CN104310316A - One-pot synthesis method of transition metal (Fe, Co, Ni) oxyhydrogen/oxyhydroxide ultrathin nanosheets - Google Patents
One-pot synthesis method of transition metal (Fe, Co, Ni) oxyhydrogen/oxyhydroxide ultrathin nanosheets Download PDFInfo
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- CN104310316A CN104310316A CN201410524809.4A CN201410524809A CN104310316A CN 104310316 A CN104310316 A CN 104310316A CN 201410524809 A CN201410524809 A CN 201410524809A CN 104310316 A CN104310316 A CN 104310316A
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 49
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 49
- 229910052759 nickel Inorganic materials 0.000 title claims description 9
- 238000000034 method Methods 0.000 title abstract description 17
- 239000002135 nanosheet Substances 0.000 title abstract 5
- 238000005580 one pot reaction Methods 0.000 title abstract 2
- 239000000243 solution Substances 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 37
- 239000001301 oxygen Substances 0.000 claims abstract description 35
- 239000007789 gas Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 238000010189 synthetic method Methods 0.000 claims description 19
- 239000013543 active substance Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 5
- 239000012279 sodium borohydride Substances 0.000 abstract description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract 2
- 239000000047 product Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229910002588 FeOOH Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- 229910017709 Ni Co Inorganic materials 0.000 description 6
- 229910003267 Ni-Co Inorganic materials 0.000 description 6
- 229910003262 Ni‐Co Inorganic materials 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 239000011807 nanoball Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229960004011 methenamine Drugs 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- -1 methane amide Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/36—Spheres fragmented
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a one-pot synthesis method of transition metal oxyhydrogen/oxyhydroxide ultrathin nanosheets, which comprises the following steps: 1) dissolving a transition metal precursor in water to obtain a mixed solution, stirring, and introducing an inert gas; 2) reacting NaBH4Adding the solution into the mixed solution obtained in the step 1), stirring, and continuously introducing an inert gas to obtain an intermediate solution; 3) introducing gas containing oxygen into the intermediate solution for reaction to obtain a solid crude product; 4) and cleaning and drying the solid crude product to obtain the ultrathin nanosheet of the transition metal oxyhydrogen/oxyhydroxide. The method has the advantages of mild reaction conditions, simple preparation process, high repeatability and strong universality, the thickness of the formed ultrathin nanosheet is less than 5nm, the size can reach the micron level, and the prepared ultrathin nanosheet has wide research value and application prospect.
Description
Technical field
The present invention relates to the preparation field of two-dimension nano materials, particularly relate to " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet.
Background technology
In recent years, ultra-thin two-dimension nano material (thickness is less than 5nm) has attracted showing great attention to of numerous research worker, and this is mainly due to compared with block materials, and this materials exhibit has gone out physicochemical property and the application direction of many novelties.The appearance of the research boom prepared along with ultrathin nanometer sheet, has emerged many ultrathin nanometer materials with peculiar property and application.Such as, the MoS that magnificent teach problem group reports individual layer is opened
2not only may be used for the nano-probe (J.Am.Chem.Soc.2013,135,5998-6001) detecting biomolecules, but also can be used for preparing the phototransistor (ACS Nano2012,6,74-80) with good response characteristics to light.Ultra-thin V
2o
50.76H
2o nanometer sheet detects at hydrogen and all shows excellent performance (Small 2013,9,716-721) in ultracapacitor.Recently, thank to firm teach problem group and also synthesized many ultra-thin two-dimension nano materials cleverly, as the C for bio-imaging
3n
4ultrathin nanometer sheet (J.Am.Chem.Soc.2013,135,18-21), have excellent visible photocatalysis water-based can individual layer SnS
2(Angew.Chem.Int.Ed.2012,51,8727-8731) etc.
And the hydrogen-oxygen/oxyhydroxide of transition metal (Fe, Co, Ni), particularly its nanometer sheet and with nanometer sheet for the multilevel hierarchy that formed of assembling primitive all has a wide range of applications in fields such as ultracapacitor, lithium ion battery, photochemical catalysis, water treatments.Usually, the nanometer sheet that thickness is little can provide the delivering path of higher specific surface area and shorter ion and electronics, and therefore ultra-thin in theory nanometer sheet can show more superior performance in above-mentioned application.
Prepare the method for transition metal (Fe, Co, Ni) hydrogen-oxygen/oxyhydroxide nanometer sheet at present, mainly comprise: (1) top-to-bottom method: mainly refer to stripping method, first the transition metal hydroxide nanometer sheet of high-temperature water thermal synthesis intercalation is utilized, then it is peeled off (J.Am.Chem.Soc.2008 in methane amide, 130,14038-14039).Although the nanometer sheet that this method obtains can reach ultra-thin thickness, exist synthesis step many, not there is the shortcomings such as universality; (2) bottom-to-top method: a. hydrothermal synthesis method: the method is report and a kind of widely used method, namely transition metal salt solution and basic cpd is utilized, as NaOH, HMT (hexamethylene tetramine), react to each other under high-temperature water heat condition, finally obtain the nanometer sheet (J.Mater.Chem.1996 of transition metal, 6,1429-1432; Chem.Eur.J.2008,14,5064-5072).Although this method operation steps is comparatively easy, there is temperature of reaction high, reaction conditions is not gentle, and the nanometer sheet thickness of synthesis is usually tens nanometers, and is difficult to reach the shortcomings such as ultra-thin thickness; B., except above-mentioned two kinds of methods, some other preparation methods are also had, as: the hydrothermal synthesis method (Chem.Mater.2008 of microwave-assisted, 20,308-316), electrochemical method (Adv.Funct.Mater.2007,17,644-650) etc.These methods also exist that reaction conditions is not gentle, synthesis step is loaded down with trivial details, versatility is poor equally and the nanometer sheet of synthesis is difficult to reach the shortcomings such as ultra-thin thickness.
Therefore, need to provide a kind of method preparing transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet that reaction conditions is gentle, preparation process is simple, repeatability is high, universality is strong, to solve the problems existed in preparation at present.
Summary of the invention
An object of the present invention is to provide " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet, to solve that the reaction conditions existed at present is not gentle, synthesis step is loaded down with trivial details, versatility is poor and the nanometer sheet of synthesis is difficult to reach the problems such as ultra-thin thickness.
For achieving the above object, the invention provides " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet, technical scheme provided by the present invention is:
" treating different things alike " synthetic method of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet, comprises the steps:
1) transition metal precursor is soluble in water, obtain mixed solution, stir, pass into inactive gas;
2) by NaBH
4solution adds step 1) described in mixed solution in, and continue to pass into inactive gas, obtain the composite nanometer particle of transition metal/boron;
3) composite nanometer particle of gas to the transition metal/boron in the aqueous solution passed into containing oxygen carries out oxidation corrosion, obtains solid crude product;
4) solid crude product is cleaned, dry, obtain the ultrathin nanometer sheet of transition metal hydrogen-oxygen/oxyhydroxide.
Preferably, described transition metal precursor is one or more in the water-soluble salt of Fe, Co, Ni; Preferred, the presoma of described transition metal is FeSO
47H
2o, CoCl
26H
2o or NiCl
26H
2one or more in O.Hydrogen-oxygen/the oxyhydroxide of transition metal (Fe, Co, Ni), particularly its nanometer sheet and the multilevel hierarchy formed for assembling primitive with nanometer sheet all have a wide range of applications in fields such as ultracapacitor, lithium ion battery, photochemical catalysis, water treatments.
Preferably, the concentration of described transition metal precursor is 1-20mmol/L; Preferred, the concentration of described transition metal precursor is 1.5mmol/L-3.5mmol/L.
Preferably, step 1) in, by described transition metal precursor and tensio-active agent soluble in water.
Preferably, described tensio-active agent is PVP, CTAB or SDS, and the product of formation is the composite Nano ball of transition metal/boron.
Preferably, the concentration of described tensio-active agent is 3mg/mL-50mg/mL; Preferred, the concentration of described tensio-active agent is 3mg/mL-30mg/mL.
Preferably, step 1) and step 2) in, described inactive gas is argon gas, nitrogen, helium or neon.
Preferably, step 1) in, the logical inactive gas time is 10-30min, to remove the dissolved oxygen in solution, ensures the oxygen-free atmosphere of reaction.
Preferably, step 2) in, described NaBH
4solution is freshly prepared solution, prevents NaBH
4solution is decomposition failure in aqueous.
Preferably, described NaBH
4solution is NaBH
4the aqueous solution.
Preferably, NaBH
4excessive, the ratio of NaBH4 and transition metal precursor is higher than 2:1; Described NaBH
4strength of solution is 0.5mg/L-15mg/L; Preferred, described NaBH
4strength of solution is 0.5mg/L-5mg/L.
Preferably, NaBH
4solution rate of addition is on the impact of reaction nothing.
Preferably, step 2) add NaBH
4after solution, the reaction times is 10-60min; Preferred, add NaBH
4after solution, the reaction times is 10-30min.
Preferably, temperature of reaction is 15-80 DEG C; Preferred, temperature of reaction is 20-30 DEG C.Reaction conditions of the present invention is gentle, at room temperature can react.
Preferably, step 3) in, the described gas containing oxygen is purity oxygen or air.Gas containing oxygen carries out oxidation corrosion to the composite Nano ball of the transition metal/boron in the aqueous solution or nano particle.
Preferably, step 3) in, the described gas containing oxygen is 10-24h to the composite Nano ball of the transition metal/boron in the aqueous solution or composite nanometer particle oxidation corrosion time; Preferred, the described gas containing oxygen to the composite Nano ball of the transition metal/boron in the aqueous solution or composite nanometer particle oxidation corrosion time for being 12-18h.
Beneficial effect of the present invention is as follows:
The invention has the advantages that:
1) reaction conditions is gentle, and preparation process is simple, and repeatability is high, and nanometer sheet thickness can reach ultra-thin, and size can reach micron level, can realize a large amount of preparation;
2) highly versatile, utilizes the method can prepare the ultrathin nanometer sheet of the hydrogen-oxygen/oxyhydroxide of multiple transition metal, also can prepare polynary transition metal hydroxide ultrathin nanometer sheet;
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
The XRD figure of the FeOOH ultrathin nanometer sheet that Fig. 1 (a) is prepared for embodiment 1, products therefrom is the FeOOH of pure phase;
The Co (OH) that Fig. 1 (b) is prepared for embodiment 2
2the XRD figure of ultrathin nanometer sheet, products therefrom is the Co (OH) of pure phase
2;
The Ni (OH) that Fig. 1 (c) is prepared for embodiment 3
2the XRD figure of ultrathin nanometer sheet, products therefrom is the Ni (OH) of pure phase
2;
The TEM image of the FeOOH ultrathin nanometer sheet that Fig. 2 (a) is prepared for embodiment 1;
The Co (OH) that Fig. 2 (b) is prepared for embodiment 2
2the TEM image of ultrathin nanometer sheet;
The Ni (OH) that Fig. 2 (c) is prepared for embodiment 3
2the TEM image of ultrathin nanometer sheet;
The afm image of the FeOOH ultrathin nanometer sheet that Fig. 3 (a) is prepared for embodiment 1, its thickness is 1.8nm;
The Co (OH) that Fig. 3 (b) is prepared for embodiment 2
2the afm image of ultrathin nanometer sheet, its thickness is 3.4nm;
The Ni (OH) that Fig. 3 (c) is prepared for embodiment 3
2the afm image of ultrathin nanometer sheet, its thickness is 2.5nm;
The dark field image of the Ni-Co binary oxyhydroxide ultrathin nanometer sheet that Fig. 4 (a) is prepared for embodiment 4; B (), (c) and (d) are its distribution diagram of element, element Ni, Co and O are evenly distributed on whole ultrathin nanometer panel region, demonstrate the formation of Ni-Co binary oxyhydroxide ultrathin nanometer sheet effectively.
Embodiment
In order to be illustrated more clearly in the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing represent with identical Reference numeral.It will be appreciated by those skilled in the art that specifically described content is illustrative and nonrestrictive, should not limit the scope of the invention with this below.
Embodiment 1
" treating different things alike " synthetic method of FeOOH ultrathin nanometer sheet
1,21mg FeSO is got
47H
2o and 100mg CTAB is dissolved in the deionized water of 25mL, ultrasonic 10min, makes it be uniformly dispersed;
2, solution is transferred in the there-necked flask of 100mL, puts into magneton, and there-necked flask both sides are sealed with plug, stir;
3, after passing into Ar gas 10min in solution, by the NaBH of freshly prepared 15mg/mL
4solution is transferred in 10mL syringe, and joins in reaction solution by side plug, adds after end with tape seal;
4, stop logical Ar gas after reacting 10min, and take off both sides plug, in solution, pass into air reaction;
5, after continuing reaction 12h, by product utilization deionized water and ethanol eccentric cleaning several, after drying, product is obtained.
Products therefrom is the FeOOH of pure phase, Fig. 1 (a) is the XRD figure of FeOOH ultrathin nanometer sheet; Fig. 2 (a) is the TEM image of FeOOH ultrathin nanometer sheet; Fig. 3 (a) is the afm image of FeOOH ultrathin nanometer sheet, and its thickness is 1.8nm.
Embodiment 2
Co (OH)
2" treating different things alike " synthetic method of ultrathin nanometer sheet
1,7.1mg CoCl is got
26H
2o and 100mg PVP, is dissolved in the deionized water of 21.5mL, and ultrasonic 10min makes it be uniformly dispersed;
2, solution is transferred in the there-necked flask of 100mL, puts into magneton, and there-necked flask both sides are sealed with plug, stir;
3, after passing into Ar gas 10min in solution, by the NaBH of freshly prepared 0.5mg/mL
4solution is transferred in 10mL syringe, and joins in reaction solution by side plug, adds after end with tape seal;
4, stop logical Ar gas after reacting 10min, and take off both sides plug, in solution, pass into air reaction;
5, after continuing reaction 12h, by product utilization deionized water and ethanol eccentric cleaning several, after drying, product is obtained.
Products therefrom is the Co (OH) of pure phase
2, Fig. 1 (b) is Co (OH)
2the XRD figure of ultrathin nanometer sheet; Fig. 2 (b) is Co (OH)
2the TEM image of ultrathin nanometer sheet; Fig. 3 (b) is Co (OH)
2the afm image of ultrathin nanometer sheet, its thickness is 3.4nm.
Embodiment 3
Ni (OH)
2" treating different things alike " synthetic method of ultrathin nanometer sheet
1,8.5mg NiCl is got
26H
2o and 100mg PVP, is dissolved in the deionized water of 21.5mL, and ultrasonic 10min makes it be uniformly dispersed;
2, solution is transferred in the there-necked flask of 100mL, puts into magneton, and there-necked flask both sides are sealed with plug, stir;
3, after passing into Ar gas 10min in solution, by the NaBH of freshly prepared 0.5mg/mL
4solution is transferred in 10mL syringe, and joins in reaction solution by side plug, adds after end with tape seal;
4, stop logical Ar gas after reacting 10min, and take off both sides plug, in solution, pass into air reaction;
5, after continuing reaction 12h, by product utilization deionized water and ethanol eccentric cleaning several, after drying, product is obtained.
Products therefrom is the Ni (OH) of pure phase
2, Fig. 1 (c) is Ni (OH)
2the XRD figure of ultrathin nanometer sheet; Fig. 2 (c) is Ni (OH)
2the TEM image of ultrathin nanometer sheet; Fig. 3 (c) is Ni (OH)
2the afm image of ultrathin nanometer sheet, its thickness is 2.5nm;
Embodiment 4
" treating different things alike " synthetic method of Ni-Co binary oxyhydroxide ultrathin nanometer sheet
1,8.5mg NiCl is got
26H
2o, 7.1mg CoCl
26H
2o and 200mg PVP, is dissolved in the deionized water of 43mL, and ultrasonic 10min makes it be uniformly dispersed;
2, solution is transferred in the there-necked flask of 100mL, puts into magneton, and there-necked flask both sides are sealed with plug, stir;
3, after passing into Ar gas 10min in solution, by the NaBH of freshly prepared 0.5mg/mL
4solution is transferred in 20mL syringe, and joins in reaction solution by side plug, adds after end with tape seal;
4, stop logical Ar gas after reacting 10min, and take off both sides plug, in solution, pass into air reaction;
5, after continuing reaction 12h, by product utilization deionized water and ethanol eccentric cleaning several, after drying, product is obtained.
Products therefrom is Ni-Co binary oxyhydroxide ultrathin nanometer sheet, and Fig. 4 (a) is the dark field image of Ni-Co binary oxyhydroxide ultrathin nanometer sheet; B (), (c) and (d) are its distribution diagram of element, element Ni, Co and O are evenly distributed on whole ultrathin nanometer panel region, demonstrate the formation of Ni-Co binary oxyhydroxide ultrathin nanometer sheet effectively.
Obviously; the above embodiment of the present invention is only for example of the present invention is clearly described; and be not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot give exhaustive to all embodiments, every belong to technical scheme of the present invention the apparent change of extending out or variation be still in the row of protection scope of the present invention.
Claims (10)
1. " treating different things alike " synthetic method of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet, is characterized in that: comprise the steps:
1) transition metal precursor is soluble in water, obtain mixed solution, stir, pass into inactive gas;
2) by NaBH
4solution adds step 1) described in mixed solution in, stir, and continue to pass into inactive gas, obtain midbody solution;
3) in midbody solution, the gas passed into containing oxygen reacts, and obtains solid crude product;
4) solid crude product is cleaned, dry, obtain the ultrathin nanometer sheet of transition metal hydrogen-oxygen/oxyhydroxide.
2. " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet according to claim 1, is characterized in that: described transition metal precursor is one or more in the water-soluble salt of Fe, Co, Ni; Preferably, described transition metal precursor is FeSO
47H
2o, CoCl
26H
2o, NiCl
26H
2one or more in O.
3. " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet according to claim 1, is characterized in that: the concentration of described transition metal precursor is 1-20mmol/L; Preferably, the concentration of described transition metal precursor is 1.5mmol/L-3.5mmol/L.
4. " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet according to claim 1, is characterized in that: step 1) in, by described transition metal precursor and tensio-active agent soluble in water.
5. " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet according to claim 4, is characterized in that: described tensio-active agent is PVP, CTAB or SDS; Preferably, the concentration of described tensio-active agent is 3mg/mL-50mg/mL; Preferred, the concentration of described tensio-active agent is 3mg/mL-30mg/mL.
6. " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet according to claim 1, is characterized in that: step 1) and step 2) in, described inactive gas is argon gas, nitrogen, helium or neon; Preferably, step 1) in, passing into the inactive gas time is 10-30min.
7. " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet according to claim 1, is characterized in that: step 2) in, described NaBH
4solution is freshly prepared NaBH
4the aqueous solution; Preferably, described NaBH
4strength of solution is 0.5mg/L-15mg/L; Preferred, described NaBH
4strength of solution is 0.5mg/L-5mg/L.
8. " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet according to claim 1, is characterized in that: step 2) in, add NaBH
4after solution, the reaction times is 10-60min; Preferably, NaBH is added
4after solution, the reaction times is 10-30min.
9. " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet according to claim 1, is characterized in that: temperature of reaction is 15-80 DEG C; Preferably, temperature of reaction is 20-30 DEG C.
10. " treating different things alike " synthetic method of a kind of transition metal hydrogen-oxygen/oxyhydroxide ultrathin nanometer sheet according to claim 1, is characterized in that: step 3) in, the described gas containing oxygen is purity oxygen or air; Step 3) in, the time that passes into of the described gas containing oxygen is 10-24h; Preferably, the time that passes into of the described gas containing oxygen is 12-18h.
Priority Applications (1)
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| CN107583651A (en) * | 2017-10-25 | 2018-01-16 | 中国科学院理化技术研究所 | Iron-based photocatalyst for preparing low-carbon olefin by photocatalytic carbon monoxide hydrogenation, and preparation method and application thereof |
| CN108339560A (en) * | 2017-04-01 | 2018-07-31 | 济南大学 | A kind of amorphous FeOOHg-C3N4Composite nano materials and the preparation method and application thereof |
| CN109621961A (en) * | 2018-11-23 | 2019-04-16 | 南昌大学 | A method of high dispersion of metal catalyst is prepared in situ in growth two-dimensional nano piece |
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| CN107583651A (en) * | 2017-10-25 | 2018-01-16 | 中国科学院理化技术研究所 | Iron-based photocatalyst for preparing low-carbon olefin by photocatalytic carbon monoxide hydrogenation, and preparation method and application thereof |
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| CN113233517B (en) * | 2021-06-29 | 2024-02-09 | 上海交通大学 | Single-layer/few-layer two-dimensional transition metal oxide nano material aqueous dispersion liquid and preparation method thereof |
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