CN115072782A - Preparation method of cobalt-doped molybdenum disulfide hollow sphere - Google Patents

Preparation method of cobalt-doped molybdenum disulfide hollow sphere Download PDF

Info

Publication number
CN115072782A
CN115072782A CN202110266780.4A CN202110266780A CN115072782A CN 115072782 A CN115072782 A CN 115072782A CN 202110266780 A CN202110266780 A CN 202110266780A CN 115072782 A CN115072782 A CN 115072782A
Authority
CN
China
Prior art keywords
cobalt
molybdenum disulfide
hollow sphere
mos
source
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110266780.4A
Other languages
Chinese (zh)
Inventor
田志坚
王小平
何盛宝
马怀军
迟克彬
王冬娥
李梦晨
郑安达
于宏悦
杨林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Petrochina Co Ltd
Original Assignee
Dalian Institute of Chemical Physics of CAS
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS, Petrochina Co Ltd filed Critical Dalian Institute of Chemical Physics of CAS
Priority to CN202110266780.4A priority Critical patent/CN115072782A/en
Publication of CN115072782A publication Critical patent/CN115072782A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G39/00—Compounds of molybdenum
    • C01G39/06—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • B01J35/51—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C01P2004/34—Spheres hollow
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Abstract

The invention discloses a preparation method of a cobalt-doped molybdenum disulfide hollow sphere, which comprises the following steps: adding an organic molybdenum source, an organic cobalt source and an organic sulfur source into a solvent according to a Co/Mo molar ratio of 0.03-1 and an S/(Mo + Co) molar ratio of 10: 1-2: 1, and fully mixing to obtain a solution or a suspension; the obtained solution or suspension is thermally reacted for 4 to 48 hours at the temperature of 120 to 200 ℃, and is aged by Oswald to obtain Co/MoS 2 The hollow ball. The preparation method is simple, the reaction conditions are easy to control, and the spherical Co/MoS 2 High yield, and large amount of (Co) MoS on the surface of the product 2 Nano meterAnd (3) slicing. Co/MoS prepared by the invention 2 The hollow sphere can be used in the fields of catalysis, hydrogen production and storage, chemical sensors and the like due to the unique internal hollow structure and the special physical and chemical properties, and has wide application prospect.

Description

Preparation method of cobalt-doped molybdenum disulfide hollow sphere
Technical Field
The invention belongs to the field of synthesis of inorganic nano materials, and particularly relates to cobalt-doped molybdenum disulfide (Co/MoS) 2 ) A preparation method of hollow spheres.
Background
The aggravation of the heavy and inferior crude oil resources and the improvement of the quality standard of the liquid fuel make the clean production and the efficient utilization of the petroleum resources face important challenges. MoS 2 Is a petroleum hydrogenation upgrading catalyst widely used in industry to improve MoS 2 The hydrogenation activity of (2) has important significance. The molybdenum disulfide hollow sphere has the advantages of large specific surface area, high catalytic activity and the like due to the unique internal hollow structure, and becomes a hotspot of research. Meanwhile, a large number of studies have shown that: the cobalt doping can obviously improve MoS 2 Hydrogenation performance of the catalyst (deep, f.l., et al., ACS Catalysis,2011,1(5), 537-. Therefore, the preparation of the cobalt-doped molybdenum disulfide hollow sphere has high performanceThe value is important, but the preparation of the cobalt-doped molybdenum disulfide hollow sphere is not reported yet at present.
The preparation method of the molybdenum disulfide hollow sphere is various, and wet chemical synthesis is most commonly used, particularly a hydrothermal or solvothermal method. Chinese patent CN108128805A reports a method for preparing molybdenum disulfide hollow spheres by a hydrothermal method, wherein a surfactant, a molybdenum source and a sulfur source are uniformly mixed, a reducing agent hydrazine hydrate is added, and then a hydrothermal reaction is carried out to obtain the molybdenum disulfide flower-shaped hollow spheres. Due to the addition of surfactants and reducing agents, the removal of impurities is difficult. The invention has the problem that the obtained molybdenum disulfide contains more impurities. Chinese patent CN106430310B takes sodium molybdate, thiourea and urea as raw materials and Polyetherimide (PEI) as a template agent, and after hydrothermal reaction, precipitates are obtained by high-temperature roasting, and finally hollow spherical molybdenum disulfide is obtained. Since this invention requires an aerobic calcination, part of the molybdenum disulfide may be oxidized.
Guo et al (Guo, B., et al, ACS appl. Mater. interfaces 2016,8,5517-5525.) dissolve sodium molybdate and thioacetamide in deionized water, then add oxalic acid to adjust the pH of the solution, after the hydrothermal reaction of the solution, collect the black precipitate, and bake the black precipitate at 800 ℃ for 2 hours in argon atmosphere, thus obtaining the molybdenum disulfide hollow sphere. The interior of the molybdenum disulfide hollow sphere obtained by the method is not completely hollow, and the hollow sphere is greatly agglomerated due to high-temperature roasting. Lou et al (Lou, X., et al., Angew. chem. int. Ed.2016,55, 7423-. Then, after the precursor is re-dispersed in ethanol, thiourea is added as a reducing agent, the solvent is subjected to a thermal reaction in a mixed solution of water and ethanol (V ethanol/V water is 3:1), and the obtained sample is subjected to Ar/H reaction 2 Annealing for 2h at the speed of 2 ℃/min in the mixed atmosphere to finally obtain the hollow spherical molybdenum disulfide with the outer diameter of about 400 nm. The method has the advantages of complicated steps and small preparation amount, and is not suitable for large-scale preparation. In conclusion, the wet preparation of the molybdenum disulfide hollow sphere generally requires the addition of a template agent and a reducing agent, and further roasting is required to form the hollow sphere. Leading to complicated preparation steps, low product yield and difficult large-scale application。
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of a cobalt-doped molybdenum disulfide hollow sphere, which takes an organic molybdenum source, an organic cobalt source and an organic sulfur source as raw materials, and prepares Co/MoS through one-step solvothermal preparation by a Stroude curing mechanism 2 The hollow ball.
To achieve the above object, the present invention provides a cobalt-doped molybdenum disulfide (Co/MoS) 2 ) The preparation method of the hollow sphere comprises the following steps:
step (1): adding an organic molybdenum source, an organic cobalt source and an organic sulfur source into a solvent according to a Co/Mo molar ratio of 0.03-1 and an S/(Mo + Co) molar ratio of 10: 1-2: 1, and fully mixing to obtain a solution or a suspension;
step (2): transferring the solution or the suspension into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven for thermal reaction;
and (3): and cooling, separating a solid product, washing and drying to obtain the nano cobalt-doped molybdenum disulfide hollow sphere.
The organic molybdenum source of the invention is at least one of molybdenum acetylacetonate, molybdenum isooctanoate and molybdenum naphthenate, and the molybdenum isooctanoate is preferred.
The organic cobalt source of the present invention is at least one of cobalt acetylacetonate and cobalt isooctanoate, preferably cobalt isooctanoate.
The organic sulfur source of the present invention is at least one of L-cysteine, glutathione and thiourea, preferably L-cysteine.
In the step (1), the concentration of the organic molybdenum source in the solution or suspension in the mixed solution is 0.05-0.30 mol/L, preferably 0.10-0.25 mol/L.
In the step (1), the molar ratio of Co/Mo in the solution or the suspension is 0.03-1, preferably 0.1-0.5; the molar ratio of S/(Mo + Co) is 10: 1-2: 1, preferably 8: 1-4: 1.
The reaction temperature of the thermal reaction is 120-200 ℃, and the reaction time is 4-48 hours.
Preferably, the reaction temperature of the thermal reaction is 160-200 ℃, and the reaction time is 12-24 hours. Thereby ensuring the full decomposition of the sulfur source and the reduction of the molybdenum source and fully utilizing the raw materials.
The solvent of the invention is at least one of ethanol, methanol and glycol.
In the step (2), the filling degree of the kettle body in the high-pressure reaction kettle is 40-70%, preferably 50-60%.
In the step (3), the drying temperature is 60-80 ℃.
The invention can adopt the conventional separation means such as suction filtration, centrifugation and the like to separate the obtained product, the product is respectively washed by deionized water and ethanol for three times, and the black powdery product, namely the cobalt-doped molybdenum disulfide hollow sphere, is obtained by drying in the modes of vacuum drying, freeze drying, natural airing and the like.
Compared with the prior art, the invention has the following advantages:
Co/MoS of the invention 2 The preparation method of the hollow sphere is simple to operate, does not need to add a template agent, and is Co/MoS 2 High yield of the product, simple product separation and suitability for large-scale production. The organic sulfur source is a vulcanizing agent and a reducing agent, no additional reducing agent is needed, dangerous reducing agents such as hydrazine hydrate are avoided, and the introduction amount of impurities is reduced. Spherical Co/MoS prepared by the invention 2 Surface is composed of a large amount of (Co) MoS 2 The nano-sheet composition increases the surface active site exposure, Co/MoS 2 The catalytic performance of the catalyst is greatly improved. In addition, the Co/MoS prepared by the invention 2 The hollow sphere can be used in the fields of catalysis, hydrogen production and storage, chemical sensors and the like due to the unique internal hollow structure and the special physical and chemical properties, and has wide application prospect.
Co/MoS of the invention 2 The formation of hollow spheres may follow the oswald ripening mechanism shown in fig. 6 (Pan, a., et al., angelw.chem., int.ed.2013,52 (8)). The organic sulfur source used in the invention has certain reducibility, and is a vulcanizing agent and a reducing agent in the reaction process. When the organic sulfur source is decomposed by heating, a part of the sulfur will convert Mo 6+ Reduction to Mo 4+ Another part of the sulfur is contacted with an organic molybdenum source and an organic cobalt sourceMolybdenum sulfide and cobalt sulfide. The organic solvent interacts with the generated molybdenum sulfide and cobalt sulfide to form a solid spherical core, and the solid spherical core is completely dissolved through Oswald ripening to finally form Co/MoS 2 The hollow ball.
Drawings
FIG. 1 shows Co/MoS obtained in examples 1 to 7 of the present invention 2 XRD images of the hollow spheres;
FIG. 2 shows the Co/MoS obtained in example 1 of the present invention 2 TEM image of the hollow sphere;
FIG. 3 shows the Co/MoS obtained in example 1 of the present invention 2 High power TEM images of the hollow spheres;
FIG. 4 shows the Co/MoS obtained in comparative example 1 of the present invention 2 TEM image of the nanosheets;
FIG. 5 shows the spherical MoS obtained in comparative example 2 of the present invention 2 A TEM image of (a);
FIG. 6 shows the Co/MoS of the present invention 2 The process of forming the hollow sphere is shown schematically.
Detailed Description
The present invention will be further specifically described with reference to the following examples, but the present invention is not limited to the following examples. Any modification which does not depart from the spirit and scope of the invention is deemed to be within the scope of the invention.
Example 1:
2mmol of molybdenum isooctanoate, 0.2mmol of cobalt isooctanoate (Co/Mo ═ 0.1) and 8.8mmol of L-cysteine were weighed in this order into a 100mL beaker, and 50mL of ethanol was added to the beaker and stirred at 500rpm for 30 min. And transferring the obtained suspension into a 100mL high-pressure reaction kettle, preserving heat for 16 hours at 200 ℃, naturally cooling, performing suction filtration, washing the precipitate with deionized water and absolute ethyl alcohol, and then performing vacuum drying for 12 hours at 70 ℃ to obtain black powder. And performing ICP-MS (inductively coupled plasma mass spectrometry), XRD (X-ray powder diffraction) and TEM (transmission electron microscope) characterization on the prepared black powder respectively. ICP data indicate resulting Co/MoS 2 The medium cobalt-molybdenum ratio is close to the charge ratio of the cobalt source and the molybdenum source (the result is shown in table 1), which indicates that the cobalt source and the molybdenum source are fully utilized. XRD characterization showed only 2H-MoS in the resulting black powder 2 Indicating that the cobalt species are uniformly dispersed in the molybdenum disulfide or are present in an amorphous state. At the same time, the diffraction peak is broadened, indicating that the obtained Co/MoS 2 The size is smaller (results are shown in figure 1). The calculated S-Mo-S interlamellar spacing is 0.96nm compared with the standard 2H-MoS 2 The S-Mo-S interlayer spacing of 0.62nm is obviously increased. TEM images show that the product is Co/MoS with the outer diameter of 0.5-1 mu m and the wall thickness of 10-20 nm 2 The hollow sphere (results are shown in fig. 2 and 3) has a large amount of MoS on the surface 2 Stacking the nano sheets. High power TEM image showed that the product is composed of a mass of bent MoS 2 The lamellae (linear structures) are cross-linked and stacked one on top of the other, each of them being about ten nanometers long (results are shown in fig. 3), with cobalt embedded in them.
Example 2:
2mmol of molybdenum acetylacetonate, 0.2mmol of cobalt acetylacetonate (Co/Mo ═ 0.1) and 8.8mmol of L-cysteine were weighed out in this order in a 100mL beaker, and 50mL of ethanol were added to the beaker and stirred at 500rpm for 30 min. And transferring the obtained suspension into a 100mL high-pressure reaction kettle, preserving heat for 16 hours at 200 ℃, naturally cooling, performing suction filtration, washing the precipitate with deionized water and absolute ethyl alcohol, and performing vacuum drying for 12 hours at 70 ℃ to obtain black powder. The results of ICP-MS and XRD characterization indicated that the cobalt species were uniformly dispersed in the molybdenum disulfide or were present in an amorphous state (results are shown in table 1 and figure 1). TEM images show that the product is Co/MoS with the outer diameter of 0.5-0.8 mu m and the wall thickness of 5-15 nm 2 Hollow ball with large amount of Co/MoS on the surface 2 Nanosheets.
Example 3:
2mmol of molybdenum naphthenate, 0.2mmol of cobalt isooctanoate (Co/Mo is 0.1) and 8.8mmol of L-cysteine are weighed in turn into a 100mL beaker, 50mL of ethanol is added into the beaker, and the mixture is stirred at 500rpm for 30 min. And transferring the obtained suspension into a 100mL high-pressure reaction kettle, preserving heat for 16 hours at 200 ℃, naturally cooling, performing suction filtration, washing the precipitate with deionized water and absolute ethyl alcohol, and then performing vacuum drying for 12 hours at 70 ℃ to obtain black powder. The ICP and XRD characterization results indicated that the cobalt species were uniformly dispersed in the molybdenum disulfide or were present in an amorphous state (results are shown in table 1 and figure 1). TEM image showed the product to be 0.5 ODCo/MoS with thickness of 1 mu m and wall thickness of 5-20 nm 2 Hollow ball with large amount of Co/MoS on the surface 2 Nanosheets.
Example 4:
2mmol of molybdenum isooctanoate, 0.2mmol of cobalt isooctanoate (Co/Mo ═ 0.1) and 8.8mmol of thiourea were weighed in this order into a 100mL beaker, and 50mL of ethanol was added to the beaker and stirred at 500rpm for 30 min. And transferring the obtained suspension into a 100mL high-pressure reaction kettle, preserving heat for 16 hours at 160 ℃, naturally cooling, performing suction filtration, washing the precipitate with deionized water and absolute ethyl alcohol, and then performing vacuum drying for 12 hours at 70 ℃ to obtain black powder. The ICP and XRD characterization results indicated that the cobalt species were uniformly dispersed in the molybdenum disulfide or were present in an amorphous state (results are shown in table 1 and figure 1). TEM images show that the product is Co/MoS with the outer diameter of 0.4-0.8 mu m and the wall thickness of 10-30 nm 2 Hollow ball with large amount of Co/MoS on the surface 2 Nanosheets.
Example 5:
2mmol of molybdenum isooctanoate, 0.06mmol of cobalt isooctanoate (Co/Mo ═ 0.03) and 8.24mmol of L-cysteine were weighed in this order into a 100mL beaker, and 50mL of ethanol was added to the beaker and stirred at 500rpm for 30 min. And transferring the obtained suspension into a 100mL high-pressure reaction kettle, preserving heat for 16 hours at 200 ℃, naturally cooling, performing suction filtration, washing the precipitate with deionized water and absolute ethyl alcohol, and then performing vacuum drying for 12 hours at 70 ℃ to obtain black powder. The ICP and XRD characterization results indicated that the cobalt species were uniformly dispersed in the molybdenum disulfide or were present in an amorphous state (results are shown in table 1 and figure 1). The TEM image shows that the product is Co/MoS with the outer diameter of 0.5-1.5 mu m and the wall thickness of 5-20 nm 2 Hollow ball with large amount of Co/MoS on the surface 2 Nanosheets.
Example 6:
example 6 was prepared in the same manner as example 1 except that the thermal reaction time was 48 hours. ICP data shows that the ratio of cobalt to molybdenum in the black powder sample is close to the charge ratio of the cobalt source and the molybdenum source (see table 1), and an XRD spectrum shows that only 2H-MoS exists in the product 2 Indicating that the cobalt species are uniformly dispersed in the molybdenum disulfide or are present in an amorphous state (results are shown in table 1 and figure 1). TEM images show that the product isCo/MoS having an outer diameter of 0.7 to 2 μm and a wall thickness of 10 to 40nm 2 The hollow ball. The product size increased slightly due to the increased solvothermal reaction time.
Example 7:
2mmol of molybdenum isooctanoate, 1mmol of cobalt isooctanoate (Co/Mo ═ 0.5) and 10.4mmol of L-cysteine were weighed in this order into a 100mL beaker, and 50mL of ethanol was added to the beaker and stirred at 500rpm for 30 min. And transferring the obtained suspension into a 100mL high-pressure reaction kettle, preserving heat for 16 hours at 200 ℃, naturally cooling, performing suction filtration, washing the precipitate with deionized water and absolute ethyl alcohol, and then performing vacuum drying for 12 hours at 70 ℃ to obtain black powder. ICP data indicate resulting Co/MoS 2 The medium cobalt-molybdenum ratio is close to the charge ratio of the cobalt source and the molybdenum source (the result is shown in table 1). XRD spectrum shows that CoS appears in the product 2 Characteristic peak and MoS of 2 Characteristic peak of (A), indicating that there is a small amount of CoS at this time 2 Formed (results are shown in figure 1). TEM images show that the product is Co/MoS with the outer diameter of 0.3-0.9 mu m and the wall thickness of 5-20 nm 2 The hollow ball.
Comparative example 1:
2mmol of molybdenum isooctanoate, 0.2mmol of cobalt isooctanoate (Co/Mo ═ 0.1) and 8.8mmol of L-cysteine were weighed in succession into a 100mL beaker, and 50mL of deionized water was added to the beaker and stirred at 500rpm for 30 min. Transferring the obtained suspension into a 100mL high-pressure reaction kettle, preserving heat for 16 hours at 200 ℃, naturally cooling, performing suction filtration, washing the precipitate with deionized water and absolute ethyl alcohol, and then performing vacuum drying for 12 hours at 70 ℃ to obtain Co/MoS 2 Nanosheets, not Co/MoS 2 The result is shown in FIG. 4.
Comparative example 2:
2mmol of molybdenum isooctanoate and 8mmol of L-cysteine were weighed in turn into a 100mL beaker, and 50mL of ethanol was added into the beaker and stirred at 500rpm for 30 min. Transferring the obtained suspension into a 100mL high-pressure reaction kettle, preserving heat for 16 hours at 200 ℃, naturally cooling, performing suction filtration, washing the precipitate with deionized water and absolute ethyl alcohol, and then performing vacuum drying for 12 hours at 70 ℃ to obtain MoS 2 The result is shown in FIG. 5.
Example 8:
the products prepared by the methods of example 1, comparative example 1 and comparative example 2 are used as catalysts, and dibenzothiophene hydrogenation is used as a model compound to evaluate the catalytic hydrogenation performance of a suspension bed, and the method comprises the following steps: in a l00mL autoclave reactor of a suspended bed reaction system was charged 0.075g of Co/MoS prepared in example 1 2 Catalyst (2.5% by weight based on dibenzothiophene) and 3g of dibenzothiophene and 30g of decalin were added. After the autoclave is installed, air is replaced by nitrogen for 3 times, then nitrogen is replaced by hydrogen (the tail gas valve is closed, then the gas inlet valve is opened, the pressure of hydrogen at l00mL/min is increased to 2MPa, then the gas inlet valve is closed, then the tail gas valve is opened, and the nitrogen is exhausted), the pressure is increased to 8MPa, stirring is started, and the stirring speed is 300 r/min. Timing when the temperature rises to 350 ℃ at the speed of 10 ℃/min, and naturally cooling after keeping for 4 hours. The results of the catalytic hydrodesulfurization reaction of dibenzothiophenes are shown in Table 2.
The present invention is further described in detail below with reference to Table 2 and example 8. The catalytic hydrodesulfurization reaction result of the dibenzothiophene comprises product selectivity and dibenzothiophene conversion rate, and the main products of hydrodesulfurization are tetrahydrodibenzothiophene (THDBT), Biphenyl (BP), phenylcyclohexane (CHB), Bicyclohexane (BCH), Methylcyclopentane (MCP) and benzene (PhH) respectively. As is clear from the results in Table 2, the Co/MoS obtained in example 1 2 The conversion rate of dibenzothiophene on the hollow sphere and the selectivity of benzene of a deep hydrodesulfurization product are both higher than those of Co/MoS obtained in comparative example 1 2 Nanosheets and MoS obtained in comparative example 2 2 The hollow ball. Co/MoS obtained in example 1 2 The conversion rate of dibenzothiophene on the hollow sphere is 84.3 percent, and the conversion rate is Co/MoS 2 The conversion rate of dibenzothiophene on the nano-chip is 1.3 times of that of MoS 2 The conversion rate of dibenzothiophene on the hollow sphere is 2.5 times. Co/MoS obtained in example 1 of the invention 2 The selectivity of the deep hydrogenation product benzene on the hollow sphere is 26.6 percent, and the product is Co/MoS 2 The selectivity of benzene on the nano-chip is 3.0 times that of MoS 2 The selectivity of benzene on the hollow spheres is 2.6 times. The reaction evaluation result shows that the Co/MoS prepared by the invention 2 The hollow sphere has excellent catalytic performance.
TABLE 1 Co/Mo Charge ratios and ICP measured Co/Mo ratios for examples 1-7
Figure BDA0002972332110000081
TABLE 2 evaluation of the results of the reaction for hydrodesulfurization of dibenzothiophenes of example 8
Figure BDA0002972332110000082

Claims (13)

1. A preparation method of a cobalt-doped molybdenum disulfide hollow sphere is characterized by comprising the following steps:
step (1): adding an organic molybdenum source, an organic cobalt source and an organic sulfur source into a solvent according to a Co/Mo molar ratio of 0.03-1 and an S/(Mo + Co) molar ratio of 10: 1-2: 1, and fully mixing to obtain a solution or a suspension;
step (2): transferring the solution or the suspension into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, and placing the high-pressure reaction kettle in a drying oven for thermal reaction;
and (3): and cooling, separating a solid product, washing and drying to obtain the nano cobalt-doped molybdenum disulfide hollow sphere.
2. The method for preparing the cobalt-doped molybdenum disulfide hollow sphere according to claim 1, wherein the organic molybdenum source is at least one of molybdenum acetylacetonate, molybdenum isooctanoate and molybdenum naphthenate.
3. The method for preparing the cobalt-doped molybdenum disulfide hollow sphere according to claim 1, wherein the organic cobalt source is at least one of cobalt acetylacetonate and cobalt isooctanoate.
4. The method for preparing the cobalt-doped molybdenum disulfide hollow sphere according to claim 1, wherein the organic sulfur source is at least one of L-cysteine, glutathione and thiourea.
5. The method for preparing the cobalt-doped molybdenum disulfide hollow sphere according to claim 1, wherein in the step (1), the concentration of the organic molybdenum source in the solution or suspension is 0.05-0.30 mol/L.
6. The method for preparing the cobalt-doped molybdenum disulfide hollow sphere according to claim 5, wherein in the step (1), the concentration of the organic molybdenum source in the solution or suspension is 0.10-0.25 mol/L.
7. The preparation method of the cobalt-doped molybdenum disulfide hollow sphere according to claim 1, wherein in the step (1), the molar ratio of Co/Mo in the solution or suspension is 0.1-0.5; the molar ratio of S/(Mo + Co) is preferably 8:1 to 4: 1.
8. The preparation method of the cobalt-doped molybdenum disulfide hollow sphere according to claim 1, wherein the reaction temperature of the thermal reaction is 120-200 ℃ and the reaction time is 4-48 hours.
9. The preparation method of the cobalt-doped molybdenum disulfide hollow sphere according to claim 8, wherein the reaction temperature of the thermal reaction is 160-200 ℃ and the reaction time is 12-24 hours.
10. The method for preparing the cobalt-doped molybdenum disulfide hollow sphere according to claim 1, wherein the solvent is at least one of ethanol, methanol and glycol.
11. The method for preparing the cobalt-doped molybdenum disulfide hollow spheres as claimed in claim 1, wherein in the step (2), the filling degree of a kettle body in the high-pressure reaction kettle is 40-70%.
12. The method for preparing the cobalt-doped molybdenum disulfide hollow spheres as claimed in claim 11, wherein in the step (2), the filling degree of a kettle body in the high-pressure reaction kettle is 50-60%.
13. The preparation method of the cobalt-doped molybdenum disulfide hollow sphere according to claim 1, wherein in the step (3), the drying temperature is 60-80 ℃.
CN202110266780.4A 2021-03-11 2021-03-11 Preparation method of cobalt-doped molybdenum disulfide hollow sphere Pending CN115072782A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110266780.4A CN115072782A (en) 2021-03-11 2021-03-11 Preparation method of cobalt-doped molybdenum disulfide hollow sphere

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110266780.4A CN115072782A (en) 2021-03-11 2021-03-11 Preparation method of cobalt-doped molybdenum disulfide hollow sphere

Publications (1)

Publication Number Publication Date
CN115072782A true CN115072782A (en) 2022-09-20

Family

ID=83241010

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110266780.4A Pending CN115072782A (en) 2021-03-11 2021-03-11 Preparation method of cobalt-doped molybdenum disulfide hollow sphere

Country Status (1)

Country Link
CN (1) CN115072782A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103904305A (en) * 2012-12-28 2014-07-02 惠州比亚迪电池有限公司 Lithium ion battery negative pole active material and preparation method thereof, and lithium ion battery
US20170369792A1 (en) * 2016-06-23 2017-12-28 King Fahd University Of Petroleum And Minerals Process for selective deep hydrodesulfurization of a hydrocarbon feedstock using an unsupported nanocatalyst made by laser pyrolysis
CN108855145A (en) * 2018-06-21 2018-11-23 青岛大学 A kind of two-step method prepares cobalt sulfide/vulcanization molybdenum composite material and in hydrogen evolution reaction application
CN112939081A (en) * 2019-12-11 2021-06-11 中国科学院大连化学物理研究所 Preparation method of cobalt-doped molybdenum disulfide with yolk-eggshell structure

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103904305A (en) * 2012-12-28 2014-07-02 惠州比亚迪电池有限公司 Lithium ion battery negative pole active material and preparation method thereof, and lithium ion battery
US20170369792A1 (en) * 2016-06-23 2017-12-28 King Fahd University Of Petroleum And Minerals Process for selective deep hydrodesulfurization of a hydrocarbon feedstock using an unsupported nanocatalyst made by laser pyrolysis
CN108855145A (en) * 2018-06-21 2018-11-23 青岛大学 A kind of two-step method prepares cobalt sulfide/vulcanization molybdenum composite material and in hydrogen evolution reaction application
CN112939081A (en) * 2019-12-11 2021-06-11 中国科学院大连化学物理研究所 Preparation method of cobalt-doped molybdenum disulfide with yolk-eggshell structure

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
王敏;闵宇霖;张元广;陈友存;: "水热法制备二硫化钴空心微球", 化学世界, no. 10, pages 577 - 579 *
薛首峰;兰新哲;周军;宋永辉;张秋利;杨勇;任萍;: "不同形貌纳米二硫化钼制备研究进展", 兵器材料科学与工程, no. 03, pages 88 - 91 *

Similar Documents

Publication Publication Date Title
WO2017012210A1 (en) Metal oxide-carbon nitride composite material and preparation method and use thereof
CN113145155B (en) Nitrogen-doped carbon-coated nickel catalyst applied to assembly of bioethanol to synthesize high-carbon alcohol and preparation method thereof
CN109759064B (en) Co @ C/biomass catalyst and preparation method and application thereof
WO2017190553A1 (en) Transition metal nanoparticle catalyst with dual confinement structure and application thereof for catalysis in selective hydrogenation reaction of dimethyl terephthalate
CN110280281B (en) Preparation method of zinc ferrite/black phosphorus microsphere compound and application of zinc ferrite/black phosphorus microsphere compound in photocatalysis field
CN113151856B (en) Preparation of high-entropy alloy phosphide nanoparticle catalyst and application of high-entropy alloy phosphide nanoparticle catalyst in hydrogen production by water electrolysis
CN112844476A (en) Biomass-based carbon material loaded nano nickel catalyst and preparation method and application thereof
CN111229276B (en) Double-layer composite type water electrolysis anode catalyst and preparation method thereof
CN108636412B (en) Preparation method of multi-core-shell hollow catalyst nickel-nickel silicate for methane and carbon dioxide reforming
CN111233040A (en) Method for preparing nano molybdenum disulfide by solvothermal method, catalyst and application
CN110586112B (en) Hydrodeoxygenation solid acid catalyst Ni/CeO2-Al2O3
CN112939081B (en) Preparation method of cobalt-doped molybdenum disulfide with yolk-eggshell structure
CN114058446A (en) Preparation of ultrahigh-load two-dimensional nickel-iron catalyst and application of catalyst in preparation of second-generation biodiesel through grease hydrogenation
CN115072782A (en) Preparation method of cobalt-doped molybdenum disulfide hollow sphere
CN115228479B (en) Alkali metal modified NiSn material and preparation method and application thereof
CN114768859B (en) Nickel-silicon catalyst suitable for methane dry reforming and preparation method thereof
CN107442134B (en) Rhodium/nickel alloy nano catalyst and preparation method and application thereof
CN113441160B (en) Nickel hydroxide/titanium carbide photo-thermal catalytic material and preparation method and application thereof
WO2023015632A1 (en) Carbon dioxide hydrogenation-based methanol preparation catalyst, and preparation method therefor and use thereof
CN115518690A (en) Cu 7 S 4 -MOF composite material and preparation method and application thereof
CN112934243A (en) Spherical non-supported suspension bed hydrodesulfurization catalyst, preparation and application
CN112934244A (en) Non-supported suspension bed hydrodesulfurization catalyst, preparation and application
CN112705234B (en) Oxygen-doped carbon-based nickel carbide nanocomposite and preparation method and application thereof
CN114345346A (en) Method for preparing metal monatomic catalyst by hydrothermal method
CN114452990A (en) Method for preparing transition metal carbide and composite catalyst

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination