CN109485084A - A kind of method and application of form controlledly synthesis cuprous oxide powder - Google Patents
A kind of method and application of form controlledly synthesis cuprous oxide powder Download PDFInfo
- Publication number
- CN109485084A CN109485084A CN201811639573.3A CN201811639573A CN109485084A CN 109485084 A CN109485084 A CN 109485084A CN 201811639573 A CN201811639573 A CN 201811639573A CN 109485084 A CN109485084 A CN 109485084A
- Authority
- CN
- China
- Prior art keywords
- powder
- tartaric acid
- hydro
- cuprous oxide
- thermal reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 43
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 17
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 45
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000008273 gelatin Substances 0.000 claims abstract description 23
- 108010010803 Gelatin Proteins 0.000 claims abstract description 22
- 229920000159 gelatin Polymers 0.000 claims abstract description 22
- 235000019322 gelatine Nutrition 0.000 claims abstract description 22
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 22
- 239000011975 tartaric acid Substances 0.000 claims abstract description 20
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- XIPWCAOMSIUHSL-UHFFFAOYSA-N copper;2,3-dihydroxybutanedioic acid Chemical compound [Cu].OC(=O)C(O)C(O)C(O)=O XIPWCAOMSIUHSL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- 239000002105 nanoparticle Substances 0.000 claims abstract description 5
- 238000007146 photocatalysis Methods 0.000 claims abstract description 5
- 238000001016 Ostwald ripening Methods 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000356 contaminant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 9
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 23
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 10
- 229940012189 methyl orange Drugs 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000877 morphologic effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002086 nanomaterial Substances 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
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- RSJOBNMOMQFPKQ-ZVGUSBNCSA-L copper;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O RSJOBNMOMQFPKQ-ZVGUSBNCSA-L 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- XQSBLCWFZRTIEO-UHFFFAOYSA-N hexadecan-1-amine;hydrobromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[NH3+] XQSBLCWFZRTIEO-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 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 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 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 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001048 orange dye Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- -1 tartrate anion Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
A kind of method and application of form controlledly synthesis cuprous oxide powder, are related to preparation and the applied technical field of cuprous oxide.In the alkaline tartaric acid copper water system being made of copper sulphate, lye and tartaric acid, directly pass through hydro-thermal reaction, Cu in cupric tartrate2+It is reduced when heated and slowly releases Cu+, Cu+With OH in system‑In conjunction with formation CuOH；CuOH dehydration forms Cu2O little crystal grain, the Cu of these monocrystalline2O forms Cu finally by Ostwald ripening mode2O cube；Or the gelatin that can play template action in right amount is introduced in the alkalinity tartaric acid copper water system, then several nano particles of formation are assembled into microballoon through hydro-thermal reaction.The Cu of two kinds of forms of preparation2O powder maximum absorption wavelength is 500nm or so (band gap is about 2.2eV), can be used for the removal of Organic Pollutants In Water, and the photocatalysis performance of spherical powder is better than a cube powder.
Description
Technical field
The present invention relates to the preparation of cuprous oxide and applied technical fields, are specifically related to a kind of form controlledly synthesis oxidation
The method and application of cuprous powder.
Background technique
Cuprous oxide (Cu2O) there is good visible light absorption, be a kind of common visible light catalyst, can use
Cook preservative, fungicide, colorant and catalyst etc..In general, using common mantoquita as raw material, in glucose, ascorbic acid, fruit
Pass through the Cu of the available different shape of reduction reaction under the action of the reducing agents such as sugar, hydrazine hydrate, sodium borohydride and polyalcohol2O
Nano material.Regular Cu in order to obtain2O is nanocrystalline, often uses some such as polyvinylpyrrolidone in the reaction system
(PVP) and templates and the surfactant such as cetyl ammonium bromide (CTAB).However, these reducing agents used and addition
Some in agent have certain toxicity to a certain extent, while cost is also higher.
Gelatin is a kind of water-soluble biological macromolecule, has many advantages, such as that nontoxic, biodegradability is strong and at low cost.It is closing
At being widely used in inorganic nano material.Han et al. has successfully prepared Fe using gelatin as template3O4Porous fibre.But
It is that gelatin is applied to the form controllable preparation of cuprous oxide, is had not been reported at present.
Summary of the invention
For the technical problems in the prior art, the present invention provides a kind of form controlledly synthesis cuprous oxide powders
Method.Meanwhile the present invention also provides a kind of applications of prepared cuprous oxide powder.
To achieve the goals above, the technical scheme adopted by the invention is as follows: a kind of form controlledly synthesis cuprous oxide powder
The method of body directly passes through hydro-thermal reaction in the alkaline tartaric acid copper water system being made of copper sulphate, lye and tartaric acid,
Cu in cupric tartrate2+It is reduced when heated and slowly releases Cu+, Cu+With OH in system-In conjunction with formation CuOH；Then,
CuOH dehydration forms Cu2O little crystal grain, the Cu of these monocrystalline2O forms Cu finally by Ostwald ripening mode2O is vertical
Cube；Alternatively, introducing the gelatin that can play template action in right amount in the alkalinity tartaric acid copper water system, then will through hydro-thermal reaction
Several Cu formed2O nano particle is assembled into Cu2O microballoon.
As a kind of optimal technical scheme of preparation method of the invention, by the CuSO of 0.005mol4·5H2O and
It after the tartaric acid mixing of 0.002mol-0.01mol and is added in appropriate amount of deionized water, again by the NaOH of 0.1g-1g after dissolution
It is added in above-mentioned solution, obtains dark blue solution；Then, by this dark blue solution be transferred in reaction kettle carry out hydro-thermal it is anti-
It answers, a cube Cu can be obtained2O powder.
As another optimal technical scheme of preparation method of the invention, by the CuSO of 0.005mol4·5H2O and
It after the tartaric acid mixing of 0.002mol-0.01mol and is added in appropriate amount of deionized water, again by the NaOH of 0.1g-1g after dissolution
It is added in above-mentioned solution, obtains dark blue solution；Then, the gelatin of 0.1g-2g is added into the reaction system, heating makes it
Navy blue colloidal solution is obtained after dissolution；Hydro-thermal reaction is carried out finally, this navy blue colloidal solution is transferred in reaction kettle, i.e.,
Spherical Cu can be obtained2O powder.
In above-mentioned synthetic method, the temperature of hydro-thermal reaction is preferably 120 DEG C, and the reaction time is preferably 3h.
The present invention is that cheap reducing agent and biological template carry out controllable preparation Cu with tartaric acid and gelatin2O powder.This method without
Special installation is needed, there are green controllable characteristics, and obtained product amount is bigger.Meanwhile the product of acquisition can with excellent
Light-exposed catalytic performance can be used for the removal of Organic Pollutants In Water.
Compared with prior art, beneficial effects of the present invention are shown:
1), the present invention uses hydrothermal reaction at low temperature, can prepare Cu in alkaline tartaric acid copper water system2O powder, control
Available cube of Cu of the dosage of tartaric acid2O powder.In above-mentioned reaction system, spherical shape can be obtained by adding suitable gelatin
Cu2O powder.Studies have shown that the dosage of reducing agent (tartaric acid) and template (gelatin) is to product when other experiment conditions are identical
Form control play crucial effect.When tartaric acid usage amount is 0.05mol, more regular cube Cu will be obtained2O
Powder, and after adding 1.0g gelatin in the system, spherical Cu will be obtained2O powder.
2), the Cu of the two kinds of forms prepared2O powder maximum absorption wavelength is 500nm or so (band gap is about 2.2eV).
Visible light catalytic the experimental results showed that, spherical Cu2The photocatalysis performance of O powder is better than a cube Cu2O powder.Further analysis is ground
Study carefully and obtain, the two goes the kinetic model of methyl orange dye in water removal to meet single order kinetic model.
Detailed description of the invention
Fig. 1 is the form and chemical composition that embodiment 1 prepares two kinds of products.
Fig. 2 is the XRD spectra that embodiment 1 prepares two kinds of products.
Fig. 3 is the SEM photograph that embodiment 2 prepares two kinds of products.
Fig. 4 is the SEM photograph that embodiment 3 prepares two kinds of products.
Fig. 5 is spherical and cube Cu2O powder granule formation mechenism schematic diagram.
Fig. 6 is that embodiment 1 prepares two kinds of different shape Cu2The uv-visible absorption spectra of O powder.
Fig. 7 is that embodiment 1 prepares two kinds of different shape Cu2The visible light photocatalytic degradation methyl orange kinetic curve of O powder
(a) and kinetic curve linear analysis (b).
Specific embodiment
The method of form controlledly synthesis cuprous oxide powder of the invention and application are made with attached drawing with reference to embodiments
It is discussed further out.
Embodiment 1
Scheme one: by the CuSO of 0.005mol4·5H2After the tartaric acid mixing of O and 0.005mol and it is added to going for 80mL
In ionized water, the NaOH of 0.5g is added in above-mentioned solution again after dissolution, obtains dark blue solution.Then, by this navy blue
Solution is transferred in reaction kettle and reacts 3h in 120 DEG C of baking ovens.
Scheme two: by the CuSO of 0.005mol4·5H2After the tartaric acid mixing of O and 0.005mol and it is added to going for 80mL
In ionized water, the NaOH of 0.5g is added in above-mentioned solution again after dissolution, obtains dark blue solution.Then, to the reactant
The gelatin of 1.5g is added in system, heating obtains navy blue colloidal solution after making it dissolve.Finally, this navy blue colloidal solution is turned
Enter into reaction kettle and reacts 3h in 120 DEG C of baking ovens.
Embodiment 1 prepares the Morphological Characterization of product:
1, sem analysis
It is well known that the form of powder granule also influences its performance to a certain extent.For this purpose, using scanning electron first
Microscope carries out morphologic observation to the obtained product of embodiment 1 and chemical composition analysis, result are as shown in Figure 1.In alkalinity
In cupric tartrate system, when the experiment parameter of use is appropriate, Electronic Speculum observation indicate that, the shape of the product obtained at this time is
Cube (shown in Fig. 1 a), grain size statistics analysis shows, the side length of cube is about 1 μm (see Fig. 1 a illustration), and power spectrum is further divided
Analysis shows that cube is to be made of two kinds of chemical elements of Cu and O (see Fig. 1 b).In the reaction that alkaline cupric tartrate and gelatin are constituted
In system, the shape of last product is reacted for spherical (see Fig. 1 c), statistics sphere diameter is about 0.7 μm (see Fig. 1 c illustration), and single
The chemical composition of a ball is Cu, O and a small amount of C (see Fig. 1 d).A small amount of C may be considered the residue after gelatin template assemblies.
2, XRD analysis
In order to further determine the object phase of above-mentioned two kinds of form products being made of two kinds of elements of Cu and O, we are to two kinds
Product has carried out XRD test analysis, and result is as shown in Figure 2.With Cu2O standard x RD diffraction spectrogram (PDF#:050667) comparison
It is found that the product for two kinds of forms that experiment obtains is Cu after analysis2O object phase.In contrast, cube Cu2The crystallinity of O powder
It is higher than spherical Cu2The crystallinity of O powder.
Embodiment 2
In order to investigate tartaric acid usage amount to Cu2The influence of O powder morphology, with embodiment 1, difference is only that preparation condition
The additive amount of tartaric acid is adjusted separately as 0.002mol, 0.02mol, morphologic observation is carried out to prepared product, result is such as
Shown in Fig. 3.System research show that the dosage of reaction system mesotartaric acid has large effect to the purity and form of product.
When tartaric acid usage amount is less (0.002mol), there is a small amount of Cu in product2O object mutually occurs (shown in Fig. 3 a).This it will be understood that
Because tartaric acid is reducing agent, amount is few, and reduction reaction is not thorough.And when tartaric acid usage amount is excessively high (0.02mol), it obtains
Cu2O is in random (shown in Fig. 3 b).Therefore, when the usage amount of tartaric acid is within the scope of 0.002mol~0.02mol, will
To some quasi- cube of Cu2O product.And when tartaric acid dosage is 0.005mol, product is more regular cube Cu2O is (see figure
Shown in 1a).It was therefore concluded that the amount of reaction system mesotartaric acid plays pass to the composition and form of final product
Key effect.0.005mol is the optimum addition of tartaric acid.
Embodiment 3
In order to investigate gelatin template usage amount to Cu2The influence of O powder morphology, preparation condition only exist with embodiment 1, difference
It adjusts separately in by the additive amount of gelatin as 0.5g, 2g, then morphologic observation is carried out to prepared product, result is as shown in Figure 4.
Serial experiment research also show that the usage amount of gelatin mainly influences the form of product, when other conditions are identical, the use of gelatin
Amount can obtain spherical Cu within the scope of 0.5g~2g2O product, (see Fig. 4 a) when usage amount less (0.5g), the Cu of acquisition2O
Sphericity is lower, and it is remaining (see Fig. 4 b) that gelatin is just had when usage amount excessively high (2g), in product.Therefore, template group is played to pretend
Gelatin, usage amount must also control in a certain range, most preferably 1.5g.
Embodiment 4
Two kinds of reaction mechanisms are probed into
Based on the above experimental result, it is believed that, in the presence of appropriate tartrate anion, Cu in cupric tartrate2+When heated
It is reduced and slowly releases Cu+, Cu+With OH in system-In conjunction with formation CuOH；Then, CuOH dehydration forms many Cu2The small crystalline substance of O
Grain, the Cu of these monocrystalline2O forms larger-size Cu finally by Ostwald ripening mode2O cube.Other realities
Test parameter it is identical when, appropriate amounts of gelatin is introduced in the reaction system, the gelatin of addition can play the role of template, if by formation
Dry Cu2O nano particle is assembled into Cu2O microballoon, to reduce the energy of entire reaction system.Cube and spherical shape Cu2The shape of O powder
It can be shown in Fig. 5 at mechanism.
Embodiment 5
Photocatalysis experiment
In order to study Cu2The photocatalytic activity of O powder, by 0.5g Cu2The aqueous solution of 200mL methyl orange is added (just in O powder
Beginning concentration is 10mg/L) in, 60 minutes progress adsorption experiments are stirred after ultrasonic disperse in the dark, it is to be adsorbed up to after balancing, it will
It, which is moved on under 300W xenon lamp (PLS-SXE300, λ > 420nm) visible light source, irradiates.The aqueous solution under different time intervals is taken, and
Its absorbance is measured with UV-vis visible absorption spectrum instrument, and the concentration (C of the corresponding methyl orange of t momentt) following formula can be used
Son estimation:
Ct=C0*At/A0
C0It (mg/L) is initial orange concentration in water body, A0Initial orange absorbance, AtIt is water-soluble for t moment methyl orange
Liquid absorbance.
Cu2O is a kind of important semiconductor material, has good visible absorption performance.Two kinds of form Cu2O powder
It can be seen that-ultra-violet absorption spectrum is as shown in Figure 6 a.As it can be seen that sum of cubes spherical shape Cu2Visible light maximum absorption wavelength (the λ of O powdermax)
It is each about 500nm, by formula Eg=1240/ λmaxThe band gap width that the two can be estimated is about 2.2eV~2.4eV (see Fig. 6 b).
Finally, we are using a certain concentration methyl orange as target contaminant, comparative study sum of cubes spherical shape Cu2O powder
Visible light catalytic performance, result are as shown in Figure 7.As can be seen that for two kinds of form Cu2O, with the visible light exposure time
Increase, the relative concentration (C of methyl orange in aqueous systemst/C0) will gradually decrease.Further analysis shows that two kinds of form Cu2O degradation
The process of methyl orange meets single order kinetic model, consistent with dyestuff degradation kinetics model reported in the literature.In contrast,
Cu2O microballoon has lower band gap, photocatalysis performance with higher due to its special micro/nano structure.Therefore, spherical
Cu2The performance of O powder degradation methyl orange is better than a cube Cu2O powder.It is observed by Electronic Speculum it is found that spherical shape Cu2O particle is by a large amount of
Cu2O nano particle is formed, and is had active interface abundant, is accelerated high oxidative OH-The formation of free radical, to enhance
The rate of methyl orange is catalytically decomposed.
The above content is just an example and description of the concept of the present invention, affiliated those skilled in the art
It makes various modifications or additions to the described embodiments or is substituted in a similar manner, without departing from invention
Design or beyond the scope defined by this claim, be within the scope of protection of the invention.
Claims (6)
1. a kind of method of form controlledly synthesis cuprous oxide powder, which is characterized in that by copper sulphate, lye and tartaric acid group
At alkaline tartaric acid copper water system in, directly by hydro-thermal reaction, Cu in cupric tartrate2+It is reduced and slowly releases when heated
Release Cu+, Cu+With OH in system-In conjunction with formation CuOH；Then, CuOH dehydration forms Cu2O little crystal grain, the Cu of these monocrystalline2O is most
Cu is formd by Ostwald ripening mode afterwards2O cube；Alternatively, being introduced in the alkalinity tartaric acid copper water system
The gelatin of template action can be played in right amount, then through hydro-thermal reaction by several Cu of formation2O nano particle is assembled into Cu2O microballoon.
2. synthetic method as described in claim 1, which is characterized in that by the CuSO of 0.005mol4·5H2O and 0.002mol-
It after the tartaric acid mixing of 0.01mol and is added in appropriate amount of deionized water, is again added to the NaOH of 0.1g-1g after dissolution above-mentioned
In solution, dark blue solution is obtained；Then, this dark blue solution is transferred in reaction kettle and carries out hydro-thermal reaction, can be obtained
Cube Cu2O powder.
3. synthetic method as described in claim 1, which is characterized in that by the CuSO of 0.005mol4·5H2O and 0.002mol-
It after the tartaric acid mixing of 0.01mol and is added in appropriate amount of deionized water, is again added to the NaOH of 0.1g-1g after dissolution above-mentioned
In solution, dark blue solution is obtained；Then, the gelatin of 0.1g-2g is added into the reaction system, heating obtains after making it dissolve
Navy blue colloidal solution；Hydro-thermal reaction is carried out finally, this navy blue colloidal solution is transferred in reaction kettle, spherical shape can be obtained
Cu2O powder.
4. synthetic method as claimed in claim 2 or claim 3, which is characterized in that the temperature of hydro-thermal reaction is 120 DEG C, the reaction time
For 3h.
5. a kind of cuprous oxide powder synthesized such as any one of claim 1-4 the method, which is characterized in that sum of cubes are spherical
Cu2The visible light maximum absorption wavelength of O powder is 500nm, and the band gap width of the two is 2.2eV~2.4eV.
6. a kind of if the cuprous oxide powder of any one of claim 1-4 the method synthesis is in photocatalysis degradation organic contaminant
In application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811639573.3A CN109485084A (en) | 2018-12-29 | 2018-12-29 | A kind of method and application of form controlledly synthesis cuprous oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811639573.3A CN109485084A (en) | 2018-12-29 | 2018-12-29 | A kind of method and application of form controlledly synthesis cuprous oxide powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109485084A true CN109485084A (en) | 2019-03-19 |
Family
ID=65713580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811639573.3A Pending CN109485084A (en) | 2018-12-29 | 2018-12-29 | A kind of method and application of form controlledly synthesis cuprous oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109485084A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111200134A (en) * | 2020-02-18 | 2020-05-26 | 金陵科技学院 | Cuprous oxide film and application thereof in fuel cell |
| CN111564326A (en) * | 2020-06-24 | 2020-08-21 | 河北工业大学 | Cu2Preparation method of O-Cu/titanium dioxide nanotube array composite electrode |
| CN112919526A (en) * | 2021-03-31 | 2021-06-08 | 辽宁工程技术大学 | Preparation method of cuprous oxide nano material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412531A (en) * | 2008-10-31 | 2009-04-22 | 浙江理工大学 | Hydrothermal preparation capable of realizing controllability of morphology of cuprous oxide crystal |
| CN107935020A (en) * | 2018-01-10 | 2018-04-20 | 合肥学院 | A kind of Cu2The controllable method for preparing of O nanofibers |
-
2018
- 2018-12-29 CN CN201811639573.3A patent/CN109485084A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412531A (en) * | 2008-10-31 | 2009-04-22 | 浙江理工大学 | Hydrothermal preparation capable of realizing controllability of morphology of cuprous oxide crystal |
| CN107935020A (en) * | 2018-01-10 | 2018-04-20 | 合肥学院 | A kind of Cu2The controllable method for preparing of O nanofibers |
Non-Patent Citations (2)
| Title |
|---|
| PEILI LIU等: "Controllable synthesis of cuprite (Cu2O) microcrystals and their shape-dependent photocatalytic performances", 《MICRO & NANO LETTERS》 * |
| 阮青锋等: "酒石酸还原Cu 制备多种形貌Cu2O晶体及形成机理", 《功能材料》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111200134A (en) * | 2020-02-18 | 2020-05-26 | 金陵科技学院 | Cuprous oxide film and application thereof in fuel cell |
| CN111200134B (en) * | 2020-02-18 | 2022-05-20 | 金陵科技学院 | Cuprous oxide film and application thereof in fuel cell |
| CN111564326A (en) * | 2020-06-24 | 2020-08-21 | 河北工业大学 | Cu2Preparation method of O-Cu/titanium dioxide nanotube array composite electrode |
| CN111564326B (en) * | 2020-06-24 | 2021-09-28 | 河北工业大学 | Cu2Preparation method of O-Cu/titanium dioxide nanotube array composite electrode |
| CN112919526A (en) * | 2021-03-31 | 2021-06-08 | 辽宁工程技术大学 | Preparation method of cuprous oxide nano material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gou et al. | Controlling the size of Cu 2 O nanocubes from 200 to 25 nm | |
| Dou et al. | Manganese doped magnetic cobalt ferrite nanoparticles for dye degradation via a novel heterogeneous chemical catalysis | |
| Ju et al. | Controllable one-pot synthesis of a nest-like Bi 2 WO 6/BiVO 4 composite with enhanced photocatalytic antifouling performance under visible light irradiation | |
| CN109485084A (en) | A kind of method and application of form controlledly synthesis cuprous oxide powder | |
| Naghdi et al. | Green and energy-efficient methods for the production of metallic nanoparticles | |
| Khairol et al. | Excellent performance integrated both adsorption and photocatalytic reaction toward degradation of congo red by CuO/eggshell | |
| CN108479811B (en) | Z-shaped acoustic catalyst for degrading antibiotic wastewater and preparation method and application thereof | |
| CN107413354B (en) | Preparation method of silver-loaded copper oxide nanocomposite | |
| CN105129835B (en) | Hexacosahedral cuprous oxide nanometer particle preparation method | |
| CN109437338A (en) | The preparation method of one type sawtooth pattern nickel cobalt iron Prussian blue analogue sintered oxide nano material | |
| CN103623847B (en) | A kind of CdSe-Bi 2wO 6the preparation method of photochemical catalyst | |
| CN104525937A (en) | Porous silver micro-nano structure and shape and size controllable preparation method thereof | |
| Yang et al. | Facile shape-controllable synthesis of Ag3PO4 photocatalysts | |
| Zhang et al. | Controllable synthesis of Cu2O microcrystals via a complexant‐assisted synthetic route | |
| CN108097277A (en) | A kind of BiOCl/ZnO hetero-junctions high visible light catalytic activity material and preparation method thereof | |
| CN109621961B (en) | Method for in-situ preparation of metal high-dispersion catalyst by growing two-dimensional nanosheets | |
| US20080067469A1 (en) | Method for Producing Iron Oxide Nano Particles | |
| CN111569882A (en) | Cobaltosic oxide supported copper nano catalyst and preparation method thereof | |
| CN110407245A (en) | The method of one kettle way preparation flake and spherical cuprous oxide nano particle | |
| CN107954463B (en) | Preparation method of cuprous oxide nanocrystalline cube and hollow polyhedron | |
| CN110155958A (en) | A kind of silk ball shape Cu2-xSe nano material and its preparation and application | |
| Jin et al. | AgPd nanocages sandwiched between a MXene nanosheet and PDA layer for photothermally improved catalytic activity and antibacterial properties | |
| CN102962470A (en) | Method for preparing spherical ultrafine nickel powder at room temperature | |
| CN108328634A (en) | A kind of copper load zinc aluminate nano-powder and preparation method thereof | |
| Lai et al. | Suspension synthesis of surfactant-free cuprous oxide quantum dots |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190319 |