CN113061930A - Preparation method of transition metal phosphide - Google Patents
Preparation method of transition metal phosphide Download PDFInfo
- Publication number
- CN113061930A CN113061930A CN202110308913.XA CN202110308913A CN113061930A CN 113061930 A CN113061930 A CN 113061930A CN 202110308913 A CN202110308913 A CN 202110308913A CN 113061930 A CN113061930 A CN 113061930A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- preparation
- phytic acid
- cobalt
- metal phosphide
- 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.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
Abstract
The invention relates to the technical field of electrocatalytic materials, in particular to a preparation method of transition metal phosphide. The invention discloses a preparation method of transition metal phosphide, which comprises the steps of dissolving transition metal salt and organic ligand in a solvent, adding phytic acid, carrying out solvothermal reaction to obtain a phytic acid-doped MOF material, and then carbonizing the material in one step to obtain the transition metal phosphide. In the preparation method, metal ions can be coordinated with an organic ligand, phytic acid has strong chelating capacity, 6 phosphate radicals with negative electricity can be combined with metal cations, and then transition metal phosphide is obtained through carbonization; according to the preparation method, phosphorus is introduced by using non-toxic phytic acid, so that the preparation process of the transition metal phosphide is green and environment-friendly, and when an electrode prepared from the transition metal phosphide obtained by the preparation method is tested in alkaline electrolyte, the material shows good HER catalytic activity and good stability.
Description
Technical Field
The invention relates to the technical field of electrocatalytic materials, in particular to a preparation method of transition metal phosphide.
Background
Along with the more and more obvious environmental pollution influence brought by the combustion of fossil fuel, the attention of people to clean sustainable energy is promoted year by year, devices of clean energy such as fuel cells and the like become the key point of research of people, hydrogen energy can be used as clean energy and can be applied to a plurality of applications, and hydrogen production by water electrolysis is a good strategy. The electrolyzed water splitting consists of a Hydrogen Evolution Reaction (HER) at the cathode and an Oxygen Evolution Reaction (OER) at the anode. The current Pt group metals are the most recognized HER catalysts that are most effective, but their high cost and resource scarcity have led to the recognition of the necessity to find non-noble metal catalysts. Good HER catalysts are used to prepare transition metal phosphides at a lower cost. However, inorganic phosphorus or organic phosphorus having toxicity is used as a phosphorus source in the preparation process.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a transition metal phosphide, the preparation method uses green and nontoxic phytic acid as a phosphorus source, the preparation process is green and environment-friendly, and the prepared transition metal phosphide has good HER catalytic activity.
The specific technical scheme is as follows:
the invention provides a preparation method of a transition metal phosphide, which comprises the following steps:
step 1: dissolving transition metal salt and an organic ligand in a solvent, adding a phytic acid solution, and heating to obtain a phytic acid-doped MOF material;
step 2: carbonizing the MOF material doped with the phytic acid to obtain the transition metal phosphide.
According to the invention, the transition metal salt and the organic ligand are dissolved in the solvent, the phytic acid is added, then the solvent heating is carried out, the metal ions can be coordinated with the organic ligand, the phytic acid has strong chelating capacity, 6 phosphate groups with negative electricity can be combined with metal cations, and the transition metal phosphide can be obtained after carbonization, so that the conductivity of the material is improved. The preparation method of the transition metal phosphide provided by the invention is simple, phosphorus is introduced by using non-toxic phytic acid, so that the preparation process of the transition metal phosphide is green and environment-friendly, and the electrode prepared from the transition metal phosphide obtained by the preparation method is tested in alkaline electrolyte, so that the material shows good HER catalytic activity and good stability.
The transition metal phosphide prepared by the preparation method of the transition metal phosphide provided by the invention is in a folded spherical shape.
In step 1 of the invention, the transition metal in the transition metal salt is selected from one or more of iron, cobalt and nickel;
the transition metal salt is one or more than two of cobalt nitrate hexahydrate, cobalt chloride, cobalt sulfate, ferric chloride hexahydrate, ferric nitrate, ferrous chloride, nickel nitrate hexahydrate, nickel chloride and nickel nitrate, preferably cobalt nitrate hexahydrate;
the organic ligand is selected from terephthalic acid, trimesic acid or dimethyl imidazole, and is preferably dimethyl imidazole;
the solvent is one or more than two of deionized water, absolute ethyl alcohol and N, N dimethylformamide, preferably a mixed solvent of the absolute ethyl alcohol and the N, N dimethylformamide, and the volume ratio of the absolute ethyl alcohol to the N, N dimethylformamide is preferably 2: 3.
the dosage ratio of the transition metal salt, the organic ligand and the phytic acid solution is 1mol:0.01mL to 1mol, 2mol, 0.06mL, preferably 1mol, 2mol, 0.3 mL;
the concentration of the phytic acid solution is 10-50 wt%, and preferably 25 wt%;
the heating temperature is 110-130 ℃, the time is 24h, and the reaction is preferably carried out for 24h at 120 ℃; the heating is carried out in a tube furnace;
the MOF material in the phytic acid-doped MOF material is MIL-101(Fe), MIL-101(Fe, Co), MIL-101(Fe, Ni), ZIF-67(Co, Fe) or ZIF-67(Co, Ni), preferably ZIF-67;
when the transition metal in the transition metal salt is iron and cobalt, the molar ratio of the iron to the cobalt is 2: (1-3);
when the transition metal in the transition metal salt is cobalt and nickel, the molar ratio of the cobalt to the nickel is 2: (1-3).
Before step 2, the method further comprises the following steps: drying the phytic acid doped MOF material;
in step 2 of the present invention, the carbonization specifically comprises: heating to 250-450 deg.C at 2-5 deg.C/min, and holding for 2-4 h, preferably heating to 350 deg.C at 2 deg.C/min, and holding for 4 h.
The carbonization is performed under an atmosphere of nitrogen or an inert gas.
The invention also provides the application of the transition metal phosphide prepared by the preparation method in hydrogen evolution reaction.
According to the technical scheme, the invention has the following advantages:
the invention provides a preparation method of transition metal phosphide, which comprises the steps of dissolving transition metal salt and organic ligand in a solvent, adding phytic acid, carrying out solvothermal reaction to obtain a phytic acid-doped MOF material, and then carbonizing the material in one step to obtain the transition metal phosphide. In the preparation method, metal ions can be coordinated with an organic ligand, phytic acid has strong chelating capacity, 6 phosphate radicals with negative electricity can be combined with metal cations, and then transition metal phosphide is obtained through carbonization; according to the preparation method, phosphorus is introduced by using non-toxic phytic acid, so that the preparation process of the transition metal phosphide is green and environment-friendly, and when an electrode prepared from the transition metal phosphide obtained by the preparation method is tested in alkaline electrolyte, the material shows good HER catalytic activity and good stability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a graph showing the results of XRD characterization of phytic acid doped MOF materials prepared in examples 1, 2 and 3 of the present invention;
FIG. 2 is a scanning electron micrograph of a transition metal phosphide prepared in example 1 of the present invention;
FIG. 3 is a graph showing the results of XRD characterization of transition metal phosphides produced in examples 1, 2 and 3 of the present invention;
FIG. 4 is a graph showing the results of XRD characterization of phytic acid doped MOF materials prepared in examples 4, 5 and 6 of the present invention;
FIG. 5 is a graph showing the results of XRD characterization of transition metal phosphides obtained in examples 4, 5 and 6 of the present invention;
FIG. 6 is a graph showing the results of HER tests using transition metal phosphide catalysts prepared in examples 1, 2 and 3 of the present invention;
FIG. 7 is a graph showing the results of HER tests using transition metal phosphide catalysts prepared in examples 4, 5 and 6 of the present invention.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example is a preparation of a transition metal phosphide, specifically including the following steps:
dissolving 0.475g of cobalt nitrate hexahydrate in 10mL of a mixed solution of ethanol and N, N-dimethylformamide (V is 2:3), dissolving 0.246g of dimethylimidazole in 10mL of a mixed solution of ethanol and N, N-dimethylformamide (V is 2:3), respectively carrying out ultrasonic homogenization, transferring the two solutions into a polytetrafluoroethylene inner container of a reaction kettle, adding 0.03mL of phytic acid solution (the concentration of the phytic acid solution is 25 wt%, and the phytic acid solution is diluted by 50 wt% through ethanol), reacting at 120 ℃ for 24 hours, and then washing and centrifuging for 3 times through ethanol to obtain the phytic acid-doped MOF material. And (3) drying the material in a vacuum drying oven at 60 ℃, and maintaining the dried material for 4 hours at the temperature of 350 ℃ at the temperature of 2 ℃/min in an argon down-tube furnace to obtain the transition metal phosphide.
Fig. 1 is an XRD pattern of the MOF material doped with phytic acid of the present example, fig. 2 is a scanning electron micrograph of the transition metal phosphide of the present example, and fig. 3 is an XRD pattern of the transition metal phosphide. As can be seen from FIG. 1, this example successfully produced phytic acid doped MOF materials. As can be seen from fig. 1 and 2, the transition metal phosphide was successfully produced in this example, and the transition metal phosphide had a wrinkled spherical shape.
Example 2
This example is a preparation of a transition metal phosphide, which is similar to example 1 except that: the metal salt cobalt nitrate hexahydrate is replaced by cobalt nitrate hexahydrate and nickel chloride hexahydrate, wherein the molar ratio is 2:1, and the mass is 0.582g and 0.237g respectively.
FIG. 3 is an XRD pattern of the transition metal phosphide of the present example. As can be seen from FIGS. 1 and 3, this example successfully produced phytic acid doped MOF materials and transition metal phosphides.
Example 3
This example is a preparation of a transition metal phosphide, which is similar to example 1 except that: the transition metal salt cobalt nitrate hexahydrate is replaced by cobalt nitrate hexahydrate and ferric chloride hexahydrate, wherein the molar ratio is 2:1, and the mass is 0.582g and 0.270g respectively.
As can be seen from FIGS. 1 and 3, this example successfully produced phytic acid doped MOF materials and transition metal phosphides.
Example 4
This example is a preparation of a transition metal phosphide, the preparation method is the same as that of example 1, and the difference between this example and example 1 is that transition metal salt cobalt nitrate hexahydrate is replaced by ferric chloride hexahydrate, the mass is 0.675 g; the organic ligand dimethyl imidazole was replaced with terephthalic acid, and the mass was 0.31 g.
Fig. 4 is an XRD pattern of the phytic acid doped MOF material of this example, and fig. 5 is an XRD pattern of the transition metal phosphide of this example. As can be seen from FIGS. 4 and 5, this example successfully produced phytic acid doped MOF materials and transition metal phosphides.
Example 5
This example is a preparation of a transition metal phosphide, which is similar to example 1 except that: replacing transition metal salt cobalt nitrate hexahydrate with ferric trichloride hexahydrate and cobalt nitrate hexahydrate at a molar ratio of 2:1, wherein the mass of the transition metal salt cobalt nitrate hexahydrate is 0.291g and 0.540g respectively; the organic ligand dimethyl imidazole was replaced with terephthalic acid, and the mass was 0.31 g.
As can be seen from FIGS. 4 and 5, this example successfully produced phytic acid doped MOF materials and transition metal phosphides.
Example 6
This example is a preparation of a transition metal phosphide, which is similar to example 1 except that: the transition metal salt cobalt nitrate hexahydrate is replaced by ferric trichloride hexahydrate and nickel chloride hexahydrate, the molar ratio is 2:1, and the mass is 0.540g and 0.237g respectively; the organic ligand dimethyl imidazole was replaced with terephthalic acid, and the mass was 0.31 g.
As can be seen from FIGS. 4 and 5, this example successfully produced phytic acid doped MOF materials and transition metal phosphides.
Example 7
This example is an example of the transition metal phosphide prepared in examples 1 to 6 as a HER catalyst, and electrochemical performance test was performed thereon.
Electrochemical performance testing was performed on an Ivium electrochemical workstation in the netherlands, using a traditional three-electrode system, a spectrally pure graphite rod (purity 99.999%) as a counter electrode, and Hg | HgO as a reference electrode. Dispersing 2mg of catalyst in 200 mul of 0.25 wt% polytetrafluoroethylene ethanol solution, performing ultrasonic dispersion treatment to form uniform slurry to obtain catalyst homogenate, transferring the catalyst homogenate to a pre-polished glassy carbon electrode to obtain a working electrode, wherein the loading amount of the catalyst on the working electrode is 2mg cm-2The prepared electrodes were all dried overnight before being subjected to electrochemical testing. Electrochemical performance tests are carried out in a 1M KOH electrolyte solution, nitrogen is introduced in advance, and potentials are compensated by IR through Thale software carried by the instrument. The measurement of polarization curve is carried out by linear sweep voltammetry, and hydrogen evolution reaction takes-0.5V as initial potential and 0.2mV s-1The rate of (2) was swept to-1.5V. The electrocatalytic activity of the catalyst was measured in a standard three-electrode system, with the potential transferred to the Reversible Hydrogen Electrode (RHE) potential. The equation for calibrating SCE to RHE is as follows: evs RHE ═ Evs Hg/HgO +0.059 pH + 0.095.
FIG. 6 is a graph showing the results of HER tests using the transition metal phosphides obtained in examples 1, 2 and 3 as catalysts, and FIG. 7 is a graph showing the results of HER tests using the transition metal phosphides obtained in examples 4, 5 and 6 as catalysts. As can be seen from FIGS. 6 and 7, the peak area is at-10 mAcm-2Overpotentials of practical examples 1 to 6, respectivelyThe compounds show obvious HER catalytic activity at 116mV, 132mV, 110mV, 180mV, 165mV and 152 mV.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a transition metal phosphide is characterized by comprising the following steps:
step 1: dissolving transition metal salt and an organic ligand in a solvent, adding a phytic acid solution, and heating to obtain a phytic acid-doped MOF material;
step 2: carbonizing the MOF material doped with the phytic acid to obtain the transition metal phosphide.
2. The method according to claim 1, wherein the transition metal in the transition metal salt in step 1 is one or more selected from iron, cobalt and nickel.
3. The method according to claim 1, wherein the transition metal salt is one or more of cobalt nitrate hexahydrate, cobalt chloride, cobalt sulfate, ferric chloride hexahydrate, ferric nitrate, ferrous chloride, nickel nitrate hexahydrate, nickel chloride, and nickel nitrate.
4. The preparation method according to claim 1, wherein the MOF material in the phytic acid doped MOF material is MIL-101, ZIF-67 or ZIF-67.
5. The process according to claim 1, wherein the organic ligand is selected from terephthalic acid, trimesic acid and dimethylimidazole.
6. The preparation method according to claim 1, wherein the transition metal salt, the organic ligand and the phytic acid are used in a ratio of 1mol:1mol:0.01mL to 1mol:2mol:0.06 mL;
the concentration of the phytic acid solution is 10-50 wt%.
7. The preparation method according to claim 1, wherein the heating temperature is 110-130 ℃ and the time is 24 h;
the carbonization is specifically as follows: heating to 250-450 ℃ at the speed of 2-5 ℃/min, and preserving the heat for 2-4 h.
8. The method according to claim 2, wherein when the transition metal in the transition metal salt is iron and cobalt, the molar ratio of iron to cobalt is 2: (1-3);
when the transition metal in the transition metal salt is cobalt and nickel, the molar ratio of the cobalt to the nickel is 2: (1-3).
9. The method according to claim 1, wherein the solvent is one or more of deionized water, absolute ethyl alcohol, and N, N-dimethylformamide.
10. Use of a transition metal phosphide produced by the production method as set forth in any one of claims 1 to 9 in a hydrogen evolution reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110308913.XA CN113061930A (en) | 2021-03-23 | 2021-03-23 | Preparation method of transition metal phosphide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110308913.XA CN113061930A (en) | 2021-03-23 | 2021-03-23 | Preparation method of transition metal phosphide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113061930A true CN113061930A (en) | 2021-07-02 |
Family
ID=76563158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110308913.XA Pending CN113061930A (en) | 2021-03-23 | 2021-03-23 | Preparation method of transition metal phosphide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113061930A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115636948A (en) * | 2022-11-03 | 2023-01-24 | 国营芜湖机械厂 | Preparation method of Fe-P composite stealth material |
| CN116037062A (en) * | 2022-12-21 | 2023-05-02 | 福州大学 | Preparation of magnetic yolk shell nitrogen-phosphorus doped carbon nanocage material and application of magnetic yolk shell nitrogen-phosphorus doped carbon nanocage material in detection of euglena bretter toxin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106573225A (en) * | 2014-06-10 | 2017-04-19 | 剑桥企业有限公司 | Metal-organic frameworks |
| CN110732331A (en) * | 2019-09-04 | 2020-01-31 | 江苏大学 | method for preparing amorphous iron-nickel-phosphorus compound composite carbon electrocatalytic material |
| CN112010361A (en) * | 2020-08-02 | 2020-12-01 | 北京理工大学 | Preparation method for synthesizing heteroatom-doped nickel sulfide with various shapes by using metal organic framework |
| CN112354549A (en) * | 2020-10-23 | 2021-02-12 | 福建师范大学 | Preparation method of metal composite porous nanosheet |
-
2021
- 2021-03-23 CN CN202110308913.XA patent/CN113061930A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106573225A (en) * | 2014-06-10 | 2017-04-19 | 剑桥企业有限公司 | Metal-organic frameworks |
| CN110732331A (en) * | 2019-09-04 | 2020-01-31 | 江苏大学 | method for preparing amorphous iron-nickel-phosphorus compound composite carbon electrocatalytic material |
| CN112010361A (en) * | 2020-08-02 | 2020-12-01 | 北京理工大学 | Preparation method for synthesizing heteroatom-doped nickel sulfide with various shapes by using metal organic framework |
| CN112354549A (en) * | 2020-10-23 | 2021-02-12 | 福建师范大学 | Preparation method of metal composite porous nanosheet |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115636948A (en) * | 2022-11-03 | 2023-01-24 | 国营芜湖机械厂 | Preparation method of Fe-P composite stealth material |
| CN116037062A (en) * | 2022-12-21 | 2023-05-02 | 福州大学 | Preparation of magnetic yolk shell nitrogen-phosphorus doped carbon nanocage material and application of magnetic yolk shell nitrogen-phosphorus doped carbon nanocage material in detection of euglena bretter toxin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109967100B (en) | Metal-doped CoP3Preparation method and application thereof | |
| Zheng et al. | Nickel–copper bimetal organic framework nanosheets as a highly efficient catalyst for oxygen evolution reaction in alkaline media | |
| CN109019554A (en) | A kind of nitrogen-phosphor codoping multiporous biological matter carbon material and preparation method thereof and the application in supercapacitor | |
| CN110518261A (en) | The preparation method of nitrogen-phosphor codoping carbon nanotube cladding ferro-cobalt bimetallic alloy original position electrode | |
| CN113061930A (en) | Preparation method of transition metal phosphide | |
| CN112349920A (en) | Preparation of iron-nitrogen co-doped porous carbon sphere electrocatalyst | |
| CN110560117A (en) | Bimetallic cobalt ruthenium-nitrogen phosphorus doped porous carbon electrocatalyst and preparation method and application thereof | |
| Zhang et al. | Coral-like hierarchical architecture self-assembled by cobalt hexacyanoferrate nanocrystals and N-doped carbon nanoplatelets as efficient electrocatalyst for oxygen evolution reaction | |
| CN112708906A (en) | Preparation method of nitrogen-doped porous carbon-coated nickel-cobalt bimetallic phosphide nanorod array electrode | |
| CN110273162B (en) | Iron/cobalt/nickel-nitrogen coupled carbon-based composite material and application thereof | |
| CN113026045A (en) | Foam nickel loaded Ni (OH)2Preparation method of/FeOOH nano-flower material | |
| CN111957336A (en) | Preparation method of ZIF-8-derived Fe-N-C oxygen reduction electrocatalyst | |
| CN105449230A (en) | LaCoO3/N-rGO compound and preparation method and application method therefor | |
| CN113594479A (en) | Preparation method of Fe and N co-doped porous carbon zinc air battery catalyst | |
| CN112938966B (en) | Phosphorus and nitrogen co-doped iron monoatomic carbon material and preparation method and application thereof | |
| CN111204761B (en) | Method for electrochemically reducing carbon dioxide by combining ionic liquid and nitrogen-doped porous carbon material | |
| CN113235076A (en) | Preparation method and application of phosphorus-doped passivated foamed nickel | |
| CN110137523B (en) | Hydrogen-making hydrazine hydrate fuel cell device | |
| CN111188057A (en) | Preparation method of self-supporting composite electrode material | |
| CN113684499B (en) | Preparation method and application of nickel-nitrogen co-doped carbon-based catalyst with high metal loading efficiency | |
| JP2020104083A (en) | Electrode catalyst, method for producing the same, and method for producing hydrogen | |
| CN112007671B (en) | Fe1Co6-P @ CC electrocatalyst and preparation method thereof | |
| CN110065932B (en) | Lithium insertion type selenium compound, and preparation method and application thereof | |
| CN110280316A (en) | A kind of metal phosphide and its preparation method and application based on MOF gel | |
| CN113451593B (en) | Preparation method and application of amorphous nitrogen-doped ferrocobalt phosphate micro-tablet |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210702 |
|
| RJ01 | Rejection of invention patent application after publication |