CN112007645A - Preparation method of hollow microsphere structure catalyst - Google Patents

Preparation method of hollow microsphere structure catalyst Download PDF

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CN112007645A
CN112007645A CN202010840622.0A CN202010840622A CN112007645A CN 112007645 A CN112007645 A CN 112007645A CN 202010840622 A CN202010840622 A CN 202010840622A CN 112007645 A CN112007645 A CN 112007645A
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catalyst
hollow microsphere
transition metal
microsphere structure
preparing
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CN112007645B (en
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陈智栋
孙雷
刘长海
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Changzhou University
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • B01J35/33—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a preparation method of a hollow microsphere structure catalyst, and belongs to the field of electrocatalysis. The catalyst of the invention takes transition metal salt (nickel, iron, cobalt and the like) and polyhydric alcohol as raw materials, and controls the size and density of the surface defects of the nano hollow microsphere of the catalyst by simple hydrothermal synthesis and annealing process and by controlling the doping of molybdenum content. The microscopic appearance of the catalyst is hollow nanospheres, and the surface of the catalyst is a shell assembled by nanosheets. The structure promotes the exposure of active sites of the catalyst and improves the electrocatalytic activity of the catalyst. Compared with other synthesis methods, the method has the advantages that the price of the adopted reagent is low, the synthesis process is simple, and the electrochemical performance test shows that the obtained catalyst has good catalytic hydrogen evolution effect. The catalyst can be widely applied to the field of electrochemical hydrogen production, lays a technical foundation for large-scale preparation of hydrogen, and has important significance in solving the future energy crisis.

Description

Preparation method of hollow microsphere structure catalyst
Technical Field
The invention belongs to the field of electrocatalysis, and particularly relates to a preparation method of a hollow microsphere structure catalyst.
Background
With the increase of consumption of fossil fuels such as petroleum and coal, serious environmental pollution and energy exhaustion are caused. As a clean energy source, hydrogen (H)2) Is praised as the most promising energy source for the future replacement of fossil fuels. Among all hydrogen production processes, electrocatalytic cracking of water is considered a clean and effective strategy. Among them, platinum-based materials have high catalytic activity for electrocatalytic hydrogen evolution, however, platinum is expensive and is easily limited in large-scale application. Therefore, there is an urgent need to develop a non-noble metal electrocatalyst instead of platinum. In order to improve the catalytic performance of these non-noble metal electrocatalysts, various means have been developed, such as structural design, atomic doping and morphology control. The coarse microsphere material having a hollow structure may provide more contact area between the electrolyte and the electrode material and expose more active centers than a typical single shell structure, and at the same time, the hollow shell layer may facilitate electrolyte permeation and shorten the transfer path of ions and charges. Research finds that the overpotential can be effectively reduced by introducing a third non-noble metal element on the basis of the traditional binary transition metal in the hydrogen evolution reaction process, because the multi-transition metal has higher catalytic activity than single metal due to the synergistic action of multiple elements, however, the existing ternary non-noble metal is still different from a noble metal catalyst. Therefore, it is of great significance to research how to further improve the activity of such catalysts.
Disclosure of Invention
The invention aims to provide a preparation method of a hollow microsphere structure catalyst, which realizes the process through a solvothermal method and annealing calcination, wherein the catalyst with the hollow rough microsphere shape assembled by nanosheets is prepared by controlling the amount of molybdenum, and shows extremely high electrocatalytic hydrogen evolution activity and good stability under an alkaline condition.
In order to achieve the purpose, the invention adopts the following technical scheme that the preparation method of the hollow microsphere structure catalyst comprises the following steps:
dissolving transition metal salt and polyalcohol in a solvent, stirring to obtain a uniformly mixed solution, carrying out solvothermal reaction, repeatedly washing and drying after the reaction is finished to obtain transition metal alkoxide nanospheres, wherein the concentration of the transition metal salt in the solution is at most 5 mg/mL;
dispersing a molybdenum source and the transition metal alkoxide nanospheres obtained in the step (1) in an organic solvent to form a uniform solution, wherein the mass of the molybdenum source accounts for 5% -20% of that of the transition metal alkoxide nanospheres, then carrying out solvothermal reaction, after the reaction is finished, repeatedly cleaning with deionized water, and drying to obtain hollow coarse microspheres;
and (3) grinding the hollow coarse microspheres obtained in the step (2) into powder, annealing and calcining in a protective atmosphere, and naturally cooling to obtain the hollow microsphere structure catalyst.
Further, the transition metal salt in the step (1) is one or more of nitrate, chloride or acetate of nickel, iron and cobalt metals.
Further, the transition metal salt in the step (1) is any one or more of nickel nitrate, nickel chloride, nickel acetate, ferric nitrate, ferric chloride, ferric acetate, cobalt nitrate, cobalt chloride or cobalt acetate.
Further, the polyhydric alcohol in the step (1) is any one of glycerol, ethylene glycol or 1, 3-propylene glycol, and the solvent is any one of isopropanol, ethanol or n-propanol.
Further, the polyol in the step (1) is glycerol, and the solvent is isopropanol.
Transition metal ions are chelated with glycerol, atomic nuclei are rich in tissue, then the transition metal ions grow to form a uniform spherical precursor, namely, the transition metal alkoxide nanospheres, the concentration of transition metal salts is too low, the uniform spherical precursor is not easy to form, the reaction with the glycerol is influenced when the concentration is too high, the agglomeration is easy, the massive precursor is formed instead of the spherical precursor, and the concentration of the transition metal salts in the step (1) is preferably 1-5 mg/mL.
Further, the hydrothermal reaction temperature in the step (1) is 100-200 ℃, and the reaction time is 5-15 hours.
Further, the molybdenum source in the step (2) is any one of phosphomolybdic acid, ammonium molybdate or sodium molybdate.
Further, the solvothermal reaction temperature in the step (2) is 100-200 ℃, and the reaction time is 5-10 hours.
Further, the annealing and calcining temperature in the step (3) is 200-500 ℃, and calcining is carried out
The burning time is 0.5-3 hours, and the annealing temperature rate is 5-10 ℃/min.
Compared with the prior art, the invention has the advantages that:
(1) the size and density of the defects on the surface of the catalyst are controlled by controlling the content of molybdenum, so that the preparation method is favorable for forming a rough microspherical structure and improving the degree of the defects on the surface of the catalyst.
(2) The method has low hydrogen evolution overpotential under the condition of alkaline aqueous solution, and obtains good chemical stability and catalytic durability.
(3) The method has low cost, is simple and feasible, and can realize large-scale industrial application.
The advantages show that the catalyst for water electrolysis and hydrogen evolution in the hierarchical hollow microsphere structure has important significance for improving the electrocatalytic performance of the water electrolysis catalyst.
Drawings
FIG. 1 is a scanning electron microscope image of cobalt nickel metal alkoxide nanospheres prepared in example 1.
FIG. 2 is a scanning electron microscope image of CoFeAlcoholic acid salt nanospheres prepared in example 2.
FIG. 3 is a scanning electron microscope image of the structure of the cobalt-nickel-molybdenum hollow microsphere in example 3.
FIG. 4 is a scanning electron microscope image of the structure of the hollow cobalt-nickel-molybdenum microspheres in example 4.
FIG. 5 is a scanning electron microscope image of the structure of the cobalt-nickel-molybdenum hollow microsphere in example 5.
FIG. 6 is a graph showing the hydrogen evolution performance of the hollow microsphere catalyst prepared in each example.
FIG. 7 is a graph showing the hydrogen evolution performance of the hollow microsphere catalyst prepared in example 3 and comparative example 1.
Detailed Description
The technical features and characteristics of the present invention are described in detail below with reference to specific embodiments, but the embodiments are not intended to limit the scope of the present invention.
Example 1:
the preparation method of the cobalt-nickel metal alkoxide nanosphere comprises the following steps:
step (1), preparing a transition metal precursor nano glycerate by adopting a solvothermal method, namely taking a clean beaker, putting cobalt nitrate, nickel nitrate, 12mL of glycerol and 50mL of isopropanol into a 100mL reaction kettle, heating to 180 ℃, preserving heat for 10 hours, washing with ethanol for three times after the reaction is finished, and drying in vacuum at 60 ℃ to obtain smooth nickel-cobalt glycerate nanospheres, namely a CoNi catalyst.
Example 2
The preparation method of the cobalt-iron metal alkoxide nanosphere comprises the following steps:
step (1), preparing transition metal precursor nano glycerate by adopting a solvothermal method, namely taking a clean beaker, putting cobalt nitrate, ferric nitrate, 12mL of glycerol and 50mL of isopropanol into a 100mL reaction kettle, heating to 180 ℃, preserving heat for 10 hours, washing with ethanol for three times after the reaction is finished, and drying in vacuum at 60 ℃ to obtain smooth cobalt-iron glycerate nanospheres, namely a CoFe catalyst.
Example 3
The preparation method of the cobalt-nickel-molybdenum hollow microsphere structure catalyst comprises the following steps:
step (1), which is the same as step (1) in example 1;
and (2) treating glycerate by adopting a solvothermal method to prepare hollow coarse microspheres, adding phosphomolybdic acid into the glycerate nickel-cobalt nanospheres (phosphomolybdic acid accounts for 5% of the mass of the glycerate nickel-cobalt nanospheres) obtained in the step (1), uniformly dissolving the phosphomolybdic acid and the glycerate nickel-cobalt nanospheres in 60mL of ethanol, pouring the mixture into a reaction kettle, heating to 160 ℃, preserving heat for 8 hours, washing with ethanol for three times after the reaction is finished, and performing vacuum drying at 60 ℃ to obtain the hollow coarse microspheres.
And (3) annealing and calcining, grinding the hollow coarse microspheres obtained in the step (2) into powder, then preserving the heat for 2 hours at 350 ℃ under the protective atmosphere of nitrogen, and then naturally cooling to obtain the cobalt-nickel-molybdenum hollow microsphere structure catalyst, namely the 5% Mo-CoNi catalyst.
Example 4:
the preparation method of the cobalt-nickel-molybdenum hollow microsphere structure catalyst comprises the following steps:
step (1), which is the same as step (1) in example 1;
and (2) treating glycerate by adopting a solvothermal method to prepare hollow coarse microspheres, adding phosphomolybdic acid into the glycerate nickel-cobalt nanospheres (phosphomolybdic acid accounts for 10% of the mass of the glycerate nickel-cobalt nanospheres) obtained in the step (1), uniformly dissolving the phosphomolybdic acid and the glycerate nickel-cobalt nanospheres in 60mL of ethanol, pouring the mixture into a reaction kettle, heating to 160 ℃, preserving heat for 8 hours, washing with ethanol for three times after the reaction is finished, and performing vacuum drying at 60 ℃ to obtain the hollow coarse microspheres.
And (3) annealing and calcining, grinding the hollow coarse microspheres obtained in the step (2) into powder, preserving the heat of the powder at 350 ℃ for 2 hours under the protective atmosphere of nitrogen, and naturally cooling to obtain the cobalt-nickel-molybdenum hollow microsphere structure catalyst, namely the 10% Mo-CoNi catalyst.
Example 5:
the preparation method of the cobalt-nickel-molybdenum hollow microsphere structure catalyst comprises the following steps:
step (1), which is the same as step (1) in example 1;
and (2) treating glycerate by adopting a solvothermal method to prepare hollow coarse microspheres, adding phosphomolybdic acid into the glycerate nickel-cobalt nanospheres (phosphomolybdic acid accounts for 15% of the mass of the glycerate nickel-cobalt nanospheres) obtained in the step (1), uniformly dissolving the phosphomolybdic acid and the glycerate nickel-cobalt nanospheres in 60mL of ethanol, pouring the mixture into a reaction kettle, heating to 160 ℃, preserving heat for 8 hours, washing with ethanol for three times after the reaction is finished, and performing vacuum drying at 60 ℃ to obtain the hollow coarse microspheres.
And (3) annealing and calcining, grinding the hollow coarse microspheres obtained in the step (2) into powder, preserving the heat of the powder at 350 ℃ for 2 hours under the protective atmosphere of nitrogen, and naturally cooling to obtain the cobalt-nickel-molybdenum hollow microsphere structure catalyst, namely the 15% Mo-CoNi catalyst.
Comparative example 1
The same procedure as in example 3 was repeated, except that the solvent isopropanol in step (1) was replaced with ethanol, and the procedure was otherwise the same as in example 3.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.

Claims (10)

1. A preparation method of a hollow microsphere structure catalyst is characterized by comprising the following steps: the method comprises the following steps:
dissolving transition metal salt and polyalcohol in a solvent, stirring to obtain a uniformly mixed solution, carrying out solvothermal reaction, repeatedly washing and drying after the reaction is finished to obtain transition metal alkoxide nanospheres, wherein the concentration of the transition metal salt in the solution is at most 5 mg/mL;
dispersing a molybdenum source and the transition metal alkoxide nanospheres obtained in the step (1) in an organic solvent to form a uniform solution, wherein the mass of the molybdenum source accounts for 5% -20% of that of the transition metal alkoxide nanospheres, then carrying out solvothermal reaction, after the reaction is finished, repeatedly cleaning with deionized water, and drying to obtain hollow coarse microspheres;
and (3) grinding the hollow coarse microspheres obtained in the step (2) into powder, annealing and calcining in a protective atmosphere, and naturally cooling to obtain the hollow microsphere structure catalyst.
2. The method for preparing a catalyst having a hollow microsphere structure according to claim 1, wherein: the transition metal salt in the step (1) is one or more of nitrate, chloride or acetate of nickel, iron and cobalt metals.
3. The method for preparing a catalyst having a hollow microsphere structure according to claim 1, wherein: the transition metal salt in the step (1) is any one or more of nickel nitrate, nickel chloride, nickel acetate, ferric nitrate, ferric chloride, ferric acetate, cobalt nitrate, cobalt chloride or cobalt acetate.
4. The method for preparing a catalyst having a hollow microsphere structure according to claim 1, wherein: the polyhydric alcohol in the step (1) is any one of glycerol, ethylene glycol or 1, 3-propylene glycol, and the solvent is any one of isopropanol, ethanol or n-propanol.
5. The method for preparing a catalyst having a hollow microsphere structure according to claim 1, wherein: the polyalcohol in the step (1) is glycerol, and the solvent is isopropanol.
6. The method for preparing a catalyst having a hollow microsphere structure according to claim 1, wherein: the concentration of the transition metal salt in the step (1) is 1-5 mg/mL.
7. The method for preparing a catalyst having a hollow microsphere structure according to claim 1, wherein: the hydrothermal reaction temperature in the step (1) is 100-200 ℃, and the reaction time is 5-15 hours.
8. The method for preparing a catalyst having a hollow microsphere structure according to claim 1, wherein: the molybdenum source in the step (2) is any one of phosphomolybdic acid, ammonium molybdate or sodium molybdate.
9. The method for preparing a catalyst having a hollow microsphere structure according to claim 1, wherein: the solvothermal reaction temperature in the step (2) is 100-200 ℃, and the reaction time is 5-10 hours.
10. The method for preparing a catalyst having a hollow microsphere structure according to claim 1, wherein: the annealing and calcining temperature in the step (3) is 200-500 ℃, the calcining time is 0.5-3 hours, and the annealing temperature rate is 5-10 ℃/min.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN113070065A (en) * 2021-04-02 2021-07-06 中国科学院合肥物质科学研究院 Hollow amorphous cobalt carbide Fenton catalyst and preparation method and application thereof
CN115055196A (en) * 2022-07-04 2022-09-16 中国科学院过程工程研究所 Heteropolyacid salt catalyst and preparation method and application thereof
CN116334689A (en) * 2023-03-24 2023-06-27 安徽大学 PVP modified NiMoS electrocatalyst and preparation method thereof

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CN108239774A (en) * 2016-12-23 2018-07-03 北京有色金属研究总院 A kind of Ni-based hydrogen evolution electrode material and preparation method thereof
CN108315762A (en) * 2018-02-08 2018-07-24 华南师范大学 The synthetic method of the Ni-Mo-Co liberation of hydrogen catalyst of high activity under a kind of acidic environment
CN108364792A (en) * 2018-01-24 2018-08-03 复旦大学 A kind of preparation method and applications of nickel cobalt selenium hollow ball-shape multilevel structure material

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CN102127776A (en) * 2010-01-15 2011-07-20 北京有色金属研究总院 Amorphous plating layer with high hydrogen evolution catalytic activity and preparation method thereof
CN103771544A (en) * 2014-02-22 2014-05-07 吉林大学 Preparation method of hollow cobaltosic oxide microsphere
CN108239774A (en) * 2016-12-23 2018-07-03 北京有色金属研究总院 A kind of Ni-based hydrogen evolution electrode material and preparation method thereof
CN108364792A (en) * 2018-01-24 2018-08-03 复旦大学 A kind of preparation method and applications of nickel cobalt selenium hollow ball-shape multilevel structure material
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113070065A (en) * 2021-04-02 2021-07-06 中国科学院合肥物质科学研究院 Hollow amorphous cobalt carbide Fenton catalyst and preparation method and application thereof
CN115055196A (en) * 2022-07-04 2022-09-16 中国科学院过程工程研究所 Heteropolyacid salt catalyst and preparation method and application thereof
CN115055196B (en) * 2022-07-04 2023-10-03 中国科学院过程工程研究所 Heteropoly acid salt catalyst and preparation method and application thereof
CN116334689A (en) * 2023-03-24 2023-06-27 安徽大学 PVP modified NiMoS electrocatalyst and preparation method thereof
CN116334689B (en) * 2023-03-24 2024-02-23 安徽大学 PVP modified NiMoS electrocatalyst and preparation method thereof

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