CN100532270C - Nano crystal constructed porous copper oxide aggregate and its preparing method - Google Patents
Nano crystal constructed porous copper oxide aggregate and its preparing method Download PDFInfo
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- CN100532270C CN100532270C CNB2006100538946A CN200610053894A CN100532270C CN 100532270 C CN100532270 C CN 100532270C CN B2006100538946 A CNB2006100538946 A CN B2006100538946A CN 200610053894 A CN200610053894 A CN 200610053894A CN 100532270 C CN100532270 C CN 100532270C
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Abstract
The invention discloses a porous copper oxide aggregate composed of nano crystals and the preparing method thereof, using bivalent copper ion water solution to react wih oxalic acid radical-containing water solution, firstly preparing cake micron spheroidic copper oxalate aggregate, then burning the synthesized copper oxalate aggregate on control process condtions, and obtaining monodisperse, high-specific surface area, porous coppoer oxide aggregate composed of nano crystals. And it can retain reacting activity of nano grains and avoid their aggregation, and the channel surface is formed by those of nano grains. As a catalyst, it is convenient to recovery and recycle. And the method is simple and convenient, controllable, low-cost and easy to implement scale industrialized production.
Description
Technical field
The present invention relates to transition metal oxide nano-material and transition metal oxide porous material technology of preparing, relate in particular to a kind of nano crystal constructed porous copper oxide aggregate and preparation method.
Background technology
Cupric oxide is a kind of important transition metal oxide, has multiple catalytic activity, be widely used in fields such as printing and dyeing, medicine, national defense industry, in multiple catalyzed reactions such as oxidation, hydrogenation, CO, solid rocket propellant, hydrocarbon combustion and fine chemistry industry be synthetic, be widely used, at C
1Chemosynthesis, NO
xFields such as reduction and gas sensitive, lithium ion battery, field emission device, oxygen electrode catalysis also demonstrate good prospects for application.Nano cupric oxide has advantages of high catalytic activity because the singularity of its structure shows the characteristic and the function that make new advances as nano cupric oxide catalytic decomposition hydrogen peroxide; Nano cupric oxide has better high power charging-discharging ability and cycle performance as the hydrogen-bearing alloy electrode of additive preparation; In three TMOS building-up reactionss, show higher activity and selectivity; As the burningrate catalyst of solid rocket propellant, not only can obviously improve the combustion speed of homogeneous propellant, reduce the pressure index, and the AP compositepropellent is also had preferably catalytic effect etc.But because the high reactivity of oxide-based nanomaterial, make in its preparation and application process bad dispersibility, reunion etc. easily.
In recent years, metal oxide with vesicular structure has caused people's very big concern, nano particle is assembled into the porous mass that has certain pore passage structure, the reactive behavior that then both can keep nano particle, avoided the reunion of nano particle again, the surface, duct is then formed by the surface of nano particle, has very high reaction and catalytic activity.Moreover, as sorbent material or catalyzer,, be convenient to recovery and reuse because this class material itself is to have good mechanical strength, help reducing cost and eliminate the secondary pollution problem.
When the procatalyst cupric oxide, the preparation method of universal method is carried on (as porous alumina, porous silicon, polymeric adsorbent etc.) on the porous support with the cupric oxide fine powder.It is the different preparation methods of the loaded copper oxide catalyst of matrix with the porous material that US2004030163, JP2002191978, CN1562472 disclose respectively.Document (1) Journal of Colloid and Interface Science 226,2000,189 reach (2) Joural ofMaterials Science Letters, 2000, in 19,1073, employing HPMC such as Nathalie Jongen are additive, prepare block cupric oxalate, the cupric oxide specific surface that obtains by calcining only is 47.5m
2/ g.Among document (3) the nature material 2003,2,386, DOMINIC etc. have prepared the macropore cupric oxide for the profound glucosides in the water-soluble right side under the room temperature is a soft template.It is the method that template prepares oxide compounds such as cupric oxide that US5881353 discloses with foamed resin.In addition, among document (4) Langmuir 2006,22,3332, Zhou J F, Zhou MF, Caruso RA. proposition as soft template, is adopted the Prepared by Sol Gel Method porous metal oxide with agar.Document (5) Chem.Mater.2006, in 18,1443, Smatt J.H, Weidenthaler C, et.al at first prepare porous silica, are that template prepares porous metal oxide again with the porous silica.
Report or disclosed method in, comparatively speaking, industrialization cost height, complex process, and process be difficult to control, gained metal oxide specific surface is not high, moreover use soft, hard template is easy to cause the pollution to product.Have than high-ratio surface, single dispersion, do not see as yet that by nano crystal constructed micron spheroid porous copper oxide report is arranged.
Summary of the invention
The object of the present invention is to provide a kind of nano crystal constructed porous copper oxide aggregate and the preparation method of single dispersion, high-ratio surface.
The technical solution adopted for the present invention to solve the technical problems is:
One, a kind of nano crystal constructed porous copper oxide aggregate
Be to assemble the vesicular structure pie micron oblate spheroid that is built into by nanocrystalline cupric oxide.
The diameter of described vesicular structure micron oblate spheroid is the 1-4 micron, and the nanocrystalline copper oxide particle that forms vesicular structure micron oblate spheroid is of a size of the 50-100 nanometer, and surface apertures is the 50-200 nanometer, and specific surface area is 150～300m
2/ g.
Two, a kind of preparation method of nano crystal constructed porous copper oxide aggregate
Carry out chemical reaction with the aqueous solution that contains bivalent cupric ion and the aqueous solution that contains oxalate, at first prepare pie micron oblate spheroid cupric oxalate aggregate, then synthetic cupric oxalate aggregate is calcined under the CONTROL PROCESS condition, obtained high-specific surface area by nano crystal constructed porous copper oxide congeries.
Cupric ion and oxalate concentration are 0.02～0.20mol/L in the aqueous solution when relating to synthesis of oxalic acid copper aggregate, and their amount of substance compares nC
2O
4 2-: nCu
2+Be 1.25～0.80:1, temperature of reaction is controlled at 5 ℃ to 60 ℃, reaction times 15～60min; Relate to the processing condition that the cupric oxalate aggregate is sintered into porous copper oxide: temperature rise rate is 2～10 ℃/min, and calcining temperature is 300～400 ℃, calcination time 4～8h.
The described oxalate aqueous solution is formed by oxalic acid or water-soluble oxalate, and described water-soluble oxalate is the oxalate of potassium, sodium or ammonium.
The described bivalent cupric ion aqueous solution is formed by water soluble bivalent nantokite, and described water-soluble mantoquita is copper sulfate, neutralized verdigris, cupric nitrate or cupric chloride.
The calcining manners that is adopted is a programmed temperature method.
The beneficial effect that the present invention has is: by the ionic deposition of oxalate and mantoquita, it is good to synthesize crystallinity in the aqueous solution, monodispersed, nanocrystalline accumulative spheroid cupric oxalate particle.And with the gained cupric oxalate be presoma pass through the calcining, make the porous copper oxide that spheroid sodium rice crystalline substance is constructed.Method is easy, and is controlled, with low cost, is easy to realize large-scale industrial production.
The outstanding advantage of this material is by this copper oxide material both can to have kept the reactive behavior of nano particle by nano crystal constructed, has avoided the reunion of nano particle again, and the surface, duct is then formed by the surface of nano particle, can improve the reaction and the catalytic activity of material.If as catalyzer,, be convenient to recovery and reuse because this class material itself is to have good mechanical strength.
Description of drawings
Fig. 1 is the stereoscan photograph of single dispersion of obtaining after the presoma calcining, nano crystal constructed porous copper oxide aggregate by the cupric oxalate of different Cu source (cupric chloride, copper sulfate, cupric nitrate or venus crystals) and oxalate (sodium oxalate, potassium oxalate, ammonium oxalate or oxalic acid) preparation for the present invention.
The cupric oxalate that Fig. 2 is made by the different Cu source for the present invention is the XRD figure spectrum that presoma is calcined the cupric oxide that obtains.X-coordinate is 2 θ, unit be (°) degree.Ordinate zou is an intensity, and unit is a.u. (absolute units).
Embodiment
The present invention prepares single dispersion, spheroid porous copper oxide technology is as follows:
Contain in the aqueous solution of oxalate, add the copper ions aqueous solution under controlled temperature, the ion deposition reaction takes place in cupric ion and oxalate in this solution system, generates spheroid cupric oxalate aggregate, with the feed liquid filter dehydration, and the dry cupric oxalate presoma that gets.The gained cupric oxalate is warming up under a certain temperature condition calcining a few hours with certain temperature rise rate, promptly gets product.
In above-mentioned chemical reaction system, the concentration of oxalate and cupric ion is 0.02～0.2mol/L, and oxalate is 1.25～0.80:1 with the amount of substance ratio of cupric ion, and the solution chemistry temperature of reaction is controlled at 5～60 ℃, 15～60 minutes reaction times.Temperature rise rate is controlled at 2～10 ℃/min during calcining, and calcining temperature is controlled at 300～400 ℃.Calcination time is controlled at 4～8h and is advisable with the height of employing calcining temperature.
Embodiment 1:
50g copper sulfate is dissolved in the 10L water, in addition with the 29g Potassium Oxalate Solution in same volume ponding; With the copper-bath under the Potassium Oxalate Solution adding stirring, temperature of reaction is 5-10 ℃; React 60min under this temperature, and ageing 2h, take out feed liquid, dehydration then, products therefrom 80 ℃ of dryings 5 hours in air obtain spheroid cupric oxalate powder.
The cupric oxalate presoma that drying is good is positioned in the retort furnace, is warming up to 400 ℃ with the speed of 5 ℃/min, insulation 4h, and the back slowly cools to room temperature with furnace temperature then, obtains nano crystal constructed porous copper oxide powder of the present invention.
Adopt Thermo NORAN VANTAGE EIS type X～ray energy dispersive spectrometry (EDS) to carry out energy spectrum analysis, determine that it consists of CuO; Adopt X-ray diffraction to characterize product structure with the full-automatic diffractometer of X pert MPD Philips (CuK α radiation), its XRD test result as shown in Figure 1, product is the single monocline phase of crystalline phase CuO, and the SEM photo adopts Hitachi S-4700 field emission scanning electron microscope to record.With He is carrier gas, adopts Micromeritics Tristar3000 type specific surface determinator to carry out low temperature N
2The test of absorption～desorption utilizes the specific surface of adsorption isothermal line with BET method calculation sample.
The cupric oxide powder analytical results that obtains is as follows: the SEM photo (sees that accompanying drawing 1a～c) shows that the porous copper oxide particle is that oblate spheroid shape, the surface particle of monodispersed 1-4 micron is about the 50-80 nanometer, surface apertures 50～200 nanometers, XRD analysis is pure cupric oxide (seeing accompanying drawing 2A), and specific surface reaches 295m
2/ g.
Embodiment 2:
The solubility oxalate adopts ammonium oxalate, presses n ((NH
4)
2C
2O
4): n (CuSO
4))=ratio of 1:1 is reinforced, and ammonium oxalate and copper sulfate materials amount are respectively 128g and 200g, and temperature of reaction is 20～30 ℃, reaction 30min; Speed with 2 ℃/min during calcining is warming up to 300 ℃ of calcining presomas, and insulation 8h, and other is implemented as method same among the embodiment 1.
The porous copper oxide material analysis result who obtains is close with embodiment 1.
Embodiment 3:
The solubility oxalate adopts sodium oxalate, presses n (Na
2C
2O
4): n (CuSO
4The ratio of)=1.25:1 is reinforced, and sodium oxalate and copper sulfate materials amount are respectively 335g and 500g, and in the sodium oxalate solution under the adding of 10L copper-bath is stirred, temperature of reaction is 50～60 ℃, reaction 15min; Speed with 10 ℃/min is warming up to 350 ℃ of calcining presomas, and insulation 6h, and other is implemented as method same among the embodiment 1.
The porous copper oxide material analysis result who obtains is close with embodiment 1.
Embodiment 4:
The 68g cupric chloride is dissolved in the 10L water, and in same volume ponding, with the Cupric Chloride Solution under the oxalic acid solution adding stirring, temperature of reaction is 20～30 ℃, reaction 30min with the 50g oxalic acid solution for other.Speed with 2 ℃/min during calcining is warming up to 300 ℃ of calcining presomas, and other is implemented as method same among the embodiment 1 to be incubated 8h.
The cupric oxide powder analytical results that obtains is as follows: the SEM photo (sees that accompanying drawing 1d～f) demonstration porous copper oxide particle is monodispersed, spherical, the surface particle of 1-4 micron are about the 50-100 nanometer, surface apertures is 50～130nm, XRD (seeing accompanying drawing 2B) analyzes and is pure cupric oxide phase, and specific surface reaches 165m
2/ g.
Embodiment 5:
The solubility oxalate adopts ammonium oxalate, presses n (C
2O
4 2-): n (Cu
2+The ratio of)=0.80:1 is reinforced, and the 50g ammonium oxalate fully is dissolved in the 10L water, and the aqueous solution that 10L is contained the 68g cupric chloride adds in the ammonium oxalate solution under the magnetic agitation, and temperature of reaction is 5～10 ℃, reaction 60min.Speed with 10 ℃/min during calcining is warming up to 400 ℃ of calcining presomas, and insulation 4h.Other is implemented as method same among the embodiment 1.
The porous copper oxide material analysis result who obtains is close with embodiment 4.
Embodiment 6:
85g cupric chloride and 100g potassium oxalate are dissolved in respectively in the 10L water, are under 50～60 ℃ the condition in temperature with Potassium Oxalate Solution, add to stir Cupric Chloride Solution down and react 15min.Speed with 2 ℃/min during calcining is warming up to 350 ℃ of calcining presomas, and insulation 6h.Other is implemented as method same among the embodiment 1.
The porous copper oxide material analysis result who obtains is close with embodiment 4.
Embodiment 7:
The 87g sodium oxalate solution adds the 121g cupric nitrate in the equal volume aqueous solution in 10L water, the two thorough mixing under the magnetic agitation, and temperature of reaction is 20～30 ℃, reaction 30min.Speed with 5 ℃/min during calcining is warming up to 400 ℃ of calcining presomas, and insulation 4h.Other is implemented as method same among the embodiment 1.
The porous copper oxide material analysis result who obtains is close with embodiment 4.
Embodiment 8:
The 120g venus crystals is dissolved in the 10L water, in addition with the 110g Potassium Oxalate Solution in same volume ponding, oxalic acid solution is added venus crystals solution under the magnetic agitation, temperature of reaction is 20-30 ℃, reaction 30min.Speed with 5 ℃/min during calcining is warming up to 300 ℃ of calcining presomas, and insulation 8h.Other is implemented as method same among the embodiment 1.
The cupric oxide powder analytical results that obtains is as follows: the SEM photo (sees that accompanying drawing 1g～i) demonstration porous copper oxide particle is monodispersed, the oblate spheroid shape of 1-3 micron, surface particle are about about the 50-70 nanometer, surface apertures is 50～120 nanometers, XRD (seeing accompanying drawing 2C) analyzes and is pure cupric oxide, and specific surface reaches 195m
2/ g.
Embodiment 9:
Earlier the 120g venus crystals is dissolved in the 10L water, the aqueous solution 10L that will contain oxalic acid 76g again adds continuously and stirs in the venus crystals solution down, and temperature of reaction maintains 50～60 ℃, reacts 20min.Speed with 2 ℃/min during calcining is warming up to 400 ℃ of calcining presomas, and insulation 6h.Other is implemented as method same among the embodiment 1.
The porous copper oxide material analysis result who obtains is close with embodiment 8.
Claims (4)
1. a nano crystal constructed porous copper oxide aggregate is characterized in that: be to assemble the vesicular structure pie micron oblate spheroid that is built into by nanocrystalline cupric oxide; The diameter of described vesicular structure pie micron oblate spheroid is the 1-4 micron, and the nanocrystalline copper oxide particle that forms vesicular structure pie micron oblate spheroid is of a size of the 50-100 nanometer, and surface apertures is the 50-200 nanometer, and specific surface area is 150～300m
2/ g.
2. the preparation method of the described nano crystal constructed porous copper oxide aggregate of a claim 1, it is characterized in that: carry out chemical reaction with the aqueous solution that contains bivalent cupric ion and the aqueous solution that contains oxalate, at first prepare pie micron oblate spheroid cupric oxalate aggregate, then synthetic cupric oxalate aggregate is calcined under the CONTROL PROCESS condition, obtained high-specific surface area by nano crystal constructed porous copper oxide aggregate; Wherein, cupric ion and oxalate concentration are 0.02～0.20mol/L in the aqueous solution during synthesis of oxalic acid copper aggregate, and their amount of substance compares nC
2O
4 2-: nCu
2+Be 1.25～0.80:1, temperature of reaction is controlled at 5 ℃ to 60 ℃, reaction times 15～60min; Relate to the processing condition that the cupric oxalate aggregate is sintered into porous copper oxide: temperature rise rate is 2～10 ℃/min, and calcining temperature is 300～400 ℃, calcination time 4～8h.
3. preparation method according to claim 2 is characterized in that: the described aqueous solution that contains oxalate is formed by oxalic acid or water-soluble oxalate, and described water-soluble oxalate is the oxalate of potassium, sodium or ammonium.
4. preparation method according to claim 2 is characterized in that: the described aqueous solution that contains bivalent cupric ion is formed by water soluble bivalent nantokite, and described water soluble bivalent nantokite is copper sulfate, neutralized verdigris, cupric nitrate or cupric chloride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102633622B (en) * | 2012-03-29 | 2014-01-15 | 山东大学 | Rodlike hydrous cupric oxalate serving as lithium ion battery cathode material and preparation method for same |
| CN102659558B (en) * | 2012-04-24 | 2014-03-19 | 山东大学 | Rodlike water containing binary oxalate for negative pole material of lithium ion battery and application thereof |
| CN104495907A (en) * | 2014-11-28 | 2015-04-08 | 夏正付 | Method for producing ultrafine cuprous oxide by microwave calcination of copper oxalate |
| CN105776311B (en) * | 2016-05-23 | 2017-10-31 | 渤海大学 | A kind of preparation method of copper oxide nano material |
| CN106115763B (en) * | 2016-06-29 | 2017-09-12 | 渤海大学 | A kind of preparation method of the spherical hierarchical organization material of cupric oxide |
| CN106098411B (en) * | 2016-06-29 | 2019-04-09 | 渤海大学 | A kind of preparation method of nickel oxide hierarchical organization material |
| CN107056565B (en) * | 2016-12-09 | 2020-07-21 | 湖北航天化学技术研究所 | Pressure index regulator of solid propellant |
| CN106745180A (en) * | 2017-03-07 | 2017-05-31 | 扬州大学 | A kind of cupric oxide electrode material of porous nanometer structure, preparation method and applications |
| CN113618075A (en) * | 2021-08-23 | 2021-11-09 | 孙珲 | Preparation method of filling high-purity nano material of ultralow-resistivity conductive paste |
| CN114487033A (en) * | 2021-12-15 | 2022-05-13 | 天津师范大学 | Preparation method of hollow spherical CuO nano material for dimethyl benzene gas detection |
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