CN109589963A - A kind of lithium niobate type oxide/attapulgite nonlinear optics composite photocatalyst material and the preparation method and application thereof - Google Patents
A kind of lithium niobate type oxide/attapulgite nonlinear optics composite photocatalyst material and the preparation method and application thereof Download PDFInfo
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- CN109589963A CN109589963A CN201811514532.1A CN201811514532A CN109589963A CN 109589963 A CN109589963 A CN 109589963A CN 201811514532 A CN201811514532 A CN 201811514532A CN 109589963 A CN109589963 A CN 109589963A
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
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Abstract
The invention belongs to new chemical materials field, in particular to a kind of lithium niobate type oxide/attapulgite (ATP) nonlinear optics composite photocatalyst material and the preparation method and application thereof.The LiNbO of uniform particle sizes is grown in attapulgite surface in situ using sol-gal process3Nanoparticle makes the magnesium elements (Mg being rich in ATP by high-temperature calcination2+) it is doped into LiNbO3Lattice.On the one hand, introducing impurity energy level reduces bandwidth, can excite in visible light wave range, expands optical response range, improves the utilization rate of sunlight；On the other hand, ATP plays good peptizaiton as catalyst carrier, the contact surface for increasing sunlight, in addition, ATP itself has biggish specific surface area and unique cellular structure, unique absorption property is played, meeting absorbed portion nitrogen during photocatalysis fixed nitrogen, with LiNbO3Collaboration is to improve photocatalysis nitrogen-fixing efficiency.
Description
Technical field
The invention belongs to new chemical materials field, in particular to a kind of lithium niobate type oxide/attapulgite nonlinear optical
Learn composite photocatalyst material and the preparation method and application thereof.
Background technique
Fixed nitrogen method in nature mainly passes through lightning and microorganism fixed nitrogen, however nitrogen fixed in nature is much full
Foot not work, the demand of agricultural production.Industrial widely applied artificial fixed nitrogen method is Haber-Bosch method Industrial Solid at present
Nitrogen produces ammonia, but equipment requirement is high, and energy consumption is high, seriously polluted.Therefore it develops and development green cleans, the artificial fixed nitrogen of low energy consumption
Technique has important social effect.With the continuous development of multiphase photocatalysis technology, photocatalysis fixed nitrogen produces ammonia technology and receives
Researcher widely pays close attention to.
In recent years, nonlinear optical material is applied in photocatalysis field.Nonlinear optical material has by certainly
By the peculiar property of the molecule spontaneous polarization of electrons and holes or ion and absorption on the surface.Internal dipole field generates electrification
Then surface is triggered photo-generated charge carriers and is moved round about.This can mitigate the compound problem of electron-hole, and normal
Rule semiconductor is compared, it improves photocatalytic activity and stability.Lithium niobate (LiNbO3) it is used as a kind of specific nonlinear optical
Material light catalysis agent is learned, Kenji Saito et al. (Dalton Trans., 2011,40) proves LiNbO3It can be by non-linear
Optical characteristics and negative conduction band value splitting water are to generate hydrogen.Harbin Institute of Technology's Guoshuai Liu et al.
(Environ.Sci.Technol., 2016,50) has found LiNbO3It can be used for photocatalysis denitrification removal nitrate.
Attapulgite (ATP) is as a kind of natural clay material, wherein magnesium elements (Mg rich in2+), have compared with
Big specific surface area, superior absorption property and unique gap structure can be used as the carrier of catalyst.It is internal containing aerobic
Change iron, so that concave convex rod also has a degree of photoresponse property.
Summary of the invention
From the point of view of thermodynamics, if photochemical catalyst have fermi level appropriate and conduction band value it is negative enough (be less than-
0.092eV), nonlinear optical material photocatalyst Li NbO3Photocatalysis fixed nitrogen reaction will be directly carried out under sunlight irradiation.
The higher light irradiation of energy, LiNbO3As nonlinear optical material, its second_harmonic generation effect makes the electronics-sky being excited
Cave is more not easy compound., only can be to ultraviolet light response however due to its greater band gap, and ultraviolet light only accounts for the 5% of sunlight, so
Under very low to the utilization rate of sunlight.
In order to make full use of the visible light to occupy the majority in solar energy, solve the problems, such as that the utilization rate of sunlight is low, originally
Invention provides a kind of lithium niobate type oxide/attapulgite nonlinear optics composite photocatalyst material, by making LiNbO3It is brilliant
Body growth in situ on attapulgite (ATP) makes the magnesium elements (Mg being rich in ATP by high-temperature calcination2+) it is doped into LiNbO3
Lattice, introducing impurity energy level reduces bandwidth, can excite in visible light wave range, expands optical response range.
The present invention passes through the LiNbO in attapulgite surface in situ growth uniform particle sizes3Nanoparticle is forged by high temperature
It burns, makes the magnesium elements (Mg being rich in ATP2+) it is doped into LiNbO3Lattice, introducing impurity energy level reduces bandwidth, can be can
The excitation of light-exposed wave band, expands optical response range, improves the utilization rate of sunlight, thus substantially increase lithium niobate type oxide/
The light-catalysed effect of concave convex rod nonlinear optics composite photocatalyst material.
Lithium niobate type oxide/concave convex rod nonlinear optics composite photocatalyst material provided by the invention is by lithium niobate type oxygen
Compound (LiNbO3、LiTaO3、MgTiO3、MnTiO3、FeTiO3、ZnTiO3、ZnZrO3) and attapulgite (ATP) composition, wherein
LiNbO3Type oxide accounts for the 10%~80% of ATP mass.
Lithium niobate type oxide of the present invention is same type of nonlinear optical material, the lithium niobate type
Oxide is preferably LiNbO3, and with LiNbO3It is specifically described as example.It is equal by growing partial size in attapulgite surface in situ
Even LiNbO3Nanoparticle makes the magnesium elements (Mg being rich in ATP by high-temperature calcination2+) it is doped into LiNbO3Lattice.One side
Face, introducing impurity energy level reduces bandwidth, can excite in visible light wave range, expands optical response range, improves sunlight
Utilization rate；On the other hand, ATP plays good peptizaiton as catalyst carrier, increases the contact surface of sunlight.
The present invention also provides a kind of above-mentioned lithium niobate/concave convex rod nonlinear optics composite photocatalyst material preparation sides
Method:
(1) by suitable niobium hydroxide (H5Nb3O10) be distributed to 50ml 0.2mol/L oxalic acid solution in, rotor stirs
It mixes, water-bath is heated to 70 DEG C -90 DEG C, heats 20min-30min, forms clear solution；Ensure rubbing for niobium hydroxide and oxalic acid
You are than being less than or equal to 2:15；
Heat and ensure that the molar ratio of niobium hydroxide and oxalic acid is less than or equal to 2:15, using water-bath to ensure niobium hydroxide
Quickly and completely dissolve.
(2) ammonia spirit is instilled in the clear solution that step (1) is formed, to carry out precipitation reaction, until white precipitate is complete
It is complete to be precipitated；Wherein the micro- excess of ammonia volume keeps precipitating more complete；
(3) lower layer's suspension that precipitating obtains in step (2) is taken, using centrifuge centrifugal sediment, distills water washing, from
The heart twice, is centrifuged 2min under the revolving speed of 8000r/min every time；
(4) will be washed in step (3), the sediment after centrifugation is dissolved in the citric acid solution of 100mL 0.04mol/L
In, by suitable hydronium(ion) lithia (LiOHH2O it) is added in the citric acid solution dissolved with sediment and is mixed
Solution；Wherein, in mixed solution each component molar ratio [Li+]:[Nb5+]=1:1, mixed solution is placed in water-bath and extremely
After 70 DEG C -90 DEG C, heating water bath 2~3 hours of heating, ATP, which is added, ensures LiNbO generated3Account for the quality of ATP 10%~
80%；Using sol-gel method, keep water bath temperature constant, rotor stirring forms clear solution precursor solution, heats 3h-
5h obtains gel sample to being evaporated；
The method of the present invention is first by a hydronium(ion) lithia (LiOHH2O) it is added to the citric acid solution dissolved with sediment
In, it carries out heating water bath and adds recessed native heating water bath afterwards for a period of time, be convenient for LiNbO3Generation, if it is recessed soil and hydroxide
Lithium is added in the citric acid solution dissolved with sediment simultaneously, and the absorption property and multi-pore channel structure of recessed soil can interfere LiNbO3
Generation.
(5) gel sample in step (4) is calcined into Muffle furnace 8-12h at 500 DEG C -600 DEG C, grinds, obtains
Lithium niobate/concave convex rod nonlinear optics composite photocatalyst material.
The present invention also provides a kind of applications of above-mentioned lithium niobate/concave convex rod nonlinear optics composite photocatalyst material, i.e.,
Photocatalysis fixed nitrogen is carried out using the composite photocatalyst material.
The beneficial effects of the present invention are:
On the one hand attapulgite in the present invention is used as doped source, the magnesium ion (Mg that will be rich in attapulgite2+) doping
Enter LiNbO3Lattice in, introduce impurity energy level, reduce LiNbO3Bandwidth, directly expand LiNbO3Photoresponse
Range, on the other hand, attapulgite is wherein more playing the role of catalyst carrier, is increasing the contact surface with light, more have
The utilization rate for improving sunlight of effect.
The present invention utilizes LiNbO3(citric acid plays the role of complexing agent, network to growth in situ in the whole process on ATP
Close Li+, Nb5+, Mg in concave convex rod2+, make LiNbO3It is successfully generated and growth in situ is on ATP) and high-temperature calcination (removal crystallization
Water and by the Mg in ATP2+More incorporation LiNbO3Lattice), make concave convex rod and nonlinear optical material with the work of ionic bond
With being strongly combined together, nonlinear optical material and the simple mechanical mixture of concave convex rod are avoided, is extended in photocatalysis
The service life of catalyst during fixed nitrogen.
Nonlinear optical material LiNbO in the present invention3It is excited as semiconductor and generates light induced electron and hole,
It is compound that the self poling effect of body is difficult to light induced electron with hole, and concave convex rod plays the work of carrier in the catalysis material
With, while the Magnesium-doped being rich in concave convex rod enters LiNbO3Lattice in, reduce LiNbO3Bandwidth, it is multiple to expand this
The optical response range of light combination catalysis material directly enhances the utilization rate of sunlight.In addition to this, ATP itself has larger
Specific surface area and unique cellular structure, played unique absorption property, can absorbed portion during photocatalysis fixed nitrogen
Nitrogen, the two collaboration is to improve photocatalysis nitrogen-fixing efficiency.
Detailed description of the invention
Fig. 1 is ATP, LiNbO prepared by the embodiment of the present invention 13And 30%LiNbO3The XRD diagram of/ATP；
Fig. 2 is 30%LiNbO prepared by the embodiment of the present invention 13The TEM of/ATP schemes；
Fig. 3 is 30%LiNbO prepared by the embodiment of the present invention 13The EDS of/ATP schemes.
Specific embodiment
Embodiment 1
(1) by the niobium hydroxide (H of 0.3g (0.676mmol)5Nb3O10) be distributed to 50ml 0.2mol/L oxalic acid solution
In, rotor stirring, water-bath heats 80 DEG C, heats 25min, forms clear solution；
(2) ammonia spirit is instilled in the clear solution formed in step (1), until white precipitate is precipitated completely；Wherein ammonia
The micro- excess of water consumption；
(3) lower layer's suspension in step (2) is taken, centrifuge centrifugal sediment distills water washing, is centrifuged twice, every time
8000r/min, 2min；
(4) sediment in step (3) is dissolved in the citric acid solution of 100mL 0.04mol/L, by mono- water of 0.0851g
Close lithium hydroxide (LiOHH2O), molar ratio [Li+]:[Nb5+]=1:1；Heating water bath is to 80 DEG C, will after heating 2 hours
The ATP of 1.0g is added in solution；Using sol-gel method, water-bath heats 80 DEG C, and rotor stirring forms precursor solution, adds
Hot 4h is to being evaporated；
(5) gel sample in step (4) is calcined into Muffle furnace 9h at 500 DEG C, ground, obtain lithium niobate/recessed
Convex stick (30%LiNbO3/ ATP) nonlinear optics composite photocatalyst material.
X-ray powder diffraction is carried out to gained sample and characterizes its structure and composition, and is seen using transmission electron microscope
The TEM picture for examining sample, the 30%LiNbO prepared according to the technique of embodiment 13The XRD diagram of/ATP is as shown in Figure 1, composite wood
Occurs LiNbO in material respectively3With the characteristic peak of ATP, illustrate LiNbO3Success is compound with ATP, has prepared LiNbO3/ ATP is non-
Linear optics composite photocatalyst material；
The obtained 30%LiNbO of the present embodiment 13The TEM of/ATP is as shown in Figure 2: on the surface of attapulgite (ATP)
It is evenly distributed LiNbO3Particle；
Fig. 3 is EDS map, can detecte out the specific element in sample, including C, O, Mg, Al, Si, Fe, Cu, Nb, C and
Cu is because filling carbon film on the copper mesh and copper mesh of sample, and Mg, Al, Si, Fe, O are the elements on attapulgite, and Nb, O are LiNbO3
Element, but because the reason of instrument detection range (power spectrum can only detect 4-94 element, and Li is No. 3), Li element because
The too small reason of atomic weight could not be shown on EDS figure.
30%LiNbO manufactured in the present embodiment is utilized the present invention also provides a kind of3/ ATP composite photocatalyst material carries out
The method of photocatalysis fixed nitrogen: using 300W xenon lamp as simulated solar radiant, using water as cooling circulating water (the flow velocity 0.5L/ of xenon lamp
min).Using the ethanol water of 0.789g/L as hole trapping agents.0.04g catalyst is added in 100mL ethanol water,
0.5h is stirred with fully dispersed.Then solution is placed under light source under agitation and is irradiated, while blasting nitrogen
(60mL/min).It takes 5mL suspension in centrifuge tube every 1h, is taken after centrifugation 2min under conditions of revolving speed is 8000r/min
Supernatant liquor, using ultraviolet-visible spectrophotometer, using ammonium concentration in Na's reagent analysis product.Specific method
It is as follows: to take that 4mL sample to be tested is put into 25mL volumetric flask and constant volume is to 25mL.0.5mL potassium sodium tartrate solution is added dropwise
(2.17mol/L) and 0.75mL nessler reagent after standing 10min, tests 420nm wavelength using ultraviolet-visible spectrophotometer
Under absorbance.Ammonium concentration (mg/L) converts to obtain using standard curve, reduction formula are as follows:
Ammonium concentration=(sample absorbance-blank sample absorbance) × 5.642.
After 4h illumination, 30%LiNbO3/ ATP has reached the amount of nitrogen fixation that ammonium concentration is 63.8mg/L.
Embodiment 2
(1) by the niobium hydroxide (H of 0.3g (0.676mmol)5Nb3O10) be distributed to 50ml 0.2mol/L oxalic acid solution
In, rotor stirring, water-bath heats 80 DEG C, heats 25min, forms clear solution；
(2) ammonia spirit is instilled in the clear solution formed in step (1), until white precipitate is precipitated completely；Wherein ammonia
The micro- excess of water consumption；
(3) lower layer's suspension in step (2) is taken, centrifuge centrifugal sediment distills water washing, is centrifuged twice, every time
8000r/min, 2min；
(4) sediment in step (3) is dissolved in the citric acid solution of 100mL 0.04mol/L, by mono- water of 0.0851g
Close lithium hydroxide (LiOHH2O), molar ratio [Li+]:[Nb5+]=1:1, heating water bath is to after 80 DEG C, 2 hours, by 3.0g's
ATP is added in solution；Sol-gel method, water-bath keep temperature-resistant, rotor stirring, form precursor solution, heating 4h is extremely
It is evaporated；
(5) gel sample in step (4) is calcined into Muffle furnace 9h at 500 DEG C, ground, obtain lithium niobate/recessed
Convex stick (10%LiNbO3/ ATP) nonlinear optics composite photocatalyst material.
Subsequent detection such as embodiment 1.
After 4h illumination, 10%LiNbO3/ ATP has reached the amount of nitrogen fixation that ammonium concentration is 46.7mg/L.
Embodiment 3
(1) by the niobium hydroxide (H of 0.3g (0.676mmol)5Nb3O10) be distributed to 50ml 0.2mol/L oxalic acid solution
In, rotor stirring, water-bath heats 80 DEG C, heats 25min, forms clear solution；
(2) ammonia spirit is instilled in the clear solution formed in step (1), until white precipitate is precipitated completely；Wherein ammonia
The micro- excess of water consumption；
(3) lower layer's suspension in step (2) is taken, centrifuge centrifugal sediment distills water washing, is centrifuged twice, every time
8000r/min, 2min；
(4) sediment in step (3) is dissolved in the citric acid solution of 100mL 0.04mol/L, by mono- water of 0.0851g
Close lithium hydroxide (LiOHH2O), molar ratio [Li+]:[Nb5+]=1:1, heating water bath is to after 80 DEG C, 2 hours, by 1.5g's
ATP is added in solution；Sol-gel method, water-bath heat 80 DEG C, and rotor stirring forms precursor solution, and heating 4h extremely steams
It is dry；
(5) gel sample in step (4) is calcined into Muffle furnace 9h at 500 DEG C, ground, obtain lithium niobate/recessed
Convex stick (20%LiNbO3/ ATP) nonlinear optics composite photocatalyst material.
Subsequent detection such as embodiment 1.
After 4h illumination, 20%LiNbO3/ ATP has reached the amount of nitrogen fixation that ammonium concentration is 53.6mg/L.
Embodiment 4
(1) by the niobium hydroxide (H of 0.3g (0.676mmol)5Nb3O10) be distributed to 50ml 0.2mol/L oxalic acid solution
In, rotor stirring, water-bath heats 80 DEG C, heats 25min, forms clear solution；
(2) ammonia spirit is instilled in the sample prepared in step (1), until white precipitate is precipitated completely；Wherein ammonium hydroxide is used
Measure micro- excess；
(3) lower layer's suspension in step (2) is taken, centrifuge centrifugal sediment distills water washing, is centrifuged twice, every time
8000r/min, 2min；
(4) sediment in step (3) is dissolved in the citric acid solution of 100mL 0.04mol/L, by mono- water of 0.0851g
Close lithium hydroxide (LiOHH2O), molar ratio [Li+]:[Nb5+]=1:1, heating water bath is to after 80 DEG C, 2 hours, by 0.6g's
ATP is added in solution；Sol-gel method, water-bath heat 80 DEG C, and rotor stirring forms precursor solution, and heating 4h extremely steams
It is dry；
(5) gel sample in step (4) is calcined into Muffle furnace 9h at 500 DEG C, ground, obtain lithium niobate/recessed
Convex stick (50%LiNbO3/ ATP) nonlinear optics composite photocatalyst material.
Subsequent detection such as embodiment 1.
After 4h illumination, 50%LiNbO3/ ATP has reached the amount of nitrogen fixation that ammonium concentration is 57.1mg/L.
Embodiment 5
(1) by the niobium hydroxide (H of 0.3g (0.676mmol)5Nb3O10) be distributed to 50ml 0.2mol/L oxalic acid solution
In, rotor stirring, water-bath heats 80 DEG C, heats 25min, forms clear solution；
(2) ammonia spirit is instilled in the clear solution formed in step (1), until white precipitate is precipitated completely；Wherein ammonia
The micro- excess of water consumption；
(3) lower layer's suspension in step (2) is taken, centrifuge centrifugal sediment distills water washing, is centrifuged twice, every time
8000r/min, 2min；
(4) sediment in step (3) is dissolved in the citric acid solution of 100mL 0.04mol/L, by mono- water of 0.0851g
Close lithium hydroxide (LiOHH2O), molar ratio [Li+]:[Nb5+]=1:1, heating water bath is to after 80 DEG C, 2 hours, by 0.375g
ATP is added in solution；Sol-gel method, water-bath heat 80 DEG C, and rotor stirring forms precursor solution, and heating 4h extremely steams
It is dry；
(5) gel sample in step (4) is calcined into Muffle furnace 9h at 500 DEG C, ground, obtain lithium niobate/recessed
Convex stick (80%LiNbO3/ ATP) nonlinear optics composite photocatalyst material.
Subsequent detection such as embodiment 1.
After 4h illumination, 80%LiNbO3/ ATP has reached the amount of nitrogen fixation that ammonium concentration is 55.7mg/L.
Embodiment 6
(1) by the tantalum hydroxide (H of 0.5g (0.676mmol)5Ta3O10) be distributed to 50ml 0.2mol/L oxalic acid solution
In, rotor stirring, water-bath heats 80 DEG C, heats 25min, forms clear solution；
(2) ammonia spirit is instilled in the clear solution formed in step (1), until white precipitate is precipitated completely；Wherein ammonia
The micro- excess of water consumption；
(3) lower layer's suspension in step (2) is taken, centrifuge centrifugal sediment distills water washing, is centrifuged twice, every time
8000r/min, 2min；
(4) sediment in step (3) is dissolved in the citric acid solution of 100mL 0.04mol/L, by mono- water of 0.0851g
Close lithium hydroxide (LiOHH2O), molar ratio [Li+]:[Ta5+]=1:1, heating water bath is to after 80 DEG C, 2 hours, by 1.7g
ATP is added in solution；Sol-gel method, water-bath heat 80 DEG C, and rotor stirring forms precursor solution, and heating 4h extremely steams
It is dry；
(5) gel sample in step (4) is calcined into 9h at 500 DEG C DEG C in Muffle furnace, grind, obtain lithium tantalate/
Concave convex rod (30%LiTaO3/ ATP) nonlinear optics composite photocatalyst material.
Subsequent detection such as embodiment 1.
After 4h illumination, 30%LiTaO3/ ATP has reached the amount of nitrogen fixation that ammonium concentration is 60.2mg/L.
Comparative example 1
(1) by the niobium hydroxide (H of 0.3g (0.676mmol)5Nb3O10) be distributed to 50ml 0.2mol/L oxalic acid solution
In, rotor stirring, water-bath heats 80 DEG C, heats 25min, forms clear solution；
(2) ammonia spirit is instilled in the clear solution that step (1) is formed, until white precipitate is precipitated completely；Wherein ammonium hydroxide
The micro- excess of dosage；
(3) lower layer's suspension in step (2) is taken, centrifuge centrifugal sediment distills water washing, is centrifuged twice, every time
8000r/min, 2min；
(4) sediment in step (3) is dissolved in the citric acid solution of 100mL 0.04mol/L, by mono- water of 0.0851g
Close lithium hydroxide (LiOHH2O it) is added in solution, molar ratio [Li+]:[Nb5+]=1:1, sol-gel method, water-bath add
80 DEG C of heat, rotor stirring form precursor solution, and 4h is to being evaporated for heating；
(5) gel sample in step (4) is calcined into Muffle furnace 9h at 500 DEG C, grinds, obtains lithium niobate
(LiNbO3) nonlinear optics catalysis material.
Subsequent detection such as embodiment 1.
After 4h illumination, this comparative example prepares LiNbO3The amount of nitrogen fixation that ammonium concentration is 37.3mg/L is reached.
This is because there was only pure lithium niobate, LiNbO in this comparative example3Greater band gap, ultraviolet light response, the utilization rate ratio of sunlight
LiNbO3/ ATP low reason.
Comparative example 2
(1) by the niobium hydroxide (H of 0.3g (0.676mmol)5Nb3O10) be distributed to 50ml 0.2mol/L oxalic acid solution
In, rotor stirring, water-bath heats 80 DEG C, heats 25min, forms clear solution；
(2) ammonia spirit is instilled in the clear solution formed in step (1), until white precipitate is precipitated completely；Wherein ammonia
The micro- excess of water consumption；
(3) lower layer's suspension in step (2) is taken, centrifuge centrifugal sediment distills water washing, is centrifuged twice, every time
8000r/min, 2min；
(4) sediment in step (3) is dissolved in the citric acid solution of 100mL 0.04mol/L, by mono- water of 0.0851g
Close lithium hydroxide (LiOHH2O it) is added in solution with the ATP of 1.0g；Wherein, molar ratio [Li+]:[Nb5+]=1:1；Using
Water-bath is heated 80 DEG C by sol-gel method, and rotor stirring forms precursor solution, and 4h is to being evaporated for heating；
(5) gel sample in step (4) is calcined into Muffle furnace 9h at 500 DEG C, ground, obtain lithium niobate/recessed
Convex stick (30%LiNbO3/ ATP) nonlinear optics composite photocatalyst material.
Subsequent detection such as embodiment 1.
After 4h illumination, this comparative example prepares LiNbO3The amount of nitrogen fixation that ammonium concentration is 47.3mg/L is reached.
This is because attapulgite and lithium hydroxide are added to simultaneously in the citric acid solution dissolved with sediment in this comparative example,
The absorption property and multi-pore channel structure of attapulgite can interfere LiNbO3Generation so that catalyst activity reduce.
Claims (6)
1. a kind of lithium niobate type oxide/attapulgite nonlinear optics composite photocatalyst material, it is characterised in that: the light is urged
Change material to be made of lithium niobate type oxide and attapulgite (ATP), wherein the lithium niobate type oxide includes LiNbO3、
LiTaO3、MgTiO3、MnTiO3、FeTiO3、ZnTiO3、ZnZrO3, dosage is the 10%~80% of ATP mass.
2. lithium niobate type oxide as described in claim 1/attapulgite nonlinear optics composite photocatalyst material, feature
Be: the lithium niobate type oxide is LiNbO3。
3. a kind of lithium niobate type oxide as described in claim 1/attapulgite nonlinear optics composite photocatalyst material
Preparation method, it is characterised in that: the preparation method the specific process is as follows:
(1) by niobium hydroxide (H5Nb3O10) be distributed to 50ml 0.2mol/L oxalic acid solution in, rotor stirring, water-bath adds
Heat forms clear solution；
(2) ammonia spirit is instilled in the clear solution that step (1) is formed, until white precipitate is precipitated completely；
(3) lower layer's suspension that precipitating obtains in step (2) is taken, using centrifuge centrifugal sediment, distills water washing, centrifugation two
It is secondary, 2min is centrifuged under the revolving speed of 8000r/min every time；
(4) will be washed in step (3), the sediment of centrifugation is dissolved in the citric acid solution of 100mL 0.04mol/L, by one
Hydronium(ion) lithia (LiOHH2O it) is added in the citric acid solution dissolved with sediment and obtains mixed solution, will mix molten
Liquid is placed in water-bath and to after being heated to 70 DEG C -90 DEG C, heating water bath 2-3 hours, ATP is added, using sol-gel
Method, keeps the temperature-resistant of water-bath, and rotor stirring forms clear solution precursor solution, heating 3h-5h to steaming after 2-3 hours
It is dry, obtain gel sample；
(5) gel sample obtained in step (4) is calcined into Muffle furnace 8-12h at 500 DEG C -600 DEG C, grinds, that is, makes
Obtain lithium niobate/concave convex rod nonlinear optics composite photocatalyst material.
4. the preparation of lithium niobate type oxide as claimed in claim 3/attapulgite nonlinear optics composite photocatalyst material
Method, it is characterised in that: the molar ratio of step (1) niobium hydroxide and oxalic acid is less than or equal to 2:15, water bath temperature 70
DEG C -90 DEG C, heating time 20min-30min.
5. the preparation of lithium niobate type oxide as claimed in claim 3/attapulgite nonlinear optics composite photocatalyst material
Method, it is characterised in that: [Li described in step (4)+]:[Nb5+] molar ratio=1:1.
6. a kind of application of lithium niobate type oxide/attapulgite nonlinear optics composite photocatalyst material, it is characterised in that: institute
Catalysis material is stated for photocatalysis fixed nitrogen.
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