CN114192130A - Preparation method of spiral transition metal nanotube catalyst - Google Patents

Preparation method of spiral transition metal nanotube catalyst Download PDF

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CN114192130A
CN114192130A CN202111442616.0A CN202111442616A CN114192130A CN 114192130 A CN114192130 A CN 114192130A CN 202111442616 A CN202111442616 A CN 202111442616A CN 114192130 A CN114192130 A CN 114192130A
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transition metal
spiral
helical
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nanotube catalyst
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CN114192130B (en
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郑浩铨
史濛柯
刘欣荣
曹睿
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Shaanxi Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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    • 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
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    • 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
    • B01J23/745—Iron
    • 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
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    • B01J23/75—Cobalt
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    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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Abstract

The invention discloses a preparation method of a spiral transition metal nanotube catalyst, which comprises the following steps of firstly dissolving amphiphilic molecules into a cosolvent system, and enabling the amphiphilic molecules to carry out self-assembly to form micelles or gels with spiral structures; then taking the self-assembly body with the spiral structure as a template, adding a transition metal source, and further assembling to obtain the transition metal with the spiral appearance; then using mesoporous SiO2And the catalyst is used as a nano film for coating, and is calcined and crystallized in the air atmosphere to prepare the spiral transition metal nanotube catalyst. Not only can maintain the original spiral distortion appearance, but also can promote the reactionThe contact area with the reactants during the process; meanwhile, irreversible agglomeration of the nano-spiral structure in the crystallization process is inhibited, the dispersibility is enhanced, the exposure of active sites of the prepared spiral nano-tube is increased, and the related performance of the catalyst is improved. The preparation method is simple, rapid, green and environment-friendly, and is suitable for industrial large-scale production.

Description

Preparation method of spiral transition metal nanotube catalyst
Technical Field
The invention belongs to the technical field of catalysts for photocatalytic decomposition of water to produce hydrogen, and particularly relates to a preparation method of a spiral transition metal nanotube catalyst, which is prepared from spiral TiO2For example, the catalyst shows excellent catalytic activity and good stability when used for photocatalytic decomposition of hydrogen produced by water under ultraviolet light and visible light.
Background
The spiral is ubiquitous in nature, ranging from universe outside the galaxy to hurricane, from vines of climbing plants to the outer skins of pineapples and pinecones, from patterns on nautilus shells to seed arrangement of sunflowers, and from cell structures of human bodies to flowers and fruits of cauliflower, and the beautiful shapes all have a common characteristic that the shapes all have a curve like the texture of the snail shells, and the curve is called spiral. Generally, helical materials can be prepared by assembly of nanoparticles or by inducing molecular polymerization from chiral molecules as templates. Since the material of the spiral structure generally has a large specific surface area and abundant surface grooves, it plays a very large role in energy storage and conversion. Therefore, it is of great significance to develop a new catalyst with a helical structure and apply it to related fields.
Compared with the traditional catalyst, the nanometer transition metal catalyst has the following advantages: (1) the main active sites of the catalyst are positioned on the surface, and the nano-scale material has a large specific surface area; more active sites are exposed, which is beneficial to improving the reaction activity. (2) When the nano catalyst is reduced to a certain degree, the small size effect and the quantum effect change the atom arrangement and the electron energy level distribution at the periphery of the crystal. (3) The preparation of the nano transition metal catalyst is easy to regulate and control the exposed crystal face and the surface atomic arrangement. (4) The nanometer transition metal catalyst is easy to load on other block or porous materials, and the strong interaction between the transition metal catalyst and the carrier is utilized to promote the catalytic activity. At present, the nano solid-phase catalyst generally exists in a highly symmetrical structural form, such as nanospheres, nanocubes, nanorods, nano regular polygons and the like.
When breaking the high symmetry to some extentThe catalyst has different reaction adsorption capacities in different areas, and the final catalytic activity of the catalytic reaction is influenced. The Janus structure catalyst is a representative catalyst, the catalyst has two surfaces with different properties, and the design of two different surfaces can realize the multi-functionalization of a single nano catalyst, so that certain series reactions are realized. The spiral structure is generally a structure having an asymmetric characteristic, which is assembled by connecting an asymmetric structure as a unit by a certain interaction force. The most important human life unit DNA has a spirally twisted structure. The asymmetry of the amino acids that make up the unit of a polypeptide in an organism plays an important role when it forms a helical secondary structure. Therefore, the transition metal catalyst with the spiral structure can further break the high symmetry of the nano catalyst, and the special structure can also affect the physicochemical properties of the internal structure and surface atoms of the transition metal catalyst. Thereby affecting the catalytic efficiency thereof. However, various helical metals and oxides thereof have been widely reported. For example, the superfine Au nanowire can be used for energy transmission by coaxially twisting to synthesize a spiral nano-rope; spiral wire-shaped carbon nanotube CNT/TiO has been developed2Energy devices for photoelectric conversion and electrochemical storage. However, a method for preparing a helical transition metal nanotube catalyst has not been reported so far. And the application of the chiral material with the spiral structure needs to be expanded in multiple fields, so that the further exploration of the chiral material with the spiral structure is necessary.
Disclosure of Invention
The invention aims to provide a preparation method of a spiral transition metal nanotube catalyst, which is used for coating a nano thin layer, so that nano particles are physically isolated to a great extent, and irreversible agglomeration is avoided. Meanwhile, the spiral transition metal nanotube catalyst is prepared through pyrolysis, and the spiral twisted appearance increases the specific surface area and the availability of catalytic active sites, so that the catalyst shows excellent activity and stability to meet the requirements of application and development in related fields.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. dissolving amphiphilic molecules in methanol or ethanol, adding deionized water, stirring for 10-20 minutes, adding a transition metal source, stirring for 20-40 minutes, heating to 40-60 ℃, continuing stirring for reaction for 2-4 hours, centrifuging, washing, and freeze-drying to obtain the spiral amphiphilic molecule/transition metal lipid fiber.
2. Dispersing spiral amphiphilic molecules/transition metal lipid fibers in methanol or ethanol, adding polyvinylpyrrolidone K30, stirring at room temperature for 8-12 hours, adding deionized water, ethyl tetrasilicate and ammonia water, stirring at room temperature for 4-6 hours, centrifuging, washing, and freeze-drying to obtain the coated SiO2The helical amphipathic molecule/transition metal lipid fiber of (a).
3. Coating SiO2The spiral amphiphilic molecule/transition metal lipid fiber is placed in a tubular furnace, heated to 600-900 ℃ in air atmosphere and kept for 2-8 hours to obtain the coated SiO2The helical transition metal of (1).
4. Coating SiO2SiO of the surface of the helical transition metal2Removing with strong alkali, and freeze drying to obtain the spiral transition metal nanotube catalyst.
In the step 1, the amphiphilic molecule is a connecting C12～C18The transition metal source is any one of titanium acetylacetonate, iron pentacarbonyl, zirconium oxychloride, copper acetylacetonate, cobalt acetylacetonate and the like; the amino acid is preferably any one of D-alanine, L-alanine, D-glutamic acid, L-glutamic acid, D-phenylalanine, L-phenylalanine, D-lysine and L-lysine.
In the step 1, the molar ratio of the amphiphilic molecules to the transition metal source is preferably 1: 5-60, the volume ratio of methanol or ethanol to deionized water is 1: 4-8, and the concentration of the amphiphilic molecules in the methanol or ethanol is preferably 3.8 × 10-3～6.5×10-3mol/L。
In the step 2, the mass ratio of the spiral amphiphilic molecules/transition metal lipid fibers to the polyvinylpyrrolidone K30 is preferably 1: 25-40, the mass-volume ratio of the spiral amphiphilic molecules/transition metal lipid fibers to the methanol or the ethanol is preferably 1mg: 3-4 mL, the volume ratio of the deionized water to the methanol or the ethanol is preferably 1: 6-7, and the volume ratio of the ammonia water to the ethyl tetrasilicate and the deionized water is preferably 1: 1.2-1.5: 150-200.
In the step 3, the heating is preferably carried out in an air atmosphere to 800-900 ℃ and the temperature is kept for 2-3 hours.
In the step 3, the heating rate is preferably 2 to 5 ℃/min.
In the above step 4, the SiO coating is applied2Adding the spiral transition metal into 2-4 mol/L NaOH aqueous solution, refluxing for 2-6 hours at 70-90 ℃, and removing SiO2。
The invention has the following beneficial effects:
the invention dissolves amphiphilic molecules in a cosolvent system, so that the amphiphilic molecules are self-assembled to form micelles or gels with a spiral structure; then taking the self-assembly body with the spiral structure as a template, adding a transition metal source, and further assembling to obtain the transition metal with the spiral appearance; then using mesoporous SiO2And coating as a nano film, and calcining at high temperature in an air atmosphere to crystallize. The method can maintain the original spiral distortion appearance and improve the contact area with reactants in the reaction process; meanwhile, irreversible agglomeration of the nano-spiral structure in the crystallization process is inhibited, the dispersibility is enhanced, the exposure of active sites of the prepared spiral nano-tube is increased, and the related performance of the catalyst is improved. The preparation method is simple, rapid, green and environment-friendly, and is suitable for industrial large-scale production.
Drawings
FIG. 1 is the TiO prepared in example 12@SiO2High power SEM spectra of (a).
FIG. 2 is the spiral TiO prepared in example 12High power SEM spectra of nanotube catalysts.
FIG. 3 is the spiral TiO prepared in example 12High power STEM pattern of nanotube catalyst.
FIG. 4 is the spiral TiO prepared in example 12Circular dichroism plots of nanotube catalysts.
FIG. 5 is the spiral TiO prepared in example 12Nanotube catalyst, spiral TiO prepared in comparative example 12And P25 as the photocatalytic hydrogen production result of the catalyst in the mixed solution of methanol and water with the volume ratio of 1:4 by illumination for 5 hours.
Detailed Description
The invention will be described in more detail below with reference to the following figures and specific examples, but the scope of the invention is not limited to these examples.
Example 1
1. 30mg (0.068mmol) of C18Adding L-glutamic acid (Angew. chem. int. Ed.2018,57, 13187-13191) into 17.2mL of methanol, stirring for 5 minutes to completely dissolve the L-glutamic acid, adding 80mL of deionized water, stirring for 15 minutes, slowly adding 292 mu L (0.812mmol) of isopropanol solution of titanium acetylacetonate with the mass concentration of 75%, stirring for 30 minutes, heating to 55 ℃, stirring for 2 hours, centrifugally washing with a mixed solution of methanol and water in a volume ratio of 1:4, and freeze-drying to obtain the helix C18-L-glutamic acid/TiO2A lipid fiber.
2. 50mg of helix C18-L-glutamic acid/TiO2Ultrasonically dispersing lipid fiber in 190mL of methanol, adding 1.6g of polyvinylpyrrolidone K30, stirring at room temperature for 10 hours, adding 30mL of deionized water, 200 mu L of ethyl tetrasilicate and 160 mu L of ammonia water, stirring at room temperature for 4 hours, centrifugally washing with methanol, and freeze-drying to obtain the coated SiO2Helix C of18-L-glutamic acid/TiO2A lipid fiber.
3. Coating SiO2Helix C of18-L-glutamic acid/TiO2Placing the lipid fiber in a tube furnace, heating to 900 deg.C at a heating rate of 5 deg.C/min in air atmosphere, and maintaining for 2 hr to obtain coated SiO2Of TiO 22Is denoted as TiO2@SiO2. As can be seen from FIG. 1, the TiO prepared2@SiO2Is a levorotatory nanotube structure.
4. Adding 30mg TiO2@SiO2Adding 10mL of 3mol/L NaOH aqueous solution, refluxing for 4 hours at 70 ℃, centrifugally washing by deionized water until the pH of the supernatant is approximately equal to 8, and freeze-drying to obtain the spiral TiO2A nanotube catalyst. The spiral nanotube structure is clearly seen in fig. 2 and 3, and the left-handed chiral signal of the nanotube can also be clearly seen in the circular dichroism spectrogram of fig. 4.
Example 2
In step 1 of this example, the isopropanol solution of titanium acetylacetonate in example 1 was replaced by an equal volume of isopropanol solution of cobalt acetylacetonate having the same molar amount as that of titanium acetylacetonate, and the other steps were the same as those of example 1 to obtain spiral Co3O4A nanotube catalyst.
Example 3
In step 1 of this example, the isopropanol solution of titanium acetylacetonate in example 1 was replaced with an equal volume of isopropanol solution of copper acetylacetonate having the same molar amount as that of titanium acetylacetonate, and the other steps were the same as in example 1, to obtain a spiral CuO nanotube catalyst.
Example 4
In step 1 of this example, the isopropanol solution of titanium acetylacetonate in example 1 was replaced with zirconium oxychloride in the same molar amount as that of titanium acetylacetonate, and the other steps were the same as in example 1, to obtain spiral ZrO2A nanotube catalyst.
Example 5
In step 1 of this example, the isopropanol solution of titanium acetylacetonate in example 1 was replaced with iron pentacarbonyl, the molar amount of iron pentacarbonyl was the same as that of titanium acetylacetonate, and the other steps were the same as in example 1, to obtain spiral Fe2O3A nanotube catalyst.
Comparative example 1
1. 30mg (0.068mmol) of C18Adding L-glutamic acid (Angew. chem. int. Ed.2018,57, 13187-13191) into 17.2mL of methanol, stirring for 5 minutes to completely dissolve the L-glutamic acid, adding 80mL of deionized water, stirring for 15 minutes, slowly adding 292 mu L (0.812mmol) of isopropanol solution of titanium acetylacetonate with the mass concentration of 75%, stirring for 30 minutes, heating to 55 ℃, stirring for 2 hours, centrifugally washing with a mixed solution of methanol and water in a volume ratio of 1:4, and freeze-drying to obtain the helix C18-L-glutamic acid/TiO2A lipid fiber.
2. Will spiral C18-L-glutamic acid/TiO2Placing the lipid fiber in a tube furnace, heating to 500 deg.C at a heating rate of 2 deg.C/min in air atmosphere, and maintaining for 2 hr to obtain spiral TiO2。
To demonstrate the beneficial effects of the present invention, the spiral TiO prepared in example 1 was used2Nanotube catalyst as catalyst for photocatalytic water splitting to produce hydrogen, simultaneously with commercial P25 and spiral TiO prepared in comparative example 12Comparative tests were carried out. The photocatalytic water splitting reaction was carried out on a Labsolar-III AG photocatalytic system (Beijing PerfectLight corporation) with a 300W xenon lamp (xenon light source PLS-SXE300/300 UV). 50mg of the catalyst was ultrasonically dispersed in 100mL of 20% by volume aqueous methanol and the resulting gas sample was analyzed by Gas Chromatography (GC) using SHIMADZU Company (GC-2014). To eliminate the thermal effect of the Xe lamp, a 278K cooling jacket surrounds the reactor during the reaction. The resulting gas was sent to a GC for argon analysis and the results are shown in FIG. 5. As can be seen from FIG. 5, after 5 hours of light irradiation, the spiral TiO prepared in example 1 was used2The hydrogen generated by the nanotube catalyst was 1772.98. mu. mol. g-1Spiral TiO prepared in comparison with comparative example 12(52.6μmol·g-1) The performance is improved by 33.71 times, compared with commercial P25(472.99 mu mol g)-1) The improvement is 3.75 times. Proving that the spiral TiO prepared by the method of the invention2The nanotube catalyst exhibits higher catalytic activity.

Claims (8)

1. A preparation method of a spiral transition metal nanotube catalyst is characterized by comprising the following steps:
(1) dissolving amphiphilic molecules in methanol or ethanol, adding deionized water, stirring for 10-20 minutes, adding a transition metal source, stirring for 20-40 minutes, heating to 40-60 ℃, continuing stirring for reaction for 2-4 hours, centrifuging, washing, and freeze-drying to obtain spiral amphiphilic molecule/transition metal lipid fibers;
the amphiphilic molecule is a connecting C12～C18Of carbon chainsThe transition metal source is any one of titanium acetylacetonate, iron pentacarbonyl, zirconium oxychloride, copper acetylacetonate and cobalt acetylacetonate;
(2) dispersing spiral amphiphilic molecules/transition metal lipid fibers in methanol or ethanol, adding polyvinylpyrrolidone K30, stirring at room temperature for 8-12 hours, adding deionized water, ethyl tetrasilicate and ammonia water, stirring at room temperature for 4-6 hours, centrifuging, washing, and freeze-drying to obtain the coated SiO2The helical amphipathic molecule/transition metal lipid fiber of (a);
(3) coating SiO2The spiral amphiphilic molecule/transition metal lipid fiber is placed in a tubular furnace, heated to 600-900 ℃ in air atmosphere and kept for 2-8 hours to obtain the coated SiO2The helical transition metal of (a);
(4) coating SiO2SiO of the surface of the helical transition metal2Removing with strong alkali, and freeze drying to obtain the spiral transition metal nanotube catalyst.
2. The method of preparing a helical transition metal nanotube catalyst of claim 1, wherein: in the step (1), the amino acid is any one selected from D-alanine, L-alanine, D-glutamic acid, L-glutamic acid, D-phenylalanine, L-phenylalanine, D-lysine and L-lysine.
3. The method of preparing a helical transition metal nanotube catalyst of claim 1, wherein: in the step (1), the molar ratio of the amphiphilic molecules to the transition metal source is 1: 5-60, the volume ratio of methanol or ethanol to deionized water is 1: 4-8, and the concentration of the amphiphilic molecules in the methanol or ethanol is 3.8 multiplied by 10-3～6.5×10-3mol/L。
4. The method of preparing a helical transition metal nanotube catalyst of claim 1, wherein: in the step (2), the mass ratio of the helical amphipathic molecules/transition metal lipid fibers to the polyvinylpyrrolidone K30 is 1: 25-40, and the mass-volume ratio of the helical amphipathic molecules/transition metal lipid fibers to the methanol or ethanol is 1mg: 3-4 mL.
5. The method of preparing a helical transition metal nanotube catalyst of claim 4, wherein: in the step (2), the volume ratio of the deionized water to the methanol or the ethanol is 1: 6-7, and the volume ratio of the ammonia water to the ethyl orthosilicate and the deionized water is 1: 1.2-1.5: 150-200.
6. The method of preparing a helical transition metal nanotube catalyst of claim 1, wherein: in the step (3), the mixture is heated to 800-900 ℃ in an air atmosphere and kept for 2-3 hours.
7. The method for preparing a helical transition metal nanotube catalyst according to claim 1 or 6, wherein: in the step (3), the heating rate is 2-5 ℃/min.
8. The method of preparing a helical transition metal nanotube catalyst of claim 1, wherein: in the step (4), the SiO coating is carried out2Adding the spiral transition metal into 2-4 mol/L NaOH aqueous solution, refluxing for 2-6 hours at 70-90 ℃, and removing SiO2。
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Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101923932A (en) * 2009-06-09 2010-12-22 南京大学 Multifunctional double-layer core-shell structure magnetic nano particle, preparation method and application thereof
WO2012074160A1 (en) * 2010-11-29 2012-06-07 Gwangju Institute Of Science And Technology Carbon nanofiber catalysts using nanofiber including low cost transition metal for fuel cells and manufacturing method thereof
CN103111296A (en) * 2013-03-12 2013-05-22 西北师范大学 Preparation of silk-like non-precious-metal nanotube oxygen reduction electrocatalyst
CN106046280A (en) * 2016-06-08 2016-10-26 长春理工大学 Inorganic and organic hybrid material as well as preparation method and application thereof
CN107262113A (en) * 2017-06-29 2017-10-20 济南大学 Core shell structure NiO/Au/Fe2O3The preparation of nano composite material
WO2017184085A1 (en) * 2016-04-21 2017-10-26 Agency For Science, Technology And Research Core-shell particles
CN107737593A (en) * 2017-11-10 2018-02-27 河北工业大学 A kind of TiO2The preparation method of nano tube supported bimetallic catalyst
CN108554411A (en) * 2018-05-10 2018-09-21 陕西师范大学 The composite carrier load nickel-base catalyst of carbon dioxide pressurized preparing synthetic gas by reforming methane
CN109569453A (en) * 2018-11-27 2019-04-05 浙江大学 A kind of preparation method of multipurpose tin, iron, zirconium doping silicon dioxide microballoon
CN112736259A (en) * 2020-12-28 2021-04-30 陕西师范大学 Method for preparing metal monoatomic electrocatalytic oxygen reduction catalyst through confined space
WO2021088310A1 (en) * 2019-11-05 2021-05-14 东莞行渡科技有限公司 Preparation method for aromatic amide fragment embedded hydrophilic and hydrophobic molecule self-assembled micelle, and preparation method for supramolecular photocatalytic assembly
CN113694961A (en) * 2021-09-26 2021-11-26 吉林化工学院 Nano hierarchical pore BEA structure molecular sieve catalyst and preparation method and application thereof

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101923932A (en) * 2009-06-09 2010-12-22 南京大学 Multifunctional double-layer core-shell structure magnetic nano particle, preparation method and application thereof
WO2012074160A1 (en) * 2010-11-29 2012-06-07 Gwangju Institute Of Science And Technology Carbon nanofiber catalysts using nanofiber including low cost transition metal for fuel cells and manufacturing method thereof
CN103111296A (en) * 2013-03-12 2013-05-22 西北师范大学 Preparation of silk-like non-precious-metal nanotube oxygen reduction electrocatalyst
WO2017184085A1 (en) * 2016-04-21 2017-10-26 Agency For Science, Technology And Research Core-shell particles
CN106046280A (en) * 2016-06-08 2016-10-26 长春理工大学 Inorganic and organic hybrid material as well as preparation method and application thereof
CN107262113A (en) * 2017-06-29 2017-10-20 济南大学 Core shell structure NiO/Au/Fe2O3The preparation of nano composite material
CN107737593A (en) * 2017-11-10 2018-02-27 河北工业大学 A kind of TiO2The preparation method of nano tube supported bimetallic catalyst
CN108554411A (en) * 2018-05-10 2018-09-21 陕西师范大学 The composite carrier load nickel-base catalyst of carbon dioxide pressurized preparing synthetic gas by reforming methane
CN109569453A (en) * 2018-11-27 2019-04-05 浙江大学 A kind of preparation method of multipurpose tin, iron, zirconium doping silicon dioxide microballoon
WO2021088310A1 (en) * 2019-11-05 2021-05-14 东莞行渡科技有限公司 Preparation method for aromatic amide fragment embedded hydrophilic and hydrophobic molecule self-assembled micelle, and preparation method for supramolecular photocatalytic assembly
CN112736259A (en) * 2020-12-28 2021-04-30 陕西师范大学 Method for preparing metal monoatomic electrocatalytic oxygen reduction catalyst through confined space
CN113694961A (en) * 2021-09-26 2021-11-26 吉林化工学院 Nano hierarchical pore BEA structure molecular sieve catalyst and preparation method and application thereof

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