Nothing Special   »   [go: up one dir, main page]

CN112604708A - Molecular sieve based monatomic catalyst and preparation method thereof - Google Patents

Molecular sieve based monatomic catalyst and preparation method thereof Download PDF

Info

Publication number
CN112604708A
CN112604708A CN202110051663.6A CN202110051663A CN112604708A CN 112604708 A CN112604708 A CN 112604708A CN 202110051663 A CN202110051663 A CN 202110051663A CN 112604708 A CN112604708 A CN 112604708A
Authority
CN
China
Prior art keywords
molecular sieve
monatomic catalyst
protein
catalyst
metal
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.)
Granted
Application number
CN202110051663.6A
Other languages
Chinese (zh)
Other versions
CN112604708B (en
Inventor
张华新
张丽丽
王洪林
杨红梅
李立威
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.)
Jingchu University of Technology
Original Assignee
Jingchu University of Technology
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 Jingchu University of Technology filed Critical Jingchu University of Technology
Priority to CN202110051663.6A priority Critical patent/CN112604708B/en
Publication of CN112604708A publication Critical patent/CN112604708A/en
Application granted granted Critical
Publication of CN112604708B publication Critical patent/CN112604708B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/0325—Noble metals
    • 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
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • B01J29/24—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/86—Borosilicates; Aluminoborosilicates
    • 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
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C07D215/06—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a molecular sieve based monatomic catalyst and a preparation method thereof. The method comprises the steps of using a molecular sieve as a matrix, firstly assembling a layer of protein on the outer surface of the molecular sieve, complexing a small amount of metal ions by using the protein, filtering, washing, drying, and pyrolyzing in a non-oxidizing gas atmosphere to obtain the molecular sieve based monatomic catalyst fixed by the aza-carbon material. According to the invention, protein is used as a coordination agent and a diluent for the first time, metal ions are uniformly fixed on the outer surface of the molecular sieve, and the monatomic catalyst with highly exposed active sites is obtained through pyrolysis. The method does not need complex large-scale instruments and equipment, the preparation process is simple and easy to implement, the prepared monatomic catalyst has larger specific surface area and pore volume and good stability, and the metal active sites are fully exposed on the outer surface of the molecular sieve material, so that the monatomic catalyst is convenient to fully contact with a substrate, has higher catalytic efficiency and can be used as a catalyst for hydrogenation reaction of organic compounds.

Description

Molecular sieve based monatomic catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation of catalyst materials, and relates to a molecular sieve based monatomic catalyst and a preparation method thereof.
Background
Metals and their complexes are the most widely used heterogeneous catalysts in industrial processes. Since the low coordinated metal atoms generally act as catalytically active centers, the specific activity per metal atom generally increases as the size of the metal particle decreases. However, as the particle size decreases, the free energy of the metal surface increases significantly and agglomeration tends to occur. The use of suitable support materials that strongly interact with the metal species to prevent such agglomeration and form highly dispersed metal sites with high catalytic activity has long been a method employed by the industry. In recent years, a monatomic catalyst (SAC) in which a metal is dispersed at an atomic level has been produced in order to maximize the efficiency of metal atom utilization. The research on the spatial arrangement and electronic properties of single atoms and the interaction between the single atoms and a carrier is gradually and deeply carried out, and the optimization of the activity, selectivity and stability of the heterogeneous catalyst is possible by adjusting the active center through the single metal atom, and the heterogeneous catalyst has shown application prospects in various industrial chemical reactions, thereby receiving great attention of people.
At present, the methods for preparing monatomic catalysts are mainly Mass Selective Soft Landing (MSSL) method, Atomic Layer Deposition (ALD) method, vapor phase transport method, and wet chemical synthesis method. The first three of themThe method needs expensive special equipment and has low yield, so that large-scale production is difficult to realize. Wet chemical synthesis is the most focused technology currently studied, and mainly has defects of engineering strategies, space limitation strategies, coordination design strategies and the like, and the core idea of the technology is to control the aggregation of single atoms in precursors. Therefore, the choice of matrix material or support material is crucial. The matrix materials that have been reported so far include metals, metal oxides, carbon materials, MOFs, molecular sieves, and the like. Among them, molecular sieves are considered as one of the most desirable substrates for monatomic catalysts because of their own porous structure and excellent stability. However, at present, the reports of the single-atom catalyst taking the molecular sieve as the matrix are rare. For example, Diuranyl et al add palladium or rhodium complexes to the gel from which the ZSM-5 molecular sieve is prepared, crystallize, and then calcine in a fixed atmosphere of oxygen or hydrogen, etc., to form a monoatomic dispersion of the metal within the molecular sieve (CN 107983401B, CN 107890881B); sun et al rhodium-ethylenediamine complex ion [ Rh (en)3 3+]Encapsulated in silicalite-1 and ZSM-5 in H2After direct reduction of the precursors, they obtained monatomic catalysts in which Rh atoms are embedded in the 5-membered ring of the MFI topology and are stabilized by framework oxygen atoms (Q. Sun, et al, Angew. chem. int. Ed., 58 (2019) 18570-18576).
The methods limit the metal in the micropore pore canal of the molecular sieve, which is not favorable for the full contact of the substrate, especially the macromolecular substrate, and limits the catalytic efficiency to a certain extent.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method for preparing a monatomic catalyst with active sites distributed on the outer surface of a molecular sieve by using protein as an auxiliary reagent. The method overcomes the limitation that the prior molecular sieve based monatomic catalyst has an active center positioned in the micropore and insufficient accessibility, and improves the catalytic efficiency of the molecular sieve based monatomic catalyst.
The technical problem to be solved by the invention is realized by the following technical scheme.
A molecular sieve based monatomic catalyst is formed by coating metal atoms on the outer surface of a molecular sieve by a nitrogen-nitrogen carbon material.
Preferably, the metal atoms include any one or more of Co, Ni, Fe, Cu, Au, Ag, Ru, Rh, Pd, Os, Ir, Pt.
Preferably, the aza-carbon material is derived from protein pyrolysis.
Preferably, the molecular sieve includes known or newly synthesized or modified microporous molecular sieves, mesoporous molecular sieves, large pore molecular sieves, and hierarchical pore molecular sieves.
Preferably, the metal atoms are dispersed on the outer surface of the molecular sieve.
A preparation method of a molecular sieve based monatomic catalyst comprises the following steps:
s1, dispersing the molecular sieve material into water, and stirring at room temperature until a uniform mixed solution is formed;
s2, adding a protein solution into the mixed solution, and stirring at room temperature until the assembly reaches the balance;
s3, adding the metal ion solution into the mixed solution, stirring at room temperature until the solution is balanced, performing suction filtration, washing with deionized water, and freeze-drying;
and S4, putting the freeze-dried sample into a tubular furnace, and pyrolyzing the sample under the protection of non-oxidizing gas to obtain the molecular sieve based monatomic catalyst.
Preferably, the protein in the protein solution in step S2 is a combination of one or more natural or synthetic or modified proteins.
Preferably, the molar ratio of the protein in the protein solution to the metal in the metal ion solution is 1: 0.5-0.01.
Preferably, the metal ions in the metal ion solution in step S3 are soluble metal salts or metal complexes.
Preferably, the non-oxidizing gas in the step S4 is N2、He、Ar、H2Any one of them.
The invention has the beneficial effects that:
1. the method has the advantages of few synthesis steps, simple and convenient operation, no need of expensive large-scale equipment, contribution to large-scale production and wide application range.
2. The monatomic catalyst prepared by the method has a novel structure, and the nitrogen-doped carbon nano particles wrapped by metal atoms are anchored on a molecular sieve substrate; both the nitrogen heterocyclic carbon and the molecular sieve are typical porous materials, so that the diffusion mass transfer of a catalytic reaction system is facilitated.
3. The monatomic catalyst prepared by the method has the advantages that metal atoms are fully exposed on the outer surface of the molecular sieve, so that the monatomic catalyst is conveniently and fully contacted with a substrate, and the catalytic efficiency is favorably improved.
4. According to the monatomic catalyst prepared by the method, metal atoms are anchored on the surface of the molecular sieve through a carbon-nitrogen structure formed by pyrolysis of protein and an organic template agent in a pore channel, the stability is good, and the monatomic catalyst can be recycled.
Drawings
Fig. 1 is a TEM image of a cobalt single-atom catalyst supported on multi-stage pore molecular sieve microspheres prepared in example 1.
Fig. 2 is an XRD pattern of the cobalt-single-atom catalyst supported on the hierarchical pore molecular sieve microspheres prepared in example 1.
FIG. 3 is a spectrum of Co K-edge FT-EXAFS of the mesoporous molecular sieve microsphere-supported cobalt monatomic catalyst prepared in example 1.
Detailed Description
The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
< example 1>
A preparation method of a hierarchical pore molecular sieve microsphere supported cobalt monoatomic catalyst comprises the following steps:
s1, preparing uniform gel of water, piperidine, diboron trioxide, aluminum isopropoxide and silicon dioxide with the molar ratio of 40: 1.5: 0.67: 0.02: 1 in a 100 mL beaker, transferring the uniform gel into a stainless steel reaction kettle provided with 120 mL of polytetrafluoroethylene lining, placing the reaction kettle into a homogeneous reactor, turning over the reaction kettle at 130 ℃ for 12 hours at the rotating speed of 60 rpm, crystallizing the reaction kettle at 170 ℃ for 72 hours, quenching the uniform gel with water to room temperature, performing suction filtration, washing the uniform gel with deionized water to be neutral, and placing the uniform gel in an oven at 80 ℃ for drying overnight to obtain the porous molecular sieve microspheres;
s2, adding 1.2 g of molecular sieve microspheres and 50 mL of deionized water into a 100 mL flask, and stirring until a uniform mixed solution is formed;
s3, adding 10 mL of aqueous solution containing 0.6 g of bovine serum albumin into the mixed solution, and stirring at room temperature for 4 hours until the adsorption reaches the balance;
s4, adding an aqueous solution containing 0.2 g of cobalt acetate tetrahydrate into the mixed solution, continuously stirring at room temperature for 1 hour, carrying out suction filtration, washing with deionized water, and carrying out freeze drying to obtain a precursor;
s5, spreading 250 mg of the precursor at the bottom of the porcelain boat, putting the porcelain boat into a tube furnace, and putting the porcelain boat into the tube furnace in a N state2And carrying out pyrolysis for 2 hours at 600 ℃ under protection to obtain a target product.
The cobalt monoatomic catalyst loaded by the hierarchical pore molecular sieve microspheres prepared in the embodiment is used for the reaction of preparing aniline through selective hydrogenation of nitrobenzene. The reaction is carried out in a high-pressure reaction kettle, and the specific reaction conditions are as follows: 0.5 mmol of nitrobenzene, 70 mg of catalyst, 6 mL of H2O, 2 MPa H2The reaction product and the product are detected by gas chromatography by an internal standard method at 100 ℃ for 4 h, the nitrobenzene conversion rate reaches 99.3 percent, and the selectivity of the aniline is 100 percent. And after 8 times of catalyst circulation, 87.6 percent of initial activity can still be maintained.
The TEM photograph (fig. 1) shows that the catalyst presents the same spherical morphology as the molecular sieve matrix, and the nanoparticles generated by protein pyrolysis can be observed on the surface of the molecular sieve, and are relatively uniformly divided into the outer surface of the molecular sieve, and the metal atoms are wrapped in the outer surface. Meanwhile, the catalyst has an XRD diffraction peak (figure 2) completely consistent with the molecular sieve matrix, which shows that the catalyst completely retains the crystal structure of the molecular sieve. Further, the catalyst did not show characteristic diffraction peaks of the crystal planes of simple cobalt 111, 200, and 220 at 2 θ = 44.2 °, 51.5 °, and 44.2 °, indicating that there was almost no aggregation of Co atoms in the catalyst.
The EXAFS spectra show that the Co-Co bond signal is located near 2.2 a in cobalt foil paper, while the catalyst has almost no signal near 2.2 a (fig. 3), indicating that no Co-Co bonds are present in the catalyst prepared in this example and that metallic Co is in a monoatomic dispersion state. While its peak near 1.4 a demonstrates the interaction between Co atoms and light atoms such as N, explaining the stability of the catalyst.
< example 2>
A preparation method of a mesoporous molecular sieve nanorod supported palladium monatomic catalyst comprises the following steps:
s1, 1.05 g of cetyltrimethylammonium bromide (CTAB) and 262.5g of ultrapure water were added to a 500 mL two-necked flask at room temperature, and the mixture was dissolved sufficiently by sonication, followed by magnetic stirring at 400 rpm for 30 minutes. Adding 7.5 mL of 25% ammonia water, continuing stirring for 30 minutes, heating the water bath to 40 ℃, when the system is stable, dropwise adding 4.6 mL of Tetraethoxysilane (TEOS) under the condition of vigorous stirring, continuing stirring at the temperature for reaction for 5 hours, after the reaction is finished, performing suction filtration to collect the obtained sample, alternately washing the sample for three times respectively by water and absolute ethyl alcohol, and drying the sample overnight at 80 ℃ in a vacuum drying oven to obtain the mesoporous molecular sieve nanorod.
S2, adding 1.0 g of mesoporous molecular sieve nanorod and 50 mL of deionized water into a 100 mL flask, and stirring until a uniform mixed solution is formed;
s3, adding 10 mL of aqueous solution containing 0.4 g of bovine serum albumin into the mixed solution, and stirring at room temperature for 4 hours until the adsorption reaches the balance;
s4, adding an aqueous solution containing 0.1 g of palladium nitrate dihydrate into the mixed solution, continuously stirring for 1 hour at room temperature, performing suction filtration, washing with deionized water, and performing freeze drying to obtain a precursor;
s5, spreading 250 mg of the precursor at the bottom of the porcelain boat, putting the porcelain boat into a tube furnace, and putting the porcelain boat into the tube furnace in a N state2And carrying out pyrolysis for 2 hours at 600 ℃ under protection to obtain a target product.
The mesoporous molecular sieve nanorod supported palladium monatomic catalyst prepared in the embodiment is used for the reaction of preparing aniline through selective hydrogenation of nitrobenzene. The reaction is carried out in a high-pressure reaction kettle, and the specific reaction conditions are as follows: 0.5 mmol of nitrobenzene, 70 mg of catalyst, 6 mL of H2O, 2 MPa H2The reaction product and the product are detected by gas chromatography by an internal standard method at 100 ℃ for 4 h, the conversion rate reaches 99.8 percent, and the aniline selectivity reaches 100 percent. And after the catalyst is circulated for 6 times, the initial activity of the catalyst can still be maintained by more than 90 percent.
< example 3>
A preparation method of a commercial MOR molecular sieve loaded nickel monatomic catalyst comprises the following steps:
s1, to a 100 mL flask, add 1.0 g MOR molecular sieve (Si/Al = 6) and 50 mL deionized water, stir until a homogeneous mixture is formed;
s2, adding 10 mL of aqueous solution containing 0.2 g of bovine serum albumin into the mixed solution, and stirring at room temperature for 4 hours until the adsorption reaches the balance;
s3, adding an aqueous solution containing 0.05g of nickel nitrate hexahydrate into the mixed solution, continuously stirring for 1 hour at room temperature, carrying out suction filtration, washing with deionized water, and carrying out freeze drying to obtain a precursor;
s4, spreading 250 mg of the precursor at the bottom of the porcelain boat, putting the porcelain boat into a tube furnace, and putting the porcelain boat into the tube furnace in a N state2And carrying out pyrolysis for 2 hours at 600 ℃ under protection to obtain a target product.
The commercial MOR molecular sieve supported nickel monatomic catalyst prepared in the embodiment is used for the reaction of preparing 1,2,3, 4-tetrahydroquinoline by selectively hydrogenating quinoline. The reaction is carried out in a high-pressure reaction kettle, and the specific reaction conditions are as follows: 0.5 mmol of quinoline, 50 mg of catalyst, 5 mL of H2O, 3 MPa H2The reactants and the products are detected by gas chromatography by adopting an internal standard method, the conversion rate of quinoline reaches 100 percent, and the selectivity of 1,2,3, 4-tetrahydroquinoline is more than 99.9 percent. And after the catalyst is circulated for 10 times, the initial activity of the catalyst can still be maintained by more than 90 percent.
The above embodiments are merely illustrative of the technical solutions and features of the present invention, and the purpose thereof is to better enable those skilled in the art to practice the invention, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention are within the scope of the present invention, wherein the prior art is not described in detail.

Claims (10)

1. A molecular sieve based monatomic catalyst is characterized in that metal atoms are coated on the outer surface of a molecular sieve by a nitrogen heterocyclic carbon material to form the molecular sieve based monatomic catalyst.
2. The molecular sieve based monatomic catalyst of claim 1, wherein the metal atoms include any one or more of Co, Ni, Fe, Cu, Au, Ag, Ru, Rh, Pd, Os, Ir, Pt.
3. The molecular sieve based monatomic catalyst of claim 1, wherein the aza-carbon material is derived from protein pyrolysis.
4. The molecular sieve-based monatomic catalyst of claim 1, wherein the molecular sieve includes a microporous molecular sieve, a mesoporous molecular sieve, a macroporous molecular sieve, and a hierarchical molecular sieve.
5. The molecular sieve based monatomic catalyst of claim 1, wherein the metal atoms are dispersed on the outer surface of the molecular sieve.
6. A preparation method of a molecular sieve based monatomic catalyst is characterized by comprising the following steps:
s1, dispersing the molecular sieve material into water, and stirring at room temperature until a uniform mixed solution is formed;
s2, adding a protein solution into the mixed solution, and stirring at room temperature until the assembly reaches the balance;
s3, adding the metal ion solution into the mixed solution, stirring at room temperature until the solution is balanced, performing suction filtration, washing with deionized water, and freeze-drying;
and S4, putting the freeze-dried sample into a tubular furnace, and pyrolyzing the sample under the protection of non-oxidizing gas to obtain the molecular sieve based monatomic catalyst.
7. The method of claim 6, wherein the protein in the protein solution of step S2 is a combination of one or more natural or synthetic or modified proteins.
8. The method of claim 6, wherein the molar ratio of the protein in the protein solution to the metal in the metal ion solution is 1: 0.5-0.01.
9. The method according to claim 6, wherein the metal ions in the solution of metal ions in step S3 are soluble metal salts or metal complexes.
10. The method according to claim 6, wherein the non-oxidizing gas in the step S4 is N2、He、Ar、H2Any one of them.
CN202110051663.6A 2021-01-15 2021-01-15 Molecular sieve based monoatomic catalyst and preparation method thereof Active CN112604708B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110051663.6A CN112604708B (en) 2021-01-15 2021-01-15 Molecular sieve based monoatomic catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110051663.6A CN112604708B (en) 2021-01-15 2021-01-15 Molecular sieve based monoatomic catalyst and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112604708A true CN112604708A (en) 2021-04-06
CN112604708B CN112604708B (en) 2024-06-21

Family

ID=75254164

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110051663.6A Active CN112604708B (en) 2021-01-15 2021-01-15 Molecular sieve based monoatomic catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112604708B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114849756A (en) * 2022-05-23 2022-08-05 衢州学院 Catalyst for synthesizing vinyl trichlorosilane, preparation method, use method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3524574A1 (en) * 2018-02-13 2019-08-14 Gaznat SA, Société pour l'pprovisionnement et le transport du gaz naturel en Suisse Romande Fe-n-c catalyst, method of preparation and uses thereof
CN110201702A (en) * 2019-06-14 2019-09-06 北京大学深圳研究生院 Carbon carries the nitrogenous compound oxygen reduction catalyst preparation method of monoatomic metal and gained catalyst
CN110947408A (en) * 2019-11-28 2020-04-03 华南理工大学 Iron monatomic catalyst and preparation method and application thereof
CN111068682A (en) * 2019-12-27 2020-04-28 中国科学院青岛生物能源与过程研究所 Biomass-based carbon material loaded monoatomic copper catalyst and preparation method and application thereof
CN111620311A (en) * 2019-02-28 2020-09-04 中国科学院化学研究所 Porous carbon-loaded monoatomic metal nitrogen coordination composite material and preparation method thereof
CN111740123A (en) * 2020-07-07 2020-10-02 常州大学 Method for preparing high-load iron monatomic catalyst by taking waste animal blood as raw material

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3524574A1 (en) * 2018-02-13 2019-08-14 Gaznat SA, Société pour l'pprovisionnement et le transport du gaz naturel en Suisse Romande Fe-n-c catalyst, method of preparation and uses thereof
CN111620311A (en) * 2019-02-28 2020-09-04 中国科学院化学研究所 Porous carbon-loaded monoatomic metal nitrogen coordination composite material and preparation method thereof
CN110201702A (en) * 2019-06-14 2019-09-06 北京大学深圳研究生院 Carbon carries the nitrogenous compound oxygen reduction catalyst preparation method of monoatomic metal and gained catalyst
CN110947408A (en) * 2019-11-28 2020-04-03 华南理工大学 Iron monatomic catalyst and preparation method and application thereof
CN111068682A (en) * 2019-12-27 2020-04-28 中国科学院青岛生物能源与过程研究所 Biomass-based carbon material loaded monoatomic copper catalyst and preparation method and application thereof
CN111740123A (en) * 2020-07-07 2020-10-02 常州大学 Method for preparing high-load iron monatomic catalyst by taking waste animal blood as raw material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHIJUN LI ET.AL: "Highly Active and Stable Palladium Single-Atom Catalyst Achieved by a Thermal Atomization Strategy on an SBA-15 Molecular Sieve for Semi-Hydrogenation Reactions" *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114849756A (en) * 2022-05-23 2022-08-05 衢州学院 Catalyst for synthesizing vinyl trichlorosilane, preparation method, use method and application thereof

Also Published As

Publication number Publication date
CN112604708B (en) 2024-06-21

Similar Documents

Publication Publication Date Title
CN109305918B (en) Synthesis method of halogenated aniline
CN108097316B (en) Preparation method of MOFs nano material loaded with nano metal particles
CN110479353B (en) Catalyst and preparation method and application thereof
CN110756225B (en) Metal/MOFs nano catalyst and preparation method and application thereof
CN109908904A (en) A kind of monatomic catalyst of transition metal and its preparation method and application
CN112495416B (en) MOFs-derived three-dimensional hierarchical-pore Co/NC composite material and preparation method thereof
CN110404573A (en) A kind of preparation method and application of extra small palladium-base alloy material
CN113559916A (en) Molecular sieve encapsulated noble metal catalyst and preparation method and application thereof
CN110152654B (en) Ordered mesoporous carbon-TiO 2 Composite material supported palladium catalyst, preparation method and application thereof
CN113333016B (en) Nano-scale KL molecular sieve loaded metal catalyst, preparation method and application
CN109078642B (en) Flower-shaped nano-gold composite metal oxide catalyst and preparation method and application thereof
CN113289666A (en) Simple preparation method of Co/CM ceramic catalytic membrane
CN113457722B (en) Methane carbon dioxide dry reforming catalyst and preparation method and application thereof
CN112604708B (en) Molecular sieve based monoatomic catalyst and preparation method thereof
CN111068669B (en) Heterogeneous catalyst for selective hydrogenation reaction of quinoline compounds and application thereof
US10737250B2 (en) PdIn alloy catalyst, method for manufacturing PdIn alloy catalyst and application thereof
CN113083325A (en) Catalyst Ru for ammonia borane hydrolysis hydrogen production1-xCox/P25 and preparation method thereof
CN112316985B (en) Catalytic material for preparing methanol by carbon dioxide hydrogenation and preparation method thereof
CN114522708B (en) Preparation method of porous aza-carbon material supported cobalt-based catalyst and application of porous aza-carbon material supported cobalt-based catalyst in CO hydrogenation reaction for preparing high-carbon alcohol
CN108940368B (en) Zeolite-like framework encapsulated metal nanoparticle catalyst and preparation method and application thereof
CN117160463A (en) Preparation method and application of cerium oxide supported copper-based catalyst
CN115283007B (en) Preparation of platinum metal nanocluster HA molecular sieve and application thereof in synthesis of 1,2,3, 4-tetrahydroquinoline
CN114558578A (en) Novel nickel-carbon catalytic material with radial center and preparation method and application thereof
CN111905835B (en) Preparation method and application of efficient photo-thermal catalytic material
CN110560123B (en) Preparation method and application of metal-free non-porous catalyst material

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
GR01 Patent grant
GR01 Patent grant