CN104801308A - NiFe2O4/TiO2/sepiolite composite photocatalyst and preparation method thereof - Google Patents

NiFe2O4/TiO2/sepiolite composite photocatalyst and preparation method thereof Download PDF

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CN104801308A
CN104801308A CN201510233949.0A CN201510233949A CN104801308A CN 104801308 A CN104801308 A CN 104801308A CN 201510233949 A CN201510233949 A CN 201510233949A CN 104801308 A CN104801308 A CN 104801308A
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sepiolite
tio
nife
catalyst
film
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CN104801308B (en
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刘少敏
朱敬林
杨清
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Anhui University of Science and Technology
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Anhui University of Science and Technology
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Abstract

The invention discloses a NiFe2O4/TiO2/sepiolite composite photocatalyst which comprises the components of sepiolite, TiO2 and NiFe2O4, wherein the sepiolite is taken as a carrier, the TiO2 coats the surface of the sepiolite in a form of film, and the NiFe2O4 is loaded on the surface of the TiO2 in a form of granule. The invention also provides a preparation method of the NiFe2O4/TiO2/sepiolite composite photocatalyst. According to the NiFe2O4/TiO2/sepiolite composite photocatalyst and the preparation method thereof disclosed by the invention, the TiO2 coats the surface of the sepiolite in the form of film, and the NiFe2O4 is loaded on the surface of the TiO2 in the form of granule; the NiFe2O4 is loaded on the surface of the TiO2 film in the form of granule, does not shield the whole TiO2 film but forms a coincidence effect with the TiO2; the sepiolite is taken as the carrier, so that the adsorption capacity of the catalyst can be further improved, and further the catalyst simultaneously has the advantages of good adsorption effect, high photocatalytic activity and capabilities of recovering and repeatedly utilizing, and widens the response range of light; the catalytic activity of the catalyst in an ultraviolet light zone is improved, and the response wavelength of the catalyst is transferred from the ultraviolet light zone to a visible light zone, so that the utilization rate of sunlight can be improved.

Description

A kind of NiFe 2o 4/ TiO 2/ sepiolite composite photo-catalyst and preparation method thereof
Technical field
The present invention relates to photocatalytic oxidation technical field, relate in particular to a kind of NiFe 2o 4/ TiO 2/ sepiolite composite photo-catalyst and preparation method thereof.
Background technology
Photochemical catalytic oxidation law technology is a kind of new and effective technology for treating industrial waste water being applied to field of wastewater over nearly twenties years.Photochemical catalyst conventional in photochemical catalytic oxidation law technology is nano-TiO 2, it is for wastewater treatment, is a new breakthrough of green technology.Nano-TiO 2photochemical catalyst is under the irradiation of ultraviolet light, the electron-hole pair that energy generation is oxidized and reducing power is stronger, the chloro phenols, halogenated hydrocarbon, dioxin, various organic acids etc. that can effectively degrade in paper waste, and except cleanliness is high, degradation speed is fast, non-secondary pollution, life cycle pollutant that is long, that be suitable for is wide, reach the object of once-used degradeable pollutant, so very extensive to its research.
At present, TiO 2to come with some shortcomings in actual application part as photochemical catalyst, such as: TiO 2photochemical catalyst quantum efficiency low, Selective adsorption is poor, and condition of cure is harsh, easily cohesion, easy in inactivation, and spectral response range is at ultraviolet region, and in solar spectrum, visible light part can not effectively utilize, and these all limit TiO 2commercial Application.For TiO 2as the deficiency that photochemical catalyst exists, domestic and international to TiO at present 2photochemical catalyst mainly carries out the study on the modification of two aspects: one is exploitation TiO 2loaded photocatalyst; Two is to TiO by doping 2carry out modification, make it be utilized better in actual applications.
At TiO 2in loaded photocatalyst research field, researcher is had to develop TiO 2/ sepiolite supported type photochemical catalyst, this catalyst is at sepiolite surface parcel TiO 2, sepiolite is moisture zeopan clay mineral, low price, and wide material sources are a kind of porous media materials with more bigger serface, can improve the adsorption effect to organic pollution.There is a large amount of microchannel in sepiolite crystal structure, be combined by countless parallel tubular shape duct, its specific area is large, and sepiolite adsorption property is subject to the restriction of its crystal structure.Sepiolite surface charge is broken by the Si-O key on its surface and Al-O key generation hydrolysis, acid can be become, also can as alkali, the hydroxyl (-OH) on the R-OH that broken key hydrolysis produces, therefore it has both sexes, these surface reactions make sepiolite surface band electric charge.Modifying function mainly makes sepiolite structure charge in aqueous and surface charge change, thus changes charging property and the adsorption activity of sepiolite.
Passing through doping to TiO 2carry out modification field, have researcher to utilize magnetic material to TiO 2carry out the composite catalyst adulterating to be formed, conventional doping gimmick has at Fe 3o 4or CoFe 2o 4surface parcel TiO 2, this composite catalyst can increase light abstraction width, photocatalytic activity.In addition owing to being doped with magnetic material, be conducive to the recovery and reuse of catalyst.
Summary of the invention
Technical problem to be solved by this invention is to provide and a kind ofly has the NiFe of advantage that advantages of good adsorption effect, photocatalytic activity are high, can reclaim and reuse simultaneously 2o 4/ TiO 2/ sepiolite composite photo-catalyst.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme: a kind of NiFe 2o 4/ TiO 2/ sepiolite composite photo-catalyst, composition comprises sepiolite, TiO 2and NiFe 2o 4, sepiolite is carrier, TiO 2be wrapped in sepiolite surface in membrane form, NiFe 2o 4load is at TiO in the form of granules 2surface.
Further, wherein the content of Ni is 1-2wt%, the content of Fe is 1.9-3.8wt%, the content of Ti is 12-18wt%, more than be divided into sepiolite.NiFe 2o 4/ TiO 2when each constituent content of/sepiolite composite photo-catalyst is within the scope of this, its good catalytic activity.
Further, the content of the content of Ni to be the content of 1.5wt%, Fe be 2.8wt%, Ti is 15wt%, more than be divided into sepiolite.
The present invention also provides described NiFe 2o 4/ TiO 2the preparation method of/sepiolite composite photo-catalyst, comprises the following steps:
(1) pretreatment of sepiolite
Sepiolite powder is broken into end, be placed in dust technology immersion 15-24h that concentration is 5-15%, filter, with water rinse to neutral post-drying, then at the temperature lower calcination 2-4h of 400-500 DEG C, filtered out by the sepiolite floating on water body upper position with water rinse, after dry, sieve gets particle diameter is that 100-125 object sepiolite powder are as carrier;
(2) TiO 2the preparation of colloidal sol
Under room temperature, by volume part, the butyl titanate of 15-20 is fully dissolved in the absolute ethyl alcohol of 40-50, then the acetylacetone,2,4-pentanedione of 5-6 is added, obtain solution A, solution B is obtained after the distilled water of 0.75-1.0 and the absolute ethyl alcohol of 20-25 fully being mixed, under the condition constantly stirred, solution B is joined in solution A gradually, then with red fuming nitric acid (RFNA) or concentrated hydrochloric acid, pH value is adjusted to 4-5, stir l-2h, add the polyethylene glycol of 1-1.5, then under the condition of 40-65 DEG C, stir l-1.5h, obtain the TiO of yellow transparent 2colloidal sol, by TiO 2colloidal sol is ageing 12-15h at room temperature;
(3) at sepiolite surface parcel TiO 2film
TiO 2the number of plies of film is 1-3 layers, every layer of TiO 2the formation method of film is: under room temperature, sepiolite is joined TiO 2in colloidal sol, be stirred to and TiO 2colloidal sol mixes completely, then dries under the condition of 70-85 DEG C, finally under the condition of 400-500 DEG C, calcines 1-3h, for subsequent use after cooling;
(4) at TiO 2film area load NiFe 2o 4particle
Under room temperature, by weight, by the Ni (NO of 2.91-5.82 3) 26H 2fe (the NO of O and 8.08-16.16 3) 39H 2o joins in the absolute ethyl alcohol of 55.3-63.2, stirs 30-60min, by the NaOH solution of 5-20mol/L, pH value is adjusted to 9-10, then adds and be enclosed with TiO 2the sepiolite of film, stirs 30-60min, then under the condition of 160-180 DEG C, reacts 18-24h, carries out Separation of Solid and Liquid, washing, finally dry under the condition of 70-85 DEG C, obtain described NiFe after cooling 2o 4/ TiO 2/ sepiolite composite photo-catalyst.
For the purpose of succinctly describing, NiFe of the present invention below 2o 4/ TiO 2/ sepiolite composite photo-catalyst referred to as this catalyst, described NiFe 2o 4/ TiO 2the preparation method of/sepiolite composite photo-catalyst is referred to as this method.
Beneficial effect of the present invention is:
(1) this catalyst is by TiO 2be wrapped in sepiolite surface in membrane form, NiFe 2o 4load is at TiO in the form of granules 2surface, NiFe 2o 4load is at TiO in the form of granules 2film surface, can not cover whole TiO 2film, but and TiO 2form a coincidence effect, using sepiolite as carrier, can further improve the adsorption capacity of catalyst, thus this catalyst is had simultaneously advantages of good adsorption effect, photocatalytic activity are high, can reclaim and reuse advantage, and expanded photoresponse scope, this catalyst is not only improved in the catalytic activity of ultraviolet region, and response wave length moves to visible region from ultraviolet region, thus can improve the utilization rate of sunshine.
(2) this catalyst have employed NiFe 2o 4, NiFe 2o 4not only there is magnetic action, be easy to reclaim and recycling, and NiFe 2o 4under ultraviolet light also can catalyzing and degrading pollutant as catalyst, its load is at TiO 2film surface, improves the degradation rate of this catalyst at ultraviolet region on the one hand, widens photoresponse scope to visible region on the other hand.
(3) this method is by NiFe with hydro-thermal method 2o 4synthesis load is at TiO 2film surface, the feature of hydro-thermal method to prepare that purity is higher, the nano particle of good dispersion, good crystalline, so just makes NiFe 2o 4with the form of nano particle very equably load at TiO 2film surface, and be that forced hydrolysis generates Ni (OH) due to what adopted before hydro-thermal reaction 2with Fe (OH) 3, do not add hydrolysis inhibitor and surfactant, thus ensure NiFe in hydro-thermal reaction subsequently 2o 4not easily exist in membrane form, but be distributed in TiO with graininess 2film surface.
(4) this method is calcined sepiolite in the preprocessing process of sepiolite, impurity in sepiolite surface and internal void can be become gaseous material to remove, thus increase sepiolite specific surface area and porosity, improve surface area and the adsorption capacity of sepiolite, be conducive to TiO 2load, improve photocatalysis performance.
(5) this method is at TiO 2in the preparation process of colloidal sol, butyl titanate and distilled water generation hydrolysis generate TiO 2colloidal sol, because the hydrolysis of butyl titanate is very violent, so add the inhibitor of acetylacetone,2,4-pentanedione as it, acetylacetone,2,4-pentanedione and butyl titanate form ligand, and a large amount of water can not be removed, and these ligands prevent hydrolysis to carry out, and TiO 2further polymerization, thus form stable colloidal solution.
(6) this method is at sepiolite surface parcel TiO 21-3 layers of TiO have been wrapped up in the process of film 2film, along with TiO 2the increase of rete number, catalytic effect can be become better and better, and works as TiO 2when rete number is more than 3 layers, catalytic effect is deteriorated.
Accompanying drawing explanation
Fig. 1 is the NiFe of the embodiment of the present invention 1 gained 2o 4/ TiO 2the scanning electron microscope (SEM) photograph of/sepiolite composite photo-catalyst.
Fig. 2 is existing TiO 2the NiFe of/sepiolite supported type photochemical catalyst and the embodiment of the present invention 1 gained 2o 4/ TiO 2the solid ultraviolet-visible light spectrogram of/sepiolite composite photo-catalyst.
Fig. 3 is the NiFe of sepiolite and the embodiment of the present invention 1 gained 2o 4/ TiO 2the infrared spectrogram of/sepiolite composite photo-catalyst.
Fig. 4 is with the NiFe of the embodiment of the present invention 1 gained 2o 4/ TiO 2the degradation efficiency figure of/sepiolite composite photo-catalyst photocatalytic degradation methylene blue solution.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
A kind of NiFe 2o 4/ TiO 2/ sepiolite composite photo-catalyst, composition comprises sepiolite, TiO 2and NiFe 2o 4, sepiolite is carrier, TiO 2be wrapped in sepiolite surface in membrane form, NiFe 2o 4load is at TiO in the form of granules 2surface, wherein the content of the content of Ni to be the content of 1.5wt%, Fe be 2.8wt%, Ti is 15wt%, more than be divided into sepiolite.
Above-mentioned NiFe 2o 4/ TiO 2the preparation method of/sepiolite composite photo-catalyst, comprises the following steps:
(1) pretreatment of sepiolite
Sepiolite powder is broken into end, be placed in concentration be 5% dust technology soak 20h, filter, with water rinse to neutral post-drying, then Muffle furnace is placed at the temperature lower calcination 4h of 400 DEG C, filtered out by the sepiolite floating on water body upper position with water rinse, after dry, sieve gets particle diameter is that 100 object sepiolite powder are as carrier;
(2) TiO 2the preparation of colloidal sol
Under room temperature, by volume part, the butyl titanate of 18 is fully dissolved in the absolute ethyl alcohol of 40, then the acetylacetone,2,4-pentanedione of 5.5 is added, obtain solution A, solution B is obtained after the distilled water of 0.88 and the absolute ethyl alcohol of 25 fully being mixed, under the condition constantly stirred, solution B is joined in solution A gradually, then with red fuming nitric acid (RFNA), pH value is adjusted to 4, stir (80r/min) 1.5h, add the polyethylene glycol of 1.2, then under the condition of 52 DEG C, stir (100r/min) lh, obtain the TiO of yellow transparent 2colloidal sol, by TiO 2colloidal sol is ageing 12h at room temperature;
(3) at sepiolite surface parcel TiO 2film
TiO 2the number of plies of film is 2 layers, every layer of TiO 2the formation method of film is: under room temperature, sepiolite is joined TiO 2in colloidal sol, stir (80r/min) 1.2h and make sepiolite and TiO 2colloidal sol mixes completely, then dries under the condition of 70 DEG C, and drying course adopts first water-bath to steam near dry, then dries with drying box, is finally placed in Muffle furnace under the condition of 500 DEG C to calcine 1h, for subsequent use after cooling;
(4) at TiO 2film area load NiFe 2o 4particle
Under room temperature, by weight, by the Ni (NO of 4.37 3) 26H 2fe (the NO of O and 12.12 3) 39H 2o joins in the absolute ethyl alcohol of 59, and magnetic agitation (120r/min) 45min, is adjusted to 9 by the NaOH solution of 5mol/L by pH value, then adds and is enclosed with TiO 2the sepiolite of film, stirs (100r/min) 30min, then under the condition of 180 DEG C, reacts 21h, carry out Separation of Solid and Liquid, washing after cooling, finally dry under the condition of 70 DEG C, obtain described NiFe 2o 4/ TiO 2/ sepiolite composite photo-catalyst.
Embodiment 2
A kind of NiFe 2o 4/ TiO 2/ sepiolite composite photo-catalyst, composition comprises sepiolite, TiO 2and NiFe 2o 4, sepiolite is carrier, TiO 2be wrapped in sepiolite surface in membrane form, NiFe 2o 4load is at TiO in the form of granules 2surface, wherein the content of the content of Ni to be the content of 1wt%, Fe be 1.9wt%, Ti is 12wt%, more than be divided into sepiolite.
Above-mentioned NiFe 2o 4/ TiO 2the preparation method of/sepiolite composite photo-catalyst, comprises the following steps:
(1) pretreatment of sepiolite
Sepiolite powder is broken into end, be placed in concentration be 10% dust technology soak 15h, filter, with water rinse to neutral post-drying, then Muffle furnace is placed at the temperature lower calcination 3h of 450 DEG C, filtered out by the sepiolite floating on water body upper position with water rinse, after dry, sieve gets particle diameter is that 112 object sepiolite powder are as carrier;
(2) TiO 2the preparation of colloidal sol
Under room temperature, by volume part, the butyl titanate of 15 is fully dissolved in the absolute ethyl alcohol of 45, then the acetylacetone,2,4-pentanedione of 5 is added, obtain solution A, solution B is obtained after the distilled water of 0.75 and the absolute ethyl alcohol of 20 fully being mixed, under the condition constantly stirred, solution B is joined in solution A gradually, then with red fuming nitric acid (RFNA), pH value is adjusted to 5, stir (120r/min) lh, add the polyethylene glycol of 1.5, then under the condition of 65 DEG C, stir (80r/min) l.2h, obtain the TiO of yellow transparent 2colloidal sol, by TiO 2colloidal sol is ageing 15h at room temperature;
(3) at sepiolite surface parcel TiO 2film
TiO 2the number of plies of film is 1 layer, every layer of TiO 2the formation method of film is: under room temperature, sepiolite is joined TiO 2in colloidal sol, stir (100r/min) 1.5h and make sepiolite and TiO 2colloidal sol mixes completely, then dries under the condition of 80 DEG C, and drying course adopts first water-bath to steam near dry, then dries with drying box, is finally placed in Muffle furnace under the condition of 450 DEG C to calcine 2h, for subsequent use after cooling;
(4) at TiO 2film area load NiFe 2o 4particle
Under room temperature, by weight, by the Ni (NO of 2.91 3) 26H 2fe (the NO of O and 8.08 3) 39H 2o joins in the absolute ethyl alcohol of 55.3, and magnetic agitation (80r/min) 30min, is adjusted to 10 by the NaOH solution of 15mol/L by pH value, then adds and is enclosed with TiO 2the sepiolite of film, stirs (120r/min) 60min, then under the condition of 160 DEG C, reacts 24h, carry out Separation of Solid and Liquid, washing after cooling, finally dry under the condition of 85 DEG C, obtain described NiFe 2o 4/ TiO 2/ sepiolite composite photo-catalyst.
Embodiment 3
A kind of NiFe 2o 4/ TiO 2/ sepiolite composite photo-catalyst, composition comprises sepiolite, TiO 2and NiFe 2o 4, sepiolite is carrier, TiO 2be wrapped in sepiolite surface in membrane form, NiFe 2o 4load is at TiO in the form of granules 2surface, wherein the content of the content of Ni to be the content of 2wt%, Fe be 3.8wt%, Ti is 18wt%, more than be divided into sepiolite.
Above-mentioned NiFe 2o 4/ TiO 2the preparation method of/sepiolite composite photo-catalyst, comprises the following steps:
(1) pretreatment of sepiolite
Sepiolite powder is broken into end, be placed in concentration be 15% dust technology soak 24h, filter, with water rinse to neutral post-drying, then Muffle furnace is placed at the temperature lower calcination 2h of 500 DEG C, filtered out by the sepiolite floating on water body upper position with water rinse, after dry, sieve gets particle diameter is that 125 object sepiolite powder are as carrier;
(2) TiO 2the preparation of colloidal sol
Under room temperature, by volume part, the butyl titanate of 20 is fully dissolved in the absolute ethyl alcohol of 50, then the acetylacetone,2,4-pentanedione of 6 is added, obtain solution A, solution B is obtained after the distilled water of 1.0 and the absolute ethyl alcohol of 23 fully being mixed, under the condition constantly stirred, solution B is joined in solution A gradually, then with concentrated hydrochloric acid, pH value is adjusted to 4.5, stir (100r/min) 2h, add the polyethylene glycol of 1, then under the condition of 40 DEG C, stir (120r/min) 1.5h, obtain the TiO of yellow transparent 2colloidal sol, by TiO 2colloidal sol is ageing 13h at room temperature;
(3) at sepiolite surface parcel TiO 2film
TiO 2the number of plies of film is 3 layers, every layer of TiO 2the formation method of film is: under room temperature, sepiolite is joined TiO 2in colloidal sol, stir (120r/min) 1h and make sepiolite and TiO 2colloidal sol mixes completely, then dries under the condition of 85 DEG C, and drying course adopts first water-bath to steam near dry, then dries with drying box, is finally placed in Muffle furnace under the condition of 400 DEG C to calcine 3h, for subsequent use after cooling;
(4) at TiO 2film area load NiFe 2o 4particle
Under room temperature, by weight, by the Ni (NO of 5.82 3) 26H 2fe (the NO of O and 16.16 3) 39H 2o joins in the absolute ethyl alcohol of 63.2, and magnetic agitation (100r/min) 60min, is adjusted to 9 by the NaOH solution of 20mol/L by pH value, then adds and is enclosed with TiO 2the sepiolite of film, stirs (80r/min) 45min, then under the condition of 170 DEG C, reacts 18h, carry out Separation of Solid and Liquid, washing after cooling, finally dry under the condition of 80 DEG C, obtain described NiFe 2o 4/ TiO 2/ sepiolite composite photo-catalyst.
Embodiment 4
To the NiFe of the embodiment of the present invention 1 gained 2o 4/ TiO 2/ sepiolite composite photo-catalyst is (hereinafter referred to as NiFe 2o 4/ TiO 2/ sepiolite) carry out electron-microscope scanning, the test of solid ultraviolet-visible light spectrogram and examination of infrared spectrum, test result is shown in Fig. 1, Fig. 2 and Fig. 3.
Be at sepiolite surface parcel TiO on the left of Fig. 1 in the embodiment of the present invention 1 2scanning electron microscope (SEM) photograph after film, right side is NiFe 2o 4/ TiO 2the scanning electron microscope (SEM) photograph of/sepiolite, as can be seen from Figure 1, sepiolite is through modified slabbing, and surface area is large, TiO 2film is defined, TiO on sepiolite surface 2film area load has granular NiFe 2o 4, therefore the present invention is conducive to increasing specific area, absorption property and photocatalytic activity.
In Fig. 2, a is existing TiO 2/ sepiolite supported type photochemical catalyst is (hereinafter referred to as TiO 2/ sepiolite) solid ultraviolet-visible light spectrogram, b is NiFe 2o 4/ TiO 2the solid ultraviolet-visible light spectrogram of/sepiolite, as can be seen from Figure 2, TiO 2there is wider energy gap (3.2eV), TiO 2the energy gap of/sepiolite is reduced to 3.18eV, and NiFe 2o 4/ TiO 2the energy gap of/sepiolite is reduced to 2.85eV further, shows the NiFe of gained of the present invention 2o 4/ TiO 2/ sepiolite composite photo-catalyst has better catalytic activity to visible ray, thus improves the utilization ratio to visible ray.The NiFe of gained of the present invention also can be found out from Fig. 2 2o 4/ TiO 2the photoresponse scope of/sepiolite composite photo-catalyst extends to visible region.
In Fig. 3, a is the infrared spectrogram of sepiolite, and b is NiFe 2o 4/ TiO 2the infrared spectrogram of/sepiolite, at 600-800cm -1time, NiFe 2o 4/ TiO 2/ sepiolite compared with the infrared spectrogram of sepiolite, 668cm -1the absworption peak at place dies down, 755cm -1the Si-O at place outwardabsworption peak disappears, this is because NiFe 2o 4/ TiO 2the cause of the Ti-O in/sepiolite.1029cm -1the Si-O at place instretching vibration peak intensity substantially remain unchanged.3570cm -1the absworption peak of the free O-H at place disappears, and 535cm -1the absworption peak of the Si-O-Mg at place weakens, and illustrates that the magnesium in sepiolite may be substituted, may make Si-O bridge falls-Si increases, thus causes hole to increase, and absorption quantitative change is large.
Embodiment 5
The NiFe of the embodiment of the present invention 1 gained 2o 4/ TiO 2the photocatalytic degradation methylene blue solution measure of merit of/sepiolite composite photo-catalyst
Reaction initial conditions: methylene blue initial concentration 50mg/L, catalyst amount 0.4g, pH=5, it is carried out degradation experiment under ultraviolet catalytic reactor, degradation time is 60min, carries out visible spectrophotometer and measures its absorbance, measure methylene blue degradation efficiency every 10min sampling.Test result as shown in Figure 4, can be found out, the NiFe of the embodiment of the present invention 1 gained 2o 4/ TiO 2/ sepiolite composite photo-catalyst degradation efficiency when 60min can reach 85.56%, and existing TiO 2/ sepiolite supported type photochemical catalyst and CoFe 2o 4-TiO 2doping photochemical catalyst at identical conditions degradation efficiency generally can only reach about 70%.
Embodiment 6
Existing TiO 2/ sepiolite supported type photochemical catalyst, existing CoFe 2o 4-TiO 2the NiFe of doping photochemical catalyst and the embodiment of the present invention 1 gained 2o 4/ TiO 2the photocatalytic degradation methylene blue solution effectiveness comparison of/sepiolite composite photo-catalyst
Experiment condition: catalyst amount 1.0g, methylene blue initial concentration 4mg/L, pH=5, and degradation experiment is carried out under visible light catalytic reactor, degradation time is 120min, carries out measuring its absorbance, calculate methylene blue degradation efficiency every 20min sampling, result of the test is as shown in table 1, as can be seen from Table 1 the NiFe of the embodiment of the present invention 1 gained 2o 4/ TiO 2the absorbance of/sepiolite composite photo-catalyst and degradation rate are all obviously better than existing TiO 2/ sepiolite supported type photochemical catalyst and existing CoFe 2o 4-TiO 2doping photochemical catalyst, this shows NiFe of the present invention 2o 4/ TiO 2/ sepiolite composite photo-catalyst also has good photocatalytic degradation effect under visible light, and existing existing TiO 2/ sepiolite supported type photochemical catalyst and existing CoFe 2o 4-TiO 2doping photochemical catalyst photocatalytic degradation effect extreme difference under visible light, does not almost respond.
Table 1
Be to be understood that example as herein described and embodiment only in order to illustrate, those skilled in the art can make various amendment or change according to it, when not departing from Spirit Essence of the present invention, all belong to protection scope of the present invention.

Claims (4)

1. a NiFe 2o 4/ TiO 2/ sepiolite composite photo-catalyst, is characterized in that: composition comprises sepiolite, TiO 2and NiFe 2o 4, sepiolite is carrier, TiO 2be wrapped in sepiolite surface in membrane form, NiFe 2o 4load is at TiO in the form of granules 2surface.
2. NiFe as claimed in claim 1 2o 4/ TiO 2/ sepiolite composite photo-catalyst, is characterized in that: wherein the content of Ni is 1-2wt%, the content of Fe is 1.9-3.8wt%, the content of Ti is 12-18wt%, more than be divided into sepiolite.
3. NiFe as claimed in claim 2 2o 4/ TiO 2/ sepiolite composite photo-catalyst, is characterized in that: the content of the content of Ni to be the content of 1.5wt%, Fe be 2.8wt%, Ti is 15wt%, more than be divided into sepiolite.
4. NiFe as claimed any one in claims 1 to 3 2o 4/ TiO 2the preparation method of/sepiolite composite photo-catalyst, comprises the following steps:
(1) pretreatment of sepiolite
Sepiolite powder is broken into end, be placed in dust technology immersion 15-24h that concentration is 5-15%, filter, with water rinse to neutral post-drying, then at the temperature lower calcination 2-4h of 400-500 DEG C, filtered out by the sepiolite floating on water body upper position with water rinse, after dry, sieve gets particle diameter is that 100-125 object sepiolite powder are as carrier;
(2) TiO 2the preparation of colloidal sol
Under room temperature, by volume part, the butyl titanate of 15-20 is fully dissolved in the absolute ethyl alcohol of 40-50, then the acetylacetone,2,4-pentanedione of 5-6 is added, obtain solution A, solution B is obtained after the distilled water of 0.75-1.0 and the absolute ethyl alcohol of 20-25 fully being mixed, under the condition constantly stirred, solution B is joined in solution A gradually, then with red fuming nitric acid (RFNA) or concentrated hydrochloric acid, pH value is adjusted to 4-5, stir l-2h, add the polyethylene glycol of 1-1.5, then under the condition of 40-65 DEG C, stir l-1.5h, obtain the TiO of yellow transparent 2colloidal sol, by TiO 2colloidal sol is ageing 12-15h at room temperature;
(3) at sepiolite surface parcel TiO 2film
TiO 2the number of plies of film is 1-3 layers, every layer of TiO 2the formation method of film is: under room temperature, sepiolite is joined TiO 2in colloidal sol, be stirred to and TiO 2colloidal sol mixes completely, then dries under the condition of 70-85 DEG C, finally under the condition of 400-500 DEG C, calcines 1-3h, for subsequent use after cooling;
(4) at TiO 2film area load NiFe 2o 4particle
Under room temperature, by weight, by the Ni (NO of 2.91-5.82 3) 26H 2fe (the NO of O and 8.08-16.16 3) 39H 2o joins in the absolute ethyl alcohol of 55.3-63.2, stirs 30-60min, by the NaOH solution of 5-20mol/L, pH value is adjusted to 9-10, then adds and be enclosed with TiO 2the sepiolite of film, stirs 30-60min, then under the condition of 160-180 DEG C, reacts 18-24h, carries out Separation of Solid and Liquid, washing, finally dry under the condition of 70-85 DEG C, obtain described NiFe after cooling 2o 4/ TiO 2/ sepiolite composite photo-catalyst.
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