CN103263943B - A kind of LaFeO 3the preparation method of/SBA-15 and application - Google Patents
A kind of LaFeO 3the preparation method of/SBA-15 and application Download PDFInfo
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- CN103263943B CN103263943B CN201310177397.7A CN201310177397A CN103263943B CN 103263943 B CN103263943 B CN 103263943B CN 201310177397 A CN201310177397 A CN 201310177397A CN 103263943 B CN103263943 B CN 103263943B
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- lafeo
- sba
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Abstract
The invention belongs to the preparing technical field of new material, specifically disclose a class, to organic dyestuff in aqueous phase solution, there is the mesoporous silicon SBA-15 load ABO that performance is eliminated in superior catalytic oxidation
3type perovskite LaFeO
3the preparation method of catalyst and application.After first corresponding metal nitrate and a certain amount of citric acid dissolve by the method in ethanol and water mixed liquid, then add a certain amount of mesoporous silicon SBA-15, adopt sol-gel process to prepare support type perovskite catalyst.Such catalyst has excellent adsorption and oxidation degradation capability to waste water from dyestuff, and degradation realization condition is simple, is only that oxidant can carry out at ambient temperature with hydrogenperoxide steam generator, and recycles when activity can be kept substantially constant.This method preparation process is simple, with low cost, environmental friendliness, excellent product performance, has broad application prospects.
Description
Technical field
The present invention relates to the preparing technical field of new material, be specifically related to a kind of support type ABO
3perovskite LaFeO
3the preparation method of/SBA-15 catalyst and the application in catalytic oxidation elimination water body organic dyestuff thereof.
Background technology
Industrial dye waste water have toxicity large, have a very wide distribution, the feature such as concentration is high, colourity is dark, extremely serious pollution is caused to environment; Also directly or indirectly can be affected the health of the mankind by the enrichment of food chain simultaneously.At present, the improvement of industrial wastewater is caused to the extensive concern of environmentalist.
Catalysis method is a kind of effective ways eliminating and administer industrial dye waste water.Such as: the catalytic wet hydrogen peroxide oxidation (CWHPO) that the eighties in 20th century occurs, it in traditional catalytic wet oxidation (WCO) treatment process, adds hydrogenperoxide steam generator (replacement oxygen) as oxidant, substantially increase the degradation efficiency to dyestuff, and reduce reaction temperature and pressure, make it can react at normal temperatures and pressures, thus reduce the cost of industrial dye waste water process.
According to the state of catalyst, homogeneous phase and heterogeneous catalytic wet oxidation can be divided into.In the former, catalyst and waste water mix completely, and the stripping phenomenon of catalyst is serious, and in order to resource regeneration, prevent secondary pollution problems, follow-up catalyst recovery process must be carried out, such that technical difficulty strengthens, processing cost raises.In the latter, catalyst is solid-phase, mainly contains noble metal, transition metal and rare earth metal.This kind of catalyst and waste water convenient separation, handling process is simple.But noble metal and rare-earth metal catalyst production process complexity, expensive, and there is the problems such as active component stripping and inactivation in acid condition in transition-metal catalyst.But, this kind of catalyst, particularly metal oxide catalyst, because its excellent catalytic performance, the advantage such as cheap, easily separated still receive in actual applications and pay attention to widely.At present that searching one class catalytic activity is high in the topmost task in this field, stable in properties and the metal oxide catalyst of reusable edible.
In recent years, in document, there is ABO
3type perovskite oxide LaFeO
3degraded for waste water from dyestuff obtains the very big concern (as: Advanced Materials Research465 (2012) 37-43) of numerous Conservation Scientist, but reaction condition is generally photocatalytic degradation, and experiment condition is relatively harsh.Also having document (Journal of Nanoparticle Research12 (2010) 967-974) to report with SBA-16 is that Template preparation has LaFeO that is poroid, bigger serface
3oxide is used for photocatalytic degradation of dye rhodamine B.LaFeO in these reports
3be use as a kind of photochemical catalyst, required experimental facilities requires higher, also there is certain difficulty in actual applications.Also document (Applied Catalysis B:Environmental125 (2012) 418-424) report LaCuO is had recently
3as catalyst hydrogenperoxide steam generator oxidation rhodamine B, but prepared specific surface area of catalyst is little, limits its adsorption and oxidation ability to dyestuff.
Summary of the invention
For the deficiencies in the prior art, the SBA-15 load LaFeO that the object of the present invention is to provide a class novel
3(i.e. LaFeO
3/ SBA-15) Catalysts and its preparation method and application.Transmission electron microscope (TEM) result shows the LaFeO in catalyst
3be highly dispersed on SBA-15 surface, grain diameter is between 10 – 20nm, and SBA-15 can also keep original pore structure not to be destroyed.The catalyst of this support type not only can improve LaFeO
3decentralization and utilization rate, simultaneously because the pore structure of SBA-15 also improves the adsorption capacity to organic dyestuff.LaFeO
3with this mutual collaboration capabilities between SBA-15 makes catalyst demonstrate efficient catalytic oxidation elimination organic dyestuff performance.Further result of study shows that this catalyst can also in wider pH range applications, and can keep active constant through to recycle at least 6 times.
Realize the technical scheme that the object of the invention takes as follows:
A kind of LaFeO
3/ SBA-15 catalyst, adopt sol-gel process preparation and obtain, its concrete preparation process is as follows:
(1) in molar ratio for lanthanum nitrate 0.01mol, ferric nitrate 0.01mol and citric acid 0.024mol are joined distilled water by the ratio of 1:1:2.4 and absolute ethyl alcohol volume ratio is in the 30mL mixed liquor of 1:2, after dissolving to be mixed, add 2g SBA-15, continue to stir and evenly mix, obtain reactant mixture.
This method does not have particular/special requirement to SBA-15, and the application SBA-15 used conventionally makes by oneself for inventor laboratory, and concrete preparation method is shown in detailed description of the invention.
(2) above reactant mixture be placed in 70 ° of C stirred in water bath and steam to gel state, being placed in 100 ° of C baking ovens dry subsequently again.
(3) taking-up of oven dry sample is placed on calcined crystalline in Muffle furnace and obtains target product.Muffle furnace temperature-rise period is as follows: rise to 500 ° of C with the heating rate of 2 ° of C/min from room temperature, after keeping 4h, then rises to 700 ° of C with the heating rate of 2 ° of C/min, then keeps 4h, be cooled to room temperature subsequently, take out and get final product.
Compared with prior art, advantage of the present invention and beneficial effect as follows:
The preparation method of product of the present invention is simple to operate, and load has LaFeO
3the SBA-15 of catalyst can keep original meso-hole structure, also improves active component LaFeO simultaneously
3degree of scatter and specific area.Catalyst LaFeO
3/ SBA-15 take hydrogenperoxide steam generator as oxidant, as a class heterogeneous Fenton reagent, all have the performance that excellent catalytic oxidation eliminates organic dyestuff, and stripping phenomenon can not occur active component under acid, alkali condition.Even if catalyst activity after six circulations still can remain unchanged, there is good actual application prospect.
Accompanying drawing explanation
Fig. 1 is LaFeO prepared by embodiment 1
3/ SBA-15 and corresponding SBA-15 and LaFeO
3(A) little angle and (B) big angle X-ray powder diffraction pattern.
Fig. 2 is LaFeO prepared by embodiment 1
3(A) N of/SBA-15
2-adsorption/desorption isotherms; (B) pore size distribution curve; (C) Fe2p photoelectron spectroscopy figure; (D) transmission electron microscope picture.
Fig. 3 is the LaFeO of (A) embodiment 1 preparation
3/ SBA-15, SBA-15 and LaFeO
3the adsorption capacity of rhodamine B is compared; (B) LaFeO of embodiment 1 preparation
3/ SBA-15 and corresponding LaFeO
3to low concentration rhodamine B (2 × 10
-5mol/L) catalytic oxidation activity; (C) LaFeO of embodiment 1 preparation
3/ SBA-15 and corresponding LaFeO
3to high concentration rhodamine B (1 × 10
-3mol/L) catalytic oxidation activity; (D) LaFeO of embodiment 1 preparation
3/ SBA-15 is to low concentration rhodamine B (2 × 10
-5mol/L) six circulation catalytic oxidation activities; (E) LaFeO of embodiment 1 preparation
3/ SBA-15 under condition of different pH in 90min to low concentration rhodamine B (2 × 10
-5mol/L) oxidative degradation activity; (F) LaFeO of embodiment 1 preparation
3/ SBA-15 is active to the catalyzing oxidizing degrading in during different dyes 2h.
Detailed description of the invention
Applicant will be described in detail preparation method of the present invention and application in conjunction with specific embodiments below, further understand so that those skilled in the art has the present invention.But following examples should not be interpreted as the restriction to request protection domain of the present invention by any way.
Embodiment 1: a kind of LaFeO
3the preparation method of/SBA-15, step is as follows:
(1) get 0.01mol lanthanum nitrate, 0.01mol ferric nitrate, 0.024mol citric acid, 10mL distilled water and 20mL absolute ethyl alcohol, they are put in after being uniformly mixed in beaker, add 2g SBA-15, and continue to stir.
The preparation method of the SBA-15 related in the present embodiment and subsequent embodiment is as follows:
Get 5g P123 to be dissolved in the mixed solvent that 75g distilled water and 150g HCl (2M) form.After under 35 ° of C, vigorous stirring is dissolved completely to P123, after slowly dripping 10.5g ethyl orthosilicate, continue to stir 24h under 35 ° of C.Then 100 ° of C crystallization 24h in crystallization tank, cooling, suction filtration, obtain white powder, and wash 5-6 time with distilled water, then cool after in the dry 24h of 100 ° of C, Muffle furnace, 550 ° of C calcine 6h, to obtain final product.
(2) above reactant mixture is placed on magnetic force heating stirrer, also steams to gel state in 70 ° of C stirred in water bath, be placed in 100 ° of C baking ovens dry subsequently again.
(3) dried sample taken out and put into Muffle furnace calcined crystalline and obtain target product.Muffle furnace temperature-rise period is as follows: rise to 500 ° of C with 2 ° of C/min from room temperature, after keeping 4h, is warming up to 700 ° of C, then is down to room temperature after keeping 4h, obtain target product LaFeO with 2 ° of C/min
3/ SBA-15.
The instrumental characterizing of product:
(1) the little angle of product and big angle X-ray powder diffraction analysis, be shown in accompanying drawing 1 (A) and (B).Small-angle diffraction test spectrogram (A) illustrates LaFeO
3/ SBA-15 catalyst maintains the meso-hole structure of carrier S BA-15; Big angle diffraction test spectrogram (B) illustrates LaFeO
3/ SBA-15 catalyst has LaFeO
3type perovskite structure and there are not other metal oxide impurities.
(2) N
2-adsorption/desorption isotherms is shown in accompanying drawing 2 (A), and result shows that product has H1 type thermoisopleth.Calculate through BET formula, the specific area of trying to achieve this mesoporous supported catalyst is less than carrier S BA-15, simultaneously according to graph of pore diameter distribution accompanying drawing 2 (B), the aperture of this mesoporous supported catalyst is less than carrier S BA-15, illustrate that active component perovskite enters into the mesopore orbit of SBA-15 or plugs cell channels, reduce surface area and aperture.
(3) x-ray photoelectron spectroscopy, is shown in accompanying drawing 2 (C), mainly exists with+3 valencys by consulting Fe element in XPS databook this supported catalyst known.
(4) transmission electron microscope picture, is shown in accompanying drawing 2 (D), clearly can see that SBA-15 meso-hole structure and particle diameter are the LaFeO of 10-20nm from figure
3particle, this characterization result and XRD, N
2-adsorption/desorption isotherms result is consistent, confirms perovskite LaFeO
3it is the surface being highly dispersed at mesoporous silicon SBA-15.
Be below the embodiment of application, all operate under room temperature (20-25 DEG C).
Embodiment 2:
The LaFeO that embodiment 1 is obtained
3/ SBA-15 is to the adsorption capacity of rhodamine B:
Experimentation is as follows: rhodamine B solution (2 × 10
-5mol/L) 50mL, LaFeO
3/ SBA-15 the amount of being incorporated as 0.1g, magnetic agitation is about 1h and reaches adsorption equilibrium, after filtration, measures the absorbance A of filtrate with 722E type visible spectrophotometer at 550nm wavelength.If the rhodamine B solution absorbance A after absorption reduces, the catalyst solid after filtration, by rejoining in the new rhodamine B solution of equal-volume same concentrations, carries out absorption again.This process repeats until the absorbance of rhodamine B no longer declines in solution, thinks that Catalyst Adsorption is saturated.By the calibration curve of concentration-absorbance, draw the rear rhodamine B concentration of absorption, and then obtain adsorbance.Adsorb saturated rear calculating to the saturated extent of adsorption of rhodamine B, Fig. 3 (A).
For inspection perovskite LaFeO
3on the impact of carrier S BA-15 absorption property, carry out check experiment.By LaFeO
3/ SBA-15 replaces with SBA-15 (0.1g), all the other operations and above-mentioned LaFeO
3/ SBA-15 adsorption experiment process is consistent, adsorbs saturated rear calculating saturated extent of adsorption, with LaFeO
3the saturated extent of adsorption of/SBA-15 compares, Fig. 3 (A).LaFeO in figure
3the adsorption capacity of/SBA-15 is slightly less than pure carrier, and this is due to LaFeO
3occupy caused by the cell channels in SBA-15.The LaFeO of non-load
3(except not adding SBA-15 carrier, all the other are with embodiment 1 in its preparation) does not adsorb (visible in Fig. 3 A) substantially to RhB, can ignore.Therefore, although LaFeO
3the adsorption capacity of/SBA-15 to RhB is less than SBA-15, but much larger than the LaFeO of non-load
3, thus can more efficiently RhB oxidation be eliminated.
Embodiment 3:
In order to detect LaFeO
3the superiority of/SBA-15, compares and has contrasted non-load LaFeO
3(except not adding SBA-15 carrier, all the other are with embodiment 1 in its preparation) catalytic degradation situation to low concentration rhodamine B solution.By adsorb in embodiment 2 saturated after LaFeO
3/ SBA-15 catalyst joins the fresh rhodamine B solution (2 × 10 of 50mL
-5mol/L), in, after magnetic agitation 30min, 1mL hydrogenperoxide steam generator (mass fraction is 30%) is added, take out 4mL solution every 30min, after filtration, measure absorbance and be converted to rhodamine B concentration, draw degrading activity to time changing curve, Fig. 3 (B).The non-load LaFeO of figure mean quality
3with support type LaFeO
3/ SBA-15 catalyst is close with the change curve in reaction time to RhB conversion ratio.But it is pointed out that LaFeO in support type perovskite
3load capacity be 55%, and carrier S BA-15 to RhB without catalytic degradation ability; In addition, LaFeO
3the rhodamine B that/SBA-15 is oxidized is adsorbed on the rhodamine B in its duct before also comprising.Therefore, on the whole, support type LaFeO
3the LaFeO of 0.055g in/SBA-15
3there is the non-load LaFeO than 0.1g
3higher to RhB catalytic degradation activity.This has not only saved active component LaFeO
3consumption, also improve and ability eliminated to the oxidation of rhodamine B.
Embodiment 4:
Although we can illustrate LaFeO from embodiment 3
3laFeO in/SBA-15
3high usage, but from figure, intuitively seem it is not clearly.Thus, for further illustrating LaFeO
3the superiority of/SBA-15, we compare non-load LaFeO
3with support type LaFeO
3/ SBA-15 is to the catalytic degradation situation of higher concentration rhodamine B solution.Rhodamine B solution concentration is increased to 10
-3mol/L, catalyst (be in embodiment 2 to rhodamine B absorption saturated after catalyst) addition be 0.3g, all the other operations are consistent with embodiment 3 method.The corresponding absorbance of different time points, draws degrading activity curve over time, Fig. 3 (C).Now can find out that the catalytic degradation ability of two class catalyst has obvious difference, support type LaFeO under the same terms
3the catalytic performance of/SBA-15 is far above the LaFeO of non-load
3(such as when reacting 3h, the former degrading activity can reach about 90%, and the latter is about 40%), clearly indicates LaFeO
3/ SBA-15 has than non-load LaFeO
3better catalytic oxidation ability.
Embodiment 5:
For detecting LaFeO
3/ SBA-15, to the service life of rhodamine B solution degradation, by the catalyst filtration after catalytic degradation reaction in embodiment 3, again joins and fills 50mL rhodamine B solution (2 × 10
-5mol/L), in beaker, stir and carry out second time catalytic degradation reaction, concrete operations are with embodiment 3.Carry out six circulations (containing first) reaction successively, the different cycle-indexes of test and comparison catalytic degradation activity when the reaction time is 120min, Fig. 3 (D).Result shows, and after six circulations, catalytic efficiency is without obvious reduction, and show catalyst stable in properties in aqueous phase dye degrades, long service life, has the prospect of commercial Application.
Embodiment 6:
In order to detect LaFeO
3/ SBA-15 to the degraded situation of rhodamine B, carries out following control experiment under different pH environment.After adding hydrogen peroxide, regulate pH to 2.28,7.3,9.29,10.46 respectively with dilute sulfuric acid or sodium hydroxide solution, remaining reaction condition and operation consistent with embodiment 3 method.The catalytic degradation activity of test and comparison when the reaction time is 120min under condition of different pH, Fig. 3 (E).From figure, catalyst can demonstrate the activity of the catalytic oxidation rhodamine B of more than 90% between pH=2-10.And the catalytic degradation reaction of traditional F enton reagent could need realize in the solution of pH<4, LaFeO is described
3/ SBA-15 catalyst expands the scope of application of traditional F enton reagent to pH during aqueous phase dye degrades.
Embodiment 7:
In order to check LaFeO
3/ SBA-15, to the degraded situation of variety classes dyestuff, carries out following control experiment.By reactive brilliant red x-3b (2 × 10
-5mol/L), dye 4BS red (2 × 10
-5and methylene blue MB (2.675 × 10 mol/L)
-5mol/L) substitute rhodamine B, remaining reaction condition and operation consistent with embodiment 3 method.When relatively the reaction time is 120min, catalyst is to the degrading activity of various organic dyestuff, Fig. 3 (F).Result shows that catalyst all has good catalytic degradation efficiency to above-mentioned four kinds of dyestuffs, is wherein best to the degradation effect of rhodamine B, reaches 100%, LaFeO is described
3/ SBA-15 has the ability of good catalytic degradation organic dyestuff, has wide prospects for commercial application.
Claims (1)
1. a LaFeO
3the preparation method of/SBA-15, its step is as follows:
(1) in molar ratio for lanthanum nitrate 0.01mol, ferric nitrate 0.01mol and citric acid 0.024mol are joined distilled water by the ratio of 1:1:2.4 and absolute ethyl alcohol volume ratio is in the 30mL mixed liquor of 1:2, after dissolving to be mixed, add 2g SBA-15, continue to stir and evenly mix, obtain reactant mixture;
(2) stir under above reactant mixture being placed in 70 C and steam to gel state, being placed in 100 C baking ovens dry subsequently again;
(3) taking-up of oven dry sample is placed on calcined crystalline in Muffle furnace and obtains target product, Muffle furnace temperature-rise period is as follows: rise to 500 C with the heating rate of 2 C/min from room temperature, after keeping 4h, 700 C are risen to again with the heating rate of 2 C/min, keep 4h again, be cooled to room temperature subsequently, take out and get final product.
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| CN114225895B (en) * | 2022-02-25 | 2022-05-13 | 农业农村部环境保护科研监测所 | La-Fe-Al composite metal oxide, preparation method and application |
| CN117623483A (en) * | 2024-01-26 | 2024-03-01 | 农业农村部环境保护科研监测所 | Application of nickel-doped lanthanum-iron perovskite in degradation of antibiotics |
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