CN111974379B - As-MnO X Composite oxide and process for producing the same - Google Patents

As-MnO X Composite oxide and process for producing the same Download PDF

Info

Publication number
CN111974379B
CN111974379B CN202010786209.0A CN202010786209A CN111974379B CN 111974379 B CN111974379 B CN 111974379B CN 202010786209 A CN202010786209 A CN 202010786209A CN 111974379 B CN111974379 B CN 111974379B
Authority
CN
China
Prior art keywords
mno
composite oxide
powder
manganese
mixture
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.)
Active
Application number
CN202010786209.0A
Other languages
Chinese (zh)
Other versions
CN111974379A (en
Inventor
吴彩红
文崇斌
王鹏飞
朱刘
胡智向
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.)
Vital Thin Film Materials Guangdong Co Ltd
Original Assignee
Vital Thin Film Materials Guangdong Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Vital Thin Film Materials Guangdong Co Ltd filed Critical Vital Thin Film Materials Guangdong Co Ltd
Priority to CN202010786209.0A priority Critical patent/CN111974379B/en
Publication of CN111974379A publication Critical patent/CN111974379A/en
Application granted granted Critical
Publication of CN111974379B publication Critical patent/CN111974379B/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
    • 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
    • B01J23/16—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G28/00—Compounds of arsenic
    • C01G28/005—Oxides; Hydroxides; Oxyacids
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention relates to an As-MnO X The preparation method of the composite oxide comprises the following steps: (1) Evenly mixing manganese sesquioxide powder and manganese arsenide powder, and sieving to obtain a mixture; (2) Placing the mixture obtained in the step (1) into a reactor, heating to 600-800 ℃, preserving heat for 80-120 min, and then cooling along with a furnace to obtain As-MnO X A composite oxide. The method of the invention adopts a vacuum sintering method, the evenly mixed mixture is put into a vacuum sintering furnace, and the As-MnO with different relative contents of oxygen vacancies can be obtained by controlling the sintering temperature and the sintering time X A composite oxide; the method has low cost and simple operation, and can control As-MnO by controlling the relative content of oxygen vacancies X Catalytic oxidation performance of the composite oxide.

Description

As-MnO X Composite oxide and process for producing the same
Technical Field
The invention relates to the technical field of catalytic material preparation, in particular to an As-MnO X Composite oxide and its preparation method are provided.
Background
Transition metal oxides are of interest to many researchers because of their low cost, wide sources, and certain catalytic capabilities. Wherein Mn can have interconversion of multiple valence states in chemical reaction, so that the Mn has better catalytic activity. Manganese oxide is therefore one of the most interesting metal oxides. Research shows that oxygen vacancies on metal oxides are one of the important factors affecting catalytic performance because of the existence of unsaturated coordination structures around the metal oxides, which are very conducive to oxygen activation.
Currently, methods for constructing oxygen vacancies include high temperature quenching, material compounding, ion doping, etc., wherein the ion doping method is widely used because of its low cost and simple process. The chinese patent with the publication number CN 107694559B discloses a method for preparing a zinc-manganese oxide-trimanganese tetroxide composite oxide with adjustable oxygen vacancies by performing a hydrothermal reaction and then performing a heating reaction and finally performing roasting, but the preparation method still has complex procedures and risks of introducing impurities.
As-doped manganese oxides, in theory, possess both redox couples-Mn 2+ /Mn 3+ And As 3+ /As 5+ Has more rapid oxygen activation and oxygen transport capacity than a single redox pair catalyst. However, a method of doping arsenic ions into manganese oxide to compete with manganese for oxygen at high temperature and changing the relative contents of the valence states of each positive valence ion to construct oxygen vacancies has not been reported yet.
Thus, an As-MnO was developed X The compound and the preparation method thereof have good practical significance.
Disclosure of Invention
The invention aims to provide an As-MnO X Composite oxide and its preparation method are provided. The preparation method adopts a vacuum sintering method, the evenly mixed mixture is put into a vacuum sintering furnace, and the As-MnO with controllable relative content of oxygen vacancies can be obtained by controlling the sintering temperature and the sintering time X A composite oxide. The method has low cost and simple operation, and can control As-MnO by controlling the relative content of oxygen vacancies X Catalytic oxidation performance of the composite oxide.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: as-MnO X The preparation method of the composite oxide is characterized by comprising the following steps:
(1) Under the protection of protective gas, evenly mixing manganese sesquioxide powder and manganese arsenide powder, and sieving to obtain a mixture;
(2) Placing the mixture obtained in the step (1) into a reactor, heating to 600-800 ℃, preserving heat for 80-120 min, and then cooling along with a furnace to obtain As-MnO X A composite oxide. Wherein 1 is<X<4/3。
As a further improvement of the invention, in the step (1), the mass ratio of the manganese sesquioxide powder to the manganese arsenide powder is 3.35:1.
As a further improvement of the invention, in the step (2), the heating rate is 5-15 ℃/min.
As a further improvement of the invention, in the step (1), the mixing time is 4-6 h.
As a further improvement of the invention, in the step (1), the screen mesh in the sieving operation process is 100-200 meshes.
As a further improvement of the present invention, in the step (1), the manganese sesquioxide powder has a particle size of 200 mesh and a purity of 3N.
As a further improvement of the invention, the granularity of the manganese arsenide powder is 150 meshes, and the purity is 3N.
As a further improvement of the present invention, in the step (2), the reactor is a vacuum sintering furnace.
As a further improvement of the present invention, in the step (1), the shielding gas is nitrogen or an inert gas.
At the same time propose an As-MnO X Composite oxide using As-MnO As described above X The composite oxide is prepared by a preparation method.
Compared with the prior art, the invention has the beneficial effects that: in the reaction process, a vacuum sintering method is adopted, the mixture which is uniformly mixed is put into a vacuum sintering furnace for sintering, so that arsenic ions and manganese ions compete for capturing oxygen ions at high temperature, and Mn can be controlled by controlling the heating temperature and the heat preservation time 2+ /Mn 3+ And As 3+ /As 5+ The relative content of each ion in the two redox pairs is controlled, so that the relative content of oxygen vacancies is controlled, and the catalytic oxidation performance is controlled.
Drawings
Figure 1 is an XRD pattern of examples 1, 2 and 3 of the present invention.
FIG. 2 is an XPS plot of Mn2p for examples 1, 2 and 3 of the present invention.
FIG. 3 shows the relative amounts of Mn in different valence states for examples 1, 2 and 3 according to the present invention.
FIG. 4 is an XPS plot of As3d for examples 1, 2 and 3 of the present invention.
FIG. 5 shows the relative amounts of the various valence states of As for examples 1, 2 and 3 of the present invention.
FIG. 6 is an XPS plot of O1s for examples 1, 2 and 3 of the present invention.
FIG. 7 shows the relative amounts of different particles of O according to examples 1, 2 and 3 of the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The invention provides an As-MnO X A method for producing a composite oxide, the method comprising the steps of:
(1) Evenly mixing manganese sesquioxide powder and manganese arsenide powder, and sieving to obtain a mixture;
(2) Placing the mixture obtained in the step (1) into a reactor, heating to 600-800 ℃, preserving heat for 80-120 min, and then cooling along with a furnace to obtain As-MnO X A composite oxide.
The invention provides an As-MnO X Preparation method of composite oxide powder capable of controlling As-MnO X The relative content of oxygen vacancies in the composite oxide powder is controlled, thereby controlling the catalytic oxidation performance thereof.
In certain embodiments of the present invention, in step (1), the mass ratio of the manganese sesquioxide powder to the manganese arsenide powder is 3.35:1. Further, in other embodiments of the present invention, the mass ratio of the manganese sesquioxide powder to the manganese arsenide powder is 2.5-7.5:1, and As-MnO can be obtained As well X Composite oxide powder.
In some embodiments of the present invention, in the step (2), the heating rate is 5 to 15 ℃/min. Too slow or too fast temperature rise can cause serious phase transition of manganese sesquioxide, and the relative content of oxygen vacancies cannot be well controlled.
In some embodiments of the present invention, in the step (1), the mixing time is 4 to 6 hours. Too short mixing time can lead to uneven powder mixing and larger relative content of redox pairs at different parts after sintering. Too short mixing time can also cause uneven distribution of the relative content of oxygen vacancies, and the relative content of the oxygen vacancies cannot be controlled; too long mixing time can cause too fine agglomeration of powder to be screened, and the agglomeration of the powder can cause uneven distribution of oxygen vacancies after sintering, so that the aim of controlling the relative content of the oxygen vacancies can not be achieved.
As a further improvement of the invention, in the step (1), the screen mesh in the sieving operation process is 100-200 meshes. The manganese oxide powder and the manganese arsenide powder with proper granularity can lead the reaction to be carried out smoothly, and oxygen vacancies after sintering are distributed uniformly.
As a further improvement of the present invention, in the step (1), the manganese sesquioxide powder has a particle size of 200 mesh and a purity of 3N.
As a further improvement of the invention, the granularity of the manganese arsenide powder is 150 meshes, and the purity is 3N.
As a further improvement of the present invention, in the step (2), the reactor is a vacuum sintering furnace.
As a further improvement of the present invention, in the step (1), the shielding gas is nitrogen or an inert gas. The existence of the protective gas can avoid the influence of air on the reaction.
At the same time propose an As-MnO X Composite oxide using As-MnO As described above X The composite oxide is prepared by a preparation method.
As a preferred embodiment of the preparation method of the present invention, further step (3): the As-MnO obtained in the step (2) is treated X Crushing the composite oxide into powder, and sieving to obtain As-MnO X Composite oxide powder. Further, the mesh number of the sieving screen is 100-325 mesh.
Example 1.
As-MnO X The preparation method of the composite oxide comprises the following steps:
(1) Under the protection of helium, 770g of manganese sesquioxide powder with the granularity of 200 meshes and 230g of manganese arsenide powder with the granularity of 150 meshes are mixed in a mixer for 4 hours and pass through a 100-mesh screen to obtain a mixture;
(2) Placing the mixture obtained in the step (1) into a vacuum sintering furnace, vacuumizing, and heating to 600 ℃ at a heating rate of 5 ℃/minPreserving heat for 80min, and cooling with furnace to obtain As-MnO X A composite oxide.
The As-MnO obtained X Crushing the composite oxide into powder, and sieving with 100 mesh sieve to obtain As-MnO with proper particle size X Composite oxide powder.
As-MnO prepared in this example X The composite oxide powder is marked As-MnO X 600 ℃. The XRD pattern of the synthesized composite oxide is shown in FIG. 1. As can be seen from the figure, the synthesized powder was As-MnO X Composite oxide in which MnO X Is MnO and Mn 3 O 4 And a relatively low MnO content; as can be seen from the X-ray photoelectron spectrum of Mn2p shown in FIG. 2 and the relative content of positive ions of manganese shown in FIG. 3, the manganese valence state of the synthesized product is positive 2 valence and positive 3 valence, and has lower Mn 2+ The content is as follows; as can be seen from the XPS diagram of As3d shown in FIG. 4 and the relative content of positive ions of arsenic shown in FIG. 5, the valence state of arsenic of the synthesized product is positive 3 and positive 5, and the synthesized product has lower As 5+ The content is as follows; from the XPS chart of O1s shown in FIG. 6 and the relative content of each particle of O shown in FIG. 7, the synthesized product has lower metal-O bond and oxygen vacancy (V O ) Concentration.
Example 2.
As-MnO X The preparation method of the composite oxide comprises the following steps:
(1) Under the protection of helium, 770g of manganese sesquioxide powder with the granularity of 200 meshes and 230g of manganese arsenide powder with the granularity of 150 meshes are mixed in a mixer for 5 hours and then pass through a 150-mesh screen to obtain a mixture;
(2) Placing the mixture obtained in the step (1) into a vacuum sintering furnace, vacuumizing, heating to 700 ℃ at a heating rate of 10 ℃/min, preserving heat for 100min, and cooling along with the furnace to obtain As-MnO X A composite oxide.
The As-MnO obtained X Crushing the composite oxide into powder, and sieving with 200 mesh sieve to obtain As-MnO with proper particle size X Composite oxide powder.
As-MnO prepared in this example X The composite oxide powder is marked As-MnO X 700 ℃. As can be seen from the XRD pattern in FIG. 1, the synthesized powder is As-MnO X Composite oxide in which MnO X Is MnO and Mn 3 O 4 And the relative content of MnO is high; as can be seen from FIGS. 2 and 3, the manganese of the synthesized product has positive 2-valent and positive 3-valent manganese and higher Mn 2+ The content is as follows; as can be seen from FIGS. 4 and 5, the arsenic in the synthesized product has a valence state of positive 3 and positive 5, and has a high As 5+ The content is as follows; from the XPS chart of O1s shown in FIG. 6 and the relative content of each particle of O shown in FIG. 7, the synthesized product has higher metal-O bond and oxygen vacancy (V O ) Concentration.
Example 3.
As-MnO X The preparation method of the composite oxide comprises the following steps:
(1) Under the protection of helium, 770g of manganese sesquioxide powder with the granularity of 200 meshes and 230g of manganese arsenide powder with the granularity of 150 meshes are mixed in a mixer for 6 hours and pass through a 200-mesh screen to obtain a mixture;
(2) Placing the mixture obtained in the step (1) into a vacuum sintering furnace, vacuumizing, heating to 800 ℃ at a heating rate of 15 ℃/min, preserving heat for 120min, and cooling along with the furnace to obtain As-MnO X A composite oxide.
The As-MnO obtained X Crushing the composite oxide into powder, and sieving with 325 mesh sieve to obtain As-MnO with proper particle size X Composite oxide powder.
As-MnO prepared in this example X The composite oxide powder is marked As-MnO X 800 ℃. As can be seen from FIG. 1, the synthesized powder is As-MnO X Composite oxide in which MnO X Is MnO and Mn 3 O 4 And the relative content of MnO is high; as can be seen from FIGS. 2 and 3, the manganese of the synthesized product has positive 2-valent and positive 3-valent manganese and has high Mn 2+ The content is as follows; as can be seen from FIGS. 4 and 5, the valence state of arsenic in the synthesized product is positive 3 and positive 5, and has high As 5+ The content is as follows; each pellet of O shown in fig. 7 and the XPS diagram of O1s shown in fig. 6The relative content of the subunits is known, and the synthesized product has high metal-O bond and oxygen vacancy (V O ) Concentration. The particle distribution of O contains water (H 2 O), which may originate from water vapor in the air.
As can be seen from examples 1 to 3, in this process, as the sintering temperature and time are changed, the concentration of oxygen vacancies is changed accordingly, resulting in oxygen vacancies at different temperatures (V as in FIG. 7 O ) The relative content of (2) is shown.
Compared with the prior art, the invention has the beneficial effects that: in the reaction process, a vacuum sintering method is adopted, the mixture which is uniformly mixed is put into a vacuum sintering furnace for sintering, so that arsenic ions and manganese ions compete for capturing oxygen ions at high temperature, and Mn can be controlled by controlling the heating temperature and the heat preservation time 2+ /Mn 3+ And As 3+ /As 5+ The relative content of each ion in the two redox pairs is controlled, so that the relative content of oxygen vacancies is controlled, and the catalytic oxidation performance is controlled.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (3)

1. As-MnO X The preparation method of the composite oxide is characterized by comprising the following steps:
(1) Under the protection of nitrogen or inert gas, evenly mixing manganese sesquioxide powder and manganese arsenide powder, wherein the granularity of the manganese sesquioxide powder is 200 meshes, the purity is 3N, the granularity of the manganese arsenide powder is 150 meshes, the purity is 3N, the mass ratio of the manganese sesquioxide powder to the manganese arsenide powder is 2.5-7.5:1, the mixing time is 4-6 h, and then sieving is carried out, wherein the mesh screen in the sieving operation process is 100-200 meshes, so as to obtain a mixture;
(2) Placing the mixture obtained in the step (1) into a vacuum sintering furnace, heating to 600-800 ℃, and heatingThe speed is 5-15 ℃/min, the temperature is kept for 80-120 min, arsenic ions and manganese ions compete for capturing oxygen ions at high temperature, and Mn is controlled 2+ /Mn 3+ And As 3+ /As 5+ The relative content of each ion in the two redox pairs is cooled along with the furnace to obtain As-MnO X Composite oxide, 1<X<4/3。
2. The method according to claim 1, wherein in the step (1), the mass ratio of the manganese sesquioxide powder to the manganese arsenide powder is 3.35:1.
3. As-MnO X A composite oxide characterized by using the As-MnO according to any one of claims 1 to 2 X The composite oxide is prepared by a preparation method.
CN202010786209.0A 2020-08-07 2020-08-07 As-MnO X Composite oxide and process for producing the same Active CN111974379B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010786209.0A CN111974379B (en) 2020-08-07 2020-08-07 As-MnO X Composite oxide and process for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010786209.0A CN111974379B (en) 2020-08-07 2020-08-07 As-MnO X Composite oxide and process for producing the same

Publications (2)

Publication Number Publication Date
CN111974379A CN111974379A (en) 2020-11-24
CN111974379B true CN111974379B (en) 2023-05-30

Family

ID=73446088

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010786209.0A Active CN111974379B (en) 2020-08-07 2020-08-07 As-MnO X Composite oxide and process for producing the same

Country Status (1)

Country Link
CN (1) CN111974379B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002373459A (en) * 2001-06-14 2002-12-26 Sumitomo Metal Mining Co Ltd Sputtering target for optical disk protecting film, and the optical disk protecting film formed by using the same
CN101978431A (en) * 2008-03-25 2011-02-16 旭硝子株式会社 Electric conductor and process for its production
CN105047738A (en) * 2015-06-30 2015-11-11 厦门神科太阳能有限公司 Sputtering target material and CIGS-based thin-film solar cell made of same
CN110224118A (en) * 2019-05-15 2019-09-10 桂林电子科技大学 Compound manganese and oxygen compound film and the preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002373459A (en) * 2001-06-14 2002-12-26 Sumitomo Metal Mining Co Ltd Sputtering target for optical disk protecting film, and the optical disk protecting film formed by using the same
CN101978431A (en) * 2008-03-25 2011-02-16 旭硝子株式会社 Electric conductor and process for its production
CN105047738A (en) * 2015-06-30 2015-11-11 厦门神科太阳能有限公司 Sputtering target material and CIGS-based thin-film solar cell made of same
CN110224118A (en) * 2019-05-15 2019-09-10 桂林电子科技大学 Compound manganese and oxygen compound film and the preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孙智 等.1.《材料概论》.2008, *

Also Published As

Publication number Publication date
CN111974379A (en) 2020-11-24

Similar Documents

Publication Publication Date Title
US10112841B2 (en) Method for catalytic ammonia synthesis under concentrated solar energy and catalysts
JP2016537511A (en) Mg-based hydrogen storage material and preparation method thereof
CN110722171A (en) Method for preparing rare earth oxide doped tungsten and molybdenum spherical powder for 3D printing
CN114471639B (en) Transition metal element doped and cadmium sulfide loaded transition metal phosphide photocatalytic material with sulfur vacancy and preparation method thereof
CN109806874B (en) Preparation method and application of carbon dioxide methanation nickel-based multi-metal catalyst
CN109261980A (en) A kind of preparation method of heavy alloy tungsten powder
CN112662881A (en) Method for preparing industrial cobalt powder by microwave reduction pyrolysis of cobalt acid lithium battery
CN112619648A (en) Copper-cobalt-based catalyst for organic sulfur hydrolysis removal and preparation method thereof
CN112007657B (en) Method for controlling metal atomic ratio in supported Cu-Pd/AC alloy catalyst
CN111974379B (en) As-MnO X Composite oxide and process for producing the same
CN114725383A (en) Prussian blue material carbon coating method for sodium ion battery
CN110919020B (en) Preparation method of molybdenum powder with large particle size
CN111085184A (en) Hollow multi-shell material and preparation method and application thereof
CN111186859A (en) Superfine V2O5Powder, method for the production thereof and use thereof
CN108654663B (en) Boron-nitrogen co-doped single crystal mesoporous TiO prepared by mixed nitrate molten salt method2Method for catalyzing materials
CN112939053B (en) Method for preparing transition metal oxide material containing oxygen vacancy
JP5621268B2 (en) Nickel oxide fine powder and method for producing the same
CN107855539A (en) A kind of method for preparing superfine metal and metal oxide
CN111968788A (en) Preparation method of high-performance iron-based superconducting precursor powder and superconducting tape
CN111468158A (en) High-efficiency hydrogen sulfide selective oxidation catalyst and preparation method thereof
CN111203207B (en) Catalyst for reducing p-nitrophenol and preparation method and application thereof
CN109261143B (en) Preparation method of titanium dioxide particles with surfaces doped with rare earth elements
CN108067277A (en) High itrogen content of getter with nitrogen doped monocrystalline TiO2The preparation method of mesoporous material
CN115233065B (en) Molybdenum-rhenium prealloy powder and preparation method thereof
CN112338198B (en) Micron-sized molybdenum powder and 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