CN104609456B - A kind of preparation method of the C/N codope cuprous nanosphere of porous oxidation based on sericin - Google Patents
A kind of preparation method of the C/N codope cuprous nanosphere of porous oxidation based on sericin Download PDFInfo
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- CN104609456B CN104609456B CN201410846015.XA CN201410846015A CN104609456B CN 104609456 B CN104609456 B CN 104609456B CN 201410846015 A CN201410846015 A CN 201410846015A CN 104609456 B CN104609456 B CN 104609456B
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- 108010013296 Sericins Proteins 0.000 title claims abstract description 48
- 239000002077 nanosphere Substances 0.000 title claims abstract description 43
- 230000003647 oxidation Effects 0.000 title claims abstract description 38
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 32
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011807 nanoball Substances 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 16
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000008103 glucose Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 27
- 239000010949 copper Substances 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 23
- 229910052802 copper Inorganic materials 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229940112669 cuprous oxide Drugs 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- -1 Schweinfurt green Chemical compound 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 241000255789 Bombyx mori Species 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000000087 stabilizing effect Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000009388 chemical precipitation Methods 0.000 abstract 1
- 239000000356 contaminant Substances 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000009392 Vitis Nutrition 0.000 description 2
- 241000219095 Vitis Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 239000011805 ball Substances 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
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- 229910001416 lithium ion Inorganic materials 0.000 description 1
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- 239000002091 nanocage Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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Abstract
The invention discloses the preparation method of a kind of C/N codope cuprous nanosphere of porous oxidation based on sericin.The present invention uses chemical precipitation method, sericin discarded in the silk industry course of processing is as template with C/N source, and glucose is reducing agent, prepares Red copper oxide sericin composite Nano ball, through high-temperature calcination, it is thus achieved that the monodispersed C/N cuprous nanosphere of codope porous oxidation.Preparation method of the present invention is not against surfactant, and operating condition is gentle, simple, and process stabilizing, favorable reproducibility.The Red copper oxide the obtained doping by C/N element, can effectively adjust its energy gap；The nano-level sphere structure of porous is possible not only to accelerate electric transmission, gives the enrichment of the big specific surface area of Red copper oxide beneficially object simultaneously, is expected to be applied to photocatalysis degradation organic contaminant.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, relate to a kind of cuprous nano material of porous oxidation, particularly relate to one
With sericin as template with the C/N source method of preparing the C/N cuprous nanosphere of codope porous oxidation.
Background technology
Red copper oxide (Cu2O) being a kind of typical p-type semi-conducting material, its energy gap is 2.0-2.2eV, can be by 620nm
Excited by visible light, energy transformation ratio is in theory up to 18%.Under the irradiation of sunlight, Red copper oxide can produce hydrogen with decomposition water
Gas and oxygen, have good catalysis activity.Additionally, Red copper oxide is nontoxic and preparation cost is relatively low, therefore solaode,
The fields such as gas sensor, photocatalyst, lithium ion battery electrode material have a wide range of applications.But, current Cu2O exists
Still there is limitation: Cu in actual application aspect2The recombination probability of the photo-generated carrier (hole and electronics) of O is high, causes quantum to be imitated
Rate reduces, and affects its photocatalysis efficiency.Therefore, how Cu is improved2The catalysis activity of O is the pass needing at present and in the future to solve
Key problem.
Recent domestic research worker is at Cu2The aspects such as design synthesis, preparation and the character of O nano structural material have been carried out greatly
The exploratory study of amount.Many for example with chemical reduction method, hydro-thermal method, sol-gel process, microemulsion method, microwave irradiation etc.
Plant preparation method, synthesize cube, octahedron, top rake octahedron, six foot type, spherical, flower-shaped, hollow cuboid, skies
The cuprous nano structural material of the different morphologies such as bulbus cordis shape, nano wire, nanotube and nanocages.Its light is urged by scholars
The research changing activity shows, the pattern of Red copper oxide and size, degree of crystallinity, is electrically separated ability and absorbability is grand with it
The physicochemical properties seen are closely related, and wherein pattern and the size of Red copper oxide are especially prominent on the impact of its catalysis activity.As
Du Yi etc. as surfactant, use high-temperature water full-boiled process to synthesize shaggy oxidation Asia with dodecyl sodium sulfate (SDS)
Copper (CN 201410340699.6).Gou etc., using cetyl trimethylammonium bromide (CTAB) as stabilizer, are prepared into
Cuprous nano cube (Gou et al., Nano Lett, 2003,3,231) to different size size.Huang etc. are with SDS
For surfactant, azanol (NH2OH.HCl) it is reducing agent, synthesizes cubical cuprous nano material.By adjusting
Whole NH2The consumption of OH.HCl, cuprous nano material is gradually octahedra, the top rake to top rake cube, top rake from cube
Dodecahedron to granatohedron structural evolution, and granatohedron present more preferable photocatalytic activity (Huang et al.,
J Am Chem Soc,2012,134,1261).Li etc. are respectively with Polyethylene Glycol (PEG) and polyvinylpyrrolidone (PVP)
For stabilizer, ascorbic acid is reducing agent, have studied different stabilizers to Red copper oxide pattern and the impact of crystal phase structure.Research
Show, the nanocube being edge (100) crystal face preferential growth for the Red copper oxide that stabilizer synthesizes with PEG, and with PVP
Red copper oxide for stabilizer synthesis is the porous nano crystal along the growth of (100) and (111) crystal face.Gained Red copper oxide
Electrocatalysis characteristic has pattern and crystal face dependency (Li et al., J Phys Chem C, 2013,117,13872).
At present, in existing open source literature and patent report, synthesis cuprous nano structural material time many use CTAB, SDS,
The surfactants such as PEG, PVP.These surfactants have amphiphilic structure, can effectively prevent nano-particle reunion or
Person regulates and controls its pattern as structure directing agent.But the concentration of surfactant often directly affects product morphology, in preparation process
Need to accurately control its concentration；Meanwhile, surfactant easily adsorbs the surface at sample, it is difficult to clean, thus it is pure to affect sample
Degree.On the other hand, owing to being limited by synthetic method etc., the usual smooth surface of Red copper oxide of synthesized various patterns, compares table
Area is less, and Rough factor is relatively low, has a strong impact on the ability that is electrically separated and the absorption property of material, and then causes Red copper oxide
Catalysis activity is relatively low.
Summary of the invention
Cuprous nano material catalytic efficiency is prepared the highest, preparation process many employings high-temperature water full-boiled process and need to making for prior art
By problems such as various surfactants, it is an object of the invention to provide that a kind of monodispersed C/N codope porous oxidation is cuprous to be received
The preparation method of rice ball.
Sericin is that a kind of water miscible globular preteins, carbon and nitrogen element account for the 50% and 14% of total amount respectively.?
In the silk industry course of processing, sericin tends to vary with degumming waste liquid and discharges together, causes the waste of resource and the pollution of water body.
The pattern of cuprous oxide micro/nano crystal copper source, reducing agent, dispersant, reaction temperature and the time etc. generally and in preparation process because of
Element is closely related；Change any condition, Red copper oxide pattern all may be caused to change.In order to reduce Red copper oxide photoproduction
The recombination probability of carrier, improves its photocatalysis performance, present invention supramolecular structure based on sericin, with sericin is
Template and C/N source, prepare the cuprous nanosphere of porous oxidation of C/N codope.The doping of C/N element can adjust Red copper oxide
Energy gap；The nano-level sphere structure of porous is possible not only to accelerate electric transmission, gives the specific surface that Red copper oxide is big simultaneously
Long-pending and beneficially object enrichment and then improve its photocatalysis efficiency.On the other hand, preparation method of the present invention is not against surface activity
Agent, operating condition is gentle, simple, and process stabilizing, favorable reproducibility.
For achieving the above object, the technical solution of the present invention is as follows:
(1) preparation of Red copper oxide-sericin composite Nano ball: the sericin that molecular weight is 1 000～50 000 is dissolved in
Water is configured to sericin solution；At 60～80 DEG C, above-mentioned sericin solution is added into the soluble copper prepared in advance
In saline solution, under magnetic agitation after mix homogeneously, regulate above-mentioned sericin-mantoquita mixed solution by the NaOH solution of 1M
PH value is 8～12；Being subsequently adding glucose reducing agent reaction 0.5～5h, 12 000rpm are centrifuged 10min and collect precipitate, warp
It is dried after centrifuge washing, obtains Red copper oxide-sericin composite Nano ball；
(2) preparation of the cuprous nanosphere of C/N codope porous oxidation: by multiple for gained Red copper oxide-sericin in step (1)
Closing nanosphere to be placed in tube furnace, under argon shield, be warming up to 400 DEG C～700 DEG C with the speed of 5 DEG C/min, constant temperature keeps 2
H, naturally cools to room temperature, obtains the C/N cuprous nanosphere of codope porous oxidation.
Described sericin solution concentration is 0.1wt%～5wt%；
Described soluble copper salt is one or both in copper sulfate, Schweinfurt green, copper chloride, copper nitrate；Described solubility
Copper salt solution concentration is 0.1～0.3mol/L；
Described sericin is 0.0001～0.5 with the mol ratio of copper ion；
Described glucose is respectively 1:2,2:2 or 3:2 with the mol ratio of mantoquita；
Described C/N codope cuprous oxide crystal is nanometer spherical, and in connection, uniform loose structure, its size
It is distributed between 100～600nm.
The present invention is compared with prior art had the beneficial effect that
The preparation method of the C/N codope cuprous nanosphere of porous oxidation based on sericin that the present invention provides, with discarded
Sericin, as template and C/N source, utilizes the supramolecular structure of sericin, prepares monodispersed C/N codope porous oxygen
Change cuprous nanosphere.Adulterated by C/N, the energy gap of Red copper oxide can be adjusted, improve its photocatalysis efficiency；Oxidation Asia
The connection of copper nanosphere, uniform loose structure give the transmission of its big specific surface area, beneficially light induced electron and the enrichment of object,
And then realize its high photocatalytic activity.On the other hand, preparation method of the present invention not against surfactant, operating condition is gentle,
Simple, and process stabilizing, favorable reproducibility.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the embodiment 1 gained C/N cuprous nanosphere of codope porous oxidation.
Fig. 2 is the FESEM photo of the embodiment 2 gained C/N cuprous nanosphere of codope porous oxidation.
Fig. 3 is the XPS collection of illustrative plates of the embodiment 3 gained C/N cuprous nanosphere of codope porous oxidation.
Fig. 4 is the FESEM photo of the embodiment 4 gained C/N cuprous nanosphere of codope porous oxidation.
Fig. 5 is the FESEM photo of the embodiment 5 gained C/N cuprous nanosphere of codope porous oxidation.
Detailed description of the invention
By further illustrating the technological means and beneficial effect thereof that the present invention taked, below in conjunction with embodiments of the invention and
Accompanying drawing is specifically described.
Embodiment 1:
(1) preparation of Red copper oxide-sericin composite Nano ball: join soluble in water for sericin that molecular weight is 1 000
Make the sericin solution that concentration is 5wt%；At 60 DEG C, above-mentioned for 100mL sericin solution is added into 100mL dense
In the degree copper-bath for 0.1mol/L, under magnetic agitation after mix homogeneously, regulate above-mentioned silk by the NaOH solution of 1M
Glue protein-copper sulfate mixed solution pH value is 8；According to the ratio that mol ratio is 3:2 of glucose Yu copper sulfate, add Fructus Vitis viniferae
Sugar reducing agent reaction 0.5h, 12 000rpm are centrifuged 10min and collect precipitate, be dried by centrifugation, obtain Red copper oxide after washing
-sericin composite Nano ball；
(2) preparation of the cuprous nanosphere of C/N codope porous oxidation: by multiple for gained Red copper oxide-sericin in step (1)
Closing nanosphere to be placed in tube furnace, under argon shield, be warming up to 400 DEG C with the speed of 5 DEG C/min, constant temperature keeps 2h, from
So being cooled to room temperature, obtain the C/N cuprous nanosphere of codope porous oxidation, its particle diameter is about 100nm.Fig. 1 is this product
XRD figure is composed.Consistent with Red copper oxide standard XRD pattern (JCPDS No.65-3288), illustrate that products therefrom is for crystallization
Spend higher Red copper oxide.
Embodiment 2:
(1) preparation of Red copper oxide-sericin composite Nano ball: join soluble in water for sericin that molecular weight is 8 000
Make the sericin solution that concentration is 2wt%；At 70 DEG C, above-mentioned for 100mL sericin solution is added into 100mL dense
In the degree copper nitrate solution for 0.3mol/L, under magnetic agitation after mix homogeneously, regulate above-mentioned silk by the NaOH solution of 1M
Glue protein-copper nitrate mixed solution pH value is 10；According to the ratio that mol ratio is 2:2 of glucose Yu copper nitrate, add Fructus Vitis viniferae
Sugar reducing agent reaction 1h, 12 000rpm be centrifuged 10min collect precipitate, by centrifugation washing after be dried, obtain Red copper oxide-
Sericin composite Nano ball；
(2) preparation of the cuprous nanosphere of C/N codope porous oxidation: by multiple for gained Red copper oxide-sericin in step (1)
Closing nanosphere to be placed in tube furnace, under argon shield, be warming up to 400 DEG C with the speed of 5 DEG C/min, constant temperature keeps 2h, from
So being cooled to room temperature, obtain the C/N cuprous nanosphere of codope porous oxidation, its particle diameter is about 200nm.Fig. 2 is this product
FESEM photo.It can be seen that gained C/N codope Nano balls of cuprous oxide has connection, uniform loose structure.
Embodiment 3:
(1) preparation of Red copper oxide-sericin composite Nano ball: join soluble in water for sericin that molecular weight is 20 000
Make the sericin solution that concentration is 0.5wt%；At 60 DEG C, above-mentioned for 100mL sericin solution is added into 100mL
Concentration is in the Schweinfurt green solution of 0.1mol/L, under magnetic agitation after mix homogeneously, regulates above-mentioned by the NaOH solution of 1M
Sericin-Schweinfurt green mixed solution pH value is 11；According to the ratio that mol ratio is 1:2 of glucose Yu copper nitrate, add Portugal
Grape sugar reducing agent reaction 3h, 12 000rpm are centrifuged 10min and collect precipitate, be dried by centrifugation, must aoxidize Asia after washing
Copper-sericin composite Nano ball；
(2) preparation of the cuprous nanosphere of C/N codope porous oxidation: by multiple for gained Red copper oxide-sericin in step (1)
Closing nanosphere to be placed in tube furnace, under argon shield, be warming up to 500 DEG C with the speed of 5 DEG C/min, constant temperature keeps 2h, from
So being cooled to room temperature, obtain the C/N cuprous nanosphere of codope porous oxidation, its particle diameter is about 400nm.Fig. 3 is this product
XPS collection of illustrative plates.It can be seen that be Cu2P combining the absworption peak at energy 932.5eV3/2Absworption peak, combine can 283.7eV,
Absworption peak occurs at 398.5eV, the most corresponding C element and the absworption peak of N element, illustrate that C element and N element are successfully mixed
Miscellaneous enter in cuprous oxide micro/nano crystal.
Embodiment 4:
(1) preparation of Red copper oxide-sericin composite Nano ball: join soluble in water for sericin that molecular weight is 50 000
Make the sericin solution that concentration is 0.1wt%；At 80 DEG C, above-mentioned for 100mL sericin solution is added into 100mL
Concentration is in the copper chloride solution of 0.2mol/L, under magnetic agitation after mix homogeneously, regulates above-mentioned by the NaOH solution of 1M
Sericin-Schweinfurt green mixed solution pH value is 12；According to the ratio that mol ratio is 2:2 of glucose Yu copper chloride, add Portugal
Grape sugar reducing agent reaction 1h, 12 000rpm are centrifuged 10min and collect precipitate, be dried by centrifugation, must aoxidize Asia after washing
Copper-sericin composite Nano ball.
(2) preparation of the cuprous nanosphere of C/N codope porous oxidation: by multiple for gained Red copper oxide-sericin in step (1)
Closing nanosphere to be placed in tube furnace, under argon shield, be warming up to 600 DEG C with the speed of 5 DEG C/min, constant temperature keeps 2h, from
So being cooled to room temperature, obtain the C/N cuprous nanosphere of codope porous oxidation, its particle diameter is about 600nm.Fig. 4 is this product
FESEM photo.It can be seen that gained C/N codope Nano balls of cuprous oxide has connection, uniform loose structure.
Embodiment 5:
(1) preparation of Red copper oxide-sericin composite Nano ball: join soluble in water for sericin that molecular weight is 8 000
Make the sericin solution that concentration is 1.5wt%；At 60 DEG C, above-mentioned for 100mL sericin solution is added into 100mL
Concentration is in the copper sulfate of 0.2mol/L and Schweinfurt green mixed solution, under magnetic agitation after mix homogeneously, with the NaOH of 1M
It is 12 that solution regulates above-mentioned mixed solution pH value；According to the ratio that mol ratio is 3:2 of glucose Yu mantoquita, add glucose
Reducing agent reaction 5h, 12 000rpm are centrifuged 10min and collect precipitate, be dried by centrifugation, obtain Red copper oxide-silk after washing
Glue protein composite Nano ball.
(2) preparation of the cuprous nanosphere of C/N codope porous oxidation: by multiple for gained Red copper oxide-sericin in step (1)
Closing nanosphere to be placed in tube furnace, under argon shield, be warming up to 700 DEG C with the speed of 5 DEG C/min, constant temperature keeps 2h, from
So being cooled to room temperature, obtain the C/N cuprous nanosphere of codope porous oxidation, its particle diameter is about 400nm.Fig. 5 is this product
FESEM photo.It can be seen that gained C/N codope Nano balls of cuprous oxide has connection, uniform loose structure.
The present invention that listed above is only is embodied as example.It is clear that the invention is not restricted to above example is sub, it is also possible to have
Many deformation.All deformation that those of ordinary skill in the art can directly derive from present disclosure or associate, all
It is considered as protection scope of the present invention.
Claims (7)
1. the preparation method of the C/N codope cuprous nanosphere of porous oxidation based on sericin, it is characterised in that using discarded sericin as template and C/N source, prepare the monodispersed C/N cuprous nanosphere of codope porous oxidation；Its preparation process comprises the steps:
(1) preparation of Red copper oxide-sericin composite Nano ball: be configured to sericin solution by soluble in water for sericin that molecular weight is 1 000 ~ 50 000；At 60 ~ 80 DEG C, being added in the soluble copper saline solution prepared in advance by above-mentioned sericin solution, under magnetic agitation after mix homogeneously, the pH value regulating above-mentioned sericin-mantoquita mixed solution by the NaOH solution of 1 M is 8 ~ 12；It is subsequently adding glucose reducing agent reaction 0.5 ~ 5 h, 12 000 rpm and is centrifuged 10 min collection precipitate, be dried after washing by centrifugation, obtain Red copper oxide-sericin composite Nano ball；
(2) preparation of the cuprous nanosphere of C/N codope porous oxidation: the Red copper oxide of gained in step (1)-sericin composite Nano ball is placed in tube furnace; under argon shield; it is warming up to 400 DEG C ~ 700 DEG C with the speed of 5 DEG C/min; constant temperature keeps 2 h; naturally cool to room temperature, obtain the C/N cuprous nanosphere of codope porous oxidation.
The preparation method of a kind of C/N codope cuprous nanosphere of porous oxidation based on sericin the most according to claim 1, it is characterised in that: described sericin is the garbage during degumming silkworm cocoons；The concentration of described sericin solution is 0.1 wt% ~ 5 wt%.
The preparation method of a kind of C/N codope cuprous nanosphere of porous oxidation based on sericin the most according to claim 1, it is characterised in that: described soluble copper salt is one or both in copper sulfate, Schweinfurt green, copper chloride, copper nitrate；Described soluble copper concentration of salt solution is 0.1 ~ 0.3 mol/L.
The preparation method of a kind of C/N codope cuprous nanosphere of porous oxidation based on sericin the most according to claim 1, it is characterised in that: described sericin is 0.0001 ~ 0.5 with the mol ratio of copper ion.
The preparation method of a kind of C/N codope cuprous nanosphere of porous oxidation based on sericin the most according to claim 1, it is characterised in that: described glucose is respectively 1:2,2:2 or 3:2 with the mol ratio of mantoquita.
The preparation method of a kind of C/N codope cuprous nanosphere of porous oxidation based on sericin the most according to claim 1, it is characterized in that: described C/N codope cuprous oxide crystal is nanometer spherical, and in connection, uniform loose structure, its particle size distribution is 100 ~ 600
Between nm.
7. the C/N codope cuprous nanosphere of porous oxidation based on sericin, it is characterised in that described nanosphere is prepared according to the method described in claim 1-6 any one.
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