CN104692445A - Preparation and application of copper oxide nanometer hollow spheres - Google Patents
Preparation and application of copper oxide nanometer hollow spheres Download PDFInfo
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Abstract
The invention relates to copper oxide nanometer hollow spheres and an application thereof. A preparation method of the copper oxide nanometer hollow spheres comprises the steps: firstly preparing Cu2O nanospheres serving as precursors by using glucose as a surface active agent at room temperature, then partially oxidizing the Cu2O nanospheres to a Cu2O/CuO core-shell structure by using persulfate as an oxidizing agent, and dissolving a Cu2O core in the Cu2O/CuO core-shell structure by using sodium thiosulfate as a complexing agent, thus forming CuO (copper oxide) nanometer hollow spheres. The preparation method has the advantages that the whole process is carried out at room temperature, the production process is environmentally friendly and energy-saving, reaction conditions are mild, the preparation technology is simple, the sizes of the hollow structures of the prepared CuO nanometer hollow spheres can be adjusted by adjusting the concentration and complexing time of the sodium thiosulfate in a complexing system, the prepared CuO nanometer hollow spheres are uniform in size and have good photocatalysis effect, and the average diameter of the nanometer hollow spheres is in the range of 280-420nn.
Description
Technical field
The present invention relates to and belongs to technical field of inorganic non-metal material preparation, particularly a kind of preparation method of cupric oxide hollow ball.
Background technology
Hollow nano-material has the features such as low density, high-specific surface area, high stability and Surface Permeability, has broad application prospects in fields such as sensing, medicament slow release, chemical storage, opto-electronic conversion and electrochemistry.Cupric oxide (CuO) is a kind of typical 3D transition metal P-type semiconductor, there is monoclinic crystalline structure, lower band gap (Eg=1.2eV), when its size reaches nano level, derive the physico-chemical property of series of novel, as large in specific surface area, high adsorption capacity, surface reaction activity are high and to extremely sensitive characteristics of external environment such as temperature, light, humidity, gases, in catalysis, sensing, high-temperature superconductor and photoelectric material etc., obtain research and apply widely.Exactly because cupric oxide hollow structure material has the special character being different from solid material, people are made to create great interest to the preparation of this type of material and performance study.
Liquid phase method is the primary synthetic methods of hollow nano-material, comprises using variously removing template or certainly sacrificing template, can remove template as carbon ball, SiO
2, the soft template such as hard template and bubble, vesicle, micella such as polystyrene.In recent years, based on the route of synthesis of Kinkendal Effect (Kirkendall effect), a new thinking is provided for obtaining hollow structure metal oxide nano-material, particularly utilize the method for direct oxidation precursor, can be simple, obtain hollow structure rapidly and be significantly oxidized cupric oxide, if the people such as Xue are with 120 DEG C of solvent-thermal method gained solid construction CuS, Cu2S is presoma, 700 DEG C of calcining 4h obtain hollow structure CuO (J.Liu, D.F. Xue.Thermal Oxidation Strategy towards Porous Metal Oxide Hollow Architectures [J] .Adv.Mater., 2008, 20:2622 – 2627), the people such as Huh with 120 DEG C of hydrothermal method gained Cu micron balls for presoma, 400 DEG C of calcining 5h obtain CuO micrometre hollow sphere Y.-S.Cho, Y.-D.Huh.Preparation of CuO Hollow Spheres by Oxidation of Cu Microspheres [J] .Bull.Korean Chem.Soc., 2009,30:1410 – 1412).As can be seen from the report of above-mentioned nano cupric oxide hollow structure product preparation method, generally Nanometer Copper or the copper compound presoma as hollow cupric oxide product will be obtained by the synthetic method of the power consumption such as hydro-thermal or solvent thermal in preparation process, and presoma is changed into the temperature required height of hollow cupric oxide structure, preparation process energy consumption is large, and the also generation objectionable impurities had is as H
2s etc., severe reaction conditions, Financial cost is high, and is unfavorable for large-scale production.
Summary of the invention
In order to overcome the defect of prior art, the invention provides the preparation method of the cupric oxide nano-hollow ball that a kind of preparation technology of preparation is simple, reproducible, environment protecting and power-saving, room temperature can be prepared.
For realizing above-mentioned technical problem, the invention provides a kind of cupric oxide nano-hollow ball, its material component comprises soluble copper salt, ammoniacal liquor, sodium hydroxide, glucose and persulphate, and whole reaction process is at room temperature carried out, and obtains through following concrete steps:
(1) water-soluble for water soluble bivalent nantokite magnetic agitation is formed solution, wherein, copper ion concentration is 0.015 ~ 0.045mol/L;
(2) in above-mentioned solution, add ammoniacal liquor and strong base solution successively, make the ratio of the volumetric molar concentration of cupric ion and ammoniacal liquor be 13:1 ~ 17:1, the ratio of cupric ion and highly basic volumetric molar concentration is 0.3:1 ~ 0.3:1.4, respectively magnetic agitation 10 ~ 20min;
(3) in above-mentioned solution, add 1 ~ 5 gram of glucose and ascorbic acid solution successively again, wherein, the ratio of the volumetric molar concentration of cupric ion and xitix is 1:1 ~ 1:3, magnetic agitation 40 ~ 60min, and centrifugation obtains Red copper oxide ball;
(4) above-mentioned Red copper oxide ball is scattered in 100 ~ 400mL water, add highly basic and persulfate solution successively, wherein strong paper mill wastewater is 0.08 ~ 0.28mol/L, Red copper oxide is 1:2 ~ 1:8 with the ratio of persulfate mole number, magnetic agitation 10 ~ 20min, obtains Cu by the centrifugation of gained dregs
2o/CuO nucleocapsid structure;
(5) by above-mentioned Cu
2o/CuO nucleocapsid structure is scattered in 100mL water, adds hypo solution and makes its concentration be 0.04 ~ 0.8mol/L, and stir 1 ~ 3h, centrifugation, gained solid is product.
Preferably, after step (5), product is used distilled water and absolute ethanol washing successively, 50 ~ 70 DEG C of vacuum-drying 3 ~ 6h.
Preferably, described cupric salt is cupric nitrate, copper sulfate or cupric chloride, or its mixture.。
Preferably, described highly basic is sodium hydroxide or potassium hydroxide.
Preferably, ascorbic acid solution hydrazine hydrate described in step (3) or halfcystine replace.
Preferably, persulphate described in step (4) is overcurrent acid potassium, Sodium Persulfate and ammonium persulphate.
Preferably, in described step (1) solution, copper ion concentration is 0.030 ~ 0.045mol/L;
The present invention also provides a kind of preparation method of above-mentioned cupric oxide nano-hollow ball, and whole preparation process is at room temperature carried out, and specifically comprises the following steps:
(1) water-soluble for water soluble bivalent nantokite magnetic agitation is formed solution, in solution, copper ion concentration is 0.015 ~ 0.045mol/L;
(2) in above-mentioned solution, ammoniacal liquor and strong base solution is added successively, the ratio of the volumetric molar concentration of cupric ion and ammoniacal liquor in solution is made to be 13:1 ~ 17:1, the ratio of cupric ion and highly basic volumetric molar concentration is 0.3:1 ~ 0.3:1.4, respectively magnetic agitation 10 ~ 20min;
(3) in above-mentioned solution, add 1 ~ 5 gram of glucose and ascorbic acid solution successively again, wherein, the ratio of the volumetric molar concentration of cupric ion and xitix is 1:1 ~ 1:3, magnetic agitation 40 ~ 60min, and centrifugation obtains Red copper oxide ball;
(4) above-mentioned Red copper oxide ball is scattered in 100 ~ 400mL water, add highly basic and persulfate solution successively, wherein strong paper mill wastewater is 0.08 ~ 0.28mol/L, Red copper oxide is 1:2 ~ 1:8 with the ratio of persulfate mole number, magnetic agitation 10 ~ 20min, obtains Cu by the centrifugation of gained dregs
2o/CuO nucleocapsid structure;
(5) by above-mentioned Cu
2o/CuO nucleocapsid structure is scattered in 100mL water, adds Sulfothiorine and makes its concentration be 0.04 ~ 0.8mol/L, and stir 1 ~ 3h, centrifugation, gained solid is product.
The present invention also provides a kind of application of above-mentioned cupric oxide nano-hollow ball, described cupric oxide nano-hollow ball is used for photocatalytic degradation Luo Dan name B solution.
Compared with prior art, the beneficial effect acquired by the present invention is: under room temperature, is that tensio-active agent first prepares precursor C u with glucose
2o nanometer ball, then be that oxygenant is by Cu with persulphate
2o nanometer ball partial oxidation becomes Cu
2o/CuO nucleocapsid structure, then be complexing agent with Sulfothiorine, by Cu
2cu in O/CuO nucleocapsid structure
2o karyolysis, thus form CuO cupric oxide nano-hollow ball, the whole process of the present invention is at room temperature carried out, production process environmental protection and energy saving, reaction conditions is gentle, and preparation technology is simple, the hollow structure size of the CuO cupric oxide nano-hollow ball made is by regulating the concentration of Sulfothiorine and the time of complexing in complex system to control, prepared CuO cupric oxide nano-hollow ball size is even, and mean diameter is between 280 ~ 420nm, and photocatalysis effect is good.
Accompanying drawing explanation
Fig. 1 is the TEM photo of the precursor prepared by embodiment 1.
Fig. 2 is the XRD spectra of the precursor prepared by embodiment 1.
Fig. 3 is the TEM photo of the product prepared by embodiment 1.
Fig. 4 is the XRD figure of the product prepared by embodiment 1.
Fig. 5 is that product prepared by each embodiment is as the rhodamine B degradation rate rate figure over time under photocatalyst.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described in detail.
Embodiment 1
(1), under room temperature (15-25 DEG C) condition, the CuSO of 10mL is got
4solution (0.15mol/L), in the beaker of 250mL, adds distilled water diluting to 100mL; (2) in beaker, NH is dripped successively
3h
2o and NaOH solution, the ratio making the volumetric molar concentration of cupric ion and ammoniacal liquor in solution is 13:1, makes the ratio of cupric ion and NaOH volumetric molar concentration be 0.3:1, and magnetic agitation 10min, now can see that generating light blue precipitation is suspended in solution respectively; (3) add the glucose of 1g again, after it dissolves, add ascorbic acid solution, wherein, the ratio of the volumetric molar concentration of cupric ion and xitix is 1:1, in several minutes, solution colour, by light blue, becomes green, finally become yellow again, magnetic agitation 40min, centrifugation obtains precursor; (4) above-mentioned precursor is scattered in 100mL water, add sodium hydroxide and Potassium Persulphate successively, wherein the concentration of Strong oxdiative sodium is 0.08mol/L, and Red copper oxide is 1:2 with the ratio of persulfate mole number, magnetic agitation 10min, obtains Cu by the centrifugation of gained dregs
2o/CuO nucleocapsid structure; (5) by Cu
2o/CuO nucleocapsid structure is scattered in 100mL water, and add Sulfothiorine and make its concentration be that 0.8 mol/L stirs 1h, centrifugation, gained solid is product.Preferably product is used distilled water and absolute ethanol washing successively, 70 DEG C of vacuum-drying 3h, obtain dry nano oxidized copper powder for subsequent use.In above raw material, copper sulfate can replace with the bivalent soluble such as cupric nitrate or cupric chloride mantoquita, sodium hydroxide can replace with potassium hydroxide, xitix can replace with the reductive agent such as hydrazine hydrate or halfcystine, and overcurrent acid potassium also can replace with the persulphate of the solution water such as Sodium Persulfate and ammonium persulphate.
The thing phase composite of above-mentioned obtained precursor and product thereof and purity are adopted Rigaku Co., Ltd. D/max – rB
type X-ray diffraction (XRD) instrument detects, Cu K α 1 target, and operating voltage is 40kV, and electric current is 80mA; Hitachi, Ltd H – 800 transmission electron microscope (TEM) (acceleration voltage 200kV) is adopted to analyze to the shape characteristic of obtained sample.Fig. 1 is the TEM photo of prepared precursor, this shows, precursor is the nanometer ball that size is comparatively even, mean diameter is about 280nm.Fig. 2 is the XRD figure of prepared precursor, and as seen from the figure, all diffraction peaks are Emission in Cubic Cu
2the diffraction peak (JCPDS card number: 05-0667) of O, does not have obvious impurity peaks to occur.Fig. 3 is the TEM photo of prepared product, as can be seen from photo, with precursor C u sized by product
2the hollow nano-sphere that O nanometer ball is close, size is even, and mean diameter is between 280nm, and hollow ball surfaces externally and internally is coarse.Fig. 4 is the XRD spectra of prepared product, and wherein 2 θ are respectively the diffraction peak at 35.7 ° and 39.0 ° places is the characteristic diffraction peak of cupric oxide, and according to standard powdery diffractometry card (JCPDS No.48-1548), its crystalline structure is isometric system.Product photocatalyst prepared by above-described embodiment, for the rhodamine B solution of the 5ppm that degrades, after photochemical catalysis 3h, the degradation rate of rhodamine B reach 93.2% (as curve in Fig. 5 a).
Embodiment 2
(1), under room temperature (15-25 DEG C) condition, the CuSO of 30mL is got
4solution (0.15mol/L), in the beaker of 250mL, adds distilled water diluting to 100mL; (2) in beaker, NH is dripped successively
3h
2o and KOH solution, the ratio making the volumetric molar concentration of cupric ion and ammoniacal liquor in solution is 17:1, makes the ratio of cupric ion and NaOH volumetric molar concentration be 0.3:1.4, and magnetic agitation 20min, now can see that generating light blue precipitation is suspended in solution respectively; (3) glucose of 5g is added again, after it dissolves, add ascorbic acid solution again, wherein, the ratio of the volumetric molar concentration of cupric ion and xitix is 1:3, in several minutes, solution colour, by light blue, becomes green, finally becomes yellow again, magnetic agitation 60min, centrifugation obtains Red copper oxide ball; (4) above-mentioned Red copper oxide ball is scattered in 400mL water, add sodium hydroxide and Potassium Persulphate successively, wherein the concentration of sodium hydroxide is 0.28mol/L, and Red copper oxide is 1:8 with the ratio of persulfate mole number, magnetic agitation 20min, obtains Cu by the centrifugation of gained dregs
2o/CuO nucleocapsid structure; (5) by Cu
2o/CuO nucleocapsid, in 100mL water, adds hypo solution and makes its concentration be 0.04mol/L, and stir 3h, centrifugation, gained solid is product.Preferably product is used distilled water and absolute ethanol washing successively, 50 DEG C of vacuum-drying 6h, obtain dry nano oxidized copper powder for subsequent use.With precursor C u sized by prepared product
2the hollow nano-sphere that O nanometer ball is close, size is even, and mean diameter is between 300nm, and hollow ball surface irregularity, its crystalline structure is isometric system.The product photocatalyst prepared by above-described embodiment, for the rhodamine B solution of the 5ppm that degrades, after photochemical catalysis 3h, the degradation rate of rhodamine B reaches 96.1% (as curve b in Fig. 5).
Embodiment 3
(1), under room temperature (15-25 DEG C) condition, the CuSO of 20mL is got
4solution (0.15mol/L), in the beaker of 250mL, adds distilled water diluting to 100mL; (2) in beaker, NH is dripped successively
3h
2o and NaOH solution, the ratio making the volumetric molar concentration of cupric ion and ammoniacal liquor in solution is 15:1, makes the ratio of cupric ion and NaOH volumetric molar concentration be 0.3:1.2, and magnetic agitation 15min, now can see that generating light blue precipitation is suspended in solution respectively; (3) glucose of 3g is added again, after it dissolves, add ascorbic acid solution again, wherein, the ratio of the volumetric molar concentration of cupric ion and xitix is 1:2, in several minutes, solution colour, by light blue, becomes green, finally becomes yellow again, magnetic agitation 50min, centrifugation obtains Red copper oxide ball; (4) above-mentioned Red copper oxide ball is scattered in 250mL water, add sodium hydroxide and Potassium Persulphate successively, wherein the concentration of sodium hydroxide is 0.18mol/L, and Red copper oxide is 1:5 with the ratio of persulfate mole number, magnetic agitation 15min, obtains Cu by the centrifugation of gained dregs
2o/CuO nucleocapsid structure; (5) by Cu
2o/CuO nucleocapsid structure is scattered in 100mL water, adds hypo solution and makes its concentration be 0.042mol/L, and stir 2h, centrifugation, gained solid is product.Preferably product is used distilled water and absolute ethanol washing successively, 60 DEG C of vacuum-drying 4.5h, obtain dry cupric oxide nano-hollow ball powder for subsequent use.With precursor C u sized by prepared product
2the hollow nano-sphere that O nanometer ball is close, size is even, and diameter is between 350nm, and hollow ball surface irregularity, its crystalline structure is isometric system.The product photocatalyst prepared by above-described embodiment, for the rhodamine B solution of the 5ppm that degrades, after photochemical catalysis 3h, the degradation rate of rhodamine B reaches 95.6% (as curve c in Fig. 5).
Embodiment 4
(1), under room temperature (15-25 DEG C) condition, the CuSO of 25mL is got
4solution (0.15mol/L), in the beaker of 250mL, adds distilled water diluting to 100mL; (2) in beaker, NH is dripped successively
3h
2o and NaOH solution, the ratio making the volumetric molar concentration of cupric ion and ammoniacal liquor in solution is 15:1, makes the ratio of cupric ion and NaOH volumetric molar concentration be 0.3:1.2, and magnetic agitation 15min, now can see that generating light blue precipitation is suspended in solution respectively; (3) glucose of 2g is added again, after it dissolves, add ascorbic acid solution again, wherein, the ratio of the volumetric molar concentration of cupric ion and xitix is 1:2, in several minutes, solution colour, by light blue, becomes green, finally becomes yellow again, magnetic agitation 50min, centrifugation obtains Red copper oxide ball; (4) above-mentioned Red copper oxide ball is scattered in 250mL water, add sodium hydroxide and Potassium Persulphate successively, wherein the concentration of Strong oxdiative sodium is 0.18mol/L, and Red copper oxide is 1:4 with the ratio of persulfate mole number, magnetic agitation 15min, obtains Cu by the centrifugation of gained dregs
2o/CuO nucleocapsid structure; (5) by Cu
2o/CuO nucleocapsid structure is scattered in 100mL water, adds Sulfothiorine and makes its concentration be 0.08mol/L, and stir 2.5h, centrifugation, gained solid is product.
Preferably product is used distilled water and absolute ethanol washing successively, 65 DEG C of vacuum-drying 4h, obtain dry cupric oxide nano-hollow ball powder for subsequent use.With precursor C u sized by prepared product
2the hollow nano-sphere that O nanometer ball is close, size is even, and mean diameter is about 420nm, and hollow ball surface irregularity, its crystalline structure is isometric system.The product photocatalyst prepared by above-described embodiment, for the rhodamine B solution of the 5ppm that degrades, after photochemical catalysis 3h, the degradation rate of rhodamine B reaches 90.8% (as curve d in Fig. 5).
Cupric oxide nano-hollow ball size prepared by the various embodiments described above evenly, diameter at 280 ~ 420nm, can prepare under room temperature condition, and photocatalysis effect is good.
It should be noted last that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (9)
1. a cupric oxide nano-hollow ball, it is characterized in that its material component comprises soluble copper salt, ammoniacal liquor, sodium hydroxide, glucose and persulphate, whole reaction process is at room temperature carried out, and obtains through following concrete steps:
(1) water-soluble for water soluble bivalent nantokite magnetic agitation is formed solution, wherein, copper ion concentration is 0.015 ~ 0.045mol/L;
(2) in above-mentioned solution, add ammoniacal liquor and strong base solution successively, make the ratio of the volumetric molar concentration of cupric ion and ammoniacal liquor be 13:1 ~ 17:1, the ratio of cupric ion and highly basic volumetric molar concentration is 0.3:1 ~ 0.3:1.4, respectively magnetic agitation 10 ~ 20min;
(3) in above-mentioned solution, add 1 ~ 5 gram of glucose and ascorbic acid solution successively again, wherein, the ratio of the volumetric molar concentration of cupric ion and xitix is 1:1 ~ 1:3, magnetic agitation 40 ~ 60min, and centrifugation obtains Red copper oxide ball;
(4) above-mentioned Red copper oxide ball is scattered in 100 ~ 400mL water, add highly basic and persulfate solution successively, wherein strong paper mill wastewater is 0.08 ~ 0.28mol/L, Red copper oxide is 1:2 ~ 1:8 with the ratio of persulfate mole number, magnetic agitation 10 ~ 20min, obtains Cu by the centrifugation of gained dregs
2o/CuO nucleocapsid structure;
(5) by above-mentioned Cu
2o/CuO nucleocapsid structure is scattered in 100mL water, adds hypo solution and makes its concentration be 0.04 ~ 0.8mol/L, and stir 1 ~ 3h, centrifugation, gained solid is product.
2. cupric oxide nano-hollow ball according to claim 1, is characterized in that: after step (5), product is used distilled water and absolute ethanol washing successively, 50 ~ 70 DEG C of vacuum-drying 3 ~ 6h.
3. cupric oxide nano-hollow ball according to claim 1, is characterized in that: described cupric salt is cupric nitrate, copper sulfate or cupric chloride, or its mixture.
4. cupric oxide nano-hollow ball according to claim 1, is characterized in that: described highly basic is sodium hydroxide or potassium hydroxide.
5. cupric oxide nano-hollow ball according to claim 1, is characterized in that: ascorbic acid solution hydrazine hydrate described in step (3) or halfcystine replace.
6. cupric oxide nano-hollow ball according to claim 1, is characterized in that: persulphate described in step (4) is overcurrent acid potassium, Sodium Persulfate and ammonium persulphate.
7. cupric oxide nano-hollow ball according to claim 1, is characterized in that: in described step (1) solution, copper ion concentration is 0.030 ~ 0.045mol/L.
8., according to a preparation method for the arbitrary described cupric oxide nano-hollow ball of claim 1 ~ 7, it is characterized in that whole preparation process is at room temperature carried out, specifically comprise the following steps:
(1) water-soluble for water soluble bivalent nantokite magnetic agitation is formed solution, in solution, copper ion concentration is 0.015 ~ 0.045mol/L;
(2) in above-mentioned solution, add ammoniacal liquor and strong base solution successively, make the ratio of the volumetric molar concentration of cupric ion and ammoniacal liquor in solution be 13:1 ~ 17:1, the ratio of cupric ion and highly basic volumetric molar concentration is 0.3:1 ~ 0.3:1.4, respectively magnetic agitation 10 ~ 20min;
(3) in above-mentioned solution, add 1 ~ 5 gram of glucose and ascorbic acid solution successively again, wherein, the ratio of the volumetric molar concentration of cupric ion and xitix is 1:1 ~ 1:3, magnetic agitation 40 ~ 60min, and centrifugation obtains Red copper oxide ball;
(4) above-mentioned Red copper oxide ball is scattered in 100 ~ 400mL water, add highly basic and persulfate solution successively, wherein strong paper mill wastewater is 0.08 ~ 0.28mol/L, Red copper oxide is 1:2 ~ 1:8 with the ratio of persulfate mole number, magnetic agitation 10 ~ 20min, obtains Cu by the centrifugation of gained dregs
2o/CuO nucleocapsid structure;
(5) by above-mentioned Cu
2o/CuO nucleocapsid structure is scattered in 100mL water, adds Sulfothiorine and makes its concentration be 0.04 ~ 0.8mol/L, and stir 1 ~ 3h, centrifugation, gained solid is product.
9., according to an application for the arbitrary described cupric oxide nano-hollow ball of claim 1 ~ 7, it is characterized in that: described cupric oxide nano-hollow ball is used for photocatalytic degradation rhodamine B solution.
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