CN108654604A - A kind of preparation method and application of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material - Google Patents
A kind of preparation method and application of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material Download PDFInfo
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- CN108654604A CN108654604A CN201710207214.XA CN201710207214A CN108654604A CN 108654604 A CN108654604 A CN 108654604A CN 201710207214 A CN201710207214 A CN 201710207214A CN 108654604 A CN108654604 A CN 108654604A
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- nitrogen
- doped carbon
- composite material
- carbon nanometer
- nanometer pipe
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- 239000002131 composite material Substances 0.000 title claims abstract description 149
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 94
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 49
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000001301 oxygen Substances 0.000 claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001354 calcination Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 claims abstract description 34
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000013049 sediment Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 87
- 239000003054 catalyst Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000005868 electrolysis reaction Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000005660 chlorination reaction Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- YLPJWCDYYXQCIP-UHFFFAOYSA-N nitroso nitrate;ruthenium Chemical compound [Ru].[O-][N+](=O)ON=O YLPJWCDYYXQCIP-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 230000002572 peristaltic effect Effects 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 84
- 235000011121 sodium hydroxide Nutrition 0.000 description 33
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 23
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 18
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000003643 water by type Substances 0.000 description 11
- 239000002041 carbon nanotube Substances 0.000 description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 230000005611 electricity Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- JWXFFWOSZTYVQD-UHFFFAOYSA-N oxygen(2-) ruthenium(3+) titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].[Ru+3] JWXFFWOSZTYVQD-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- PNPIRSNMYIHTPS-UHFFFAOYSA-N nitroso nitrate Chemical compound [O-][N+](=O)ON=O PNPIRSNMYIHTPS-UHFFFAOYSA-N 0.000 description 3
- 238000009938 salting Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- -1 ruthenium salt Chemical class 0.000 description 1
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000002604 ultrasonography Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/40—
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of preparation methods of nitrogen-doped carbon nanometer pipe ruthenic oxide composite material, and this method comprises the following steps：1) nitrogen-doped carbon nanometer pipe solution is mixed with ruthenium source solution, obtains mixed liquor, then lye is added into mixed liquor, be uniformly mixed, obtain the precursor liquid that pH is 10~12；2) precursor liquid is aged to 3~5h, then centrifuge washing at a temperature of 50~90 DEG C, obtains sediment；3) sediment is subjected to hydro-thermal reaction or calcining, obtains nitrogen-doped carbon nanometer pipe ruthenic oxide composite material.The nitrogen-doped carbon nanometer pipe ruthenic oxide composite material that the preparation method obtains has excellent OER catalytic performances and electric conductivity.Application of the composite material obtained the invention also discloses the preparation method in being catalyzed oxygen evolution reaction.
Description
Technical field
The present invention relates to technical field of nano material.It is multiple more particularly, to a kind of nitrogen-doped carbon nanometer pipe-ruthenic oxide
The preparation method and application of condensation material.
Background technology
Nano oxidized ruthenium (i.e. nanometer titanium dioxide ruthenium) is a kind of metal oxide containing precious metals, high with very high than table capacitance
Conductivity and low-resistivity have in ultracapacitor, catalyst and electrochemical catalysis and are widely applied very much.It is answered in catalyst
It uses, nano oxidized ruthenium, which is proved to its (110) crystal face, has preferable OER (oxygen evolution reaction) catalytic performance, but due to its price
Expensive, easy reunion and electric conductivity are also short of and limit its application.
Currently, the technology for preparing carbon nanotube-ruthenium-oxide composite material both at home and abroad is more, universal preparation method is using in situ heavy
Area method prepares carbon family-ruthenium-oxide composite material.Such as：In the Chinese invention patent application file of Publication No. CN1806914A
A kind of preparation method of carbon nanotube-ruthenium-oxide composite material is disclosed, preparation method is：Carbon nanotube is added to trichlorine
To change in ruthenium solution, sonic oscillation, at room temperature, hydrogen peroxide is slowly added dropwise with micro-sampling pump, temperature rising reflux reacts, through filtering,
Washing, dry, obtained carbon nanotube supported nanometer hydrated ruthenium oxide.This method disadvantage is to use hydrogen peroxide strong oxidizer
Itself has certain toxicity, is unfavorable for environmental protection, and the ruthenium tetroxide for easy ting produce severe toxicity is mixed with ruthenium trichloride, has one
Fixed danger.It is disclosed in the Chinese invention patent application file of Publication No. CN101122040A a kind of carbon nanotube loaded
Ruthenium oxide hydration nano powder composite material, the preparation method are：Carbon nanotube is scattered in prepared electric depositing solution,
By electro-deposition method, the deposition load of hydroxide ruthenium is made to obtain predecessor on the carbon nanotubes, later certainly by predecessor heat treatment
So carbon nano-tube loading ruthenium oxide hydration nano powder composite material is obtained after cooling.This method disadvantage is to use electro-deposition side
Method energy consumption is more serious, and economy is poor.
Accordingly, it is desirable to provide a kind of new ruthenic oxide composite material and preparation method, to solve the above technical problems.
Invention content
First of the present invention is designed to provide a kind of preparation side of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material
Method, with solve existing ruthenic oxide because it is expensive, be easy to reunite and electric conductivity is short of due to cannot preferably be applied
Technical problem, meanwhile, the preparation method is simple and environmentally-friendly, good economy performance, and the nitrogen-doped carbon nanometer pipe-titanium dioxide being prepared
Ruthenium composite material has excellent electric conductivity and OER catalytic performances.
Second object of the present invention is to provide the preparation side of above-mentioned nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material
The nitrogen-doped carbon nanometer pipe that method is prepared-ruthenic oxide composite material.
Third object of the present invention is to provide a kind of application of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, which is characterized in that including walking as follows
Suddenly：
1) nitrogen-doped carbon nanometer pipe solution is mixed with ruthenium source solution, obtains mixed liquor, then lye is added into mixed liquor, mixed
It closes and uniformly obtains the precursor liquid that pH is 10~12；
2) precursor liquid is aged to 3~5h, then centrifuge washing at a temperature of 50~90 DEG C, obtains sediment；
3) sediment is subjected to hydro-thermal reaction or calcining, obtains nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
In the preparation method of the present invention, by the way that lye is added, come the pH value of the precursor liquid adjusted.Obtained composite wood
The granule-morphology of ruthenic oxide, size are very sensitive to the variation of the pH value of precursor liquid in material.PH value is excessively high, then what is obtained is compound
The pattern of ruthenic oxide is poor in material, size Control difficulty is big, and pH value is too low, then reaction yield is low, and ruthenic oxide pattern
Difference.According to the preferred embodiment of the present invention, the pH of the precursor liquid is 10~11, at this point, dioxy in obtained composite material
The granule-morphology for changing ruthenium is regular, and dimensional homogeneity is good, and can uniformly combine on the surface and inside of nitrogen-doped carbon nanometer pipe, multiple
The electric conductivity and OER catalytic performances of condensation material are preferable；It is highly preferred that the pH of the precursor liquid is 10, foregoing advantages are most at this time
It is good.
Aging condition in the present invention also has an impact the preparation of composite material.Aging Temperature is excessively high, and solvent volatilization is serious,
Reflow treatment is needed, Aging Temperature is too low, then reaction speed is slow, and reaction time is long.According to the preferred embodiment of the present invention,
When the temperature of the ageing is 70~80 DEG C, more preferably, it is highly preferred that when the temperature of the ageing is 80 DEG C, this is imitated composite effect
Fruit is best.
According to the preferred embodiment of the present invention, in step 1), the nitrogen-doped carbon in the nitrogen-doped carbon nanometer pipe solution
Nanotube and the mass ratio in the ruthenium source in the solution of ruthenium source are 1:1~1:5.Preferably, the quality of nitrogen-doped carbon nanometer pipe and ruthenium source
Than being 1:1~1:3, ruthenic oxide can uniformly combine the table in nitrogen-doped carbon nanometer pipe in the composite material being prepared at this time
Face and inside, the electric conductivity and OER catalytic performances of composite material are preferable.It is highly preferred that nitrogen-doped carbon nanometer pipe and ruthenium source
Mass ratio is 1:1.
According to the preferred embodiment of the present invention, in step 1), the uniformly mixed method uses to be added dropwise dropwise
Lye is added in mixed liquor method, and stirs simultaneously, and stir speed (S.S.) is 100~600r/min, preferably 200~400r/
Min, more preferably 300r/min.At this point, can guarantee the uniformity of mixing, it is more advantageous to and obtains size uniformity, regular appearance
Nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
According to the preferred embodiment of the present invention, in step 1), the uniformly mixed method is to be rotated using hypergravity
Bed strength mixes, and high-gravity rotating bed peristaltic pump feed rate is 200~600mL/min, and high-gravity rotating bed rotating speed is
800~2500r/min；Preferably, high-gravity rotating bed peristaltic pump feed rate is 400~600mL/min, hypergravity rotation
The rotating speed of bed is 1200~1800r/min；It is highly preferred that high-gravity rotating bed peristaltic pump feed rate is 600mL/min, surpass
The rotating speed of gravity revolving bed is 1200r/min.At this point, mixture homogeneity higher, nitrogen-doped carbon nanometer pipe-ruthenic oxide of acquisition
Ruthenic oxide scale particle size smaller, pattern are more regular in composite material.
According to the preferred embodiment of the present invention, in step 3), the temperature of the hydro-thermal reaction is 100~230 DEG C, the time
For 4~for 24 hours.In the preparation method of composite material of the present invention, ruthenic oxide is received with nitrogen-doped carbon in the composite material being prepared
Bond strength between mitron is very sensitive to the temperature and time of hydro-thermal reaction, too high or too low for temperature, the time mistake of hydro-thermal reaction
The homogeneity of the long or too short regular appearance and granular size for influencing composite material, and temperature is too low, obtained composite wood
The OER catalytic performances of material are deteriorated even without OER catalytic performances.Preferably, the temperature of the hydro-thermal reaction is 200~230 DEG C, when
Between be 8~12h, the composite material obtained at this time have preferable OER catalytic performances.It is highly preferred that the temperature of the hydro-thermal reaction
Degree is 230 DEG C, time 12h.The OER catalytic performances of the material obtained at this time are best.
According to the preferred embodiment of the present invention, in step 3), the calcining carries out in atmosphere of inert gases, described lazy
Property gas is preferably nitrogen.It is calcined under an inert atmosphere, nitrogen-doped carbon nanometer pipe-dioxy of regular appearance can be prepared
Change ruthenium composite material.
According to the preferred embodiment of the present invention, in step 3), the temperature of the calcining is 300~500 DEG C, calcination time
For 12~36h.Preferably 18~for 24 hours.During obtaining composite material by the way of calcining, the pattern of composite material and
OER catalytic performances are very sensitive to the change of calcination condition.Under this optimum condition, nitrogen-doped carbon nanometer pipe in gained composite material
It is uniformly dispersed with ruthenic oxide, while the OER catalytic performances that have had of the composite material and electric conductivity.Calcination time is long or mistake
It is short to make the reduction of OER catalytic performances.It is highly preferred that the temperature of the calcining is 300 DEG C, calcination time is for 24 hours, at this point, multiple
The OER catalytic performances of condensation material are optimal.
According to the preferred embodiment of the present invention, in step 1), the ruthenium source in the solution of the ruthenium source is selected from ruthenic chloride, trichlorine
Change the mixing that six ammoniums close one or more of ruthenium, nitrosyl nitrate ruthenium.Wherein, ruthenic chloride can be such as ruthenium trichloride.
According to the preferred embodiment of the present invention, in step 1), alkali in the lye be selected from sodium hydroxide, sodium carbonate,
The mixing of one or more of ammonium hydroxide.
According to the preferred embodiment of the present invention, in step 1), ruthenium source solution and the solvent difference in the alkali are only
The vertical mixing selected from one or both of water, ethyl alcohol.
Nitrogen-doped carbon nanometer pipe in the present invention can be commercially available by conventional commercial.In the present invention, it is being added without oxidation
It is compound and to each step of compound condition by using nitrogen-doped carbon nanometer pipe and ruthenic oxide under the premise of the additives such as agent
Selection and the regulation and control of technological parameter so that the pattern of nitrogen-doped carbon nanometer pipe-ruthenic oxide particle, size, dispersibility are more controllable,
The conversion ratio and selectivity of reaction are increased substantially, technique, flow are simplified.In the preparation method of the present invention, to technological parameter
Regulation and control are mainly reflected in：The preparation process of nitrogen-doped carbon nanometer pipe-ruthenic oxide includes hybrid reaction, precursor post-processing, mistake
The series of process processes such as filter, washing, drying, calcining/hydro-thermal.It is exactly mutually to be closed between these steps, parameter etc. in the present invention
Connection, collective effect, which realizes in the present invention, to be solved nitrogen-doped carbon nanometer pipe-ruthenium-oxide granule-morphology, size, dispersibility etc. and asks
Topic so that ruthenic oxide particle is uniform and is firmly bonded to the surface and inside of nitrogen-doped carbon nanometer pipe, on the one hand improves
The electric conductivity of ruthenic oxide, on the other hand the composite material have compare purer ruthenic oxide with better OER catalytics
Energy.Assign the higher application performance of product and wider application range.It has been established applied to catalyst field for it good
Basis.Therefore, it in order to obtain nitrogen-doped carbon nanometer pipe-ruthenium-oxide composite material of preferable OER catalytic performances, needs to above
Condition carries out stringent control, any one condition cannot all change.And just because of the regulation and control of above-mentioned technological parameter and
Cooperation so that the particle size of nanometer titanium dioxide ruthenium product can regulate and control between 1~20nm in the composite material finally obtained,
The even surface and inside for being dispersed in nitrogen-doped carbon nanometer pipe, and there is preferable OER catalytic performances and electric conductivity.
To reach above-mentioned second purpose, the present invention provides above-mentioned nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material
The nitrogen-doped carbon nanometer pipe that preparation method is prepared-ruthenic oxide composite material.Nitrogen-doped carbon nanometer pipe-the ruthenic oxide
Ruthenic oxide particle is incorporated evenly among the surface and inside of nitrogen-doped carbon nanometer pipe in composite material；Nitrogen-doped carbon nanometer pipe is long
Degree be 0.5~30 μm, a diameter of 30~50nm, ruthenium-oxide granule-morphology be ball-type or club shaped structure, particle scale be 1~
20nm。
To reach above-mentioned third purpose, the present invention provides the nitrogen-doped carbon nanometer pipe-that above-mentioned preparation method is prepared
Application of the ruthenic oxide composite material as catalyst in the oxygen evolution reaction of catalytic electrolysis water.
The nitrogen-doped carbon nanometer pipe that the present invention is prepared-ruthenic oxide composite material is in ultracapacitor, other catalysis
Also there is good application in terms of field.
It is unless otherwise specified, raw materials used to be obtained by commercially available purchase in the present invention.
Beneficial effects of the present invention are as follows：
1) present invention employs gravity Methods to prepare nitrogen-doped carbon nanometer pipe and ruthenium-oxide composite material, institute's application method letter
Single, environmental protection；Ruthenic oxide is compound preferably with nitrogen-doped carbon nanometer pipe, wherein doped carbon nanometer pipe length is 0.5~30 μm, directly
Diameter is 30~50nm, and compound nanometer titanium dioxide ruthenium granule-morphology is ball-type or club shaped structure, particle scale can reach 1~
20nm, for nanometer titanium dioxide ruthenium Particles dispersed in nitrogen-doped carbon nanometer pipe surface and inside, composite material is well dispersed.
2) composite material prepared by the present invention has higher OER catalytic performances and electric conductivity, passes through chemical property
Test can reach 50mV/min or more in OER catalysis overpotential, compare, have more with other ruthenic oxide composite materials
Excellent catalytic performance.
3) technological process used in the present invention is simple, easily operated, and products obtained therefrom is easy to preserve, product purity height, matter
It measures, assay reproducibility is strong, is easy to amplify.
Description of the drawings
Specific embodiments of the present invention will be described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the TEM figures of 1 gained composite material of the embodiment of the present invention.
Fig. 2 shows the TEM of 2 gained composite material of embodiment of the present invention figures.
Fig. 3 shows the embodiment of the present invention 1, embodiment 9 and 7 gained composite material of comparative example as LSV catalysis figures.
Fig. 4 shows the high gravity rotating packed bed reactor schematic diagram used in the embodiment of the present invention 10.
Fig. 5 shows 11 bushing type annular micro passage reaction schematic diagram of the embodiment of the present invention.
Specific implementation mode
In order to illustrate more clearly of the present invention, the present invention is done further with reference to preferred embodiments and drawings
It is bright.Similar component is indicated with identical reference numeral in attached drawing.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
Embodiment 1
A kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, includes the following steps：
1) six ammonium of 0.4g tri-chlorinations conjunction ruthenium is dissolved in 40ml ethyl alcohol, six ammonium of tri-chlorination is made and closes ruthenium solution；
2) 0.22g sodium hydroxides are dissolved in 40ml ethyl alcohol, sodium hydroxide solution is made；
3) it takes the nitrogen-doped carbon mitron that 7mL solid contents are 3wt% to close ruthenium solution with six ammonium of tri-chlorination and mixes (N doping at this time
The mass ratio that carbon nanotube closes ruthenium with six ammonium of tri-chlorination is 1:2) sodium hydroxide solution, controlling reaction temperature, are added dropwise later
It it is 25 DEG C, stir speed (S.S.) 600r/min, the final ph that reaction system is adjusted and controlled with sodium hydroxide solution is 10；
4) after the final ph requirement for reaching reaction system, 70 DEG C of constant temperature are aged 4h；
5) solution being aged being used into centrifuge washing, is transferred in reaction kettle and carries out hydro-thermal, hydrothermal temperature is 200 DEG C,
The hydro-thermal time is 12h.
6) the reaction solution drying after hydro-thermal be can be obtained into nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Fig. 1 is the present embodiment products obtained therefrom tem analysis figure, it can be seen from the figure that gained nitrogen-doped carbon nanometer pipe-dioxy
It is compound preferably to change ruthenium composite material, wherein ruthenium-oxide granular size is more regular spherical structure in 3~10nm.
It is applied obtained composite material as catalyst in the oxygen evolution reaction of catalytic electrolysis water, method is：
Using electro-chemical systems (AFMSRX rotating devices, AFCBP1 double potentiostats, Pine companies of the U.S.), rotation is utilized
Ring-disc electrode (RRDE) technology carrys out the oxygen reduction and oxygen evolution catalytic activity of Study of Catalyst.Electrode tip is by vitreous carbon disk
Electrode (diameter 5mm, geometrical surface 0.196cm2) and peripheral platinum loop electrode (geometrical surface 0.125cm2) constitute.
Electro-chemical test carries out at room temperature, is platinum filament, reference electrode Ag/ to electrode using standard three electrode system
AgCl electrodes (3mol/L Cl-), working electrode is the rotation equipped with glassy carbon electrode head (being covered with catalyst in glass carbon surface)
Rotating disc electrode (RDE), electrolyte are 0.1mol/L KOH solutions.Sample preparation：First weigh the N doping of 50mg being prepared
Carbon nanotube-ruthenic oxide composite material is dissolved in the Nafion solution of the ethyl alcohol and 50 μ L of 1mL, ultrasonic half an hour, then with shifting
Nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material sol drop that liquid rifle draws 5 μ L every time at twice enters vitreous carbon disk electrode.
Using electrochemical workstation, test obtains LSV curves.It is found that the electric current that every square centimeter ought reach is more than from LSV curves
When 10mA, overpotential 1.59V.
As a comparison, the nitrogen-doped carbon nanometer pipe in above-mentioned oxygen-absorbing reaction method-ruthenic oxide composite material is changed into city
The ruthenic oxide sold measures LSV curves, and when the electric current every square centimeter reached is more than 10mA, overpotential is more than 1.7V, that is,
It has been more than the range for measuring overpotential.
It follows that composite material, which is prepared, can effectively reduce the overpotential of oxygen evolution reaction, electrolysis elutriation is improved
The efficiency of oxygen reaction, oxygen evolution reaction that can preferably as catalyst electrolysis water.
Embodiment 2
A kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, includes the following steps：
1) 3g ruthenium trichlorides are dissolved in 150ml water, solution of ruthenium trichloride is made；
2) 1.50g sodium hydroxides are dissolved in 150ml water, sodium hydroxide solution is made；
3) it is that the nitrogen-doped carbon mitron of 3wt% mixes (nitrogen-doped carbon at this time with solution of ruthenium trichloride to take 78.75mL solid contents
The mass ratio of nanotube and ruthenium trichloride is 1:2) sodium hydroxide solution, is added dropwise later, controlling reaction temperature is 25 DEG C, is stirred
Rate 500r/min is mixed, the final ph that reaction system is adjusted and controlled with sodium hydroxide solution is 10；
4) after the final ph requirement for reaching reaction system, 60 DEG C of constant temperature are aged 5h；
5) solution being aged is used into centrifuge washing, is put into crucible later, is calcined in nitrogen atmosphere, calcining temperature
Degree is 300 DEG C, calcination time 14h；
6) composite material calcined taking-up is obtained into nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Fig. 2 is 2 products obtained therefrom tem analysis figure of the embodiment of the present invention, it can be seen from the figure that gained nitrogen-doped carbon nanometer
Pipe-ruthenic oxide composite material is compound preferably, and ruthenium-oxide granular size is more regular in 5~20nm wherein in composite material
Spherical structure.The oxygen evolution reaction in catalytic electrolysis water is applied using obtained composite material as the method for catalyst such as embodiment 1
In.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, overpotential 1.54V, that is, the composite material
The overpotential of oxygen evolution reaction can be effectively reduced, preferably the oxygen evolution reaction as catalyst electrolysis water.
Embodiment 3
A kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, includes the following steps：
1) it is 1 1g nitrosyl nitrate rutheniums to be dissolved in 100mL ratios:In 1 deionized water/ethyl alcohol, ultrasonic 0.5h；
2) it is 1 0.56g sodium hydroxides to be dissolved in 100mL ratios:In 1 deionized water/ethyl alcohol, ultrasonic 0.5h；
3) it is that the nitrogen-doped carbon mitron solution of 3wt% mixes (this with nitrosyl nitrate ruthenium solution to take 78.75mL solid contents
When nitrogen-doped carbon nanometer pipe and nitrosyl nitrate ruthenium mass ratio be 1:2) mixed solution, is added dropwise in sodium hydroxide solution
In, controlling reaction temperature is 35 DEG C, stir speed (S.S.) 800r/min, is adjusted with sodium hydroxide solution and controls the final of reaction system
PH value is 11；
4) after the final ph requirement for reaching reaction system, 90 DEG C is warming up to, 3h is aged；
5) solution being aged is washed using dialysis, is put into crucible later, is calcined in nitrogen atmosphere, calcining temperature
Degree is 500 DEG C, and calcination time is for 24 hours；
6) composite material calcined taking-up is obtained into nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Gained nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material is compound preferably, ruthenium-oxide particle wherein in composite material
Size is more regular spherical structure in 10~25nm.It is answered obtained composite material as the method for catalyst such as embodiment 1
In the oxygen evolution reaction of catalytic electrolysis water.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, mistake
Potential is 1.56V, that is, the composite material can effectively reduce the overpotential of oxygen evolution reaction, be preferably electrolysed as catalyst
The oxygen evolution reaction of water.
Embodiment 4
A kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, includes the following steps：
1) it is 1 by 20g proportionings:1 hydrate ruthenium trichloride and six ammonium of tri-chlorination closes ruthenium and is dissolved in 2000ml deionized waters, makes
Obtain ruthenium solution；
2) 5mol/L ammonia spirits are configured, 8ml ammonium hydroxide is taken out and is added in 1992ml deionized waters, ammonia spirit is made；
3) taking 350mL solid contents to be mixed with ruthenium source solution for the nitrogen-doped carbon mitron solution of 3wt%, (nitrogen-doped carbon is received at this time
The mass ratio that mitron closes ruthenium total amount with hydrate ruthenium trichloride and six ammonium of tri-chlorination is 1:2) it, is added dropwise in mixed solution later
Ammonia spirit, controlling reaction temperature are 25 DEG C, stir speed (S.S.) 600r/min, are adjusted with ammonia spirit and control reaction system most
Whole pH value is 12；
4) after the final ph requirement for reaching reaction system, 70 DEG C of ageing 5h；
5) solution being aged is dialysed and is washed, solution is transferred in hydrothermal reaction kettle carry out hydro-thermal later, when hydro-thermal
Between 12h, 100 DEG C of hydrothermal temperature；
6) the complete solution of hydro-thermal is dried, you can obtain nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Gained nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material is compound preferably, ruthenium-oxide particle wherein in composite material
Size is more regular spherical structure in 1~15nm.It is answered obtained composite material as the method for catalyst such as embodiment 1
In the oxygen evolution reaction of catalytic electrolysis water.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, mistake
Potential is in 1.7V or more, and there is no the overpotential for reducing oxygen evolution reaction for the composite material.
Embodiment 5
A kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, includes the following steps：
1) it is 1 by 1g ratios:1:1 ruthenium trichloride, nitrosyl nitrate ruthenium, six ammonium of tri-chlorination close ruthenium and are dissolved in 100mL's
1:In 2 deionized waters/ethyl alcohol, ruthenium source solution is made；
2) 0.3g potassium hydroxide is dissolved in the 1 of 100mL:In 2 deionized waters/ethyl alcohol, potassium hydroxide solution is made；
3) taking 14mL solid contents to be mixed with ruthenium source solution for the nitrogen-doped carbon mitron solution of 3wt%, (nitrogen-doped carbon is received at this time
The mass ratio that mitron closes ruthenium total amount with ruthenium trichloride, nitrosyl nitrate ruthenium, six ammonium of tri-chlorination is 1:2), by potassium hydroxide solution
It is added dropwise in the solution of ruthenium source, controlling reaction temperature is 30 DEG C, stir speed (S.S.) 500r/min, adjusts and controls reaction system most
Whole pH value is 10；
4) after the final ph requirement for reaching reaction system, 80 DEG C is warming up to, 3h is aged；
5) solution transfer crucible is calcined in argon atmosphere, is calcined by the solution filtering and washing that will be aged later
Time for 24 hours, 300 DEG C of calcination temperature；
6) composite material calcined taking-up is obtained into nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Gained nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material is compound preferably, ruthenium-oxide particle wherein in composite material
Size is regular spherical structure in 1~3nm.It is applied obtained composite material as the method for catalyst such as embodiment 1
In the oxygen evolution reaction of catalytic electrolysis water.In the LSV curves such as Fig. 3 of gained composite material shown in curve 5.It is tested through LSV it is found that working as
When the electric current every square centimeter reached is more than 10mA, overpotential 1.51V, that is, occur oxygen evolution reaction overpotential it is low, have compared with
Good OER catalytic performances, oxygen evolution reaction that can preferably as catalyst electrolysis water.
Embodiment 6
A kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, includes the following steps：
1) 2g hydrate ruthenium trichlorides are dissolved in 200mL deionized waters, solution of ruthenium trichloride is made；
2) 1.5g sodium hydroxides are dissolved in 100mL deionized waters, sodium hydroxide solution is made；
3) it is that the nitrogen-doped carbon mitron solution of 3wt% mixes (N doping at this time with solution of ruthenium trichloride to take 70mL solid contents
The mass ratio of carbon nanotube and hydrate ruthenium trichloride is 1:2), sodium hydroxide solution is instilled to solution of ruthenium trichloride dropwise, controlled
Reaction temperature is 50 DEG C, stir speed (S.S.) 900r/min, is adjusted with sodium hydroxide solution and the final ph for controlling reaction system is
12；
4) after the final ph requirement for reaching reaction system, 80 DEG C is warming up to, 3h is aged；
5) solution being aged is dialysed and is washed, solution is transferred in hydrothermal reaction kettle carry out hydro-thermal later, when hydro-thermal
Between 4h, 160 DEG C of hydrothermal temperature；
6) the complete solution of hydro-thermal is dried, you can obtain nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Gained nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material is compound preferably, wherein ruthenium-oxide granular size 1~
7nm is more regular spherical structure.It is applied obtained composite material as the method for catalyst such as embodiment 1 in catalysis electricity
In the oxygen evolution reaction of Xie Shui.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, overpotential is in 1.7V
More than, there is no the overpotential for reducing oxygen evolution reaction for the composite material.
Embodiment 7
A kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, includes the following steps：
1) it is 1 by 1.5g ratios:1 six ammonium of tri-chlorination closes ruthenium, nitrosyl nitrate ruthenium is dissolved in 105ml water, and ruthenium is made
Source solution；
2) 5mol/L ammonia spirits will be configured, 2ml ammonium hydroxide is taken out and is added in 118mL deionized waters；
3) it is that the nitrogen-doped carbon mitron solution of 3wt% mixes (N doping at this time with solution of ruthenium trichloride to take 21mL solid contents
It is 1 that carbon nanotube closes the total mass ratio of ruthenium, nitrosyl nitrate ruthenium with six ammonium of tri-chlorination:2) ruthenium, is added dropwise in ammonia spirit
Source solution, controlling reaction temperature are 40 DEG C, and stir speed (S.S.) 300r/min is adjusted with sodium hydroxide solution and controlled reaction system
Final ph is 11；
4) after the final ph requirement for reaching reaction system, 70 DEG C is warming up to, 4h is aged；
5) solution being aged is dialysed and is washed, solution is transferred in hydrothermal reaction kettle carry out hydro-thermal later, when hydro-thermal
Between 12h, 130 DEG C of hydrothermal temperature；
6) the complete solution of hydro-thermal is dried, places and is calcined in nitrogen atmosphere in crucible, the calcination time is 12h, temperature
Degree is 300 DEG C；
7) composite material calcined taking-up is obtained into nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Gained nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material is compound preferably, wherein ruthenium-oxide granular size 5~
15nm is more regular spherical structure.It is applied obtained composite material as the method for catalyst such as embodiment 1 in catalysis electricity
In the oxygen evolution reaction of Xie Shui.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, overpotential is
1.57V, that is, the composite material can effectively reduce the overpotential of oxygen evolution reaction, can be preferably as catalyst electrolysis water
Oxygen evolution reaction.
Embodiment 8
A kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, includes the following steps：
1) 1g nitrosyl nitrate rutheniums are dissolved in 10mL deionized waters, ruthenium source solution is made；
2) 0.56g sodium hydroxides are dissolved in 40mL deionized waters, sodium hydroxide solution is made；
3) it is that the nitrogen-doped carbon mitron solution of 3wt% mixes (nitrogen-doped carbon at this time with solution of ruthenium trichloride to take 7mL solid contents
The mass ratio of nanotube and nitrosyl nitrate ruthenium is 1:2) ruthenium source solution, control reaction, is added dropwise in sodium hydroxide solution
Temperature is 35 DEG C, stir speed (S.S.) 400r/min, and the final ph that reaction system is adjusted and controlled with sodium hydroxide solution is 10；
4) after the final ph requirement for reaching reaction system, 50 DEG C is warming up to, 5h is aged；
5) solution being aged is dialysed and is washed, solution is transferred in hydrothermal reaction kettle carry out hydro-thermal later, when hydro-thermal
Between 12h, 230 DEG C of calcination temperature；
6) the complete solution of hydro-thermal is dried, places and is calcined in argon atmosphere in crucible, the calcination time is 12h, temperature
Degree is 500 DEG C；
7) composite material calcined taking-up is obtained into nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Gained nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material is compound preferably, wherein ruthenium-oxide granular size 10~
25nm is more regular spherical structure.It is applied obtained composite material as the method for catalyst such as embodiment 1 in catalysis electricity
In the oxygen evolution reaction of Xie Shui.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, overpotential is
1.53V, that is, the composite material can effectively reduce the overpotential of oxygen evolution reaction, can be preferably as catalyst electrolysis water
Oxygen evolution reaction.
Embodiment 9
Embodiment 5 is repeated, difference lies in be changed to 12h, remaining condition is constant, and nitrogen-doped carbon is prepared by calcination time
Nanotube-ruthenic oxide composite material.Its OER catalytic performance is as shown in the curve 4 in Fig. 3.
Comparative example 1
A kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, includes the following steps：
1) 5g hydrate ruthenium trichlorides are dissolved in 500mL ethyl alcohol, solution of ruthenium trichloride is made；
2) 3.5g sodium carbonate is dissolved in 500mL ethyl alcohol, sodium carbonate liquor is made；
3) it is that the nitrogen-doped carbon mitron solution of 3wt% mixes (N doping at this time with solution of ruthenium trichloride to take 35mL solid contents
The mass ratio of carbon nanotube and hydrate ruthenium trichloride is 1:2) solution of ruthenium trichloride, is added dropwise in sodium carbonate liquor, control is anti-
It is 35 DEG C, stir speed (S.S.) 600r/min to answer temperature, and the final ph that reaction system is adjusted and controlled with sodium carbonate liquor is 7；
4) after the final ph requirement for reaching reaction system, 90 DEG C is warming up to, 3h is aged；
5) solution transfer crucible is calcined, when calcination by the solution filtering and washing that will be aged in argon atmosphere later
Between 4h, 100 DEG C of calcination temperature；
6) composite material calcined taking-up is obtained into nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Wherein ruthenium-oxide granular size dispersibility is larger in gained nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material,
Grain size is in 10~40nm, and gained composite material regularity is poor.
Comparative example 2
Embodiment 5 is repeated, difference lies in by step 3), the pH value of reaction system is controlled 8, remaining condition is constant, system
It is standby to obtain nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.The grain size of ruthenic oxide reaches 5~30nm in the composite material,
Granule-morphology regularity is poor.It is applied obtained composite material as the method for catalyst such as embodiment 1 in catalytic electrolysis water
Oxygen evolution reaction in.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, overpotential 1.68V, that is,
The ability that the composite material reduces the overpotential of oxygen evolution reaction is poor.
Comparative example 3
Embodiment 5 is repeated, difference lies in, by step 3), the pH value of reaction system is controlled 13, remaining condition is constant,
Nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material is prepared.In the composite material grain size of ruthenic oxide reach 3~
30nm, granule-morphology regularity are poor.It is applied obtained composite material as the method for catalyst such as embodiment 1 in catalysis electricity
In the oxygen evolution reaction of Xie Shui.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, overpotential is
1.66V, that is, the ability that the composite material reduces the overpotential of oxygen evolution reaction is poor.
Comparative example 4
Embodiment 5 is repeated, difference lies in by step 4), Aging Temperature is changed to 40 DEG C, remaining condition is constant, is prepared into
To nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.The grain size of ruthenic oxide reaches 3~32nm, particle in the composite material
Regular appearance is poor.The analysis in catalytic electrolysis water is applied using obtained composite material as the method for catalyst such as embodiment 1
In oxygen reaction.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, overpotential is in 1.7V or more, that is,
The ability that the composite material reduces the overpotential of oxygen evolution reaction is poor.
Comparative example 5
Embodiment 5 is repeated, difference lies in by step 5), calcination temperature is changed to 700 DEG C, remaining condition is constant, is prepared into
To nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.The grain size of ruthenic oxide reaches 12~28nm, particle in the composite material
Regular appearance is poor.
Comparative example 6
Embodiment 5 is repeated, difference lies in by step 5), calcination temperature is changed to 250 DEG C, remaining condition is constant, is prepared into
To nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.The grain size of ruthenic oxide reaches 8~30nm, particle in the composite material
Regular appearance is poor.The analysis in catalytic electrolysis water is applied using obtained composite material as the method for catalyst such as embodiment 1
In oxygen reaction.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, overpotential is in 1.7V or more, that is,
The ability that the composite material reduces the overpotential of oxygen evolution reaction is poor.
Comparative example 7
Embodiment 5 is repeated, difference lies in by step 5), calcination time is changed to 10h, 4h, 2h, 1h, remaining condition is not
Become, nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material is prepared.In the composite material grain size of ruthenic oxide reach 8~
35nm, granule-morphology regularity are poor.Shown in curve 1~3 in composite material OER catalytic performances such as chart 3.From Fig. 3
It is found that when calcination temperature is less than 12h, when the electric current every square centimeter reached is more than 10mA, overpotential is very big, the composite material
The ability for reducing the overpotential of oxygen evolution reaction is poor.
Comparative example 8
Embodiment 5 is repeated, difference lies in by step 5), calcination time is changed to 40h, remaining condition is constant, is prepared
Nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.The grain size of ruthenic oxide reaches 20~40nm, granulated in the composite material
Looks regularity is poor.
Embodiment 10
High gravity rotating packed bed reactor used in the present invention is the prior art, such as published patent
(ZL95215430.7)；The present invention use high gravity rotating packed bed reactor schematic diagram as shown in figure 4, in figure it is each number institute's generation
The meaning of table is：1- rutheniums salt/nitrogen-doped carbon nanometer pipe mixed solution feed inlet, 2- lye feed inlets, 3- fillers, 4- motors, 5-
Suspension exports.
A kind of side preparing nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material using high gravity rotating packed bed reactor
Method includes the following steps：
1) 5g ruthenium trichlorides are dissolved in the deionized water of 300ml, the nitrogen-doped carbon rice that 35mL solid contents are 3wt% is added
Pipe solution, by mixed liquor, it is added in ruthenium salt/nitrogen-doped carbon nanometer pipe mixed solution storage tank；It is by sodium hydroxide mass concentration
0.5% aqueous solution 300ml is added in lye storage tank；
2) hypergravity rotating device is opened, adjusts rotating speed to 2500rpm；
3) feed pump is opened, mixed solution and lye are delivered to progress precipitated crystal reaction in revolving bed simultaneously, and control
The feed rate ratio of ruthenium salting liquid and lye processed is 1:1, the temperature for controlling reaction system is 25 DEG C；
4) wait for that ruthenium salting liquid and lye charging finish, reaction gained reaction solution all after outflow hypergravity rotating device, closes
Close hypergravity rotating device；
5) gained reaction solution is transferred to dispersion tank, opens the ultrasonic disperse device of dispersion tank, is ultrasonically treated reaction solution 4min, instead
It is 70 DEG C to answer temperature；
6) using dialysis washing impurity, reaction solution is transferred to crucible later, is calcined in nitrogen atmosphere, calcination temperature is
300 DEG C, calcination time is for 24 hours；
7) composite material calcined taking-up is obtained into nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Gained nitrogen-doped carbon nanometer pipe and ruthenium-oxide composite material are compound preferably, wherein ruthenium-oxide granular size 10~
25nm is more regular spherical structure.The composite material has preferable OER catalytic performances.Using obtained composite material as
The method of catalyst such as embodiment 1 is applied in the oxygen evolution reaction of catalytic electrolysis water.From LSV curves it is found that when every square centimeter
When the electric current reached is more than 10mA, overpotential is relatively low, which has the ability for the overpotential for reducing oxygen evolution reaction.
Embodiment 11
Bushing type annular micro passage reaction used in the present invention is the prior art, such as published patent
(200710177291.1 or 200810116581.X).The present invention uses bushing type annular micro passage reaction schematic diagram such as Fig. 5
It is shown.In figure it is each number representated by meaning be：6- inner tubes, 7- outer tubes, the outlet of 8- continuous phases, 9- annulars microchannel, 10- micropores
Film, 11- continuous phase imports, 12- dispersed phase fluid imports, 13- flanges.
A kind of side preparing nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material using bushing type annular micro passage reaction
Method includes the following steps：
1) 2g nitrosyl nitrate rutheniums are dissolved in the 1 of 100mL:In 3 deionized waters/ethyl alcohol, 14mL solid contents, which are added, is
Mixed liquor is added in ruthenium source/nitrogen-doped carbon nanometer pipe accumulator tank the nitrogen-doped carbon mitron solution of 3wt%；By the hydrogen-oxygen of 1.12g
Change sodium and is dissolved in the 1 of 100mL:It is added in alkali storage slot in 3 deionized waters/ethyl alcohol；
2) temperature of control reaction system is 25 DEG C；Feed pump is opened, mixed solution and lye are delivered to casing simultaneously
Precipitated crystal reaction is carried out in formula annular micro passage reaction, and the feed rate for controlling ruthenium salting liquid and lye is respectively 2L/
Min and 2L/min；
3) gained reaction solution is transferred to dispersion tank, opens the ultrasonic disperse device of dispersion tank, is ultrasonically treated reaction solution 3h, ultrasound
Temperature is 80 DEG C；
4) centrifuge washing impurity is used, reaction solution is transferred to crucible later, is calcined in nitrogen atmosphere, calcination temperature is
500 DEG C, calcination time is for 24 hours；
5) composite material calcined taking-up is obtained into nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
Gained nitrogen-doped carbon nanometer pipe and ruthenium-oxide composite material are compound preferably, wherein ruthenium-oxide granular size 15~
25nm is more regular spherical structure.It is applied obtained composite material as the method for catalyst such as embodiment 1 in catalysis electricity
In the oxygen evolution reaction of Xie Shui.From LSV curves it is found that when the electric current every square centimeter reached is more than 10mA, overpotential be it is relatively low,
The composite material has the ability for the overpotential for reducing oxygen evolution reaction.
Embodiment 12
Repeat embodiment 10, the difference is that only, used molecular mixing enhanced reactor be supergravity reactor,
One in rotatable reactor, rotor-stator reactor, static mixing reactor, Y types micro passage reaction, T-type micro passage reaction
Kind, remaining process conditions is similar；Its implementation result is similar to Example 10.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is every to belong to this hair
Row of the obvious changes or variations that bright technical solution is extended out still in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material, which is characterized in that include the following steps：
1) nitrogen-doped carbon nanometer pipe solution is mixed with ruthenium source solution, obtains mixed liquor, then lye is added into mixed liquor, mixing is equal
It is even, obtain the precursor liquid that pH is 10~12；
2) precursor liquid is aged to 3~5h, then centrifuge washing at a temperature of 50~90 DEG C, obtains sediment；
3) sediment is subjected to hydro-thermal reaction or calcining, obtains nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material.
2. preparation method according to claim 1, which is characterized in that in step 1), the nitrogen-doped carbon nanometer pipe solution
In nitrogen-doped carbon nanometer pipe and ruthenium source solution in the mass ratio in ruthenium source be 1:1~1:5, preferably 1:1~1:3, more preferably
It is 1:1.
3. preparation method according to claim 1, which is characterized in that in step 1), the pH of the precursor liquid is 10~11,
Preferably 10.
4. preparation method according to claim 1, which is characterized in that in step 1), the uniformly mixed method is to adopt
Lye is added in mixed liquor with the method being added dropwise dropwise, and is stirred simultaneously, stir speed (S.S.) is 100~600r/min, preferably
200~400r/min, more preferably 300r/min；Alternatively, the uniformly mixed method is to use high-gravity rotating bed strength
Mixing, high-gravity rotating bed peristaltic pump feed rate be 200~600mL/min, high-gravity rotating bed rotating speed be 800~
2500r/min；Preferably, high-gravity rotating bed peristaltic pump feed rate is 400~600mL/min, high-gravity rotating bed
Rotating speed is 1200~1800r/min；It is highly preferred that high-gravity rotating bed peristaltic pump feed rate is 600mL/min, hypergravity
The rotating speed of revolving bed is 1200r/min.
5. preparation method according to claim 1, which is characterized in that in step 2), Aging Temperature is 70~80 DEG C, preferably
It is 80 DEG C.
6. preparation method according to claim 1, which is characterized in that in step 3), the temperature of the hydro-thermal reaction is 100
~230 DEG C, the time be 4~for 24 hours；Preferably, the temperature of hydro-thermal reaction is 200~230 DEG C, and the time is 8~12h；It is highly preferred that
The temperature of hydro-thermal reaction is 230 DEG C, time 12h.
7. preparation method according to claim 1, which is characterized in that in step 3), the calcining is in atmosphere of inert gases
Middle progress, the inert gas are preferably nitrogen；The temperature of the calcining is 300~500 DEG C, and calcination time is 12~36h；More
Preferably, the temperature of the calcining is 300 DEG C, and calcination time is for 24 hours.
8. preparation method according to claim 1, which is characterized in that in step 1), the ruthenium source choosing in the solution of the ruthenium source
The mixing of one or more of ruthenium, nitrosyl nitrate ruthenium is closed from ruthenic chloride, six ammonium of tri-chlorination；Alkali in the lye is selected from
The mixing of one or more of sodium hydroxide, sodium carbonate, ammonium hydroxide；Solvent in ruthenium source solution and the alkali is independently
The mixing selected from water, one or both of ethyl alcohol.
9. nitrogen-doped carbon nanometer pipe-ruthenic oxide as claim 1~8 any one of them preparation method is prepared is compound
Material, which is characterized in that ruthenic oxide particle is incorporated evenly among in the nitrogen-doped carbon nanometer pipe-ruthenic oxide composite material
The surface and inside of nitrogen-doped carbon nanometer pipe；Nitrogen-doped carbon nanometer pipe length is 0.5~30 μm, a diameter of 30~50nm, oxidation
Ruthenium granule-morphology is ball-type or club shaped structure, and particle scale is 1~20nm.
10. nitrogen-doped carbon nanometer pipe-ruthenic oxide as claim 1~8 any one of them preparation method is prepared is multiple
Application of the condensation material as catalyst in the oxygen evolution reaction of catalytic electrolysis water.
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