CN102502770A - Flower-like copper oxide catalyst and preparation method and application thereof - Google Patents
Flower-like copper oxide catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a flower-shaped copper oxide catalyst and a preparation method and application thereof to the direct synthesis of an organic silicon monomer. The preparation method of the flower-shaped copper oxide catalyst comprises the following steps: (1) adding copper salt to ethanol or mixed solvent of ethanol and water to form solution; and (2) stirring and adding ammonia, strong alkali and nitrate to the solution in sequence to obtain a homogeneous solution, transferring the homogeneous solution to a reactor to carry out the thermal reaction of a solvent, and controlling the amount of the product of reaction, the reaction temperature and the reaction time to obtain the lower-shaped copper oxide catalyst. The preparation process of the flower-shaped copper oxide catalyst has simple experiment procedures and low cost, is convenient to operate, is environment-friendly and can be produced on a large scale. The prepared flower-shaped copper oxide powder can be used as the catalyst to the field of the direct synthesis of the organic silicon monomer, and particularly, the flower-shaped copper oxide powder is highly selective for the dimethyldichlorosilane monomer.
Description
Technical field
The present invention relates to a kind of catalyzer, Its Preparation Method And Use, relate in particular to a kind of flower-shaped copper oxide catalyst, its preparation method and in the application in direct method synthesizing organosilicon monomer field.
Background technology
As one type of p type transition metal oxide, cupric oxide shows peculiar physics and chemical property in fields such as electricity, magnetic and catalysis, causes people's extensive concern, is widely used in key areas such as printing and dyeing, pottery, electrode active material and catalyzer.The physics of cupric oxide and chemical property receive pattern, size and structure influence.In recent years, the copper oxide material that has the different-shape structure causes and people's very big interest has prepared cupric oxide nano line, nanometer rod, nanometer sheet, nanotube, nano belt etc. through different methods.The structure that some are more complicated such as flower-shaped, cellular, hollow ball etc. also have relevant report.Wherein, flower-shaped cupric oxide has characteristics such as high-ratio surface, low bulk density, how active crystal face position because of it, have great application prospect at catalytic field.Therefore, the synthetic extensive concern that causes people of flower-shaped cupric oxide.
People such as Chu prepare the mixing solutions that ammonium sulfate, sodium hydroxide and trace Sodium orthomolybdate (sodium wolframate) and sodium lauryl sulphate are formed earlier, Copper Foil is immersed in utilizes hydrothermal oxidization to be reflected at copper foil surface in the above-mentioned solution to have obtained by the flower-shaped or cellular CuO film material (Liu.Y. that forms then; Chu.Y.; Zhuo.Y.; LiM.; Li.M.; Dong.L.Cryst.Growth Des.2007,7,467.).
People such as Vaseem are raw material with the neutralized verdigris, under alkaline condition are that template is passed through liquid phase reaction and prepared flower-shaped cupric oxide (Vaseem.M. with the vulkacit H; Umar.A.; Kim.S.H.; Hahn.Y.B.J.Phys.Chem.C.2008,112,5729).
People such as Li are raw material with the cupric chloride, use ionic liquid 1-octyl group-3-Methylimidazole trifluoroacetate as solvent and template, under alkaline condition, have obtained flower-shaped and leaf shape cupric oxide (Xia.J. through the microwave heating reaction; Li.H.; Luo, Z.; Shi.L.; Wang.K.; Shu.H.; Yan.Y.J.Phys.Chem.Solids.2009,70,1461.).
Can find out that from above-mentioned flower-shaped cupric oxide preparing method's report in the preparation process, generally will use expensive organism as template, its defective is that cost is higher, is unfavorable for large-scale production.
In addition; Also be only limited to liquid-solid phase catalytic reaction about flower-shaped cupric oxide at the applied research report of catalytic field; Oxidizing reaction like photocatalytic degradation of dye or organism alcohols; And also do not see relevant report for the applied research of direct method synthesizing organosilicon monomer in equal heterogeneous catalytic reaction of gas-solid such as the industry; Especially in the building-up process of an organosilane monomer, the reaction between reactant methyl chloride gas and the silica flour belongs to the gas-solid reaction that contacts, thereby this just requires can fully contact fast reaction speed between catalyzer and the reactant.
Therefore, for increasing the contact probability of catalyzer and reactant, the catalyzer that design has the special appearance of high-ratio surface is one of key factor that improves catalyst efficient.In sum, carry out the flower-shaped cupric oxide preparing method's with industrialization prospect research, and explore flower-shaped cupric oxide and have important scientific meaning and using value in the applied research of direct method synthesizing organosilicon monomer as catalyzer.
Summary of the invention
Deficiency to prior art; One of the object of the invention is that a kind of pattern is provided and particle size is controlled, technology simple, be easy to the preparation method that industrialized no template is synthesized flower-shaped cupric oxide; And, finally the catalyzer of a kind of novel organosilicon monomer that has an application prospect in synthetic is provided through the present invention with prepared cupric oxide its catalytic performance of evaluating catalyst as the direct method synthesizing organosilicon monomer.
The preparation method of flower-shaped copper oxide catalyst provided by the present invention may further comprise the steps:
1) mantoquita is joined in the mixed solvent of ethanol, water or alcohol-water forms solution;
2) under agitation in step 1) gained solution, add ammoniacal liquor, highly basic and nitrate salt successively and obtain homogeneous phase solution;
3) with step 2) gained solution transfers to and carries out solvent thermal reaction in the reaction kettle;
4) washing of step 3) products therefrom, drying are obtained flower-shaped copper oxide catalyst.
Wherein, mantoquita described in the step 1) is cupric nitrate, copper sulfate, cupric chloride or neutralized verdigris, or its mixture.
As preferably, copper ion concentration is 0.02mol/L～1.0mol/L in the said solution, preferred 0.08mol/L～1.0mol/L, further preferred 0.2mol/L～0.8mol/L.
As preferably, the alcoholic acid volume percent is 0～100% in the said ethanol-water mixed solvent, and is preferred 0～56%, further preferred 10%～40%.
Step 2) used ammoniacal liquor is 25wt%～28wt% in; Ammonia concn is 5.0mol/L～10.0mol/L in the said homogeneous phase solution, preferred 6mol/L～8mol/L.
As preferably, highly basic is sodium hydroxide or Pottasium Hydroxide, or its mixture; Said strong base concentrations is 0.1mol/L～2.0mol/L, preferred 0.2mol/L～1.5mol/L, further preferred 0.2mol/L～1.0mol/L.
As preferably, nitrate salt is SODIUMNITRATE, saltpetre or an ammonium nitrate, or its mixture; Said nitrate concentration is 0.5mol/L～2.0mol/L, preferred 0.7mol/L～2.0mol/L, further preferred 1mol/L～1.8mol/L.
In order to make preparation method provided by the present invention obtain circulation ratio preferably, copper ion concentration, ethanol volume percent, ammonia concn, highly basic and concentration, nitrate salt and concentration thereof have been provided as above preferred range.
Solvent thermal reaction temperature described in the step 3) is 80 ℃～160 ℃, and the reaction times is 0.25h～48h; Preferable reaction temperature is 110 ℃～160 ℃, and the reaction times is 8h～48h; Further preferable reaction temperature is 120 ℃～140 ℃, and the reaction times is 10h～20h.As preferably, reaction kettle described in the step 3) is the stainless steel still.The temperature and time of solvent thermal reaction has bigger influence for shape, the size of final products therefrom.The present invention has confirmed this preparing method's suitable reaction temperature and the reaction times through a large amount of experimental exploring, has obtained having the flower-shaped copper oxide catalyst of excellent properties.
One of the object of the invention also is to provide the flower-shaped copper oxide catalyst according to method preparation provided by the present invention.
One of the object of the invention also is to provide according to the application, the particularly application in the synthesization of dimethyl dichlorosilane in the synthesizing organosilicon monomer field of the flower-shaped copper oxide catalyst of method preparation provided by the present invention.
Flower-shaped cupric oxide preparing method's provided by the present invention advantage is:
1) the present invention has realized not adding in the solvent thermal process organic formwork agent and has obtained flower-shaped cupric oxide, for the multilevel hierarchy copper oxide material provides a new route of synthesis.
2) preparation technology of the present invention is succinct, and whole technological process is carried out in reaction kettle, need not any complex apparatus, is a kind of simple and effective, cheap, environmental friendliness, is easy to the preparation method that the mass-producing synthetic prepares flower-shaped cupric oxide.
3) the present invention regulates and control pattern, structure and the particle size of cupric oxide through concentration, temperature of reaction and the reaction times of regulating solvent composition, ammonia concn, alkali and inorganic salt, and control condition and means are easy to implement, and is beneficial to industriallization and synthesizes.
The flower-shaped copper oxide particle size homogeneous that utilizes present method to make, controlled amount has higher specific surface.The catalytically active assessment result shows simultaneously, and the flower-shaped cupric oxide that the present invention is prepared in the reaction of direct method synthesizing organosilicon monomer, shows the selectivity of higher dimethyldichlorosilane(DMCS) and the transformation efficiency of reactant silica flour.
Description of drawings
The XRD spectra of the black product that Fig. 1 obtains for embodiment 1.
The SEM figure of the cupric oxide that Fig. 2 obtains for embodiment 1.
The TEM figure of the cupric oxide that Fig. 3 obtains for embodiment 1.
The nitrogen adsorption of the flower-shaped cupric oxide of black that Fig. 4 obtains for embodiment 1/desorption isotherm figure.
The graph of pore diameter distribution of the flower-shaped cupric oxide of black that Fig. 5 obtains for embodiment 1.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment only is used for helping to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment one
Take by weighing 1.0gCu (NO
3)
23H
2O is dissolved in (copper ion concentration is 0.08mol/L) in the 50.0ml absolute ethyl alcohol, adds 30.0ml strong aqua (commercially available massfraction is 25-28wt%), 0.4gNaOH and 5.0gNaNO successively in room temperature
3, stir the blue solution (ammonia concentration 6.2mol/L, NaOH concentration 0.1mol/L, the NaNO that obtain clear after 30 minutes
3Concentration 0.7mol/L), transfers to then in the stainless steel cauldron of 150ml inner liner polytetrafluoroethylene, be warming up to 130 ℃ of reaction 18h.After reaction finishes, the black product is filtered, water, absolute ethyl alcohol respectively wash 5 times, and 60 ℃ of dry 8h obtain the 0.3g copper oxide catalyst in vacuum drying oven, yield 90.9wt%.
The copper oxide catalyzation agent material of above-mentioned preparation is carried out the XRD test on the X ' Pert PRO MPD type multi-functional X-ray diffractometer that Dutch Panalytical company (PANalytical) produces.The XRD spectra of the black product that Fig. 1 obtains for embodiment 1, wherein 2 θ are respectively 35.7 ° and 39.0 ° of characteristic diffraction peaks that the diffraction peak of locating is a cupric oxide, and according to standard powdery diffractometry card (JCPDS No.05-0667), its crystalline structure is an isometric system.
The copper oxide catalyzation agent material of above-mentioned preparation is observed surface topography at the JSM6700 model field emission scanning electron microscope that company of NEC produces.The SEM figure of the cupric oxide that Fig. 2 obtains for embodiment 1 can find out that by figure the cupric oxide pattern presents flower-like structure, and its flower-shaped particle size is at 2～3 μ m.
The JEM-2100 lanthanum hexaborane transmission electron microscopy observation particle information that the copper oxide catalyzation agent material of above-mentioned preparation is produced in company of NEC.The TEM figure of the cupric oxide that Fig. 3 obtains for embodiment 1 can find out that by figure flower-shaped cupric oxide is assembled by the nanometer sheet of wide 50～150nm.
The copper oxide catalyzation agent material of above-mentioned preparation is tested specific surface and pore size distribution at the specific surface and the lacunarity analysis appearance of the NOVA3200e model of U.S. Kang Ta company production.Figure 4 and 5 are respectively the nitrogen adsorption/desorption isotherm figure and the graph of pore diameter distribution of the flower-shaped cupric oxide of black that embodiment 1 obtains.Hysteresis loop shows that at the IV type thermo-isopleth at relative about 0.8 place of dividing potential drop flower-shaped copper oxide material has the secondary vesicular structure that particle packing forms, and the BET specific surface is 23.2m
2/ g can reach the aperture and be about 33.1nm.
Embodiment two
Take by weighing 0.2gCu (NO
3)
23H
2O is dissolved in the mixed solvent of 28.0ml absolute ethyl alcohol and 22.0ml water (copper ion concentration is 0.02mol/L), adds 22.0ml strong aqua (25-28wt%), 0.3gNaOH and 2.8g NaNO successively in room temperature
3, stir the blue solution (ammonia concentration 5.0mol/L, NaOH concentration 0.1mol/L, the NaNO that obtain clear after 30 minutes
3Concentration 0.5mol/L), transfers to then in the stainless steel cauldron of 150ml inner liner polytetrafluoroethylene, be warming up to 80 ℃ of reaction 48h.After reaction finishes, the black product is filtered, water, absolute ethyl alcohol respectively wash 5 times, and 60 ℃ of dry 8h obtain the 0.05g copper oxide catalyst in vacuum drying oven, yield 91.0wt%.The XRD spectra assay products is isometric system CuO for its crystalline structure, and the SEM photo shows that the cupric oxide pattern presents flower-like structure, and its flower-shaped particle size is at 3～5 μ m, and it is 22.5m that the nitrogen adsorption appearance is measured specific surface
2/ g can reach the aperture and be about 35.2nm.
Embodiment three
Take by weighing 12.1gCu (NO
3)
23H
2O is dissolved in the mixed solvent of 2.5ml absolute ethyl alcohol and 47.5ml water (copper ion concentration is 1.0mol/L), adds 77.2ml strong aqua (25-28wt%), 10.2gNaOH and 21.6gNaNO successively in room temperature
3, stir the blue solution (ammonia concentration 10.0mol/L, NaOH concentration 2.0mol/L, NaNO3 concentration 2.0mol/L) that obtains clear after 30 minutes, transfer to then in the stainless steel cauldron of 150ml inner liner polytetrafluoroethylene, be warming up to 160 ℃ of reaction 0.25h.After reaction finishes, the black product is filtered, water, absolute ethyl alcohol respectively wash 5 times, and 60 ℃ of dry 8h obtain the 3.8g copper oxide catalyst in vacuum drying oven, yield 95.0wt%.The XRD spectra assay products is isometric system CuO for its crystalline structure, and the SEM photo shows that the cupric oxide pattern presents flower-like structure, and its flower-shaped particle size is at 5～6 μ m, and it is 18.5m that the nitrogen adsorption appearance is measured specific surface
2/ g can reach the aperture and be about 38.5nm.
Embodiment four
Take by weighing 0.4gCuCl
22H
2O is dissolved in the mixed solvent of 20.0ml absolute ethyl alcohol and 30.0ml water (copper ion concentration is 0.05mol/L), adds 47.2ml strong aqua (25-28wt%), 0.8gNaOH and 8.3g NaNO successively in room temperature
3, stir the blue solution (ammonia concentration 8.0mol/L, NaOH concentration 0.2mol/L, the NaNO that obtain clear after 30 minutes
3Concentration 1.0mol/L), transfers to then in the stainless steel cauldron of 100ml inner liner polytetrafluoroethylene, be warming up to 140 ℃ of reaction 20h.After reaction finishes, the black product is filtered, water, absolute ethyl alcohol respectively wash 5 times, and 60 ℃ of dry 8h obtain the 0.18g copper oxide catalyst in vacuum drying oven, yield 92.0wt%.The XRD spectra assay products is isometric system CuO for its crystalline structure, and the SEM photo shows that the cupric oxide pattern presents flower-like structure, and its flower-shaped particle size is at 4～5 μ m, and it is 20.5m that the nitrogen adsorption appearance is measured specific surface
2/ g can reach the aperture and be about 36.6nm.
Embodiment five
Take by weighing 2.0gCu (CH
3COO)
2H
2O is dissolved in the mixed solvent of 10.0ml absolute ethyl alcohol and 40.0ml water (copper ion concentration is 0.2mol/L), adds 37.0ml strong aqua (25-28wt%), 3.5gNaOH and 10.4gNH successively in room temperature
4NO
3, stir the blue solution (ammonia concentration 7.0mol/L, naoh concentration 1.0mol/L, the NH that obtain clear after 30 minutes
4NO
3Concentration 1.5mol/L), transfers to then in the stainless steel cauldron of 150ml inner liner polytetrafluoroethylene, be warming up to 120 ℃ of reaction 10h.After reaction finishes, the black product is filtered, water, absolute ethyl alcohol respectively wash 5 times, and 60 ℃ of dry 8h obtain the 0.74g copper oxide catalyst in vacuum drying oven, yield 93.0wt%.The XRD spectra assay products is isometric system CuO for its crystalline structure, and the SEM photo shows that the cupric oxide pattern presents flower-like structure, and its flower-shaped particle size is at 4～5 μ m, and it is 19.5m that the nitrogen adsorption appearance is measured specific surface
2/ g can reach the aperture and be about 37.3nm.
Embodiment six
Take by weighing 10.0gCuSO
45H
2O is dissolved in the mixed solvent of 5.0ml absolute ethyl alcohol and 45.0ml water (copper ion concentration is 0.8mol/L), adds 60.2ml strong aqua (25-28wt%), 9.2gKOH and 20.0g KNO successively in room temperature
3, stir the blue solution (ammonia concentration 9.0mol/L, KOH concentration 1.5mol/L, the KNO that obtain clear after 30 minutes
3Concentration 1.8mol/L), transfers to then in the stainless steel cauldron of 150ml inner liner polytetrafluoroethylene, be warming up to 110 ℃ of reaction 8h.After reaction finishes, the black product is filtered, water, absolute ethyl alcohol respectively wash 5 times, and 60 ℃ of dry 8h obtain the 3.1g copper oxide catalyst in vacuum drying oven, yield 96.0wt%.The XRD spectra assay products is isometric system CuO for its crystalline structure, and the SEM photo shows that the cupric oxide pattern presents flower-like structure, and its flower-shaped particle size is at 5～6 μ m, and it is 19.0m that the nitrogen adsorption appearance is measured specific surface
2/ g can reach the aperture and be about 38.0nm.
Catalytically active assessment
At diameter is in the glass fixed bed of 15mm, adds by silica flour 10g the uniform mixture that the copper oxide catalyst 1g for preparing in zinc powder 0.1g and the foregoing description forms; Be heated to 325 ℃, the methyl chloride after the feeding preheating reacts, and methyl chloride speed is 25mL/min; Reaction 24h; Obtain mix products, calculate, can obtain catalytic activity results's (seeing table 1) such as selectivity and silica flour transformation efficiency of dimethyldichlorosilane(DMCS) through gas chromatographic analysis.
Table 1 copper oxide catalyst catalytically active assessment result
Annotate: (1) M
1: monomethyl trichlorosilane, M
2: dimethyldichlorosilane(DMCS), M
3: tri-methyl-chlorosilane
Wherein, W is the weight of material.
Can be known that by table 1 all 80.0%～85.0%, the silica flour transformation efficiency is 25%～40% to the selectivity of dimethyldichlorosilane(DMCS) for the flower-shaped copper oxide catalyst through method of the present invention preparation, these two important techniques indexs all are better than commercial catalysts.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technical process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technical process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technical process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (8)
1. the preparation method of a flower-shaped copper oxide catalyst may further comprise the steps:
1) mantoquita is joined in the mixed solvent of ethanol, water or alcohol-water forms solution;
2) under agitation in step 1) gained solution, add ammoniacal liquor, highly basic and nitrate salt successively and obtain homogeneous phase solution;
3) with step 2) gained solution transfers to and carries out solvent thermal reaction in the reaction kettle;
4) washing of step 3) products therefrom, drying are obtained flower-shaped copper oxide catalyst.
2. method according to claim 1 is characterized in that, mantoquita described in the step 1) is cupric nitrate, copper sulfate, cupric chloride or neutralized verdigris, or its mixture;
Preferably, copper ion concentration is 0.02mol/L～1.0mol/L in the said solution, preferred 0.08mol/L～1.0mol/L, further preferred 0.2mol/L～0.8mol/L;
Preferably, the alcoholic acid volume percent is 0～100% in the said ethanol-water mixed solvent, preferred 0～56%, further preferred 10%～40%.
3. method according to claim 1 is characterized in that step 2) in used ammoniacal liquor be 25wt%～28wt%; Ammonia concn is 5.0mol/L～10.0mol/L in the said homogeneous phase solution, preferred 6mol/L～8mol/L;
Preferably, highly basic is sodium hydroxide or Pottasium Hydroxide, or its mixture; Said strong base concentrations is 0.1mol/L～2.0mol/L, preferred 0.2mol/L～1.5mol/L, further preferred 0.2mol/L～1.0mol/L;
Preferably, nitrate salt is SODIUMNITRATE, saltpetre or an ammonium nitrate, or its mixture; Said nitrate concentration is 0.5mol/L～2.0mol/L, preferred 0.7mol/L～2.0mol/L, further preferred 1mol/L～1.8mol/L.
4. method according to claim 1 is characterized in that, the solvent thermal reaction temperature described in the step 3) is 80 ℃～160 ℃, and the reaction times is 0.25h～48h; Preferable reaction temperature is 110 ℃～160 ℃, and the reaction times is 8h～48h; Further preferable reaction temperature is 120 ℃～140 ℃, and the reaction times is 10h～20h.
5. method according to claim 1 is characterized in that, reaction kettle described in the step 3) is the stainless steel still.
6. a flower-shaped copper oxide catalyst is characterized in that making according to each described preparation method of claim 1～5.
7. the purposes of flower-shaped copper oxide catalyst according to claim 6 is characterized in that, described flower-shaped copper oxide catalyst is used for the synthesizing organosilicon monomer field.
8. purposes according to claim 7 is characterized in that, said flower-shaped copper oxide catalyst is used for the synthesization of dimethyl dichlorosilane.
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| CN102786075A (en) * | 2012-07-18 | 2012-11-21 | 西安交通大学 | Preparation method of flower-like nanometer copper oxide powder |
| CN103265062A (en) * | 2013-06-07 | 2013-08-28 | 南京信息工程大学 | Method for preparing flower-shaped copper oxide nanometer photocatalyst |
| CN103272599A (en) * | 2013-06-20 | 2013-09-04 | 南京信息工程大学 | Preparation method of 3D flower-like copper oxide nanometer photocatalyst |
| CN103762349A (en) * | 2014-01-26 | 2014-04-30 | 长沙矿冶研究院有限责任公司 | CuO/Cu nanowire negative electrode material in core-shell structure and preparation method and application thereof |
| 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 |
| CN103920493A (en) * | 2014-04-16 | 2014-07-16 | 河北工程大学 | Preparation method of hollow copper oxide catalyst for synthesizing methyl chlorosilane |
| CN104181068A (en) * | 2014-07-21 | 2014-12-03 | 中国科学院理化技术研究所 | Copper-oxide-decorated quartz crystal microbalance sensor having opposite response signals for hydrogen cyanide gas and water vapor |
| CN105731517A (en) * | 2016-01-15 | 2016-07-06 | 电子科技大学 | Flower-shaped copper oxide nanostructure material and preparation method thereof |
| CN108906049A (en) * | 2018-06-25 | 2018-11-30 | 山东京博石油化工有限公司 | The preparation method and photoelectrocatalysis of flower-shaped copper oxide restore CO2Method |
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| CN112499662A (en) * | 2020-11-13 | 2021-03-16 | 安徽清水湖新材料技术有限公司 | Copper oxide nano material and preparation method thereof |
| CN115490258A (en) * | 2021-06-18 | 2022-12-20 | 中国科学院大连化学物理研究所 | Copper oxide nanosheet catalyst, preparation method and application in electrocatalytic reduction of carbon dioxide and carbon monoxide |
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2011
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| MOHAMMAD VASEEM ET AL.: "Low-Temperature Synthesis of Flower-Shaped CuO Nanostructures by Solution Process:Formation Mechanism and Structural Properties", 《J. PHYS. CHEM. C》 * |
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| CN102786075B (en) * | 2012-07-18 | 2014-05-28 | 西安交通大学 | Preparation method of flower-like nanometer copper oxide powder |
| CN103265062A (en) * | 2013-06-07 | 2013-08-28 | 南京信息工程大学 | Method for preparing flower-shaped copper oxide nanometer photocatalyst |
| CN103272599A (en) * | 2013-06-20 | 2013-09-04 | 南京信息工程大学 | Preparation method of 3D flower-like copper oxide nanometer 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 |
| CN103771485B (en) * | 2014-01-21 | 2016-01-06 | 中国计量学院 | A kind of controllable method for preparing of cupric oxide three-dimensional manometer self-assembly |
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| CN103920493B (en) * | 2014-04-16 | 2015-09-23 | 河北工程大学 | A kind of preparation method of the hollow copper oxide catalyst for the synthesis of methylchlorosilane |
| CN103920493A (en) * | 2014-04-16 | 2014-07-16 | 河北工程大学 | Preparation method of hollow copper oxide catalyst for synthesizing methyl chlorosilane |
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| CN108906049A (en) * | 2018-06-25 | 2018-11-30 | 山东京博石油化工有限公司 | The preparation method and photoelectrocatalysis of flower-shaped copper oxide restore CO2Method |
| 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 |
| CN112499662A (en) * | 2020-11-13 | 2021-03-16 | 安徽清水湖新材料技术有限公司 | Copper oxide nano material and preparation method thereof |
| CN115490258A (en) * | 2021-06-18 | 2022-12-20 | 中国科学院大连化学物理研究所 | Copper oxide nanosheet catalyst, preparation method and application in electrocatalytic reduction of carbon dioxide and carbon monoxide |
| CN115490258B (en) * | 2021-06-18 | 2024-02-23 | 中国科学院大连化学物理研究所 | Copper oxide nano-sheet catalyst, preparation method and application thereof in electrocatalytic reduction of carbon dioxide and carbon monoxide |
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