CN112194178A - Titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material and preparation method thereof - Google Patents
Titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a titanium dioxide and Prussian blue ordered assembled mesomorphic nano material, which is characterized in that a hydrothermal method is utilized to prepare a novel flower-shaped mesomorphic nano material formed by a nanowire array; taking potassium ferrocyanide and titanium sulfate as raw materials, PVP as a stabilizer and dilute hydrochloric acid as a solvent, and reacting at a specific temperature to prepare the monodisperse high-purity flower-shaped titanium dioxide and Prussian blue composite material (TiO)2-PB) with simple preparation process, reliable design principle, low production cost, short period and environment-friendly application, and the prepared composite material has good monodispersity, high purity, uniform morphology and wide application prospect in many aspects. The solid film constructed by the composite material can be conveniently applied to the surface of conventional paper to produce the inkless printing rewritable paper with the same hand feeling and appearance. The composite material and the solid film are simple and convenient to produce, and the optical printing mode is simple, environment-friendly, safe and efficient.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material synthesized by a one-step method and a preparation method thereof.
Background
Metal Organic Frameworks (MOFs) and Inorganic Nanocrystals (INC) are powerful materials that help to alleviate the energy crisis and solve environmental problems. Some examples of successful assembly of the complementary functions of MOF and INCS provide good reference for new material design, e.g., TiO grown in MIL-101 pores2NCs produce a novel catalyst that utilizes TiO2And MOF to promote photocatalytic reduction of CO2While generating O2。
However, self-assembly of MOF-INC with defined crystallographic orientation has not been completed. MOFs and INCs have different lattice parameters and synthesis methods. Since the self-assembly solution of colloidal particles is dominated by entropy and energy interactions, mixing different types of MOFs and INCS often results in uncontrolled phase separation. It is generally found that the INCs are incorporated into the pores of the MOF in a random orientation and not atomically coherent. This is an inherent limitation that severely limits the usefulness of MOF-INC in advanced applications.
To our knowledge, this is the first about obtaining inorganic nanoparticles (TiO) by ordered assembly2) And metal organic framework (PB) mesogenic composites. The method can overcome the assembly limitation specific to the nano particles, broadens the selection of the artificial construction of the ordered assembly material and improves the universality of the ordered assembly method. More research opportunities are brought to the realization of the versatility of MOFs and INCs. Successfully prepares titanium dioxide and Prussian blue ordered assembly medium by a strategy of a one-step hydrothermal methodCrystalline nanomaterials and can be applied to high efficiency inkless recyclable photo-printing.
Disclosure of Invention
The invention aims to provide a titanium dioxide and Prussian blue ordered assembly state mesomorphic nanometer material synthesized by a one-step strategy as a photochromic medium for repeatable inkless photo printing, aiming at the defects of the prior art. The invention synthesizes titanium dioxide and Prussian blue compound with uniform size as photochromic material by a hydrothermal method. Uniformly dispersing the compound and hydroxyethyl cellulose in H2O and glycol to obtain a dirty body, and finally uniformly coating the dirty body on a conventional paper and drying. The invention has low cost and simple method, provides the preparation method of the photochromic composite material, has good economic benefit and environmental benefit, and can be applied to large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme:
(1) weighing a Prussian blue precursor and a stabilizer, stirring and dissolving in a dilute hydrochloric acid solution at room temperature to prepare a Prussian blue precursor solution A;
(2) adding a titanium dioxide precursor into the solution A obtained in the step (1), fully stirring and dissolving, and performing ultrasonic treatment to form a mixed solution B;
(3) pouring the mixed solution B obtained in the step (2) into a high-pressure reaction kettle for constant-temperature reaction;
(4) cooling the solution reacted in the step (3) along with a furnace, performing centrifugal separation, washing and drying until the water is completely volatilized to obtain dark green powdery titanium dioxide-Prussian blue composite material (TiO)2-PB)。
Further, the Prussian blue precursor in the step (1) is non-toxic potassium hexacyanoferrate trihydrate; the stabilizer is polyvinylpyrrolidone (PVP), the dosage of potassium ferrocyanide is 0.12g, and the dosage of polyvinylpyrrolidone is 3.8 g.
Further, the concentration of the dilute hydrochloric acid solution in the step (1) is 0.1 mol/L.
Further, the stirring and dissolving in the step (1) specifically comprises: stirring by magnetic force at the stirring speed of 500 rpm; the stirring time was 30 min.
Further, the titanium dioxide precursor in the step (2) is titanium sulfate, and the using amount of the titanium sulfate is 0.682 g.
Further, the stirring and dissolving time in the step (2) is 5min, and the ultrasonic treatment time is 25 min.
Further, the capacity of the high-pressure reaction kettle in the step (3) is 100 ml.
Further, the isothermal reaction in the step (3) is specifically as follows: the reaction is carried out for 24h at a constant temperature of 80 ℃.
Further, the washing solvents in the step (4) are deionized water and ethanol, the use amounts of the deionized water and the ethanol are both 60ml, the washing times are both 3 times, the drying temperature is 60 ℃, the drying time is 12 hours, and the drying condition is vacuum drying.
The invention discloses a titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material which can also be applied to high-efficiency inkless recyclable photo-printing, and comprises the following steps:
1) dispersing titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material in deionized water, then adding hydroxyethyl cellulose solution and ethylene glycol, and stirring the mixed solution in an oil bath kettle at 60 ℃ for 30 minutes; finally, uniformly coating the mixed solution on common paper, and drying in a drying oven at 40 ℃ for 72 hours to obtain optical printing paper;
2) printing letters or patterns on common transparent paper by using a commercial printer, covering the letters or patterns on the optical printing paper prepared in the step 1), placing the optical printing paper under a xenon lamp for irradiating for a period of time to finish printing, and if the printing needs to be carried out again, placing the optical printing paper in an oven at 120 ℃ for heat preservation for 30min so as to be used for optical printing again.
The invention has the following remarkable advantages:
1) according to the invention, a hydrothermal method is adopted, and the titanium dioxide and Prussian blue ordered assembled mesomorphic nanomaterial is prepared in one step. The composite material has uniform size and good dispersion, and the two are closely connected. The method widens the element selection of ordered assembly, and the equipment and materials required by the preparation method are easy to obtain, the process operation is simple, the process conditions are not complex, and the method has the advantages of low cost, safety and high efficiency, and is easy to popularize and apply.
2) The titanium dioxide and Prussian blue ordered assembled mesomorphic nanomaterial prepared by the method has the advantages of high response speed, good repeatability, visible light response and the like when being applied to photo-printing because photogenerated electrons of the titanium dioxide can be rapidly transferred to Prussian blue, and is suitable for large-scale commercial application. The method is energy-saving and environment-friendly, can reduce the use of paper and protect forests.
Drawings
FIG. 1 shows TiO in example 12-a micro-topography of the PB;
FIG. 2 shows TiO in example 12-X-ray diffraction (XRD) pattern of PB;
FIG. 3 shows TiO in example 12-infrared spectrum (FI-IR) diagram of PB;
FIG. 4 shows TiO in example 12-X-ray photoelectron spectroscopy (XPS) plots of PB;
FIG. 5 shows TiO in example 12-Transmission Electron Microscope (TEM) elemental distribution (Mapping) map of PB;
FIG. 6 shows TiO in example 12-a selected area electron diffraction (sea) map of PB;
FIG. 7 is a diagram showing an example of optical printing in application example 1;
FIG. 8 is a graph of an example of a graph of the photo-printing rate in application example 1 and in application comparative 1 and comparative 2;
fig. 9 is a graph of the cycle stability performance of the photo-printing applied in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features mentioned in the embodiments of the present invention described below may be combined as long as they do not conflict with each other.
Example 1
(1) Completely dissolving 0.12g of potassium ferrocyanide and 3.8g of polyvinylpyrrolidone in a dilute hydrochloric acid solution, and stirring in a magnetic stirrer with the rotation speed of 500 revolutions for 30min until the solid is completely dissolved to obtain a solution A.
(2) Adding 0.682g of titanium sulfate into the solution A, stirring for 5min, carrying out ultrasonic treatment for 25min, then placing the solution into a 100ml high-pressure reaction kettle, and carrying out hydrothermal reaction for 24h at the temperature of 80 ℃.
(3) Washing with 60ml alcohol and 60ml deionized water for 3 times respectively, and washing at 60 deg.CoAnd C, drying in an oven for 12h to obtain the orderly-assembled composite material.
Comparative example 1
(1) Completely dissolving 0.12g of potassium ferrocyanide and 3.8g of polyvinylpyrrolidone in a dilute hydrochloric acid solution, and stirring in a magnetic stirrer with the rotation speed of 500 revolutions for 30min until the solid is completely dissolved to obtain a solution A.
(2) The solution A is put into a 100ml high-pressure reaction kettle and undergoes hydrothermal reaction for 24 hours at the temperature of 80 ℃.
(3) The composite material is obtained by washing 3 times with 60ml of alcohol and 60ml of deionized water respectively and drying in an oven at 60 ℃ for 12 h.
(4) Stirring the prepared Prussian blue and commercial rutile type titanium dioxide together, wherein the mass ratio of the Prussian blue to the commercial rutile type titanium dioxide is TiO2PB =2.3:1 (vs. PB and TiO in the composite of example 1)2The proportions of (a) and (b) are consistent).
Comparative example 2
(1) Completely dissolving 0.12g of potassium ferrocyanide and 3.8g of polyvinylpyrrolidone in a dilute hydrochloric acid solution, and stirring in a magnetic stirrer with the rotation speed of 500 revolutions for 30min until the solid is completely dissolved to obtain a solution A.
(2) Adding 0.682g of titanium sulfate into the solution A, stirring for 5min, carrying out ultrasonic treatment for 25min, then placing the solution into a 100ml high-pressure reaction kettle, and carrying out hydrothermal reaction for 24h at the temperature of 80 ℃.
(3) The orderly assembled composite material is obtained by washing 3 times with 60ml of alcohol and 60ml of deionized water respectively and drying in an oven at 60 ℃ for 12 h.
(4) Dispersing the composite material in hydrochloric acid, stirring for 20min, and selectively etching PB to obtain flower-like titanium dioxide.
(5) The Prussian blue flower-shaped titanium dioxide obtained in the preparation comparative example 2 is stirred together, and the mass ratio of the Prussian blue flower-shaped titanium dioxide to the Prussian blue flower-shaped titanium dioxide is TiO2PB =2.3:1 (vs. PB and TiO in the composite of example 1)2The proportions of (a) and (b) are consistent).
Inkless photo printing experiment
Application example 1
(1) 20mg of the composite powder was dispersed in 12ml of deionized water to obtain solution A.
(2) To the above solution A, 5ml of a hydroxyethylcellulose solution and 2ml of ethylene glycol were added, and the mixture was stirred in an oil bath at 60 ℃ for 30 minutes.
(3) And finally, uniformly coating the mixed solution on common paper, and drying in an oven at 40 ℃ for 72 hours.
(4) Printing letters or patterns on common transparent paper by a commercial printer, covering the plain paper with the letters or patterns, and finally placing the plain paper under a xenon lamp for irradiating for a period of time to finish printing. If printing is needed again, the printing paper can be placed in an oven with the temperature of 120 ℃ for heat preservation for 30min and then can be used for optical printing again.
(5) The absorbance spectrum of prussian blue was measured by uv-vis absorbance spectroscopy.
Application comparative example 1
(1) 20mg of PB of comparative example 1 and commercial TiO2The mixed powder of (2) was dispersed in 12ml of deionized water to obtain solution A.
(2) To the above solution A, 5ml of a hydroxyethylcellulose solution and 2ml of ethylene glycol were added, and the mixture was stirred in an oil bath at 60 ℃ for 30 minutes.
(3) And finally, uniformly coating the mixed solution on common paper, and drying in an oven at 40 ℃ for 72 hours.
(4) Printing letters or patterns on common transparent paper by a commercial printer, covering the plain paper with the letters or patterns, and finally placing the plain paper under a xenon lamp for irradiating for a period of time to finish printing. If printing is needed again, the printing paper can be placed in an oven with the temperature of 120 ℃ for heat preservation for 30min and then can be used for optical printing again.
(5) The absorbance spectrum of prussian blue was measured by uv-vis absorbance spectroscopy.
Comparative application example 2
(6) 20mg of PB in comparative example 1 and flower-like TiO in comparative example 22The mixed powder of (2) was dispersed in 12ml of deionized water to obtain solution A.
(7) Adding 5ml of hydroxyethyl cellulose solution and 2ml of ethylene glycol into the solution A, and adding the mixed solution at 60%oStir in oil bath for 30 minutes.
(8) And finally, uniformly coating the mixed solution on common paper, and drying in an oven at 40 ℃ for 72 hours.
(9) Printing letters or patterns on common transparent paper by a commercial printer, covering the plain paper with the letters or patterns, and finally placing the plain paper under a xenon lamp for irradiating for a period of time to finish printing. If printing is needed again, the printing paper can be placed in an oven with the temperature of 120 ℃ for heat preservation for 30min and then can be used for optical printing again.
(10) The absorbance spectrum of prussian blue was measured by uv-vis absorbance spectroscopy.
Analysis of results
TiO obtained in example 12The micro-morphology of the PB ordered assembly mesomorphic nanocomposite is shown in fig. 1; the resulting TiO2The X-ray diffraction (XRD) results of PB are shown in FIG. 2; the resulting TiO2The infrared spectrum (FI-IR) result of-PB is shown in FIG. 3; the resulting TiO2The X-ray photoelectron spectroscopy (XPS) results of PB are shown in FIG. 4; the resulting TiO2The results of elemental distribution (Mapping) in a PB Transmission Electron Microscope (TEM) are shown in fig. 5; the resulting TiO2-PB field Electron diffraction (SEAD) is shown in FIG. 6. Analysis found that TiO was synthesized2-PB nanocomposite material consisting of Prussian blue and rutile titanium dioxide, both mesogenic and spatially separatedThe cloth is uniformly arranged in 90-degree order. The obtained composite material is a mesomorphic nano composite material formed by orderly assembling titanium dioxide and Prussian blue.
The effect of the optical printing in application example 1 is shown in fig. 7; the optical printing speeds of application example 1, application comparative example 1 and application comparative example 2, as shown in the time bar chart of fig. 8; the stability of the photo printing in application example 1 is shown in fig. 9. Analysis shows that when the photo-printing is performed in the embodiment 1, various patterns and characters can be obtained, the resolution is high (at least 50 um), and the stability is good (>100 cycles), completing the print suitable for commercial printing. As shown in fig. 8, the time for completing one photo-printing was 20 seconds for both application example 1 and application example 2, whereas only 5 seconds were required for application example 1; that is, the optical printing speed of application example 1 was 4 times that of application comparative example 1 and application comparative example 2. This is due to TiO2And PB are orderly assembled in space, and strong interaction force exists between interfaces, so that TiO2Can be rapidly transferred into the PB so that the PB is reduced to Prussian White (PW).
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A preparation method of titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material is characterized in that: the method comprises the following steps:
(1) weighing a Prussian blue precursor and a stabilizer, stirring and dissolving in a dilute hydrochloric acid solution at room temperature to prepare a Prussian blue precursor solution A;
(2) adding a titanium dioxide precursor into the solution A obtained in the step (1), fully stirring and dissolving, and performing ultrasonic treatment to form a mixed solution B;
(3) pouring the mixed solution B obtained in the step (2) into a high-pressure reaction kettle for constant-temperature reaction;
(4) and (4) cooling the solution reacted in the step (3) along with a furnace, and performing centrifugal separation, washing and drying until the water is completely volatilized to obtain the dark green powdery titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material.
2. The method for preparing the titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material according to claim 1, which is characterized in that: the Prussian blue precursor in the step (1) is non-toxic potassium hexacyanoferrate trihydrate, and the stabilizer is polyvinylpyrrolidone.
3. The method for preparing the titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material according to claim 1, which is characterized in that: the dosage of the potassium ferrocyanide is 0.12g, and the dosage of the polyvinylpyrrolidone is 3.8 g.
4. The method for preparing the titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material according to claim 1, which is characterized in that: the concentration of the dilute hydrochloric acid solution in the step (1) is 0.1 mol/L.
5. The method for preparing the titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material according to claim 1, which is characterized in that: the titanium dioxide precursor in the step (2) is titanium sulfate, and the using amount of the titanium sulfate is 0.682 g.
6. The method for preparing the titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material according to claim 1, which is characterized in that: the stirring and dissolving time in the step (2) is 5min, and the ultrasonic treatment time is 25 min.
7. The method for preparing the titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material according to claim 1, which is characterized in that: the constant temperature reaction in the step (3) is specifically as follows: the reaction is carried out for 24h at a constant temperature of 80 ℃.
8. The method for preparing the titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material according to claim 1, which is characterized in that: and (4) the washing solvents in the step (4) are deionized water and ethanol, the dosage of the deionized water and the dosage of the ethanol are both 60ml, the washing times are both 3 times, the drying temperature is 60 ℃, the drying time is 12 hours, and the drying condition is vacuum drying.
9. Titanium dioxide and Prussian blue ordered assembly mesogenic nanomaterial prepared by the preparation method of any one of claims 1-8.
10. The use of the titanium dioxide and Prussian blue ordered assembly mesogenic nanomaterial of claim 9 in inkless optical printing, wherein: the method comprises the following steps:
1) dispersing titanium dioxide and Prussian blue ordered assembly state mesomorphic nano material in deionized water, then adding hydroxyethyl cellulose solution and ethylene glycol, and stirring the mixed solution in an oil bath kettle at 60 ℃ for 30 minutes; finally, uniformly coating the mixed solution on common paper, and drying in a drying oven at 40 ℃ for 72 hours to obtain optical printing paper;
2) printing letters or patterns on common transparent paper by using a commercial printer, covering the plain printing paper prepared in the step 1) with the letters or patterns, placing the plain printing paper under a xenon lamp for irradiating for a period of time to finish printing, and if the plain printing paper needs to be printed again, placing the plain printing paper in an oven at 120 ℃ for heat preservation for 30min so as to be used for the plain printing again.
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CN116351471A (en) * | 2023-03-13 | 2023-06-30 | 南方医科大学 | Prussian blue/g-C 3 N 4 Composite photocatalyst, preparation method and application thereof |
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