CN108816258B - Hollow carbon material doped with hollow cobalt phosphide nanoparticles in situ, preparation method and application of hollow carbon material in hydrogen production by catalytic electrolysis of water - Google Patents
Hollow carbon material doped with hollow cobalt phosphide nanoparticles in situ, preparation method and application of hollow carbon material in hydrogen production by catalytic electrolysis of water Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 58
- 239000010941 cobalt Substances 0.000 title claims abstract description 58
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 19
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000002086 nanomaterial Substances 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 29
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 14
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 12
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 10
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 65
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 229960003638 dopamine Drugs 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000011056 performance test Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
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- 238000005119 centrifugation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000004832 voltammetry Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- -1 platinum group metals Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
A preparation method of a hollow carbon material with dodecahedron morphology and in-situ doped hollow cobalt phosphide nanoparticles and application thereof in hydrogen production by catalytic electrolysis of water belong to the technical field of hydrogen production by catalytic electrolysis of water. The method comprises the following specific steps: (1) preparing a cobalt ion-containing metal organic framework material ZIF-67 with a dodecahedron shape; (2) reacting a metal framework material ZIF-67 containing cobalt with a dopamine monomer to generate a hollow polymer nano material containing cobalt coordination doping; (3) preparing a cobalt oxide/carbon composite hollow nano material; (4) and (3) preparing the hollow cobalt phosphide/carbon composite hollow nano material. The size of the material can be adjusted according to the size of ZIF-67; in the performance test of hydrogen production by catalytic electrolysis of water, the electrode material used as the cathode shows very good electrocatalytic activity and stability. Therefore, the material has a very good application prospect when being used as an electrode material for catalyzing electrolysis of water to produce hydrogen.
Description
Technical Field
The invention belongs to the technical field of hydrogen production by catalytic electrolysis, and particularly relates to a dodecahedron-shaped hollow carbon material doped with hollow cobalt phosphide nanoparticles in situ, a preparation method and application thereof in hydrogen production by catalytic electrolysis of water.
Background
Due to global energy crisis and related environmental problems, researchers are encouraged to search for renewable energy sources capable of replacing fossil fuels, wherein hydrogen production by water electrolysis is a promising approach. Due to the advantages of high energy conversion efficiency, almost no pollution, wide application prospect and the like, the hydrogen production by electrolyzing water draws extensive attention of researchers to electrode materials. At present, platinum group metals have the highest hydrogen production activity, but the defects of high cost and low yield limit the wide application of the platinum group metals. Therefore, the catalyst has high catalysisThe search for active non-noble metal materials has received much attention. Although many emerging materials have some obvious advantages compared with noble metal materials, the current hydrogen-generating electrode materials still have some defects, such as complex manufacturing process, low catalytic activity, small specific surface area and the like. The factors influencing the catalytic activity are mainly two, one is the interaction energy between the metal and hydrogen, and the other is the structure and the specific surface area of the material. In contrast, the above problems can be effectively overcome by using a hollow carbon material having a large specific surface area and loading transition metal nanoparticles having a high hydrogen adsorption capacity therein. For example, the Chen research group takes a metal organic framework material ZIF-8@ ZIF-67 with a core-shell structure as a template[1]The composite material with a hollow structure and containing cobalt phosphide nano-particles is prepared through carbonization and phosphorization, and the material shows excellent hydrogen production and oxygen production performance (the current density is 10 mA/cm)-2The overpotential was 115mV and 310mV, respectively).
Based on the above, the invention provides a hollow nano material compounded by hollow metal phosphide and carbon as an electrode material applied to hydrogen production by catalytic electrolysis of water. The hollow cobalt-loaded polymer nano material is prepared by a coordination competition induced polymerization method, and then is carbonized and phosphorized to obtain a hollow carbon material containing hollow cobalt phosphide particles, so that the composition of the hollow carbon material and the hollow carbon material is realized, and high catalytic activity and stability are shown.
Disclosure of Invention
The invention aims to provide a dodecahedral hollow cobalt phosphide/carbon composite hollow carbon material doped with hollow cobalt phosphide nanoparticles in situ, a preparation method and application thereof in hydrogen production by catalytic electrolysis of water. The catalytic activity of the material can be effectively improved by loading the hollow metal phosphide in the hollow carbon nano-particles with the dodecahedron morphology. Meanwhile, the hollow material can provide more active sites, the overall stability of the material is improved, the material has longer service life, and the hollow material is more suitable for actual production.
The invention firstly adopts a metal organic framework material ZIF-67 containing cobalt ions as a template, and prepares the hollow polymer nano material doped with the cobalt ions by utilizing a coordination competition induced polymerization method. And then carrying out high-temperature carbonization under the protection of inert gas atmosphere to obtain the cobalt oxide/carbon composite hollow nano material. And finally, phosphorizing the material to convert cobalt oxide in the material into hollow cobalt phosphide nano particles, thereby obtaining the hollow cobalt phosphide/carbon composite hollow nano material. The material shows excellent performance and stability on hydrogen production by catalytic electrolysis.
The raw materials used in the invention are all commercially available substances, the reaction process is simple, the experimental operation is simple, the conditions are mild, the risk is low, the repeatability is very good, and the batch production can be carried out.
The hollow cobalt phosphide/carbon composite hollow carbon material with the dodecahedron morphology, which is doped with the hollow cobalt phosphide nanoparticles in situ, can be prepared by the following steps: (1) preparing a cobalt ion-containing metal organic framework material ZIF-67 with a dodecahedron shape; (2) reacting a metal framework material ZIF-67 containing cobalt with a dopamine monomer to generate a hollow polymer nano material containing cobalt coordination doping; (3) preparing a cobalt oxide/carbon composite hollow nano material; (4) and (3) preparing the hollow cobalt phosphide/carbon composite hollow nano material. In particular, the amount of the solvent to be used,
(1) preparing a cobalt ion-containing metal organic framework material ZIF-67 with a dodecahedron morphology: mixing 200-1000 mg Co (NO)3)2·6H2Dissolving O and 500-3000 mg of 2-methylimidazole in 25-100 mL of methanol respectively to obtain a clear solution, then uniformly mixing the two solutions to obtain a purple solution, and standing at room temperature for 6-24 hours; then, treating the reaction product through centrifugation (3000-5000 rpm for 10-15 min), washing the reaction product for 3-5 times by using methanol, and drying the reaction product for 10-15 h at the temperature of 40-60 ℃ to obtain a cobalt ion-containing metal organic framework material ZIF-67 with a dodecahedron shape;
(2) preparing a hollow polymer nano material containing cobalt coordination doping: weighing 40-60 mg of ZIF-67 prepared in the step (1), and dispersing the ZIF-67 in 50-75 mL of methanol to obtain a ZIF-67 dispersion liquid; then taking 10-15 mL of 20mM dopamine hydrochloride methanol solution, mixing the obtained ZIF-67 dispersion liquid with the dopamine hydrochloride methanol solution, placing the reaction system at 40-60 ℃, carrying out reflux stirring for 6-12 h, centrifuging (3000-5000 rpm for 8-15 min) the obtained product, and washing for 3-5 times by using methanol until the supernatant is colorless and clear; removing the supernatant, and retaining the solid product, thereby obtaining the hollow polymer nano material containing the coordination doping of cobalt;
(3) preparing a cobalt oxide/carbon composite hollow nano material: carbonizing the hollow polymer nano material containing the cobalt coordination doping prepared in the step (2) at 700-800 ℃ for 2-4 h (the heating rate is 3-5 ℃/min) under the condition of introducing argon protection, and cooling to room temperature to obtain a cobalt oxide/carbon composite hollow nano material;
(4) preparing a hollow cobalt phosphide/carbon composite hollow nano material: under the protection of argon, the cobalt oxide/carbon composite hollow nano material obtained in the step (3) is phosphated, and the phosphorus source is NaH2PO2·H2And O, the phosphorization temperature is 300-400 ℃, the phosphorization time is 1-3 h (the heating rate is 2-5 ℃/min), and the hollow cobalt phosphide/carbon composite hollow carbon material with the dodecahedron morphology, which is doped with the hollow cobalt phosphide nanoparticles in situ, is obtained after cooling to the room temperature.
Drawings
FIG. 1: transmission electron microscope and scanning electron microscope photographs of the hollow cobalt phosphide/carbon composite hollow nanomaterial prepared in example 1; (A) the picture is a transmission electron microscope, and (B) is a scanning electron microscope;
FIG. 2: transmission electron microscope and scanning electron microscope photographs of the hollow cobalt phosphide/carbon composite hollow nanomaterial prepared in example 2. (A) The picture is a transmission electron microscope, and (B) is a scanning electron microscope;
FIG. 3: an X-ray diffraction pattern of the hollow cobalt phosphide/carbon composite hollow nanomaterial prepared in example 1;
FIG. 4: the hydrogen performance curve of the hollow cobalt phosphide/carbon composite hollow nano material prepared in the embodiment 1 is produced by catalytic electrolysis of water; (A) the curve is a linear volt-ampere scanning curve, (B) is a tafel slope curve, (C) is a hydrogen production stability test curve, and (D) is an alternating current impedance spectrum curve.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to be limiting.
Example 1
(1) Preparing a cobalt ion-containing metal organic framework material ZIF-67 with a dodecahedron morphology: 498mg of Co (NO)3)2·6H2O and 1400mg of 2-methylimidazole were dissolved in 50mL of methanol, respectively, and then the two solutions were mixed uniformly to obtain a purple solution and left to stand at room temperature for 6 hours. And (3) purifying the product by centrifuging (5000rpm,10min), washing with methanol for three times, and drying at 60 ℃ for 12h to finally obtain the metal organic framework material ZIF-67 with the dodecahedron morphology, wherein the mass of the product is 400 mg.
(2) Preparing a hollow polymer nano material containing cobalt coordination doping: ZIF-6760 mg prepared in step (1) was weighed and dispersed in 75mL of methanol. Then 56.9mg of dopamine hydrochloride is weighed and dissolved in 15mL of methanol to prepare a dopamine solution. Mixing the ZIF-67 dispersion liquid with a dopamine solution, and placing the reaction system at 60 ℃ for refluxing and stirring for 6 hours. The resulting product was treated by centrifugation (5000rpm,10min) and washed three times with methanol until the supernatant was colorless and clear to give a cobalt-containing polymeric hollow nanomaterial with a product mass of 25 mg.
(3) Preparing a cobalt oxide/carbon composite hollow nano material: carbonizing the prepared hollow polymer nano material at 700 ℃ for 2h (the heating rate is 5 ℃/min) under the protection of argon, and cooling to room temperature to obtain the cobalt oxide/carbon composite hollow nano material, wherein the mass of the product is 20 mg.
(4) Preparing a hollow cobalt phosphide/carbon composite hollow nano material: putting 20mg of the hollow material obtained in the step (3) at one end of a porcelain boat and putting 500mg of NaH at the other end of the porcelain boat under the protection of argon2PO2·H2O is phosphorized at the temperature of 300 ℃ for 2h (the heating rate is 3 ℃/min), and after the mixture is cooled to the room temperature, the in-situ doped hollow cobalt phosphide nano particles are obtainedThe mass of the hollow carbon material having a dodecahedral morphology of the product was 22 mg.
The size of the prepared hollow cobalt phosphide/carbon composite hollow nano material is about 200-260 nm, the shape of the hollow cobalt phosphide/carbon composite hollow nano material maintains the dodecahedral shape of the template material ZIF-67, and meanwhile, the hollow cobalt phosphide/carbon composite hollow nano material has a hollow structure, and hollow cobalt phosphide particles are distributed in a cavity, as shown in figure 1. As can be seen from the XRD characterization of fig. 3, the cobalt in the material is present in the form of cobalt phosphide.
Example 2
(1) Preparing a cobalt ion-containing metal organic framework material ZIF-67 with a dodecahedron morphology: 498mg Co (NO)3)2·6H2O and 700mg of 2-methylimidazole were dissolved in 50mL of methanol, respectively, to give a purple clear solution, and then the solutions were mixed well and left to stand at room temperature for 24 hours. And (3) purifying the product by centrifuging (5000rpm,10min), washing with methanol for three times, and drying at 60 ℃ for 12h to finally obtain the metal organic framework material ZIF-67 with the dodecahedron morphology, wherein the mass of the product is 100 mg.
(2) Preparing a hollow polymer nano material containing cobalt coordination doping: ZIF-6760 mg prepared in step (1) was weighed and dispersed in 75mL of methanol. Then 56.9mg of dopamine hydrochloride is weighed and dissolved in 15mL of methanol to prepare a dopamine solution. Mixing the ZIF-67 dispersion liquid with a dopamine solution, and placing the reaction system at 60 ℃ for reflux stirring for 12 hours. The resulting product was treated by centrifugation (5000rpm,10min) and washed three times with methanol until the supernatant was colorless and clear to give a cobalt-containing polymeric hollow nanomaterial with a product mass of 25 mg.
(3) Preparing a cobalt oxide/carbon composite hollow nano material: carbonizing the prepared hollow polymer nano material at 700 ℃ for 2h (the heating rate is 5 ℃/min) under the protection of argon, and cooling to room temperature to obtain the cobalt oxide/carbon composite hollow nano material, wherein the mass of the product is 20 mg.
(4) Preparing a hollow cobalt phosphide/carbon composite hollow nano material: putting 20mg of the hollow material obtained in the step (3) at one end of a porcelain boat and putting 500mg of NaH at the other end of the porcelain boat under the protection of argon2PO2·H2And O, phosphorizing at 300 ℃ for 2h (the heating rate is 3 ℃/min), and cooling to room temperature to obtain the dodecahedral hollow carbon material doped with the hollow cobalt phosphide nanoparticles in situ, wherein the product mass is 22 mg.
The size of the prepared hollow cobalt phosphide/carbon composite hollow nano material is about 450-500 nm, the shape of the hollow cobalt phosphide/carbon composite hollow nano material maintains the dodecahedral shape of the template material ZIF-67, and meanwhile, the hollow cobalt phosphide/carbon composite hollow nano material has a hollow structure, and hollow cobalt phosphide particles are distributed in a cavity, as shown in figure 2.
Example 3
(1) Preparing an electrocatalytic working electrode: 10mg of the hollow cobalt phosphide/carbon composite hollow nanomaterial prepared in example 1 was dissolved in a mixed solvent of 900. mu.L of methanol and 100. mu.L of 2 wt% perfluorosulfonic acid resin, and subjected to ultrasonic treatment for 30min to obtain a uniform dispersion. Then 10. mu.L of the dispersion was dropped on a glassy carbon electrode and dried at room temperature.
(2) Linear voltammetry test: the voltage range for the linear voltammetric test was 0 to-0.6V, the scan rate was 10mV per second, and the electrolyte used was 0.5M sulfuric acid solution.
(3) And (3) testing the catalytic stability: firstly, through cyclic voltammetry scanning, the test voltage range is 0 to-0.6V, the scanning speed is 100mV per second, and the number of scanning turns is 1000. And (3) performing a linear voltammetry scanning test in the step (2), and comparing the result with the result in the step (2).
(4) Electrochemical alternating current impedance test: the current density was 10mA/cm in the results obtained by the Linear voltammetry test-2The corresponding voltage is the initial voltage, the high frequency is 105Hz, low frequency 0.1 Hz.
The results of hydrogen production performance by catalytic electrolysis of water are shown in FIG. 4, and the current density of the hollow cobalt phosphide/carbon composite hollow material is 10mA/cm-2The overpotential is only 119mV, and the catalyst still can keep better catalytic activity after 1000 cycles. The current density decayed to only 90% of the original current density after the voltage was continuously applied for 12 h. The above results show that the material has excellent catalytic activity, high stability and long cycle life.
Reference to the literature
[1]Pan,Y.；Sun,K.；Liu,S.；Cao,X.；Wu,K.；Cheong,W-C.；Chen,Z.；Wang,Y.；Li,Y.；Liu,Y.；Wang,D.；Peng,Q.；Chen,C.；Li,Y.J.Am.Chem.Soc.2018,140,2610-2618.
Claims (3)
1. A method for preparing a hollow carbon material with a dodecahedron shape by in-situ doping hollow cobalt phosphide nanoparticles comprises the following steps:
(1) preparing a cobalt ion-containing metal organic framework material ZIF-67 with a dodecahedron morphology: mixing 200-1000 mg Co (NO)3)2·6H2Dissolving O and 500-3000 mg of 2-methylimidazole in 25-100 mL of methanol respectively to obtain a clear solution, then uniformly mixing the two solutions to obtain a purple solution, and standing at room temperature for 6-24 hours; then centrifuging the reaction product, washing the reaction product for 3-5 times by using methanol, and drying the reaction product for 10-15 hours at the temperature of 40-60 ℃ to obtain a metal organic framework material ZIF-67 containing cobalt ions and having a dodecahedron shape;
(2) preparing a hollow polymer nano material containing cobalt coordination doping: weighing 40-60 mg of ZIF-67 prepared in the step (1), and dispersing the ZIF-67 in 50-75 mL of methanol to obtain a ZIF-67 dispersion liquid; then taking 10-15 mL of 20mM dopamine hydrochloride methanol solution, mixing the obtained ZIF-67 dispersion liquid with the dopamine hydrochloride methanol solution, placing the reaction system at 40-60 ℃, refluxing and stirring for 6-12 hours, centrifuging the obtained product, and washing for 3-5 times by using methanol until the supernatant is colorless and clear; removing the supernatant, and retaining the solid product, thereby obtaining the hollow polymer nano material containing the coordination doping of cobalt;
(3) preparing a cobalt oxide/carbon composite hollow nano material: carbonizing the hollow polymer nano material containing the cobalt coordination doping prepared in the step (2) at 700-800 ℃ for 2-4 h under the protection of argon, and cooling to room temperature to obtain a cobalt oxide/carbon composite hollow nano material;
(4) preparing a hollow cobalt phosphide/carbon composite hollow nano material: under the protection of argon, the cobalt oxide/carbon composite hollow obtained in the step (3)The nano material is phosphorized, and the phosphorus source is NaH2PO2·H2And O, the phosphorization temperature is 300-400 ℃, the phosphorization time is 1-3 h, and the hollow cobalt phosphide/carbon composite hollow carbon material with the dodecahedron morphology, which is doped with hollow cobalt phosphide nanoparticles in situ, is obtained after cooling to room temperature.
2. A hollow carbon material with dodecahedron morphology and in-situ doped hollow cobalt phosphide nanoparticles is characterized in that: is prepared by the method of claim 1.
3. The use of the hollow carbon material with dodecahedron morphology of in-situ doped hollow cobalt phosphide nanoparticles as claimed in claim 2 in the production of hydrogen by catalytic electrolysis of water.
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| CN109663608B (en) * | 2018-12-27 | 2022-01-25 | 北京印刷学院 | Carbon-cobalt-molybdenum bimetal phosphide composite material and preparation method thereof |
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| CN110102348B (en) * | 2019-05-23 | 2022-03-08 | 中国科学院上海硅酸盐研究所 | Electrocatalyst with hollow structure and preparation method thereof |
| CN110652992A (en) * | 2019-09-12 | 2020-01-07 | 天津大学 | Synthesis method and application of hollow oxide/phosphide carbon-coated composite material for electrocatalytic hydrogen production |
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| CN113403638A (en) * | 2021-05-21 | 2021-09-17 | 南京师范大学 | Electrocatalytic oxygen evolution catalyst and preparation method thereof |
| CN113832477B (en) * | 2021-09-30 | 2023-03-21 | 浙江大学杭州国际科创中心 | Efficient water decomposition catalyst hollow cobalt phosphide and preparation method thereof |
| CN114744191B (en) * | 2022-03-24 | 2023-11-24 | 河北科技大学 | Cobalt phosphide anode material and preparation method and application thereof |
| CN116474799B (en) * | 2023-04-04 | 2024-10-15 | 复旦大学 | Br-CoP@C nano catalyst for ammonia borane hydrolysis hydrogen production and preparation method thereof |
| CN116779831B (en) * | 2023-08-25 | 2023-11-21 | 山东华源特新材料科技有限公司 | Sea urchin structure electrode material, preparation method and application thereof in battery |
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