CN1736583A - Synthesis method and application of boron-doped nano oxide - Google Patents
Synthesis method and application of boron-doped nano oxide Download PDFInfo
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- CN1736583A CN1736583A CN 200510090847 CN200510090847A CN1736583A CN 1736583 A CN1736583 A CN 1736583A CN 200510090847 CN200510090847 CN 200510090847 CN 200510090847 A CN200510090847 A CN 200510090847A CN 1736583 A CN1736583 A CN 1736583A
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Abstract
The invention discloses a method for synthesizing boron doped nano oxide and discloses the utility, belonging to the art of preparing and using functional material. Cosolvent boric acid reacts with reactant and metallic salt in closed condition to prepare boron doped oxide or composite oxides of metal. The process is easy to control, and carries out in a low temperature. For the crystal defect caused by adding B slightly, the prepared TiO2: B, SnO2: B, CeO2: B, Cr2O3: B, ZnO: B, Sn2O3: B, ZrO2: B or the composite oxides have a potential utility in the art of photocatalysis, purification catalysis, and so on. It has high catalytic activity to the degradation of organic contaminant and to the oxidization of CO with the effort of ultraviolet or visible high.
Description
Technical field
The invention belongs to the preparation and the application of functional material, particularly can in multiple organic pollution of light degradation and purifying vehicle exhaust, bring into play the synthetic method and the purposes of a kind of boron-doped nanometer oxide of catalytic action.
Background technology
The skin effect of nano-oxide, quantum size effect and macro quanta tunnel effect have caused their physics, atom, the molecule that chemical characteristic both had been different from microcosmic, are different from body phase material again.Nano-oxide often demonstrates some special optics, electricity and magnetic performance.Simultaneously, the specific area of nano material is quite big, has very high chemism.Thereby nano material has a wide range of applications at aspects such as catalysis, fine ceramics, magnetic material, fluorescent material, air-sensitive/moisture sensor and infrared absorbing materials.As nano SnO
2The electric conductivity of surf zone is very responsive to atmosphere of living in, and it interacts by surface absorption and reducing gas, causes that surperficial free electron density changes, thereby becomes the gas sensor that people receive much attention.Nano-TiO for another example
2When the illumination that is subjected to being equal to or greater than its band-gap energy is penetrated, can produce electronics and hole on its surface.Photohole has very strong oxidability, can make most oxidation operations, and electron acceptor can be reduced by the electronics of accepting the surface.Nano-TiO
2This specific character and bigger skin effect thereof make it become the photochemical catalyst of tool potentiality.Though nano-oxide has many special nature and wide application prospect, often also exist the some shortcomings of self.As TiO
2Electronics and hole take place easily compoundly, photocatalysis efficiency is low; Its greater band gap can only be in ultra-violet (UV) band display light chemism, and is very low to solar energy utilization rate.An important means optimizing the nano-oxide performance is exactly that a certain amount of foreign ion is incorporated in their lattice.When foreign ion replaces the atom on the dot matrix case or enters interstitial site, can in crystal, form lattice defect, in the forbidden band of crystal, cause some local energy level; Simultaneously, the introducing of impurity also can influence the degree of crystallinity of crystal, has improved their chemism.Thereby, in nano-oxide, mix, improve their performance such as optics, electricity, catalysis sometimes significantly.
In recent years, people are in the doping research of nano-oxide, and most cations that adopt especially concentrate on transition metal ions, rare earth ion as adulterant.Comparatively speaking, nonmetalloid will lack the doping research of nano-oxide.At present, people mainly adopt B, N, C, F, S etc. to the nonmetal doping of nano-oxide.Wherein boron mixes and realizes in a plurality of nano oxidized objects systems.As, the chemistry Zhao Jincai of institute professor seminar of the Chinese Academy of Sciences adopts sol-gal process to synthesize TiO
2-xB
x, its absorption spectrum moves to the visible light direction significantly, thereby this material can effectively utilize solar energy; Egyptian scientist Seif A.Nasser employing high temperature sputtering method has synthesized mixes the B nano SnO
2Film is owing to mixing of B, at SnO
2Lattice in form the oxygen room, and then produce a certain amount of " quasi-free electron ", improved SnO
2Carrier concentration, thereby improve its electric conductivity significantly.
Boron has the oxytropism of height.Generally speaking, in B doped with nanometer oxide lattice, B may occupy the case of original metal ion, also may enter in the gap of lattice; Under some specific conditions (as inert atmosphere, high temperature), B also can replace oxygen atom.B mixes the Lewis acidic site and the intensity that can increase on the one hand oxide surface, can form impurity substitutional defect, interstitial defect, vacancy defect etc. on the one hand in crystal.The change on these surfaces and the defective in the crystal have determined many physical and chemical performances of material just.
At present, the preparation method of nonmetal doping nano-oxide mainly contains sputtering method, burning infiltration method, high temperature solid-state method, sol-gal process etc.Mainly adopt sol-gal process and sputtering method to synthesize and mix the B nano-oxide, and at present most of research mainly concentrate on and mix the B nano-TiO
2Study on the synthesis.There are following shortcoming in sol-gal process and sputtering method: the step that relates in building-up process is more; Need higher temperature, energy consumption is bigger; The factor that influence is synthesized is more, makes that the reappearance of product is relatively poor; The synthetic method versatility is relatively poor, is difficult to realize TiO
2, SnO
2, ZnO, CeO
2, Cr
2O
3, Sb
2O
3, ZrO
2B etc. numerous oxides mixes.
In recent years, some scientific research personnel adopt a kind of method-boric acid flux growth metrhod of similar water thermal synthesis both at home and abroad, many novel borate crystals have been synthesized, as the transition metal of alkali metal, alkaline-earth metal and divalence, trivalent, rare earth multi-borate etc., but still nobody is applied to the synthetic of B doping oxide with this method.Applicant has successfully been explored the boric acid flux growth metrhod that can synthesize multiple boron-doped nanometer oxide on the basis of deeply experiment.This method is not only easy and simple to handle, building-up process is easy to control, and it is lower to consume energy, and the product reappearance is better.Simultaneously, Xiang Guan experimental work proves that also the prepared B oxide of mixing is showing excellent performance aspect photocatalysis and the catalytic oxidation.
Summary of the invention
The objective of the invention is to propose a kind of preparation method and application simple, effectively boron-doped nanometer oxide.The preparation method of described boron-doped nanometer oxide is to use boric acid to react in airtight system as the salt of cosolvent and reactant and metal, to obtain the boron doping oxide of metal, perhaps the boron doped composite oxide of metal.It is characterized in that its processing step is as follows:
(1) this slaine and boric acid, pH value conditioning agent are mixed, its three's mol ratio is 1: 0.1～50: 0～1.
(2) the above-mentioned reaction mass that mixes is packed in the closed reactor, under 140 ℃-300 ℃ temperature, be incubated 0.5～40 hour, after this reactant is cooled to room temperature.
(3) behind the taking-up reactant it is spent deionised water, remove impurity and accessory substance, can obtain boron doping oxide product.
(4) (1), step (2) and (3) operation promptly obtain the boron doped composite oxide of above-mentioned metal set by step with the salt of two or more metallic element.
Above-mentioned metallic element comprises Ti, Sn, Cr, Ce, Sb, Zn or Zr;
Above-mentioned slaine comprises nitrate, chloride, sulfate, carbonate, oxalates or formates;
Used pH value conditioning agent is nitric acid, hydrochloric acid, oxalic acid, NaOH, ammoniacal liquor or urea;
Used mixing of materials method is methods such as stirring, grinding or ball milling;
Used reactor is airtight reaction vessel, the reaction vessel of making as materials such as stainless steel, polytetrafluoroethylene (PTFE);
The present invention provides effective catalyst for fields such as photocatalysis, catalytic ozonation, catalytic wet oxidation, purifying vehicle exhausts.
The present invention adopts the synthetic boron-doped nanometer oxide of boric acid flux growth metrhod to have following advantage:
1. broad covered area, this method can be synthesized multiple boron-doped nanometer oxide.
2. building-up process is simple and easy to control, and product reappearance and purity are higher.
3. building-up process is carried out at a lower temperature, energy savings.
4. a small amount of B's mixes, can cause impurity substitutional defect, interstitial defect, vacancy defect in the structure, these crystal defects may make the energy gap of oxide narrow down, may cause the behavior of appraising at the current rate in the oxide, also may cause the enhancing of oxide surface acidity, thereby make them in multiple occasion, can be used as catalyst efficiently, have a good application prospect at aspects such as photocatalysis, catalytic ozonation, catalytic wet oxidation, purifying vehicle exhaust catalysis.
Description of drawings
The SnO that Fig. 1 the present invention is synthesized
2: the x-ray diffractogram of powder of B;
The TiO that Fig. 2 the present invention is synthesized
2: the x-ray diffractogram of powder of B;
Fig. 3 SnO
2: B makees catalyst, the degradation rate of ultraviolet degradation benzamide and time history;
The SnO that Fig. 4 the present invention is synthesized
2: the uv-visible absorption spectra figure of B;
Fig. 5 is under the effect of visible light, with the TiO that the present invention synthesized
2: B is as photochemical catalyst, methylene blue degradation rate and time history;
The specific embodiment
The present invention proposes a kind of preparation method and application simple, effectively boron-doped nanometer oxide.The preparation method of this boron-doped nanometer oxide uses boric acid to react in airtight system as the salt of cosolvent and reactant and metal, to obtain the boron doping oxide of metal, perhaps boron doped composite oxide.Its processing step is as follows:
(1) this slaine and boric acid, pH value conditioning agent are mixed, its three's mol ratio is 1: 0.1～50: 0～1;
(2) the above-mentioned reaction mass that mixes is packed in the closed reactor, under 140 ℃-300 ℃ temperature, be incubated 0.5～40 hour, after this reactant is cooled to room temperature.
(3) behind the taking-up reactant it is spent deionised water, remove impurity and accessory substance, can obtain boron doping oxide product.
(4) (1), step (2) and (3) operation promptly obtain the boron doped composite oxide of above-mentioned metal set by step with the salt of two or more metallic element.
Above-mentioned metallic element comprise Ti, Sn, Cr, Ce, Sb, Zn and Zr one or more;
Above-mentioned slaine comprises nitrate, chloride, sulfate, carbonate, oxalates or formates;
Used pH value conditioning agent is nitric acid, hydrochloric acid, oxalic acid, NaOH, ammoniacal liquor or urea;
Used mixing of materials method is methods such as stirring, grinding or ball milling;
Used reactor is airtight reaction vessel, the reaction vessel of making as materials such as stainless steel, polytetrafluoroethylene (PTFE).
The present invention provides effective catalyst for fields such as photocatalysis, catalytic ozonation, catalytic wet oxidation, purifying vehicle exhausts.
Further specify the present invention below in conjunction with drawings and Examples:
Embodiment 1:SnO
2: B's is synthetic
With 1.5g SnCl
22H
2O mixes with 6.2g boric acid, after fully mill is spared in agate mortar, in the band teflon-lined stainless steel cauldron of packing into, places 190 ℃ baking oven to heat 10 hours.Question response allows reactor cool off naturally after finishing, and takes out post reaction mixture, spends deionised water, removes excessive boric acid, and air dry can obtain the SnO that B mixes
2, its X-ray diffracting spectrum as shown in Figure 1.
Embodiment 2:TiO
2: B's is synthetic
2g NaOH is mixed with 6.18g boric acid, and fully mill is even in agate mortar, splashes into the TiCl of 3ml 20% then
3Solution is packed said mixture in the band teflon-lined stainless steel cauldron into, places 220 ℃ of baking ovens heating 36 hours.Question response allows reactor cool off naturally after finishing, and takes out post reaction mixture, spends deionised water, removes excessive boric acid, and air dry can obtain the TiO that B mixes
2, its X-ray diffracting spectrum as shown in Figure 2.
Embodiment 3:Ti
xSn
yO
2: synthetic (the boron doped composite oxides) of B
With 0.75g SnCl
22H
2O mixes with 6.18g boric acid, and fully mill is even in agate mortar, splashes into the TiCl of 1.5ml 15%-20% then
3Solution is packed said mixture in the band teflon-lined stainless steel cauldron into, places 200 ℃ baking oven heating 36 hours.After question response finishes, allow reactor cool off naturally, the taking-up post reaction mixture spends deionised water, removes excessive boric acid, and air dry can obtain the composite oxides of B Doped with Titanium and tin.
Embodiment 4: use SnO
2: B makees catalyst, the ultraviolet degradation benzamide
Utilize homemade photo catalysis reactor, as model substance, estimate SnO with benzamide (not possessing volatility) with carcinogenic toxicity
2: the ultraviolet catalytic activity of B powder, and with commercial goods---the P-25 type TiO that generally acknowledges at present both at home and abroad
2(German Degussa company) carries out performance comparison.Experimentation is as follows: with SnO
2: B catalyst 0.10g is scattered in the benzamide solution of 0.02mol/L, and under the condition that keeps electromagnetic agitation, (dominant wavelength 254nm) is light source with the 5W low pressure mercury lamp, shines above-mentioned suspension, makes benzamide generation degradation reaction.Sampling at regular intervals after centrifugation, is analyzed benzamide concentration by Tianjin, island LC210A type high performance liquid chromatograph (HPLC).Calculate the degradation rate of benzamide according to following formula:
Degradation rate=(c
0-c
t)/c
0* 100%
c
0---the benzamide initial concentration solution
c
t---reaction back benzamide solution concentration
With carry out P-25 type TiO with quadrat method
2Photocatalysis experiment, as a comparison.
Experimental result shows SnO
2: the ultraviolet catalytic degrading activity of B paraphenylene terephthalamide obviously is better than P-25 type TiO
2(see figure 3).
Embodiment 5: use TiO
2: B makees catalyst, the visible light degradation of methylene blue
Because TiO
2: B has more absorption (see figure 4) in the visible region, it can be removed and degradation of contaminant as visible light catalyst by the excited by visible light of wavelength greater than 400nm.With common dyestuff methylene blue is model substance, still utilizes the similar means of embodiment 7, estimates TiO
2: the visible light catalysis activity of B powder.For obtaining visible light source, to the high-pressure sodium lamp (dominant wavelength 365nm) of 300W, the employing cutoff wavelength is the ultraviolet light part in the 420nm filter plate emission spectrum.TiO with 0.20g
2: the B catalyst is scattered in the methylene blue solution of 0.01mol/L, electromagnetic agitation, and sampling at regular intervals after centrifugation, is analyzed the concentration of methylene blue with ultraviolet-uisible spectrophotometer.Experimental result shows under the effect of visible light, TiO
2: B has obvious catalysis to the degraded of methyl blue. (see figure 5).
Embodiment 6: use SnO
2: B does oxidation catalyst
With CuO tester (that generally acknowledges at present has the catalyst of fine catalytic oxidation performance to CO), assessment SnO
2: B is to the catalytic oxidation performance of CO.Appreciation condition: CO 6.0v%, O
23.6v%, N
2Be balance gas, the reaction mixture gas flow velocity is 30ml/min; Powder sample keeps down 1 minute in flakes through 2Mp pressure, gets 40～80 order sample 20mg and 2g quartz sand mixes through fragmentation; Chromel-alumel thermocouple control reaction bed temperature; Reaction mixture gas feeds reaction bed and stablize the surplus of measuring CO after 1 hour under reaction temperature, measures altogether 5 times, averages and calculates the conversion ratio of CO, CO conversion ratio %=(the blank CO of 1-reaction back CO/) * 100%.Test result is as follows: (*: be the CO conversion ratio of 693K)
| Sample | 373K | 473K | 573K | 623K | 673K | 775K | T 90 |
| CuO SnO 2:B | 0.9 3.1 | 24.5 7.8 | 50.2 48.4 | 80.7 87.1 | 87.7 98.8 | 98.7 99.7* | 687K 637K |
The result shows, more than 350 ℃, and SnO
2: B obviously is better than CuO to the catalytic oxidation ability of CO, and conversion ratio to reach 90% o'clock temperature lower 50 ℃ than CuO.
By the foregoing description as can be known, in the synthetic boron-doped nanometer oxide process of boric acid flux growth metrhod, fusion boric acid is reaction medium, is again the source of boron in the doped with nanometer oxide simultaneously.The metal ion that fusion boric acid is very easily lower with valence state, radius is bigger, as the transition metal of alkali metal, alkaline-earth metal and divalence, trivalent, rare earth metal plasma in conjunction with forming multi-borate.And the metal ion very high for valence state, that radius is less is (as Mo
6+, V
5+, Sb
5+Deng), they can not with the boric acid combination, the one because positive and negative charge is very concentrated in the multi-borate system of these ions, make such system extremely unstable; The 2nd, even because these ions acutely hydrolysis in the presence of low amounts of water (fusion boric acid system is because there is certain water partial pressure in the dehydration of boric acid).From the thermodynamics angle, valence state is not that high especially, radius is not especially little Ti
4+, Sn
4+, Sb
3+, Zr
4+There are the certain reaction tendency in plasma and fusion boric acid.But the hydrolysis of these ions tendency is bigger, and in fusion acid reaction system, the water effect that they are main and boric acid is sloughed forms oxide.Because water partial pressure is less in the fusion boric acid system, hydrolytic process is not too violent, so just allows Ti
4+, Sn
4+, Sb
3+, Zr
4+Plasma combines with a spot of borate, and its result has formed to mix the B nano-oxide.For Cr
3+, Ce
3+, Zn
2+Plasma then need add a certain amount of alkali in system, avoid boratory formation.Because the viscosity of fusion boric acid is bigger, the chance of the collision combination between the formed oxide particle of hydrolysis is less, so the particle diameter of the nano-oxide that the boric acid flux growth metrhod obtains is generally all less.
The present invention has utilized less water partial pressure of faint binding ability, the fusion boric acid system of fusion boric acid and some ion and the suitable viscosity of fusion boric acid, synthetic boron-doped nanometer oxide.Simultaneously, also can carry out suitable adjusting, for example add a spot of water, acid or alkali, synthetic multiple boron-doped nanometer oxide (M fusion boric acid system
xO
y: B, M can be transition metal, rare earth metal etc.).Should synthetic thinking both avoid a large amount of boratory formation, stop the thorough hydrolysis of metal ion again, and make the boron element snugly enter into the lattice of oxide as doped chemical.
Claims (6)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010146161A2 (en) | 2009-06-18 | 2010-12-23 | Innovcoat Nanocoatings And Surface Products Industry, Sales And R&D Incorporation | Photocatalytic nanocomposite structured with boron |
| CN104437465A (en) * | 2014-12-28 | 2015-03-25 | 桂林理工大学 | Visible light responsive photocatalyst LiNb2BO7 and its preparation method |
| CN109835976A (en) * | 2019-04-02 | 2019-06-04 | 河南省化工研究所有限责任公司 | A method of industrial wastewater is handled for ozone deep oxidation |
| CN109999781A (en) * | 2019-03-27 | 2019-07-12 | 江苏金环环保设备有限公司 | A kind of boracic rare earth oxide composite material and its processing method handling uns-dimethylhydrazine waste water |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3514348A (en) * | 1967-05-10 | 1970-05-26 | Ncr Co | Method for making semiconductor devices |
| CN1369572A (en) * | 2001-04-03 | 2002-09-18 | 中国科学院长春光学精密机械与物理研究所 | Electrically conducting transparent oxide film |
| CN100475335C (en) * | 2003-09-22 | 2009-04-08 | 中国科学院化学研究所 | Photocatalyst with visible light response, preparation method and application thereof |
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- 2005-08-18 CN CNB2005100908474A patent/CN100398195C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010146161A2 (en) | 2009-06-18 | 2010-12-23 | Innovcoat Nanocoatings And Surface Products Industry, Sales And R&D Incorporation | Photocatalytic nanocomposite structured with boron |
| WO2010146161A3 (en) * | 2009-06-18 | 2011-12-01 | Innovcoat Nanocoatings And Surface Products Industry, Sales And R&D Incorporation | Photocatalytic nanocomposite structured with boron |
| US9364821B2 (en) | 2009-06-18 | 2016-06-14 | Innovcoat Nanocoatings And Surface Products Industry, Sales And R&D Incorporation | Photocatalytic nanocomposite structured with boron |
| CN104437465A (en) * | 2014-12-28 | 2015-03-25 | 桂林理工大学 | Visible light responsive photocatalyst LiNb2BO7 and its preparation method |
| CN109999781A (en) * | 2019-03-27 | 2019-07-12 | 江苏金环环保设备有限公司 | A kind of boracic rare earth oxide composite material and its processing method handling uns-dimethylhydrazine waste water |
| CN109999781B (en) * | 2019-03-27 | 2019-11-08 | 江苏金环环保设备有限公司 | A kind of boracic rare earth oxide composite material and its processing method handling uns-dimethylhydrazine waste water |
| CN109835976A (en) * | 2019-04-02 | 2019-06-04 | 河南省化工研究所有限责任公司 | A method of industrial wastewater is handled for ozone deep oxidation |
| CN114053866A (en) * | 2021-11-16 | 2022-02-18 | 江苏富淼科技股份有限公司 | Fixed bed photocatalytic reactor and method for treating chloromethane waste gas by using same |
| CN114053866B (en) * | 2021-11-16 | 2024-02-23 | 江苏富淼科技股份有限公司 | Fixed bed photocatalytic reactor and method for treating chloromethane waste gas by using same |
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