CN106744755A - The preparation method of black phosphorus nanometer sheet and noble metal nano particles composite - Google Patents
The preparation method of black phosphorus nanometer sheet and noble metal nano particles composite Download PDFInfo
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- CN106744755A CN106744755A CN201710182141.3A CN201710182141A CN106744755A CN 106744755 A CN106744755 A CN 106744755A CN 201710182141 A CN201710182141 A CN 201710182141A CN 106744755 A CN106744755 A CN 106744755A
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/02—Preparation of phosphorus
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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Abstract
The invention discloses a kind of black phosphorus nanometer sheet and the preparation method of noble metal nano particles composite, block black phosphorus crystal is peeled off using liquid phase stripping method first and obtains sheet black phosphorus, then chemical reduction method is used, palladium bichloride in-situ reducing is caused that noble metal nano particles are adsorbed onto the surface of graphene nanometer sheet, material requested is can obtain after then suction filtration is dried.Material prepared by the inventive method has potential application in fields such as electrochemical sensor, electro-catalysis, energy storage.
Description
Technical field
The present invention relates to a kind of black phosphorus nanometer sheet and the preparation method of noble metal nano particles composite, belong to a nanometer material
Material preparing technical field.
Background technology
Black phosphorus is a kind of crystal structure of multilayer, similar to graphite.With many excellent performances, such as carrier higher
Mobility, obvious anisotropy and band gap width can be regulated and controled by the number of plies, it is considered to be most it is potential be applied to energy storage and
The two-dimensional material of semiconductor applications.Current study show that the black phosphorus nanometer of individual layer or multilayer can be obtained by liquid phase separation method
Piece.Noble metal nano particles are widely used to various fields due to its unique performance.The catalysis of noble metal nano particles is lived
Property be depend on nano-particle dispersiveness and surface property.Because the performance of noble metal nano particles depends significantly on its aggregation
State, size and distribution etc., in order that its size uniformity, being uniformly dispersed, one appropriate matrix material of selection is expensive to control
The dispersion of metal nanoparticle and deposition size are particularly significant.Therefore, it is badly in need of a kind of rationally efficient preparation method, black phosphorus is received
Rice piece and noble metal nano particles are effectively combined, and form the composite wood with the two excellent physicochemical characteristics
Material, widens its potential application in fields such as energy storage, electrochemical sensing, electro-catalysis.
The content of the invention
Present invention aim in order to overcome the shortcomings of the presence of prior art, there is provided simple efficient black phosphorus nanometer sheet
With the preparation method of noble metal nano particles composite, the Adsorption on Surface noble metal using in-situ method in black phosphorus nanometer sheet receives
Rice corpuscles, belongs to technical field of nanometer material preparation so that composite has widely application.
To achieve the above object, the technical solution adopted by the present invention is：
The method specifically includes following steps：
1) dispersion in organic solvent of the black phosphorus nanometer sheet that 20 mL concentration are 1 ~ 2 mg/mL is weighed, 20 mL water, mixed liquor are added
2 h of ultrasound；
2) 20-30 mg PdCl and then are while stirring added2, add NaOH to adjust pH value to 9-10, stirring 2-3 h；
3) after standing 10 ~ 12h, then dropwise to step 2) 300-350 mL concentration is added dropwise in the mixed liquor that obtains is 1 mg/mL
Fresh KBH4The aqueous solution；
4) after cleaning filtering, drying（Drying temperature is 40 DEG C~80 DEG C, and the time is 10~12 h）After obtain black phosphorus nanometer sheet
With noble metal nano particles composite.
Step 1) described in organic solvent be any one in ethanol, NMP and DMF.
Preferably, step 2 of the present invention) NaOH regulation pH value be 10.
Preferably, the KBH of 1 mg/mL4The aqueous solution be added dropwise 320 mL.
The beneficial effects of the present invention are：The black phosphorus nanometer sheet that the present invention is provided and noble metal nano particles composite
Preparation method, using in-situ method in the Adsorption on Surface noble metal nano particles of black phosphorus nanometer sheet, realizes noble metal nano particles
Effectively adsorb on the surface of black phosphorus nanometer sheet.Led using the catalytic performance and black phosphorus nanometer sheet of noble metal nano particles are special
The coordinating effect of electrical property, can apply to the fields such as electro-catalysis, electrochemical sensing, ultracapacitor.Currently without any
Document and patent report cross the method.Therefore preparation method of the invention has filled up this blank, in the compound of black phosphorus nanometer sheet
There is extensive application in thing preparation method.
Brief description of the drawings
Fig. 1 is the SEM of Pd nano particle and black phosphorus nanosheet composite material obtained in embodiment 1（SEM）
Photo；
Fig. 2 be Pd nano particle obtained in embodiment 1 and black phosphorus nanosheet composite material EDS power spectrums in Pd elements, O elements,
The distribution map of Cl elements and P element；
Fig. 3 be the Pd nano particle that prepared by the local reduction way that uses in the inventive method and black phosphorus nanosheet composite material with it is black
The CV test curves of phosphorus nanometer sheet.
Specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited only to these embodiments.
Embodiment 1
1) alcohol dispersion liquid of the black phosphorus nanometer sheet that 20mL concentration is 1mg/mL is weighed, 20ml water, mixed liquor ultrasound 2h is added；
2) 25mgPdCl and then is while stirring added2, add NaOH to adjust pH value to 10, stir 2.5h；
3) after standing 12h, then dropwise to step 2) mixed liquor that obtains be added dropwise 300mL 1mg/mL KBH4The aqueous solution；
4) after cleaning filtering, black phosphorus nanometer sheet and noble metal nano particles composite are obtained after drying.
Embodiment 2
1) the NMP dispersion liquids of the black phosphorus nanometer sheet that 20mL concentration is 2mg/mL are weighed, 20ml water, 2 h of mixed liquor ultrasound is added；
2) 25mg PdCl and then are while stirring added2, add NaOH to adjust pH value to 10, stir 2.5h；
3) after standing 10 h, then dropwise to step 2) mixed liquor that obtains be added dropwise 320 mL 1 mg/mL KBH4The aqueous solution；
4) after cleaning filtering, black phosphorus nanometer sheet and noble metal nano particles composite are obtained after drying.
Embodiment 3
1) the DMF dispersion liquids of the black phosphorus nanometer sheet that 20mL concentration is 1.5mg/mL are weighed, 20ml water, mixed liquor ultrasound 2h is added；
2) 30 mg PdCl and then are while stirring added2, add NaOH to adjust pH value to 9, stir 3 h；
3) after standing 11 h, then dropwise to step 2) mixed liquor that obtains be added dropwise 350 mL 1 mg/mL KBH4The aqueous solution；
4) after cleaning filtering, black phosphorus nanometer sheet and noble metal nano particles composite are obtained after drying.
Using interior-redox probe system [Fe (CN)6]3− The research of electrochemical behavior is carried out to sample.Different electricity
Pole surface modification has different dynamic responses.When bare electrode surface answering by black phosphorus quantum dot and palladium and black phosphorus quantum dot
After condensation material decoration, peak point current（I p）Increase, at the same time, two electrodes being modifiedValue is reduced.Such as Fig. 3
It is BPS, bare GCE and Pd/BPS in 5.0 mM [Fe (CN)6]3− In solution, tested under 50 mV/s sweep speeds
CV figure.It can be seen that its spike potential difference is reduced to 75 mV from 86 mV, peak current is to present to increase successively
Trend, Pd/BPS electron transfer rates are maximum.
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modification, should all belong to covering scope of the invention.
Claims (7)
1. the preparation method of a kind of black phosphorus nanometer sheet and noble metal nano particles composite, it is characterised in that：Liquid is used first
Block black phosphorus crystal is peeled off and obtains sheet black phosphorus by phase stripping method, then using chemical reduction method, palladium bichloride in-situ reducing is made
The surface that noble metal nano particles are adsorbed onto black phosphorus nanometer sheet is obtained, black phosphorus nanometer sheet is obtained after then suction filtration is dried receives with noble metal
Rice corpuscles composite.
2. the preparation method of black phosphorus nanometer sheet according to claim 1 and noble metal nano particles composite, its feature
It is：Specifically include following steps：
1) dispersion in organic solvent of 20 mL black phosphorus nanometer sheets is weighed, 20 mL water, 2 h of mixed liquor ultrasound are added；
2) 20-30mgPdCl and then is while stirring added2, add NaOH to adjust pH value to 9-10, stir 2-3h；
3) after standing, then dropwise to step 2) the fresh KBH of 300-350mL is added dropwise in the mixed liquor that obtains4The aqueous solution；
4) after cleaning filtering, black phosphorus nanometer sheet and noble metal nano particles composite are obtained after drying.
3. preparation method as claimed in claim 2, it is characterised in that：Step 1) described in organic solvent for ethanol, NMP and
Any one in DMF.
4. preparation method as claimed in claim 2, it is characterised in that：Step 1) described in black phosphorus nanometer sheet organic solvent
The concentration of dispersion liquid is 1~2 mg/mL.
5. the preparation method as described in right 2, it is characterised in that：Step 3) described in time of repose be 10~12 h.
6. the preparation method as described in right 2, it is characterised in that：Step 3) described in KBH4The concentration of the aqueous solution is 1 mg/mL.
7. the preparation method as described in right 2, it is characterised in that：Step 4）The technological parameter of the drying is：Drying temperature is
40 DEG C~80 DEG C, the time is 10~12 h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107221685A (en) * | 2017-06-16 | 2017-09-29 | 福州大学 | A kind of two-dimentional inlay structure catalyst and preparation method and application |
| CN107464939A (en) * | 2017-06-16 | 2017-12-12 | 福州大学 | A kind of cerium oxide base catalyst of black phosphorus alkene cladding and preparation method and application |
| CN107469845A (en) * | 2017-08-04 | 2017-12-15 | 深圳先进技术研究院 | A kind of black phosphorus/noble metal composite-material, its preparation method and application |
| CN107658475A (en) * | 2017-09-25 | 2018-02-02 | 青岛大学 | A kind of platinum/black phosphorus@carbon ball methanol fuel cell anode catalyzers and preparation method thereof |
| CN107802835A (en) * | 2017-12-04 | 2018-03-16 | 中南大学 | A kind of black phosphorus nanometer sheet/nano platinum particle composite and its preparation method and application |
| CN109713325A (en) * | 2018-12-29 | 2019-05-03 | 四川大学 | A kind of preparation method of palladium nano catalyst used for direct methanoic acid fuel cell |
| CN110975896A (en) * | 2019-12-20 | 2020-04-10 | 湘潭大学 | Au/BP heterojunction composite material and preparation method and application thereof |
| CN111707718A (en) * | 2020-05-09 | 2020-09-25 | 上海应用技术大学 | Functionalized black phosphorus-based modified enzyme-free sensor and preparation method and application thereof |
| CN113751035A (en) * | 2020-06-03 | 2021-12-07 | 深圳先进技术研究院 | Composite catalyst and preparation method thereof |
| CN114180543A (en) * | 2021-12-29 | 2022-03-15 | 西北工业大学 | Passivation method of black phosphorus nanosheet, passivated black phosphorus nanosheet and application thereof |
| CN114345408A (en) * | 2021-12-04 | 2022-04-15 | 湖北兴发化工集团股份有限公司 | Black phosphorus supported palladium nanoparticle composite material and preparation method thereof |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107464939A (en) * | 2017-06-16 | 2017-12-12 | 福州大学 | A kind of cerium oxide base catalyst of black phosphorus alkene cladding and preparation method and application |
| CN107464939B (en) * | 2017-06-16 | 2019-09-13 | 福州大学 | A kind of cerium oxide base catalyst and the preparation method and application thereof of black phosphorus alkene cladding |
| CN107221685A (en) * | 2017-06-16 | 2017-09-29 | 福州大学 | A kind of two-dimentional inlay structure catalyst and preparation method and application |
| CN107469845A (en) * | 2017-08-04 | 2017-12-15 | 深圳先进技术研究院 | A kind of black phosphorus/noble metal composite-material, its preparation method and application |
| WO2019024146A1 (en) * | 2017-08-04 | 2019-02-07 | 深圳先进技术研究院 | Black phosphorus/precious metal composite material, preparation method and application thereof |
| CN107469845B (en) * | 2017-08-04 | 2020-07-03 | 深圳先进技术研究院 | Black phosphorus/precious metal composite material, and preparation method and application thereof |
| CN107658475A (en) * | 2017-09-25 | 2018-02-02 | 青岛大学 | A kind of platinum/black phosphorus@carbon ball methanol fuel cell anode catalyzers and preparation method thereof |
| CN107802835B (en) * | 2017-12-04 | 2020-12-08 | 中南大学 | Black phosphorus nanosheet/platinum nanoparticle composite material and preparation method and application thereof |
| CN107802835A (en) * | 2017-12-04 | 2018-03-16 | 中南大学 | A kind of black phosphorus nanometer sheet/nano platinum particle composite and its preparation method and application |
| CN109713325A (en) * | 2018-12-29 | 2019-05-03 | 四川大学 | A kind of preparation method of palladium nano catalyst used for direct methanoic acid fuel cell |
| CN110975896A (en) * | 2019-12-20 | 2020-04-10 | 湘潭大学 | Au/BP heterojunction composite material and preparation method and application thereof |
| CN111707718A (en) * | 2020-05-09 | 2020-09-25 | 上海应用技术大学 | Functionalized black phosphorus-based modified enzyme-free sensor and preparation method and application thereof |
| CN113751035A (en) * | 2020-06-03 | 2021-12-07 | 深圳先进技术研究院 | Composite catalyst and preparation method thereof |
| WO2021243970A1 (en) * | 2020-06-03 | 2021-12-09 | 深圳先进技术研究院 | Composite catalyst and preparation method therefor |
| CN114345408A (en) * | 2021-12-04 | 2022-04-15 | 湖北兴发化工集团股份有限公司 | Black phosphorus supported palladium nanoparticle composite material and preparation method thereof |
| CN114180543A (en) * | 2021-12-29 | 2022-03-15 | 西北工业大学 | Passivation method of black phosphorus nanosheet, passivated black phosphorus nanosheet and application thereof |
| CN114180543B (en) * | 2021-12-29 | 2023-12-26 | 西北工业大学 | Passivation method of black phosphorus nano-sheet, passivated black phosphorus nano-sheet and application thereof |
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Application publication date: 20170531 |