CN113388645A - Batch synthesis of basic carbonate and metal oxide nano-tube by urea enzymolysis method - Google Patents

Batch synthesis of basic carbonate and metal oxide nano-tube by urea enzymolysis method Download PDF

Info

Publication number
CN113388645A
CN113388645A CN202110696928.8A CN202110696928A CN113388645A CN 113388645 A CN113388645 A CN 113388645A CN 202110696928 A CN202110696928 A CN 202110696928A CN 113388645 A CN113388645 A CN 113388645A
Authority
CN
China
Prior art keywords
nanotube
nanotubes
synthesizing
urea
size distribution
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
CN202110696928.8A
Other languages
Chinese (zh)
Other versions
CN113388645B (en
Inventor
王荷芳
王婷
王正午
朱义州
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.)
Nankai University
Original Assignee
Nankai University
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 Nankai University filed Critical Nankai University
Priority to CN202110696928.8A priority Critical patent/CN113388645B/en
Publication of CN113388645A publication Critical patent/CN113388645A/en
Application granted granted Critical
Publication of CN113388645B publication Critical patent/CN113388645B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • 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
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • 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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

Simple and template-free method for synthesizing basic carbonate nanotubes and corresponding metal oxide nanotubes by urea enzymolysisThe method of (1). The method is characterized in that: synthesizing the basic carbonate nanotube under mild conditions, and calcining to obtain various biological metal oxide nanotubes. The method comprises the following steps: 1) the metal hydrochloride or nitrate, urea and enzyme are mixed evenly according to a certain proportion, the feeding ratio and the feeding speed are adjusted, and the reaction is carried out under mild conditions to obtain the basic carbonate nanotube. 2)500-1000 oAnd C, calcining the basic carbonate to obtain the corresponding metal oxide nanotube. The invention has the advantages and effects that: the NH with uniform appearance can be obtained by controlling the reaction time and the concentration of the urea4Ga(OH)2CO3Nanotube, NH4Al(OH)2CO3Nanotube, gallium oxide nanotube, aluminum oxide nanotube and corresponding composite nanotube. The method is simple, easy to operate, high in yield, uniform in product appearance and large in specific surface area, and is suitable for large-scale application in the aspects of serving as a catalyst, a catalyst carrier, an adsorption material and the like.

Description

Batch synthesis of basic carbonate and metal oxide nano-tube by urea enzymolysis method
Technical Field
The invention relates to a synthesis technology of a double-metal basic carbonate nanotube of Ga, Al basic carbonate, Ga-Al, Ga-Mn, Al-Mn and Al-Ti and a synthesis method of an oxide nanotube after calcination.
Background
In recent years, one-dimensional nano materials, especially nanotube materials, have attracted great attention due to their advantages of excellent photoelectric properties, large specific surface area, high light utilization rate, and the like, but most nanotube synthesis methods require high-temperature processes or templating agent molecules, and have the problems of time consumption, energy consumption, low yield, and the like. The types of nanotubes that have been reported are also relatively limited, which limits the broad application of nanotubes. Therefore, the synthesis of nanotube materials by a mild and convenient method is still a hot spot of current research.
The metal basic carbonate and the metal oxide have wide application prospect in the field of catalysis, and the construction of a heterojunction and a composite catalyst is concerned. Alumina is an excellent catalyst carrier due to small biological toxicity, large specific surface area and good stability, but most of the currently reported synthesis steps of many alumina carriers are complicated, multi-step synthesis is needed, the morphology is difficult to control, and the alumina exists in a form that a catalyst is attached to the carrier, so that the alumina is not favorable for full dispersion of the catalyst. Gallium oxide is a semiconductor with stable crystal structure, strong chemical stability and thermal stability, and has excellent photocatalytic activity. The heterojunction can be constructed according to the energy band structure of gallium oxide, so that the light absorption capacity and the catalytic activity are enhanced, but the construction of the heterojunction requires sufficient contact between two phases to realize the transfer of carriers, and a general construction method needs multi-step functionalization and is difficult to fully contact. Therefore, the method has great significance for synthesizing the composite catalyst and the heterojunction nanotube with controllable shapes and uniform dispersion of the aluminum oxide and the gallium oxide in one step.
Disclosure of Invention
The invention provides a mild template-free method for synthesizing metal basic carbonate nanotubes by urea enzymolysis, and calcined products, namely various metal oxides, of the method can still keep the nanotube morphology with a large specific surface area.
The method comprises the following steps:
1) the metal hydrochloride or nitrate, urea, enzyme and the like are uniformly mixed according to a certain proportion, the feeding ratio and the feeding speed are adjusted, and the hydrothermal reaction is carried out under mild conditions to obtain the metal salt nanotube.
2）500-1000 oAnd C, calcining the metal alkali carbonate nanotube to obtain the corresponding metal oxide nanotube.
The invention has the advantages and effects that: by controlling the reaction time and the concentration of urea, the basic gallium carbonate (aluminum) nanotube, gallium oxide and aluminum oxide nanotube with uniform appearance can be obtained. The method can be used for constructing composite catalyst, such as Al catalyst, and can also be used for preparing bimetallic oxide nanotubes after calcination2O3-Mn2O3，Al2O3-Ga2O3，Ga2O3-Mn2O3Nanotube composite structures, and the like.
Description of the drawings:
FIG. 1 shows NH synthesized according to the present invention4Ga(OH)2CO3Transmission electron micrograph of nanotubes showing: the synthetic material is a nanotube.
FIG. 2 is a transmission electron microscope image of a calcined synthesized gallium oxide nanotube.
FIG. 3 is a transmission electron microscope image of the synthesized alumina nanotubes after calcination.
FIG. 4 NH synthesized according to the invention4Ga(OH)2CO3-NH4Al(OH)2CO3Scanning electron microscopy of nanotubes.
[ embodiments ] of the present invention:
example 1
Synthesis of NH4Ga(OH)2CO3Method for making nanotubes. It is characterized in that NH with uniform appearance is conveniently synthesized by a simple and mild method4Ga(OH)2CO3A nanotube. The method comprises the following steps:
1) dissolving gallium salt in water, adding 0.5-2.5 g urea under stirring, and stirring for 30 min.
2) Adjusting pH of the above solution to 7-8 with ammonia water, adding urease, stirring for 30 min, placing into a polytetrafluoroethylene lined reaction kettle, and adding into a reactor with 37 deg.C oC, reacting for 24 hours in an oven.
3) The precipitate obtained from the reaction was collected by centrifugation, washed with water until the supernatant was neutral, and dried under vacuum.
Example 2
Synthetic chromium-doped NH4Ga(OH)2CO3A method of nanotubes. The method is characterized in that the method is simple and mild, and chromium-doped NH with uniform appearance can be conveniently synthesized4Ga(OH)2CO3And (4) nanorods. The steps and the method are basically the same as the embodiment 1, except that the chromium nitrate solution with the corresponding proportion is added in the step 1, and NH with different chromium doping amount can be obtained4Ga(OH)2CO3A nanotube.
Example 3
A method for synthesizing gallium oxide nanotubes with different crystal forms. It is characterized in that the gallium oxide nano-tube with larger specific surface area is obtained. The method comprises the following steps: reacting the obtained NH4Ga(OH)2CO3The nanotube passes through 500-1000- oCalcining C for a certain time to obtain alpha-Ga2O3Nanotubes and beta-Ga2O3A nanotube.
Example 4
A method for synthesizing chromium-doped gallium oxide nanotubes with different crystal forms. The method is characterized in that the chromium-doped gallium oxide nanotube with larger specific surface area is obtained. Precursor of the material is doped with NH4Ga(OH)2CO3The synthesis of nanotubes was performed as in example 2 and the calcination procedure was as in example 3.
Example 5
Synthesis of NH4Al(OH)2CO3A method of nanotubes. It is characterized by using the letterSimple and mild method for conveniently synthesizing NH with uniform appearance4Al(OH)2CO3A nanotube. The procedure and method were substantially the same as in example 1 except that the Ga salt added in step 1 was replaced with an Al salt.
Example 6
A method for synthesizing an alumina nanotube. It is characterized in that the alumina nano-tube with larger specific surface area is obtained. The method comprises the following steps: NH obtained by the reaction in example 54Al(OH)2CO3The nanotube passes through 500-1000 oCalcining C for a period of time to obtain Al2O3A nanotube.
Example 7
Synthesis of NH4Ga(OH)2CO3-NH4Al(OH)2CO3A method of nanotubes. It is characterized in that NH with uniform appearance is conveniently synthesized by a simple and mild method4Ga(OH)2CO3-NH4Al(OH)2CO3A nanotube. The method comprises the following steps:
1) preparing a solution A: dissolving gallium salt in water, adding 0.5-2.5 g of urea while stirring, adjusting the pH of the system to 7-8 by using ammonia water, and adding urease.
2) Preparing a solution B: dissolving aluminum salt in water, and adding 0.5-2.5 g of urea while stirring.
3) And (3) filling the solution B into a separating funnel, slowly dripping the solution B into the solution A at a constant speed, keeping stirring the solution A during the dripping process for about 40 min, and keeping stirring for 30 min after the dripping is finished.
4) Putting the mixed solution into a polytetrafluoroethylene lined reaction kettle, and putting the polytetrafluoroethylene lined reaction kettle into a reactor with 37 percent of the mixed solution oC, reacting for 24 hours in an oven.
5) The precipitate obtained from the reaction was collected by centrifugation, washed with water until the supernatant was neutral, and dried under vacuum.
Example 8
Synthesis of NH4Al(OH)2CO3-TiO2A method of nanotubes. It is characterized in that NH with uniform appearance is conveniently synthesized by a simple and mild method4Al(OH)2CO3-TiO2A nanotube. Step by stepThe method comprises the following steps:
1) dissolving Al salt in water, adding 0.5-2.5 g urea under stirring, adjusting system pH to 7-8 with ammonia water, adding urease, and stirring for 30 min.
2) Preparing 10% v/v ethanol solution of tetrabutyl titanate, and slowly dripping the ethanol solution into the solution (1).
3) Stirring for 30 min, placing into a reaction kettle with polytetrafluoroethylene lining, and adding into a reactor with a polytetrafluoroethylene lining oC, reacting for 24 hours in an oven.
4) The precipitate obtained from the reaction was collected by centrifugation, washed with water until the supernatant was neutral, and dried under vacuum.
Example 9
Synthetic Al2O3-Mn2O3A method of nanotubes. It is characterized by that it uses simple method to conveniently synthesize Al whose morphology is uniform and Al and Mn are uniformly dispersed2O3-Mn2O3A nanotube. The procedure and method were substantially the same as in example 8 except that 10% of tetrabutyl titanate was used in place of the Mn salt in step 2 and a calcination process was added.
Example 10
Synthesis of Ga2O3-Mn2O3A method of nanotubes. It is characterized by that it uses simple method to conveniently synthesize Ga with uniform appearance2O3-Mn2O3A nanotube. The procedure and method were substantially the same as in example 9, except that the aluminum salt was replaced with a gallium salt.

Claims (7)

1. A method for synthesizing basic gallium (aluminum) carbonate nanotubes and corresponding metal oxide nanotubes. The method is characterized in that the basic gallium (aluminum) carbonate nanotube with uniform appearance is conveniently synthesized by a simple and mild method. The method comprises the following steps:
1) dissolving gallium salt or aluminum salt in water, adding 0.5-2.5 g urea under stirring, and stirring for 30 min.
2) Adjusting pH of the above solution to 7-8 with ammonia water, adding urease, stirring for 30 min, placing into a polytetrafluoroethylene lined reaction kettle, and adding into a reactor with 37 deg.C oC, reacting for 24 hours in an oven.
3) The precipitate obtained from the reaction was collected by centrifugation, washed with water until the supernatant was neutral, and dried under vacuum.
2. The method of claim 1, wherein the step of synthesizing nanotubes with uniform size distribution comprises: the synthesized nanotube is NH4Ga(OH)2CO3Or NH4Al(OH)2CO3。
3. The method of claim 1, wherein the step of synthesizing nanotubes with uniform size distribution comprises: first adopt 37oC, synthesis, namely, continuously calcining to generate the gallium oxide or the alumina nanotube, wherein the calcining temperature is 500-1000-oC。
4. The method of claim 1, wherein the step of synthesizing nanotubes with uniform size distribution comprises: the nano-tube is synthesized by decomposing urea with urease.
5. The method of claim 1, wherein the step of synthesizing nanotubes with uniform size distribution comprises: the length of the synthesized basic gallium carbonate (aluminum) nano-tube is 500-2000 nm.
6. The method of claim 1, wherein the step of synthesizing nanotubes with uniform size distribution comprises: the yield of the basic gallium (aluminum) carbonate nano-tube is 50-80%.
7. The method of claim 1, wherein the step of synthesizing nanotubes with uniform size distribution comprises: different raw materials can be added to synthesize different heterojunction nanotubes or nanotubes loaded with other oxides.
CN202110696928.8A 2021-06-23 2021-06-23 Batch synthesis of basic carbonate and metal oxide nano-tubes by urea enzymolysis method Active CN113388645B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110696928.8A CN113388645B (en) 2021-06-23 2021-06-23 Batch synthesis of basic carbonate and metal oxide nano-tubes by urea enzymolysis method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110696928.8A CN113388645B (en) 2021-06-23 2021-06-23 Batch synthesis of basic carbonate and metal oxide nano-tubes by urea enzymolysis method

Publications (2)

Publication Number Publication Date
CN113388645A true CN113388645A (en) 2021-09-14
CN113388645B CN113388645B (en) 2022-09-13

Family

ID=77623699

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110696928.8A Active CN113388645B (en) 2021-06-23 2021-06-23 Batch synthesis of basic carbonate and metal oxide nano-tubes by urea enzymolysis method

Country Status (1)

Country Link
CN (1) CN113388645B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103194491A (en) * 2013-03-25 2013-07-10 北京工业大学 Method for inducing and synthesizing TiO2-ZnO by adsorbing enzyme on functionalized graphene oxide
CN103515169A (en) * 2012-06-21 2014-01-15 上海联影医疗科技有限公司 Nano field emission electron source and its preparation method
CN110589894A (en) * 2019-09-17 2019-12-20 北京化工大学 Preparation method of hollow metal oxide nano material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103515169A (en) * 2012-06-21 2014-01-15 上海联影医疗科技有限公司 Nano field emission electron source and its preparation method
CN103194491A (en) * 2013-03-25 2013-07-10 北京工业大学 Method for inducing and synthesizing TiO2-ZnO by adsorbing enzyme on functionalized graphene oxide
CN110589894A (en) * 2019-09-17 2019-12-20 北京化工大学 Preparation method of hollow metal oxide nano material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BAOCHANG CHENG: "Al2O3:Cr3+ Nanotubes Synthesized via Homogenization Precipitation Followed by Heat Treatment", 《THE JOURNAL OF PHYSICAL CHEMISTRY B》 *

Also Published As

Publication number Publication date
CN113388645B (en) 2022-09-13

Similar Documents

Publication Publication Date Title
CN107262133B (en) A kind of preparation method of the photochemical catalyst based on monodisperse bismuth with elementary and carbonitride
CN109534307B (en) g-C3N4 crystalline phase/amorphous homogeneous junction and preparation method and application thereof
CN114367299B (en) Graphite phase carbon nitride photocatalyst for photocatalytic hydrogen production and preparation method thereof
CN103663559B (en) Dibismuth trimolybdenum dodecaoxide nanocrystalline as well as preparation method and application thereof
CN113145138B (en) Thermal response type composite photocatalyst and preparation method and application thereof
CN113289653A (en) g-C of load metal monoatomic3N4Method for preparing photocatalyst
CN113198505A (en) Sodium bismuth titanate/graphite phase carbon nitride heterojunction piezoelectric photocatalyst and preparation method thereof
CN113087016A (en) Preparation method of rod-shaped bismuth sulfide/reduced graphene oxide composite material
CN107115859A (en) The preparation method of tungsten trioxide nano crystalline substance photochemical catalyst
CN111151275B (en) MoS 2 /Mo 2 C Complex, MoS 2 /Mo 2 C/CdS composite material and preparation method and application thereof
CN113713796B (en) Ni-NiO/C-TiO 2 Preparation method of core-shell structure nanorod-shaped material photocatalyst
CN111889127B (en) In-situ growth preparation of beta-Bi 2 O 3 /g-C 3 N 4 Method for preparing nano composite photocatalyst
CN112844392A (en) Method for constructing indium oxide micron rod epitaxial growth copper oxide nanosheet photocatalyst
CN112774703A (en) Elemental red phosphorus-loaded titanium dioxide composite catalyst for efficient photocatalytic decomposition of water to produce hydrogen
CN116726973A (en) Flower-ball-shaped sulfur indium zinc/carbon nitride heterojunction photocatalyst, and preparation method and application thereof
CN113388645B (en) Batch synthesis of basic carbonate and metal oxide nano-tubes by urea enzymolysis method
CN114160131B (en) Preparation method of freeze-dried modified sepiolite group mineral supported Pd monoatomic catalyst
CN113877556B (en) Indium oxyhydroxide/modified attapulgite photocatalytic composite material and preparation method and application thereof
CN115029724A (en) Preparation method and application of metal-doped 2H-phase molybdenum disulfide electrocatalyst
CN114289047A (en) Cobalt hydroxide/carbon nitride photocatalytic material and preparation method and application thereof
CN114160180A (en) Microwave-assisted thermal copolymerization method for preparing CNQDs/g-C3N4Method for compounding materials
CN112871183A (en) Preparation method of bismuth/bismuth tungstate/ferroferric oxide composite photocatalyst
CN112871165A (en) Two-dimensional WO modified by noble metal loading3Preparation method of nanosheet photocatalyst
CN112371161A (en) Carbon-point-modified graphite-phase carbon nitride hollow sphere photocatalyst and preparation method and application thereof
CN114870843B (en) Photocatalyst for reducing carbon dioxide by flower-like structure, preparation method and application thereof

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