CN102491404A - Copper oxide micro-nano composite structural material and preparation method thereof - Google Patents
Copper oxide micro-nano composite structural material and preparation method thereof Download PDFInfo
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- CN102491404A CN102491404A CN2011104280192A CN201110428019A CN102491404A CN 102491404 A CN102491404 A CN 102491404A CN 2011104280192 A CN2011104280192 A CN 2011104280192A CN 201110428019 A CN201110428019 A CN 201110428019A CN 102491404 A CN102491404 A CN 102491404A
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Abstract
The invention discloses a copper oxide micro-nano composite structural material, which consists of CuO microspheres with nano flaky secondary structures, fan-shaped/bar-shaped CuO and CuO nanosheets in any ratio, wherein the CuO microspheres are 7-10 microns in diameter, and are formed by self-assembling nanosheets; the fan-shaped/bar-shaped CuO is formed by self-assembling bar-shaped CuO; and CuO bars are 6-12 microns in length and 400-600 nanometers in diameter. The copper oxide micro-nano composite structural material can be taken as a solar energy transformation material, a photocatalyst and a fluorescent material. A preparation method of the copper oxide micro-nano composite structural material comprises the following step of: preparing by taking copper chloride, ammonia water and sodium hydrate as raw materials and taking sodium dodecylbenzene sulfonate as a template under a low-temperature condition with a hydro-thermal method. The preparation method has the advantages of mild reaction condition, easiness for operating, low preparation cost, high product structure controllability, high repeatability and easiness for realizing large-scale production, contributes to large-scale popularization and application, and has great production and practical meanings.
Description
Technical field
The present invention relates to the nano material preparation technical field, particularly relate to a kind of cupric oxide micron and nanometer composite structure material and preparation method.
Background technology
Cupric oxide CuO enjoys people to pay close attention to as low-gap semiconductor owing to having a good application prospect in fields such as catalyzer, gas sensor, conversion of solar energy materials.
Because the pattern of material has very big influence to its character, so that the CuO of multiple different-shape is designed is synthetic, like nano wire, nanometer rod, nano particle etc.Although the CuO nanoparticle has advantages of high catalytic activity usually, it is very easily reunited in the heterogeneous catalytic reaction process, thereby reduces its activity greatly, and because its particle diameter is too little, is difficult to reclaim with traditional method, also big limitations its practical application.And design synthetizing micro-nano composite structure CuO can effectively overcome above shortcoming.CuO microballoon with secondary structure has polymolecularity, photon acquisition performance preferably usually, and because its particle diameter is bigger, traditional gravity settling method capable of using reclaims, thereby is the out-phase photocatalyst that has application prospect.
When practicable synthetic route of design, except considering effective control, also to consider with simple device, quick and maneuverable compound method to the product pattern.The domestic method of synthetic CuO comprises pyrolytic decomposition/dehydration, galvanic deposit, gas-solid phase reaction and sonochemistry synthesis method etc., and these methods are inappropriate for large-scale application because needing shortcoming such as high temperature, long reaction time, required conversion unit costliness or building-up process complicacy.Hydrothermal synthesis method has that equipment is simple, reaction conditions is gentle, easy large-scale production; And advantages such as the product particle diameter is even, better crystallinity degree; Be the good method of mass preparation cupric oxide micro Nano material, and use low-cost reaction raw materials to prepare the precondition that CuO is its large-scale application.
Summary of the invention
The objective of the invention is to above-mentioned existing problems; A kind of cupric oxide micron and nanometer composite structure material and preparation method are provided; It uses low-cost cupric chloride, ammoniacal liquor, sodium hydroxide and X 2073 to be reaction raw materials and template, utilizes one pot of hydrothermal synthesis method to prepare the cupric oxide microballoon with nano-sheet secondary structure at a lower temperature; This method have the reaction conditions gentleness, simple to operate, preparation cost is low, the product structure controllability is strong, favorable reproducibility and be prone to realize the advantage of scale operation, helps large-scale promotion application, be of great practical significance.
Technical scheme of the present invention:
A kind of cupric oxide micron and nanometer composite structure material; A kind of or two or more arbitrary proportions by in the CuO microballoon with nano-sheet secondary structure, fan/bar-shaped CuO and the CuO nanometer sheet are formed; Said CuO diameter of micro ball is the 7-10 micron, and each CuO microballoon forms by the nanometer sheet self-assembly, and the nanometer sheet that constitutes the CuO microballoon is irregularly shaped; Its size is the 300-600 nanometer, and thickness is the 30-40 nanometer; Said fan/bar-shaped CuO is formed by the bar-shaped CuO self-assembly, and the length of CuO rod is the 6-12 micron, and diameter is the 400-600 nanometer; The thickness of said CuO nanometer sheet is the 30-40 nanometer, and size is the 400-900 nanometer.
A kind of said cupric oxide micron and nanometer composite structure preparation methods is a raw material with cupric chloride, ammoniacal liquor and sodium hydroxide, is template with the X 2073, under coldcondition, adopts Hydrothermal Preparation, may further comprise the steps:
1) with cupric chloride (CuCl
22H
2O) under stirring, be dissolved in the deionized water; Under magnetic agitation, be that 25% ammoniacal liquor, solid sodium hydroxide and X 2073 add in the above-mentioned solution successively with mass percentage concentration respectively then; Continue then to stir 15 minutes, generate blue four ammino copper [Cu (NH
3)
4]
2+Complex cation and tetrahydroxy close copper [Cu (OH)
4]
2-The complex anion mixed solution;
2) above-mentioned mixed solution immigration is equipped with in the stainless steel cauldron of teflon lined, after the sealing reaction kettle was placed 100-180 ℃ of thermostatic drying chamber internal heating 1-12 hour, obtain the black product;
3) reaction kettle is naturally cooled to room temperature; Then with the black product spinning that generates; The gained solid is spent ionized water and absolute ethanol washing respectively to remove residual soluble ion and tensio-active agent SDBS in the throw out; Under 60 ℃ temperature dry 5 hours then, the cupric oxide pressed powder that obtains was cupric oxide micron and nanometer composite structure material.
The mol ratio of said cupric chloride, deionized water, ammoniacal liquor, sodium hydroxide and X 2073 is 1: 80-160: 0-120: 0-14: 0-0.7.
The consumption of said ammoniacal liquor, solid sodium hydroxide and three kinds of materials of X 2073 must not be zero simultaneously and have only a kind of consumption of material at most is zero or all non-vanishing, when ammonia volume is zero, prepares uniform morphology CuO nanometer sheet; When sodium hydroxide concentration is zero, prepare fan/bar-shaped CuO; When the X 2073 consumption is zero, prepare CuO nanometer sheet and a small amount of CuO mixture of microspheres; When said three kinds of material consumptions are all non-vanishing, through regulating the homogeneity of its add-on may command spherical products pattern.
The washing times of said deionized water and absolute ethyl alcohol is three times, and the volume ratio of deionized water or absolute ethyl alcohol and solids wash thing is 2: 1.
Said cupric oxide micron and nanometer composite structure material can be used as photocatalyst, gas sensing material or conversion of solar energy material.
Advantage of the present invention and positively effect:
The invention provides a kind of cupric oxide micron and nanometer composite structure preparation methods; It is under coldcondition; Use low-cost raw material; Adopt one pot of hydrothermal synthesis method to prepare cupric oxide micro-sphere material with secondary structure, the two-dimensional nano material of the alternative preparation of the experiment parameter cupric oxide through regulation and control reactions, have the reaction conditions gentleness, quick, simple to operate, preparation cost is low, the product structure controllability strong, favorable reproducibility and be prone to realize the advantage of scale operation; Help large-scale promotion application, be of great practical significance.
Description of drawings
Fig. 1 is X-ray diffraction XRD figure and the x-ray photoelectron spectroscopy XPS with nano-sheet secondary structure CuO microballoon, and among the figure: a is that XRD, b are that XPS composes entirely, c is Cu2p3 district XPS spectrum figure.
Fig. 2 is the sem SEM figure with nano-sheet secondary structure CuO microballoon, and among the figure: a is high-amplification-factor figure for low magnification figure, b.
Fig. 3 is the transmission electron microscope figure with nano-sheet secondary structure CuO microballoon, and among the figure: a is that transmission electron microscope TEM, b are high resolution transmission electron microscopy HRTEM photo.
Fig. 4 is the SEM figure of the CuO of preparation when a kind of consumption in ammoniacal liquor, sodium hydroxide and three kinds of materials of X 2073 is zero, and among the figure: a is that ammonia volume is zero, b is that sodium hydroxide concentration is zero, c is zero for the X 2073 consumption.
Fig. 5 is the spectrogram with nano-sheet secondary structure CuO microballoon, and among the figure: a is that ir spectra, b are that ultraviolet-visible diffuse-reflectance absorption spectrum, c are fluorescence spectrum.
Embodiment
In order to make those skilled in the art person understand the present invention program better, the present invention is done further detailed description below in conjunction with accompanying drawing and embodiment.
The present invention is a reaction raw materials with cupric chloride, ammoniacal liquor and sodium hydroxide, is template with the X 2073, under coldcondition, adopts Hydrothermal Preparation to have the CuO micro-sphere material of nano-sheet secondary structure.This method has that equipment is simple, reaction conditions is gentle, quick, operating process simple, low price, product structure controllability are strong, favorable reproducibility and be prone to realize the advantage of scale operation.
Embodiment 1:
A kind of preparation method with cupric oxide micro-sphere material of nano-sheet secondary structure may further comprise the steps:
1) with 0.6g cupric chloride (CuCl
22H
2O) under stirring, be dissolved in the 5mL deionized water; Under magnetic agitation, be that 25% ammoniacal liquor, 1.5g solid sodium hydroxide and 0.61g X 2073 add in the above-mentioned solution successively with the 15mL mass percentage concentration respectively then; Continue then to stir 15 minutes, generate blue four ammino copper [Cu (NH
3)
4]
2+Complex cation and tetrahydroxy close copper [Cu (OH)
4]
2-The complex anion mixed solution;
2) above-mentioned mixed solution immigration is equipped with in the stainless steel cauldron of teflon lined, the volume of reaction kettle is 25mL, after the sealing reaction kettle is placed 180 ℃ of thermostatic drying chamber internal heating 8 hours, obtains the black product;
3) reaction kettle is naturally cooled to room temperature; Then with the black product spinning that generates; The gained solid is spent ionized water and absolute ethanol washing three times respectively to remove residual soluble ion and tensio-active agent SDBS in the throw out; The volume ratio of deionized water or absolute ethyl alcohol and solids wash thing is 2: 1, and under 60 ℃ temperature dry 5 hours then, the cupric oxide pressed powder that obtains was the cupric oxide micro-sphere material with nano-sheet secondary structure.
Fig. 1 is x-ray diffraction pattern and the x-ray photoelectron spectroscopy with CuO microballoon of nano-sheet secondary structure, and Fig. 2, Fig. 3 are respectively the ESEM and the transmission electron microscope photo of above-mentioned CuO microballoon.It is thus clear that the CuO microballoon of this method preparation is an oblique crystal tenorite structure, cupric oxide product percent crystallinity and purity are all very high, and non-oxidation is cuprous, template molecule or foreign ion, like impurity such as sodium ion, cl ionss.The CuO diameter of micro ball is the 7-10 micron; Have secondary structure, each CuO microballoon forms by countless nanometer sheet self-assemblies, this nanometer sheet out-of-shape; Size is the 300-600 nanometer; Thickness is the 30-40 nanometer, is ganoid monocrystalline, and the median size of calculating the primary particle that constitutes the cupric oxide nano sheet through the Scherrer formula is 21.9 nanometers.
Fig. 5 is ir spectra, ultraviolet-visible diffuse-reflectance absorption spectrum and the fluorescence spectrum with nano-sheet secondary structure CuO microballoon.Visible by ir spectra, the CuO surface has more rich surface hydroxyl, and surface hydroxyl has stronger photoreduction property, can be with the organic pollutant reduction that is adsorbed on the CuO surface; Visible by its ultraviolet-visible diffuse-reflectance absorption spectrum, the CuO microballoon has stronger light capture ability in the ultraviolet-visible light district, comprehensive above two aspect character, and we infer that this CuO microballoon is good photocatalyst and conversion of solar energy material.Visible by fluorescence spectrum, prepared CuO microballoon can send blue-fluorescence, so it still is a kind of potential fluorescent material.
At the prepared CuO microballoon of the present invention more rich surface hydroxyl arranged, have stronger photoabsorption in the ultraviolet-visible light district and it produces photohole and light induced electron respectively in valence band and conduction band under illumination condition, so it can be used as conversion of solar energy material and photocatalyst with nano-sheet secondary structure.In addition, prepared CuO microballoon can send blue-fluorescence, so it also can be used as fluorescent material.
Embodiment 2:
A kind of preparation method of cupric oxide nano sheet material may further comprise the steps:
1) with 0.6g cupric chloride (CuCl
22H
2O) under stirring, be dissolved in the 5mL deionized water, under magnetic agitation, respectively 1.5g solid sodium hydroxide and 0.61g X 2073 added in the above-mentioned solution successively then, continue then to stir 15 minutes, generate blue verditer Cu (OH)
2Suspension liquid;
2) above-mentioned suspension liquid immigration is equipped with in the stainless steel cauldron of teflon lined, the volume of reaction kettle is 25mL, after the sealing reaction kettle is placed 180 ℃ of thermostatic drying chamber internal heating 8 hours, obtains the black product;
3) reaction kettle is naturally cooled to room temperature; Then with the black product spinning that generates; The gained solid is spent ionized water and absolute ethanol washing three times respectively to remove residual soluble ion and tensio-active agent SDBS in the throw out; The volume ratio of deionized water or absolute ethyl alcohol and solids wash thing is 2: 1, and under 60 ℃ temperature dry 5 hours then, the cupric oxide pressed powder that obtains was the cupric oxide nano sheet material.
The SEM figure of Fig. 4 a prepared CuO when being zero when ammonia volume, the thickness of the CuO nanometer sheet that visible ammonia volume makes when being zero is the 30-40 nanometer, size is the 400-900 nanometer.
When ammonia volume was zero, product was the CuO nanometer sheet of uniform morphology.When the mol ratio of cupric chloride and ammoniacal liquor is 1: 6, make the cupric ion deposition just fully, the ammoniacal liquor of continuation adding different volumes has certain influence to the homogeneity of spherical products pattern: along with the raising of ammonia vol, the ratio of spherical CuO product progressively improves.
Embodiment 3:
The preparation method of a kind of fan/bar-shaped copper oxide material may further comprise the steps:
1) with 0.6g cupric chloride (CuCl
22H
2O) under stirring, be dissolved in the 5mL deionized water; Under magnetic agitation, be that 25% ammoniacal liquor and 0.61g X 2073 add in the above-mentioned solution successively with the 15mL mass percentage concentration respectively then; Continue then to stir 15 minutes, generate blue four ammino copper [Cu (NH
3)
4]
2+Complex cation solution;
2) with above-mentioned blue four ammino copper [Cu (NH
3)
4]
2+Complex cation solution moves into and is equipped with in the stainless steel cauldron of teflon lined, and the volume of reaction kettle is 25mL, after the sealing reaction kettle is placed 180 ℃ of thermostatic drying chamber internal heating 8 hours, obtains the black product;
3) reaction kettle is naturally cooled to room temperature; Then with the black product spinning that generates; The gained solid is spent ionized water and absolute ethanol washing three times respectively to remove residual soluble ion and tensio-active agent SDBS in the throw out; The volume ratio of deionized water or absolute ethyl alcohol and solids wash thing is 2: 1, and under 60 ℃ temperature dry 5 hours then, the cupric oxide pressed powder that obtains was fan/bar-shaped copper oxide material.
The SEM figure of Fig. 4 b prepared CuO when being zero when sodium hydroxide concentration, the fan-shaped CuO of preparation was formed by the bar-shaped CuO self-assembly when visible sodium hydroxide concentration was zero, and the length that CuO is excellent is the 6-12 micron, and diameter is the 400-600 nanometer;
When sodium hydroxide concentration was zero, the CuO product was fan-shaped and bar-shaped mixture, but productive rate is very low, had only the small amount of precipitate thing to generate, and reaction back solution still is blue, shows that the most copper raw material is still with [Cu (NH
3)
4]
2+The complex cation form exists.Along with the raising of sodium hydroxide concentration, the productive rate of product and the ratio of spherical CuO increase, when the mol ratio of sodium hydroxide and cupric chloride during more than or equal to 3.5: 1 the cupric ion in the solution be converted into black CuO deposition fully, it is colourless that solution is.When the mol ratio of cupric chloride and sodium hydroxide was 1: 10.5, the pattern homogeneity of the spherical CuO that obtains was best.Continue to improve sodium hydroxide concentration, the homogeneity of product pattern has decline slightly.
Embodiment 4:
A kind of cupric oxide nano sheet with have the micro-sphere material preparation process of mixture of nano-sheet secondary structure, may further comprise the steps:
1) with 0.6g cupric chloride (CuCl
22H
2O) being dissolved in the 5mL deionized water in stirring down, is that 25% ammoniacal liquor and 1.5g solid sodium hydroxide add in the above-mentioned solution successively with the 15mL mass percentage concentration respectively under magnetic agitation then, and the continuation stirring is 15 minutes then, generates blue four ammino copper [Cu (NH
3)
4]
2+Complex cation and tetrahydroxy close copper [Cu (OH)
4]
2-The complex anion mixed solution;
2) above-mentioned mixed solution immigration is equipped with in the stainless steel cauldron of teflon lined, the volume of reaction kettle is 25mL, after the sealing reaction kettle is placed 180 ℃ of thermostatic drying chamber internal heating 8 hours, obtains the black product;
3) reaction kettle is naturally cooled to room temperature; Then with the black product spinning that generates; The gained solid is spent ionized water and absolute ethanol washing three times respectively to remove residual soluble ion and tensio-active agent SDBS in the throw out; The volume ratio of deionized water or absolute ethyl alcohol and solids wash thing is 2: 1, and under 60 ℃ temperature dry 5 hours then, the cupric oxide pressed powder that obtains was cupric oxide nano sheet and the micro-sphere material mixture with nano-sheet secondary structure.
The SEM figure of Fig. 4 c prepared CuO when being zero when the X 2073 consumption, visible, mainly be to generate the nano-sheet cupric oxide when not having X 2073 to participate in reaction, the microballoon product formation that has the nano-sheet secondary structure is on a small quantity arranged simultaneously.
When the X 2073 consumption is zero, prepare CuO nanometer sheet and a small amount of CuO mixture of microspheres.When the mol ratio of cupric chloride and X 2073 is 1: during 0.23-0.5, spherical products pattern homogeneity is better.
Change the consumption of deionized water, the pattern of product is not had obvious influence.It is thus clear that ammoniacal liquor, sodium hydroxide and X 2073 have decisive role for the formation with nano-sheet secondary structure CuO microballoon.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (5)
1. cupric oxide micron and nanometer composite structure material; It is characterized in that: a kind of or two or more arbitrary proportions by in the CuO microballoon with nano-sheet secondary structure, fan/bar-shaped CuO and the CuO nanometer sheet are formed; Said CuO diameter of micro ball is the 7-10 micron, and each CuO microballoon forms by the nanometer sheet self-assembly, and the nanometer sheet that constitutes the CuO microballoon is irregularly shaped; Its size is the 300-600 nanometer, and thickness is the 30-40 nanometer; Said fan/bar-shaped CuO is formed by the bar-shaped CuO self-assembly, and the length of CuO rod is the 6-12 micron, and diameter is the 400-600 nanometer; The thickness of said CuO nanometer sheet is the 30-40 nanometer, and size is the 400-900 nanometer.
2. cupric oxide micron and nanometer composite structure preparation methods according to claim 1; It is characterized in that with cupric chloride, ammoniacal liquor and sodium hydroxide be raw material; With the X 2073 is template, under coldcondition, adopts Hydrothermal Preparation, may further comprise the steps:
1) with cupric chloride (CuCl
22H
2O) under stirring, be dissolved in the deionized water; Under magnetic agitation, be that 25% ammoniacal liquor, solid sodium hydroxide and X 2073 add in the above-mentioned solution successively with mass percentage concentration respectively then; Continue then to stir 15 minutes, generate blue four ammino copper [Cu (NH
3)
4]
2+Complex cation and tetrahydroxy close copper [Cu (OH)
4]
2-The complex anion mixed solution;
2) above-mentioned mixed solution immigration is equipped with in the stainless steel cauldron of teflon lined, after the sealing reaction kettle was placed 100-180 ℃ of thermostatic drying chamber internal heating 1-12 hour, obtain the black product;
3) reaction kettle is naturally cooled to room temperature; Then with the black product spinning that generates; The gained solid is spent ionized water and absolute ethanol washing respectively to remove residual soluble ion and tensio-active agent SDBS in the throw out; Under 60 ℃ temperature dry 5 hours then, the cupric oxide pressed powder that obtains was cupric oxide micron and nanometer composite structure material.
3. according to the said cupric oxide micron and nanometer composite structure of claim 2 preparation methods, it is characterized in that: the mol ratio of said cupric chloride, deionized water, ammoniacal liquor, sodium hydroxide and X 2073 is 1: 80-160: 0-120: 0-14: 0-0.7.
4. according to the said cupric oxide micron and nanometer composite structure of claim 2 preparation methods; It is characterized in that: the consumption of said ammoniacal liquor, solid sodium hydroxide and three kinds of materials of X 2073 must not be zero simultaneously and have only a kind of consumption of material at most is zero or all non-vanishing; When ammonia volume is zero, prepare uniform morphology CuO nanometer sheet; When sodium hydroxide concentration is zero, prepare fan/bar-shaped CuO; When the X 2073 consumption is zero, prepare CuO nanometer sheet and a small amount of CuO mixture of microspheres; When said three kinds of material consumptions are all non-vanishing, through regulating the homogeneity of its add-on may command spherical products pattern.
5. according to the said cupric oxide micron and nanometer composite structure of claim 2 preparation methods, it is characterized in that: the washing times of said deionized water and absolute ethyl alcohol is three times, and the volume ratio of deionized water or absolute ethyl alcohol and solids wash thing is 2: 1.
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| CN103272598A (en) * | 2013-06-20 | 2013-09-04 | 南京信息工程大学 | Method for preparing straw-bundle-like copper oxide manometer photocatalyst |
| CN103771485A (en) * | 2014-01-21 | 2014-05-07 | 中国计量学院 | Controllable preparation method for three-dimensional nano self-assembly of copper oxide |
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| CN103030169B (en) * | 2012-12-26 | 2015-07-15 | 中北大学 | Shape-controlled preparation method of nanometer copper oxide |
| CN103151540A (en) * | 2013-02-20 | 2013-06-12 | 上海交通大学 | Copper oxide awl micro-level and nano-level array structure material, and preparation method and electrode apparatus thereof |
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| CN103272598A (en) * | 2013-06-20 | 2013-09-04 | 南京信息工程大学 | Method for preparing straw-bundle-like copper oxide manometer photocatalyst |
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| CN110510657A (en) * | 2019-09-11 | 2019-11-29 | 山东理工大学 | Copper oxide micro-sphere structure, these hydrogen sulfide gas sensor and preparation method thereof |
| CN110510657B (en) * | 2019-09-11 | 2022-12-23 | 山东理工大学 | Copper oxide microsphere structure, hydrogen sulfide gas sensor and preparation method thereof |
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