CN102502770B - 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 synthesis organosilane monomer field.
Background technology
As a class p-type transition metal oxide, cupric oxide shows peculiar physics and chemistry performance in fields such as electricity, magnetic and catalysis, causes people's extensive concern, is widely used in the key areas such as printing and dyeing, pottery, electrode active material and catalyzer.The physics and chemistry performance of cupric oxide is subject to pattern, size and structure influence.In recent years, the copper oxide material with different-shape structure causes people's very big interest, by different methods, has prepared cupric oxide nano line, nanometer rod, nanometer sheet, nanotube, nano belt etc.Some more complicated structures also have relevant report as flower-shaped, cellular, hollow ball etc.Wherein, flower-shaped cupric oxide has the features such as high-ratio surface, low bulk density, how active crystal face position because of it, at catalytic field, have huge application prospect.Therefore, the synthetic extensive concern that causes people of flower-shaped cupric oxide.
The people such as Chu first prepare the mixing solutions of ammonium sulfate, sodium hydroxide and trace Sodium orthomolybdate (sodium wolframate) and sodium lauryl sulphate composition, then Copper Foil are immersed in above-mentioned solution and utilize hydrothermal oxidization reaction to obtain by the flower-shaped or cellular CuO film material (Liu.Y. forming at copper foil surface; Chu.Y.; Zhuo.Y.; LiM.; Li.M.; Dong.L.Cryst.Growth Des.2007,7,467.).
The people such as Vaseem be take neutralized verdigris as raw material, and the vulkacit H of take under alkaline condition has been prepared flower-shaped cupric oxide (Vaseem.M. by liquid phase reaction as template; Umar.A.; Kim.S.H.; Hahn.Y.B.J.Phys.Chem.C.2008,112,5729).
The people such as Li be take cupric chloride as raw material, use ionic liquid 1-octyl group-3-Methylimidazole trifluoroacetate as solvent and template, under alkaline condition, by microwave heating, are reacted and have been obtained flower-shaped and leaf shape cupric oxide (Xia.J.; Li.H.; Luo, Z.; Shi.L.; Wang.K.; Shu.H.; Yan.Y.J.Phys.Chem.Solids.2009,70,1461.).
From above-mentioned flower-shaped cupric oxide preparation method's report, can find out, in preparation process, generally will use expensive organism as template, its defect is that cost is higher, is unfavorable for large-scale production.
In addition, about flower-shaped cupric oxide, at the applied research report of catalytic field, be also only limited to liquid-solid phase catalyzed reaction, as the oxidizing reaction of photocatalytic degradation of dye or organism alcohols, and equate that for gas-solid heterogeneous catalytic reaction yet there are no relevant report as the applied research of industrial direct synthesis organosilane monomer, especially in the building-up process of organosilane monomer, reaction between reactant methyl chloride gas and silica flour belongs to vapor solid contact reacts, thereby this just requires can fully contact fast reaction speed between catalyzer and 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 improving catalyst efficiency.In sum, carry out the research of the flower-shaped cupric oxide preparation method with industrialization prospect, and explore flower-shaped cupric oxide and in the applied research of direct synthesis organosilane monomer, there is important scientific meaning and using value as catalyzer.
Summary of the invention
For the deficiencies in the prior art, one of object of the present invention is to provide a kind of pattern and particle size is controlled, technique simple, be easy to the industrialized preparation method without the synthetic flower-shaped cupric oxide of template, and its catalytic performance of evaluating catalyst using prepared cupric oxide as direct synthesis organosilane monomer, finally by the invention provides the catalyzer of a kind of novel organosilicon monomer that has an application prospect in synthetic.
The preparation method of flower-shaped copper oxide catalyst provided by the present invention, comprises the following steps:
1) mantoquita is joined in the mixed solvent of ethanol, water or alcohol-water and form solution;
2) under agitation to step 1) add successively ammoniacal liquor, highly basic and nitrate to obtain homogeneous phase solution in gained solution;
3) by step 2) gained solution transfers to and in reactor, carries out solvent thermal reaction;
4) by step 3) products therefrom washing, dryly obtain flower-shaped copper oxide catalyst.
Wherein, step 1) described in, mantoquita is cupric nitrate, copper sulfate, cupric chloride or neutralized verdigris, or its mixture.
As preferably, in described solution, copper ion concentration is 0.02mol/L～1.0mol/L, preferred 0.08mol/L～1.0mol/L, further preferred 0.2mol/L～0.8mol/L.
As preferably, in described ethanol-water mixed solvent, the volume percent of ethanol is 0～100%, preferably 0～56%, further preferably 10%～40%.
Step 2) in, ammoniacal liquor used is 25wt%～28wt%; In described homogeneous phase solution, ammonia concn is 5.0mol/L～10.0mol/L, preferably 6mol/L～8mol/L.
As preferably, highly basic is sodium hydroxide or potassium hydroxide, or its mixture; Described 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 is SODIUMNITRATE, saltpetre or ammonium nitrate, or its mixture; Described 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 good circulation ratio, copper ion concentration, ethanol volume percent, ammonia concn, highly basic and concentration, nitrate and concentration thereof have been provided to as above preferred scope.
Step 3) the solvent thermal reaction temperature described in 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, step 3) described in, reactor is stainless steel still.The temperature and time of solvent thermal reaction has larger impact for shape, the size of final products therefrom.The present invention, through a large amount of experimental exploring, has determined this preparation method's suitable temperature of reaction and the reaction times, has obtained having the flower-shaped copper oxide catalyst of excellent properties.
One of object of the present invention is also to provide the flower-shaped copper oxide catalyst of preparing according to method provided by the present invention.
One of object of the present invention is also to provide the flower-shaped copper oxide catalyst prepared according to method provided by the present invention application, the particularly application in synthesization of dimethyl dichlorosilane in synthesizing organosilicon monomer field.
Flower-shaped cupric oxide preparation method's provided by the present invention advantage is:
1) the present invention has realized in solvent thermal process and has not added organic formwork agent to obtain flower-shaped cupric oxide, for 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 reactor, without any complex apparatus, is a kind of simple and effective, cheap, environmental friendliness, is easy to the preparation method of the synthetic flower-shaped cupric oxide of preparation of mass-producing.
3) the present invention is by regulating concentration, temperature of reaction and the reaction times of solvent composition, ammonia concn, alkali and inorganic salt to regulate and control pattern, structure and the particle size of cupric oxide, and control condition and means are easy to implement, and it is synthetic to be beneficial to industrialization.
The flower-shaped copper oxide particle size homogeneous that utilizes present method to make, size is controlled, has higher specific surface.Catalytically active assessment result shows simultaneously, and the flower-shaped cupric oxide that the present invention is prepared, in the reaction of direct synthesis organosilane monomer, shows the selectivity of higher dimethyldichlorosilane(DMCS) and the transformation efficiency of reactant silica flour.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the black product that obtains of embodiment 1.
Fig. 2 is the SEM figure of the cupric oxide that obtains of embodiment 1.
Fig. 3 is the TEM figure of the cupric oxide that obtains of embodiment 1.
Fig. 4 is nitrogen adsorption/desorption isotherm figure of the flower-shaped cupric oxide of black that obtains of embodiment 1.
Fig. 5 is the graph of pore diameter distribution of the flower-shaped cupric oxide of black that obtains of embodiment 1.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only, for helping to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment mono-
Take 1.0gCu (NO
3)
23H
2o is dissolved in (copper ion concentration is 0.08mol/L) in 50.0ml dehydrated alcohol, in room temperature, adds successively 30.0ml strong aqua (commercially available massfraction is 25-28wt%), 0.4gNaOH and 5.0gNaNO
3, stir the blue solution (ammonia concentration 6.2mol/L, NaOH concentration 0.1mol/L, the NaNO that after 30 minutes, obtain clear
3concentration 0.7mol/L), then transfer in the stainless steel cauldron of 150ml inner liner polytetrafluoroethylene, be warming up to 130 ℃ of reaction 18h.After reaction finishes, black product is filtered, water, dehydrated alcohol respectively wash 5 times, and in vacuum drying oven, 60 ℃ of dry 8h, obtain 0.3g copper oxide catalyst, yield 90.9wt%.
On the X ' Pert PRO MPD type Multi-functional X ray diffractometer that the copper oxide catalyzation agent material of above-mentioned preparation is produced in Dutch Panalytical company (PANalytical), carry out XRD test.Fig. 1 is the XRD spectra of the black product that obtains of embodiment 1, wherein 2 θ are respectively 35.7 ° and 39.0 ° of characteristic diffraction peaks that the diffraction peak of locating is cupric oxide, according to standard powdery diffractometry card (JCPDS No.05-0667), its crystalline structure is isometric system.
The JSM6700 model field emission scanning electron microscope observation surface topography that the copper oxide catalyzation agent material of above-mentioned preparation is produced in NEC company.Fig. 2 is the SEM figure of the cupric oxide that obtains of embodiment 1, and cupric oxide pattern presents flower-like structure as seen from the figure, 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 NEC company.Fig. 3 is the TEM figure of the cupric oxide that obtains of embodiment 1, and flower-shaped cupric oxide is assembled by the nanometer sheet of wide 50～150nm as seen from the figure.
The specific surface of the NOVA3200e model that the copper oxide catalyzation agent material of above-mentioned preparation is produced in U.S. Kang Ta company and lacunarity analysis instrument test specific surface and pore size distribution.Figure 4 and 5 are respectively 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 thermoisopleth at relative dividing potential drop approximately 0.8 place flower-shaped copper oxide material has the secondary vesicular structure that particle packing forms, and BET specific surface is 23.2m
2/ g, can and aperture be about 33.1nm.
Embodiment bis-
Take 0.2gCu (NO
3)
23H
2o is dissolved in the mixed solvent of 28.0ml dehydrated alcohol and 22.0ml water (copper ion concentration is 0.02mol/L), in room temperature, adds successively 22.0ml strong aqua (25-28wt%), 0.3gNaOH and 2.8g NaNO
3, stir the blue solution (ammonia concentration 5.0mol/L, NaOH concentration 0.1mol/L, the NaNO that after 30 minutes, obtain clear
3concentration 0.5mol/L), then transfer in the stainless steel cauldron of 150ml inner liner polytetrafluoroethylene, be warming up to 80 ℃ of reaction 48h.After reaction finishes, black product is filtered, water, dehydrated alcohol respectively wash 5 times, and in vacuum drying oven, 60 ℃ of dry 8h, obtain 0.05g copper oxide catalyst, yield 91.0wt%.XRD spectra assay products for its crystalline structure be isometric system CuO, SEM photo shows that cupric oxide pattern presents flower-like structure, its flower-shaped particle size is at 3～5 μ m, it is 22.5m that nitrogen adsorption instrument is measured specific surface
2/ g, can and aperture be about 35.2nm.
Embodiment tri-
Take 12.1gCu (NO
3)
23H
2o is dissolved in the mixed solvent of 2.5ml dehydrated alcohol and 47.5ml water (copper ion concentration is 1.0mol/L), in room temperature, adds successively 77.2ml strong aqua (25-28wt%), 10.2gNaOH and 21.6gNaNO
3stir the blue solution (ammonia concentration 10.0mol/L, NaOH concentration 2.0mol/L, NaNO3 concentration 2.0mol/L) that obtains clear after 30 minutes, then transfer in the stainless steel cauldron of 150ml inner liner polytetrafluoroethylene, be warming up to 160 ℃ of reaction 0.25h.After reaction finishes, black product is filtered, water, dehydrated alcohol respectively wash 5 times, and in vacuum drying oven, 60 ℃ of dry 8h, obtain 3.8g copper oxide catalyst, yield 95.0wt%.XRD spectra assay products for its crystalline structure be isometric system CuO, SEM photo shows that cupric oxide pattern presents flower-like structure, its flower-shaped particle size is at 5～6 μ m, it is 18.5m that nitrogen adsorption instrument is measured specific surface
2/ g, can and aperture be about 38.5nm.
Embodiment tetra-
Take 0.4gCuCl
22H
2o is dissolved in the mixed solvent of 20.0ml dehydrated alcohol and 30.0ml water (copper ion concentration is 0.05mol/L), in room temperature, adds successively 47.2ml strong aqua (25-28wt%), 0.8gNaOH and 8.3g NaNO
3, stir the blue solution (ammonia concentration 8.0mol/L, NaOH concentration 0.2mol/L, the NaNO that after 30 minutes, obtain clear
3concentration 1.0mol/L), then transfer in the stainless steel cauldron of 100ml inner liner polytetrafluoroethylene, be warming up to 140 ℃ of reaction 20h.After reaction finishes, black product is filtered, water, dehydrated alcohol respectively wash 5 times, and in vacuum drying oven, 60 ℃ of dry 8h, obtain 0.18g copper oxide catalyst, yield 92.0wt%.XRD spectra assay products for its crystalline structure be isometric system CuO, SEM photo shows that cupric oxide pattern presents flower-like structure, its flower-shaped particle size is at 4～5 μ m, it is 20.5m that nitrogen adsorption instrument is measured specific surface
2/ g, can and aperture be about 36.6nm.
Embodiment five
Take 2.0gCu (CH
3cOO)
2h
2o is dissolved in the mixed solvent of 10.0ml dehydrated alcohol and 40.0ml water (copper ion concentration is 0.2mol/L), in room temperature, adds successively 37.0ml strong aqua (25-28wt%), 3.5gNaOH and 10.4gNH
4nO
3, stir the blue solution (ammonia concentration 7.0mol/L, naoh concentration 1.0mol/L, the NH that after 30 minutes, obtain clear
4nO
3concentration 1.5mol/L), then transfer in the stainless steel cauldron of 150ml inner liner polytetrafluoroethylene, be warming up to 120 ℃ of reaction 10h.After reaction finishes, black product is filtered, water, dehydrated alcohol respectively wash 5 times, and in vacuum drying oven, 60 ℃ of dry 8h, obtain 0.74g copper oxide catalyst, yield 93.0wt%.XRD spectra assay products for its crystalline structure be isometric system CuO, SEM photo shows that cupric oxide pattern presents flower-like structure, its flower-shaped particle size is at 4～5 μ m, it is 19.5m that nitrogen adsorption instrument is measured specific surface
2/ g, can and aperture be about 37.3nm.
Embodiment six
Take 10.0gCuSO
45H
2o is dissolved in the mixed solvent of 5.0ml dehydrated alcohol and 45.0ml water (copper ion concentration is 0.8mol/L), in room temperature, adds successively 60.2ml strong aqua (25-28wt%), 9.2gKOH and 20.0g KNO
3, stir the blue solution (ammonia concentration 9.0mol/L, KOH concentration 1.5mol/L, the KNO that after 30 minutes, obtain clear
3concentration 1.8mol/L), then transfer in the stainless steel cauldron of 150ml inner liner polytetrafluoroethylene, be warming up to 110 ℃ of reaction 8h.After reaction finishes, black product is filtered, water, dehydrated alcohol respectively wash 5 times, and in vacuum drying oven, 60 ℃ of dry 8h, obtain 3.1g copper oxide catalyst, yield 96.0wt%.XRD spectra assay products for its crystalline structure be isometric system CuO, SEM photo shows that cupric oxide pattern presents flower-like structure, its flower-shaped particle size is at 5～6 μ m, it is 19.0m that nitrogen adsorption instrument is measured specific surface
2/ g, can and aperture be about 38.0nm.
Catalytically active assessment
In the glass fixed bed that is 15mm at diameter, add by silica flour 10g, the uniform mixture that the copper oxide catalyst 1g preparing in zinc powder 0.1g and above-described embodiment forms, be heated to 325 ℃, the methyl chloride passing into after preheating reacts, and methyl chloride speed is 25mL/min, reaction 24h, obtain mix products, through gas chromatographic analysis, calculate, can obtain the catalytic activity results (in Table 1) such as the selectivity of dimethyldichlorosilane(DMCS) and silica flour transformation efficiency.
Table 1 copper oxide catalyst catalytically active assessment result
Note: (1) M
1: monomethyl trichlorosilane, M
2: dimethyldichlorosilane(DMCS), M
3: tri-methyl-chlorosilane
Wherein, the weight that W is material.
As shown in Table 1, the flower-shaped copper oxide catalyst of preparing by method of the present invention is to the selectivity of dimethyldichlorosilane(DMCS) all 80.0%～85.0%, and silica flour transformation efficiency is 25%～40%, and these two important technical indicators are all better than commercial catalysts.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to the selection of the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (15)
1. a preparation method for flower-shaped copper oxide catalyst, comprises the following steps:
1) mantoquita is joined in the mixed solvent of ethanol, water or alcohol-water and form solution;
Wherein, in solution, copper ion concentration is 0.02mol/L～1.0mol/L;
2) under agitation in step 1) gained solution, add successively ammoniacal liquor, highly basic and nitrate to obtain homogeneous phase solution;
Wherein, in homogeneous phase solution, ammonia concn is 5.0mol/L～10.0mol/L, and strong base concentrations is 0.1mol/L～2.0mol/L, and nitrate concentration is 0.5mol/L～2.0mol/L;
3) by step 2) gained solution transfers to and in reactor, carries out solvent thermal reaction;
Wherein, solvent thermal reaction temperature is 80 ℃～160 ℃, and the reaction times is 0.25h～48h;
4) by step 3) products therefrom washing, dryly obtain flower-shaped copper oxide catalyst.
2. method according to claim 1, is characterized in that, mantoquita described in step 1) is cupric nitrate, copper sulfate, cupric chloride or neutralized verdigris, or its mixture.
3. method according to claim 1 and 2, is characterized in that, described in step 1), in solution, copper ion concentration is 0.08mol/L～1.0mol/L.
4. method according to claim 3, is characterized in that, in described solution, copper ion concentration is 0.2mol/L～0.8mol/L.
5. method according to claim 1 and 2, is characterized in that, described in step 1), in ethanol-water mixed solvent, the volume percent of ethanol is 0～100%.
6. method according to claim 1 and 2, is characterized in that, in described ethanol-water mixed solvent, the volume percent of ethanol is 0～56%.
7. method according to claim 1 and 2, is characterized in that, in described ethanol-water mixed solvent, the volume percent of ethanol is 10%～40%.
8. method according to claim 1, is characterized in that step 2) in ammoniacal liquor used be 25wt%～28wt%; In described homogeneous phase solution, ammonia concn is 6mol/L～8mol/L.
9. according to the method described in claim 1 or 8, it is characterized in that step 2) in highly basic used be sodium hydroxide or potassium hydroxide, or its mixture; Described strong base concentrations is 0.2mol/L～1.5mol/L.
10. method according to claim 9, is characterized in that, described strong base concentrations is 0.2mol/L～1.0mol/L.
11. the method according to described in claim 1 or 8, is characterized in that step 2) middle nitrate is SODIUMNITRATE, saltpetre or ammonium nitrate, or its mixture; Described nitrate concentration is 0.7mol/L～2.0mol/L.
12. methods according to claim 11, is characterized in that, described nitrate concentration is 1mol/L～1.8mol/L.
13. methods according to claim 1, is characterized in that, the solvent thermal reaction temperature described in step 3) is 110 ℃～160 ℃, and the reaction times is 8h～48h.
14. methods according to claim 13, is characterized in that, described solvent thermal reaction temperature is 120 ℃～140 ℃, and the reaction times is 10h～20h.
15. methods according to claim 1, is characterized in that, reactor described in step 3) is stainless steel still.
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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 |
| CN103762349B (en) * | 2014-01-26 | 2016-05-11 | 长沙矿冶研究院有限责任公司 | Nucleocapsid structure CuO/Cu nano wire negative material and its preparation method and application |
| 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 |
| CN104181068B (en) * | 2014-07-21 | 2016-06-01 | 中国科学院理化技术研究所 | Hydrogen cyanide gas and water vapour are had the quartz crystal microbalance sensor that the cupric oxide of contrary response signal is modified |
| CN105731517B (en) * | 2016-01-15 | 2017-06-13 | 电子科技大学 | A kind of cupric oxide flower-like 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 |
| 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 |
| 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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| Low-Temperature Synthesis of Flower-Shaped CuO Nanostructures by Solution Process:Formation Mechanism and Structural Properties;Mohammad Vaseem et al.;《J. Phys. Chem. C》;20080320;第112卷;5729-5735 * |
| Mohammad Vaseem et al..Low-Temperature Synthesis of Flower-Shaped CuO Nanostructures by Solution Process:Formation Mechanism and Structural Properties.《J. Phys. Chem. C》.2008,第112卷5729-5735. |
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