CN105800676B - Two-dimentional titanate nano material and preparation method thereof - Google Patents
Two-dimentional titanate nano material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of two-dimentional titanate nano materials and preparation method thereof.Wherein two-dimentional titanate nano material includes modified protonation titanate film, and modified protonation titanate film has organic group and the Cr elements of doping.The two dimension titanate nano material is conducive to widen the Absorber Bandwidth of two-dimentional titanate nano material by adulterating Cr elements, make that while ultraviolet light is absorbed visible ray can also be absorbed, and then its light absorption, the efficiency of opto-electronic conversion are substantially increased, so as to improve photocatalysis efficiency.And it is used as the balance media of nanometer sheet by adulterating this opposite macromolecular of organic group, prepared two-dimentional titanate nano material is made to be not easy to crimp, with metastable two-dimensional structure, and then with relatively large surface area, so as to further improve photocatalysis efficiency.
Description
Technical field
The present invention relates to photocatalysis fields, and in particular, to a kind of two dimension titanate nano material and preparation method thereof.
Background technology
Lamellar compound is excellent harmful ion and adsorbent, while can be used as the compound of the high activity of inorganic matter
Catalyst and catalyst carrier are, it can be achieved that cracking to water；Inorganic layered compounds are many due to its distinctive layer structure
Chemical reaction provides a nanoscale reaction compartment, meanwhile, the nanoscale monolithic layer after stripping can make other nanostructureds
Elementary cell.
The structure of inorganic layered compounds is that two-dimentional laminate longitudinal direction ordered arrangement forms three-dimensional crystalline structure, atom in laminate
Between be mostly Covalent bonding together, interlayer for Van der Waals force or reduction learn ionic bond, interfloor distance is generally between several nanometers.Metatitanic acid is received
Meter Jing is a kind of wide band gap semiconducter, is widely used in photochemical catalyst, gas sensor, solar cell；Utilize its ion
Exchangeability, available for sewage disposal.
One kind is conventionally synthesized nano titanic acid tablets monocrystal and includes in the prior art：Using sodium hydroxide+hydrofining as alkali
Class melting agent using titanium dioxide is metatitanic acid raw material, using deionized water as cleaning agent, detergent and extractant, using absolute ethyl alcohol as
Detergent and dry carrier, under normal pressure 0.1MPa, under 200 DEG C of low temperature, synthesis nano metatitanic acid piece monocrystal.
The metatitanic acid piece prepared by above-mentioned existing technology is easily curled into tubulose and becomes one-dimentional structure, makes its surface area opposite
It is smaller, and photocatalysis field application in light Absorber Bandwidth only in ultraviolet region, not high to the utilization rate of light, this is resulted in
The catalytic efficiency of existing this nano titanic acid tablets monocrystal is relatively low.
The content of the invention
The purpose of the invention is to improve the Absorber Bandwidth of existing two-dimentional titanate nano material light only in ultraviolet region,
The problem of not high to the utilization rate of light, provides a kind of two-dimentional titanate nano material and preparation method thereof.
To achieve these goals, according to an aspect of the invention, there is provided a kind of two dimension titanate nano material bag
Modified protonation titanate film is included, the protonation titanate film of the modification has organic group and the Cr of doping members
Element.
According to another aspect of the present invention, a kind of preparation method of two-dimentional titanate nano material, the preparation are provided
Method comprises the following steps：With alkali carbonate and unformed TiO2For raw material, the layered titanate of protonation is prepared；In heat
Under treatment conditions, make protonation titanate and bichromate haptoreaction, form the layered titanate of doping Cr；And it is stirring
Under the conditions of, make the layered titanate and organic amine haptoreaction in liquid-phase substrate of the doping Cr, remove and form the two dimension
Titanate nano material.
Above-mentioned technical proposal of the present invention by adulterating Cr elements in two-dimentional titanate nano material, is conducive to widen two
The Absorber Bandwidth of titanate nano material is tieed up, makes it that can also absorb visible ray simultaneously, and then substantially increases its light absorption, light
The efficiency of electricity conversion, so as to further improve photocatalysis efficiency
Meanwhile it is used as nanometer sheet by adulterating the relatively large organic group of molecular weight in two-dimentional titanate nano material
Balance media, it is made to be not easy to crimp, there is metastable two-dimensional structure, and then with relatively large surface area, so as to
Improve photocatalysis efficiency.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is together for explaining the present invention, but be not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is that (unit length is for the TEM photos of two-dimentional titanate nano material prepared by according to embodiments of the present invention 1
50nm)；
Fig. 2 is that (unit length is for the TEM photos of two-dimentional titanate nano material prepared by according to embodiments of the present invention 1
200nm)；
Fig. 3 is the atomic force microscope test collection of illustrative plates of two-dimentional titanate nano material prepared by according to embodiments of the present invention 1；
Fig. 4 is the UV-vis absorption spectrum collection of illustrative plates of two-dimentional titanate nano material prepared by according to embodiments of the present invention 1；With
And
Fig. 5 is the UV-vis absorption spectrum collection of illustrative plates of two-dimentional titanate nano material prepared by comparative example 2 according to the present invention.
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with attached drawing.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Term " protonation titanate " refers to the alkali metal cation in alkali metal titanate being substituted in the present invention
A kind of hydrionic compound.Term " modified protonation titanate film " refers to through organic group and Cr elements to proton
Change titanate film and be modified formed modified film.
As background section is introduced, the Absorber Bandwidth of light in being applied in the prior art there are photocatalysis field
Only in ultraviolet region, it is not high to the utilization rate of light the problem of, in order to improve this problem, inventor provides one kind two
Dimension titanate nano material contains modified protonation titanate, and the protonation titanate of the modification has organic group and doping
Cr elements.
Above-mentioned technical proposal of the present invention by adulterating Cr elements in two-dimentional titanate nano material, is conducive to widen two
The Absorber Bandwidth of titanate nano material is tieed up, makes it that can also absorb visible ray simultaneously, and then substantially increases its light absorption, light
The efficiency of electricity conversion, so as to further improve photocatalysis efficiency
Meanwhile it is used as nanometer sheet by adulterating the relatively large organic group of molecular weight in two-dimentional titanate nano material
Balance media, it is made to be not easy to crimp, there is metastable two-dimensional structure, and then with relatively large surface area, so as to
Improve photocatalysis efficiency.
In the present invention for the doping of Cr elements adulterated there is no particular/special requirement, the energy as long as Cr elements are adulterated
Enough purposes for realizing the Absorber Bandwidth for widening two-dimentional titanate nano material.In the present invention for the organic group that is adulterated
Doping is there is no particular/special requirement, as long as its molecular structure is bigger compared with the crystal structure of protonation titanate so that two dimension
Titanate nano material extends laterally within the specific limits.In the preferred embodiment of the present invention, above-mentioned modification
Protonation titanate film in the organic group containing 2-15wt.%, the Cr elements of 13-32wt.%.The content of Cr is limited
Be conducive to enhance the stability of titanate lattice in the range, and improve its light absorption band edge.The content of organic group is limited
The fixed photocatalysis efficiency and lateral dimension for being conducive to improve two-dimentional titanate nano material in the range at the same time.
In the present invention for above-mentioned organic group there is no particular/special requirement, received as long as it can be entrained in two-dimentional titanate
In rice material, and have no adverse effects to the application of two-dimentional titanate nano material.Preferred above-mentioned organic amine in the present invention
Weight average molecular weight be 250-450；The weight average molecular weight of organic group it is too small, for the interlayer of the layered titanate of protonation
With reference to the influence unobvious of power (charge stripping efficiency), and weight average molecular weight is too big, it is possible to wrap up nonwoven fabric from filaments and wind, group occurs
It is poly-, peeling effect is influenced, the setting of its molecular weight is conducive to while required stripping product is obtained, carry in the range
Height is correspondingly improved efficiency) effect.Preferred organic group is drawn by protonation titanate and organic amine reaction in the present invention
Enter, the organic amine that can preferably use in the present invention includes but not limited to tetrabutylammonium hydroxide, ethamine, polyethyleneimine
One or more in amine, diethylin and tetramethyl amine.
In the preferred embodiment of the present invention, the two-dimentional titanate nano material, which further includes, is dispersed in described change
Property protonation titanate film surface alkanone class dispersant.The above-mentioned two-dimentional titanate nano material of the present invention, by two
In the preparation process for tieing up titanate nano material, alkanone class dispersant is added in the layered titanate of protonation, utilizes alkanone
Peptizaiton specific to class dispersant promotes the layered titanate of protonation to be easily peeled off, and obtains two-dimentional metatitanic acid after removing
Salt nano material is not easy again two-dimentional titanate nano material that is compound, and then forming stable.
Simultaneously as introducing ketone dispersant in prepared two-dimentional titanate nano material, two are may advantageously facilitate
Dimension titanate nano material itself is not easy to combine, and then it is made to be not easy to crimp, and has metastable two-dimensional structure, and then has
Relatively large surface area.
Preferably, the weight ratio of above-mentioned alkanone class dispersant and the protonation titanate of the modification is 1-5：100, more
It is preferred that the weight average molecular weight of above-mentioned alkanone class dispersant is 100-200, the weight average molecular weight of alkanone class dispersant is too small, rises
The effect unobvious that the promotion arrived is removed, and weight average molecular weight is too big, it is possible that product package winding will be removed, group occurs
It is poly-, peeling effect is influenced, its molecular weight is set in the range to have and shortens splitting time, improves the effect of charge stripping efficiency.
Preferably, in the present invention the alkanone class dispersant that can be used includes but not limited to N- ethyl pyrrolidones, N- methyl arsenic is coughed up
One or more in alkanone and N- vinylpyrrolidones.
In the preferred embodiment of the present invention, two-dimentional titanate nano material described above mutually hangs down with thickness direction
Straight cross-section lengths are 0.1-100 μm (width is less than or equal to length), and the thickness of the two dimension titanate nano material is 1-
10nm。
Two dimension titanate nano material of the present invention is referred to prepare two-dimentional titanate nano material in the prior art
Method prepare, as long as adulterating Cr thereto after the layered titanate of protonation is prepared, and be mixed into organic amine and optional alkane
Ketone dispersant.
In the preferred embodiment of the present invention, a kind of preparation side of two-dimentional titanate nano material is additionally provided
Method, the preparation method comprise the following steps：With alkali carbonate and unformed TiO2For raw material, the layered titanium of protonation is prepared
Hydrochlorate；Under heat treatment condition, make protonation titanate and bichromate haptoreaction, form the layered titanate of doping Cr；
Under agitation, the layered titanate of the protonation and organic amine haptoreaction in liquid-phase substrate are made, stripping forms institute
State two-dimentional titanate nano material.
The above method provided by the present invention makes protonation titanate be connect with bichromate by using the mode of heat treatment
Reaction is touched, with the Cr elements adulterated in the titanate lattice of prepared two-dimentional titanate nano material, and then enhances titanate
While the stability of lattice, the Absorber Bandwidth of two-dimentional titanate nano material is widened, makes it that can also absorb visible ray simultaneously,
And then substantially increase its light absorption, the efficiency of opto-electronic conversion.
Meanwhile by adding in the relatively large organic amine of molecular weight in the layered titanate of protonation, utilize organic amine
The characteristics of middle ammonium root or hydroxyl are easy to react with hydrogen ion passes through the hydrogen with the layered titanate interlayer positioned at protonation
Ion reacts, and organic group is made to enter the layered titanate interlayer of protonation, and then by the layered titanate of protonation
Inter-layer bonding force, make it easier to remove.
In the above method of the present invention, for heat treatment condition there is no particular/special requirement, as long as Cr can be promoted3+With metatitanic acid
Salt reacts to form hybrid.However, in order to reduce energy consumption, product quality is improved, preferably heat treatment condition is, at heat
It is 300~600 DEG C to manage temperature, and heat treatment time is 5~10h.It is preferred that the weight of bichromate and the layered titanate of protonation
Than for 0.3~0.6：1.It is preferred that the bichromate that can be used includes but not limited in ammonium dichromate, potassium bichromate, sodium dichromate
One or more.
For stirring condition there is no particular/special requirement in the above method of the present invention, as long as providing certain driving force, make
The layered titanate of protonation and organic amine haptoreaction in liquid-phase substrate.It is however relatively small in order to obtain thickness
Two-dimentional titanate nano material, in the present invention preferred stirring condition be：Mixing speed 100-180rpm, mixing time 1-14
My god.
In the above method of the present invention, the weight ratio of preferably organic amine and the layered titanate of the protonation is 10-25：
100, the preferably weight average molecular weight of organic amine is 250-450；It is preferred that the organic amine that can be used includes but not limited to tetrabutylammonium hydrogen
One or more in amine-oxides, ethamine, polyethyleneimine, diethylin and tetramethyl amine；It is preferred that the titanate that can be used
One or more including but not limited in potassium titanate, sodium titanate, lithium titanate, metatitanic acid rubidium, metatitanic acid caesium.
In the above method of the present invention, contacted for the layered titanate for protonation with organic amine in liquid-phase substrate instead
The liquid-phase substrate that the condition that provides should and be removed for two-dimentional titanate nano material includes but not limited to water, ethyl alcohol, propyl alcohol and different
One or more in propyl alcohol.
In the preferred embodiment of the present invention, making in the preparation method of above-mentioned two-dimentional titanate nano material
State the layered titanate of protonation and organic amine in liquid-phase substrate the step of haptoreaction after, further include：In ultrasonic vibration item
Under part, alkanone class dispersant is further added in into liquid-phase substrate, alkanone class dispersant is made to be mixed with the layered titanate protonated
The step that splice grafting touches.
In the preparation method of the above-mentioned dimension titanate nano material of the present invention, by being added in the layered titanate of protonation
Alkanone class dispersant using peptizaiton specific to alkanone class dispersant, is engaged with the relatively large organic amine of molecular weight,
The layered titanate of protonation is promoted to be easily peeled off, and obtains two-dimentional titanate nano material after removing because surface attachment has alkane
Ketone dispersant so that be not easy compound again between the two-dimentional titanate nano material in liquid-phase substrate, and then be conducive to shape
Into stable two-dimentional titanate nano material.
In the above method of the present invention, the preferred weight of the layered titanic acid salt compound of alkanone class dispersant and the protonation
Amount is than being 1-5：100.It is preferred that the weight average molecular weight of alkanone class dispersant is 100-200.It is preferred that the alkanone class that can be used is disperseed
Agent includes but not limited to the one or more in N- ethyl pyrrolidones, N- methyl arsenic pyrrolidones and N- vinylpyrrolidones.
In the above-mentioned methods, be stirred at the same time under conditions of contact and ultrasonic vibration contact, for stirring condition and
Ultrasonic vibration condition is there is no particular/special requirement, as long as adding in organic amine in the state of stirring, adds under conditions of ultrasonic vibration
Enter alkane ketone compounds.However, it is relatively large in order to form cross-section lengths (the perpendicular direction with thickness), and thickness
Relatively small two dimension titanate nano material, preferably stirring condition is mixing speed 100-180rpm, mixing time 1-5 days；
It is preferred that ultrasonic vibration condition is, supersonic frequency 25-40KHZ, the concussion time is 1-5 days.
In the above method of the present invention, to prepare protonation layered titanate the step of there is no particular/special requirement, references
The process of this field routine.In the preferred embodiment of the present invention, the layered titanium of above-mentioned preparation protonation
The step of hydrochlorate, includes：By alkali carbonate and unformed TiO2Mixed grinding obtains mixed-powder；By the mixed-powder
Roasting, solid phase reaction obtain layered titanic acid salt powder；Neutrality will be washed to after layered metatitanic acid salt powder acid adding pickling, dried
It is dry, the layered titanate protonated.
In the above-mentioned methods by alkali carbonate and unformed TiO2In the step of mixed grinding, preferably by alkali metal carbon
Hydrochlorate and unformed TiO2By 1:3.3~7.3 mixed in molar ratio are ground, and preferably obtain the mixed-powder that grain size is 0.2-0.6 μm；
It is preferred that the alkali carbonate that can be used includes but not limited to the one or more in potassium carbonate, sodium carbonate and rubidium carbonate.
It is not special for the condition of mixed-powder roasting in the step of mixed-powder is roasted in the above-mentioned methods
Different requirement, however, in order to enable the abundant progress of solid phase reaction, to obtain more complete and larger cross-section lengths stratiform knot
Structure, when preferred roasting condition is that roasting 20~40 is small at 700~1100 DEG C in the present invention.
In the above method in the step of layered titanic acid salt powder acid adding pickling, the step of for pickling there is no it is special will
It asks, as long as layered titanic acid salt powder can be formed to the layered titanate of protonation.However, in order to simplify operation, at this
Include in invention the step of preferred acid adding pickling：Pickling 1-3 times, in each acid cleaning process, pickling temperature is 15-40 DEG C, pickling
Time is 15-25h.Preferably, in each acid cleaning process, H is added in every gram of layered titanate+Concentration is the acid solution of 1mol/L
It measures as 75-85ml, it is preferable that the acid solution that can be used includes but not limited to for the one or more in hydrochloric acid, sulfuric acid, nitric acid.
Meanwhile a kind of preparation method by any one above-mentioned two-dimentional titanate nano material is additionally provided in the present invention
Two dimension titanate nano material obtained.
Two-dimentional titanate nano material and preparation method thereof is further illustrated the present invention below with reference to specific embodiment
Advantageous effect.
Embodiment 1
(1), two-dimentional titanate nano material preparation method includes：
(1) by selecting sodium carbonate (analysis is pure) and unformed TiO2(analysis is pure) is raw material, and the two is pressed 1:5.3 mole
Than mixed grinding, the mixed-powder that particle mean size is 400nm is formed；
(2) mixed-powder is calcined in 700 DEG C 40 it is small when carry out high temperature solid state reaction layered titanic acid salt fines be made in advance
End；
(3) layered titanate is added in into stirring and pickling 15h in the hydrochloric acid solution (analysis is pure) that concentration is 1mol/L, every gram of layer
Shape titanate adds in the amount of hydrochloric acid as 75ml, sample is washed to neutrality again after pickling 3 times, drying filtering is protonated
Layered titanate；
(4) dichromic acid amine (dichromic acid amine and the layered titanate of protonation are added in protonation titanate after the drying
Weight ratio be 0.6：1) 8h, is heat-treated in 400 DEG C, obtains chromium-doped layered titanate；
(5) by chromium-doped layered titanate and tetrabutylammonium hydroxide (tetrabutylammonium hydroxide and the stratiform of protonation
The weight ratio of titanate is 5：100) it is added in liquid-phase substrate water, is stirred 3 days with the speed of 150rpm；N- ethyl arsenic is added in cough up
(weight ratio of N- ethyl arsenic pyrrolidones and the layered titanic acid salt compound of protonation is 1 to alkanone：100), using supersonic frequency as
25KHZ, ultrasonic vibration 1 day, stripping form the two-dimentional titanate nano material.
(2), the measure of two-dimentional titanate nano material
(1) the raw material composition detection of the two-dimentional titanate nano material prepared by.
Assay method：
1. the two-dimentional titanate nano material Agilent companies production that the stripping of Example 1 obtains is gas chromatography combined
The content of alkanone dispersant is measured with instrument (model AgilentGC6890-5975IMS).
2. it removes the alkanone in obtained two-dimentional titanate nano material using conventional dialysis procedures removal embodiment 1 to disperse
Agent, measurement remove the modified raw material composition for protonating titanate film after alkanone dispersant.
Modified protonation titanate film crystal form after removal alkanone dispersant is freeze-dried then progress material phase analysis,
Using Dutch III type XRD analysis instrument of Rigaku company D/max Ultima.Major parameter is as follows：Target for Cu (λ=
0.15405nm, 40kV, 30mA)；Step-length is 0.01 °, and the XRD test angles scope of the experiment is 3-80 °, measures titanate
Content.
Philips-FEI will be used after modified protonation titanate film crystal form freeze-drying after removal alkanone dispersant
The scanning electron microscope of company's XL30ESEM-TMP models, accelerating potential 20KV carry out energy spectrum analysis, measure Cr3+Content.
It removes except being modified after alkanone dispersant protonates the gas chromatography combined of titanate film Agilent companies production
The content of organic amine is measured with instrument (model AgilentGC6890-5975IMS).
Measurement result：Disperse in two-dimentional titanate nano material containing 0.7wt.%N- ethyl arsenic pyrrolidones, removal alkanone
Contain 62wt.% metatitanic acids (protonation titanate), the organic group of 4.5wt.% in modified protonation titanate film after agent
(C4H9)4The Cr elements of N-, 32wt.% and impurity 1.5%.
(2) length measurment of the cross section perpendicular with thickness direction of the two-dimentional titanate nano material prepared by.
Measuring method：Final product will be removed to centrifuge by 10000rpm/min, then centrifugation time takes supernatant for 15min
Liquid, using Japanese JEOL companies JEM-2010 type transmission electron microscopes, accelerating potential is arranged to the shape of 200KV observation titanates
Looks and size.
Measurement result：It is sample part shape appearance figure as depicted in figs. 1 and 2.About 20 μm of the length of its cross section.
(3) thickness measurement of the two-dimentional titanate nano material prepared by.
Measuring method：Final product will be removed to centrifuge by 10000rpm/min, then centrifugation time takes supernatant for 15min
Liquid, using 5500 model atomic force microscope of Agilent companies of the U.S., scanner resolution ratio is XY：0.2nm,Into
Row test analysis.
Measurement result：As shown in Figure 3.As seen from Figure 3, the titanate nano film thickness in final product is 1nm.
Embodiment 2
(1), two-dimentional titanate nano material preparation method includes：
(1) by selecting rubidium carbonate (analysis is pure) and unformed TiO2(analysis is pure) is raw material, and the two is pressed 1:3.3 mole
Than mixed grinding, the mixed-powder that particle mean size is 400nm is formed；
(2) mixed-powder is calcined in 1100 DEG C 30 it is small when carry out high temperature solid state reaction layered titanic acid salt fines be made in advance
End；
(3) layered titanate is added in into stirring and pickling 25h in the hydrochloric acid solution (analysis is pure) that concentration is 1mol/L, every gram of layer
Shape titanate adds in the amount of hydrochloric acid as 80ml, sample is washed to neutrality again after pickling 3 times, drying filtering is protonated
Layered titanate；
(4) dichromic acid amine (dichromic acid amine and the layered titanium of the protonation are added in protonation titanate after the drying
The weight ratio of hydrochlorate is 25：100) 10h, is heat-treated in 300 DEG C, obtains chromium-doped layered titanate；
(5) by chromium-doped layered titanate and diethylamine, (weight ratio of diethylamine and the layered titanate of protonation is
8：100) it is added in liquid-phase substrate water, is stirred 5 days with the speed of 150rpm；Adding in N- methyl arsenic pyrrolidone, (N- methyl arsenic is coughed up
Alkanone and the weight ratio of the layered titanic acid salt compound of protonation are 3：100), using supersonic frequency as 25KHZ, ultrasonic vibration 2 days,
Stripping forms the two-dimentional titanate nano material.
(2), the measure of two-dimentional titanate nano material
The raw material composition detection of prepared two-dimentional titanate nano material.
Assay method：With embodiment 1.
Measurement result：Disperse in two-dimentional titanate nano material containing 2.5wt.%N- methyl arsenic pyrrolidones, removal alkanone
Cr elements containing 79wt.% metatitanic acids (protonation titanate) doping 13% in modified protonation titanate film after agent,
Organic group (the C of 6.7wt.%2H5)2N- and impurity 1.3%.
Embodiment 3
(1), two-dimentional titanate nano material preparation method includes：
(1) by selecting sodium carbonate (analysis is pure) and unformed TiO2(analysis is pure) is raw material, and the two is pressed 1:7.3 mole
Than mixed grinding, the mixed-powder that particle mean size is 400nm is formed；
(2) mixed-powder is calcined in 1000 DEG C 20 it is small when carry out high temperature solid state reaction layered titanic acid salt fines be made in advance
End；
(3) layered titanate is added in into stirring and pickling 20h in the hydrochloric acid solution (analysis is pure) that concentration is 1mol/L, every gram of layer
Shape titanate adds in the amount of hydrochloric acid as 85ml, sample is washed to neutrality again after pickling 3 times, drying filtering is protonated
Layered titanate；
(4) dichromic acid amine (dichromic acid amine and the layered titanium of the protonation are added in protonation titanate after the drying
The weight ratio of hydrochlorate is 45：100) 5h, is heat-treated in 600 DEG C, obtains chromium-doped layered titanate；
(5) by chromium-doped layered titanate and the tetramethyl amine (weight of tetramethyl amine and the layered titanate of protonation
Than for 15：100) it is added in liquid-phase substrate water, is stirred 2 days with the speed of 100rpm；Add in N- vinylpyrrolidone (N- second
The weight ratio of alkenyl arsenic pyrrolidone and the layered titanic acid salt compound of protonation is 5：100), using supersonic frequency as 25KHZ, ultrasound
Concussion 5 days, stripping form the two-dimentional titanate nano material.
(2), the measure of two-dimentional titanate nano material
The raw material composition detection of prepared two-dimentional titanate nano material.
Assay method：With embodiment 1.
Measurement result：Disperse in two-dimentional titanate nano material containing 4.3wt.%N- ethyl arsenic pyrrolidones, removal alkanone
Modified protonate after agent contains 61.8wt.% metatitanic acids (protonation titanate) in titanate film, doping 23.5%Cr elements,
Organic group (the CH of 13wt.%3)4N- and impurity 1.7%.
Embodiment 4
(1), two-dimentional titanate nano material preparation method includes：With reference to embodiment 1, wherein difference lies in：
(5) by chromium-doped layered titanate and tetrabutylammonium hydroxide (tetrabutylammonium hydroxide and the stratiform of protonation
The weight ratio of titanate is 7：100) it is added in liquid-phase substrate water, is stirred with the speed of 150rpm and remove within 10 days the two-dimentional titanium of formation
Silicate nanometer material.
(2), the measure of two-dimentional titanate nano material
(1) the raw material composition detection of the two-dimentional titanate nano material prepared by.
Assay method：With embodiment 1.
Measurement result：Two-dimentional titanate nano material (not containing the modified protonation titanate film after alkanone dispersant)
In containing 61.2wt.% metatitanic acids (protonation titanate), doping 32%Cr elements, the organic group (C of 6.4wt.%4H9)4N-,
And impurity 0.4%.
Embodiment 5
(1), two-dimentional titanate nano material preparation method includes：With reference to embodiment 1, wherein difference lies in：
In step (4), the weight ratio of dichromic acid amine and the layered titanate of protonation is 30：100；
In step (5), the weight ratio of tetrabutylammonium hydroxide and the layered titanate of protonation is 4：100, N- ethyl arsenic
The weight ratio of pyrrolidone and the layered titanic acid salt compound of protonation is 6：100.
(2), the measure of two-dimentional titanate nano material
(1) the raw material composition detection of the two-dimentional titanate nano material prepared by.
Assay method：With embodiment 1.
Measurement result：Disperse in two-dimentional titanate nano material containing 5.2wt.%N- ethyl arsenic pyrrolidones, removal alkanone
Modified protonate after agent contains 81.2wt.% metatitanic acids (protonation titanate) in titanate film, doping 14.8%Cr elements,
Organic group (the C of 3.5wt.%4H9)4N- and impurity 0.5%.
Comparative example 1
Titanate nano material preparation method includes：
By bases of sodium hydroxide+hydrofining melt agent, using titanium dioxide as metatitanic acid raw material, using deionized water as cleaning
Agent, detergent and extractant, using absolute ethyl alcohol as detergent and dry carrier, under normal pressure 0.1MPa, under 200 DEG C of low temperature,
Synthesize tubulose (one-dimensional) titanate nano material.
Comparative example 2
(1), two-dimentional titanate nano material preparation method includes：With reference to embodiment 1, wherein difference lies in：Do not include step
Suddenly (4), and step (5) is as follows：
(5) protonation titanate and tetrabutylammonium hydroxide (tetrabutylammonium hydroxide and the stratiform of protonation after drying
The weight ratio of titanate is 5：100) it is added in liquid-phase substrate water, is stirred 3 days with the speed of 160rpm；N- ethyl arsenic is added in cough up
(weight ratio of N- ethyl arsenic pyrrolidones and the layered titanic acid salt compound of protonation is 1 to alkanone：100), using supersonic frequency as
30KHZ, ultrasonic vibration 1 day, stripping form the two-dimentional titanate nano material.
(2), the measure of two-dimentional titanate nano material
(1) the raw material composition detection of the two-dimentional titanate nano material prepared by.
Assay method：With embodiment 1.
Measurement result：Disperse in two-dimentional titanate nano material containing 0.73wt.%N- ethyl arsenic pyrrolidones, removal alkanone
Contain 95wt.% metatitanic acids (protonation titanate), the organic group of 4.7wt.% in modified protonation titanate film after agent
(C4H9)4N- and impurity 0.3%.
Test one：
(1) test event and method：
Absorber Bandwidth is tested：Using Shimadzu companies UV-2450 type spectrophotometers, Example 1 to 5 and comparison
Two-dimentional titanate nano material prepared by example 2 is appropriate, and supernatant is taken to take and be uniformly dispersed in the appropriate dilution of distilled water after centrifugation
Sample suspension injection light path be 10mm quartz colorimetric utensil in tested.
(2) test result：Such as Fig. 4-5.
Fig. 4 is two-dimentional titanate nano material prepared by according to embodiments of the present invention 1 (doped with Cr3+) absorption spectrum
(embodiment 2-5 is similar with it), wherein be respectively 0.015ppm, 0.021ppm including two-dimentional titanate nano material concentration,
Absorption spectrum curve when 0.026ppm, 0.031ppm and 0.037ppm, Fig. 5 are the two-dimentional titanates according to prepared by comparative example 2
The absorption spectrum of nano material (undoped with there is Cr), wherein be respectively 0.014ppm including two-dimentional titanate nano material concentration,
Absorption spectrum curve when 0.015ppm, 0.019ppm, 0.023ppm and 0.025ppm.
It can be seen that by Fig. 4 and Fig. 5：It is not roomy with reference to the absorption band of the two-dimentional titanate nano material of Cr in comparative example 2
It causes, in 260nm, to be only located at ultraviolet region.And the absorption band of the two-dimentional titanate nano material after the doping of the embodiment of the present invention 1 Cr
While in the case of comprising 260nm (ultraviolet CD-ROM drive), while be extended in the scope of about 450nm (visible ray).And by Fig. 4 and figure
5 comparisons are as can be seen that the absorbance of the two increases with the increase of concentration it can be said that bright such film is in liquid-phase substrate
In it is horizontal scattered in quasi-molecule.
Test two：
(1) test event and method.
(1) thickness (minimum) test method：Embodiment 1 to 5 and comparative example 1 and 2 are removed final product to pass through
10000rpm/min is centrifuged, and then centrifugation time takes supernatant for 15min, using 5500 model atom of Agilent companies of the U.S.
Force microscope, scanner resolution ratio are XY：0.2nm, Carry out test analysis；
(2) cross-section lengths (maximum) test method：Embodiment 1 to 5 and comparative example 1 and 2 are removed final product to pass through
10000rpm/min is centrifuged, then centrifugation time takes supernatant for 15min, and electricity is transmitted using Japanese JEOL companies JEM-2010 types
Sub- microscope, accelerating potential are arranged to the pattern and size of 200KV observation titanates；
(3) test method of optical wavelength is absorbed：Use Shimadzu companies UV-2450 type spectrophotometers, Example 1
It is appropriate to the two-dimentional titanate nano material prepared by 4 and comparative example 1-2, supernatant is taken after centrifugation in appropriate dilute of distilled water
It releases, it is to be tested in the quartz colorimetric utensil of 10mm to take finely dispersed sample suspension injection light path；
(4) test method of electricity conversion：By indium tin oxide electro-conductive glass (ITO) successively with third in ultrasonic device
Ketone, deionized water, washes of absolute alcohol, drying；Titanate nano material prepared by embodiment 1 to 5 is prepared into certain dense
Colloid, is then uniformly applied on the conducting surface of electro-conductive glass by the nano thin-film colloid of degree, room temperature naturally dry；Use silver conductive adhesive
A copper conductor is drawn in the electro-conductive glass substrate of non-film, and with insulating cement by the side of conducting wire exposed part and electro-conductive glass
Edge is sealed to get nano tube structure electrode.
Photoelectrochemical experiments use the three electrolysis equipment with quartz window, using the ITO/ nano thin-films of preparation as work
Electrode uses saturated calomel electrode as reference electrode, using Pt electrodes as to electrode, with 0.04molL-1 Potassium Hydrogen Phthalates
Solution is that the 0.1molL-1KSCN solution of bottom liquid is supporting electrolyte, with potentiostat (Potentiostat/
Galvanostat Model 263A) when measuring photoelectric current control of Electric potentials is carried out, using 300W xenon lamps as light source, pass through monochromator
According on the working electrode (s, light intensity is demarcated with LPE-1A types Laser Power/energy Meter.
(2) test result：As shown in table 1.
Table 1.
Turned by the photoelectricity of the two-dimentional titanate nano material prepared by 1-5 of the embodiment of the present invention it can be seen from data in table 1
Change electricity conversion of the efficiency much larger than titanate nano material in comparative example 1 and 2.
Above-mentioned technical proposal of the present invention by adulterating Cr elements in two-dimentional titanate nano material, is conducive to widen two
The Absorber Bandwidth of titanate nano material is tieed up, makes it that can also absorb visible ray simultaneously, and then substantially increases its light absorption, light
The efficiency of electricity conversion, so as to further improve photocatalysis efficiency.
Meanwhile it is used as nanometer sheet by adulterating the relatively large organic group of molecular weight in two-dimentional titanate nano material
Balance media, it is made to be not easy to crimp, there is metastable two-dimensional structure, and then with relatively large surface area, so as to
Improve photocatalysis efficiency.
The preferred embodiment of the present invention is described in detail above in association with attached drawing, still, the present invention is not limited to above-mentioned realities
The detail in mode is applied, within the scope of the technical concept of the present invention, a variety of letters can be carried out to technical scheme
Monotropic type, these simple variants all belong to the scope of protection of the present invention.
It is further to note that the specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (24)
1. a kind of two dimension titanate nano material, which is characterized in that the two dimension titanate nano material includes modified proton
Change titanate film, the protonation titanate film of the modification has the Cr elements of organic group and doping and the modification
Protonation titanate film in the organic group containing 2-15wt.%, the Cr elements of 13-32wt.%；
Wherein, the organic group is introduced by protonation titanate and organic amine and/or tetrabutylammonium hydroxide reaction, described
Organic amine is the one or more in ethamine, polyethyleneimine and diethylamide.
2. two dimension titanate nano material according to claim 1, wherein, the two dimension titanate nano material further includes
It is dispersed in the alkanone class dispersant on the protonation titanate film surface of the modification.
3. two dimension titanate nano material according to claim 2, wherein, the alkanone class dispersant and the modification
The weight ratio for protonating titanate is 1-5：100.
4. two dimension titanate nano material according to claim 2, wherein, the weight average molecular weight of the alkanone class dispersant
For 100-200.
5. two dimension titanate nano material according to claim 3, wherein, the alkanone class dispersant is N- N-ethyl pyrrole Ns
One or more in alkanone, N- methyl arsenic pyrrolidones and N- vinylpyrrolidones.
6. two dimension titanate nano material according to claim 1, wherein, the two dimension titanate nano material and thickness
The length of the perpendicular cross section in direction is 0.1-100 μm, and the thickness of the two dimension titanate nano material is 1-10nm.
7. a kind of preparation method of two dimension titanate nano material, which is characterized in that the preparation method comprises the following steps：
With alkali carbonate and unformed TiO2For raw material, the layered titanate of protonation is prepared；
Under heat treatment condition, make protonation titanate and bichromate haptoreaction, form the layered titanate of doping Cr；
Under agitation, make the layered titanate for adulterating Cr with organic amine and/or tetrabutylammonium hydroxide in liquid phase base
Haptoreaction in matter, stripping form the two-dimentional titanate nano material；
Wherein, the weight ratio of the bichromate and the layered titanate of the protonation is 0.3-0.6：1, the organic amine
And/or tetrabutylammonium hydroxide and the weight ratio of the layered titanate of the protonation are 10-25：100；
Wherein, the organic amine is the one or more in ethamine, polyethyleneimine and diethylamide.
8. preparation method according to claim 7, wherein, the heat treatment condition is that heat treatment temperature is 300 ~ 600
DEG C, heat treatment time is 5 ~ 10h.
9. preparation method according to claim 7, wherein, the bichromate is dichromic acid amine, potassium bichromate and weight chromium
One or more in sour sodium.
10. preparation method according to claim 7, wherein, the stirring condition is：Mixing speed 100-180rpm, is stirred
Mix the time 1-14 days.
11. according to the preparation method any one of claim 7-10, wherein, make the layered titanate of the doping Cr
With organic amine and/or tetrabutylammonium hydroxide in liquid-phase substrate the step of haptoreaction after, be additionally included in ultrasonic vibration condition
Under, alkanone class dispersant is further added in into the liquid-phase substrate, makes alkanone class dispersant and the layered titanate of protonation
The step of being mixed.
12. preparation method according to claim 11, wherein, the alkanone class dispersant and the layered titanium of the protonation
The weight ratio of phosphate compounds is 1-5：100.
13. preparation method according to claim 11, wherein, the weight average molecular weight of the alkanone class dispersant is 100-
200。
14. preparation method according to claim 12, wherein, the alkanone class dispersant is N- ethyl pyrrolidones, N-
One or more in methyl arsenic pyrrolidone and N- vinylpyrrolidones.
15. preparation method according to claim 11, wherein, the stirring condition is that mixing speed 100-180rpm is stirred
Mix the time 1-5 days；The ultrasonic vibration condition is supersonic frequency 25-40kHZ, and the concussion time is 1-5 days.
16. preparation method according to claim 11, wherein, described the step of preparing the layered titanate protonated, wraps
It includes：
By alkali carbonate and unformed TiO2Mixed grinding obtains mixed-powder；
The mixed-powder is roasted, solid phase reaction obtains layered titanic acid salt powder；
Neutrality will be washed to after layered metatitanic acid salt powder acid adding pickling, dried, the layered titanate protonated.
17. preparation method according to claim 16, wherein, it is described by alkali carbonate and unformed TiO2Mixing is ground
In the step of mill：By alkali carbonate and unformed TiO2By 1:3.3 ~ 7.3 mixed in molar ratio are ground.
18. preparation method according to claim 17, wherein, obtain the mixed-powder that grain size is 0.2-0.6 μm.
19. preparation method according to claim 17, wherein, the alkali carbonate is potassium carbonate, sodium carbonate, carbonic acid
One or more in lithium, rubidium carbonate, cesium carbonate.
20. preparation method according to claim 16, wherein, in described the step of roasting the mixed-powder, roasting
When condition is that roasting 20 ~ 40 is small at 700 ~ 1100 DEG C.
21. preparation method according to claim 16, wherein, the step of the salt powder acid adding pickling to layered titanic acid
In：Pickling 1-3 times, in each acid cleaning process, pickling temperature is 15-40 DEG C, pickling time 15-25h.
22. preparation method according to claim 21, wherein, in each acid cleaning process, H is added in every gram of layered titanate+
The amount for the acid solution that concentration is 1mol/L is 75-85ml.
23. preparation method according to claim 21, wherein, the acid is one kind or more in hydrochloric acid, sulfuric acid and nitric acid
Kind.
24. a kind of two dimension titanate nano material, which is characterized in that the two dimension titanate nano material is by claim 7-23
Any one of preparation method be prepared.
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