CN106882774A - A kind of transition metal phosphide nano wire and preparation method and application - Google Patents
A kind of transition metal phosphide nano wire and preparation method and application Download PDFInfo
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- CN106882774A CN106882774A CN201710044973.9A CN201710044973A CN106882774A CN 106882774 A CN106882774 A CN 106882774A CN 201710044973 A CN201710044973 A CN 201710044973A CN 106882774 A CN106882774 A CN 106882774A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
- C01B25/088—Other phosphides containing plural metal
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a kind of transition metal phosphide nano wire and preparation method and application, the transition metal phosphide nano wire is ternary Ni Mo P nano wire of the homoepitaxial in substrate.Its preparation method includes：Nickel chloride and sodium molybdate are mixed into prepared precursor mixed solution；Substrate and precursor mixed solution are transferred in autoclave in the lump, and are reacted 300~500 minutes at 120~180 DEG C, so as to NiMoO be obtained in substrate4Nano wire；To the NiMoO in substrate and substrate4Nano wire is dried, then by substrate together with NiMoO4Nano wire is placed in phosphorus powder together, and is heated 0.5~2 hour with 450~600 DEG C under the protection of protective gas, is cooled to room temperature.The present invention not only has a more preferable electrolysis water catalytic performance than existing transition metal phosphide, and preparation process is simple, rapidly and efficiently, it is with low cost, environment friendly and pollution-free, be adapted to large-scale industrial production.
Description
Technical field
The present invention relates to transition metal phosphide field of nanometer material technology, more particularly to a kind of transition metal phosphide nano wire
And preparation method and application.
Background technology
With becoming increasingly conspicuous for energy problem and environmental problem, find a kind of renewable, environment-friendly novel energy into
It is the focus of global concern.Hydrogen Energy has the advantages that efficiency high, pollution-free, therefore is considered as always most preferable, most potential
Energy carrier, but current hydrogen producing technology has mostly, and power consumption is high, the low shortcoming of efficiency, this causes hydrogen manufacturing cost very
Height, therefore it is also difficult to achieve large-scale commercial applications application at present.
At present, existing hydrogen producing technology mainly include solar photoelectric hydrogen manufacturing, water electrolysis hydrogen production, reforming biomass hydrogen preparation,
Light biological hydrogen producing and photocatalysis hydrogen production etc.；Water electrolysis hydrogen production therein has the advantages that efficiency high, easily forms industrialization, therefore electricity
Solution water hydrogen manufacturing is most one of extensive, the most promising hydrogen manufacturing mode of research at present.
In existing water electrolysis hydrogen production technology, noble metal is (for example：Bore, ruthenium, silver etc.) it is maximally effective water electrolysis hydrogen production
Catalyst, but precious metal material is rare, expensive, therefore develop a kind of environment-friendly, inexpensive, the electrolysis of efficient stable
Water catalyst for preparing hydrogen is always the research emphasis of this area.Current research finds：Transition metal phosphide has good leading
Electrical conductivity energy and thermodynamic stability, thus transition metal phosphide in terms of water electrolysis hydrogen production aspect application receive extensively
General concern, but its electrolysis water catalytic performance of existing transition metal phosphide is unsatisfactory.
The content of the invention
For above-mentioned weak point of the prior art, the invention provides a kind of transition metal phosphide nano wire and its
Preparation method and application, not only have more preferable electrolysis water catalytic performance, and preparation technology than existing transition metal phosphide
Simply, rapidly and efficiently, it is with low cost, environment friendly and pollution-free, be adapted to large-scale industrial production.
The purpose of the present invention is achieved through the following technical solutions：
A kind of transition metal phosphide nano wire, the transition metal phosphide nano wire is three of homoepitaxial in substrate
First Ni-Mo-P nano wires.Preferably, described substrate uses carbon cloth, nickel foam or titanium foil.
A kind of preparation method of transition metal phosphide nano wire, comprises the following steps：
Step A, nickel chloride and sodium molybdate are mixed, thus be obtained chlorination nickel concentration be 0.5~2.0 mM/
Liter, the precursor mixed solution that molybdic acid na concn is 0.5~2.0 mM/l；
Step B, substrate is transferred in autoclave in the lump with described precursor mixed solution, and at 120~180 DEG C
Reaction 300~500 minutes, so as to NiMoO be obtained in described substrate4Nano wire；
Step C, to the NiMoO in described substrate and substrate4Nano wire is dried, then according to described forerunner
Body mixed solution:Phosphorus powder=1:30 mass ratio, by substrate together with NiMoO4Nano wire is placed in phosphorus powder together, and in protection gas
Heated 0.5~2 hour with 450~600 DEG C under the protection of body, be cooled to room temperature, so as to above-mentioned technical side be obtained in substrate
Transition metal phosphide nano wire described in case.
Preferably, described substrate uses carbon cloth, nickel foam or titanium foil.
Preferably, it is described by substrate together with NiMoO4Nano wire is placed in phosphorus powder together, and in the protection of protective gas
Under included within 0.5~2 hour with 450~600 DEG C of heating：By substrate together with NiMoO4Nano wire is placed in the porcelain boat for filling phosphorus powder together
In, and the porcelain boat is placed in tube furnace, then heated 0.5~2 hour with 450~600 DEG C under the protection of protective gas.
The application of transition metal phosphide nano wire described in above-mentioned technical proposal in electrochemical decomposition water.
The obtained transition metal phosphide nano wire in substrate described in above-mentioned technical proposal is directly as electrochemistry
The working electrode of decomposition water.
As seen from the above technical solution provided by the invention, transition metal phosphide provided in an embodiment of the present invention is received
Rice noodles are made together with nickel element, molybdenum element and P elements this three adulterates by the way that hydro-thermal method and high temperature phosphorization method organically combined
So as to the ternary Ni-Mo-P nano wires being made, ternary Ni-Mo-P nano wires can show excellent under different pH environment
Electrolysis water catalytic performance more more preferable than existing transition metal phosphide, therefore the present invention is not only than existing transition metal phosphide tool
Have a more preferable electrolysis water catalytic performance, and preparation process is simple, rapidly and efficiently, it is with low cost, environment friendly and pollution-free, be adapted to big rule
Mould industrialized production.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be to that will use needed for embodiment description
Accompanying drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the present invention, for this
For the those of ordinary skill in field, on the premise of not paying creative work, other can also be obtained according to these accompanying drawings
Accompanying drawing.
It is obtained with CFC as substrate in the step of Fig. 1 is CFC used in the present invention, the embodiment of the present invention 1 b1
NiMoO4The Electronic Speculum of nano wire and the final obtained ternary Ni-Mo-P nano wires with CFC as substrate of the embodiment of the present invention 1 is swept
Retouch photo.
Fig. 2 is to use energy dispersive spectrometer obtained ternary Ni- with CFC as substrate final to the embodiment of the present invention 1
Mo-P nano wires carry out elementary analysis so as to obtain energy spectrum diagram.
Fig. 3 is to use that element M apping (Element Mapping) is final obtained to the embodiment of the present invention 1 to be with CFC
The ternary Ni-Mo-P nano wires of substrate carry out elementary analysis distribution diagram of element obtained from.
Fig. 4 is to use to the final obtained ternary Ni-Mo-P nano wires with CFC as substrate of the embodiment of the present invention 1 in acid
Property under the conditions of carry out water electrolysis hydrogen production test obtained from polarization curve.
Fig. 5 is to use to the final obtained ternary Ni-Mo-P nano wires with CFC as substrate of the embodiment of the present invention 1 in alkali
Property under the conditions of carry out water electrolysis hydrogen production test obtained from polarization curve.
Specific embodiment
With reference to the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground description, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on this
Inventive embodiment, the every other implementation that those of ordinary skill in the art are obtained under the premise of creative work is not made
Example, belongs to protection scope of the present invention.
Transition metal phosphide nano wire provided by the present invention and preparation method and application is retouched in detail below
State.
A kind of transition metal phosphide nano wire, the transition metal phosphide nano wire is three of homoepitaxial in substrate
First Ni-Mo-P nano wires.Wherein, described substrate uses carbon cloth, nickel foam or titanium foil.
Specifically, the preparation method of the transition metal phosphide nano wire may comprise steps of：
Step A, nickel chloride and sodium molybdate are mixed in water, so that it is 0.5~2.0 milli that chlorination nickel concentration is obtained
Mol/L, the precursor mixed solution that molybdic acid na concn is 0.5~2.0 mM/l.In actual applications, can be in water
Nickel chloride and sodium molybdate are added so that nickel chloride and sodium molybdate are mixed in water.
Step B, substrate is transferred in autoclave in the lump with described precursor mixed solution, and at 120~180 DEG C
Reaction 300~500 minutes, so as to NiMoO be obtained in described substrate4Nano wire.Wherein, described substrate uses carbon fiber
Cloth (Carbon Fiber Cloth, CFC), nickel foam or titanium foil, but in actual applications preferably with carbon cloth (for example：
Size is the carbon cloth of 1X 3cm).
Step C, to the NiMoO in described substrate and substrate4Nano wire is dried, then according to described forerunner
Body mixed solution:Phosphorus powder=1:30 mass ratio, by substrate together with NiMoO4Nano wire is placed in phosphorus powder together, and in protection gas
Heated 0.5~2 hour with 450~600 DEG C under the protection of body (protective gas is rare gas or nitrogen), be cooled to room
Temperature, so as to ternary Ni-Mo-P nano wires (the transition metal phosphide nanometer i.e. described in above-mentioned technical proposal be obtained in substrate
Line).Transition metal phosphide nano wire connection substrate can be directly as the working electrode of electrochemical decomposition water.
Specifically, substrate is together with NiMoO4Nano wire is preferably placed in the porcelain boat for filling phosphorus powder together, and by the porcelain boat
It is placed in tube furnace, is then heated 0.5~2 hour with 450~600 DEG C under the protection of protective gas.
Further, transition metal phosphide nano wire provided by the present invention at least has following technique effect：
(1) existing transition metal phosphide is generally binary transition metal phosphide, and the preparation method that the present invention is provided
The uniform sequential ternary Ni-Mo-P nano wires being grown in substrate of obtained transition metal phosphide nano wire, and this three
First Ni-Mo-P nano wires have more preferable electrolysis water catalytic performance than binary transition metal phosphide.
(2) the ternary Ni-Mo-P nano wires obtained by the preparation method that the present invention is provided can directly be made together with substrate
It is the working electrode of water electrolysis hydrogen production reaction.
(3) preparation method that the present invention is provided only needs the conventional conventional equipment in laboratory, is not required to special equipment, technical process
It is simple to operation.
(4) abundant raw material, pollution-free and cheap and easy to get that the preparation method that the present invention is provided is used, therefore be very suitable for
Prepared by largely, low cost, large-scale production, this suitable future industrializes large-scale application in terms of the energy, hydrogen manufacturing.
As fully visible, the embodiment of the present invention not only has more preferable electrolysis water catalytic than existing transition metal phosphide
Can, and preparation process is simple, rapidly and efficiently, it is with low cost, environment friendly and pollution-free, be adapted to large-scale industrial production.
In order to more clearly from show technical scheme provided by the present invention and produced technique effect, below with tool
Body embodiment is described in detail to transition metal phosphide nano wire provided by the present invention and preparation method and application.
Embodiment 1
A kind of transition metal phosphide nano wire, it is be homoepitaxial in CFC substrates ternary Ni-Mo-P nanometers
Line, is prepared from using following steps：
Step a1, to adding nickel chloride and sodium molybdate in water and mix so that be obtained chlorination nickel concentration be 1.0 mMs/
Liter, the precursor mixed solution that molybdic acid na concn is 1.0 mM/ls.
Step b1, it is the CFC of 1X 3cm with size as substrate, by the precursor mixed solution described in CFC and step a1
It is transferred in the autoclave of 40mL in the lump, and is reacted 360 minutes at 160 DEG C, so as to the NiMoO with CFC as substrate is obtained4Receive
Rice noodles.
Step c1, to the NiMoO with CFC as substrate4Nano wire is dried, then molten according to described presoma mixing
Liquid:Phosphorus powder=1:30 mass ratio, by the NiMoO with CFC as substrate4Nano wire is placed in the porcelain boat for filling 40mg phosphorus powders, and
The porcelain boat is placed in tube furnace, is heated 1.5 hours with 500 DEG C under the protection of argon gas, then naturally cool to room temperature, so that i.e.
The ternary Ni-Mo-P nano wires with CFC as substrate can be obtained.
Specifically, the inspection of morphology observations, constituent analysis and performance is carried out during the embodiments of the present invention 1 are implemented
Survey, so as to obtain following result：
(1) CFC, the step of the embodiment of the present invention 1 for being used the embodiment of the present invention 1 respectively using SEM
The obtained NiMoO with CFC as substrate in rapid b14Nano wire and the embodiment of the present invention 1 are final obtained with CFC as substrate
Ternary Ni-Mo-P nano wires are observed and shoot, so as to obtain field emission scanning electron microscope as shown in Figure 1
(FESEM) photo；Wherein, Fig. 1 a are the FESEM photos of CFC used in the present invention, the step of Fig. 1 b are the embodiment of the present invention 1
The obtained NiMoO with CFC as substrate in b14The FESEM photos of nano wire, Fig. 1 c are the final obtained embodiment of the present invention 1
The low power FESEM photos of the ternary Ni-Mo-P nano wires with CFC as substrate, Fig. 1 d be the embodiment of the present invention 1 it is final obtained with
CFC is the high power FESEM photos of the ternary Ni-Mo-P nano wires of substrate.As seen from Figure 1：The step of embodiment of the present invention 1
The obtained NiMoO with CFC as substrate in b14Nano wire and final obtained ternary Ni-Mo-P nanometers with CFC as substrate
Line is all uniform sequential to be closely grown on CFC.
(2) energy dispersive spectrometer (EDS) is used to the final obtained ternary with CFC as substrate of the embodiment of the present invention 1
Ni-Mo-P nano wires carry out elementary analysis, so as to obtain energy spectrum diagram as shown in Figure 2.As seen from Figure 2：The present invention is implemented
The final obtained ternary Ni-Mo-P nano wires with CFC as substrate of example 1 are made up of tri- kinds of first prime elements of Ni, Mo, P, and C comes from
In carbon cloth, O from the partial oxidation being placed in air.
(3) it is final to the embodiment of the present invention 1 obtained with CFC as substrate with element M apping (Element Mapping)
Ternary Ni-Mo-P nano wires carry out elementary analysis, so as to obtain distribution diagram of element as shown in Figure 3；Wherein, Fig. 3 a are whole
The distribution diagram of element of all elements on the final obtained ternary Ni-Mo-P nano wires with CFC as substrate of the embodiment of the present invention 1,
Fig. 3 b are the element of P element on the final obtained ternary Ni-Mo-P nano wires with CFC as substrate of the whole embodiment of the present invention 1
Distribution map, Fig. 3 c are Mo units on the final obtained ternary Ni-Mo-P nano wires with CFC as substrate of the whole embodiment of the present invention 1
The distribution diagram of element of element, Fig. 3 d are final obtained ternary Ni-Mo-P nanometers with CFC as substrate of the whole embodiment of the present invention 1
The distribution diagram of element of Ni elements on line.As seen from Figure 3：It is real that tri- kinds of elements of Ni, Mo, P are evenly distributed in the whole present invention
Apply on the final obtained ternary Ni-Mo-P nano wires with CFC as substrate of example 1.
(4) it is obtained with CFC in the step of CFC, the embodiment of the present invention 1 for respectively being used the embodiment of the present invention 1 b1
It is the NiMoO of substrate4The final obtained ternary Ni-Mo-P nano wires with CFC as substrate of nano wire, the embodiment of the present invention 1 are made
For the working electrode of water electrolysis hydrogen production reaction, using silver/silver chlorate as reference electrode, using Pt as to electrode, it is in concentration
The H of 0.5mol/L2SO4Water electrolysis hydrogen production test is carried out in solution, and is lied prostrate with linear scan using occasion China's 760e electrochemical workstations
Peace method (surface sweeping scope is -0.8~0V, sweeps speed for 2mV/s) is measured respectively, so as to obtain polarization curve as shown in Figure 4
Figure.As seen from Figure 4：In acid condition, the step of CFC for being used with the embodiment of the present invention 1 and the embodiment of the present invention 1
The obtained NiMoO with CFC as substrate in b14Both nano wires are compared, and the embodiment of the present invention 1 is finally obtained to be with CFC
The ternary Ni-Mo-P nano wires of substrate have lower overpotential, catalysis activity higher.
(5) it is obtained with CFC in the step of CFC, the embodiment of the present invention 1 for respectively being used the embodiment of the present invention 1 b1
It is the NiMoO of substrate4The final obtained ternary Ni-Mo-P nano wires with CFC as substrate of nano wire, the embodiment of the present invention 1 are made
For the working electrode of water electrolysis hydrogen production reaction, using silver/silver chlorate as reference electrode, using Pt as to electrode, it is in concentration
Water electrolysis hydrogen production test is carried out in the KOH solution of 1.0mol/L, and is lied prostrate with linear scan using occasion China's 760e electrochemical workstations
Peace method (surface sweeping scope is -0.8~0V, sweeps speed for 2mV/s) is measured respectively, so as to obtain polarization curve as shown in Figure 5
Figure.As seen from Figure 5：In the basic conditions, the step of CFC for being used with the embodiment of the present invention 1 and the embodiment of the present invention 1
The obtained NiMoO with CFC as substrate in b14Both nano wires are compared, and the embodiment of the present invention 1 is finally obtained to be with CFC
The ternary Ni-Mo-P nano wires of substrate have lower overpotential, catalysis activity higher.Complex chart 4 and Fig. 5 understand：With this
The obtained NiMoO with CFC as substrate in the step of CFC that inventive embodiments 1 are used and the embodiment of the present invention 1 b14Nanometer
Both lines are compared, and the final obtained ternary Ni-Mo-P nano wires with CFC as substrate of the embodiment of the present invention 1 are in different pH rings
Excellent electrolysis water catalytic performance can be shown under border.
As fully visible, the embodiment of the present invention not only has more preferable electrolysis water catalytic than existing transition metal phosphide
Can, and preparation process is simple, rapidly and efficiently, it is with low cost, environment friendly and pollution-free, be adapted to large-scale industrial production.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any one skilled in the art in the technical scope of present disclosure, the change or replacement that can be readily occurred in,
Should all be included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Enclose and be defined.
Claims (7)
1. a kind of transition metal phosphide nano wire, it is characterised in that the transition metal phosphide nano wire exists for homoepitaxial
Ternary Ni-Mo-P nano wires in substrate.
2. transition metal phosphide nano wire according to claim 1, it is characterised in that described substrate uses carbon fiber
Cloth, nickel foam or titanium foil.
3. a kind of preparation method of transition metal phosphide nano wire, it is characterised in that comprise the following steps：
Step A, nickel chloride and sodium molybdate are mixed, so that it is 0.5~2.0 mM/l, molybdenum that chlorination nickel concentration is obtained
Sour na concn is 0.5~2.0 mM/l of precursor mixed solution；
Step B, substrate is transferred in autoclave in the lump with described precursor mixed solution, and is reacted at 120~180 DEG C
300~500 minutes, so as to NiMoO be obtained in described substrate4Nano wire；
Step C, to the NiMoO in described substrate and substrate4Nano wire is dried, then mixed according to described presoma
Close solution:Phosphorus powder=1:30 mass ratio, by substrate together with NiMoO4Nano wire is placed in phosphorus powder together, and in protective gas
Under protection with 450~600 DEG C heat 0.5~2 hour, be cooled to room temperature, so as in substrate be obtained the claims 1 to
Transition metal phosphide nano wire any one of 2.
4. the preparation method of transition metal phosphide nano wire according to claim 3, it is characterised in that described substrate
Using carbon cloth, nickel foam or titanium foil.
5. the preparation method of the transition metal phosphide nano wire according to claim 3 or 4, it is characterised in that described
By substrate together with NiMoO4Nano wire is placed in phosphorus powder together, and with 450~600 DEG C of heating 0.5 under the protection of protective gas
Include within~2 hours：By substrate together with NiMoO4Nano wire is placed in the porcelain boat for filling phosphorus powder together, and the porcelain boat is placed in into tubular type
In stove, then heated 0.5~2 hour with 450~600 DEG C under the protection of protective gas.
6. the transition metal phosphide nano wire any one of the claims 1 to 2 in electrochemical decomposition water should
With.
7. the obtained transition metal phosphide nano wire in substrate any one of the claims 3 to 5 is directly made
It is the working electrode of electrochemical decomposition water.
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| CN113584521A (en) * | 2021-05-05 | 2021-11-02 | 浙江大学杭州国际科创中心 | Branch-leaf type heterostructure full-hydrolysis catalyst and preparation method thereof |
| CN114059082A (en) * | 2021-11-30 | 2022-02-18 | 安徽理工大学 | N, P codoped NF @ NiMoO4Hollow nanowire composite material and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107740137A (en) * | 2017-09-14 | 2018-02-27 | 广州大学 | A kind of phosphatization tantalum oxide nanotube and preparation method thereof |
| CN108325544A (en) * | 2018-01-31 | 2018-07-27 | 中国科学院合肥物质科学研究院 | A kind of ternary Cu-Co-P nanometer rods and the preparation method and application thereof |
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| CN114059082A (en) * | 2021-11-30 | 2022-02-18 | 安徽理工大学 | N, P codoped NF @ NiMoO4Hollow nanowire composite material and preparation method and application thereof |
| CN114059082B (en) * | 2021-11-30 | 2024-03-19 | 安徽理工大学 | N, P co-doped NF@NiMoO 4 Hollow nanowire composite material and preparation method and application thereof |
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