CN106847526B - A kind of nickel manganese double-metal hydroxide composite material, photochemical catalyst and electrode material - Google Patents
A kind of nickel manganese double-metal hydroxide composite material, photochemical catalyst and electrode material Download PDFInfo
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- CN106847526B CN106847526B CN201611220974.6A CN201611220974A CN106847526B CN 106847526 B CN106847526 B CN 106847526B CN 201611220974 A CN201611220974 A CN 201611220974A CN 106847526 B CN106847526 B CN 106847526B
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- metal hydroxide
- nickel manganese
- double
- bismuthyl carbonate
- nickel
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- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 71
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 239000007772 electrode material Substances 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 title abstract description 8
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229910015279 Ni1−xMnx(OH)2 Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- ZWEKKXQMUMQWRN-UHFFFAOYSA-J manganese(2+);nickel(2+);dicarbonate Chemical compound [Mn+2].[Ni+2].[O-]C([O-])=O.[O-]C([O-])=O ZWEKKXQMUMQWRN-UHFFFAOYSA-J 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 102000004310 Ion Channels Human genes 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000006479 redox reaction Methods 0.000 abstract description 2
- 239000002057 nanoflower Substances 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 229910052748 manganese Inorganic materials 0.000 description 13
- 239000011572 manganese Substances 0.000 description 13
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 238000001514 detection method Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000013507 mapping Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 5
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of bismuthyl carbonate-nickel manganese double-hydroxide composite materials, comprising: bismuthyl carbonate；It is supported on the nickel manganese double-metal hydroxide on the bismuthyl carbonate surface.Compared with prior art, nickel manganese double-metal hydroxide composite material provided by the invention is using bismuthyl carbonate as carrier, bismuthyl carbonate area load has nickel manganese double-metal hydroxide, and the matrix that bismuthyl carbonate is grown as nickel manganese double-metal hydroxide can guide and control its appearance structure；And bismuthyl carbonate more sufficiently, quickly can provide ion channel with closely connecting for nickel manganese double-metal hydroxide for redox reaction；Under nickel manganese double-metal hydroxide and bismuthyl carbonate collective effect, the composite material that enables to while there is preferable chemical property and photocatalysis performance.The present invention also provides a kind of electrode material and photochemical catalysts.
Description
Technical field
The present invention relates to nickel manganese double-metal hydroxide technical field more particularly to a kind of nickel manganese double-metal hydroxide,
Photochemical catalyst and electrode material.
Background technique
Layered double-hydroxide (layered Double Hydroxide, abbreviation LDHs) is also known as Layered compound or class water
Neatly stone ore (Hydrotalcite, molecular formula Mg existing for talc compound, crystal structure and nature6Al2(OH)16CO3 4H2O) structure is similar.It has been studied since layered double-hydroxide self-discovery it is lasting, in catalytic chemistry, ion
Exchanger, adsorbent, electrochemistry, photochemistry etc., are widely used.Layered double-hydroxide lamella rich in,
Can be used as the electrode material of supercapacitor, it can utilize two kinds of energy storage mechnisms of electric double layer capacitance and pseudo capacitance simultaneously,
On the one hand electric double layer capacitance is improved by providing bigger serface, on the other hand also using the oxidation of transition metal element on laminate
Original reaction provides higher pseudo capacitance.Moreover, the unique space structure of layered double hydroxide makes it have alkali
Property, interlayer anion interchangeability, thermal stability.Due to these characteristics, layered double hydroxide is increasingly becoming more satisfactory
Electrode material for super capacitor.
Meanwhile LDHs is also rising as the research of photochemical catalyst, since the laminate ion of layered double-hydroxide has
There is substitutability, by such as Zn of the ion with photocatalytic activity2+Or Ti2+As the metal cation in LDHs composition, can make
The standby substance with photocatalytic activity.
The double-hydroxide type currently prepared is rich and varied, including NiMn-LDH, NiAl-LDH, CoMn-LDH, CoAl-
LDH, NiCo-LDH etc..NiMn-LDH can make full use of the synergistic effect of two kinds of metals in these double-hydroxides, can
Guarantee more abundant, quick ionic adsorption and desorption and cyclical stability.But nickel manganese double hydroxide nano piece is recycling
The swelling of structure and the caused capacity attenuation that collapses limit its further development in practice in the process, therefore improve
The chemical property of nickel manganese double-hydroxide becomes the focus of people's research.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of nickel manganese double-metal hydroxide composite material, the present invention is mentioned
The nickel manganese double-metal hydroxide composite material of confession has preferable chemical property and photocatalysis performance simultaneously.
The present invention provides a kind of nickel manganese double-metal hydroxide composite materials, comprising:
Bismuthyl carbonate；
It is supported on the nickel manganese double-metal hydroxide on the bismuthyl carbonate surface.
Preferably, the nickel manganese double-metal hydroxide are as follows:
Ni1-xMnx(OH)2·mH2O
Wherein, 0 < x < 1, m are 1~10.
Preferably, the mass ratio of the bismuthyl carbonate and nickel manganese double-metal hydroxide is (1~4): (1~2).
The present invention provides a kind of preparation sides of nickel manganese double-metal hydroxide composite material described in above-mentioned technical proposal
Method, comprising:
Bismuthyl carbonate and alkaline matter is soluble in water, obtain dispersion liquid；
The dispersion liquid, nickel salt and manganese salt are reacted, nickel manganese double-metal hydroxide composite material is obtained.
Preferably, the alkaline matter is selected from NH4NO3、C6H12N4、C6H5Na3O7, Na (OH), one in K (OH) and urea
Kind is several.
Preferably, the nickel salt is selected from one or more of nickel nitrate, nickel sulfate, nickelous carbonate and nickel chloride.
Preferably, the manganese salt is selected from one or more of manganese nitrate, manganese sulfate, manganese carbonate and manganese chloride.
Preferably, the temperature of the reaction is 70~100 DEG C.
The present invention provides a kind of photochemical catalysts, compound including nickel manganese double-metal hydroxide described in above-mentioned technical proposal
Material.
The present invention provides a kind of electrode materials, compound including nickel manganese double-metal hydroxide described in above-mentioned technical proposal
Material.
Compared with prior art, nickel manganese double-metal hydroxide composite material provided by the invention is to carry with bismuthyl carbonate
Body, bismuthyl carbonate area load have nickel manganese double-metal hydroxide, and bismuthyl carbonate is grown as nickel manganese double-metal hydroxide
Matrix can guide and control its appearance structure；And bismuthyl carbonate can with closely connecting for nickel manganese double-metal hydroxide
More sufficiently, ion channel quickly is provided for redox reaction；Make jointly in nickel manganese double-metal hydroxide and bismuthyl carbonate
Under, the composite material that enables to while there is preferable chemical property and photocatalysis performance.
In the present invention, above-mentioned nickel manganese double-metal hydroxide composite structure is stable, size is controllable, chemical property
It is superior, specific capacitance and energy density with higher, and also electrochemical cycle stability is preferable, after circulation, composite structure
Keep complete.Meanwhile this nickel manganese double-metal hydroxide composite material also has good photocatalysis performance.Therefore, this hair
The nickel manganese double-metal hydroxide composite material of bright offer can be used as electrode material and photocatalyst applications.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention for those of ordinary skill in the art without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the SEM detection figure for the bismuthyl carbonate nano flower that the embodiment of the present invention 1 is prepared；
Fig. 2 is the SEM figure of nickel manganese double-metal hydroxide composite material prepared by the embodiment of the present invention 2；
Fig. 3 is the SEM figure of nickel manganese double-metal hydroxide composite material prepared by the embodiment of the present invention 2；
Fig. 4 is the SEM-mapping for the nickel manganese double-metal hydroxide composite material that the embodiment of the present invention 2 is prepared
Figure；
Fig. 5 is the SEM-mapping for the nickel manganese double-metal hydroxide composite material that the embodiment of the present invention 2 is prepared
Figure；
Fig. 6 is the SEM-mapping for the nickel manganese double-metal hydroxide composite material that the embodiment of the present invention 2 is prepared
Figure；
Fig. 7 is the SEM-mapping for the nickel manganese double-metal hydroxide composite material that the embodiment of the present invention 2 is prepared
Figure；
Fig. 8 is the SEM-mapping for the nickel manganese double-metal hydroxide composite material that the embodiment of the present invention 2 is prepared
Figure；
Fig. 9 is the XRD diagram for the nickel manganese double-metal hydroxide composite material that the embodiment of the present invention 2 is prepared；
Figure 10 is the chronopotentiogram for the nickel manganese double-metal hydroxide composite material that embodiment 2 is prepared；
Figure 11 is the cyclic voltammogram for the nickel manganese double-metal hydroxide composite material that embodiment 2 is prepared；
Figure 12 is the visible light catalytic effect picture for the nickel manganese double-metal hydroxide composite material that embodiment 2 is prepared.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment shall fall within the protection scope of the present invention.
The present invention provides a kind of nickel manganese double-metal hydroxide composite materials, comprising:
Bismuthyl carbonate；
It is supported on the nickel manganese double-metal hydroxide on the bismuthyl carbonate surface.
In the present invention, the bismuthyl carbonate preferably has bismuthyl carbonate nanometer flower structure, and bismuthyl carbonate nano flower is layer
Shape structure has biggish specific surface area, can also conduct while can load more nickel manganese double-metal hydroxide
The growing substrate of nickel manganese double-metal hydroxide, the nickel manganese double-metal hydroxide composite material made have preferable structure
Pattern, and then improve the chemical property and photocatalysis performance of nickel manganese double-metal hydroxide composite material.In the present invention, institute
The diameter for stating bismuthyl carbonate nano flower is preferably 1~5 μm, more preferably 1~2 μm, most preferably 1.5 μm.
The present invention does not have special limitation to the type of the nickel manganese double-metal hydroxide and source, using this field skill
Nickel manganese double-metal hydroxide known to art personnel.In the present invention, the nickel manganese double-metal hydroxide are as follows:
Ni1-xMnx(OH)2·mH2O
Wherein, 0 < x < 1, preferably 0.1~0.8, more preferably 0.2~0.6, most preferably 0.3；M is 1~10, excellent
It is selected as 2~8, more preferably 2~6, more preferably 2~4, most preferably 2.
In the present invention, the mass ratio of the bismuthyl carbonate and nickel manganese double-metal hydroxide is preferably (1~4): (1~
2), more preferably (2~3): (1.2~1.8), more preferably 2.5:(1.4~1.6), most preferably 4:1 or 1:2.
In the present invention, the diameter of the nickel manganese double-metal hydroxide composite material is preferably 1~5 μm, more preferably 1
~2 μm, most preferably 1.5 μm.
The present invention provides the preparation method of the nickel manganese double-metal hydroxide composite material described in above-mentioned technical proposal, packets
It includes:
Bismuthyl carbonate and alkaline matter is soluble in water, obtain dispersion liquid；
The dispersion liquid, nickel salt and manganese salt are reacted, nickel manganese double-metal hydroxide composite material is obtained.
In the present invention, it is preferred to be stirred bismuthyl carbonate and alkaline matter are soluble in water, dispersion liquid is obtained.In this hair
In bright, the stirring is preferably magnetic agitation.In the present invention, the time of the magnetic agitation is preferably 8~12 minutes, more excellent
It is selected as 10 minutes.
In the present invention, the bismuthyl carbonate is preferably bismuthyl carbonate nano flower.The present invention is to the bismuthyl carbonate nanometer
Colored source does not have special limitation, is prepared using method well known to those skilled in the art.In the present invention, institute
The preparation method for stating bismuthyl carbonate nano flower is preferred are as follows:
Bismuth and ammonium citrate and urea are reacted, bismuthyl carbonate nano flower is obtained.
In the present invention, it is preferred to then soluble in water be stirred of bismuth and ammonium citrate and urea is reacted again, obtain
Bismuthyl carbonate nano flower.In the present invention, the stirring is preferably magnetic agitation.In the present invention, the magnetic agitation when
Between preferably 25~35min, more preferably 30min.In the present invention, the temperature of the reaction is preferably 160~200 DEG C, more
Preferably 170~190 DEG C, most preferably 180 DEG C.In the present invention, the time of the reaction is preferably 8~15 hours, more excellent
It is selected as 10~13 hours, most preferably 12 hours.In the present invention, it is described after the reaction was completed, the reaction product that will preferably obtain
It cleaned, dried, obtain bismuthyl carbonate nano flower.In the present invention, it is preferred to successively be cleaned using water and alcohol.
In the present invention, the mass ratio of the bismuth and ammonium citrate and urea is preferably (1.2~2): (0.5~1), more preferably
For (1.4~1.8): (0.6~0.8), most preferably 1.66:0.72.In the present invention, the quality of the bismuth and ammonium citrate and water
Than preferably (1.2~2): (70~80), more preferably (1.4~1.8): (73~77), most preferably 1.66:75.
In the present invention, the alkaline matter is preferably selected from NH4NO3、C6H12N4、C6H5Na3O7, Na (OH), K (OH) and urine
One or more of element, more preferably urea.
In the present invention, mass content of the bismuthyl carbonate in dispersion liquid is preferably 0.2~0.8mol/L, more preferably
For 0.4~0.6mol/L, most preferably 0.5mol/L.In the present invention, the dosage of the alkaline matter is preferably dispersing it
Concentration in liquid is 0.5~5mol/L, more preferably 1~4mol/L, most preferably 2~3mol/L.
Nickel salt and manganese salt are preferably added in dispersion liquid by the present invention to react, and it is multiple to obtain nickel manganese double-metal hydroxide
Condensation material, in the present invention, the temperature of the reaction are preferably 70~100 DEG C, more preferably 80~90 DEG C, most preferably 85
℃.In the present invention, the time of the reaction is preferably 2~12 hours, and more preferably 5~10 hours, most preferably 6~8 is small
When.
In the present invention, the dispersion liquid, nickel salt and manganese salt carry out after the reaction was completed, preferably that obtained reaction product is clear
It is dry after washing, obtain nickel manganese double-metal hydroxide composite material.In the present invention, the cleaning preferably successively using water and
Ethyl alcohol cleaning.In the present invention, the temperature of the drying is preferably 50~70 DEG C, more preferably 55~65 DEG C, most preferably 60
℃。
In the present invention, the nickel salt is preferably selected from one of nickel nitrate, nickel sulfate, nickelous carbonate and nickel chloride or several
Kind, more preferably nickel nitrate.In the present invention, the manganese salt is preferably selected from manganese nitrate, manganese sulfate, manganese carbonate and manganese chloride
One or more, more preferably manganese nitrate.In the present invention, the molar ratio of the nickel salt and manganese salt is preferably (1~3): (1~
3), more preferably (1.5~2.5): (1.5~2.5), most preferably 1:3,1:1 or 3:1.In the present invention, the bismuthyl carbonate
Quality and the ratio of nickel salt and manganese salt gross mass be preferably (1~4): (1~2), more preferably (2~3): (1.2~1.8),
More preferably 2.5:(1.4~1.6), most preferably 4:1 or 1:2.
The present invention provides a kind of photochemical catalyst, including nickel manganese double-metal hydroxide composite wood described in above-mentioned technical proposal
Material.The present invention also provides a kind of electrode materials, including nickel manganese double-metal hydroxide composite wood described in above-mentioned technical proposal
Material.Nickel manganese double-metal hydroxide composite material provided by the invention has preferable chemical property and photocatalytic simultaneously
Can, it not only can be used as electrode material but also can be used as photochemical catalyst and applied.
Raw material used in following embodiment of the present invention is commercial goods.
The preparation of 1 bismuthyl carbonate nano flower of embodiment
The urea of the bismuth and ammonium citrate of 1.66g and 0.72g is dissolved in the water of 75mL, the high pressure polytetrafluoro of 100mL is poured into
Obtained presoma is reacted 12h at 180 DEG C, by obtained product respectively in water by magnetic agitation 30min in ethylene reaction kettle
With cleaned in alcohol, it is dry to get arriving required (BiO)2CO3Nano flower.
The bismuthyl carbonate nano flower that the embodiment of the present invention 1 is prepared carries out SEM detection, testing result as shown in Figure 1,
Fig. 1 is the SEM detection figure for the bismuthyl carbonate nano flower that the embodiment of the present invention 1 is prepared, as shown in Figure 1, the embodiment of the present invention 1
The bismuthyl carbonate nano flower being prepared is regular cluster nano flower form, and stable structure is uniform in size.
The preparation of 2 bismuthyl carbonates of embodiment-nickel manganese double-hydroxide composite material
The bismuthyl carbonate nano flower that the embodiment 1 of 50mg is prepared, is dispersed in the aqueous solution of 50mL, is added
The urea of 300mg adjusted alkalinity, with magnetic stirrer 10 minutes.Then the nickel nitrate of 270mg and the nitre of 0.35mL is added
Sour manganese carries out heating in water bath for reaction, and the temperature of reaction is 85 DEG C, and the time of reaction is 6 hours.The product water and second that will be obtained
Alcohol cleaning obtains bismuthyl carbonate-nickel manganese double-hydroxide composite material then in 60 DEG C of dryings.
The bismuthyl carbonate that the embodiment of the present invention 2 is prepared-nickel manganese double-hydroxide composite material carries out SEM detection,
Testing result is as shown in Figures 2 and 3, the double hydroxides of the bismuthyl carbonate that Fig. 2 and Fig. 3 are prepared for the embodiment of the present invention 2-nickel manganese
The SEM of object composite material schemes, by Fig. 2 and Fig. 3 it is found that bismuthyl carbonate-nickel manganese double-hydroxide thin slice is interspersed in bismuthyl carbonate
Petal in, be bordering on parallel state with petal holding, and extend to outside, lamella is very thin, and be translucent shape.
The bismuthyl carbonate that the embodiment of the present invention 2 is prepared-nickel manganese double-hydroxide composite material carries out SEM-
Mapping detection, for testing result as shown in Fig. 4~Fig. 8, Fig. 4~Fig. 8 is the bismuthyl carbonate-that the embodiment of the present invention 2 is prepared
The SEM-mapping of nickel manganese double-hydroxide composite material schemes, and the element of compound forms it can be seen from Fig. 4~Fig. 8 are as follows:
O, Bi, C, Ni, Mn, and Elemental redistribution is uniform, it is successful for further demonstrating load.
The bismuthyl carbonate that the embodiment of the present invention 2 is prepared-nickel manganese double-hydroxide composite material carries out the inspection of XRD diffraction
It surveys, testing result is as shown in figure 9, Fig. 9 is that the bismuthyl carbonate that the embodiment of the present invention 1 is prepared and embodiment 2 are prepared
Bismuthyl carbonate-nickel manganese double-hydroxide composite material XRD diagram, as shown in Figure 9, compound had both remained typical bismuthyl carbonate
XRD characteristic peak, while there is the characteristic peak of nickel manganese double-metal hydroxide, both illustrate it is compound be effective.
The bismuthyl carbonate that the embodiment of the present invention 2 is prepared-nickel manganese double-hydroxide composite material carries out electrochemistry
It can detect, detection method are as follows:
Bismuthyl carbonate-nickel manganese double-hydroxide composite material and carbon black, PVDF are mixed according to the ratio of 7:2:1, are coated in
In the nickel foam of 1cm × 1.5cm, after being dried in vacuo at 120 DEG C, obtained sample is working electrode, and platinized platinum is used as to electrode, satisfies
With calomel electrode as reference electrode, connects into CHI660E electrochemical workstation, carry out electro-chemical test.
For testing result as shown in Figure 10 and shown in Figure 11, Figure 10 is chronopotentiogram of the sample under different current densities,
Figure 11 is cyclic voltammogram of the sample under different scanning speed, by Figure 10 and Figure 11 it is found that the embodiment of the present invention 2 is prepared
Bismuthyl carbonate-nickel manganese double-hydroxide composite material specific capacitance can achieve 250F g-1, and have preferable high rate performance and
Cyclical stability.
The bismuthyl carbonate that the embodiment of the present invention 2 is prepared-nickel manganese double-hydroxide composite material carries out photocatalytic
It can detect, detection method are as follows:
Bismuthyl carbonate-nickel manganese double-hydroxide the composite material for weighing 0.1g is dissolved in 50ml water, and ultrasound keeps its dispersion equal
It is even, it pours into 12 hours dry in the culture dish that diameter is 12cm.The sample prepared is placed in closed environment, NO gas is passed through
Body, and radiation of visible light is carried out to sample, record the variation of NO gas concentration.
Testing result is as shown in figure 12, the nickel manganese double-metal hydroxide composite material that Figure 12 embodiment of the present invention 2 obtains
Visible light catalytic effect picture.As shown in Figure 12, the bismuthyl carbonate that the embodiment of the present invention 2 is prepared-nickel manganese double-hydroxide is multiple
Condensation material can achieve 50% to the catalytic performance of NO.
Embodiment 3
The bismuthyl carbonate nano flower that the embodiment 1 of 200mg is prepared, is dispersed in the aqueous solution of 100mL, is added
The urea of 500mg adjusted alkalinity, with magnetic stirrer 10 minutes.Then the nickel nitrate of 450mg and the manganese nitrate of 2mL is added
Heating in water bath for reaction is carried out, the temperature of reaction is 70 DEG C, and the time of reaction is 12 hours.Obtained product water and ethyl alcohol is clear
It washes then in 60 DEG C of dryings, obtains bismuthyl carbonate-nickel manganese double-hydroxide composite material.
Bismuthyl carbonate-nickel manganese double-hydroxide that the embodiment of the present invention 3 is prepared according to the method for embodiment 2 is compound
Material electrochemical and photocatalytic can be carried out detection, and testing result is the bismuthyl carbonate-that the embodiment of the present invention 3 is prepared
Nickel manganese double-hydroxide composite material chemical property is superior, and specific capacitance can achieve 500F g-1, and after circulation 2000,
Specific capacitance retains 98%, has good cyclical stability；52% can reach to the decomposition of NO in photocatalysis performance.
Embodiment 4
The bismuthyl carbonate nano flower that the embodiment 1 of 100mg is prepared, is dispersed in the aqueous solution of 80mL, is added
The urea of 400mg adjusted alkalinity, with magnetic stirrer 10 minutes.Then the nickel nitrate of 300mg and the nitric acid of 0.6mL is added
Manganese carries out heating in water bath for reaction, and the temperature of reaction is 100 DEG C, and the time of reaction is 2 hours.The product water and ethyl alcohol that will be obtained
Cleaning obtains bismuthyl carbonate-nickel manganese double-hydroxide composite material then in 60 DEG C of dryings.
Bismuthyl carbonate-nickel manganese double-hydroxide that the embodiment of the present invention 4 is prepared according to the method for embodiment 2 is compound
Material electrochemical and photocatalytic can be carried out detection, and testing result is the bismuthyl carbonate-that the embodiment of the present invention 4 is prepared
The specific capacitance performance of nickel manganese double-hydroxide composite material electrochemistry reaches 580F g-1, after recycling 2000 times, specific capacitance retains
98.5%；Photocatalysis performance can achieve 58% to the decomposition of NO.
As seen from the above embodiment, the present invention provides a kind of bismuthyl carbonate-nickel manganese double-hydroxide composite material, packets
It includes: bismuthyl carbonate；It is supported on the nickel manganese double-metal hydroxide on the bismuthyl carbonate surface.Compared with prior art, of the invention
For the bismuthyl carbonate of offer-nickel manganese double-hydroxide composite material using bismuthyl carbonate as carrier, bismuthyl carbonate area load has nickel manganese
Double-metal hydroxide, the matrix that bismuthyl carbonate is grown as nickel manganese double-metal hydroxide, can guide and control its pattern
Structure；And bismuthyl carbonate can be more sufficiently, quickly that redox is anti-with closely connecting for nickel manganese double-metal hydroxide
Ion channel should be provided；Under nickel manganese double-metal hydroxide and bismuthyl carbonate collective effect, the composite material that enables to
There is preferable chemical property and photocatalysis performance simultaneously.
Claims (7)
1. a kind of electrode material, including nickel manganese double-metal hydroxide composite material；
The nickel manganese double-metal hydroxide composite material, comprising:
Bismuthyl carbonate；
It is supported on the nickel manganese double-metal hydroxide on the bismuthyl carbonate surface；
The mass ratio of the bismuthyl carbonate and nickel manganese double-metal hydroxide is (1~4): (1~2).
2. electrode material according to claim 1, which is characterized in that the nickel manganese double-metal hydroxide are as follows:
Ni1-xMnx(OH)2·mH2O
Wherein, 0 < x < 1, m are 1~10.
3. electrode material according to claim 1, which is characterized in that the nickel manganese double-metal hydroxide composite material
Preparation method, comprising:
Bismuthyl carbonate and alkaline matter is soluble in water, obtain dispersion liquid；
The dispersion liquid, nickel salt and manganese salt are reacted, nickel manganese double-metal hydroxide composite material is obtained.
4. electrode material according to claim 3, which is characterized in that the alkaline matter is selected from NH4NO3、C6H12N4、
C6H5Na3O7, Na (OH), one or more of K (OH) and urea.
5. electrode material according to claim 3, which is characterized in that the nickel salt is selected from nickel nitrate, nickel sulfate, nickelous carbonate
One or more of with nickel chloride.
6. electrode material according to claim 3, which is characterized in that the manganese salt is selected from manganese nitrate, manganese sulfate, manganese carbonate
One or more of with manganese chloride.
7. electrode material according to claim 3, which is characterized in that the temperature of the reaction is 70~100 DEG C.
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