfide nanosheets are easy to accumulate and the like, the molybdenum disulfide is subjected to shape improvement and doped with high-conductivity materials to improve the specific surface area and the electrolytic water catalytic activity further needs to be researched, and the molybdenum disulfide is compounded with a porous carbon material, so that the conductive capacity of the molybdenum disulfide can be greatly improved, and meanwhile, as the surface area of the porous carbon material is large, the molybdenum disulfide can be effectively prevented from being accumulated, and the catalytic hydrogen evolution activity of the molybdenum disulfide in the electrolyzed water is effectively improved.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a porous carbon electrocatalytic hydrogen evolution material loaded with molybdenum disulfide nanoflowers and a preparation method thereof, and solves the problem of poor activity of electrocatalytic decomposition of molybdenum disulfide in water evolution.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: a porous carbon electrocatalytic hydrogen evolution material loaded with molybdenum disulfide nanoflowers is prepared by the following steps:

(1) adding methacrylate-based alkoxy phosphate, acrylonitrile, divinyl benzene, hexadecane and azobisisobutyronitrile into a reactor, mixing to obtain an oil phase, mixing sodium dodecyl sulfate, sodium nitrite and distilled water to obtain a water phase, slowly adding the oil phase into the water phase, uniformly stirring, heating to 60-80 ℃ in a nitrogen atmosphere, and reacting for 6-10 hours to obtain phosphorus-containing polyacrylonitrile;

(2) adding distilled water, phosphorus-containing polyacrylonitrile and zinc chloride into a reactor, uniformly stirring, carrying out vacuum drying to remove moisture, placing the dried product into a tubular furnace, pre-oxidizing for 1-3h at 300 ℃ in an air atmosphere at 260-;

(3) adding a nitrogen-phosphorus co-doped porous carbon material, sodium molybdate, tetrabutylammonium bromide, sodium fluoride and thiourea into a distilled water solvent, adding dilute hydrochloric acid to adjust the pH value of the solution to 5-6, uniformly stirring, transferring to a reaction kettle, reacting at 180-220 ℃ for 20-30h, centrifuging, washing and drying the product, placing the product in a tubular furnace, annealing at 700-750 ℃ for 1-2h under the nitrogen atmosphere, and obtaining the porous carbon electrocatalytic hydrogen evolution material loaded with the molybdenum disulfide nanoflowers.

Preferably, the mass ratio of the methacrylate-based alkoxy phosphate, the acrylonitrile, the divinylbenzene, the hexadecane, the azobisisobutyronitrile, the sodium dodecyl sulfate and the sodium nitrite in the step (1) is 10-25:100:0.8-1.2:4.5-6.5:1.5-2.5:1-1.8: 0.3-0.4.

Preferably, the tube furnace device in the step (2) comprises a motor, the motor is fixedly connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating wheel, the rotating wheel is movably connected with a sliding plate, the sliding plate is fixedly connected with a furnace body, the furnace body is fixedly connected with a furnace tube, and a display is arranged on the surface of the tube furnace device.

Preferably, the mass ratio of the polyacrylonitrile containing phosphorus to the zinc chloride in the step (2) is 100: 120-160.

Preferably, the mass ratio of the nitrogen and phosphorus co-doped porous carbon material, the sodium molybdate, the tetrabutylammonium bromide, the sodium fluoride and the thiourea in the step (3) is 100:380-420:15-20: 75-82.

(III) advantageous technical effects

Compared with the prior art, the invention has the following experimental principles and beneficial technical effects:

according to the porous carbon electrocatalytic hydrogen evolution material loaded with the molybdenum disulfide nanoflowers, an acrylonitrile monomer and methacrylate alkoxy phosphate are copolymerized under the action of an azodiisobutyronitrile initiator to obtain a phosphorus-containing polyacrylonitrile copolymer, a polyacrylonitrile component is used as a carbon source and a nitrogen source, a methacrylate alkoxy phosphate component is used as a phosphorus source, zinc chloride is used as a pore-making agent, and the nitrogen-phosphorus co-doped porous carbon material is obtained through high-temperature calcination, wherein due to the fact that electronegativity and carbon of nitrogen atoms are close to each other, lone electrons in the nitrogen atoms enable charge distribution of the porous carbon material to be changed, electrochemical properties and electrochemical catalytic activity of the porous carbon material are improved, the phosphorus atoms exist in an embedded form in a porous carbon framework, the porous structure and the specific surface area of the porous carbon are effectively improved, and the phosphorus-containing porous carbon has higher contents of graphite nitrogen and pyridine nitrogen and higher specific surface area, so that the porous carbon material has more excellent catalytic hydrogen evolution activity of electrolyzed water.

According to the porous carbon electro-catalysis hydrogen evolution material loaded with the molybdenum disulfide nanoflowers, nitrogen and phosphorus co-doped porous carbon materials are used as carriers, in the process of synthesizing the nanoflower-shaped molybdenum disulfide by a hydrothermal method, small bumps are formed on the surfaces of crystal nuclei under the action of tetrabutylammonium bromide serving as a surfactant, crystals preferentially grow towards crystal faces with lower tuberculosis energy along with the progress of reaction, finally, the condensation nuclei grow into the nanoflower-shaped molybdenum disulfide with unique morphology, the specific surface area of the molybdenum disulfide is remarkably increased, the catalytic activity sites of the molybdenum disulfide are increased, and the catalytic activity of the molybdenum disulfide is effectively improved; the porous carbon material has a plurality of nanometer-sized pore channels, so that molybdenum disulfide can be deposited in the pore channels, and the molybdenum disulfide nanoflowers are uniformly distributed in the pores of the porous carbon material to form the composite catalytic material.

Drawings

FIG. 1 is a schematic view of the construction of a tube furnace apparatus;

fig. 2 is a partially enlarged schematic view of the slide plate.

1-a tube furnace apparatus; 2, a motor; 3-a rotating shaft; 4-rotating wheel; 5, a sliding plate; 6-furnace body; 7-furnace tube; 8-display.

Detailed description of the preferred embodiments

To achieve the above object, the present invention provides the following embodiments and examples: a porous carbon electrocatalytic hydrogen evolution material loaded with molybdenum disulfide nanoflowers and a preparation method thereof comprise the following steps:

(1) adding methacrylate-based alkoxy phosphate, acrylonitrile, divinylbenzene, hexadecane and azobisisobutyronitrile into a reactor, mixing to obtain an oil phase, mixing sodium dodecyl sulfate, sodium nitrite and distilled water to obtain a water phase, wherein the mass ratio of the methacrylate-based alkoxy phosphate, the acrylonitrile, the divinylbenzene, the hexadecane, the azobisisobutyronitrile, the sodium dodecyl sulfate and the sodium nitrite is 10-25:100:0.8-1.2:4.5-6.5:1.5-2.5:1-1.8:0.3-0.4, slowly adding the oil phase into the water phase, uniformly stirring, heating to 60-80 ℃ in a nitrogen atmosphere, and reacting for 6-10 hours to obtain phosphorus-containing polyacrylonitrile;

(2) adding phosphorus-containing polyacrylonitrile and zinc chloride into a distilled water solvent, wherein the mass ratio of the phosphorus-containing polyacrylonitrile to the zinc chloride is 100: 120-;

(3) adding a nitrogen-phosphorus co-doped porous carbon material, sodium molybdate, tetrabutylammonium bromide, sodium fluoride and thiourea into a distilled water solvent, wherein the mass ratio of the nitrogen-phosphorus co-doped porous carbon material to the sodium molybdate to the tetrabutylammonium bromide to the sodium fluoride to the thiourea is 100:380-420: 15: 20:75-82, adding dilute hydrochloric acid to adjust the pH value of the solution to 5-6, uniformly stirring, transferring the solution to a reaction kettle, reacting at the temperature of 180-220 ℃ for 20-30h, centrifuging, washing and drying the product, placing the product in a tubular furnace, and annealing at the temperature of 700-750 ℃ for 1-2h under the nitrogen atmosphere to obtain the porous carbon electrocatalytic hydrogen evolution material loaded with the molybdenum disulfide nanoflowers.

Example 1

(1) Adding methacrylate group alkoxy phosphate, acrylonitrile, divinylbenzene, hexadecane and azobisisobutyronitrile into a reactor, mixing to obtain an oil phase, mixing sodium dodecyl sulfate, sodium nitrite and distilled water to obtain a water phase, slowly adding the oil phase into the water phase, uniformly stirring, and heating to 60 ℃ in a nitrogen atmosphere to react for 6 hours to obtain phosphorus-containing polyacrylonitrile, wherein the mass ratio of the methacrylate group alkoxy phosphate, the acrylonitrile, the divinylbenzene, the hexadecane, the azobisisobutyronitrile, the sodium dodecyl sulfate and the sodium nitrite is 10:100:0.8:4.5:1.5:1: 0.3;

(2) adding phosphorus-containing polyacrylonitrile and zinc chloride into a distilled water solvent, wherein the mass ratio of the phosphorus-containing polyacrylonitrile to the zinc chloride is 100:120, uniformly stirring, carrying out vacuum drying to remove moisture, putting a dried product into a tubular furnace, wherein the tubular furnace comprises a motor, the motor is fixedly connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating wheel, the rotating wheel is movably connected with a sliding plate, the sliding plate is fixedly connected with a furnace body, the furnace body is fixedly connected with a furnace tube, a display is arranged on the surface of the tubular furnace, pre-oxidizing the surface for 1h at 260 ℃ in the air atmosphere, carbonizing the surface for 30min at 700 ℃ in the nitrogen atmosphere, washing and centrifuging the product to obtain a nitrogen-phosphorus co-doped porous carbon material;

(3) adding a nitrogen-phosphorus co-doped porous carbon material, sodium molybdate, tetrabutylammonium bromide, sodium fluoride and thiourea into a distilled water solvent, wherein the mass ratio of the nitrogen-phosphorus co-doped porous carbon material to the sodium molybdate to the tetrabutylammonium bromide to the sodium fluoride to the thiourea is 100:380:15:75, adding dilute hydrochloric acid to adjust the pH of the solution to 5, uniformly stirring, transferring the solution to a reaction kettle, reacting at 180 ℃ for 20 hours, centrifuging, washing and drying the product, placing the product in a tubular furnace, annealing at 700 ℃ for 1 hour under the nitrogen atmosphere, and obtaining the porous carbon electro-catalysis hydrogen evolution material loaded with the molybdenum disulfide nanoflowers.

Example 2

(1) Adding methacrylate group alkoxy phosphate, acrylonitrile, divinylbenzene, hexadecane and azobisisobutyronitrile into a reactor, mixing to obtain an oil phase, mixing sodium dodecyl sulfate, sodium nitrite and distilled water to obtain a water phase, slowly adding the oil phase into the water phase, uniformly stirring, heating to 70 ℃ in a nitrogen atmosphere, and reacting for 7 hours to obtain phosphorus-containing polyacrylonitrile, wherein the mass ratio of the methacrylate group alkoxy phosphate, the acrylonitrile, the divinylbenzene, the hexadecane, the azobisisobutyronitrile, the sodium dodecyl sulfate and the sodium nitrite is 15:100:0.95:5.2:1.8:1.3: 0.33;

(2) adding phosphorus-containing polyacrylonitrile and zinc chloride into a distilled water solvent, wherein the mass ratio of the phosphorus-containing polyacrylonitrile to the zinc chloride is 100:134, uniformly stirring, carrying out vacuum drying to remove moisture, putting a dried product into a tubular furnace, wherein the tubular furnace comprises a motor, the motor is fixedly connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating wheel, the rotating wheel is movably connected with a sliding plate, the sliding plate is fixedly connected with a furnace body, the furnace body is fixedly connected with a furnace tube, a display is arranged on the surface of the tubular furnace, pre-oxidizing the surface for 2 hours at 280 ℃ in an air atmosphere, carbonizing the surface for 40 minutes at 760 ℃ in a nitrogen atmosphere, washing and centrifuging the product to obtain a nitrogen-phosphorus co-doped porous carbon material;

(3) adding a nitrogen-phosphorus co-doped porous carbon material, sodium molybdate, tetrabutylammonium bromide, sodium fluoride and thiourea into a distilled water solvent, wherein the mass ratio of the nitrogen-phosphorus co-doped porous carbon material to the sodium molybdate to the tetrabutylammonium bromide to the sodium fluoride to the thiourea is 100:394:17.5:78, adding dilute hydrochloric acid to adjust the pH value of the solution to 6, uniformly stirring, transferring the solution into a reaction kettle, reacting for 26 hours at 190 ℃, centrifuging, washing and drying a product, placing the product in a tubular furnace under the atmosphere of nitrogen, and annealing at 720 ℃ for 1.5 hours to obtain the porous carbon electrocatalytic hydrogen evolution material loaded with the molybdenum disulfide nanoflowers.

Example 3

(1) Adding methacrylate group alkoxy phosphate, acrylonitrile, divinylbenzene, hexadecane and azobisisobutyronitrile into a reactor, mixing to obtain an oil phase, mixing sodium dodecyl sulfate, sodium nitrite and distilled water to obtain a water phase, slowly adding the oil phase into the water phase, uniformly stirring, and heating to 70 ℃ in a nitrogen atmosphere to react for 8 hours to obtain phosphorus-containing polyacrylonitrile, wherein the mass ratio of the methacrylate group alkoxy phosphate, the acrylonitrile, the divinylbenzene, the hexadecane, the azobisisobutyronitrile, the sodium dodecyl sulfate and the sodium nitrite is 20:100:1.1:5.9:2.1:1.6: 0.36;

(2) adding phosphorus-containing polyacrylonitrile and zinc chloride into a distilled water solvent, wherein the mass ratio of the phosphorus-containing polyacrylonitrile to the zinc chloride is 100:148, uniformly stirring, carrying out vacuum drying to remove moisture, putting a dried product into a tubular furnace, wherein the tubular furnace comprises a motor, the motor is fixedly connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating wheel, the rotating wheel is movably connected with a sliding plate, the sliding plate is fixedly connected with a furnace body, the furnace body is fixedly connected with a furnace tube, a display is arranged on the surface of the tubular furnace, pre-oxidizing the surface for 2 hours at 280 ℃ in an air atmosphere, carbonizing the surface for 50 minutes at 760 ℃ in a nitrogen atmosphere, washing and centrifuging the product to obtain a nitrogen-phosphorus co-doped porous carbon material;

(3) adding a nitrogen-phosphorus co-doped porous carbon material, sodium molybdate, tetrabutylammonium bromide, sodium fluoride and thiourea into a distilled water solvent, wherein the mass ratio of the nitrogen-phosphorus co-doped porous carbon material to the sodium molybdate to the tetrabutylammonium bromide to the sodium fluoride to the thiourea is 100:408:19:80, adding dilute hydrochloric acid to adjust the pH of the solution to 6, uniformly stirring, transferring the solution to a reaction kettle, reacting at 210 ℃ for 28 hours, centrifuging, washing and drying the product, placing the product in a tubular furnace under the atmosphere of nitrogen, and annealing at 740 ℃ for 1.5 hours to obtain the porous carbon electrocatalytic hydrogen evolution material loaded with the molybdenum disulfide nanoflowers.

Example 4

(1) Adding methacrylate group alkoxy phosphate, acrylonitrile, divinylbenzene, hexadecane and azobisisobutyronitrile into a reactor, mixing to obtain an oil phase, mixing sodium dodecyl sulfate, sodium nitrite and distilled water to obtain a water phase, slowly adding the oil phase into the water phase, uniformly stirring, and heating to 80 ℃ in a nitrogen atmosphere to react for 10 hours to obtain phosphorus-containing polyacrylonitrile, wherein the mass ratio of the methacrylate group alkoxy phosphate, the acrylonitrile, the divinylbenzene, the hexadecane, the azobisisobutyronitrile, the sodium dodecyl sulfate and the sodium nitrite is 25:100:1.2:6.5:2.5:1.8: 0.4;

(2) adding phosphorus-containing polyacrylonitrile and zinc chloride into a distilled water solvent, wherein the mass ratio of the phosphorus-containing polyacrylonitrile to the zinc chloride is 100:160, uniformly stirring, carrying out vacuum drying to remove moisture, putting a dried product into a tubular furnace, wherein the tubular furnace comprises a motor, the motor is fixedly connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating wheel, the rotating wheel is movably connected with a sliding plate, the sliding plate is fixedly connected with a furnace body, the furnace body is fixedly connected with a furnace tube, a display is arranged on the surface of the tubular furnace, pre-oxidizing the surface for 3 hours at 300 ℃ in an air atmosphere, carbonizing the surface for 60 minutes at 800 ℃ in a nitrogen atmosphere, washing and centrifuging the product to obtain a nitrogen-phosphorus co-doped porous carbon material;

(3) adding a nitrogen-phosphorus co-doped porous carbon material, sodium molybdate, tetrabutylammonium bromide, sodium fluoride and thiourea into a distilled water solvent, wherein the mass ratio of the nitrogen-phosphorus co-doped porous carbon material to the sodium molybdate to the tetrabutylammonium bromide to the sodium fluoride to the thiourea is 100:420:20:82, adding dilute hydrochloric acid to adjust the pH of the solution to 6, uniformly stirring, transferring the solution to a reaction kettle, reacting for 30 hours at 220 ℃, centrifuging, washing and drying the product, placing the product in a tube furnace under the nitrogen atmosphere, and annealing for 2 hours at 750 ℃ to obtain the porous carbon electro-catalysis hydrogen evolution material loaded with the molybdenum disulfide nanoflowers.

Comparative example 1

(1) Adding methacrylate group alkoxy phosphate, acrylonitrile, divinylbenzene, hexadecane and azobisisobutyronitrile into a reactor, mixing to obtain an oil phase, mixing sodium dodecyl sulfate, sodium nitrite and distilled water to obtain a water phase, slowly adding the oil phase into the water phase, uniformly stirring, and heating to 90 ℃ in a nitrogen atmosphere to react for 12 hours to obtain phosphorus-containing polyacrylonitrile, wherein the mass ratio of the methacrylate group alkoxy phosphate, the acrylonitrile, the divinylbenzene, the hexadecane, the azobisisobutyronitrile, the sodium dodecyl sulfate and the sodium nitrite is 30:100:1.35:7.2:2.8:2.1: 0.43;

(2) adding phosphorus-containing polyacrylonitrile and zinc chloride into a distilled water solvent, wherein the mass ratio of the phosphorus-containing polyacrylonitrile to the zinc chloride is 100:174, uniformly stirring, carrying out vacuum drying to remove moisture, putting a dried product into a tubular furnace, wherein the tubular furnace comprises a motor, the motor is fixedly connected with a rotating shaft, the rotating shaft is fixedly connected with a rotating wheel, the rotating wheel is movably connected with a sliding plate, the sliding plate is fixedly connected with a furnace body, the furnace body is fixedly connected with a furnace tube, a display is arranged on the surface of the tubular furnace, pre-oxidizing the surface for 3 hours at 320 ℃ in the air atmosphere, carbonizing the surface for 70 minutes at 800 ℃ in the nitrogen atmosphere, washing and centrifuging the product to obtain a nitrogen-phosphorus co-doped porous carbon material;

(3) adding a nitrogen-phosphorus co-doped porous carbon material, sodium molybdate, tetrabutylammonium bromide, sodium fluoride and thiourea into a distilled water solvent, wherein the mass ratio of the nitrogen-phosphorus co-doped porous carbon material to the sodium molybdate to the tetrabutylammonium bromide to the sodium fluoride to the thiourea is 100:434:21.5:84, adding dilute hydrochloric acid to adjust the pH of the solution to 7, uniformly stirring, transferring the solution into a reaction kettle, reacting at 230 ℃ for 32 hours, centrifuging, washing and drying a product, placing the product in a tubular furnace, annealing at 760 ℃ for 3 hours under the atmosphere of nitrogen, and obtaining the porous carbon electrocatalytic hydrogen evolution material loaded with the molybdenum disulfide nanoflowers.

The method comprises the steps of dispersing a porous carbon electro-catalysis hydrogen evolution material loaded with molybdenum disulfide nanoflowers into a mixed solvent of water and N, N-dimethylformamide, adding a Nafion solution, uniformly dripping the solution on the surface of a glassy carbon electrode to obtain an electrochemical hydrogen evolution working electrode, using a platinum electrode as a counter electrode, using an Ag/AgCl electrode as a reference electrode, using a 0.5mol/L sulfuric acid solution as electrolyte, and testing hydrogen evolution overpotential and electrochemical hydrogen evolution activity of the porous carbon electro-catalysis hydrogen evolution material loaded with the molybdenum disulfide nanoflowers by using a FOXBORO electrochemical analyzer, wherein the testing standard is GB 32311 2015.