CN105239093B - A kind of nano combined anode material and preparation method and application - Google Patents
A kind of nano combined anode material and preparation method and application Download PDFInfo
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- 239000010405 anode material Substances 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title claims description 12
- 229910003119 ZnCo2O4 Inorganic materials 0.000 claims abstract description 91
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000010931 gold Substances 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011165 3D composite Substances 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims 1
- 238000012546 transfer Methods 0.000 abstract description 7
- 238000005844 autocatalytic reaction Methods 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 description 15
- 229910017052 cobalt Inorganic materials 0.000 description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 15
- 150000002500 ions Chemical class 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
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- 229910021281 Co3O4In Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
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- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910001408 cation oxide Inorganic materials 0.000 description 1
- QVCCUCPJAKTFEW-UHFFFAOYSA-N chloric acid gold Chemical compound Cl(=O)(=O)O.[Au] QVCCUCPJAKTFEW-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 239000011238 particulate composite Substances 0.000 description 1
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- -1 polyethylene pyrrole Pyrrolidone Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention proposes a kind of N doped CNT/ZnCo2O4/ Au core-shell nano tubular composite materials, nitrogen-doped carbon nanometer pipe is by outer layer ZnCo2O4Nano particle is coated, and Au is particle studded in ZnCo2O4In nano particle.Replace the Co of four sides position with Zn so that Co utilization rates reach 100%, and by ZnCo2O4It is grown on the CNT of N doping, so as to improve ZnCo2O4Electric conductivity and specific surface area, and then increase ZnCo2O4Active site and mass-transfer efficiency；ZnCo is embedded in by Au nano particles2O4In, improve ZnCo2O4Middle Co ionic valence conditions, make it further improve autocatalysis performance.
Description
Technical field
The present invention relates to energy storage material application field, more particularly to a kind of Ndoped-CNT/ZnCo2O4/ Au receives
Rice composite anode materials and preparation method and application.
Background technology
In order to the utilization ratio for supporting sustainable economic development, the energy becomes more and more important, the exploitation of regenerative resource
Using the theme for more turning into energy field.Current main regenerative resource, such as wind energy and solar energy not only possess sustainable
The characteristics of, it is often more important that their not subsidiary harm that environment and the mankind are caused.But, the regenerative resource of the overwhelming majority
It is owned by a common shortcoming, that is, intermittent, the influence that the change in season and the change in region are caused to it is extremely huge
Greatly.However, the power generation unit in local energy reserves system will disappear this uncertainty in energy supply system
Remove.In this system framework, electrolysis water plays vital effect in sustainable energy system.Water electrolysis system is one
Electrochemical energy converting system is planted, the water of intermittent energy supply can be changed into the energy of sustainable energy supply for it：Hydrogen (and oxygen
Gas).After vanTrostwijk and Deiman was tentatively studied and reported in 1789 to electrolysis aqueous systems, water system is electrolysed
Unification is directly furtherd investigate, however, water electrolysis system also rests on theoretical research, is not suitable for practical application, therefore
Substantial amounts of research still needs to input.In actual applications, electrolysis aqueous systems have possessed flexible operability, zero-emission, height
The features such as purity gases output, and solving efficiency and stability these two aspects problem becomes water electrolysis system and has economy high
The premise of benefit.
Recently, new cheap anode of electrolytic water catalysis material, such as manganese, nickel, cobalt, urge because it has equivalent to noble metal base
Change the electrolytic water electric catalysis activity high of material, by extensive concern and primary study.In these anode electrocatalysis materials, point
Spar type cobalt base oxide (such as Co3O4) because enjoying pass as the efficient anode electrocatalysis material in alkaline aqueous solution system
Note.However, having due to cobalt-based catalyst material its intrinsic low electric conductivity, low specific surface area, mass-transfer efficiency and to environment larger
Toxicity, and relative to the low electro-chemical activity of other materials, and be extremely limited in actual applications, thus in order to
Overcome the above difficult, it is necessary to be carried out to cobalt-based catalyst material rational modified so as to reach catalytic performance higher.
ZnCo2O4With respect to Co3O4For, in cubic spinel structure, the Zn ions of divalent state in occupation of four sides position,
The Co ions of three valence states are in occupation of octahedral position.The cation of isomery replaces so that this multi-element metal center possesses multivalent state shape
State, and activation energy when electronics is shifted between cation is reduced, so as to improve overall electric conductivity.On the other hand,
Co3O4Divalent state Co ions in occupation of four sides position, three valence state Co ions in occupation of octahedral position, yet with four sides position
It is not active site during anode-catalyzed, so not only causes that the utilization rate of Co ions is low, and the Co of a large amount of toxicity is tight
Endanger environment in important place.The substitution of Zn ion pairs four sides position Co ions does not reduce the activity of integer catalyzer not only, and
The utilization rate of Co ions can be improved and the pollution to environment is reduced.
In order to simultaneously overcome the problem that electric conductivity is relatively low, specific surface area is relatively low and mass-transfer efficiency is poor, with high electrical conductivity,
The addition of the cobalt base oxide growth substrate of high-specific surface area turns into first-selection.Additionally, growth substrate also must simultaneously possess higher
Mechanical stability with this come stable and uniform be distributed in its surface electrocatalysis material and improve material utilization rate.Carbon nanometer
Pipe, as a member of c-based nanomaterial, has the advantages that various uniquenesses：Electron conduction high, high-specific surface area, machinery high are strong
Degree, preferable Structural flexibility, therefore for cobalt-based electrocatalysis material provides a kind of ideal growth substrate.Meanwhile, nitrogen
Introducing can change the primary attribute of carbon material, because the electronegativity of nitrogen is eager to excel compared with carbon, therefore relative to being evenly distributed in each
The C-C conjugated pi electrons of carbon atom, the N-C conjugated pi electrons centered on nitrogen can then shift；And exactly this distribution is not
Uniformly, so that carbon atom turns into positive valence state anode activated centre.On the other hand, N-C conjugated pi electrons due to Co metals from
Son is coordinated, and enhances the stability of electronics conferrer (Co ions), and live for cobalt-base catalyst provides more catalysis
Property point.
Inlaying for Au nano particles is that another improves cobalt-based anode catalyst Activity Strategy, and Au nano particles can be made
Co cation oxides are modified for electronegativity electronic slot high so that Co ionic valence conditions are raised, therefore change its anode
Electro catalytic activity.Meanwhile, cobalt-base catalyst can inherently improve anode electro-catalysis with the synergic catalytic effect of foreign substance
Activity.
The Co for being found at present3O4Nano catalytic material, shows good performance in terms of anode-catalyzed electrolysis water, but
It is due to Co3O4Intrinsic resistance is big, poorly conductive, and the nano material being synthesized all has compared with low specific surface area, so that
Its active site is few, and mass-transfer efficiency is low.Compared to noble metal catalyst catalytic performance, Co3O4Electro-chemical activity could not also reach reality
The standard of border application.Further, since Co3O4In tetrahedral Co ions do not have catalysis activity, therefore Co3O4There is Co profits
With the low problem of rate.
The content of the invention
An object of the present invention is to provide a kind of nano combined anode material with good anode electrocatalysis characteristic.
The second object of the present invention is to provide a kind of preparation method of nano combined anode material, in order to overcome existing skill
Cobalt base oxide is difficult to grow problem on the carbon nanotubes in art, and Au metal nanoparticles are not easily-controllable in growth course
Problem processed, there is provided a kind of simple directly by small size ZnCo2O4Nano particle is wrapped in CNT outer layers, and Au nano particles are inlayed
In ZnCo2O4Method in nano particle.
The third object of the present invention proposes a kind of application of nano combined anode material in electrolysis water, has expanded the material
Practical application.
The technical proposal of the invention is realized in this way：
A kind of nano combined anode material is N doped-CNT/ZnCo2O4/ Au core-shell nano tubular composite materials.
Preferably, the N doped-CNT/ZnCo2O4/ Au core-shell nano tubular composite materials are made up of following structure：
Nitrogen-doped carbon nanometer pipe is by outer layer ZnCo2O4Nano particle is coated, and Au is particle studded in ZnCo2O4In nano particle.
A kind of preparation method of nano combined anode material, comprises the following steps：
Step one, by CNT and ZnCo after acidifying2O4Precursor aqueous solution is mutually mixed and is flowed back, thereafter by mixed solution
Hydro-thermal reaction is carried out, ZnCo is finally obtained2O4The three-dimensional composite material of core-shell structure of nano particle cladding N doping CNT；
Step 2, by N doped-CNT/ZnCo2O4Composite is placed in Au precursor aqueous solutions, and by the xenon lamp short time
Illumination, makes Au nano particles be embedded in N doped-CNT/ZnCo2O4In composite.
Preferably, described ZnCo2O4Precursor aqueous solution is made up of following component：Zinc acetate, cobalt acetate, ammoniacal liquor, polyethylene pyrrole
Pyrrolidone, ethanol, water；The Au precursor aqueous solutions are made up of following component：Gold chloride, water.
Preferably, described ZnCo2O4The specific composition of precursor aqueous solution is：The Zn (OAc) of 0.0128mol/L2·2H2O、
The Co (OAc) of 0.0064mol/L2·4H2O, mass percent concentration are 25% ammoniacal liquor, second alcohol and water, wherein ethanol and water
Volume ratio is 24:1；The Au precursor aqueous solutions are the aqueous solution of chloraurate of 0.1mmol/L.
Preferably, the reflux time in step one is 20h, and reaction temperature is 80 DEG C；Hydro-thermal reaction temperature in step one
It is 150 DEG C to spend, and the reaction time is 3h.
Preferably, Xenon light shining intensity described in step 2 is 300mW/cm2, light application time is 15min.
Preferably, a diameter of 20nm of the CNT.
A kind of application of nano combined anode material in electrolysis water.
Combination electrode material of the invention can be used as anode electrode catalyst material, and in order to solve cobalt-based catalyst material, its is intrinsic
Low electric conductivity, low specific surface area, low mass transfer efficiency and the problems such as there is larger toxicity to environment, and relative to other materials
The low electro-chemical activity of material, cobalt base oxide electric conductivity is improved by providing one kind using CNT, increases its specific surface area,
Strengthen the technology of mass-transfer efficiency；A kind of Co on utilization Zn substitutions four sides position is provided, the technology of catalyst toxicity is reduced；There is provided
One kind utilizes Au nano particles, improves the technology of cobalt base oxide activity.
N doping CNT and ZnCo with excellent anode-catalyzed performance provided by the present invention2O4Nano particle and Au nanometers
Particulate composite, its formula is：N doped-CNT/ZnCo2O4, its pattern is ZnCo2O4Nano particle is wrapped in nitrogen
On doping CNT, Au nano particles are embedded in ZnCo2O4In.The material had both possessed the high conductivity that CNT brings, high-specific surface area etc.
Feature, while having ZnCo concurrently again2O4Excellent catalytic performance.
In the inventive solutions, by setting suitable ZnCo2O4The component and its ratio of precursor aqueous solution, make
ZnCo2O4Energy fixed growth is on CNT；By setting suitable ZnCo2O4Hydro-thermal time and temperature, it is suitable to obtain
ZnCo2O4Nanoparticle size；By setting suitable Au nano particles reducing condition so that Au nano particles are uniformly embedded in
ZnCo2O4In.
Beneficial effects of the present invention are：
Nano combined anode material of the invention is N doped-CNT/ZnCo2O4/ Au core-shell nano tubular composite materials,
Zn will be used to replace the Co of four sides position so that Co utilization rates reach 100%, and by ZnCo2O4It is grown on the CNT of N doping,
So as to improve ZnCo2O4Electric conductivity and specific surface area, and then increase ZnCo2O4Active site and mass-transfer efficiency；By Au nanometers
It is particle studded in ZnCo2O4In, improve ZnCo2O4Middle Co ionic valence conditions, make it further improve autocatalysis performance.
In the present invention program, by various reaction conditions, regulate and control ZnCo2O4The growth of nano particle and Au nano particles,
Obtain the N doped-CNT/ZnCo that anode-catalyzed performance is further lifted2O4/ Au composites.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also
Other accompanying drawings are obtained with according to these accompanying drawings.
(a) and (b) is ESEM (SEM) picture of CNT under different multiples in Fig. 1；C () and (d) is N under different multiples
doped-CNT/ZnCo2O4ESEM (SEM) picture.
(a) is N doped-CNT/ZnCo in Fig. 22O4/Au、ZnCo2O4With X-ray diffraction (XRD) spectrogram of CNT, (b,
C) it is N doped-CNT/ZnCo under different multiples2O4ESEM (SEM) picture of/Au composites, (d) is N doped-
CNT/ZnCo2O4Transmission electron microscope (TEM) picture of/Au composites.
(a) is N doped-CNT/ZnCo in Fig. 32O4/Au、N doped-CNT/ZnCo2O4、N doped-CNT/Co3O4
And ZnCo2O4Polarization curve；B () is N doped-CNT/ZnCo2O4/Au、N doped-CNT/ZnCo2O4、N doped-
CNT/Co3O4And ZnCo2O4Tafel slope figure；C () is N doped-CNT/ZnCo2O4/Au、N doped-CNT/
ZnCo2O4、N doped-CNT/Co3O4And ZnCo2O4Electrochemical surface area figure；D () is N doped-CNT/ZnCo2O4/
Au、N doped-CNT/ZnCo2O4、N doped-CNT/Co3O4And ZnCo2O4Impedance diagram.
(a) is N doped-CNT/ZnCo in Fig. 42O4/ Au and CNT/IrO2Polarization curve；B () is N doped-
CNT/ZnCo2O4/ Au and CNT/IrO2Tafel slope figure.
The N doped-CNT/ZnCo of different the hydro-thermal reaction times in Fig. 52O4ESEM (SEM) picture of composite：
(a)0.5h；(b)1h；(c)1.5h；(d)2h；(e)2.5h；(f)3h.
In Fig. 6 (a-c) be different multiples under the hydro-thermal reaction time be 4h after N doped-CNT/ZnCo2O4Composite
ESEM (SEM) picture.
ZnCo in Fig. 72O4The growth mechanism schematic diagram grown on CNT.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described case study on implementation is only a part of embodiment of the invention, rather than whole embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art obtained under the premise of creative work is not made it is all its
His embodiment, belongs to the scope of protection of the invention.
Embodiment 1
ZnCo2O4Growth on N doping CNT be by the co-electrodeposition method that flows back, and hydrothermal decomposition crystallisation realize.
Before backflow co-deposition is carried out, business CNT need to be by the acidifying of concentrated acid so that CNT surface generation can allow ZnCo2O4Presoma into
Functional group's (carboxyl) of core.The acidifying flow is：In putting 1g CNT into 250mL round-bottomed flasks, and add the 23mL concentrated sulfuric acids, room
The lower stirring 12h of temperature.Hereafter, heating stirring to temperature reaches 40 DEG C in flask being transferred into oil bath pan, and keeping temperature is constant, will
0.416g potassium nitrate is added into flask, is then lentamente added into flask 1g potassium permanganate, is stirred at maintaining the temperature at 40 DEG C
30min.3mL distilled water is first added toward flask afterwards, 3mL distilled water is added after 5min, 40mL distilled water is added after 5min,
140mL distilled water is added after 15min and 10mL concentration is 30% hydrogen peroxide, and stir 30min.Then will be mixed in flask
Closing solution carries out decompression suction filtration, washes, and the oxidation CNT that will be obtained after filtering is freezed, and is stored for future use thereafter.
By 0.3188g Co (OAc)2With 0.1405g Zn (OAc)2Add into the mixed solution of 100mL second alcohol and waters
(VEthanol:VWater=24:1), after the solid in solution is completely dissolved, take the CNT after the above-mentioned acidifyings of 0.068g and add above solution
In, the ammoniacal liquor that 1mL concentration is 25% is added dropwise toward solution for ultrasonic 20min, and mixed solution is transferred into 250mL round-bottomed flasks, and
It is placed in oil bath pan and flows back, reflux temperature is 80 DEG C, and return time is 20h.Above-mentioned solution is transferred in reactor, in 150
DEG C hydro-thermal reaction 1h.Mixed solution after hydro-thermal reaction is carried out into decompression suction filtration, washing, is dried, obtain N doped-CNT/
ZnCo2O4。
By dried N doped-CNT/ZnCo2O4Mixed solution is coated in FTO conduction glass by ultrasound in distilled water
On glass, FTO electro-conductive glass is immersed in the chloric acid gold solution of 0.1mmol/L, and 1h is stood under dark surrounds, will then contained
There is the chlorauric acid solution of the FTO electro-conductive glass illumination 15min under xenon lamp, take out FTO electro-conductive glass, washing is dried, finally given
N doped-CNT/ZnCo2O4/Au。
Performance test：CNT to preparing has carried out X-ray powder diffraction test (XRD) and has used Flied emission Scanning Electron
Microscope carries out morphology observation, and as a result as shown in Fig. 1 (a, b) and Fig. 2 (a), X-ray powder diffraction figure shows crystallinity very
CNT spectrograms high, and CNT peaks are not subjected to displacement, show that the CNT after acidifying does not change in structure, sweep
Retouch electron microscope picture and also show CNT after acidified, surface is unusual light, and its pattern does not change.To bag
ZnCo is covered2O4Material afterwards has been also carried out X-ray powder diffraction test and have taken scanning electron microscope diagram, from Fig. 2
A () understands, the made composite spectral peak for obtaining and ZnCo2O4Standard card matches, and indicates the synthesis of this Success in Experiment
ZnCo2O4；By Fig. 1 (c, d) it can be seen that ZnCo2O4The nano particle of 3nm is about for size, and is uniformly coated on
CNT surface.Finally to prepared N doped-CNT/ZnCo2O4/ Au composites carried out X-ray powder diffraction test with
And Flied emission Scanning Electron microscope figure and transmission electron microscope figure are shot, be can be seen that by Fig. 2 (a), in N doped-CNT/
ZnCo2O4Removed in the XRD spectrum of/Au, in composite and contain ZnCo2O4Peak beyond, also XRD peaks of also CNT and Au, this
Demonstrate CNT and successfully load ZnCo2O4Nano particle and Au nano particles.Secondly shown by Fig. 2 (b-d), Au nanometers
Grain is equably inlayed, is covered in N doped-CNT/ZnCo2O4On, form a kind of three-dimensional nanometer material.
By N doped-CNT/ZnCo2O4/ Au carries out down electrocatalysis characteristic survey in a cell as anode electrode material
Examination, is studied its catalytic performance.From Fig. 3 (a), cobalt base oxide its catalytic performance with CNT as substrate is relative
Cobalt base oxide without CNT substrates will get well, and be presented as that the take-off potential of cobalt base oxide with CNT as substrate is low, in height
Its current density is big during potential.Meanwhile, from Fig. 3 (a), in high potential, N doped-CNT/ZnCo2O4Compare N
doped-CNT/Co3O4Produce current density higher, show more preferable catalytic performance, this be due to the doping of Zn ions,
So that N doped-CNT/ZnCo2O4Multi-element metal center is internally formed, possesses multivalent state state, and then reduce electronics in sun
Activation energy when interionic is shifted, so as to improve overall electric conductivity.Finally, from Fig. 3 (a), by N doped-
CNT/ZnCo2O4It is modified, Au nano particles is embedded in ZnCo2O4In, ZnCo2O4Performance further have been improved,
Because Au nano particles are used as electronic slot, the electronics in Co ions is deviateed Co centers, improve the valence state of Co ions；And
Reported according to early stage lot of documents, the Co ions of high-valence state play the effect of key during aquatic products oxygen is electrolysed, therefore Au receives
The addition of rice grain, improves overall N doped-CNT/ZnCo2O4Catalytic performance.
N doped-CNT/ZnCo2O4The high catalytic performance of/Au can be summarized as following three points：(1) dynamic (dynamical) change, from
Fig. 3 (b) is visible, N doped-CNT/ZnCo2O4The Tafel slope of/Au is minimum, it is meant that N doped-CNT/ZnCo2O4/Au
Electrolysis aquatic products oxygen during dynamic performance preferably, this is attributable to Au nano particles and Zn ion pair cobalt base oxides again
It is modified；(2) increase of active site, from Fig. 3 (c), N doped-CNT/ZnCo2O4/ Au possesses more electro-chemical activity
Site, the increase of this avtive spot is attributable to the doping of Au nano particles and N element is doped in CNT；(3) electric conductivity
Enhancing, from Fig. 3 (d), N doped-CNT/ZnCo2O4The nyquist diagram of/Au possesses the semicircle of minimum, that is, gathers around
There is the resistance of minimum, this is attributable to CNT as growth substrate, improves overall electric conductivity.
By to N doped-CNT/ZnCo2O4/ Au and CNT/IrO2Make performance comparison, the carrying current by Fig. 4 (a) is bent
Line can be seen that, although using CNT as the IrO of substrate2Take-off potential than N doped-CNT/ZnCo2O4/ Au is small, but
With the enhancing of potential, N doped-CNT/ZnCo2O4/ Au compares CNT/IrO2There is bigger current density, that is, possess and preferably urge
Change performance, this result is attributed to N doped-CNT/ZnCo2O4/ Au compares CNT/IrO2There is more preferable dynamic performance, this is pushed away
Break and embodied in the Tafel slope of Fig. 4 (b), i.e. N doped-CNT/ZnCo2O4/ Au possesses smaller Tafel slope.
In sum, the N doped-CNT/ZnCo of this synthesis2O4/ Au as anode electrode material, with superior electricity
Catalytic performance, and it is with low cost, it is environmentally friendly, therefore bigger economic benefit can be possessed in following practical application.
Embodiment 2
Scheme of the present invention based on embodiment 1, by regulating and controlling different reaction conditions, influences ZnCo2O4In N doping CNT
On growth, its relation is as shown in table 1 and Fig. 7.
Table 1.ZnCo2O4Adjusting and controlling growth
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (8)
1. a kind of nano combined anode material, it is characterised in that：The nano combined anode material is Ndoped-CNT/
ZnCo2O4/ Au core-shell nano tubular composite materials；The Ndoped-CNT/ZnCo2O4/ Au core-shell nano tubular composite materials are
It is made up of following structure：Nitrogen-doped carbon nanometer pipe is by outer layer ZnCo2O4Nano particle is coated, and Au is particle studded in ZnCo2O4Nanometer
In particle.
2. a kind of preparation method of nano combined anode material as claimed in claim 1, it is characterised in that comprise the following steps：
Step one, by CNT and ZnCo after acidifying2O4Precursor aqueous solution is mutually mixed and is flowed back, and thereafter carries out mixed solution
Hydro-thermal reaction, finally obtains ZnCo2O4The three-dimensional composite material of core-shell structure of nano particle cladding N doping CNT；
Step 2, by Ndoped-CNT/ZnCo2O4Composite is placed in Au precursor aqueous solutions, and by the illumination of xenon lamp short time,
Au nano particles are made to be embedded in Ndoped-CNT/ZnCo2O4In composite.
3. the preparation method of nano combined anode material as claimed in claim 2, it is characterised in that：Described ZnCo2O4Forerunner
Solution is made up of following component：Zinc acetate, cobalt acetate, ammoniacal liquor, polyvinylpyrrolidone, ethanol, water；The Au precursor aqueous solutions by
Following component composition：Gold chloride, water.
4. the preparation method of nano combined anode material as claimed in claim 2, it is characterised in that：Described ZnCo2O4Forerunner
The specific composition of solution is：The Zn (OAc) of 0.0128mol/L2·2H2The Co (OAc) of O, 0.0064mol/L2·4H2O, quality
Percent concentration is 25% ammoniacal liquor, second alcohol and water, and wherein ethanol and the volume ratio of water is 24:1；The Au precursor aqueous solutions are
The aqueous solution of chloraurate of 0.1mmol/L.
5. the preparation method of nano combined anode material as claimed in claim 2, it is characterised in that：Backflow in step one is anti-
It is 20h between seasonable, reaction temperature is 80 DEG C；Hydrothermal temperature is 150 DEG C in step one, and the reaction time is 3h.
6. the preparation method of nano combined anode material as claimed in claim 2, it is characterised in that：Xenon lamp described in step 2
Intensity of illumination is 300mW/cm2, light application time is 15min.
7. the preparation method of nano combined anode material as claimed in claim 2, it is characterised in that：The CNT's is a diameter of
20nm。
8. a kind of application of the nano combined anode material in electrolysis water as claimed in claim 1.
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