CN110102236A - Preparation method and application of monodisperse metal compound for rapid load growth on flexible carbon substrate by microwave technology - Google Patents
Preparation method and application of monodisperse metal compound for rapid load growth on flexible carbon substrate by microwave technology Download PDFInfo
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000000758 substrate Substances 0.000 title claims abstract description 41
- 238000005516 engineering process Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 239000004744 fabric Substances 0.000 claims description 43
- 238000004090 dissolution Methods 0.000 claims description 19
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 17
- 239000004917 carbon fiber Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 17
- 239000003575 carbonaceous material Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 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 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- -1 transition metal salt Chemical class 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001548 drop coating Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 238000002484 cyclic voltammetry Methods 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000011056 performance test Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 2
- 235000011164 potassium chloride Nutrition 0.000 claims 1
- 239000001103 potassium chloride Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 41
- 238000001994 activation Methods 0.000 abstract description 20
- 230000004913 activation Effects 0.000 abstract description 18
- 238000010891 electric arc Methods 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 abstract 1
- 239000007833 carbon precursor Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000004146 energy storage Methods 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- 230000008595 infiltration Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007725 thermal activation Methods 0.000 description 3
- 229910001567 cementite Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003911 water pollution 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method and application of a monodisperse metal compound rapidly loaded and grown on a flexible carbon substrate by a microwave technology, and belongs to the technical field of preparation of functional nano materials. Mixing and dissolving the carbon precursor and metal salt in deionized water or an organic solvent, uniformly and dropwisely coating the mixture on a flexible carbon substrate after microwave activation to perform microwave reaction, generating electric arc in the microwave reaction to bring extremely high temperature, and achieving the purpose of rapid dispersion; and (3) annealing at high temperature in an inert atmosphere to obtain the monodisperse metal compound which is loaded and grown on the flexible carbon substrate. The preparation method has the advantages of short time consumption, low energy consumption, controllable reaction, simple operation and the like, and can be applied to flexible wearable devices and solving environmental problems.
Description
Technical field
The present invention relates to one kind fast-growth single dispersion metal compound can be applied to the energy in flexible carbon substrate and deposit
The use microwave technology of storage and water treatment field, belongs to the preparation technical field of function nano material.
Background technique
Social fast-developing, people have higher requirement to oneself living environment, quality of the life.Water pollution becomes tired
The a great problem of people is disturbed, material for water treatment often has difficult recycling at present, in current water the problems such as easy damaged, constrains
Practical application.It is the effective ways for solving the problems, such as this at present that flexible substrates, which load treatment function material,.On the other hand, with electricity
The development of sub- technology, more and more wearable devices are used to make the life better quality and obtain fast development, and such device is wanted
Ask energy storage device that there is small in size, speciality flexible.Recently the supercapacitor studied, ion battery, since device is rigidity
Structure and be not suitable for large-scale integrated mobile electronic device.Therefore need to develop excellent novel of light-weight, small in size, energy storage
The energy storage devices such as flexible super capacitor, ion battery.Recently, people are made that many effort to explore with plane and fiber
The light-duty and flexible electronic energy storage device of shape structure.Flexible electronic device is a kind of emerging, promising next-generation phototube
Part technology.Flexible carbon-based material has biggish specific surface area, micropore abundant and meso-hole structure, excellent such as carbon cloth and carbon fiber
The advantages that different electric conductivity, higher thermal stability, high specific strength, good chemical inertness and good biocompatibility
It can preferably solve the above problems.By loading functional water-purifying material, the flexible material with water purification function can be obtained, effectively
Solve the problems, such as material recovery, material damage；There is the material of energy storage property by loading, can obtain with energy storage capacity
Flexible energy storage material, the characteristics such as bending needed for being suitable for wearable device, fold.But in practical study, pure carbon substrate
Material is because of its intrinsic feature, and energy-storage property is low, and there is hydrophobic effect strongly on another aspect carbon-based material surface, in water process
Real contact area is low in the process, it is therefore desirable to which it is flexible carbon-based to be promoted that functionalized modification and surface activation process are carried out to it
Interfacial property and chemical property.It is modified by the hetero atom or metal composite in situ, doping, its leaching can be improved
Moisten area, electric conductivity, PhotoelectrochemicalProperties Properties etc., to obtain preferable storage effect and water treatment efficiency.At the interface of material
Modified aspect, the method that flexible carbon-based material has had a series of surface activation process, such as: plasma-activated, liquid phase is lived
Change, high temperature thermal activation, electrochemical activation etc..Above method is compared, high temperature thermal activation can change the surface of flexible carbon-based material
Group, be it is a kind of quickly, efficiently, process stabilizing and lower-cost method.But main high temperature thermal activation at present is main
Concentrate on the activation method of traditional heat temperature raising, a kind of method of quick generation high temperature is urgently developed.Furthermore in flexible material
Functionalization in terms of, mainly by hydrothermal synthesis method, chemical vapor deposition (CVD) method, pyrolysismethod, carbothermic method etc..These
The disadvantages of there are speed for method slowly, low yield, uncontrollable growth.Therefore, it is carbon-based quickly to prepare monodispersed function flexibility for original position
Composite material is current problem.
It is prepared in situ and needs quick chemical process, above-mentioned technology is difficult to meet quick requirement.Microwave technology
It is a kind of by release microwave, is generated with different materials and effects, the technology being quickly modified to material such as penetrate, reflect, absorb.With
Traditional heating is compared, and microwave reaction has the advantages that speed is fast, energy is high, can be mass-produced.Microwave current method often by with
In preparing metal composite, reaction mechanism is directly to absorb microwave to be rapidly achieved and react required energy.It mentions in this form
It is low (~100 DEG C) often to there is temperature in the reaction energy of confession, and it is compound in carbon-based Rapid Modification single dispersion metal to be insufficient for it
Object.This technology, which is utilized conducting electrons and generates quick frictional vibration in microwave, can generate electric arc.Carbon-based material is a kind of excellent
Conductor, the quick frictional vibration of electronics under the action of microwave generates high electric arc, and the temperature that electric arc is discharged reaches several
Thousand degrees Celsius, to can be achieved at the same time, carbon based surfaces are oxygen enrichment and precursor salt loads.Since reaction speed is fast, precursor salt energy
Quickly monodisperse in situ is in carbon-based material surface.Compared with traditional microwave technology prepares compound, the electric discharge of this technology generation
Arc temperature is higher, therefore the compound dispersibility obtained is splendid.
Summary of the invention
The purpose of the present invention is to provide a kind of to generate high-temperature electric arc using microwave technology to reach former on carbon-based material
The method of position controllable load single dispersion metal purpose, this method is with the time is short, high-efficient, energy saving, operating procedure is simple
And temperature it is high the features such as, solve the disadvantages of slow speed in prior synthesizing method, troublesome in poeration and uncontrollable growth.
Technical solution proposed by the present invention is: one kind Fast Load in flexible carbon substrate grows single dispersion metal compound
Microwave technology, the preparation method the following steps are included:
A, it prepares precursor solution: 0.01~10g metal salt being dissolved in 1~50mL water phase or organic solvent, adds 0
~20g carbon containing presoma is as carbon source, dissolution；
B, the different carbon-based bottom surfaces of flexibility is activated with micro-wave oven；
C, in the flexible carbon substrate after activating the precursor solution drop coating of the not carbonaceous sources in a into b, with micro-wave oven into
Row reaction can quickly obtain the compound of the load growth single dispersion metal in flexible carbon substrate；
D, in the flexible carbon substrate after activating the precursor solution drop coating containing carbon source in a into b, with micro-wave oven into
Row reaction, resulting product optionally 200~1200 DEG C of 0.5~10h of calcining of the tubular type furnace high-temperature under different atmosphere,
Heating rate is 1~10 DEG C/min, can quickly obtain the compound of the load growth single dispersion metal in flexible carbon substrate.
Preferably, metal salt used in the step a is transition metal salt.
Preferably, metal salt used in the step a is the combination of a variety of different transition metal salts, different proportion.
Preferably, solvent used in the step a is deionized water or organic alcohol solvent.
Preferably, carbon source used in the step a is carbohydrate, organic molecule and its salt containing N, C element.
Preferably, the flexible carbon substrate in the step b be it is carbon containing have substrate flexible, carbon cloth, carbon paper, carbon fiber or
Load has the flexible substrates of carbon material.
Preferably, the microwave time in the step c is 5~600s.
Preferably, the atmosphere in the step d be inert gas, reducibility gas or inert atmosphere and reducing atmosphere not
Gaseous mixture in proportion.
Preferably, metal salt used in the step a is the chlorate or nitrate of transition metal, used in the step a
Solvent be deionized water or alcoholic solution, carbon source used in the step a is polysaccharide, melamine, cdicynanmide sodium or double cyanogen
Amine is dissolved as ultrasonic dissolution in the step a, and the flexible carbon substrate in the step b is carbon cloth or carbon fiber, the step
The microwave time in c is 30s, and the atmosphere in the step d is argon gas/hydrogen mixed gas, nitrogen or ammonia.
It is proposed by the present invention another solution is that the microwave technology Fast Load growth in flexible carbon substrate is single
The application of dispersed metal compound, the production method that the flexible material is used as electro-catalysis analysis oxygen, liberation of hydrogen material, steps are as follows:
It is that chlorination is saturated with Ag ∣ AgCl ∣ to electrode with platinum plate electrode directly using flexible carbon-based material as working electrode
Potassium electrode is reference electrode, using the 1.0M KOH solution dissolved with saturation nitrogen as electrolyte, is built in 5 mouthfuls of electrolytic cells；It will
Assembled electrolytic cell carries out battery performance test on electrochemical workstation, and test condition is rotary rpm, and: 1600rpm is swept
Retouching mode is cyclic voltammetry CV, OER voltage range be -0.2V-0.8V vs.Ag/AgCl and HER voltage range for -
0.8V--1.8V vs.Ag/AgCl carries out linear voltammetric scan LSV, OER electricity when CV is swept to the circle current potential of front and back 2 and no longer changes
It is -0.8V--1.8V vs.Ag/AgCl that pressure range, which is -0.2V- 0.8V vs.Ag/AgCl and HER voltage range,.
Beneficial effect
Compared with other load the method for growth single dispersion metal compound in flexible carbon substrate, this technology can be in flexibility
The single dispersion metal being prepared in situ in carbon substrate.This method is simple and easy, and carbon cloth and carbon fiber easily obtain, at low cost.And
It is generated in preparation process without pernicious gas, meets the theory of Green Chemistry.Microwave, calcinating consumption are low, and the used time is short, easy to operate,
Suitable for producing in enormous quantities.Carbonaceous and presoma after microwave are adsorbed on the surface of flexible carbon substrate entirely, and in flexible carbon substrate
The metal dispersion of upper load growth is good.Metal and carbon are compounded in flexible carbon substrate by the material, can be efficiently applied to store up
It can field and water treatment field.
Detailed description of the invention
Further explanation is made to the present invention with reference to the accompanying drawing.
Fig. 1 is the carbon cloth of (a) and (b) after microwave reaction, pyroreaction after microwave reaction in the embodiment of the present invention 1
Fig. 2 be in the embodiment of the present invention 1 after microwave reaction after (a, b) and microwave reaction, pyroreaction (c, d) carbon cloth
The scanning electron microscope image (SEM) on surface
Fig. 3 is the x-ray diffraction pattern (XRD) of the carbon cloth after microwave reaction, high temperature cabonization in the embodiment of the present invention 1
Fig. 4 is the carbon cloth of (a) and (b) after microwave reaction, high temperature cabonization after microwave reaction in the embodiment of the present invention 2
Fig. 5 be in the embodiment of the present invention 2 after microwave reaction after (a, b) and microwave reaction, high temperature cabonization (c, d) carbon cloth
The scanning electron microscope image (SEM) on surface
Fig. 6 is the x-ray diffraction pattern (XRD) of the carbon cloth after microwave reaction, high temperature cabonization in the embodiment of the present invention 2
Fig. 7 is the carbon fiber in the embodiment of the present invention 3 after microwave reaction
Fig. 8 be in the embodiment of the present invention 3 after microwave reaction after (a, b) and microwave reaction, high temperature cabonization (c, d) carbon cloth
The scanning electron microscope image (SEM) on surface
Fig. 9 is the carbon fiber in the embodiment of the present invention 4 after microwave reaction
Figure 10 be in the embodiment of the present invention 4 after microwave reaction after (a, b) and microwave reaction, high temperature cabonization (c, d) carbon cloth
The scanning electron microscope image (SEM) on surface
Figure 11 is the scanning electron microscope image (SEM) of carbon cloth surfaces various concentration after microwave reaction in the embodiment of the present invention 5
Figure 12 is the scanning electron microscope of the carbon cloth surfaces various concentration after microwave reaction, high temperature cabonization in the embodiment of the present invention 5
Image (SEM)
Figure 13 is that the X- ray of carbon cloth surfaces various concentration spreads out after microwave reaction, high temperature cabonization in the embodiment of the present invention 5
Penetrate figure (XRD)
Figure 14 is the scanning electron microscope image (SEM) of carbon cloth surfaces after microwave reaction in the embodiment of the present invention 6
Figure 15 is the scanning electron microscope image (SEM) of carbon cloth surfaces after microwave reaction in the embodiment of the present invention 7
Figure 16 is electro-catalysis (OER and HER) performance map of carbon cloth after microwave reaction in the embodiment of the present invention 7
Figure 17 be in the embodiment of the present invention 8 after microwave reaction after (a, b) and microwave reaction, high temperature cabonization (c, d) carbon cloth
The scanning electron microscope image (SEM) on surface
Specific embodiment
Below with reference to embodiment the invention will be further described technical solution of the invention, these embodiments cannot
It is not understood as the limitation to technical solution.
Embodiment 1:
2g iron chloride is dissolved in 10mL deionized water, after ultrasonic dissolution, adds 4g cdicynanmide sodium, ultrasonic dissolution.It will
The carbon cloth of about 10 × 10cm carries out microwave and activates 30s, and the carbon cloth surfaces after solution is uniformly added to activation will be prepared after activation.It will leaching
The carbon cloth of profit carries out microwave reaction 60s, and obtained sample is under nitrogen atmosphere with the heating rate of 5 DEG C/min to 900 DEG C of calcinings
1h.It obtains product and observes the evenly dispersed particle for having about 10~20nm size of carbon cloth fiber surface in SEM electron-microscope scanning figure,
XRD crystal phase is Fe3C crystal phase.
Embodiment 2:
2g nickel nitrate is dissolved in 10mL deionized water, after ultrasonic dissolution, adds 4g cdicynanmide sodium, ultrasonic dissolution.It will
The carbon cloth of about 10 × 10cm carries out microwave and activates 30s, and the carbon cloth surfaces after solution is uniformly added to activation will be prepared after activation.It will leaching
The carbon cloth of profit carries out microwave reaction 60s, and obtained sample is under nitrogen atmosphere with the heating rate of 5 DEG C/min to 900 DEG C of calcinings
1h.It obtains product and observes that carbon cloth fiber surface is evenly dispersed in SEM electron-microscope scanning figure having a particle, XRD crystal phase is Ni simple substance
Crystal phase.
Embodiment 3:
2g iron chloride is dissolved in 10mL deionized water, after ultrasonic dissolution, adds 4g cdicynanmide sodium, ultrasonic dissolution.It will
The carbon fiber of about 10cm carries out microwave and activates 30s, and the solution of preparation is uniformly added to the carbon cloth surfaces after activation after activation.It will leaching
The carbon fiber of profit carries out microwave reaction 30s, and obtained sample is forged with the heating rate of 5 DEG C/min to 900 DEG C under nitrogen atmosphere
Burn 1h.It obtains product and observes that carbon fiber surface is evenly dispersed in SEM electron-microscope scanning figure having particle.
Embodiment 4:
2g nickel nitrate is dissolved in 10mL deionized water, after ultrasonic dissolution, adds 4g cdicynanmide sodium, ultrasonic dissolution.It will
The carbon fiber of about 10cm carries out microwave and activates 30s, and the solution of preparation will be uniformly added to the carbon cloth surfaces after activating after activation.It will
The carbon fiber of infiltration carries out microwave reaction 30s, and obtained sample is under nitrogen atmosphere with the heating rate of 5 DEG C/min to 900 DEG C
Calcine 1h.It obtains product and observes that carbon fiber surface is evenly dispersed in SEM electron-microscope scanning figure having particle.
Embodiment 5:
2g iron chloride is dissolved in 10mL deionized water, after ultrasonic dissolution, adds 4g cdicynanmide sodium, ultrasonic dissolution conduct
Mother liquor.By the mother liquor prepared be diluted to respectively mother liquid concentration 1%, 10%, 100% 3 kind basic, normal, high strength solution.By 10
The carbon cloth of × 10cm carries out microwave and activates 30s, after the solution of three kinds of various concentrations is uniformly added to activation with dropper after activation
Carbon cloth surfaces.The carbon cloth of infiltration is subjected to 30 s of microwave reaction, obtained sample is under nitrogen atmosphere with the heating speed of 5 DEG C/min
It spends to 900 DEG C of calcining 1h.The product in 3 obtained various concentration regions has 10~20nm's by the way that SEM observation is all evenly dispersed
Particle, XRD prove that its crystal phase is Fe3C and Fe4The mixed phase of C.
Embodiment 6:
0.132g cobalt nitrate is dissolved in 50mL deionized water, after ultrasonic dissolution, ultrasonic dissolution.By about 10 × 10cm's
Carbon cloth carries out microwave and activates 30s, and the solution of preparation is uniformly added to the carbon cloth surfaces after activation after activation.By the carbon fiber of infiltration
Carry out microwave reaction 30s.It obtains final product and of about 5~20nm is evenly distributed in carbon cloth fiber surface by SEM observation
Grain.
Embodiment 7:
86.52mg ferric nitrate and 632mg nickel nitrate are dissolved in 50mL deionized water, ultrasonic dissolution.By about 10 × 10cm
Carbon cloth carry out microwave activate 30s, after activation by the solution of preparation uniformly be added to activation after carbon cloth surfaces.By the carbon fiber of infiltration
Dimension carries out microwave reaction 70s, and carries out oxygen precipitation and Hydrogen evolving reaction test to product.Final product is obtained to observe by SEM
It was found that being evenly distributed with the particle of about 5~20nm in carbon cloth fiber surface.OER the and HER performance of product is excellent.
Embodiment 8:
0.5g ferric nitrate, 0.125g nickel nitrate are dissolved in 25mL ethylene glycol, after ultrasonic dissolution, add 4g dicyandiamide,
Ultrasonic dissolution.The carbon cloth of about 2 × 2cm is subjected to microwave and activates 30s, solution is uniformly added to after activation with dropper the carbon after activation
Cloth surface.The carbon fiber of infiltration is subjected to microwave reaction 30s, obtained sample is under ammonia atmosphere with the heating speed of 5 DEG C/min
It spends to 800 DEG C of calcining 2h.It obtains final product and is evenly distributed with about 20nm's in carbon cloth fiber surface by SEM observation discovery
Particle.
Claims (10)
1. a kind of preparation method of microwave technology Fast Load growth single dispersion metal compound in flexible carbon substrate, feature
Be, the preparation method the following steps are included:
A, it prepares precursor solution: 0.01~10g metal salt is dissolved in 1~50mL water phase or organic solvent, add 0~
20g carbon containing presoma is as carbon source, dissolution；
B, the different carbon-based bottom surfaces of flexibility is activated with micro-wave oven；
C, it in the flexible carbon substrate after activating the precursor solution drop coating of the not carbonaceous sources in a into b, is carried out instead with micro-wave oven
It answers, can quickly obtain the compound of the load growth single dispersion metal in flexible carbon substrate；
D, it in the flexible carbon substrate after activating the precursor solution drop coating containing carbon source in a into b, is carried out instead with micro-wave oven
It answers, resulting product optionally 200~1200 DEG C of 0.5~10h of calcining of the tubular type furnace high-temperature under different atmosphere, heating
Speed is 1~10 DEG C/min, can quickly obtain the compound of the load growth single dispersion metal in flexible carbon substrate.
2. microwave technology according to claim 1 Fast Load growth single dispersion metal compound in flexible carbon substrate
Preparation method, which is characterized in that metal salt used in the step a is transition metal salt.
3. microwave technology according to claim 2 Fast Load growth single dispersion metal compound in flexible carbon substrate
Preparation method, which is characterized in that metal salt used in the step a is the combination of a variety of different transition metal salts, different proportion.
4. microwave technology according to claim 1 Fast Load growth single dispersion metal compound in flexible carbon substrate
Preparation method, which is characterized in that solvent used in the step a is deionized water or organic alcohol solvent.
5. microwave technology according to claim 1 Fast Load growth single dispersion metal compound in flexible carbon substrate
Preparation method, which is characterized in that carbon source used in the step a is carbohydrate, organic molecule and its salt containing N, C element.
6. microwave technology according to claim 1 Fast Load growth single dispersion metal compound in flexible carbon substrate
Preparation method, which is characterized in that the flexible carbon substrate in the step b is carbon containing with substrate flexible, carbon cloth, carbon paper, carbon
Fiber or load have the flexible substrates of carbon material.
7. a kind of microwave technology according to claim 1 Fast Load growth single dispersion metal in flexible carbon substrate is compound
The preparation method of object, which is characterized in that the microwave time in the step c is 5~600s.
8. a kind of microwave technology according to claim 1 Fast Load growth single dispersion metal in flexible carbon substrate is compound
The preparation method of object, which is characterized in that the atmosphere in the step d is inert gas, reducibility gas or inert atmosphere and goes back
The gaseous mixture of originality atmosphere different proportion.
9. a kind of microwave technology according to claim 1 Fast Load growth single dispersion metal in flexible carbon substrate is compound
The preparation method of object, it is characterised in that: metal salt used in the step a is the chlorate or nitrate of transition metal, described
Solvent used in step a is deionized water or alcoholic solution, and carbon source used in the step a is polysaccharide, melamine, cdicynanmide
Sodium or dicyandiamide are dissolved as ultrasonic dissolution in the step a, and the flexible carbon substrate in the step b is carbon cloth or carbon fiber,
The microwave time in the step c is 30s, and the atmosphere in the step d is argon gas/hydrogen mixed gas, nitrogen or ammonia.
10. microwave technology according to claim 1 Fast Load in flexible carbon substrate grows single dispersion metal compound
Application, which is characterized in that the flexible material be used as electro-catalysis analysis oxygen, liberation of hydrogen material production method, steps are as follows:
It is to electrode, with Ag ∣ AgCl ∣ saturation potassium chloride electricity with platinum plate electrode directly using flexible carbon-based material as working electrode
Extremely reference electrode is built in 5 mouthfuls of electrolytic cells using the 1.0M KOH solution dissolved with saturation nitrogen as electrolyte；It will assembling
Good electrolytic cell carries out battery performance test on electrochemical workstation, and test condition is rotary rpm: 1600rpm, scans mould
Formula is cyclic voltammetry CV, and OER voltage range is that -0.2V-0.8V vs.Ag/AgCl and HER voltage range are -0.8V--1.8V
Vs.Ag/AgCl carries out linear voltammetric scan LSV when CV is swept to front and back 2 and encloses current potential and no longer change, and OER voltage range is-
0.2V-0.8V vs.Ag/AgCl and HER voltage range is -0.8V--1.8V vs.Ag/AgCl.
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