CN104609456A - Preparation method for C/N co-doped porous cuprous oxide nanospheres based on sericin protein - Google Patents
Preparation method for C/N co-doped porous cuprous oxide nanospheres based on sericin protein Download PDFInfo
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- 108010013296 Sericins Proteins 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 32
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 13
- 239000002077 nanosphere Substances 0.000 title abstract 5
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 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 15
- 239000008103 glucose Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000002699 waste material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 37
- 239000011805 ball Substances 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 34
- 238000007254 oxidation reaction Methods 0.000 claims description 34
- 239000010949 copper Substances 0.000 claims description 30
- 239000011807 nanoball Substances 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 24
- 229910052802 copper Inorganic materials 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 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 15
- 238000002156 mixing Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- 150000001879 copper Chemical class 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
- 229960003280 cupric chloride Drugs 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 241000255789 Bombyx mori Species 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000009388 chemical precipitation Methods 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 19
- 239000013543 active substance Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
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- 238000005215 recombination Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 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
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000013456 study Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The invention discloses a preparation method for C/N co-doped porous cuprous oxide nanospheres based on sericin protein. In a processing procedure of a cocoon filament industry, waste sericin protein is taken as a template and a C/N source, and glucose is taken as a reducing agent, and cuprous-oxide-sericin-protein composite nanospheres are prepared by adopting the chemical precipitation method; the prepared nanospheres are calcined at a high temperature, so that mono-dispersed C/N co-doped porous cuprous oxide nanospheres are obtained. The preparation method does not depend on a surface active agent, and the operation conditions are mild, simple and feasible; furthermore, the technology is stable, and the reproducibility is good; the forbidden band width of the obtained cuprous oxide can be effectively regulated through the doping of C/N elements; a porous nanoscale spherical structure can not only accelerate electron transportation, but also provide the cuprous oxide with large specific surface area which facilitates the enrichment of target objects; the preparation method is expected to be applied to performing photo-catalytic degradation on organic pollutants.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, relate to the cuprous nano material of a kind of porous oxidation, particularly relate to a kind of method taking sericin as template and C/N source and prepare the cuprous nanometer ball of C/N codoped porous oxidation.
Background technology
Red copper oxide (Cu
2o) be a kind of typical p-N-type semiconductorN material, its energy gap is 2.0-2.2 eV, can by 620 nm excited by visible light, and energy transformation ratio can reach 18 % in theory.Under the irradiation of sunlight, Red copper oxide can produce hydrogen and oxygen by water of decomposition, has good catalytic activity.In addition, Red copper oxide is nontoxic and preparation cost is lower, therefore has a wide range of applications in fields such as solar cell, gas sensor, photocatalyst, lithium ion battery electrode materials.But, current Cu
2still there is limitation in O: Cu in practical application
2the recombination probability of the photo-generated carrier (hole and electronics) of O is high, causes quantum yield to reduce, affects its photocatalysis efficiency.Therefore, how Cu is improved
2the catalytic activity of O is the critical problem needing at present and in the future to solve.
Recent domestic researchist is at Cu
2a large amount of exploratory studys has been carried out in design and synthesis, the aspect such as preparation and character of O nano structural material.Such as adopt the multiple preparation methods such as chemical reduction method, hydrothermal method, sol-gel method, microemulsion method, microwave irradiation, synthesize the cuprous nano structured material of cubes, octahedron, top rake octahedron, six sufficient types, spherical, flower-shaped, the different morphologies such as hollow cuboid, hollow ball-shape, nano wire, nanotube and nanocages.The research of scholars to its photocatalytic activity shows, the physicochemical property of the pattern of Red copper oxide and size, degree of crystallinity, electronics separating power and adsorptive power and its macroscopic view are closely related, wherein the pattern of Red copper oxide and size particularly outstanding on the impact of its catalytic activity.As Du Yi etc. with sodium laurylsulfonate (SDS) for tensio-active agent, adopt high temperature hydrothermal method to synthesize shaggy Red copper oxide (CN 201410340699.6).Gou etc. using cetyl trimethylammonium bromide (CTAB) as stablizer, prepare different size size cuprous nano cubes (Gou et al.,
nano Lett, 2003,3,231).Huang etc. take SDS as tensio-active agent, azanol (NH
2oH.HCl) be reductive agent, synthesize cubical cuprous nano material.By adjustment NH
2the consumption of OH.HCl, cuprous nano material from cubes gradually, top rake dodecahedron octahedra to top rake cubes, top rake to rhombic dodecahedron structural evolution, and rhombic dodecahedron present better photocatalytic activity (Huang et al.,
j Am Chem Soc, 2012,134,1261).Li etc. respectively with polyoxyethylene glycol (PEG) and polyvinylpyrrolidone (PVP) for stablizer, xitix is reductive agent, have studied the impact of different stabilizers on Red copper oxide pattern and crystal phase structure.Research shows, is that the Red copper oxide of stablizer synthesis is along the nanocubes of (100) crystal face preferential growth with PEG, and take PVP as the Red copper oxide of stablizer synthesis is the porous nano crystal grown along (100) and (111) crystal face.The electrocatalysis characteristic of gained Red copper oxide have 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, the tensio-active agent such as many use CTAB, SDS, PEG, PVP during synthesis cuprous nano structured material.These tensio-active agents have amphiphilic structure, effectively can prevent the reunion of nano particle or regulate and control its pattern as structure directing agent.But the concentration of tensio-active agent often directly affects product morphology, need accurately to control its concentration in preparation process; Meanwhile, tensio-active agent is very easily adsorbed on the surface of sample, is difficult to cleaning, thus affects sample purity.On the other hand, due to the restriction by synthetic method etc., the usual smooth surface of Red copper oxide of synthesized various pattern, specific surface area is less, Rough factor is lower, has a strong impact on electronics separating power and the absorption property of material, and then causes the catalytic activity of Red copper oxide lower.
Summary of the invention
Cuprous nano material catalyzes efficiency is prepared not high for prior art, preparation process many employings high temperature hydrothermal method and need use the problems such as various tensio-active agents, the object of the present invention is to provide the preparation method of the cuprous nanometer ball of a kind of monodispersed C/N codoped porous oxidation.
Sericin is a kind of water miscible globular preteins, and carbon and nitrogen element account for 50% and 14% of total amount respectively.In the silk industry course of processing, sericin is often discharged with the waste liquid that comes unstuck, and causes the waste of resource and the pollution of water body.The factors such as the pattern of the cuprous oxide micro/nano crystal copper source usually and in preparation process, reductive agent, dispersion agent, temperature of reaction and time are closely related; Change any condition, Red copper oxide pattern all may be caused to change.In order to reduce the recombination probability of Red copper oxide photo-generated carrier, improving its photocatalysis performance, the present invention is based on the supramolecular structure of sericin, take sericin as template and C/N source, the cuprous nanometer ball of porous oxidation of preparation C/N codoped.The doping of C/N element can adjust the energy gap of Red copper oxide; The nano-level sphere structure of porous not only can accelerate electric transmission, gives the large specific surface area of Red copper oxide simultaneously and is beneficial to the enrichment of target compound and then improves its photocatalysis efficiency.On the other hand, preparation method of the present invention disobeys abutment surface promoting agent, and operational condition is gentle, simple, and process stabilizing, favorable reproducibility.
For achieving the above object, technical solution of the present invention is as follows:
(1) preparation of Red copper oxide-sericin composite Nano ball: by molecular weight be 1 000 ~ 50 000 sericin be soluble in waterly mixed with sericin solution; At 60 ~ 80 DEG C, above-mentioned sericin solution is added in the soluble copper salts solution prepared in advance, after mixing under magnetic agitation, regulates above-mentioned sericin-mantoquita mixing solutions pH value to be 8 ~ 12 by the NaOH solution of 1 M; Then the centrifugal 10 min collecting precipitation things of Reduction of Glucose agent reaction 0.5 ~ 5 h, 12 000 rpm are added, dry after centrifuge washing, obtain Red copper oxide-sericin composite Nano ball;
(2) preparation of the cuprous nanometer ball of C/N codoped porous oxidation: gained Red copper oxide-sericin composite Nano ball in step (1) is placed in tube furnace; under argon shield; 400 DEG C ~ 700 DEG C are warming up to the speed of 5 DEG C/min; constant temperature keeps 2 h; naturally cool to room temperature, obtain the cuprous nanometer ball of C/N codoped porous oxidation.
Described sericin strength of solution is 0.1 wt% ~ 5 wt%;
Described soluble copper salt is one or both in copper sulfate, neutralized verdigris, cupric chloride, cupric nitrate; Described soluble copper concentration of salt solution is 0.1 ~ 0.3 mol/L;
Described sericin and the mol ratio of cupric ion are 0.0001 ~ 0.5;
Described glucose and the mol ratio of mantoquita are respectively 1:2,2:2 or 3:2;
Described C/N codoped cuprous oxide crystal is nanometer spherical, and is connection, uniform vesicular structure, and its particle size distribution is between 100 ~ 600 nm.
The beneficial effect that the present invention is compared with prior art had is:
The preparation method of the cuprous nanometer ball of C/N codoped porous oxidation based on sericin provided by the invention, using discarded sericin as template and C/N source, utilize the supramolecular structure of sericin, prepare the cuprous nanometer ball of monodispersed C/N codoped porous oxidation.Adulterated by C/N, the energy gap of Red copper oxide can be adjusted, improve its photocatalysis efficiency; Nano balls of cuprous oxide is communicated with, its large specific surface area given by uniform vesicular structure, is beneficial to the transmission of light induced electron and the enrichment of target compound, and then realizes its high photocatalytic activity.On the other hand, preparation method of the present invention disobeys abutment surface promoting agent, and operational condition is gentle, simple, and process stabilizing, favorable reproducibility.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the cuprous nanometer ball of embodiment 1 gained C/N codoped porous oxidation.
Fig. 2 is the FESEM photo of the cuprous nanometer ball of embodiment 2 gained C/N codoped porous oxidation.
Fig. 3 is the XPS collection of illustrative plates of the cuprous nanometer ball of embodiment 3 gained C/N codoped porous oxidation.
Fig. 4 is the FESEM photo of the cuprous nanometer ball of embodiment 4 gained C/N codoped porous oxidation.
Fig. 5 is the FESEM photo of the cuprous nanometer ball of embodiment 5 gained C/N codoped porous oxidation.
Embodiment
For further setting forth the technique means and beneficial effect thereof that the present invention takes, be specifically described below in conjunction with embodiments of the invention and accompanying drawing thereof.
embodiment 1:
(1) preparation of Red copper oxide-sericin composite Nano ball: by molecular weight be 1 000 sericin be soluble in waterly mixed with the sericin solution that concentration is 5 wt%; At 60 DEG C, it is in the copper-bath of 0.1 mol/L that the above-mentioned sericin solution of 100 mL is added into 100 mL concentration, after mixing, regulates above-mentioned sericin-copper sulfate mixing solutions pH value to be 8 by the NaOH solution of 1 M under magnetic agitation; Be the ratio of 3:2 according to the mol ratio of glucose and copper sulfate, add Reduction of Glucose agent and react 0.5 h, the centrifugal 10 min collecting precipitation things of 12 000 rpm, dry after centrifuge washing, obtain Red copper oxide-sericin composite Nano ball;
(2) preparation of the cuprous nanometer ball of C/N codoped porous oxidation: gained Red copper oxide-sericin composite Nano ball in step (1) is placed in tube furnace; under argon shield; 400 DEG C are warming up to the speed of 5 DEG C/min; constant temperature keeps 2 h; naturally cool to room temperature; obtain the cuprous nanometer ball of C/N codoped porous oxidation, its particle diameter is about 100 nm.Fig. 1 is the XRD figure spectrum of this product.Consistent with Red copper oxide standard XRD pattern (JCPDS No.65-3288), illustrate that products therefrom is the Red copper oxide that degree of crystallinity is higher.
embodiment 2:
(1) preparation of Red copper oxide-sericin composite Nano ball: by molecular weight be 8 000 sericin be soluble in waterly mixed with the sericin solution that concentration is 2 wt%; At 70 DEG C, it is in the copper nitrate solution of 0.3 mol/L that the above-mentioned sericin solution of 100 mL is added into 100 mL concentration, after mixing, regulates above-mentioned sericin-cupric nitrate mixing solutions pH value to be 10 by the NaOH solution of 1 M under magnetic agitation; Be the ratio of 2:2 according to the mol ratio of glucose and cupric nitrate, add Reduction of Glucose agent and react 1 h, the centrifugal 10 min collecting precipitation things of 12 000 rpm, dry after centrifuge washing, obtain Red copper oxide-sericin composite Nano ball;
(2) preparation of the cuprous nanometer ball of C/N codoped porous oxidation: gained Red copper oxide-sericin composite Nano ball in step (1) is placed in tube furnace; under argon shield; 400 DEG C are warming up to the speed of 5 DEG C/min; constant temperature keeps 2 h; naturally cool to room temperature; obtain the cuprous nanometer ball of C/N codoped porous oxidation, its particle diameter is about 200 nm.Fig. 2 is the FESEM photo of this product.Can find out, gained C/N codoped Nano balls of cuprous oxide has connection, uniform vesicular structure.
embodiment 3:
(1) preparation of Red copper oxide-sericin composite Nano ball: by molecular weight be 20 000 sericin be soluble in waterly mixed with the sericin solution that concentration is 0.5 wt%; At 60 DEG C, it is in the neutralized verdigris solution of 0.1 mol/L that the above-mentioned sericin solution of 100 mL is added into 100 mL concentration, after mixing, regulates above-mentioned sericin-neutralized verdigris mixing solutions pH value to be 11 by the NaOH solution of 1 M under magnetic agitation; Be the ratio of 1:2 according to the mol ratio of glucose and cupric nitrate, add Reduction of Glucose agent and react 3 h, the centrifugal 10 min collecting precipitation things of 12 000 rpm, dry after centrifuge washing, obtain Red copper oxide-sericin composite Nano ball;
(2) preparation of the cuprous nanometer ball of C/N codoped porous oxidation: gained Red copper oxide-sericin composite Nano ball in step (1) is placed in tube furnace; under argon shield; 500 DEG C are warming up to the speed of 5 DEG C/min; constant temperature keeps 2 h; naturally cool to room temperature; obtain the cuprous nanometer ball of C/N codoped porous oxidation, its particle diameter is about 400 nm.Fig. 3 is the XPS collection of illustrative plates of this product.Can find out, be Cu at the absorption peak at combination energy 932.5 eV places
2P 2/3absorption peak, 283.7 eV, 398.5 eV places can occur absorption peak in combination, the absorption peak of corresponding C element and N element, illustrates that C element and N element are successfully doped in cuprous oxide micro/nano crystal respectively.
embodiment 4:
(1) preparation of Red copper oxide-sericin composite Nano ball: by molecular weight be 50 000 sericin be soluble in waterly mixed with the sericin solution that concentration is 0.1 wt%; At 80 DEG C, it is in the Cupric Chloride Solution of 0.2 mol/L that the above-mentioned sericin solution of 100 mL is added into 100 mL concentration, after mixing, regulates above-mentioned sericin-neutralized verdigris mixing solutions pH value to be 12 by the NaOH solution of 1 M under magnetic agitation; Be the ratio of 2:2 according to the mol ratio of glucose and cupric chloride, add Reduction of Glucose agent and react 1 h, the centrifugal 10 min collecting precipitation things of 12 000 rpm, dry after centrifuge washing, obtain Red copper oxide-sericin composite Nano ball.
(2) preparation of the cuprous nanometer ball of C/N codoped porous oxidation: gained Red copper oxide-sericin composite Nano ball in step (1) is placed in tube furnace; under argon shield; 600 DEG C are warming up to the speed of 5 DEG C/min; constant temperature keeps 2 h; naturally cool to room temperature; obtain the cuprous nanometer ball of C/N codoped porous oxidation, its particle diameter is about 600 nm.Fig. 4 is the FESEM photo of this product.Can find out, gained C/N codoped Nano balls of cuprous oxide has connection, uniform vesicular structure.
embodiment 5:
(1) preparation of Red copper oxide-sericin composite Nano ball: by molecular weight be 8 000 sericin be soluble in waterly mixed with the sericin solution that concentration is 1.5 wt%; At 60 DEG C, the above-mentioned sericin solution of 100 mL is added in the copper sulfate and neutralized verdigris mixing solutions that 100 mL concentration are 0.2 mol/L, after mixing under magnetic agitation, regulates above-mentioned mixing solutions pH value to be 12 by the NaOH solution of 1 M; Be the ratio of 3:2 according to the mol ratio of glucose and mantoquita, add Reduction of Glucose agent and react 5 h, the centrifugal 10 min collecting precipitation things of 12 000 rpm, dry after centrifuge washing, obtain Red copper oxide-sericin composite Nano ball.
(2) preparation of the cuprous nanometer ball of C/N codoped porous oxidation: gained Red copper oxide-sericin composite Nano ball in step (1) is placed in tube furnace; under argon shield; 700 DEG C are warming up to the speed of 5 DEG C/min; constant temperature keeps 2 h; naturally cool to room temperature; obtain the cuprous nanometer ball of C/N codoped porous oxidation, its particle diameter is about 400 nm.Fig. 5 is the FESEM photo of this product.Can find out, gained C/N codoped Nano balls of cuprous oxide has connection, uniform vesicular structure.
What more than enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above examples of implementation, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (7)
1., based on a preparation method for the cuprous nanometer ball of C/N codoped porous oxidation of sericin, it is characterized in that, using discarded sericin as template and C/N source, preparing the cuprous nanometer ball of monodispersed C/N codoped porous oxidation; Its preparation process comprises the steps:
(1) preparation of Red copper oxide-sericin composite Nano ball: by molecular weight be 1 000 ~ 50 000 sericin be soluble in waterly mixed with sericin solution; At 60 ~ 80 DEG C, above-mentioned sericin solution is added in the soluble copper salts solution prepared in advance, after mixing under magnetic agitation, regulates the pH value of above-mentioned sericin-mantoquita mixing solutions to be 8 ~ 12 by the NaOH solution of 1 M; Then the centrifugal 10 min collecting precipitation things of Reduction of Glucose agent reaction 0.5 ~ 5 h, 12 000 rpm are added, dry after centrifuge washing, obtain Red copper oxide-sericin composite Nano ball;
(2) preparation of the cuprous nanometer ball of C/N codoped porous oxidation: the Red copper oxide-sericin composite Nano ball of gained in step (1) is placed in tube furnace; under argon shield; 400 DEG C ~ 700 DEG C are warming up to the speed of 5 DEG C/min; constant temperature keeps 2 h; naturally cool to room temperature, obtain the cuprous nanometer ball of C/N codoped porous oxidation.
2. the preparation method of a kind of cuprous nanometer ball of C/N codoped porous oxidation based on sericin according to claim 1, is characterized in that: described sericin is the waste in degumming silkworm cocoons process; The concentration of described sericin solution is 0.1 wt% ~ 5 wt%.
3. the preparation method of a kind of cuprous nanometer ball of C/N codoped porous oxidation based on sericin according to claim 1, is characterized in that: described soluble copper salt is one or both in copper sulfate, neutralized verdigris, cupric chloride, cupric nitrate; Described soluble copper concentration of salt solution is 0.1 ~ 0.3 mol/L.
4. the preparation method of a kind of cuprous nanometer ball of C/N codoped porous oxidation based on sericin according to claim 1, is characterized in that: described sericin and the mol ratio of cupric ion are 0.0001 ~ 0.5.
5. the preparation method of a kind of cuprous nanometer ball of C/N codoped porous oxidation based on sericin according to claim 1, is characterized in that: described glucose and the mol ratio of mantoquita are respectively 1:2,2:2 or 3:2.
6. the preparation method of a kind of cuprous nanometer ball of C/N codoped porous oxidation based on sericin according to claim 1, it is characterized in that: described C/N codoped cuprous oxide crystal is nanometer spherical, and be connection, uniform vesicular structure, its particle size distribution is between 100 ~ 600 nm.
7. based on the cuprous nanometer ball of C/N codoped porous oxidation of sericin, it is characterized in that, described nanometer ball is according to the method preparation of claim 1-6 described in any one.
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