CN107740135A - A kind of hollow polyhedral preparation method and applications of meso-hole structure NiCoS - Google Patents
A kind of hollow polyhedral preparation method and applications of meso-hole structure NiCoS Download PDFInfo
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- CN107740135A CN107740135A CN201710918719.7A CN201710918719A CN107740135A CN 107740135 A CN107740135 A CN 107740135A CN 201710918719 A CN201710918719 A CN 201710918719A CN 107740135 A CN107740135 A CN 107740135A
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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Abstract
A kind of hollow polyhedral preparation method and applications of meso-hole structure NiCoS, belong to clean energy resource preparing technical field.Methods described is as follows：1st, divalent cobalt and 2 methylimidazoles are dissolved in methanol solution, it is static, obtain ZIF 67；2nd, ZIF 67 is mixed with nickel nitrate, centrifuges, intermediate ZIF 67/NiCo LDH are obtained after vacuum drying；3rd, intermediate is dispersed in ethanol solution, adds thioacetamide and be stirred, hydro-thermal reaction will be carried out in mixed liquor placing response kettle; pelleting centrifugation washing obtained by after reaction; vacuum drying, then calcines in protective atmosphere, obtains hollow meso-hole structure NiCoS polyhedrons.It is an advantage of the invention that：The inventive method is simple, green, cost is cheap, easily operated control, is adapted to industrialization serialization scale of mass production.Raw material of the present invention are environmentally friendly, cheap；Excellent performance, it is expected to realize large-scale application.
Description
Technical field
The invention belongs to clean energy resource preparing technical field, and in particular to a kind of hollow meso-hole structure NiCoS is polyhedral
Preparation method and applications.
Background technology
With the fast development of human living standard, people to the demand of the energy also in sustainable growth, energy problem also with
.Hydrogen gradually causes the concern of global scientist as 21 century optimal clean energy resource.Electrolysis water technology is based on
The principle of electrochemical decomposition water, it is hydrogen and oxygen using Reproduceable electricity or Driven by Solar Energy water decomposition, it is considered to be most have
The production hydrogen approach of future and sustainability.However, water electrolysis hydrogen production technology needs high activity, the hydrogen of high stability separates out and oxygen analysis
Going out catalyst makes cell reaction economical and energy saving.In the research of elctro-catalyst of high activity is explored, many research major limitations exist
The compound and oxide of under under acid condition or alkalescence condition and other rare precious metals, have worked and your gold are shown
Category（Pt, Pt/Ru）And metal oxide containing precious metals（RuO2, IrO2）It is effective evolving hydrogen reaction（HER）And oxygen evolution reaction（OER）Electricity is urged
Agent, show high active and relatively low overpotential.But the resource of these noble metals on earth is not enriched, and price is held high
It is expensive, it is unsuitable for Engineering application, is not preferable catalyst.Efficiently durable water oxidation catalyst is developed at low cost
A huge challenge is still for vast researcher.
At present, transient metal sulfide has been considered to the electrocatalysis material with fine development prospect.Compared to binary
Sulfide, ternary cobalt nickel sulfide can preferably adjust the crystal and electronic structure of material, expose more avtive spots, so as to
Improve electrocatalysis characteristic.
And in recent years, it is organic with the metal that metal ion and organic ligand are self-assembly of with the development of Coordinative Chemistry
Skeleton (Metal-Organic Frameworks, MOFs) structural material causes the highest attention of academia.Wherein class zeolite miaow
Azoles ester framework material (zeolitic imidazolate frameworks, ZIFs) is by divalent transitional race metal ion and miaow
A kind of novel metal with the zeolite topological-organic framework compounds material formed after oxazolyl ligand complex.In recent years,
Because of its unique texture and physicochemical properties, the application in electrochemical energy conversion receives much concern for ZIFs and its derivative.
MOFs has following distinguishing feature as elctro-catalyst：（1）With highly ordered porous structure, pore-size distribution is homogeneous, than
Surface area is big, is advantageous to the scattered of active component, a large amount of avtive spots are provided for electrocatalytic reaction；（2）The Modulatory character in aperture,
Ultramicropore is can obtain to the material in mesoporous various apertures by adjusting metal center and organic ligand, is advantageous to complicated porous catalytic
The preparation of agent；（3）Easy functionalization and modification, are advantageous to ZIFs and are combined with other functional materials, prepare composite, improve
The electrocatalysis characteristics of ZIFs in itself.
The content of the invention
The invention aims to solve the problems, such as that current elctro-catalyst cost is higher, activity is poor, there is provided Yi Zhongzhong
The empty polyhedral preparation method and applications of meso-hole structure NiCoS, this method pass through hydro-thermal and calcining using ZIF-67 as template
Method prepares the NiCoS polyhedral structures with hollow meso-hole structure, and has preferable electro catalytic activity in alkaline solution
And stability.
To achieve the above object, the technical scheme that the present invention takes is as follows：
A kind of hollow polyhedral preparation methods of meso-hole structure NiCoS, methods described step are as follows：
Step 1：3.495g divalent cobalts are dissolved in 120mL methanol (AR, 99.5%), 3.942g 2-methylimidazoles is molten
In 40mL methanol (AR, 99.5%), obtain two kinds of solution are mixed, it is static, obtain ZIF-67；
Step 2：The ZIF-67 that step 1 prepares and nickel nitrate are mixed, centrifuge 10min, rotating speed 10000r/
Min, it is dried in vacuo 12 hours, that is, obtains intermediate ZIF-67/NiCo double-layered hydroxides；
Step 3：The intermediate ZIF-67/NiCo double-layered hydroxides that step 2 obtains are dispersed in 20 mL ethanol solutions,
Add 0.06g thioacetamides to be stirred, be then placed into reactor and carry out hydro-thermal reaction, hydrothermal temperature is 120 DEG C, water
The hot time is 4 ~ 6h, resulting pelleting centrifugation after reaction, centrifugation time 10min, centrifugal rotational speed 10000r/min, vacuum drying
10h, then 350 DEG C of calcining 2h in protective atmosphere, obtain hollow meso-hole structure NiCoS polyhedrons.
A kind of hollow polyhedral applications of meso-hole structure NiCoS of above-mentioned preparation, as the application of elctro-catalyst, specifically
For：Under ultrasound condition, the hollow meso-hole structure NiCoS polyhedrons of 2mg are taken to be dispersed in 500μIn the L 5wt.% Nafion aqueous solution,
Then modify on glass-carbon electrode, obtain modifying the glass-carbon electrode of sample.
It is of the invention to be relative to the beneficial effect of prior art：
（1）The prepared NiCoS polyhedrons with unique hollow meso-hole structure are with more bigger serface（123m2 g-1）, more have
Beneficial to the transmission of electronics, the release of bubble, more number of active sites can be exposed, so as to substantially increase in oxygen evolution reaction
（OER）Etc. electrocatalysis characteristic.
（2）3-D nano, structure NiCo prepared by the present invention2S4Electrode material is used for OER electrode materials, not only with relatively low
Overpotential (current density is in 10 mA cm-2, its overpotential is 320 mV), while there is good cyclical stability（Following
After ring reacts 40000 seconds, its current density still maintains initial 95%）, show excellent OER catalytic stability energy.
（3）The inventive method is simple, green, cost is cheap, easily operated control, is adapted to the industrialization big rule of serialization
Modulus is produced.Raw material of the present invention are environmentally friendly, cheap；Excellent performance, it is expected to realize large-scale application.
Brief description of the drawings
Fig. 1 synthesizes schematic diagram for the hollow meso-hole structure NiCoS polyhedrons of the present invention.
The polyhedral SEM figures of hollow meso-hole structure NiCoS that Fig. 2 is 500nm prepared by the present invention.
The polyhedral SEM figures of hollow meso-hole structure NiCoS that Fig. 3 is 200nm prepared by the present invention.
The polyhedral TEM figures of hollow meso-hole structure NiCoS that Fig. 4 is 500nm prepared by the present invention.
The polyhedral TEM figures of hollow meso-hole structure NiCoS that Fig. 5 is 200nm prepared by the present invention.
Fig. 6 is the hollow polyhedral XRDs of meso-hole structure NiCoS.
Fig. 7 is hollow meso-hole structure NiCoS polyhedrons N prepared by the present invention2Adsorption desorption curve map.
Fig. 8 is hollow meso-hole structure NiCoS polyhedron graph of pore diameter distribution prepared by the present invention.
Fig. 9 is the Linear Circulation volt that hollow meso-hole structure NiCoS polyhedrons prepared by the present invention contrast OER with other materials
Pacify (lsv) curve map.
Figure 10 is hollow meso-hole structure NiCoS polyhedrons and Co3S4Time current curve figure.
Embodiment
Technical scheme is further described with reference to the accompanying drawings and examples, but is not limited thereto,
It is every technical solution of the present invention to be modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention,
It all should cover in protection scope of the present invention.
Embodiment one：What present embodiment was recorded is a kind of hollow polyhedral preparation sides of meso-hole structure NiCoS
Method, as shown in figure 1, methods described step is as follows：
Step 1：3.495g divalent cobalts are dissolved in 120mL methanol (AR, 99.5%), 3.942g 2-methylimidazoles are dissolved in
In 40mL methanol (AR, 99.5%), obtain two kinds of solution are mixed, it is static, obtain ZIF-67（Class zeolite imidazole ester bone
Frame -67）；
Step 2：The ZIF-67 that step 1 prepares and nickel nitrate are mixed, centrifuge 10min, rotating speed 10000r/
Min, it is dried in vacuo 12 hours, that is, obtains intermediate ZIF-67/NiCo double-layered hydroxides（NiCo-LDH）, such as Fig. 2, Fig. 3 institute
Show；
Step 3：The intermediate ZIF-67/NiCo double-layered hydroxides that step 2 obtains are dispersed in 20 mL ethanol solutions,
Add 0.06g thioacetamides to be stirred, be then placed into reactor and carry out hydro-thermal reaction, hydrothermal temperature is 120 DEG C, water
The hot time is 4 ~ 6h, resulting pelleting centrifugation after reaction, centrifugation time 10min, centrifugal rotational speed 10000r/min, vacuum drying
10 ~ 12h, then 350 DEG C of calcining 2h in protective atmosphere, obtain hollow meso-hole structure NiCoS polyhedrons.
Embodiment two：A kind of hollow polyhedral preparations of meso-hole structure NiCoS described in embodiment one
Method, in step 1, the divalent cobalt is Co (NO3)2•6H2O、CoSO4•H2O、CoCl2•6H2O or Co (CH3COO)2•
4H2O。
Embodiment three：A kind of hollow polyhedral preparations of meso-hole structure NiCoS described in embodiment one
Method, in step 1, the molal weight ratio of the divalent cobalt and 2-methylimidazole is 1: 4.
Embodiment four：A kind of hollow polyhedral preparations of meso-hole structure NiCoS described in embodiment one
Method, in step 1, the quiescent time should be 24 hours.
Embodiment five：A kind of hollow polyhedral preparations of meso-hole structure NiCoS described in embodiment one
Method, in step 2, the mass ratio of ZIF-67 and nickel nitrate is 1: 3, and the product morphology of acquirement can be made optimal for the ratio and performance
It is optimal.
Embodiment six：A kind of hollow polyhedral preparations of meso-hole structure NiCoS described in embodiment one
Method, in step 2, ZIF-67 and nickel nitrate mix the time and should be 30min.
Embodiment seven：A kind of hollow polyhedral preparations of meso-hole structure NiCoS described in embodiment one
Method, in step 3, the protective atmosphere is N2, one or more in Ar and He.
Embodiment eight：A kind of hollow polyhedral preparations of meso-hole structure NiCoS described in embodiment one
Method, in step 3, the temperature of the hydro-thermal reaction is 120 DEG C, time 6h.Through repeatedly it is demonstrated experimentally that in this hydrothermal temperature
Under, the NiCoS faceted materials of the higher hollow meso-hole structure of well-grown, purity can be synthesized, are optimal process conditions.
Embodiment nine：What in a kind of embodiment one to eight prepared by any embodiment is hollow mesoporous
The polyhedral applications of structure NiCoS, as the application of elctro-catalyst, it is specially：Under ultrasound condition, the hollow meso-hole structures of 2mg are taken
NiCoS polyhedrons are dispersed in 500μIn the L 5wt.% Nafion aqueous solution, then modify on glass-carbon electrode, obtain modifying sample
The glass-carbon electrode of product.
Embodiment 1：
First, the hollow meso-hole structure NiCoS materials of sheet are prepared：
As shown in figure 1, using ZIF-67 as presoma with sacrificing template, synthesized ZIF-67 and nickel nitrate stirring reaction, system
Standby ZIF-67/Ni-Co-LDH core shell structures.Using thioacetamide as sulphur source, due to ion diffusion effect in water-heat process,
Metal ion with small diameter is gradually to external diffusion, and the sulphion of larger ionic radius is gradually as interior diffusion.Therefore, it is interior
The metal framework in portion is gradually etched dissolving, eventually forms the NiCoS polyhedrons with hollow meso-hole structure.
2nd, the feature of hollow meso-hole structure NiCoS materials：
SEM tests are carried out to hollow meso-hole structure NiCoS materials：Fig. 2, Fig. 3 are that the SEM of hollow meso-hole structure NiCoS materials shines
Piece, it shows typical rhombus polyhedral structure, the nm of diameter about 500, rough surface and is made up of many nano-particles..
TEM tests are carried out to hollow meso-hole structure NiCoS materials：Fig. 4, Fig. 5 are hollow meso-hole structure NiCoS materials TEM
Electron microscope, it shows that sample interior is hollow structure, and its outer casing thickness about makes it in sulphur in 30 nm or so, enough thickness
Change and still maintain the constant of holding structure after calcining.
XRD tests are carried out to hollow meso-hole structure NiCoS materials：Fig. 6 is Co-MOF X-ray diffractogram, and its peak can be with
With base peak to upper, so as to show that synthesized sample is required sample.
To hollow meso-hole structure NiCoS materials N2Adsorption desorption curve is tested：Fig. 7 is hollow meso-hole structure NiCoS materials N2Inhale
Desorption curve test chart, it can be found out with NiCoS materials with typical H4 types hysteresis loop, it was demonstrated that it has meso-hole structure.Its
Specific surface area is up to 123 m2 g−1, aperture size concentrates on ~ 18.2 nm, and Fig. 8 is hollow meso-hole structure prepared by the present invention
NiCoS polyhedron graph of pore diameter distribution.
3rd, the preparation of electro catalytic electrode：
1st, by a diameter of 3 mm glass-carbon electrode respectively with having adsorbed 1μThe sand paper of m aluminum oxide suspensions and adsorb 0.3μm
The sand paper sanding and polishing of aluminum oxide suspension.
2nd, the good glass-carbon electrode of sanding and polishing is successively placed on after being cleaned by ultrasonic 30 seconds in deionized water, in 0.5M KCl+
K3[Fe(CN)6] scan cycle volt-ampere curve in solution, with test electrode whether milled, finally obtain the glass-carbon electrode of cleaning, dry in the air
Do with stand-by.
3rd, the hollow meso-hole structure NiCoS for taking 2 mg steps to prepare is added by 500μIn the L Nafion aqueous solution（Perfluor sulphur
Acid/distilled water/isopropanol=0.05:4:1）, ultrasonic mixing, mixed solution is made, then by 7μL mixed solutions are using coating
Method modifies the clean glassy carbon electrode surface in a diameter of 3 mm, and producing hollow meso-hole structure NiCoS electricity after naturally dry urges
Polarizing electrode.
4th, electrolyte is configured：
Using potassium hydroxide as electrolyte, wherein, concentration of potassium hydroxide is 1 mol/L.
5th, the electrocatalysis characteristic of detecting electrode：
Hollow meso-hole structure NiCoS electro catalytic electrodes are placed in 1 mol/L KOH solution and are measured.
Using electrochemical workstation, the electrode to be measured of preparation is being passed through the electrolyte solution of about half an hour oxygen in advance
In, cyclic voltammetry scan is first carried out, then under the current potential between -0.2~0.9 V, sweep speed control is 5 mV/s, is carried out
Linear voltammetric scan, the chemical property of test sample.
Linear Circulation voltammetry shown in Fig. 9 (LSV) is in 1 M KOH solution, respectively to NiCoS, Co3S4, RuO2
With LSV curve of the electrode that the glass-carbon electrode (GC) of no modification etc. is modified as working electrode test gained.It can be seen that
The glass-carbon electrode for not having modified does not almost have catalytic performance to OER.And in the mA cm of current density j=10-2When corresponding mistake
Current potential be weigh OER elctro-catalyst performances important parameter wherein, LSV corresponding to NiCoS cross position voltage be only 320m
V vs.RHE.And under some circumstances, Co as a comparison3S4And RuO2The overpotential of electrode is respectively 391 mV and 332 mV,
These data are above the overpotential corresponding to hollow meso-hole structure NiCoS.
Figure 10 shows the hollow meso-hole structure NiCoS and Co of sample3S4Time current curve.In circular response 40000s
Afterwards, hollow meso-hole structure NiCoS materials still maintain its most initial current 95%, and Co3S4Then decay to 83%.In confirming
Empty meso-hole structure NiCoS materials catalytic stability excellent in alkaline solution.
Claims (9)
- A kind of 1. hollow polyhedral preparation methods of meso-hole structure NiCoS, it is characterised in that：Methods described step is as follows：Step 1：3.495g divalent cobalts are dissolved in 120mL methanol, 3.942g 2-methylimidazoles are dissolved in 40mL methanol, Obtain two kinds of solution are mixed, it is static, obtain ZIF-67；Step 2：The ZIF-67 that step 1 prepares and nickel nitrate are mixed, centrifuge 10min, rotating speed 10000r/ Min, it is dried in vacuo 12 hours, that is, obtains intermediate ZIF-67/NiCo double-layered hydroxides；Step 3：The intermediate ZIF-67/NiCo double-layered hydroxides that step 2 obtains are dispersed in 20 mL ethanol solutions, Add 0.06g thioacetamides to be stirred, be then placed into reactor and carry out hydro-thermal reaction, hydrothermal temperature is 120 DEG C, water The hot time is 4 ~ 6h, resulting pelleting centrifugation after reaction, centrifugation time 10min, centrifugal rotational speed 10000r/min, vacuum drying 10h, then 350 DEG C of calcining 2h in protective atmosphere, obtain hollow meso-hole structure NiCoS polyhedrons.
- A kind of 2. hollow polyhedral preparation methods of meso-hole structure NiCoS according to claim 1, it is characterised in that：Step In rapid one, the divalent cobalt is Co (NO3)2•6H2O、CoSO4•H2O、CoCl2•H2O or Co (CH3COO)2•4H2O。
- A kind of 3. hollow polyhedral preparation methods of meso-hole structure NiCoS according to claim 1, it is characterised in that：Step In rapid one, the divalent cobalt and the molten molal weight ratio of 2-methylimidazole are 1: 4.
- A kind of 4. hollow polyhedral preparation methods of meso-hole structure NiCoS according to claim 1, it is characterised in that：Step In rapid one, the quiescent time should be 24 hours.
- A kind of 5. hollow polyhedral preparation methods of meso-hole structure NiCoS according to claim 1, it is characterised in that：Step In rapid two, the mass ratio of ZIF-67 and nickel nitrate is 1: 3.
- A kind of 6. hollow polyhedral preparation methods of meso-hole structure NiCoS according to claim 1, it is characterised in that：Step In rapid two, ZIF-67 should be 30min with the nickel nitrate mixing time.
- A kind of 7. hollow polyhedral preparation methods of meso-hole structure NiCoS according to claim 1, it is characterised in that：Step In rapid three, the protective atmosphere is N2, one or more in Ar and He.
- A kind of 8. hollow polyhedral preparation methods of meso-hole structure NiCoS according to claim 1, it is characterised in that：Step In rapid three, hydrothermal temperature is 120 DEG C, and the hydro-thermal time is 6h.
- 9. the hollow polyhedral applications of meso-hole structure NiCoS that in a kind of claim 1 ~ 8 prepared by any claim, its feature It is：As the application of elctro-catalyst, it is specially：Under ultrasound condition, the hollow meso-hole structure NiCoS polyhedrons of 2mg are taken to be dispersed in 500μIn the L 5wt.% Nafion aqueous solution, then modify on glass-carbon electrode, obtain modifying the glass-carbon electrode of sample.
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