CN102559138B - Fluorine ion and metal ion-doped cerium oxide-based nanometer ultraviolet shielding material and preparation method thereof - Google Patents
Fluorine ion and metal ion-doped cerium oxide-based nanometer ultraviolet shielding material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a fluorine ion and metal ion-doped cerium oxide-based nano ultraviolet shielding material and a preparation method thereof. The fluorine ion and metal ion-doped cerium oxide-based nano ultraviolet shielding material is characterized by having a chemical formula of CexMyOzFw, wherein M is at least one of divalent alkaline-earth metals and non-cerium rare-earth metals, x is not less than 0.8 and is less than 1, y is more than 0 and is not more than 0.2, z is not less than 1.65 and is less than 2, w is more than 0 and is not more than 0.3, and the chemical formula CexMyOzFw meets charge balance. According to the invention, by adopting a nonhazardous carbonate as a precipitator, the fluorine ion and metal ion-doped cerium oxide-based nano ultraviolet shielding material is prepared through the coprecipitation method. The fluorine ion and metal ion-doped cerium oxide-based nano ultraviolet shielding material can be used in materials and products such as textiles, outdoor articles for everyday use, sunscreen cream, rubber, asphalt, glass, coatings in daylight lamps, macromolecule fibers, macromolecule plastics, paintings, and industrial and civil paints with the requirements of high ultraviolet absorption rate, high visible light transmission rate and low oxidization catalytic activity.
Description
Technical field
The invention belongs to the ultraviolet shielded Material Field of nanometer, be specifically related to the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion and metal ion, specifically by while doped with fluorine ion and metal ion in preparation process, cerium oxide is carried out to doping vario-property, obtain the ultraviolet shielded material of excellent performance.
Technical background
The Spectral range of ultraviolet (UV) radiation in solar radiation spectrum is between 400～200nm, its energy accounts for 6% left and right of solar radiation total amount, can be divided into three sections of long wave ultraviolet UVA (400～320nm), ultraviolet B radiation UVB (320～280nm) and short wave ultraviolet UVC (280～200nm).UVC is stopped absorption by ozonosphere, can not arrive ground, and what can arrive ground only has UVA and UVB.In recent years, people more and more find the harm of uv-radiation.Ultraviolet excessive exposure, can cause skin carcinoma.Making earnest efforts the U.S. of light bath, the sickness rate of skin carcinoma is the summation of prostate cancer, mammary cancer, lung cancer and carcinoma of the pancreas.In addition, ultraviolet ray can make the macromolecular chain degraded in plastics, synthetic resins, rubber and synthetic glass, causes material aging; Also can make the weathering resistance variation of paint, make its easy efflorescence, easy to crack, even come off; The even flavescence of paper, become fragile etc. also all relevant with ultraviolet ray.
For to protect mankind skin and various material are not subject to the infringement of ultraviolet radiation, people actively find various ultraviolet light screeners.Ultraviolet light screener can be divided into organic and the large class of mineral-type two by effective constituent.The organic UV light absorber, as benzazoles, benzophenone compounds etc., due to good with the organic polymer material consistency, once be applied to the fields such as daily cosmetics, textiles, rubber, plastics by light is general, but the organic UV light absorber exists, the wavelength of shielding ultraviolet rays is shorter, light stability is poor, have the shortcomings such as toxicity to a certain degree.In recent years, the anti-ultraviolet function of inorganic nanometer powder receives much concern, and has become the focus of current research, and major cause is that inorganic nano ultraviolet screening agent stability is strong, nontoxic, uv-shielding capacity is strong, and visible ray can see through.
The inorganic nanometer powder that can be used as at present ultraviolet light screener has nano-TiO
2, nano-ZnO, nano Ce O
2, nanometer Al
2o
3, nano-MgO etc., wherein applying more is nano-TiO
2, nano-ZnO.But, nano-TiO
2with nano-ZnO, organic materials is had to very strong photocatalytic Degradation, add the degraded that usually causes material in organic materials to, the way that general employing surface coats amorphous silicon or silicon oxide reduces their photocatalytic activity, but on seeing through of ultraviolet absorption and visible ray, affects larger after coating.Therefore, nano-TiO
2with nano-ZnO, in the application aspect ultraviolet shielded material, be greatly limited.Large quantity research shows, nano Ce O
2ultraviolet ray is had to good sorption, and it to the Photocatalytic activity of organic materials far below nano-TiO
2, nano-ZnO, therefore, nano Ce O
2be considered to nano-TiO
2, nano-ZnO substitute, there is potential using value at ultraviolet shielded Material Field.The ultraviolet light screener general requirement has higher uv absorption property and visible light transmissivity, and oxidation catalytic activity and photocatalytic activity are low, and color is light color.
Pure nano Ce O
2it is yellow that powder is, and while being applied in daily cosmetics, textiles, rubber, plastic or other material, may affect material modified primary colours.Cerium dioxide also has higher oxidation catalytic activity, and reason is in the crystalline structure of cerium dioxide, Ce
4+radius
the positive ion critical radius of the cube structure that to be less than ligancy be 8.Therefore, cerium oxide is in the crystalline structure unsure state.Due to Ce
3+/ Ce
4+mutual conversion institute energy requirement not high, be 36.72ev, and
therefore in the fluorite structure of cerium oxide, for stablizing the unsettled crystalline structure of cerium oxide itself, Ce
4+be converted into Ce
3+to stablize the trend of fluorite structure.Therefore, cerium oxide is actually the CeO with non-stoichiometric
2-xoxide form exists.At CeO
2-xfluorite structure in, due to Ce
3+with Ce
4+the valence state difference, make original CeO
2the negative charge surplus has appearred in structure.In order to keep the electric neutrality of whole crystal, CeO
2must some negative oxygen ion in crystal leave its equilibrium theory of tide and transit to beyond crystal, and form the oxygen room to keep the electric neutrality of crystal at crystals.From the above, the cerium dioxide crystal is with non-stoichiometric CeO
2-xoxide form exists has intrinsic point defects (Ce
3+) and the fluorite structure crystal of oxygen vacancy defect, thereby, CeO
2itself there is stronger oxidation catalytic activity.CeO
2oxidation catalytic activity be mainly manifested in separating out of Sauerstoffatom in the cerium oxide crystal and in conjunction with and plane of crystal Ce
3+/ Ce
4+in the oxidation reduction cycle reaction.Sauerstoffatom in the cerium oxide crystal breaks away from crystal, form active very strong high-energy Sauerstoffatom (230.095kJ/mol), the high-energy Sauerstoffatom is unstable, mutually combine and generate low energy (0kJ/mol), stable oxygen, emit energy with its ambient substance of oxidation catalysis simultaneously, thereby shown the oxidation catalytic activity of cerium oxide.Formula (1-1) separates out and combines the expression formula of oxygen for cerium dioxide.
(means the oxygen room)
Therefore, the oxidation catalytic activity of reduction cerium oxide will suppress CeO at all exactly
2in crystal, Sauerstoffatom separates out.
In order to improve these characteristics of cerium oxide, Shinryo Yabe, the people such as Tsugio Sato have reported take sodium hydroxide as precipitation agent, the standby Ca of soft solution legal system
2+or Zn
2+the cerium oxide of doping.Prepared doped cerium oxide powder is white in color, the transmitance of uv-shielding capacity and visible ray increases, photocatalytic activity and oxidation catalytic activity reduce (Shinryo Yabe, Tsugio Sato, " Cerium oxide for sunscreen cosmetics ", Journal of Solid State Chemisty 171 (2003) 7-11).On this basis, Ahmed Mohamed El-Toni, the people such as Shu Yin adopt the crystal seed polymerization technique in doping Ca
2+cerium oxide surface coated silica, the oxidation catalysis of finding prepared cerium oxide further reduces (Ahmed Mohamed El-Toni, Shu Yin, Tsugio Sato, " Synthesis and silica coatiing of calcia-doped ceria/mica nanocomposite by seeded polymeization technique ", Applied Surface Science 252 (2006) 5063-5070).
These two pieces of methods that article is reported, all make the uv-shielding capacity of cerium oxide and catalytic performance obtain improvement to a certain degree, still, and doping Ca
2+or Zn
2+the cerium oxide oxidation catalytic activity still very strong, after its surperficial coated silica, oxidation catalytic activity reduces the reduction but brought uv-shielding capacity and visible light transmissivity.And using sodium hydroxide highly basic is precipitation agent, in finished product, remaining a small amount of sodium makes the use of product have certain potential safety hazard.
L.Sronek, the people such as J.Majimel have studied Ca
2+, F
-the nano-cerium oxide of codoped, powder is white in color, ultraviolet absorption is strengthened, and the high (L.Sronek of transmitance to visible ray, J.Majimel, Y.Kihn, et, " New Highly Divided Ce-Ca-Based Oxyfluorides with UV-Shielding Properties:Study of the Ce
1-xca
xo
2-xand Ce
1-xca
xo
2-x-y/2f
yseries ", Chem.Mater.2007,19,5110-5121).
But, the positively charged ion Ca of doping
2+valence state lower than Ce
4+, for keeping the electric neutrality of cerium oxide crystal, itself also can cause the oxygen room calcium ion of doping, thereby makes oxidation catalytic activity still higher.In addition, it is precipitation agent that preparation process adopts highly basic sodium hydroxide, and the potential safety hazard that product is used still exists, and preparation technology's flow process complexity, and the industrialization expanding production is more difficult.
Summary of the invention
An object of the present invention is to provide that a kind of uv-shielding capacity is superior, visible light transmissivity is high, the cerium oxide-based nanometer ultraviolet shielding material of oxidation catalytic activity doped with fluorine ion and metal ion low the time.
Another object of the present invention is to provide that a kind of uv-shielding capacity is superior, visible light transmissivity is high, the simple and effective preparation method of oxidation catalytic activity cerium oxide-based nanometer ultraviolet shielding material of doped with fluorine ion and metal ion low the time.
For achieving the above object, to propose a kind of chemical constitution be Ce in the present invention
xm
yo
zf
wthe doped with fluorine ion and the ultraviolet shielded material of cerium oxide base of metal ion, wherein M is one or more in divalent alkaline-earth metal or non-Ce rare earth metal, 0.8≤x<1,0<y≤0.2,1.65≤z<2,0<w≤0.3.It can be also 0.85≤x<1,0<y≤0.15,1.75≤z<2,0<w≤0.2.And the method for this material of proposition preparation, by negatively charged ion F
-, divalent alkaline-earth metal or non-Ce rare earth metal positively charged ion altogether in doped ceria, optimization by preparation technology, obtain that particle diameter is controlled, the nano-cerium oxide of doped with fluorine ion and metal ion when size uniform, this material is powder, powder is the cubic fluorite structure, the pattern almost spherical, good dispersity.
Basic ideas of the present invention are: according to electric neutrality principle, the stability of crystalline structure, the CeO of crystalline structure
2the principles such as crystalline structure characteristics, lattice defect chemistry and solid solution characteristic, adopt divalent alkaline-earth metal or non-Ce rare earth metallic cation, negatively charged ion F
-codoped, to stablize the crystalline structure of cerium oxide, reduces Ce in the cerium oxide lattice
4+to Ce
3+conversion, suppress the reaction of formula (1-1) and carry out to the right, thereby reach the purpose of the oxidation catalytic activity that reduces cerium oxide.Alkaline-earth metal ions Sr
2+or Ba
2+valence state is lower than Ce
4+, dopant ion itself also can cause the generation in oxygen room, but Sr during eight-coordinate
2+ 
or Ba
2+ 
radius be greater than Ca
2+ and Ce
3+ 
radius, the oxygen room number caused by dopant ion itself is less than the oxygen room number that it can suppress, thereby can be to a certain extent than Ca
2+more can suppress CeO
2the separating out of oxygen room in crystal, and the negatively charged ion F of doping
-radius and electric charge all are less than O
2-ion, reduce its oxidation catalytic activity to the lattice parameter that increases cerium oxide and also played certain effect.For the non-Ce rare earth metal ion, when ligancy is 8, the trivalent ion radius almost all is greater than Ce
4+radius, and F
-ionic radius is less than O
2-the radius of ion, therefore, doped with being beneficial to the negative ions radius ratio that increases cerium oxide, stablize its crystalline structure, reduces oxidation catalytic activity; Though the trivalent rare earth ions valence state of doping is lower than Ce
4+the oxygen room that can bring equally dopant ion itself to cause, but they belong to lanthanon together, have special 4f electron structure, the hydridization of the 4f electronics after doping hydridization is arranged and can be suppressed the generation in oxygen room, and the production rate in the oxygen room that valence state can be brought drops to minimum; And, because doped with rare-earth elements and Ce elements belong to lanthanon, doped with rare-earth elements is more likely occupying CeO
2ce in lattice
4+case the time also partly enter CeO
2the negative oxygen ion hexahedron gap of lattice, or occupying CeO
2ce in lattice
4+case the time make the Ce be replaced
4+ion enters CeO
2the negative oxygen ion hexahedron gap of lattice, the rare earth element of doping just can not cause the generation in oxygen room like this; To sum up 3 described, simultaneously doped with fluorine ion and non-Ce rare earth metal ion are conducive to reduce the oxidation catalytic activity of cerium oxide.
CeO
2uv absorption property be mainly reflected on its characteristic of semiconductor, CeO
2band-gap energy be 3.1ev (E
g), the energy (λ that to be equivalent to wavelength be the 400nm photon
g=1240/E
g).When energy is equal to or greater than CeO
2the rayed CeO of band-gap energy
2the time, in the electronics (e of valence band
-) will absorb UV-light and be excited on conduction band, and produce corresponding hole (h on valence band
+).At CeO
2in, the compound tense compole of electron-hole pair is short, has little time to move to particle surface and can occur compound, and the form with heat or light discharges by absorbed luminous energy, thereby the photocatalytic activity of cerium oxide is extremely low, and there is good light stability, can continue to absorb UV-light and not be degraded.Negatively charged ion (F
-) and the positively charged ion codoped make CeO
2the electronics of the electronics of the 4f track of middle cerium and the 2p track of oxygen hydridization is again arranged, and has reduced CeO
2band-gap energy, thereby increased CeO
2ultraviolet absorption edge, strengthened its uv absorption property.
The preparation method of a kind of doped with fluorine ion that the present invention proposes and the cerium oxide-based nanometer ultraviolet shielding material of metal ion, concrete steps are as follows:
Step 1: cerium solution is mixed by the stoichiometric ratio proportioning with the doping metals compound, stir, obtain metallic ion mixed liquor;
Step 2: precipitant solution is mixed by the stoichiometric ratio proportioning with fluorizating agent, obtain fluorine-containing precipitant mix solution;
Step 3: the metallic ion mixed liquor in step (1) is at the uniform velocity added in the mixing solutions of (2), stir, the fully rear ageing of precipitation, form slurry;
Step 4: by gained slurries filtration in step (3), washing, drying, roasting, be cooled to room temperature, obtains the nano cerium oxide powder of codoped.
In the present invention, the described cerium salt of step 1 is at least one in cerous nitrate, ceric ammonium nitrate, cerous sulfate, ammonium cerous sulfate, Cerium II Chloride and cerous acetate, and concentration is 0.1～1mol/L.
In the present invention, the described doping bivalent metallic compound of step 1 or non-cerium metal element compound are a kind of in nitrate, acetate, chlorate and vitriol.
In the present invention, the described precipitation agent of step 2 is a kind of in volatile salt, bicarbonate of ammonia, bicarbonate of ammonia+ammoniacal liquor, oxalic acid solution, and concentration is 0.5～2mol/L.
In the present invention, the amount of the described precipitation agent of step 2 is theoretical amount 1～4 times.
In the present invention, the described fluorine-containing solution of step 2 is at least one in Neutral ammonium fluoride, ammonium bifluoride, hydrofluoric acid.
In the present invention, the described precipitin reaction pH of step 3 is 6～9, and temperature of reaction is 10～95 ℃, and churning time is 2～4 hours.
In the present invention, the described digestion time of step 3 is 2～30 hours.
In the present invention, the described drying temperature of step 4 is 80 ℃～120 ℃, and be 2～24 hours time of drying.
In the present invention, the described maturing temperature of step 4 is 500 ℃～1000 ℃, constant temperature calcining 2～10 hours.
This cerium oxide-based nanometer ultraviolet shielding material has chemical constitution Ce
xm
yo
zf
w, wherein M is divalent alkaline-earth metal or non-Ce rare earth metal, especially strontium, barium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium, wherein y has maximum 0.2, common 0.05～0.15 optimum, w has maximum 0.3, common 0.1～0.2 optimum.Strontium is especially preferred, because strontium fluoride has the cubic fluorite structure identical with cerium oxide, and lattice parameter is greater than the lattice parameter of cerium oxide and fluorite, be conducive to farthest increase the crystal lattice distortion rate of cerium oxide, make it more approach the fluorite rock steady structure, the reaction of inhibition formula (1-1) is carried out to the right, reduces the oxidation catalytic activity of cerium oxide.It is careful that but the use of barium is selected to need, because barium fluoride is highly toxic substance, the micro-barium fluoride formed in its preparation process can limit its safety in utilization.The selection of rare earth element and consumption also need to ask the impact of considering color and luster, and for example the doping meeting of excessive didymum brings impact to the color of shielding material, during use, must consider addition.
In order to make performance more superior, the cerium oxide of doped with fluorine ion and metal ion must be nanocrystalline nature, and for example their size is 1～200nm lower than 1 micron with preferred size, especially 5～150nm, especially 10～50nm.In addition, can be to irradiating ultraviolet ray thereon to all directions scattering because be less than the particle of ultraviolet wavelength, thus reducing the uitraviolet intensity of direction of illumination, low particle size makes Nanocrystalline materials more effectively as ultraviolet shielded material.
Anion doped dose of (F
-) and the cation doping agent can be in principle one of in the following manner and be introduced in cerium oxide nanoparticles:
I) in forming process as be entrained in particle by co-precipitation
Ii) dopant ion is adsorbed onto on the precursor surface containing cerium, and dopant ion is fired in material subsequently
Iii) double decomposition process, the salt of cerium and doping agent for example wherein, as nitrate or muriate react with precipitation agent, and wash to remove water-soluble substance by the gained throw out, and dry roasting is to change into required doping oxide
Technology except (ii) obviously can cause having uniform doped element to distribute in cerium oxide particle, and the second technology can cause the surface doping occupied the majority, but this is unimportant, because these three kinds of modes are not single carrying out, be more likely that the three carries out that zwitterion is introduced in cerium oxide nanoparticles simultaneously.
Doping in forming process generally includes, and the water-soluble salt of mixing water dissolubility cerium salt and doping agent in the aqueous solution joins it in precipitation agent and fluorizating agent mixing solutions, is settled out required doped cerium oxide throw out in the solution that is 8 or 7～9 at pH.
Suitable salt comprises nitrate, acetate, chlorate and vitriol.PH is determined by used precipitation agent, generally need to reach 8, and common 7～9 pH is optimum.
Temperature of reaction should be controlled at 10～95 ℃, but, in order to reduce energy consumption, general room temperature gets final product.
As mentioned above, doping agent also can be introduced into by firing.Dopant ion can be introduced in the host lattice of cerium oxide by the roasting under 500 ℃～1000 ℃.Usually 2～10 hours constant temperature firing times, for example 5 hours, obtain dopant material.
The introduction volume of doping agent can be regulated by the controlled doping amount, and this is that those skilled in the art are understandable.
The advantage of ultraviolet shielded material prepared by the present invention is:
(1) ultraviolet shielded material of the present invention is greater than 90% to the ultraviolet specific absorption of wavelength 280～400nm, and visible ray can see through fully; For the oxidation catalytic activity of Viscotrol C, than the oxidation catalytic activity of the pure zirconia cerium prepared under similarity condition, oxidation catalytic activity reduces more than 30%.
(2) carbonate that preparation method of the present invention adopts safety non-toxic to do harm to is precipitation agent, and preparation technology is simple, is easy to realize suitability for industrialized production.
(3) ultraviolet shielded material of the present invention is nontoxic, tasteless, particle diameter is controlled, the nano-cerium oxide of doped with fluorine ion and metal ion when size uniform, can be used for textiles, outdoor daily necessities, sunscreen, rubber, pitch, glass, fluorescent lamp undercoat, macromolecular fibre, high molecule plastic, coating, industry and civilian paint etc. and requires, visible ray high to ultraviolet radiation absorption to see through high, that oxidation catalytic activity is low material and goods.
The accompanying drawing explanation
Field emission scanning electron microscope (FESEM) figure that Fig. 1 is the prepared pure zirconia cerium of Comparative Examples 1
X-ray diffraction (XRD) collection of illustrative plates of the nano-cerium oxide that Fig. 2 is the prepared codoped fluorine calcium of Comparative Examples 2
Field emission scanning electron microscope (FESEM) figure of the nano-cerium oxide that Fig. 3 is the prepared codoped fluorine calcium of Comparative Examples 2
X-ray diffraction (XRD) collection of illustrative plates of the nano-cerium oxide that Fig. 4 is the prepared codoped fluorine strontium of embodiment 1
Field emission scanning electron microscope (FESEM) figure of the nano-cerium oxide that Fig. 5 is the prepared codoped fluorine strontium of embodiment 1
The uv absorption spectra that Fig. 6 is the prepared cerium oxide of Comparative Examples 1, Comparative Examples 2, embodiment 1
In Fig. 2, Fig. 4, abscissa is 2-θ, and ordinate is intensity; In Fig. 6, abscissa is wavelength, and ordinate is specific absorption.
In Fig. 6, A is Comparative Examples 1 ultra-violet absorption spectrum, and B is Comparative Examples 2 ultra-violet absorption spectrums, the ultra-violet absorption spectrum that C is embodiment 1.
Embodiment
Hereinafter, by embodiment, describe in further detail the present invention, still, following examples and Comparative Examples are only for understanding the present invention, and the present invention is not limited to them or is limit by them.
Comparative Examples 1: preparation pure zirconia cerium powder
The cerous nitrate solution of preparation 0.35mol/L and the sal volatile of 1mol/L are stand-by.Get 2 times of volatile salts of the precipitation agent to theoretical amount, salpeter solution is at the uniform velocity splashed in sal volatile, stirring at room 3h, the fully rear ageing 20h of precipitation, filter washing, 100 ℃ of dry 12h after forming slurry, in 600 ℃ of constant temperature calcining 5h, be cooled to room temperature, make unadulterated pure zirconia cerium powder.
Fig. 1 is field emission scanning electron microscope (FESEM) figure of the prepared pure zirconia cerium of Comparative Examples 1, and the pure zirconia cerium is sheet, and grain diameter is micron order.A curve in Fig. 6 is the uv absorption spectra of pure zirconia cerium, and its rate of absorbing UV is starkly lower than the rate of absorbing UV of doped cerium oxide, very poor at the assimilation effect of ultraviolet region.
Comparative Examples 2: preparation Ce
0.9ca
0.1o
1.82f
0.16powder
The cerous nitrate solution of preparation 0.35mol/L and the sal volatile of 1mol/L are stand-by.According to cerium ion: calcium ion: the mol ratio of fluorion is the amount of getting reactant cerous nitrate, nitrocalcite, Neutral ammonium fluoride at 0.9: 0.1: 0.16, got cerous nitrate solution is mixed with nitrocalcite, after stirring calcium, cerium metal Ar ion mixing solution.Get 2 times of volatile salts of the precipitation agent to theoretical amount, sal volatile is mixed with Neutral ammonium fluoride, then calcium, cerium metal Ar ion mixing solution are at the uniform velocity splashed into wherein, stirring at room 3h, the fully rear ageing 20h of precipitation, filter after the formation slurry, washing, 100 ℃ of dry 12h, in 600 ℃ of constant temperature calcining 5h, be cooled to the nano cerium oxide powder that room temperature makes codoped.
Fig. 2 and Fig. 3 are codoped F
-, Ca
2+nano Ce O
2the X-ray diffraction of powder (XRD) collection of illustrative plates and field emission scanning electron microscope (FESEM) figure.In Fig. 1, the raw-material peak of dephasign or unreacted do not detected, this shows that starting material are fully to be transformed into highly purified doped F
-, Ca
2+ceO
2.FESEM in Fig. 3 shows, the particle diameter of described powder is 50～200nm, and grain diameter is very inhomogeneous.By analysis, the gained powder is stoichiometric Ce
0.9ca
0.1o
1.82f
0.16.B curve in Fig. 6 is codoped F
-, Ca
2+nano Ce O
2the uv absorption spectra of powder, known its rate of absorbing UV is greater than 85%, and visible ray can see through.Codoped F
-, Ca
2+the oxidation catalysis reduction by 20% of the oxidation catalysis of the nano-cerium oxide oxidation catalysis Viscotrol C pure zirconia cerium prepared than Comparative Examples 1.
Embodiment 1: preparation Ce
0.9sr
0.1o
1.82f
0.16powder
The cerous nitrate solution of preparation 0.35mol/L and the sal volatile of 1mol/L are stand-by.According to cerium ion: strontium ion: the mol ratio of fluorion is the amount of getting reactant cerous nitrate, strontium nitrate, Neutral ammonium fluoride at 0.9: 0.1: 0.16, got cerous nitrate solution is mixed with strontium nitrate, after stirring strontium, cerium metal Ar ion mixing solution.Get 2 times of volatile salts of the precipitation agent to theoretical amount, sal volatile is mixed with Neutral ammonium fluoride, then strontium, cerium metal Ar ion mixing solution are at the uniform velocity splashed into wherein, stirring at room 3h, the fully rear ageing 20h of precipitation, filter after the formation slurry, washing, 100 ℃ of dry 12h, in 600 ℃ of constant temperature calcining 5h, be cooled to the nano cerium oxide powder that room temperature makes codoped.
Fig. 4 and Fig. 5 are codoped F
-, Sr
2+nano Ce O
2the X-ray diffraction of powder (XRD) collection of illustrative plates and field emission scanning electron microscope (FESEM) figure.In Fig. 1, the raw-material peak of dephasign or unreacted do not detected, this shows that starting material are fully to be transformed into highly purified doped F
-, Sr
2+ceO
2.FESEM in Fig. 2 shows, the particle diameter of described powder is in the 50nm left and right, and particle size distribution is even.By analysis, the gained powder is stoichiometric Ce
0.9sr
0.1o
1.82f
0.16.C curve in accompanying drawing 6 is codoped F
-, Sr
2+nano Ce O
2the uv absorption spectra of powder, known its rate of absorbing UV is greater than 98%, and visible ray can see through fully, and A curve (being the pure zirconia cerium of Comparative Examples 1), the B curve of contrast accompanying drawing 6 (are the F of Comparative Examples 2
-, Ca
2+the codoped cerium oxide) codoped F
-, Sr
2+the cerium oxide rate of absorbing UV strengthen, the ultraviolet absorption edge red shift, energy gap narrows down.Codoped F
-, Sr
2+the oxidation catalysis reduction by 50% of the oxidation catalysis of the nano-cerium oxide oxidation catalysis Viscotrol C pure zirconia cerium prepared than Comparative Examples 1.
Embodiment 2: preparation Ce
0.8la
0.2o
1.75f
0.3powder
The ceric ammonium nitrate solution of preparation 0.6mol/L and the ammonium bicarbonate soln of 1mol/L are stand-by.According to cerium ion: lanthanum ion: the mol ratio of fluorion is the amount of getting reactant ceric ammonium nitrate, lanthanum nitrate, ammonium bifluoride at 0.8: 0.2: 0.3, got ceric ammonium nitrate solution is mixed with lanthanum nitrate, after stirring lanthanum and cerium metal Ar ion mixing solution.Get 3 times of bicarbonate of ammonia of the precipitation agent to theoretical amount, ammonium bicarbonate soln is mixed with ammonium bifluoride, lanthanum, cerium metal Ar ion mixing solution are at the uniform velocity splashed into wherein, and temperature of reaction is controlled 40 ℃ of left and right, stirs 2h, the fully rear ageing 10h of precipitation, filter washing, 90 ℃ of dry 20h after forming slurry, in 600 ℃ of roasting 5h, be cooled to the nano cerium oxide powder that room temperature makes codoped.
Codoped F
-, La
3+nano Ce O
2powder does not detect dephasign, the about 70nm of particle diameter left and right, uniform particles.By analysis, the gained powder is stoichiometric Ce
0.8la
0.2o
1.75f
0.3.Rate of absorbing UV is greater than 90%, and visible ray can see through, the ultraviolet absorption edge red shift, and energy gap narrows down.The oxidation catalysis reduction by 46% of the pure zirconia cerium prepared than Comparative Examples 1 to the oxidation catalytic activity of Viscotrol C.
Embodiment 3: preparation Ce
0.96eu
0.04o
1.93f
0.1powder
The cerous acetate solution of preparation 0.4mol/L and the sal volatile of 1mol/L are stand-by.According to cerium ion: europium ion: the mol ratio of fluorion is the amount of getting reactant cerous acetate, acetic acid europium, hydrofluoric acid at 0.96: 0.04: 0.1, got cerous acetate solution is mixed with the acetic acid europium, after stirring europium, cerium metal Ar ion mixing solution.Get 3 times of volatile salts of the precipitation agent to theoretical amount, sal volatile is mixed with hydrofluoric acid, europium, cerium metal Ar ion mixing solution are at the uniform velocity splashed into wherein, stirring at room 2h, the fully rear ageing 4h of precipitation, filter after the formation slurry, washing, 80 ℃ of dry 24h, in 500 ℃ of roasting 10h, be cooled to the nano cerium oxide powder that room temperature makes codoped.
Codoped F
-, Eu
3+nano Ce O
2powder does not detect dephasign, the about 180nm of particle diameter left and right, uniform particles.By analysis, the gained powder is stoichiometric Ce
0.96eu
0.04o
1.93f
0.1.Rate of absorbing UV is greater than 90%, and visible ray can see through, the ultraviolet absorption edge red shift, and energy gap narrows down.The oxidation catalysis reduction by 30% of the pure zirconia cerium prepared than Comparative Examples 1 to the oxidation catalytic activity of Viscotrol C.
Embodiment 4: preparation Ce
0.92nd
0.08o
1.91f
0.1powder
The solution of cerium chloride by oxidation of preparation 1mol/L and the ammonium bicarbonate soln of 2mol/L are stand-by.According to cerium ion: neodymium ion: the mol ratio of fluorion is the amount of getting reactant Cerium II Chloride, Neodymium trichloride, Neutral ammonium fluoride at 0.92: 0.08: 0.1, got solution of cerium chloride by oxidation is mixed with the acetic acid neodymium, after stirring neodymium, cerium metal Ar ion mixing solution.Get the required precipitation agent bicarbonate of ammonia of theoretical amount, ammonium bicarbonate soln is mixed with Neutral ammonium fluoride, neodymium, cerium metal Ar ion mixing solution are at the uniform velocity splashed into wherein, and temperature of reaction is controlled at 95 ℃ of left and right, stirs 3h, the fully rear ageing 30h of precipitation, filter washing, 120 ℃ of dry 2h after forming slurry, in 1000 ℃ of roasting 2h, be cooled to the nano cerium oxide powder that room temperature makes codoped.
Codoped F
-, Nd
3+nano Ce O
2powder does not detect dephasign, the about 220nm of particle diameter left and right, uniform particles.By analysis, the gained powder is stoichiometric Ce
0.92nd
0.08o
1.91f
0.1powder.Rate of absorbing UV is greater than 92%, and visible ray can see through, the ultraviolet absorption edge red shift, and energy gap narrows down.The oxidation catalysis reduction by 37% of the pure zirconia cerium prepared than Comparative Examples 1 to the oxidation catalytic activity of Viscotrol C.
Embodiment 5: preparation Ce
0.85y
0.15o
1.85F0.15powder
The cerous sulfate solution of preparation 0.1mol/L and the oxalic acid solution of 1mol/L are stand-by.According to cerium ion: ruthenium ion: the mol ratio of fluorion is the amount of getting reactant cerous sulfate, yttrium sulfate, ammonium bifluoride at 0.85: 0.15: 0.15, got cerous sulfate solution is mixed with yttrium sulfate, after stirring yttrium, cerium metal Ar ion mixing solution.Get 2 times of oxalic acid of the precipitation agent to theoretical amount, oxalic acid solution is mixed with ammonium bifluoride, yttrium, cerium metal Ar ion mixing solution are at the uniform velocity splashed into wherein, stirring at room 3h, the fully rear ageing 15h of precipitation, filter after the formation slurry, washing, 100 ℃ of dry 12h, in 800 ℃ of roasting 3h, be cooled to the nano cerium oxide powder that room temperature makes codoped.
Codoped F
-, Y
3+nano Ce O
2powder does not detect dephasign, the about 120nm of particle diameter left and right, uniform particles.By analysis, the gained powder is stoichiometric Ce
0.85y
0.15o
1.85f
0.15powder.Rate of absorbing UV is greater than 94%, and visible ray can see through, the ultraviolet absorption edge red shift, and energy gap narrows down.The oxidation catalysis reduction by 42% of the pure zirconia cerium prepared than Comparative Examples 1 to the oxidation catalytic activity of Viscotrol C.
Embodiment 6: preparation Ce
0.95ba
0.05o
1.91f
0.08powder
The cerous acetate solution of preparation 0.7mol/L and the sal volatile of 0.5mol/L are stand-by.According to cerium ion: barium ion: the mol ratio of fluorion is the amount of getting reactant cerous acetate, barium acetate, Neutral ammonium fluoride at 0.95: 0.05: 0.08, got cerous acetate solution is mixed with barium acetate, after stirring barium, cerium metal Ar ion mixing solution.Get 2 times of volatile salts of the precipitation agent to theoretical amount, sal volatile is mixed with Neutral ammonium fluoride, barium, cerium metal Ar ion mixing solution are at the uniform velocity splashed into wherein, control 60 ℃ of left and right of temperature of reaction, stir 2h, the fully rear ageing 18h of precipitation, filter washing, 100 ℃ of dry 12h after forming slurry, in 800 ℃ of roasting 4h, be cooled to the nano cerium oxide powder that room temperature makes codoped.
Codoped F
-, Ba
2+nano Ce O
2powder does not detect dephasign, the about 300nm of particle diameter left and right, uniform particles.By analysis, the gained powder is stoichiometric Ce
0.95ba
0.05o
1.91f
0.08powder.Rate of absorbing UV is greater than 88%, and visible ray can see through, the ultraviolet absorption edge red shift, and energy gap narrows down.The oxidation catalysis reduction by 43% of the pure zirconia cerium prepared than Comparative Examples 1 to the oxidation catalytic activity of Viscotrol C.
Embodiment 7: preparation Ce
0.88pr
0.12o
1.87f
0.14powder
The mixing solutions of the cerous nitrate solution of preparation 0.45mol/L and the bicarbonate of ammonia of 1mol/L and ammoniacal liquor is stand-by.According to cerium ion: praseodymium ion: the mol ratio of fluorion is the amount of getting reactant Cerium II Chloride, praseodymium chloride, ammonium bifluoride at 0.88: 0.12: 0.14, got solution of cerium chloride by oxidation is mixed with praseodymium chloride, after stirring praseodymium, cerium metal Ar ion mixing solution.Get the mixing solutions of 2 times of bicarbonate of ammonia of the precipitation agent to theoretical amount and ammoniacal liquor, it is mixed with ammonium bifluoride, praseodymium, cerium metal Ar ion mixing solution are at the uniform velocity splashed into wherein, stirring at room 4h, the fully rear ageing 14h of precipitation, filter after the formation slurry, washing, 100 ℃ of dry 12h, in 700 ℃ of roasting 4h, be cooled to the nano cerium oxide powder that room temperature makes codoped.
Codoped F
-, the nano Ce O of Pr
2powder does not detect dephasign, the about 60nm of particle diameter left and right, uniform particles.By analysis, the gained powder is stoichiometric Ce
0.88pr
0.12o
1.87f
0.14powder.Rate of absorbing UV is greater than 90%, and visible ray can see through, the ultraviolet absorption edge red shift, and energy gap narrows down.The oxidation catalysis reduction by 40% of the pure zirconia cerium prepared than Comparative Examples 1 to the oxidation catalytic activity of Viscotrol C.
Embodiment 8: preparation Ce
0.8sr
0.2o
1.65f
0.3powder
The cerous nitrate solution of preparation 0.5mol/L and the ammonium bicarbonate soln of 1mol/L are stand-by.According to cerium ion: strontium ion: the mol ratio of fluorion is the amount of getting reactant cerous nitrate, strontium nitrate, Neutral ammonium fluoride at 0.8: 0.2: 0.3, got cerous nitrate solution is mixed with strontium nitrate, after stirring strontium, cerium metal Ar ion mixing solution.Get 2 times of bicarbonate of ammonia of the precipitation agent to theoretical amount, ammonium bicarbonate soln is mixed with Neutral ammonium fluoride, strontium, cerium metal Ar ion mixing solution are at the uniform velocity splashed into wherein, and temperature of reaction is controlled at 10 ℃ of left and right, stirs 3h, the fully rear ageing 15h of precipitation, filter washing, 100 ℃ of dry 12h after forming slurry, in 800 ℃ of roasting 6h, be cooled to the nano cerium oxide powder that room temperature makes codoped.
Codoped F
-, Sr
2+nano Ce O
2powder does not detect dephasign, the about 100nm of particle diameter left and right, uniform particles.By analysis, the gained powder is stoichiometric Ce
0.8sr
0.2o
1.65f
0.3powder.Rate of absorbing UV is greater than 95%, and visible ray can see through, the ultraviolet absorption edge red shift, and energy gap narrows down.The oxidation catalysis reduction by 45% of the pure zirconia cerium prepared than Comparative Examples 1 to the oxidation catalytic activity of Viscotrol C.
Embodiment 9: preparation Ce
0.86sm
0.14o
1.83f
0.2powder
The ammonium cerous sulfate solution of preparation 0.25mol/L and the sal volatile of 1mol/L are stand-by.According to cerium ion: samarium ion: the mol ratio of fluorion is the amount of getting reactant cerous nitrate, samaric nitrate, Neutral ammonium fluoride at 0.86: 0.14: 0.2, got cerous nitrate solution is mixed with samaric nitrate, after stirring samarium, cerium metal Ar ion mixing solution.Get 4 times of volatile salts of the precipitation agent to theoretical amount, sal volatile is mixed with Neutral ammonium fluoride, samarium, cerium metal Ar ion mixing solution are at the uniform velocity splashed into wherein, stirring at room 3h, the fully rear ageing 20h of precipitation, filter after the formation slurry, washing, 110 ℃ of dry 8h, in 600 ℃ of roasting 5h, be cooled to the nano cerium oxide powder that room temperature makes codoped.
Codoped F
-, Sm
3+nano Ce O
2powder does not detect dephasign, the about 180nm of particle diameter left and right, uniform particles.By analysis, the gained powder is stoichiometric Ce
0.86sm
0.14o
1.83f
0.2powder.Rate of absorbing UV is greater than 90%, and visible ray can see through, the ultraviolet absorption edge red shift, and energy gap narrows down.The oxidation catalysis reduction by 36% of the pure zirconia cerium prepared than Comparative Examples 1 to the oxidation catalytic activity of Viscotrol C.
The embodiment data are asked for an interview the nextpage list:
Claims (16)
1. the cerium oxide-based nanometer ultraviolet shielding material of a doped with fluorine ion and metal ion, is characterized in that, its chemical constitution is Ce
xm
yo
zf
w, wherein M is strontium, 0.8≤x<1,0<y≤0.2,1.65≤z<2,0<w≤0.3, and chemical formula Ce
xm
yo
zf
wmeet charge balance.
2. the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 1 and metal ion, is characterized in that 0.85≤x<1,0<y≤0.15,1.75≤z<2,0<w≤0.2.
3. the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 1 and 2 and metal ion, is characterized in that, its grain-size D50≤1 micron.
4. the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 1 and 2 and metal ion, is characterized in that, its grain-size D50 is 1～200nm.
5. the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 1 and 2 and metal ion, is characterized in that, its ultraviolet specific absorption to wavelength 280～400nm is greater than 90%, and visible ray can see through fully.
6. the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 1 and 2 and metal ion, it is characterized in that, its oxidation catalytic activity for Viscotrol C is than the oxidation catalytic activity of the pure zirconia cerium prepared under similarity condition, and oxidation catalytic activity reduces more than 30%.
7. the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a doped with fluorine ion claimed in claim 1 and metal ion, its concrete steps are as follows:
(1) cerium solution is mixed by the stoichiometric ratio proportioning with the doping metals compound, stir, obtain metallic ion mixed liquor;
(2) precipitant solution is mixed by the stoichiometric ratio proportioning with fluorizating agent, obtain fluorine-containing precipitant mix solution;
(3) metallic ion mixed liquor in step (1) is at the uniform velocity added in the mixing solutions of (2), stir, the fully rear ageing of precipitation, form slurry;
(4) by gained slurries filtration in step (3), washing, drying, roasting, be cooled to room temperature, obtains the nano cerium oxide powder of codoped.
8. the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 7 and metal ion, it is characterized in that the cerium solution described in step (1) is at least one in cerous nitrate, ceric ammonium nitrate, cerous sulfate, ammonium cerous sulfate, Cerium II Chloride and cerous acetate, concentration is 0.1～1mol/L.
9. the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 7 and metal ion, is characterized in that the doping metals compound described in step (1) is a kind of in nitrate, acetate, chlorate and vitriol.
10. the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 7 and metal ion, it is characterized in that the precipitation agent described in step (2) is a kind of in volatile salt, bicarbonate of ammonia, bicarbonate of ammonia+ammoniacal liquor, oxalic acid solution, concentration is 0.5～2mol/L.
11. the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 7 and metal ion, the amount that it is characterized in that the precipitation agent described in step (2) is theoretical amount 1～4 times.
12. the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 7 and metal ion, is characterized in that the fluorizating agent described in step (2) is at least one in Neutral ammonium fluoride, ammonium bifluoride, hydrofluoric acid.
13. the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 7 and metal ion, is characterized in that described in step (3), temperature of reaction is 10～95 ℃, churning time is 2～4 hours.
14. the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 7 and metal ion, is characterized in that the digestion time described in step (3) is 2～30 hours.
15. the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 7 and metal ion, is characterized in that the drying temperature described in step (4) is 80 ℃～120 ℃, be 2～24 hours time of drying.
16. the preparation method of the cerium oxide-based nanometer ultraviolet shielding material of a kind of doped with fluorine ion according to claim 7 and metal ion, is characterized in that the maturing temperature described in step (4) is 500 ℃～1000 ℃, constant temperature calcining 2～10 hours.
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| CN105565373B (en) * | 2015-12-31 | 2017-04-26 | 包头稀土研究院 | Rare earth oxide-based nanometer ultraviolet shielding material and preparation method thereof |
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