CN112354549A - Preparation method of metal composite porous nanosheet - Google Patents
Preparation method of metal composite porous nanosheet Download PDFInfo
- Publication number
- CN112354549A CN112354549A CN202011146637.3A CN202011146637A CN112354549A CN 112354549 A CN112354549 A CN 112354549A CN 202011146637 A CN202011146637 A CN 202011146637A CN 112354549 A CN112354549 A CN 112354549A
- Authority
- CN
- China
- Prior art keywords
- metal
- porous nanosheet
- metal composite
- compound
- nanosheet
- 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
- 239000002135 nanosheet Substances 0.000 title claims abstract description 66
- 239000002905 metal composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 238000004729 solvothermal method Methods 0.000 claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- -1 2-methylimidazole compound Chemical class 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052810 boron oxide Inorganic materials 0.000 claims description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 229940068041 phytic acid Drugs 0.000 claims description 2
- 235000002949 phytic acid Nutrition 0.000 claims description 2
- 239000000467 phytic acid Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 13
- 229910017052 cobalt Inorganic materials 0.000 description 11
- 239000010941 cobalt Substances 0.000 description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 4
- 239000013384 organic framework Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QAXZWHGWYSJAEI-UHFFFAOYSA-N n,n-dimethylformamide;ethanol Chemical compound CCO.CN(C)C=O QAXZWHGWYSJAEI-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a metal composite porous nanosheet. The method comprises the following steps: adding Fe, Co and Ni metal salt or compound metal salt thereof into an organic/inorganic mixed solvent, and then adding 1-methylimidazole or 2-methylimidazole compound; transferring the mixture into a solvothermal reaction kettle for thermal reaction, and filtering, washing and drying the mixture after the thermal reaction to obtain a metal organic framework compound nanosheet; placing the metal organic framework compound in a tube furnace for heat treatment to obtain a metal oxide porous nanosheet; placing the metal oxide porous nanosheet in the center of the tubular furnace again, and placing a heteroatom compound at the front end of the airflow; and cleaning for three times, and then carrying out secondary heat treatment to prepare the metal composite porous nanosheet. The preparation method has low requirements on instruments and equipment, strong controllability, simple flow, easy amplification preparation and strong applicability to various metals. The prepared metal composite material has obvious performance in the field of electrocatalysis, can be applied to various electrocatalysis reactions, and has wide application prospect.
Description
Technical Field
The invention relates to a preparation method of a metal composite porous nanosheet, and belongs to the field of electrocatalysis of a material synthesis technology.
Background
Since the twenty-first century, a great deal of new inventions and technologies in the field of electrochemical energy gradually bring great convenience to production and life of modern society. These typical technologies include fuel cell, metal-air battery, water electrolysis to produce hydrogen, electrochemical organic fuel and ammonia synthesis, which are considered as one of the core elements of the next generation electrochemical energy technology. In these new energy technologies, the reaction processes involved include oxygen reduction (ORR) and Oxygen Evolution (OER) reactions, Hydrogen Oxidation (HOR) and Hydrogen Evolution (HER) reactions, and various organic small molecule oxidation reactions. The rate and energy consumption of these reactions determine the efficiency of the above electrochemical energy conversion techniques and the extent to which they are applied. In order to accelerate the progress of these reactions and to reduce their overpotentials, highly efficient and stable electrocatalysts are required. According to the research reported at present, the transition metals Fe, Co and Ni are cheap catalytic materials, have optimizable partial hollow d-orbital electronic structures and crystalline/amorphous structures, and show wide application prospects in various electrocatalysis. The structural design of the catalyst is one of the most important factors determining various properties of the catalyst, including activity, stability and selectivity. Considering from the micro-nano scale, the two-dimensional structure material has the very obvious advantages that: large specific surface area, good mechanical properties, high thermoelectric conductivity. Thus, the two-dimensional structure material satisfies essential elements in the electrocatalytic process, for example, more surface active sites, better catalytic durability and electron transfer characteristics. To further improve the electrocatalytic properties of secondary structure materials by enhancing mass transfer efficiency, abundant pore structures can be fabricated on the surface of the two-dimensional structure. However, up to now, the porous two-dimensional structure metal-based material still lacks a universal synthesis method.
In the invention, a solvent thermal method is utilized to firstly grow metal organic framework compound nanosheets, then the nanosheets are subjected to heat treatment in the air to form pores, and the nanosheets are further subjected to thermal doping or chemical combination to form the two-dimensional metal composite nanosheets with porous structures. The synthesis process form adopted by the method has strong universality and lower requirements on instruments and equipment, and is suitable for large-scale production. The application of the porous nanosheet catalytic material in the electrocatalytic hydrogen and oxygen evolution shows a wide application prospect.
Disclosure of Invention
The invention aims to overcome the problems of mass transfer bottleneck, low electrocatalytic activity and stability and the like in electrocatalytic reaction, prepare a metal composite material with a porous two-dimensional structure by a simple solvothermal process and heat treatment in air atmosphere and other atmospheres, and realize the application of the metal composite material in electrochemical catalytic reaction. The invention provides a preparation method and application field of a metal composite porous nanosheet, and the typical synthesis characteristics are solvothermal treatment and under-air heat treatment, the typical structural characteristics are the formation of a metal organic framework nanosheet and the formation of an oxide/composite porous nanosheet, and the typical composition characteristics of a catalyst are a single-component or multi-component metal composite material of Fe, Co and Ni.
The technical scheme adopted for realizing the purpose of the invention is as follows:
(1) adding 0.1-40 g of Fe, Co and Ni metal salt or multiple Fe, Co and Ni compound metal salt into each liter of organic/inorganic mixed solvent, adding 0.1-30 g of 1-methylimidazole or 2-methylimidazole compound, and rapidly stirring the mixed solution to completely dissolve the mixed solution;
the mixed solvent is a mixed solvent of any two or three of water, ethanol and DMF;
the Fe, Co and Ni metal salts refer to nitrate, chloride and sulfate;
the compound metal salt refers to nitrate, chloride and sulfate compounded by any two or three of Fe, Co and Ni.
(2) Quickly transferring the mixed solution obtained in the step (1) into a solvothermal reaction kettle for solvothermal reaction, cooling and filtering a reactant after the reaction is finished, washing the reactant for 3-5 times by using deionized water, and drying the reactant in a drying oven to obtain a metal organic framework compound;
the solvent is subjected to thermal reaction at the temperature of 100-250 ℃ for 1-72 hours.
(3) Placing the metal organic framework compound obtained in the step (2) in a tubular furnace, carrying out heat treatment in the air atmosphere, and cooling to obtain a corresponding metal oxide porous nanosheet;
the heat treatment is carried out at the temperature of 200-1000 ℃ for 1-48 hours.
(4) Placing the metal oxide porous nanosheet obtained in the step (3) in the center of the tubular furnace again, and placing the easily-decomposed heteroatom compound at the front end of the airflow; vacuumizing and cleaning in protective gas atmosphere for three times, and then carrying out secondary heat treatment to prepare the metal composite porous nanosheet;
the easily decomposed heteroatom compounds are sodium hypophosphite, melamine, dicyandiamide, boron oxide, phytic acid and sulfur;
the protective gas is Ar gas, N2，CO2，Ar/H2And NH3；
The secondary heat treatment is carried out at the temperature of 200-1000 ℃ for 1-12 hours.
Compared with the existing synthesis method of the porous nanosheet material and the synthesized metal porous nanosheet material, the metal composite porous nanosheet material and the preparation method thereof have the following obvious synthesis and structure characteristics:
(1) in the general preparation process of the porous nano-sheet material, the control requirement on the synthesis condition is strict, and the synthesis process is complicated. The synthesis process involved in the invention is simple, each step is mature, and the controllability is strong. In addition, the synthesis process related to the method has low requirements on instrument conditions, the efficiency of the whole process is high, and the method is favorable for large-scale production.
(2) The synthesis of the common porous nano sheet material is difficult to realize the regulation and control of material elements. According to the preparation method, various component elements of the porous nanosheet are regulated and controlled through selection of metal salts in solvothermal, heat treatment in air atmosphere and combined heat treatment of a compound containing heteroatom, and the preparation method has wide applicability to synthesis of different types of metal porous nanosheets.
(3) Compared with the commonly synthesized metal composite porous nano sheet material. The metal composite porous nanosheet material synthesized in the invention also contains a certain amount of carbon component doping, so that the electric conductivity of the synthesized material can be effectively improved (the single metal composite material is generally poor in electric conductivity), and the electrocatalytic efficiency and the current density can be improved in the electrocatalytic process.
The metal composite porous nanosheet material can effectively utilize the rigidity of the nanosheet structure to improve the stability, utilize the porous structure to improve the mass transfer efficiency, and utilize the multi-component controllability and the larger specific surface area of the porous nanosheet to improve the catalytic activity, so that the metal composite porous nanosheet material is a porous nanosheet electrocatalyst with very good application prospect.
Drawings
Fig. 1 is a high-low magnification TEM characterization of the oxyphosphorus-doped cobalt porous nanoplates prepared in example 1;
figure 2 is an XPS characterization of the oxyphosphorus-doped cobalt porous nanoplates prepared in example 1;
fig. 3 is the electrolytic water performance of the oxygen-phosphorus doped cobalt porous nanosheet prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1
Preparation and physical/electrochemical characterization of oxygen-phosphorus doped cobalt porous nanosheet
(1) Preparation of metal organic framework compound: 1g of cobalt nitrate hexahydrate was mixed with 60ml of a water-ethanol-DMF mixed solvent (volume ratio: 1: 1), and stirred to uniformly dissolve the metal salt. 0.5g of 2-methylimidazole is added rapidly and dissolved with stirring. Transferring the mixed solution into a 100ml solvent thermal reaction kettle with Teflon, packaging and carrying out reaction solvent thermal reaction for 12h at 160 ℃. After cooling, washing with deionized water for several times, and vacuum drying at 80 ℃ overnight to obtain the cobalt organic framework compound nanosheet.
(2) Preparation of metal oxide/compound porous nanosheet: and (2) putting 200mg of the cobalt organic framework compound nanosheet into a porcelain boat, putting the porcelain boat into a tube furnace, heating to 500 ℃ at the speed of 5 ℃/min under the air atmosphere, and keeping for 1 hour to prepare the cobaltosic oxide porous nanosheet. 200mg of the above cobaltosic oxide powder was placed in a porcelain boat and placed in the center of a tube furnace, and 4g of sodium hypophosphite was placed in the porcelain boat and placed in front of the air flow in the tube furnace, with a distance of about 20cm between the two samples. Vacuumizing, introducing Ar gas, cleaning for 3 times, heating to 350 ℃ at the speed of 5 ℃/min under the condition that the Ar flow rate is 15sccm, keeping for 4 hours, and cooling to obtain the oxygen-phosphorus doped cobalt porous nanosheet.
Characterization of the oxygen-phosphorus doped cobalt porous nanosheet:
fig. 1 is a high-low magnification TEM image of the synthesized oxygen-phosphorus doped cobalt porous nanosheet, indicating that the material has a porous nanosheet structure.
FIG. 2 is an XPS diagram of the synthesized oxygen-phosphorus doped cobalt porous nanosheet, and shows that the composite material contains Co, O, P and other elements.
Fig. 3 is the performance of the composite material in water electrolysis in 1M KOH solution, which shows that the oxygen-phosphorus doped cobalt porous nanosheet has higher activity than the oxide porous nanosheet and the metal organic framework compound alone.
Example 2
Preparation of oxygen-phosphorus doped nickel-iron porous nanosheet
0.5g of nickel chloride and ferric chloride are dissolved in 60ml of ethanol-DMF mixed solvent under the stirring action (the volume ratio is 1: 1), 1g of 2-methylimidazole is rapidly added and the mixture is stirred and dissolved. Transferring the mixed solution into a solvothermal reaction kettle, and carrying out solvothermal reaction for 12h at 180 ℃. And after cooling, washing with deionized water for several times, and drying overnight in vacuum at 80 ℃ to obtain the nickel-iron organic framework compound nanosheet. And (3) heating 100mg of the nickel-iron organic framework compound nanosheet to 500 ℃ at a speed of 10 ℃/min in a tubular furnace under an air atmosphere, and keeping for 3 hours to prepare the nickel oxide/iron oxide porous nanosheet. And (3) heating all the nickel oxide/iron oxide porous nanosheets and 2g of sodium hypophosphite to 350 ℃ at the speed of 5 ℃/min in a tube furnace under the protection of Ar gas, keeping the temperature for two hours, and cooling to prepare the oxygen-phosphorus doped ferronickel porous nanosheets.
Example 3
Preparation of boron-doped nickel porous nanosheet
Mixing 2g of nickel sulfate with 60ml of a water-ethanol-DMF mixed solvent (volume ratio is 1: 1: 1), stirring for dissolution, adding 2g of 1-methylimidazole, and quickly stirring for dissolution. Transferring the mixed solution into a solvothermal reaction kettle, and carrying out solvothermal reaction for 24 hours at the temperature of 180 ℃. After cooling, it was washed several times with deionized water and ethanol and dried in a freeze-drying oven 24. Placing 5g of boric acid at the front end of the tube furnace, placing 200mg of the obtained sample in the middle of the tube furnace, heating to 700-900 ℃ at the speed of 10 ℃/min under the protection of argon-hydrogen atmosphere, keeping for 1 hour, and cooling to obtain the boron-doped nickel porous nanosheet.
It should be understood that the above description is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (9)
1. A preparation method of a metal composite porous nanosheet is characterized by comprising the following steps:
(1) adding 0.1-40 g of Fe, Co and Ni metal salt or multiple Fe, Co and Ni compound metal salt into each liter of organic/inorganic mixed solvent, adding 0.1-30 g of 1-methylimidazole or 2-methylimidazole compound, and rapidly stirring the mixed solution to completely dissolve the mixed solution;
(2) quickly transferring the mixed solution obtained in the step (1) into a solvothermal reaction kettle for solvothermal reaction, cooling and filtering a reactant after the reaction is finished, washing the reactant for 3-5 times by using deionized water, and drying the reactant in a drying oven to obtain a metal organic framework compound;
(3) placing the metal organic framework compound obtained in the step (2) in a tubular furnace, carrying out heat treatment in the air atmosphere, and cooling to obtain a corresponding metal oxide porous nanosheet;
(4) placing the metal oxide porous nanosheet obtained in the step (3) in the center of the tubular furnace again, and placing the easily-decomposed heteroatom compound at the front end of the airflow; vacuumizing and cleaning in protective gas atmosphere for three times, and then carrying out secondary heat treatment to prepare the metal compound porous nanosheet.
2. A method for preparing metal composite porous nanosheet according to claim 1, wherein the mixed solvent is a mixed solvent of any two or three of water, ethanol, and DMF.
3. The method for preparing the metal composite porous nanosheet according to claim 1, wherein the metal salts of Fe, Co and Ni are nitrates, chlorides and sulfates.
4. The method for preparing the metal composite porous nanosheet according to claim 1, wherein the compounded metal salt is nitrate, chloride or sulfate compounded with any two or three of Fe, Co and Ni.
5. The method for preparing the metal composite porous nanosheet according to claim 1, wherein the solvothermal reaction is carried out at a temperature of 100-250 ℃ for 1-72 hours.
6. A preparation method of a metal composite porous nanosheet according to claim 1, wherein the heat treatment is carried out at a temperature of 200-1000 ℃ for 1-48 hours.
7. The method for preparing a metal composite porous nanosheet according to claim 1, wherein the readily decomposable heteroatom compound is sodium hypophosphite, melamine, dicyandiamide, boron oxide, phytic acid, sulfur.
8. The method for preparing porous nanosheet of metal composite according to claim 1, wherein the shielding gas is Ar gas, N2，CO2，Ar/H2And NH3。
9. The method for preparing the metal composite porous nanosheet as claimed in claim 1, wherein the secondary heat treatment is carried out at a temperature of 200-1000 ℃ for 1-12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011146637.3A CN112354549A (en) | 2020-10-23 | 2020-10-23 | Preparation method of metal composite porous nanosheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011146637.3A CN112354549A (en) | 2020-10-23 | 2020-10-23 | Preparation method of metal composite porous nanosheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112354549A true CN112354549A (en) | 2021-02-12 |
Family
ID=74511855
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011146637.3A Pending CN112354549A (en) | 2020-10-23 | 2020-10-23 | Preparation method of metal composite porous nanosheet |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112354549A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061930A (en) * | 2021-03-23 | 2021-07-02 | 广东工业大学 | Preparation method of transition metal phosphide |
| CN113258083A (en) * | 2021-03-24 | 2021-08-13 | 宁波工程学院 | CoXBifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof |
| CN113817287A (en) * | 2021-08-25 | 2021-12-21 | 中国地质大学（武汉） | Bio-based nano synergistic flame retardant and preparation method and application thereof |
| CN115224293A (en) * | 2022-08-17 | 2022-10-21 | 郑州大学 | ORR and OER bifunctional catalyst, and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120152845A1 (en) * | 2010-05-27 | 2012-06-21 | Vanderbilt University | Porous silica-metal organic composite adsorbents and methods of making and using the same |
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN106925330A (en) * | 2017-03-14 | 2017-07-07 | 福建医科大学 | A kind of lamellar structure composites of graphite-phase nitrogen carbide nanometer sheet/ZiF 67 |
| CN107252700A (en) * | 2017-06-26 | 2017-10-17 | 中国石油大学(华东) | A kind of catalytic center equally distributed many metal phosphide nano tube catalysts and low temperature preparation method |
| CN109055962A (en) * | 2018-08-29 | 2018-12-21 | 中北大学 | A kind of porous nitrogen-doped carbon nanometer pipe of flexible 3 D/phosphatization cobalt composite material and its preparation method and application |
| CN109590019A (en) * | 2017-09-30 | 2019-04-09 | 株式会社模范 | Catalyst and its preparation and the application of paraxylene are directly prepared for synthesis gas |
| CN109663608A (en) * | 2018-12-27 | 2019-04-23 | 北京印刷学院 | A kind of carbon-cobalt molybdenum double-metal phosphide composite material and preparation method |
| CN109967099A (en) * | 2019-03-11 | 2019-07-05 | 浙江大学 | A kind of Co with hollow nanostructures2P@C composite and its preparation method and application |
| CN110479271A (en) * | 2019-08-26 | 2019-11-22 | 西北师范大学 | It is a kind of for being electrolysed the preparation method of the two-dimentional nickel carbon nanosheet catalyst of aquatic products hydrogen |
| CN110639565A (en) * | 2018-06-27 | 2020-01-03 | 北京印刷学院 | Carbon-bimetal phosphide composite material and preparation method thereof |
| CN110773233A (en) * | 2019-08-28 | 2020-02-11 | 浙江工业大学 | Preparation method of electrocatalytic full-hydrolytic nanosheet array material |
-
2020
- 2020-10-23 CN CN202011146637.3A patent/CN112354549A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120152845A1 (en) * | 2010-05-27 | 2012-06-21 | Vanderbilt University | Porous silica-metal organic composite adsorbents and methods of making and using the same |
| CN105107536A (en) * | 2015-10-09 | 2015-12-02 | 清华大学 | Preparation method of polyhedral cobalt phosphide catalyst for hydrogen production through water electrolysis |
| CN106925330A (en) * | 2017-03-14 | 2017-07-07 | 福建医科大学 | A kind of lamellar structure composites of graphite-phase nitrogen carbide nanometer sheet/ZiF 67 |
| CN107252700A (en) * | 2017-06-26 | 2017-10-17 | 中国石油大学(华东) | A kind of catalytic center equally distributed many metal phosphide nano tube catalysts and low temperature preparation method |
| CN109590019A (en) * | 2017-09-30 | 2019-04-09 | 株式会社模范 | Catalyst and its preparation and the application of paraxylene are directly prepared for synthesis gas |
| CN110639565A (en) * | 2018-06-27 | 2020-01-03 | 北京印刷学院 | Carbon-bimetal phosphide composite material and preparation method thereof |
| CN109055962A (en) * | 2018-08-29 | 2018-12-21 | 中北大学 | A kind of porous nitrogen-doped carbon nanometer pipe of flexible 3 D/phosphatization cobalt composite material and its preparation method and application |
| CN109663608A (en) * | 2018-12-27 | 2019-04-23 | 北京印刷学院 | A kind of carbon-cobalt molybdenum double-metal phosphide composite material and preparation method |
| CN109967099A (en) * | 2019-03-11 | 2019-07-05 | 浙江大学 | A kind of Co with hollow nanostructures2P@C composite and its preparation method and application |
| CN110479271A (en) * | 2019-08-26 | 2019-11-22 | 西北师范大学 | It is a kind of for being electrolysed the preparation method of the two-dimentional nickel carbon nanosheet catalyst of aquatic products hydrogen |
| CN110773233A (en) * | 2019-08-28 | 2020-02-11 | 浙江工业大学 | Preparation method of electrocatalytic full-hydrolytic nanosheet array material |
Non-Patent Citations (2)
| Title |
|---|
| HONG LI ET AL: "MOF-Derived Ultrathin Cobalt Phosphide Nanosheets as Efficient Bifunctional Hydrogen Evolution Reaction and Oxygen Evolution Reaction Electrocatalysts", 《NANOMATERIALS》 * |
| SHOU FENG ET AL.: "Hydrothermal stable ZIF-67 nanosheets via morphology regulation strategy to construct mixed-matrix membrane for gas separation", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061930A (en) * | 2021-03-23 | 2021-07-02 | 广东工业大学 | Preparation method of transition metal phosphide |
| CN113258083A (en) * | 2021-03-24 | 2021-08-13 | 宁波工程学院 | CoXBifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof |
| CN113258083B (en) * | 2021-03-24 | 2022-09-06 | 宁波工程学院 | Co X Bifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof |
| CN113817287A (en) * | 2021-08-25 | 2021-12-21 | 中国地质大学（武汉） | Bio-based nano synergistic flame retardant and preparation method and application thereof |
| CN115224293A (en) * | 2022-08-17 | 2022-10-21 | 郑州大学 | ORR and OER bifunctional catalyst, and preparation method and application thereof |
| CN115224293B (en) * | 2022-08-17 | 2024-01-16 | 郑州大学 | ORR and OER dual-function catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108385124B (en) | Preparation method of transition metal/carbon tube/graphene electrocatalyst for hydrogen evolution reaction | |
| CN108554413B (en) | Three-dimensional multi-stage structure high-dispersion nickel-based electro-catalytic material and preparation method thereof | |
| CN107376958B (en) | NiFeP difunctional transition metal phosphide catalyst and preparation and application thereof | |
| CN112354549A (en) | Preparation method of metal composite porous nanosheet | |
| CN109524678B (en) | Oxygen evolution iron-cobalt alloy-cobalt ferrite/nitrogen doped carbon nanotube composite catalyst and preparation method and application thereof | |
| CN107252700B (en) | Multi-metal phosphide nanotube catalyst with uniformly distributed catalytic centers and low-temperature preparation method | |
| CN111659401B (en) | Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof | |
| CN101820066B (en) | Single metal/multi-wall carbon nano tube type composite material, preparation method and application thereof | |
| CN109811360B (en) | NiFeMo ternary electrolytic water electrode and preparation method thereof | |
| CN109967099A (en) | A kind of Co with hollow nanostructures2P@C composite and its preparation method and application | |
| CN110368969B (en) | Preparation method and application of heteroatom-doped molybdenum carbide hydrogen evolution catalyst loaded on carbon paper or carbon cloth | |
| Ye et al. | Self-supported three-dimensional Cu/Cu 2 O–CuO/rGO nanowire array electrodes for an efficient hydrogen evolution reaction | |
| CN107346826A (en) | A kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron | |
| CN111155146B (en) | Preparation method of vanadium-doped nickel phosphide composite nitrogen-sulfur double-doped reduced graphene oxide electrocatalytic material | |
| CN111036247B (en) | Cobalt-iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material and preparation method and application thereof | |
| Wu et al. | Mo, Co co-doped NiS bulks supported on Ni foam as an efficient electrocatalyst for overall water splitting in alkaline media | |
| CN111777102A (en) | Metal oxide-based bifunctional water decomposition nano material and preparation method thereof | |
| CN114875442A (en) | Ruthenium-modified molybdenum-nickel nanorod composite catalyst and preparation method and application thereof | |
| Xie et al. | Ultrasmall Co-NiP embedded into lantern shaped composite achieved by coordination confinement phosphorization for overall water splitting | |
| CN117187856A (en) | Preparation method of bifunctional phosphide catalyst and full water decomposition application thereof | |
| CN108832141A (en) | A kind of fuel cell honeycomb nickel cobalt boron alloy catalyst and preparation method thereof | |
| CN109926095B (en) | Cobalt-based oxygen evolution catalyst based on eutectic solvent, preparation method and electrocatalytic oxygen evolution application thereof | |
| Dai et al. | Facile fabrication of self-supporting porous CuMoO 4@ Co 3 O 4 nanosheets as a bifunctional electrocatalyst for efficient overall water splitting | |
| CN115961299A (en) | Zn 2 SnO 4 Preparation method and application of/ZnO nano material | |
| CN112779550B (en) | Three-dimensional micron tubular hydrogen evolution reaction electrocatalyst and preparation method 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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210212 |