CN111744520A - Heteroatom-doped carbon-coated metal bifunctional water decomposition nano material and preparation method thereof - Google Patents
Heteroatom-doped carbon-coated metal bifunctional water decomposition nano material and preparation method thereof Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 77
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 20
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 42
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- 239000002243 precursor Substances 0.000 claims abstract description 20
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 9
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 56
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- 150000003839 salts Chemical class 0.000 claims description 26
- 239000012924 metal-organic framework composite Substances 0.000 claims description 18
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- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- 239000002905 metal composite material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- 239000010949 copper Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- RYTYSMSQNNBZDP-UHFFFAOYSA-N cobalt copper Chemical compound [Co].[Cu] RYTYSMSQNNBZDP-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
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- 239000001301 oxygen Substances 0.000 description 10
- 239000002923 metal particle Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
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- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000002070 nanowire Substances 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
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- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 229920002521 macromolecule Polymers 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 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
- B01J27/24—Nitrogen compounds
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- B01J35/33—
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- 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
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- C25B1/04—Hydrogen or oxygen by electrolysis of water
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Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a heteroatom-doped carbon-coated metal bifunctional water decomposition nano material and a preparation method thereof. The invention prepares the metal precursor nanometer material by a coprecipitation method; then growing a metal organic framework on the surface of the metal precursor nano material; finally, preparing the heteroatom-doped carbon-coated metal bifunctional water decomposition nanometer material through limited-area thermal conversion. The invention utilizes the high specific surface area and the pore structure of the metal organic framework to limit the diffusion process of metal ions in the high-temperature heat treatment process, so that the metal ions are uniformly distributed in the heteroatom-doped carbon material; more metal-heteroatom chemical bonds are formed in the heat treatment process, and the doping content of heteroatoms in the carbon material is improved. The material prepared by the invention has the advantages of regular and ordered structure, good dispersibility, large specific surface area, excellent conductivity, good mechanical and chemical stability, simple process, low cost, safety, reliability and convenience for large-scale preparation.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a heteroatom-doped carbon-coated metal bifunctional water decomposition nano material and a preparation method thereof.
Background
The heteroatom-doped carbon-coated metal nano material has the advantages that the metal and the doped carbon have strong synergistic effect, so that the properties of the material in the aspect of electricity can be greatly improved, and the material is widely concerned by people.
The existing preparation method of heteroatom doped carbon-coated metal nano material mainly comprises the following steps: the method comprises the following steps of (1) simply and mechanically mixing, namely mechanically mixing the existing metal particles and the heteroatom-doped carbon material by a simple ultrasonic mode or a stirring mode. The disadvantages are that: poor uniformity, easy agglomeration, small synergistic effect and the like. ② in-situ sintering, wherein metal salt and carbon-containing precursor are uniformly mixed, and then heteroatom-doped carbon-coated material is obtained by high-temperature sintering, but the control of material in nano-scale is lacked, and metal particles are not uniform. And thirdly, self-assembling, namely obtaining various heteroatom-doped carbon-coated metal materials by utilizing a surfactant, polymer macromolecule surface modification, electrostatic attraction and the like in a self-assembling mode. The disadvantages of this method are: the material has poor conductivity, and the bonding force between the metal particles and the heteroatom-doped carbon material is weak, so that the metal particles and the heteroatom-doped carbon material are easily separated, the service life of the material is shortened, and the material is not favorable for further practical application. Deposition method, depositing carbon layer on the surface of metal particle through chemical vapor deposition, physical vapor deposition and electric deposition. The method has the disadvantages of long time consumption, expensive instrument and equipment and difficult batch production.
Therefore, the heteroatom-doped carbon-coated metal nanomaterial with a uniform structure is prepared by a practical and effective method, and has very important theoretical and practical significance in both basic scientific research and technical application.
Disclosure of Invention
The invention aims to provide a heteroatom-doped carbon-coated metal bifunctional decomposition water nanomaterial and a preparation method thereof, aiming at the problems that the fine structure of the heteroatom-doped carbon-coated metal nanomaterial is lack of effective control and the bifunctional decomposition water property is poor in the existing method.
The invention utilizes a limited-area thermal conversion method to prepare the heteroatom-doped carbon-coated metal nano material with excellent properties of fully decomposing water to generate hydrogen and generating oxygen. The method has the advantages of convenient operation, easy control, mass production and the like; and the obtained heteroatom doped carbon-coated metal nano material has excellent performances of good structural stability, strong synergistic effect, good conductivity and the like, and can be used as a functional material to be applied to the technology of preparing hydrogen by using an industrial water electrolyzer.
The invention provides a preparation method of a heteroatom-doped carbon-coated metal bifunctional water decomposition nanometer material, which comprises the steps of preparing a metal precursor nanometer material by a coprecipitation method; then growing a metal organic framework on the surface of the metal precursor nano material; finally, preparing the heteroatom-doped carbon-coated metal bifunctional decomposed water nanometer material through limited-domain thermal conversion; the method comprises the following specific steps:
(1) preparation of Metal precursors
Adding metal salt and ethylene glycol into the aqueous solution, and carrying out ultrasonic stirring treatment for 1-200 min to obtain a solution I; adding an alkali solution into the solution I, centrifuging and removing a supernatant, wherein a lower-layer precipitate is a metal precursor;
(2) preparation of metal/metal organic framework composite material
Dissolving the metal precursor prepared in the step (1), metal salt and polyvinylpyrrolidone into an organic solution, and carrying out ultrasonic treatment for 1-200 min to obtain a dispersion liquid I; dissolving dimethyl imidazole in an organic solvent, and carrying out ultrasonic treatment for 1-200 min to obtain a dispersion liquid II; adding the dispersion liquid II into the dispersion liquid I, reacting for 0.1-72 h, centrifuging and removing supernatant, wherein the lower-layer precipitate is the metal/metal organic framework composite material;
(3) preparation of heteroatom doped carbon-coated metal nano material
Heating the metal/metal organic framework composite material prepared in the step (2) to 600-1000 ℃ at a heating rate of 0.5-50 ℃/min, and carrying out inert atmosphere (such as N)2Ar) performing heat treatment for 0.1-5 h to obtain the heteroatom-doped carbon-coated bifunctional water decomposition nano material.
In the present invention, the metal salt in the step (1) is a metal salt different from the metal salt in the step (2).
In the invention, the metal salt in the step (1) is one or more of copper chloride, nickel chloride, cobalt chloride or ferric chloride.
In the invention, the mass ratio of the metal salt to the ethylene glycol in the step (1) is 1: 1-1: 10; the volume ratio of the metal salt solution to the alkali solution is 1: 1-1: 10.
In the invention, the metal salt in the step (2) is one of cobalt nitrate or zinc nitrate.
In the invention, the mass ratio of the metal precursor to the metal salt in the step (2) is 1: 0.5-1: 10; the mass ratio of the metal salt to the dimethyl imidazole is 1: 1-1: 10.
According to the heteroatom-doped carbon-coated metal nano material prepared by the invention, because the thermal decomposition properties of the metal precursor and the metal organic framework are completely different, metal ions are limited in the pore structure of the metal framework in the heat treatment process so as to prevent the metal ions from self-aggregating at a higher calcination temperature; meanwhile, the introduction of metal ions can further reserve the heteroatoms in the organic framework and improve the doping amount of the heteroatoms. The metal nano material has the characteristics of large specific surface area, good conductivity, controllable components, good mechanical stability and the like, can better realize the synergistic effect between metal particles and the heteroatom doped carbon material compared with simple mechanical mixing, and is more convenient for the heteroatom doped carbon coated metal nano material to realize functional application. For example, the method can be applied to the field of hydrogen preparation by decomposing water in an electrolytic bath.
The invention has the advantages that:
1. the method adopts the procedures of chemical coprecipitation, in-situ heat conversion and the like, has simple process and convenient operation, is beneficial to large-scale production and is convenient to popularize and apply;
2. the method is easy to regulate and control, and the components and the structure can be controlled by simply changing the proportion of adding the metal salt; therefore, the method can be widely applied to the preparation of various heteroatom doped carbon-coated metal nano materials;
3. the invention adopts cheap transition metal elements, has low cost and is easy to realize large-scale production.
Drawings
FIG. 1 shows Cu (OH) prepared in example 12Transmission Electron Microscopy (TEM) images of cobalt metal organic framework precursors.
Fig. 2 is a TEM image of the nitrogen-doped carbon-coated copper-cobalt nanomaterial prepared in example 1.
Fig. 3 is a graph of hydrogen evolution performance by decomposition of the nitrogen-doped carbon-coated copper-cobalt nanomaterial prepared in example 1.
Fig. 4 is a graph of water decomposition and oxygen generation performance of the nitrogen-doped carbon-coated copper cobalt particle nano-material prepared in example 1.
Detailed Description
The technical solution of the present invention is further described below with reference to the specific embodiments.
Example 1:
a preparation method of a heteroatom-doped carbon-coated metal bifunctional water decomposition nanometer material comprises the following specific steps:
（a） Cu(OH)2preparation of the precursor
180 mg of CuCl2 and 200 mg of ethylene glycol are dissolved in 200 mL of deionized water, and after uniform stirring, 1.2 mL of 6M NaOH solution is dropwise added into the solution, and then the solution is stirred for 30 min. And after the reaction is finished, centrifuging to obtain blue precipitate, repeatedly cleaning and centrifuging for 5 times by using deionized water and an ethanol solution, and finally obtaining the Cu (OH)2 nanowire.
（b） Cu(OH)2Preparation of metal organic framework composite material
30 mg of Cu (OH)2 nanowires obtained in step (a), 1 mmol of Co (NO)3)2And 200 mg of polyvinylpyrrolidone is dissolved in 25 mL of methanol solution, and ultrasonic treatment is carried out for 10 min to obtain dispersion I. And weighing 800 mg of 2-methylimidazole, dissolving in 25 mL of methanol solution, and performing ultrasonic treatment for 5min to obtain a dispersion liquid II. The dispersion II was added to the dispersion I and reacted at room temperature for 24 hours. The obtained precipitate is centrifugally washed by methanol for a plurality of times to finally obtain Cu (OH)2Cobalt metal organic framework composite material.
(c) Preparation of nitrogen-doped carbon-coated copper-cobalt nano material
1g of Cu (OH) obtained in step (b)2The cobalt metal organic framework composite material is subjected to heat treatment in an inert atmosphere at the heating rate of 3 ℃/min (the temperature is 800 ℃, and the time is 2 hours), so that the nitrogen-doped carbon-coated copper cobalt nano material is obtained.
Cu (OH) produced by the above-mentioned production process2The metal organic framework composite material is observed by a transmission electron microscope, and is shown in figure 1; and (3) observing the nitrogen-doped carbon-coated copper-cobalt nano material by a transmission electron microscope, wherein the observation is shown in figure 2, the electrocatalytic hydrogen evolution performance is tested, the observation is shown in figure 3, and the electrocatalytic oxygen generation property is tested, the observation is shown in figure 4.
From the analysis of the test results, it can be seen that the metal organic framework can be grown on the cu (oh)2 nanowires, and from the TEM image (fig. 1), it can be seen that the cu (oh)2 nanowires are uniformly dispersed in the metal organic framework. After the nitrogen-doped carbon-coated copper-cobalt nano material is converted by limited-area heat, metal particles are uniformly embedded in the porous carbon skeleton, and the size of the metal particles is 15-25 nm (shown in figure 2). Further proves that the metal organic framework has a limited domain effect on Cu ions, and the self-aggregation of the Cu ions in the heat treatment process is effectively prevented. Further, it is inferred that different heteroatom-doped carbon-coated metal particle nano materials can be prepared by the method. Meanwhile, the nitrogen-doped carbon-coated copper-cobalt nano material has good structural stability and corrosion resistance. Under a three-electrode system, the starting overpotential for decomposing water and hydrogen of the nitrogen-doped carbon-coated copper-cobalt nano material is 115 mV, and only 145 mV overpotential is needed to obtain 10 mA cm-2Current density of (2) (fig. 3); in the oxygen production reaction of decomposing water, 10 mA cm can be obtained under 345 mV overpotential-2Shows excellent water-splitting property (fig. 4).
Example 2:
the preparation method of the heteroatom-doped carbon-coated metal bifunctional water decomposition nanometer material is the same as that in example 1, wherein:
in the step (a), the mass ratio of the CuCl2 to the ethylene glycol is 1:1, and the volume ratio of the metal salt solution to the alkali solution is 1: 1; in the step (b), the metal precursor and Co (NO)3)2In a mass ratio of 1:0.5, the metalThe mass ratio of the salt to the dimethyl imidazole is 1: 1; in the step (c), the heating rate is 0.5 ℃/min, the heat treatment temperature is 600 ℃, and the heat treatment time is 0.1 h. The nitrogen-doped carbon-coated copper-cobalt nano material prepared in the embodiment obtains 10 mA cm in the hydrogen evolution reaction by decomposing water-2The overpotential of the current density was 298 mV; in the oxygen reaction for decomposing water, 10 mA cm is obtained-2The overpotential for the current density was 460 mV.
Example 3:
the preparation method of the heteroatom-doped carbon-coated metal bifunctional water decomposition nanometer material is the same as that in example 1, wherein:
in the step (a), the mass ratio of the CuCl2 to the ethylene glycol is 1:10, and the volume ratio of the metal salt solution to the alkali solution is 1: 10; in the step (b), a metal precursor and Co (NO)3)2The mass ratio of the metal salt to the dimethyl imidazole is 1:10, and the mass ratio of the metal salt to the dimethyl imidazole is 1: 10; in the step (c), the heating rate is 50 ℃/min, the heat treatment temperature is 1000 ℃, and the heat treatment time is 5 h. The nitrogen-doped carbon-coated copper-cobalt nano material prepared in the embodiment obtains 10 mA cm in the hydrogen evolution reaction by decomposing water-2The overpotential of the current density is 221 mV; in the oxygen reaction for decomposing water, 10 mA cm is obtained-2The overpotential for the current density was 412 mV.
Example 4:
in the step (b), 100 mg of Cu (OH)2 prepared in the step (a) is dissolved in 20 mL of methanol solution to obtain a mixed solution I, and 1.07 g of Zn (NO) is added3)2Dissolving in 50 mL of methanol solution, and performing ultrasonic treatment for 5min to obtain a solution II; dissolving 2.36 g of polyvinylpyrrolidone into 50 mL of methanol solution, and performing ultrasonic treatment for 5min to obtain a solution III; slowly adding the mixed solution I and the solution III into the solution II, and reacting for 24 hours at normal temperature to obtain Cu (OH)2A zinc metal organic framework composite material; in said step (c), 1g of Cu (OH) obtained in step (b) is added2The zinc/metal organic framework composite material is subjected to heat treatment in an inert atmosphere at the temperature rise rate of 10 ℃/min (the temperature is 1000 ℃, and the time is 3 hours) to obtain the nitrogen-doped carbon-coated copper-zinc nano material. In the reaction of decomposing water to separate out hydrogen, 10 mA cm was obtained-2The overpotential for the current density is 289 mV; in the oxygen reaction for decomposing water, 10 mA cm is obtained-2The overpotential for the current density was 438 mV.
Example 5:
the preparation method of the heteroatom-doped carbon-coated metal bifunctional water decomposition nanometer material is the same as that in example 1, wherein:
in the step (a), the metal salt is NiCl2, 360 mg of NiCl2 and 200 mg of ethylene glycol are dissolved in 200 mL of deionized water, 1.2 mL of 6M NaOH solution is dropwise added into the solution after the solution is uniformly stirred, and then the solution is stirred for 30 min. Centrifuging to obtain green precipitate, repeatedly washing with deionized water and ethanol solution for 5 times to obtain Ni (OH)2, dissolving 100 mg of Ni (OH)2 prepared in step (a) in 20 mL of methanol solution to obtain mixed solution I, and adding 1.07 g of Zn (NO)3)2Dissolving in 50 mL of methanol solution, and performing ultrasonic treatment for 5min to obtain a solution II; dissolving 2.36 g of polyvinylpyrrolidone into 50 mL of methanol solution, and performing ultrasonic treatment for 5min to obtain a solution III; slowly adding the mixed solution I and the solution III into the solution II, and reacting for 24 hours at normal temperature to obtain Ni (OH)2A zinc metal organic framework composite material; in said step (c), 1g of Ni (OH) obtained in step (b) is added2The zinc/metal organic framework composite material is subjected to heat treatment in an inert atmosphere at the temperature rise rate of 5 ℃/min (the temperature is 900 ℃ and the time is 3 hours) to obtain the nitrogen-doped carbon-coated nickel-zinc nano material. In the reaction of decomposing water to separate out hydrogen, 10 mA cm was obtained-2The overpotential for the current density was 174 mV; in the oxygen reaction for decomposing water, 10 mA cm is obtained-2The overpotential for the current density was 406 mV.
Example 6:
the preparation method of the heteroatom-doped carbon-coated metal bifunctional water decomposition nanometer material is the same as that in example 1, wherein:
in the step (a), the metal salt is NiCl2, 360 mg of NiCl2 and 200 mg of ethylene glycol are dissolved in 200 mL of deionized water, 1.2 mL of 6M NaOH solution is dropwise added into the solution after the solution is uniformly stirred, and then the solution is stirred for 30 min. Centrifuging after the reaction is finished to obtain green precipitate, and reusing the green precipitateRepeatedly washing with deionized water and ethanol solution, centrifuging for 5 times to obtain Ni (OH)2, dissolving 200 mg of Ni (OH)2 prepared in step (a) in 20 mL of methanol solution to obtain mixed solution I, and adding 291 mg of Co (NO)3)2And dissolving 400 mg of polyvinylpyrrolidone into 25 mL of methanol solution, and performing ultrasonic treatment for 10 min to obtain a dispersion liquid II. And weighing 800 mg of 2-methylimidazole, dissolving in 25 mL of methanol solution, and performing ultrasonic treatment for 5min to obtain a dispersion liquid III. Slowly adding the mixed solution I and the solution III into the solution II, and reacting for 12 h at normal temperature to obtain Ni (OH)2A metal organic framework composite material; in said step (c), 1g of Ni (OH) obtained in step (b) is added2The cobalt metal organic framework composite material is subjected to heat treatment in an inert atmosphere at the temperature rise rate of 10 ℃/min (the temperature is 800 ℃, and the time is 2 hours), so that the nitrogen-doped carbon-coated nickel-cobalt nano material is obtained. In the reaction of decomposing water to separate out hydrogen, 10 mA cm was obtained-2The overpotential of the current density was 161 mV; in the oxygen reaction for decomposing water, 10 mA cm is obtained-2The overpotential for the current density was 378 mV.
Example 7:
the preparation method of the heteroatom-doped carbon-coated metal bifunctional water decomposition nanometer material is the same as that in example 1, wherein:
in the step (a), the metal salts are CuCl2 and NiCl2, 129 mg of NiCl2 and 135 mg of CuCl2And 300 mg of ethylene glycol into 200 mL of deionized water, after stirring uniformly, dropwise adding 2.4 mL of 6M NaOH solution into the solution, and then stirring for 30 min. Centrifuging to obtain precipitate after reaction, repeatedly washing with deionized water and ethanol solution, centrifuging for 5 times to obtain Ni (OH)2/Cu (OH)2 complex, dissolving 200 mg of Ni (OH)2/Cu (OH)2 complex prepared in step (a) in 25 mL of methanol solution to obtain mixed solution I, and dissolving 291 mg of Co (NO)3)2And dissolving 400 mg of polyvinylpyrrolidone into 25 mL of methanol solution, and performing ultrasonic treatment for 10 min to obtain a dispersion liquid II. And weighing 800 mg of 2-methylimidazole, dissolving in 25 mL of methanol solution, and performing ultrasonic treatment for 5min to obtain a dispersion liquid III. Slowly adding the mixed solution I and the solution III into the solution II, and reacting for 12 h at normal temperature to obtain Ni (OH)2/Cu (OH) 2/cobaltA metal organic framework composite material; in the step (c), 1g of the Ni (OH)2/Cu (OH) 2/cobalt metal organic framework composite material obtained in the step (b) is subjected to heat treatment in an inert atmosphere at the temperature rise rate of 5 ℃/min (the temperature is 800 ℃, and the time is 2 h), so that the nitrogen-doped carbon-coated nickel-copper-cobalt nano material is obtained. In the reaction of decomposing water to separate out hydrogen, 10 mA cm was obtained-2The overpotential of the current density is 126 mV; in the oxygen reaction for decomposing water, 10 mA cm is obtained-2The overpotential for the current density was 332 mV.
Claims (6)
1. A preparation method of a heteroatom-doped carbon-coated metal bifunctional water decomposition nanometer material is characterized in that a metal precursor nanometer material is prepared by a coprecipitation method; then growing a metal organic framework on the surface of the metal precursor nano material; finally, preparing the heteroatom-doped carbon-coated metal bifunctional decomposed water nanometer material through limited-domain thermal conversion; the method comprises the following specific steps:
(1) preparation of Metal precursors
Adding metal salt and ethylene glycol into the aqueous solution, and carrying out ultrasonic stirring treatment for 1-200 min to obtain a solution I; adding an alkali solution into the solution I, centrifuging and removing a supernatant, wherein a lower-layer precipitate is a metal precursor;
(2) preparation of metal/metal organic framework composite material
Dissolving the metal precursor prepared in the step (1), metal salt and polyvinylpyrrolidone into an organic solution, and carrying out ultrasonic treatment for 1-200 min to obtain a dispersion liquid I; dissolving dimethyl imidazole in an organic solvent, and carrying out ultrasonic treatment for 1-200 min to obtain a dispersion liquid II; adding the dispersion liquid II into the dispersion liquid I, reacting for 0.1-72 h, centrifuging and removing supernatant, wherein the lower-layer precipitate is the metal/metal organic framework composite material;
the metal salt in the step (2) is different from the metal salt in the step (1);
(3) preparation of heteroatom doped carbon-coated metal nano material
And (3) heating the metal/metal organic framework composite material prepared in the step (2) to 600-1000 ℃ at a heating rate of 0.5-50 ℃/min, and carrying out heat treatment for 0.1-5 h in an inert atmosphere to prepare the heteroatom doped carbon coated bifunctional decomposition water nanometer material.
2. The preparation method according to claim 1, wherein the metal salt in step (1) is one or more of copper chloride, nickel chloride, cobalt chloride or ferric chloride.
3. The preparation method according to claim 1, wherein the mass ratio of the metal salt to the ethylene glycol in the step (1) is 1:1 to 1: 10; the volume ratio of the metal salt solution to the alkali solution is 1: 1-1: 10.
4. The method according to claim 1, wherein the metal salt in the step (2) is one of cobalt nitrate and zinc nitrate.
5. The preparation method according to claim 1, wherein the mass ratio of the metal precursor to the metal salt in the step (2) is 1:0.5 to 1: 10.
6. A heteroatom-doped carbon-coated metal bifunctional water splitting nano material obtained by the preparation method of any one of claims 1 to 6.
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| US20180056269A1 (en) * | 2015-12-07 | 2018-03-01 | Research Center For Eco-Environmental Sciences, Chinese Academy Of Sciences | Manganese dioxide nanowire @ multidimensional mesoporous metal-organic framework adsorbent and preparation therefor |
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| MIN KUANG ET AL: ""Cu, Co-Embedded N-Enriched Mesoporous Carbon for Efficient Oxygen Reduction and Hydrogen Evolution Reactions"", 《ADV. ENERGY MATER》 * |
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