CN108686685A - A kind of copper nano particles/black phosphorus nanosheet composite material and the preparation method and application thereof - Google Patents
A kind of copper nano particles/black phosphorus nanosheet composite material and the preparation method and application thereof Download PDFInfo
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- CN108686685A CN108686685A CN201810436846.8A CN201810436846A CN108686685A CN 108686685 A CN108686685 A CN 108686685A CN 201810436846 A CN201810436846 A CN 201810436846A CN 108686685 A CN108686685 A CN 108686685A
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 83
- 239000010949 copper Substances 0.000 title claims abstract description 83
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000002135 nanosheet Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical group O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- FGOSNANIQLJNSZ-UHFFFAOYSA-N acetonitrile copper Chemical compound [Cu].CC#N.CC#N.CC#N.CC#N FGOSNANIQLJNSZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005749 Copper compound Substances 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 4
- 229960004424 carbon dioxide Drugs 0.000 claims 1
- 229910002090 carbon oxide Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 14
- 239000013078 crystal Substances 0.000 abstract description 9
- 239000001569 carbon dioxide Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- 235000013339 cereals Nutrition 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000710013 Lily symptomless virus Species 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- RHFUXPCCELGMFC-UHFFFAOYSA-N n-(6-cyano-3-hydroxy-2,2-dimethyl-3,4-dihydrochromen-4-yl)-n-phenylmethoxyacetamide Chemical compound OC1C(C)(C)OC2=CC=C(C#N)C=C2C1N(C(=O)C)OCC1=CC=CC=C1 RHFUXPCCELGMFC-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
-
- B01J35/33—
-
- B01J35/393—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of copper nano particles/black phosphorus nanosheet composite material and the preparation method and application thereof, which includes the copper nano particles of carrier black phosphorus nanometer sheet and load on this carrier;Preparation method is that first black phosphorus and sodium hydroxide are scattered in organic solvent, mixed liquor is made, the mixed liquor is placed in supercritical reaction kettle, 3~4h is reacted under the conditions of 40~70 DEG C, 15~20MPa, black phosphorus nanometer sheet is made, after then the black phosphorus nanometer sheet is mixed with copper phase solution, 10~120min is reacted under the conditions of 50~60 DEG C, and composite material is made.The composite material is applied to electrochemical catalysis and restores carbon dioxide.The present invention remarkable advantage be:The composite material large specific surface area, the load capacity of copper nano particles is big, and crystal property and catalytic performance are excellent;Preparation method is simple, at low cost, environmental-friendly;Simultaneously CO is restored applied to electrochemical catalysis2, catalytic activity is high, stability is strong, has lower applied voltage.
Description
Technical field
The invention belongs to field of compound material more particularly to a kind of copper nano particles/black phosphorus nanosheet composite material and its
Preparation method and application.
Background technology
CO2Thermodynamics relatively stable (standard molar formation enthalpy is -393.51kJmol-1), inertia, not easily-activated (C=
O key bond energys are 750kJmol-1).Therefore, CO is realized2Chemical conversion in a mild condition is one and extremely challenging grinds
Study carefully.CO2The electric energy of the renewable energy conversions such as solar energy, wind energy can be further converted into chemical energy by electrochemical reduction, storage
In the fuel and chemicals of high added value.Although CO2Electrochemical reduction gradually causes the concern of scientists from all over the world and research emerging
Interest, but the field still has many urgent problems to be solved, such as:(1) excessively high applying electrical potential (or low-yield efficiency);
(2) slow electron transmission dynamics;(3) selectivity of product is undesirable;(4) too low (only tens milliamperes every for bias current density
Square centimeter);(5) stability of catalyst and durability not good enough (being less than 100 hours) etc..The above problem significantly limits
There are practical application and the commercialization of electrode catalytic materials.Based on this, high performance catalysis material is developed, reduces CO2Electrochemistry is also
Former overpotential, the activity, selectivity and stability for improving catalysis material have important scientific meaning and industrial value.
Although the two-dimension nano materials such as some graphenes are applied to CO2Electrochemical reduction field (Atomically
Dispersed Ni (i) as the active site for electrochemical CO2reduction, Nature
Energy, 2018,3,140-147), but this method experimentation is complicated, limits popularization and application.
Invention content
Goal of the invention:The first object of the present invention is to provide the big copper of excellent crystal property, large specific surface area, copper load capacity and receives
Rice grain/black phosphorus nanosheet composite material;
The second object of the present invention is to provide the preparation method of the composite material, this method is simple, at low cost, the time is short,
It is environmental-friendly;
The third object of the present invention is to provide the application of the composite material, is applied to electro-catalysis CO2, catalytic performance is excellent
More.
Technical solution:Copper nano particles/black phosphorus nanosheet composite material of the present invention, including carrier black phosphorus nanometer sheet and negative
Carry copper nano particles on this carrier.
The composite material of the present invention loads copper nano particles by using black phosphorus nanometer sheet as carrier, not only large specific surface area,
Copper nano particles load is sufficient, and crystal property, catalyst performance are excellent, and stability is strong.Furtherly, copper nanometer in composite material
The grain size of particle is 2~5nm.The composite material of the present invention can load the copper nano particles that grain size is 2~5nm, the grain size model
The copper nano particles enclosed further enhance the catalytic activity of composite material.
The method that the present invention prepares copper nano particles/black phosphorus nanosheet composite material, includes the following steps:
(1) black phosphorus nanometer sheet is prepared:First black phosphorus and sodium hydroxide are scattered in organic solvent, mixed liquor is made, then
The mixed liquor is placed in supercritical reaction kettle, 3~4h is reacted under the conditions of 40~70 DEG C, 15~20MPa, through centrifuge washing
Afterwards, black phosphorus nanometer sheet is made;
(2) composite material is prepared:After black phosphorus nanometer sheet is mixed with copper phase solution, under the conditions of 50~60 DEG C react 10~
Copper nano particles/black phosphorus nanosheet composite material is made after centrifuge washing in 120min.
It further says, the step of preparation method of the present invention in (1), the mass ratio of black phosphorus and sodium hydroxide is 1:1~2.
Organic solvent preferably can be n-cyclohexyl-2-pyrrolidone, N- cyclohexyl pyrrolidones or isopropanol.By using N- hexamethylenes
The organic solvent of the anhydrous and oxygen-free of base -2-Pyrrolidone, N- cyclohexyl pyrrolidones or isopropanol is black so as to effectively prevent
Phosphorus oxidation is degraded.
Furtherly, in the step of preparation method of the present invention (2), copper phase solution may include that mass volume ratio is 1:1~
1:0.5 solute and solvent, wherein solute can be monovalence copper compound, further preferably can be four acetonitrile copper of hexafluorophosphoric acid.This
Invention uses monovalence copper compound, and generate bivalent cupric ion and nano copper particle in the reaction finally makes after centrifuge washing
Copper particulate load is obtained in black phosphorus nanometer sheet, and the grain size of the copper particle is 2~5nm.Solvent preferably can be n-butanol or acetone.
The speed of centrifugation preferably can be 9000~13000r/min.
Copper nano particles/black phosphorus nanosheet composite material of the present invention is applied to electrochemical catalysis and restores carbon dioxide.
Advantageous effect:Compared with prior art, remarkable advantage of the invention is:The copper nano particles/black phosphorus nanometer sheet is multiple
Condensation material, with black phosphorus nanometer sheet for carrier loaded copper nano particles, thickness can reach several nanometers to tens nanometers, specific surface area
Greatly, the load capacity of copper nano particles is big, and crystal property and catalytic performance are excellent;Its preparation method is simple, the time is short, at low cost, ring simultaneously
Border is friendly;In addition, the composite material, which is applied to electrochemical catalysis, restores CO2, catalytic activity is high, stability is strong, it is lower to have
Applied voltage, and the grain size for the copper nano particles being supported in the composite material in black phosphorus nanometer sheet can reach 2nm or so, the grain
Copper nano particles within the scope of diameter further enhance the catalytic performance of the composite material.
Description of the drawings
Fig. 1 is the low power transmission electron microscope picture of copper nano particles/black phosphorus nanosheet composite material of the present invention;
Fig. 2 is the high-resolution-ration transmission electric-lens figure of copper nano particles/black phosphorus nanosheet composite material of the present invention;
Fig. 3 is the electrochemical property test curve graph of copper copper nano particles/black phosphorus nanosheet composite material of the present invention.
Specific implementation mode
Technical scheme of the present invention is described in further details with reference to the accompanying drawings and embodiments.
Embodiment 1
Copper nano particles/black phosphorus nanosheet composite material of the present invention, including black phosphorus nanometer sheet carrier and it is supported on the load
The grain size of copper nano particles on body, the copper nano particles is 2~4nm.
The preparation method of composite material of the present invention includes the following steps:
(1) 10mg bulks black phosphorus is weighed, 10mg sodium hydroxides are scattered in 30ml n-cyclohexyl-2-pyrrolidone, acquisition
Mixed liquor, it is spare;
(2) above-mentioned mixed liquor is put into the autoclave of overcritical device, waits for that the temperature of autoclave reaches
At 40 DEG C, by CO2It is pumped into autoclave, when autoclave pressure reaches 15MPa, system reaches supercriticality, dimension
Hold 3h;
(3) after reaction, the CO in autoclave is released2, it is cooled to room temperature, then ultrasound should under the conditions of 100W
Mixed liquor 6h, centrifugation, washing, obtains the polyatom layer black phosphorus nanometer sheet of black;
(4) obtained black phosphorus nanoscale twins and copper solution is mixed to carry out being sufficiently mixed processing, it is pre- under the conditions of 50 DEG C
The composite material is made in thermal response 20min, centrifugation, washing;Wherein, copper mixes hexafluorophosphoric acid four acetonitrile copper of the solution by 4mg
And the n-butanol composition of 6ml.Wherein, the speed of centrifugation is 10000r/min.
Copper nano particles/black phosphorus nanosheet composite material prepared by the embodiment is observed, result such as Fig. 1 of acquisition
And shown in Fig. 2.It is mostly former by the Fig. 1 and Fig. 2 it is found that adhering to a large amount of copper nano particles in the multilayer black phosphorus lamella of the present invention
The lattice of sublayer black phosphorus be 0.25nm, and the lattice of copper particle be 0.18nm, it can thus be appreciated that copper nano particles be successfully supported on it is black
On phosphorus lamella.
Copper nano particles prepared by the embodiment/black phosphorus nanosheet composite material is applied to electrochemical catalysis and restores dioxy
Change in carbon, specifically comprises the following steps:
(1) it carries out on electrochemical workstation, is configured using three-electrode battery, the glass-carbon electrode (RDE) with 5mm diameters
As working electrode, platinum foil is used as to electrode and saturation calomel as reference electrode (SCE).It is catalyzed to prepare, by 50~100 μ l
5%Nafion solution as electroconductive binder is introduced into 100~300 μ l water-ethanol solution with isometric water and ethyl alcohol
And it is ultrasonically treated 0.5~1h;
(2) composite material prepared by the present invention is applied on vitreous carbon RDE and it is made to dry in air, obtain 0.1
~0.2mgcm-2Catalyst loadings, by by CO2(99.99%) it purges to 0.5MKHCO3In prepare CO2Saturation electrolysis
30min in matter aqueous solution, and CO is kept on electrolyte during entire electrochemical measurement2Flowing;
(3) according to Nernst equation (ERHE=ESCE+0.0591 × pH+0.241V, at 25 DEG C) to reversible hydrogen electrode
(RHE) all current potentials of gradation calculations.Linear sweep voltammetry figure (LSVs) is with 5mVs-1Sweep speed collect.
Contrasting detection 1
Using electrolysis step substantially the same manner as Example 1, the difference is that any material is not covered on vitreous carbon RDE
Material.
Contrasting detection 2
Using electrolysis step substantially the same manner as Example 1, the difference is that applying black phosphorus nanometer on vitreous carbon RDE
Piece.
Embodiment 1 and the result of contrasting detection 1-2 obtain as shown in Figure 3.By the figure it is found that compared to blank carbon cloth,
Carbon cloth-black phosphorus nanometer sheet, carbon cloth-copper nano particles/black phosphorus nanometer sheet applied voltage is minimum, illustrates that its catalytic performance is superior.
Embodiment 2
Copper nano particles/black phosphorus nanosheet composite material of the present invention, including black phosphorus nanometer sheet carrier and it is supported on the load
Copper nano particles on body.The grain size of the copper nano particles is 2~5nm.
The preparation method of composite material of the present invention includes the following steps:
(1) 10mg bulks black phosphorus is weighed, 15mg sodium hydroxides are scattered in 30ml n-cyclohexyl-2-pyrrolidone, acquisition
Mixed liquor, it is spare;
(2) mixed liquor is put into the autoclave of overcritical device, waits for that the temperature of autoclave reaches 40 DEG C
When, by CO2It is pumped into autoclave, when autoclave pressure reaches 15MPa, system reaches supercriticality, maintains 3h;
(3) after reaction, the CO in autoclave is released2, cold to take to room temperature, then ultrasound should under the conditions of 150W
Mixed liquor 4h, centrifugation, washing, obtains the polyatom layer black phosphorus nanometer sheet of black;
(4) obtained black phosphorus nanoscale twins and copper are mixed into solution and carries out mixed processing, pre- thermal response under the conditions of 50 DEG C
40min, centrifugation, washing, is made the composite material;Wherein, copper mixes hexafluorophosphoric acid four acetonitrile copper and 6ml of the solution by 5mg
N-butanol composition.Wherein, the speed of centrifugation is 9000r/min.
Copper nano particles prepared by the embodiment/black phosphorus nanosheet composite material is applied to electrochemical catalysis and restores dioxy
Change in carbon it is found that it is with superior catalytic performance.
Embodiment 3
Copper nano particles/black phosphorus nanosheet composite material of the present invention, including black phosphorus nanometer sheet carrier and it is supported on the load
Copper nano particles on body.The grain size of the copper nano particles is 2~5nm.
The preparation method of composite material of the present invention includes the following steps:
(1) 10mg bulks black phosphorus is weighed, 20mg sodium hydroxides are scattered in 30ml n-cyclohexyl-2-pyrrolidone, acquisition
Mixed liquor, it is spare;
(2) mixed liquor is put into the autoclave of overcritical device, waits for that the temperature of autoclave reaches 40 DEG C
When, by CO2It is pumped into autoclave, when autoclave pressure reaches 15MPa, system reaches supercriticality, maintains 3h;
(3) after reaction, the CO in autoclave is released2, cold to take to room temperature, then ultrasound should under the conditions of 120W
Mixed liquor 5h, centrifugation, washing, obtains the polyatom layer black phosphorus nanometer sheet of black;
(4) obtained black phosphorus nanoscale twins and copper are mixed into solution and carries out mixed processing, preheated under the conditions of 60 DEG C anti-
40min, centrifugation, washing is answered to obtain the black phosphorus nanometer sheet compound of copper particle attachment;Wherein, copper mixes solution by the six of 6mg
The n-butanol of four acetonitrile copper of fluorophosphoric acid and 6ml form.Wherein, the speed of centrifugation is 13000r/min.
Copper nano particles prepared by the embodiment/black phosphorus nanosheet composite material is applied to electrochemical catalysis and restores dioxy
Change in carbon it is found that it is with superior catalytic performance.
Embodiment 4
5 groups of parallel tests are designed, basic step is same as Example 1, the difference is that the matter of black phosphorus and sodium hydroxide
Amount ratio, specially 1:0.5,1:1,1:1.5,1:2,1:2.5.Composite material prepared by the embodiment is carried out structural characterization can
Know, the mass ratio of black phosphorus and sodium hydroxide is 1:Not only large specific surface area, the copper nano particles load of 1~2 composite material prepared
Abundance, catalytic performance is strong, and crystal property and stability are strong.And when mass ratio is 1:0.5, i.e., when addition amount of sodium hydroxide is few,
Then black phosphorus stability is poor;And when mass ratio is 1:2.5, it is 1 with mass ratio:As 1.5, the two sodium hydroxide is both supersaturated shape
State, and stability reaches same desired effect, i.e., when amount of sodium hydroxide is excessive, is also at hypersaturated state, and be unfavorable for saving
Resource.
Embodiment 5
5 groups of parallel tests are designed, basic step is same as Example 1, the difference is that solute and molten in copper phase solution
The mass volume ratio of agent, specially 1:0.3,1:0.5,1:1,1:1.5,1:2.Composite material prepared by the embodiment is tied
Structure characterizes it is found that the mass volume ratio of solute and solvent is 1:0.5~1.5 composite material not only large specific surface area, the copper prepared
Nano particle load is sufficient, and catalytic performance is strong, and crystal property and stability are strong.And when mass volume ratio is 1:0.3, i.e. solvent
When amount is few, then solute cannot be completely dissolved;And when mass volume ratio is 1:2, i.e., when quantity of solvent is high, the concentration of solution is low, then copper
The content of nano particle load is relatively low.
Embodiment 6
4 groups of parallel tests are designed, basic step is same as Example 1, the difference is that by black phosphorus nanometer sheet and copper phase
The mixed reaction temperature of solution, specially 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C.Composite structure table prepared by the embodiment
Sign it is found that the composite material prepared under the conditions of 50~60 DEG C not only large specific surface area, copper nano particles load are sufficient, catalytic
Can be strong, and crystal property and stability are strong.And when temperature is less than 50 DEG C, reaction rate slows down, then copper nano particles load capacity
It reduces, when being higher than 60 DEG C, copper ion is not easy to be converted to copper nano particles, then copper nano particles load capacity is reduced.
Embodiment 7
6 groups of parallel tests are designed, basic step is same as Example 1, the difference is that by black phosphorus nanometer sheet and copper phase
Solution mixed reaction time, specially 5min, 10min, 50min, 100min, 120min, 130min.By the embodiment system
Standby composite structure characterization is it is found that the composite materials that prepare of 10~120min of reaction not only large specific surface area, copper nanometer
Particle loading is sufficient, and catalytic performance is strong, and crystal property and stability are strong.And when reacted between be less than 10min when, the reaction time
Few, copper ion reduction number is few, then copper nano particles load capacity reduces;When higher than 120min, copper particle exposure duration is long, then
It can be further oxidized to copper oxide.
Embodiment 8
Basic step is same as Example 1, the difference is that organic solvent is N- cyclohexyl pyrrolidones or isopropanol,
Solvent is acetone, and the raw material that the present invention uses is purchased from commercially available.First black phosphorus and sodium hydroxide are disperseed when preparing black phosphorus nanometer sheet
In organic solvent, mixed liquor is made, then the mixed liquor is placed in supercritical reaction kettle, it is anti-under the conditions of 70 DEG C, 20MPa
4h is answered, after centrifuge washing, black phosphorus nanometer sheet is made.
By above-described embodiment it is found that the large specific surface area of the composite material of the present invention, the load capacity of copper nano particles is big,
Crystal property and catalytic performance are excellent;Preparation method is simple simultaneously, at low cost, environmental-friendly;CO is restored applied to electrochemical catalysis2, urge
Change activity is high, stability is strong, has lower applied voltage.
Claims (9)
1. a kind of copper nano particles/black phosphorus nanosheet composite material, it is characterised in that:Including carrier black phosphorus nanometer sheet and it is supported on
Copper nano particles on the carrier.
2. copper nano particles according to claim 1/black phosphorus nanosheet composite material, it is characterised in that:The copper nanometer
The grain size of particle is 2~5nm.
3. a kind of method preparing copper nano particles described in claim 1/black phosphorus nanosheet composite material, it is characterised in that packet
Include following steps:
(1) black phosphorus nanometer sheet is prepared:First black phosphorus and sodium hydroxide are scattered in organic solvent, mixed liquor is made, it then should
Mixed liquor is placed in supercritical reaction kettle, and 3~4h is reacted under the conditions of 40~70 DEG C, 15~20MPa, after centrifuge washing, system
Obtain black phosphorus nanometer sheet;
(2) composite material is prepared:After above-mentioned black phosphorus nanometer sheet is mixed with copper phase solution, under the conditions of 50~60 DEG C react 10~
Copper nano particles/black phosphorus nanosheet composite material is made after centrifuge washing in 120min.
4. the method according to claim 3 for preparing copper nano particles/black phosphorus nanosheet composite material, it is characterised in that:
In step (1), the mass ratio of the black phosphorus and sodium hydroxide is 1:1~2.
5. the method according to claim 3 for preparing copper nano particles/black phosphorus nanosheet composite material, it is characterised in that:
In step (1), the organic solvent is n-cyclohexyl-2-pyrrolidone, N- cyclohexyl pyrrolidones or isopropanol.
6. the method according to claim 3 for preparing copper nano particles/black phosphorus nanosheet composite material, it is characterised in that:
In step (2), the copper phase solution includes that mass volume ratio is 1:0.5~1.5 solute and solvent, wherein the solute is
Monovalence copper compound, solvent are n-butanol or acetone.
7. the method according to claim 6 for preparing copper nano particles/black phosphorus nanosheet composite material, it is characterised in that:
The monovalence copper compound is four acetonitrile copper of hexafluorophosphoric acid.
8. the method according to claim 3 for preparing copper nano particles/black phosphorus nanosheet composite material, it is characterised in that:
In step (2), the speed of the centrifugation is 9000~13000r/min.
9. copper nano particles according to claim 1/black phosphorus nanosheet composite material, which is applied to electrochemical catalysis, restores two
Carbonoxide.
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