CN108816258A - A kind of hollow carbon material, preparation method and its application in catalytic electrolysis aquatic products hydrogen in situ for adulterating hollow phosphatization cobalt nanoparticle - Google Patents
A kind of hollow carbon material, preparation method and its application in catalytic electrolysis aquatic products hydrogen in situ for adulterating hollow phosphatization cobalt nanoparticle Download PDFInfo
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 56
- 239000010941 cobalt Substances 0.000 title claims abstract description 56
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 23
- 239000001257 hydrogen Substances 0.000 title claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 17
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 title claims description 9
- 239000002086 nanomaterial Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 13
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 12
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 8
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000000047 product Substances 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 230000000717 retained effect Effects 0.000 claims 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 abstract description 12
- 229960003638 dopamine Drugs 0.000 abstract description 6
- 239000007772 electrode material Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 2
- 238000011056 performance test Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 239000011796 hollow space material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 239000007769 metal material Substances 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 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
- 239000000523 sample Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 1
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 1
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
-
- B01J35/33—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A kind of preparation method of the hollow carbon material with dodecahedron pattern of the hollow phosphatization cobalt nanoparticle of original position doping and its application in catalytic electrolysis aquatic products hydrogen, belong to catalytic electrolysis aquatic products hydrogen technical field.The specific steps are：(1) preparation of the metal-organic framework material ZIF-67 with dodecahedron pattern containing cobalt ions；(2) metal containing cobalt has frame material ZIF-67 and dopamine monomer reaction to generate the hollow polymer nano material containing cobalt coordination doping；(3) cobalt oxide/carbon composite hollow nano material preparation；(4) hollow phosphatization cobalt/carbon composite hollow nano material preparation.The size of the material can be adjusted according to the size of ZIF-67；In the performance test of catalytic electrolysis aquatic products hydrogen, extraordinary electro catalytic activity and stability are shown as the electrode material of cathode.Therefore, material of the present invention has extraordinary application prospect in the electrode material as catalytic electrolysis aquatic products hydrogen.
Description
Technical field
The invention belongs to catalytic electrolysis aquatic products hydrogen technical fields, and in particular to a kind of hollow phosphatization cobalt nanometer of doping in situ is micro-
The hollow carbon material with dodecahedron pattern, preparation method and its application in catalytic electrolysis aquatic products hydrogen of grain.
Background technique
Due to global energy crisis and its relevant environmental problem etc., researcher is promoted to strive to find and can replace
The renewable energy of fossil fuel, wherein electrolysis aquatic products hydrogen is one and extremely has promising approach.It is converted and is imitated due to high-energy
Rate, almost pollution-free, the advantages that wide application prospect, it is extensive for electrode material that electrolysis aquatic products hydrogen causes researcher
Concern.Currently, there is a highest production hydrogen activity in platinum group metal, but high cost, the shortcomings that low output, limits its extensive use.
Therefore, probe into have obtained more concerns to the non-noble metallic materials with high catalytic activity.Although many brand-new material phases
Than having had some apparent advantages in precious metal material, but there are still some disadvantages, examples for production hydrogen electrode material at present
Such as complex manufacturing technology, catalytic activity is low, and specific surface area is small etc..There are two the factor of influence catalytic activity is main, one is gold
Belong to and hydrogen between effect energy, one be material structure and specific surface area.In this regard, using the biggish hollow carbon materials of specific surface area
Material, and more than wherein load can effectively overcome the problems, such as with the transition metal nanoparticles of high absorption Hydrogen Energy power.Such as
Chen study group is using the metal-organic framework material ZIF-8@ZIF-67 with core-shell structure as template[1], by carbonization, phosphorus
Change, has prepared the composite material with hollow structure and containing phosphatization cobalt nanometer particle, which shows excellent
Catalytic electrolysis aquatic products hydrogen and production oxygen performance (current density 10mA/cm-2When, overpotential is respectively 115mV and 310mV).
Based on this, the invention proposes a kind of hollow metal phosphides and the compound hollow nanometer material of carbon as electrode material
Material is applied in catalytic electrolysis aquatic products hydrogen.The polymer hollow that load has cobalt is prepared by the method for coordination competition and inducement polymerization
Nano material, later by carbonization, phosphatization obtains the hollow carbon material containing hollow phosphatization cobalt particle, realizes answering for the two
It closes, shows higher catalytic activity and stability.
Summary of the invention
There is dodecahedron pattern the purpose of the present invention is to provide a kind of hollow phosphatization cobalt nanoparticle of doping in situ
Hollow phosphatization cobalt/carbon composite hollow carbon material, preparation method and its application in catalytic electrolysis aquatic products hydrogen.By having
Hollow metal phosphide is loaded in the hollow carbon nano-particles of dodecahedron pattern, the catalysis that can effectively improve material is living
Property.Meanwhile hollow material can provide more active sites, promote material overall stability, and material is made to have longer make
With the service life, it is more suitable in actual production.
The present invention is competed first using the metal-organic framework material ZIF-67 for containing cobalt ions as template using coordination
The method of induced polymerization is prepared for the hollow polymer nano material containing ZnO thin film.It is protected later in the atmosphere of inert gas
Shield is lower to carry out high temperature cabonization, has obtained cobalt oxide/carbon composite hollow nano material.Finally, this kind of material is carried out phosphatization, make it
In cobalt oxide be converted into hollow phosphatization cobalt nanometer particle, just obtained hollow phosphatization cobalt/carbon composite hollow nano material.The material
Material shows excellent performance and outstanding stability on catalytic electrolysis aquatic products hydrogen.
The raw material that the present invention uses all is the substance being commercially available, and reaction process is simple, and experimental implementation is simple, item
Part is mild, and risk is small, and has extraordinary repeatability, can be produced in batches.
The hollow phosphatization cobalt with dodecahedron pattern in situ for adulterating hollow phosphatization cobalt nanoparticle of the present invention/
Carbon composite hollow carbon material can be made by the steps to obtain：(1) containing cobalt ions with dodecahedron pattern
The preparation of metal-organic framework material ZIF-67；(2) metal containing cobalt has frame material ZIF-67 and dopamine monomer reaction raw
At the hollow polymer nano material containing cobalt coordination doping；(3) cobalt oxide/carbon composite hollow nano material preparation；(4) in
The preparation of empty phosphatization cobalt/carbon composite hollow nano material.Specifically,
(1) preparation of the metal-organic framework material ZIF-67 with dodecahedron pattern containing cobalt ions：By 200~
Co (the NO of 1000mg3)2·6H2The 2-methylimidazole of O and 500~3000mg be dissolved separately in 25~100mL methanol obtain it is clear
Clear solution, later by two kinds of solution be uniformly mixed obtain purple solution and at room temperature standing 6~for 24 hours；Then by above-mentioned reaction
Product is washed 3~5 times by centrifugation (3000~5000rpm, 10~15min) processing with methanol, under the conditions of 40~60 DEG C
10~15h is dried, the metal-organic framework material ZIF-67 with dodecahedron pattern containing cobalt ions is obtained；
(2) preparation of the hollow polymer nano material containing cobalt coordination doping：Weigh 40~60mg step (1) preparation
ZIF-67 is dispersed in 50~75mL methanol, obtains ZIF-67 dispersion liquid；10~15mL, 20mM hydrochloric acid DOPA are taken later
The methanol solution of amine mixes the ZIF-67 dispersion liquid being previously obtained with the methanol solution of Dopamine hydrochloride, and by reaction system
It is refluxed 6~12h under the conditions of being placed in 40~60 DEG C, obtained product is centrifuged at (3000~5000rpm, 8~15min)
Reason, and 3~5 times are washed until supernatant achromaticity and clarification with methanol；Supernatant is removed, retains solid product, to be contained
The hollow polymer nano material of cobalt coordination doping；
(3) cobalt oxide/carbon composite hollow nano material preparation：By step (2) preparation containing in cobalt coordination doping
For empty polymer nano material under conditions of logical argon gas is protected, (heating rate is 3~5 to the 2~4h that is carbonized at 700~800 DEG C
DEG C/min), cobalt oxide/carbon composite hollow nano material is obtained after being cooled to room temperature；
(4) hollow phosphatization cobalt/carbon composite hollow nano material preparation：Under conditions of the protection of logical argon gas, by step (3)
Obtained cobalt oxide/carbon composite hollow nano material carries out phosphatization, phosphorus source NaH2PO2·H2O, phosphatization temperature are 300~400
DEG C, phosphating time is 1~3h (2~5 DEG C/min of heating rate), is obtained in doping in situ of the present invention after being cooled to room temperature
Hollow phosphatization cobalt/carbon composite hollow carbon material with dodecahedron pattern of empty phosphatization cobalt nanoparticle.
Detailed description of the invention
Fig. 1：Hollow phosphatization cobalt/carbon composite hollow nano material transmission electron microscope and scanning prepared by embodiment 1
Electron micrograph；It (A) is the photo of transmission electron microscope, (B) is the photo of scanning electron microscope；
Fig. 2：Hollow phosphatization cobalt/carbon composite hollow nano material transmission electron microscope and scanning prepared by embodiment 2
Electron micrograph.It (A) is the photo of transmission electron microscope, (B) is the photo of scanning electron microscope；
Fig. 3：Hollow phosphatization cobalt/carbon composite hollow nano material X ray diffracting spectrum prepared by embodiment 1；
Fig. 4：Hollow phosphatization cobalt/carbon composite hollow nano material catalytic electrolysis water H2-producing capacity prepared by embodiment 1 is bent
Line；It (A) is linear voltammetric scan curve, (B) is Tafel slope curve, and (C) is to produce stabilized hydrogen test curve, and (D) is to hand over
Flow impedance spectral curve.
Specific embodiment
Below with reference to example, the present invention is further elaborated, rather than to limit the invention.
Embodiment 1
(1) preparation of the metal-organic framework material ZIF-67 with dodecahedron pattern containing cobalt ions：498mg's
Co(NO3)2·6H2The 2-methylimidazole of O and 1400mg is dissolved separately in 50mL methanol, is later uniformly mixed two kinds of solution
It obtains purple solution and stands 6h at room temperature.Product is washed by centrifugation (5000rpm, 10min) processing purification with methanol
Three times, 12h is dried under the conditions of 60 DEG C, has finally just obtained the metal-organic framework material ZIF- with dodecahedron pattern
67, product quality 400mg.
(2) preparation of the hollow polymer nano material containing cobalt coordination doping：Weigh the ZIF-67 prepared in step (1)
60mg is dispersed in 75mL methanol.56.9mg Dopamine hydrochloride is weighed later and is dissolved in 15mL methanol is made into dopamine
Solution.ZIF-67 dispersion liquid is mixed with dopamine solution, and reaction system is placed under the conditions of 60 DEG C and is refluxed 6h.It obtains
Product by centrifugation (5000rpm, 10min) handle and washed three times with methanol until supernatant achromaticity and clarification, just obtain
Polymer hollow nano material containing cobalt, product quality 25mg.
(3) cobalt oxide/carbon composite hollow nano material preparation：By prepared hollow polymer nano material in logical argon
700 DEG C of carbonization 2h (heating rate is 5 DEG C/min), after being cooled to room temperature, have just obtained cobalt oxide/carbon under conditions of gas shielded
Composite hollow nano material, product quality 20mg.
(4) hollow phosphatization cobalt/carbon composite hollow nano material preparation：Under conditions of the protection of logical argon gas, by step (3)
Obtained in hollow material 20mg be placed on one end of porcelain boat, the other end is put into 500mg NaH2PO2·H2O carries out phosphatization, and temperature is
300 DEG C, phosphating time is 2h (3 DEG C/min of heating rate), after being cooled to room temperature, has just obtained original position of the present invention and has mixed
The hollow carbon material with dodecahedron pattern of miscellaneous hollow phosphatization cobalt nanoparticle, product quality 22mg.
Prepared hollow phosphatization cobalt/carbon composite hollow nano material size is about 200~260nm, and pattern maintains
The dodecahedral shape of mould material ZIF-67, while there is hollow structure, hollow phosphatization cobalt particle is distributed in the cavities, such as
Shown in Fig. 1.Cobalt in material it can be seen from the XRD characterization of Fig. 3 be in the form of phosphatization cobalt existing for.
Embodiment 2
(1) preparation of the metal-organic framework material ZIF-67 with dodecahedron pattern containing cobalt ions：498mg
Co(NO3)2·6H2O and 700mg 2-methylimidazole, which are dissolved separately in 50mL methanol, obtains purple clear solution, later will be molten
Liquid is uniformly mixed and stands at room temperature for 24 hours.Product is washed by centrifugation (5000rpm, 10min) processing purification with methanol
Three times, 12h is dried under the conditions of 60 DEG C, has finally just obtained the metal-organic framework material ZIF- with dodecahedron pattern
67, product quality 100mg.
(2) preparation of the hollow polymer nano material containing cobalt coordination doping：Weigh the ZIF-67 prepared in step (1)
60mg is dispersed in 75mL methanol.56.9mg Dopamine hydrochloride is weighed later and is dissolved in 15mL methanol is made into dopamine
Solution.ZIF-67 dispersion liquid is mixed with dopamine solution, and reaction system is placed under the conditions of 60 DEG C and is refluxed 12h.?
The product arrived is handled by centrifugation (5000rpm, 10min) and is washed three times with methanol until supernatant achromaticity and clarification, is just obtained
Polymer hollow nano material containing cobalt, product quality 25mg.
(3) cobalt oxide/carbon composite hollow nano material preparation：By prepared hollow polymer nano material in logical argon
700 DEG C of carbonization 2h (heating rate is 5 DEG C/min), after being cooled to room temperature, have just obtained cobalt oxide/carbon under conditions of gas shielded
Composite hollow nano material, product quality 20mg.
(4) hollow phosphatization cobalt/carbon composite hollow nano material preparation：Under conditions of the protection of logical argon gas, by step (3)
Obtained in hollow material 20mg be placed on one end of porcelain boat, the other end is put into 500mgNaH2PO2·H2O carries out phosphatization, and temperature is
300 DEG C, phosphating time is 2h (3 DEG C/min of heating rate), after being cooled to room temperature, has just obtained original position of the present invention and has mixed
The hollow carbon material with dodecahedron pattern of miscellaneous hollow phosphatization cobalt nanoparticle, product quality 22mg.
Prepared hollow phosphatization cobalt/carbon composite hollow nano material size is about 450~500nm, and pattern maintains
The dodecahedral shape of mould material ZIF-67, while there is hollow structure, hollow phosphatization cobalt particle is distributed in the cavities, such as
Shown in Fig. 2.
Embodiment 3
(1) preparation of electro-catalysis working electrode：By hollow phosphatization cobalt/carbon composite hollow nanometer prepared in embodiment 1
Material 10mg is dissolved in the in the mixed solvent of 900 μ L methanol and the perfluorinated sulfonic resin of 100 μ L, 2wt%, and ultrasonic treatment 30min makes
It becomes uniform dispersion liquid.It takes 10 μ L dispersant liquid drops on glass-carbon electrode later, dries at room temperature.
(2) linear volt-ampere test：The voltage range of linear volt-ampere test is 0~-0.6V, and scanning speed is that 10mV is per second,
The electrolyte used is the sulfuric acid solution of 0.5M.
(3) catalytic stability is tested：First by cyclic voltammetry scan, test voltage range is 0~-0.6V, scanning speed
Degree is that 100mV is per second, and scanning circle number is 1000.The linear voltammetric scan test in step (2) is carried out again later, by result and step
Suddenly the Comparative result in (2).
(4) electrochemical AC impedance is tested：Linear volt-ampere is tested in obtained result, current density 10mA/cm-2When
Corresponding voltage is initial voltage, high frequency 105Hz, low frequency 0.1Hz.
Catalytic electrolysis aquatic products hydrogen results of property is as shown in figure 4, hollow phosphatization cobalt/carbon composite hollow material is in current density
10mA/cm-2When overpotential be only 119mV, and recycle 1000 circle after be still able to maintain preferable catalytic activity.It is being continuously applied
Current density only decays to original 90% after voltage 12h.These results suggest that the material has excellent catalytic activity, Gao Wen
Qualitative and long circulation life.
Bibliography
[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 kind of preparation method of the hollow carbon material with dodecahedron pattern in situ for adulterating hollow phosphatization cobalt nanoparticle,
Its step are as follows：
(1) preparation of the metal-organic framework material ZIF-67 with dodecahedron pattern containing cobalt ions：By 200~
Co (the NO of 1000mg3)2·6H2The 2-methylimidazole of O and 500~3000mg be dissolved separately in 25~100mL methanol obtain it is clear
Clear solution, later by two kinds of solution be uniformly mixed obtain purple solution and at room temperature standing 6~for 24 hours；Then by above-mentioned reaction
Product wash 3~5 times with methanol by centrifugal treating, 10~15h of drying under the conditions of 40~60 DEG C, obtain containing cobalt from
The metal-organic framework material ZIF-67 with dodecahedron pattern of son；
(2) preparation of the hollow polymer nano material containing cobalt coordination doping：Weigh the ZIF- of 40~60mg step (1) preparation
67, it is dispersed in 50~75mL methanol, obtains ZIF-67 dispersion liquid；10~15mL, 20mM Dopamine hydrochloride are taken later
The ZIF-67 dispersion liquid being previously obtained is mixed with the methanol solution of Dopamine hydrochloride, and reaction system is placed in by methanol solution
It is refluxed 6~12h under the conditions of 40~60 DEG C, the product centrifugal treating that will be obtained, and 3~5 times are washed until supernatant with methanol
Liquid achromaticity and clarification；Supernatant is removed, solid product is retained, to obtain the hollow polymer nanometer material for being coordinated doping containing cobalt
Material；
(3) cobalt oxide/carbon composite hollow nano material preparation：Step (2) preparation is contained into the hollow poly- of cobalt coordination doping
Object nano material is closed under conditions of logical argon gas is protected, be carbonized 2~4h at 700~800 DEG C, is aoxidized after being cooled to room temperature
Cobalt/carbon composite hollow nano material；
(4) hollow phosphatization cobalt/carbon composite hollow nano material preparation：Under conditions of the protection of logical argon gas, step (3) is obtained
Cobalt oxide/carbon composite hollow nano material carry out phosphatization, phosphorus source NaH2PO2·H2O, phosphatization temperature are 300~400 DEG C, phosphorus
The change time is 1~3h, obtained after being cooled to room temperature it is in situ adulterate hollow phosphatization cobalt nanoparticle with dodecahedron pattern
Hollow phosphatization cobalt/carbon composite hollow carbon material.
2. a kind of hollow carbon material with dodecahedron pattern in situ for adulterating hollow phosphatization cobalt nanoparticle, feature exist
In：It is to be prepared by claim 1 the method.
3. a kind of hollow carbon with dodecahedron pattern in situ for adulterating hollow phosphatization cobalt nanoparticle as claimed in claim 2
Application of the material in catalytic electrolysis aquatic products hydrogen.
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