CN111454710A - Photochromic titanyl oxalate material and preparation method thereof - Google Patents
Photochromic titanyl oxalate material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 132
- QKKWJYSVXDGOOJ-UHFFFAOYSA-N oxalic acid;oxotitanium Chemical compound [Ti]=O.OC(=O)C(O)=O QKKWJYSVXDGOOJ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 58
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 claims abstract description 53
- 239000010936 titanium Substances 0.000 claims abstract description 44
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 13
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 18
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000002371 ultraviolet--visible spectrum Methods 0.000 claims description 13
- 238000007789 sealing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 abstract description 19
- 238000010146 3D printing Methods 0.000 abstract description 8
- 239000007787 solid Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- -1 silver halide Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
Abstract
The invention provides a photochromic titanyl oxalate material and a preparation method thereof. The preparation method of the photochromic titanium oxyoxalate material comprises the following steps: s1: adding a certain amount of titanium potassium oxalate into deionized water, and stirring to obtain a titanium potassium oxalate solution; s2: adding hydrochloric acid with the concentration of 36 wt% -38 wt% into the titanium potassium oxalate solution obtained in the step S1, uniformly stirring to obtain a precursor solution, and carrying out hydrothermal treatment on the precursor solution to obtain a reaction product; s3: and (4) centrifugally separating the reaction product obtained in the step (S2), washing, and drying at 60-80 ℃ for 3-5h to obtain the photochromic titanyl oxalate material. The photochromic titanyl oxalate material prepared by the invention is polyhedral in shape, changes from white to blue gray under the irradiation of 365nm ultraviolet light in a solid state, can change from blue gray to white after the irradiation of a 500W xenon lamp, has excellent reversible photochromic property, light stability and fatigue resistance, and can be used as a photo-reversible material to be applied to the fields of anti-counterfeiting, reversible color-developing films, erasable 3D printing and the like.
Description
Technical Field
The invention provides a photochromic titanyl oxalate material and a preparation method thereof, belonging to the technical field of photochromism.
Background
The photochromic material is widely applied in the fields of information storage, photochromic glass, sensors, erasable 3D printing, anti-counterfeiting, molecular switching, drug slow release and the like. The photochromic compounds mainly fall into three categories, namely, traditional inorganic photochromic compounds, organic photochromic compounds and inorganic-organic hybrid photochromic compounds which are continuously developed. Compared with organic and inorganic-organic hybrid compounds, the inorganic photochromic compound has the advantages of good thermal stability and fatigue resistance, strong oxidation resistance, simple preparation process, durable photochromic property and the like, and can be used for preparing synthetic nano materials, glass, crystals and composite film materials.
Common inorganic photochromic materials such as silver halide, CdCl2、TiO2、WO3、MoO3BeO, and the like, which are mainly applied to the fields of color-changing glass, sensors, erasable 3D printing and anti-counterfeiting, so that the inorganic photochromic material is required to have good fatigue resistance and durable photochromic property. However, due to the defects of the material structure, the traditional inorganic photochromic material cannot maintain the lasting photochromic property while meeting the fatigue resistance, so that the service life of the inorganic photochromic material is greatly shortened, and the practical application is limited. The titanyl oxalate as a semiconductor material can be adjusted in structure by limiting the synthesis process and has excellent photostability and color development variability. Therefore, the invention discloses a colorless titanyl oxalate material which can realize persistent reversible photochromism only through light source change, and has great potential application value in the fields of color-changing glass, sensors, erasable 3D printing and anti-counterfeiting.
In view of the above, it is necessary to provide a photochromic titanyl oxalate material and a preparation method thereof to solve the above problems.
Disclosure of Invention
The photochromic titanium oxyoxalate material prepared by the invention is in a polyhedral shape, can be switched in colors in two color states after being irradiated by ultraviolet light and a xenon lamp in a solid state, has excellent reversible photochromic property, light stability and fatigue resistance, and can be used as a photo-reversible material to be applied to the fields of anti-counterfeiting, reversible color-developing films, erasable 3D printing and the like.
In order to realize the aim, the invention provides a preparation method of a photochromic titanyl oxalate material, which comprises the following steps:
s1: adding a certain amount of titanium potassium oxalate (K) into deionized water2TiO(C2O4)2) Stirring to obtain a titanium potassium oxalate solution with the concentration of 0.05-0.35M;
s2: adding hydrochloric acid with the concentration of 36 wt% -38 wt% into the titanium potassium oxalate solution obtained in the step S1, uniformly stirring to obtain a precursor solution, and carrying out hydrothermal treatment on the precursor solution to obtain a reaction product;
s3: and (4) centrifugally separating the reaction product obtained in the step (S2), washing, and drying at 60-80 ℃ for 3-5h to obtain the photochromic titanyl oxalate material.
As a further improvement of the invention, the step S1 is to add the potassium titanium oxalate into the deionized water with the pH value of 6 and the weight of 30m L, wherein the dosage of the potassium titanium oxalate is 0.53g, 1.06g, 2.12g, 2.65g, 3.18g, 3.71g or 4.24 g.
As a further improvement of the present invention, in step S1, the heating temperature after the titanium potassium oxalate is added to the deionized water is 45 ± 5 ℃, and the stirring is performed for 10-15min until the titanium potassium oxalate is completely dissolved, so as to obtain the titanium potassium oxalate solution.
As a further improvement of the present invention, the step S2 specifically includes:
s21, stopping heating and stirring of the potassium titanium oxalate solution in the step S1, after the potassium titanium oxalate solution is cooled to 25 +/-1 ℃, rapidly adding hydrochloric acid with the concentration of 36-38 wt%, continuously stirring at 25 +/-1 ℃, and uniformly stirring to obtain a precursor solution;
and S22, transferring the precursor solution obtained in the step S21 into a reaction kettle, sealing the reaction kettle, and then placing the reaction kettle in an oven for hydrothermal treatment to obtain a reaction product.
As a further improvement of the invention, in the step S21, the hydrochloric acid with the concentration of 36 wt% -38 wt% is used in an amount of 3.0 +/-0.2 m L.
As a further improvement of the invention, the hydrochloric acid is added in the step S21 and then stirred for 10-15min at 25 +/-1 ℃ until the hydrochloric acid and the titanium potassium oxalate solution are uniformly mixed.
As a further improvement of the invention, in the step S2, the temperature of the hydrothermal treatment is 100 ℃ and 110 ℃, and the time of the hydrothermal treatment is 12 h.
In order to realize the aim, the invention provides a photochromic titanyl oxalate material, which is prepared by adopting the preparation method of the photochromic titanyl oxalate material; the photochromic titanyl oxalate material has a polyhedral shape and a particle size of 8-12 mu m.
As a further improvement of the invention, the photochromic titanium oxyoxalate material has a first color state which is white, when 365nm ultraviolet light irradiates on the photochromic titanium oxyoxalate material in the first color state, the photochromic titanium oxyoxalate material is changed from the first color state which is white to a second color state which is blue-gray, and when the photochromic titanium oxyoxalate material in the second color state is irradiated by a xenon lamp of 500W, the photochromic titanium oxyoxalate material is changed from the second color state which is blue-gray to a third color state which is white again.
As a further improvement of the invention, the UV-vis absorption spectrum of the photochromic titanyl oxalate material in the first color state has an absorption peak at 300-390nm, the UV-vis absorption spectrum of the photochromic titanyl oxalate material in the second color state has an absorption peak at 300-800nm, and the UV-vis absorption spectrum of the photochromic titanyl oxalate material in the third color state has an absorption peak at 300-390 nm; and the first color state and the third color state have a consistent intrinsic structure and the same apparent color.
The invention has the beneficial effects that:
(1) the preparation method and the synthesis process of the photochromic titanyl oxalate material are limited, and the material is firstly used in the photochromic field, so that the photochromic titanyl oxalate material is synthesized by a low-temperature method for the first time.
(2) The photochromic titanyl oxalate material prepared by the one-step hydrothermal method has a polyhedral shape, can obtain a better crystal phase without subsequent secondary treatment, and has a simple and easily-controlled preparation process.
(3) The photochromic titanyl oxalate material synthesized by the method has excellent reversible photochromic performance, and can be changed from white to blue gray after being irradiated by ultraviolet light and then changed from blue gray to white after being irradiated by a xenon lamp; the photochromic titanyl oxalate material can be applied to the fields of anti-counterfeiting, reversible color developing films, erasable 3D printing and the like as a photo-reversible material.
Drawings
FIG. 1 is a low magnification SEM photograph of a photochromic titanium oxyoxalate material prepared in example 1 of the present invention.
FIG. 2 is a high magnification SEM photograph of a photochromic titanyl oxalate material prepared in example 1 of the present invention.
FIG. 3 is a color development real object diagram of the photochromic titanium oxyoxalate material prepared in example 1 of the present invention.
FIG. 4 is an electron spin resonance spectrum (ESR spectrum) of the photochromic titanium oxyoxalate material prepared in example 1 of the present invention.
FIG. 5 is a low magnification SEM photograph of a photochromic titanium oxyoxalate material prepared in example 2 of the present invention.
FIG. 6 is a high power SEM photograph of a photochromic titanium oxyoxalate material prepared in example 2 of the present invention.
FIG. 7 is a color development real object diagram of the photochromic titanium oxyoxalate material prepared in example 2 of the present invention.
FIG. 8 is a UV-vis absorption spectrum of the photochromic titanyl oxalate material prepared in example 2 of the present invention.
FIG. 9 is a low magnification SEM photograph of a photochromic titanium oxyoxalate material prepared in example 3 of the present invention.
FIG. 10 is a high power SEM photograph of a photochromic titanium oxyoxalate material prepared in example 3 of the present invention.
FIG. 11 is an X-ray photoelectron spectroscopy (XPS spectrum) of a photochromic titanium oxyoxalate material prepared in example 3 of the present invention.
FIG. 12 is a low magnification SEM photograph of a photochromic titanium oxyoxalate material prepared in example 4 of the present invention.
FIG. 13 is a high power SEM photograph of a photochromic titanium oxyoxalate material prepared in example 4 of the present invention.
FIG. 14 is a color development real object diagram of the photochromic titanium oxyoxalate material prepared in example 4 of the invention.
FIG. 15 is an X-ray diffraction pattern (XRD pattern) of the photochromic titanium oxyoxalate material prepared in example 4 of the present invention.
FIG. 16 is a low magnification SEM photograph of a photochromic titanium oxyoxalate material prepared in example 5 of the present invention.
FIG. 17 is a high power SEM photograph of a photochromic titanium oxyoxalate material prepared in example 5 of the present invention.
FIG. 18 is an infrared spectrum (FTIR spectrum) of a photochromic titanium oxyoxalate material prepared in example 5 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the aspects of the present invention are shown in the drawings, and other details not closely related to the present invention are omitted.
In addition, it is also to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a photochromic titanyl oxalate material and a preparation method thereof, wherein the preparation method comprises the following steps:
s1: adding a certain amount of titanium potassium oxalate (K) into deionized water2TiO·(C2O4)2) Stirring to obtain a titanium potassium oxalate solution with the concentration of 0.05-0.35M;
s2: adding hydrochloric acid with the concentration of 36 wt% -38 wt% into the titanium potassium oxalate solution obtained in the step S1, uniformly stirring to obtain a precursor solution, and carrying out hydrothermal treatment on the precursor solution to obtain a reaction product;
s3: and (4) centrifugally separating the reaction product obtained in the step (S2), washing, and drying at 60-80 ℃ for 3-5h to obtain the photochromic titanyl oxalate material.
In the following description, the steps S1-S3 will be described in detail.
In the present invention, step S1 specifically includes: adding titanium potassium oxalate (K)2TiO·(C2O4)2) Adding the titanium oxalate solution into deionized water, and stirring to obtain a titanium potassium oxalate solution, namely, taking the titanium potassium oxalate solution as a titanium source to participate in the subsequent reaction in the application.
In a preferred embodiment of the invention, the pH of the deionized water is 6, the dosage of the deionized water is 30M L, the stirring and heating temperature of the potassium titanium oxalate added into the deionized water is 45 +/-5 ℃, the stirring time is 10-15min until the potassium titanium oxalate is completely dissolved, so as to prepare a potassium titanium oxalate solution with the concentration of 0.05-0.35M, preferably, the stirring and heating temperature is 45 ℃, and further, the dosage of the potassium titanium oxalate in the application is any one of 0.53g, 1.06g, 2.12g, 2.65g, 3.18g, 3.71g and 4.24 g.
Step S2 specifically includes:
s21, stopping heating and stirring of the potassium titanium oxalate solution in the step S1, after the potassium titanium oxalate solution is cooled to 25 +/-1 ℃, rapidly adding hydrochloric acid with the concentration of 36-38 wt%, continuously stirring at 25 +/-1 ℃, and uniformly stirring to obtain a precursor solution;
and S22, transferring the precursor solution obtained in the step S21 into a reaction kettle, sealing the reaction kettle, and then placing the reaction kettle in an oven for hydrothermal treatment to obtain a reaction product.
Specifically, in step S21, heating and stirring of the potassium titanium oxalate solution should be stopped before adding hydrochloric acid, and hydrochloric acid should be added quickly after the potassium titanium oxalate solution is cooled to 25 + -1 ℃, so that it is possible to prevent the hydrochloric acid from generating an intermediate product during the dissolution process to affect the growth of titanyl oxalate nuclei, further, after adding hydrochloric acid to the potassium titanium oxalate solution cooled to 25 + -1 ℃, stirring is continued at 25 + -1 ℃ for 10-15min until the hydrochloric acid and the potassium titanium oxalate solution are uniformly mixed to prepare a precursor solution, preferably, hydrochloric acid with a concentration of 36 wt% to 38 wt% is used in an amount of 3.0m L.
In step S22, the hydrothermal temperature of the hydrothermal treatment is 100 ℃ and 110 ℃, the hydrothermal time of the hydrothermal treatment is 12 hours, and the capacity of the reaction kettle during the hydrothermal treatment is 80m L.
Specifically, the novel photochromic titanyl oxalate material synthesized by a hydrothermal method has excellent reversible photochromic performance, and when the hydrothermal temperature is lower than 100 ℃ or the hydrothermal time is less than 12 hours, the crystal nucleus of the titanyl oxalate does not completely grow, and the obtained sample is irregular titanyl oxalate particles and does not have reversible photochromic performance; when the hydrothermal temperature is higher than 110 ℃ or the hydrothermal time is longer than 12 hours, the crystal grains of the titanyl oxalate overgrow or hydrolyze to form TiO2Nor reversible photochromic properties; therefore, in the invention, the temperature of the precursor solution is 100-110 ℃, and the hydrothermal time is 12 h.
It should be noted that in a preferred embodiment of the present invention, the reaction kettle for hydrothermal treatment is an 80m L ptfe hydrothermal reaction kettle, but in other embodiments of the present invention, the specific type of the hydrothermal reaction kettle can be selected according to actual needs, and is not limited herein.
Step S3 specifically includes: and (4) centrifugally separating the reaction product obtained in the step (S2), washing, and drying at 60-80 ℃ for 3-5h to obtain the photochromic titanyl oxalate material.
In the invention, the photochromic titanyl oxalate material is in a polyhedral shape and has a first white color state in a solid state, after 365nm ultraviolet light irradiation, the photochromic titanyl oxalate material is changed from the first white color state to a second blue-gray color state, and further, the second blue-gray color state is changed into a third white color state after 500W xenon lamp irradiation, namely, the photochromic titanyl oxalate material in the first color state and the photochromic titanyl oxalate material in the third color state have the same apparent color, so that the photochromic titanyl oxalate material has excellent reversible photochromic property, light stability and fatigue resistance, and can be used as a photo-reversible material in the fields of anti-counterfeiting, reversible color developing films, erasable 3D printing and the like.
Furthermore, the UV-vis absorption spectrum of the photochromic titanyl oxalate material in the first white color state has an absorption peak at 300-390nm, the UV-vis absorption spectrum of the photochromic titanyl oxalate material in the second blue-gray color state after being irradiated and discolored by 365nm ultraviolet light has an absorption peak at 300-800nm, and further the UV-vis absorption spectrum of the photochromic titanyl oxalate material in the third white color state after being irradiated and discolored by a 500W xenon lamp has an absorption peak at 300-390nm, namely the photochromic titanyl oxalate material in the first color state and the photochromic titanyl oxalate material in the third color state have the same internal structure.
It should be noted that the types of the washing solutions used for washing the reaction products after the centrifugal separation and the operation requirements of the washing process are common in the prior art, and only the reaction products need to be cleaned to meet the subsequent use requirements.
The following description will further describe the preparation method of the photochromic titanyl oxalate material of the present invention by specific examples.
Example 1
Adding 0.53g of titanium potassium oxalate into 30m L deionized water with the pH value of 6, heating and stirring for 10min at 45 ℃ until the titanium potassium oxalate is completely dissolved to obtain a titanium potassium oxalate solution, stopping stirring, after the titanium potassium oxalate solution is naturally cooled to 25 ℃, quickly adding 3.0m L hydrochloric acid into the titanium potassium oxalate solution, stirring for 15min at 25 ℃ until the hydrochloric acid and the titanium potassium oxalate solution are uniformly mixed to obtain a precursor solution, transferring the precursor solution into an 80m L reaction kettle, sealing, placing in an oven, carrying out hydrothermal reaction for 12h at 110 ℃ to obtain a reaction product, centrifugally separating the reaction product, washing, and drying for 3h at 60 ℃ to obtain the photochromic titanium oxyoxalate material with the particle size of 8 mu m.
Referring to fig. 1 and 2, SEM pictures of the photochromic titanyl oxalate material prepared in example 1 are shown, which has the characteristics of polyhedral morphology, good dispersibility, uniform morphology, and complete grain growth.
Please refer to fig. 3, which shows that the photochromic titanyl oxalate material prepared in example 1 is changed from the first color state of white to the second color state of blue-gray by 365nm ultraviolet light irradiation, and the photochromic titanyl oxalate material in the second color state can be changed from the second color state of blue-gray to the third color state of white by 500W xenon lamp irradiation, and the colors of the first color state and the third color state are the same, which indicates that the photochromic titanyl oxalate material prepared in the present invention has excellent reversible photochromic performance.
Referring to fig. 4, the ESR absorption peak (g 2.004 position) of the photochromic titanyl oxalate material prepared in example 1 is significantly increased after irradiation with 365nm ultraviolet light, which shows that the novel photochromic titanyl oxalate material prepared in the present invention can generate oxygen vacancy when irradiated with ultraviolet light.
Example 2
Adding 2.12g of titanium potassium oxalate into 30m L deionized water with the pH value of 6, heating and stirring for 10min at 45 ℃ until the titanium potassium oxalate is completely dissolved to obtain a titanium potassium oxalate solution, stopping stirring, after the titanium potassium oxalate solution is naturally cooled to 25 ℃, quickly adding 3.0m L hydrochloric acid into the titanium potassium oxalate solution, stirring for 15min at 25 ℃ until the hydrochloric acid and the titanium potassium oxalate solution are uniformly mixed to obtain a precursor solution, transferring the precursor solution into a reaction kettle of 80m L, sealing, placing in an oven, carrying out hydrothermal reaction for 12h at 100 ℃ to obtain a reaction product, centrifugally separating the reaction product, washing, and drying for 3h at 60 ℃ to obtain the photochromic titanium oxyoxalate material with the particle size of 10 mu m.
Referring to fig. 5 and 6, the photochromic titanyl oxalate material prepared in example 2 has polyhedral morphology, poor dispersibility and diverse morphology, and the particles do not grow completely.
Referring to fig. 7, the photochromic titanyl oxalate material prepared in example 2 is changed from a first white color state to a second blue-gray color state by 365nm ultraviolet light irradiation, and the photochromic titanyl oxalate material in the second color state can be changed from the second blue-gray color state to a third white color state after 500W xenon lamp irradiation, and the same color of the first color state and the third color state is the same or substantially the same, which indicates that the photochromic titanyl oxalate material prepared in the present invention has excellent reversible photochromic performance.
Further referring to FIG. 8, the UV-vis absorption spectrum of the photochromic titanyl oxalate material prepared in example 2 in the first white color state has an absorption peak at 300-390nm, the UV-vis absorption spectrum of the second blue-gray color state after the photochromic titanyl oxalate material is irradiated by 365nm ultraviolet light has an absorption peak at 300-800nm, and the UV-vis absorption spectrum of the third white color state after the photochromic titanyl oxalate material is irradiated by 500W xenon lamp has an absorption peak only at 300-390 nm.
Example 3
Adding 2.65g of titanium potassium oxalate into 30m L deionized water with the pH value of 6, heating and stirring for 15min at 45 ℃ until the titanium potassium oxalate is completely dissolved to obtain a titanium potassium oxalate solution, stopping stirring, after the titanium potassium oxalate solution is naturally cooled to 25 ℃, quickly adding 3.0m L of hydrochloric acid into the titanium potassium oxalate solution, stirring for 15min at 25 ℃ until the hydrochloric acid and the titanium potassium oxalate solution are uniformly mixed to obtain a precursor solution, transferring the precursor solution into an 80m L reaction kettle, sealing, placing in an oven, carrying out hydrothermal reaction for 12h at 110 ℃ to obtain a reaction product, centrifugally separating the reaction product, washing, and drying for 5h at 70 ℃ to obtain the photochromic titanium oxyoxalate material with the particle size of 12 microns.
Referring to fig. 9 and 10, the photochromic titanyl oxalate material prepared in example 3 has polyhedral shape, uniform particle size, good dispersibility and complete grain growth.
Referring to FIG. 11, the photochromic grass prepared in example 3The surface of the acid titanyl salt material mainly contains three elements of Ti, O and C, and the high-resolution spectrum of each element shows that Ti exists in the heterojunction4+And surface OVAnd Ti4+And surface OVIs beneficial to the reversible photochromic performance of the sample.
Example 4
Adding 1.06g of titanium potassium oxalate into 30m L deionized water with the pH value of 6, heating and stirring at 45 ℃ for 15min until the titanium potassium oxalate is completely dissolved to obtain a titanium potassium oxalate solution, stopping stirring, after the titanium potassium oxalate solution is naturally cooled to 25 ℃, rapidly adding 3.0m L of hydrochloric acid into the titanium potassium oxalate solution, stirring at 25 ℃ for 15min until the hydrochloric acid and the titanium potassium oxalate solution are uniformly mixed to obtain a precursor solution, transferring the precursor solution into an 80m L reaction kettle, sealing, placing the reaction kettle in an oven, carrying out hydrothermal reaction at 100 ℃ for 12h to obtain a reaction product, carrying out centrifugal separation on the reaction product, washing, and drying at 60 ℃ for 3h to obtain the novel photochromic titanium oxyoxalate material with the particle size of 8 mu m.
Referring to fig. 12 and 13, the photochromic titanyl oxalate material prepared in example 4 has polyhedral morphology, good dispersibility, obvious morphology change and incomplete particle growth.
As shown in fig. 14, the photochromic titanyl oxalate material prepared in example 4 changes from the first color state of white to the second color state of blue-gray after being irradiated by 365nm ultraviolet light, and further changes from the second color state of blue-gray to the third color state of white after being irradiated by a 500W xenon lamp, and the colors of the first color state and the third color state are the same, which also shows that the photochromic titanyl oxalate material prepared in the present invention has excellent reversible photochromic performance.
Referring to fig. 15, XRD of the photochromic titanyl oxalate material prepared in example 4 is consistent with JCPDS No.54-0330 of the standard card and has no other peaks, which indicates that the sample prepared in the present invention is pure titanyl oxalate, and the phase composition of the sample is not changed after irradiation with uv light and xenon lamp, indicating that the photochromic titanyl oxalate material prepared in the present invention has excellent structural stability.
Example 5
Adding 1.06g of titanium potassium oxalate into 30m L deionized water with the pH value of 6, heating and stirring at 45 ℃ for 15min until the titanium potassium oxalate is completely dissolved to obtain a titanium potassium oxalate solution, stopping stirring, after the titanium potassium oxalate solution is naturally cooled to 25 ℃, quickly adding 3.0m L of hydrochloric acid into the titanium potassium oxalate solution, stirring at 25 ℃ for 15min until the hydrochloric acid and the titanium potassium oxalate solution are uniformly mixed to obtain a precursor solution, transferring the precursor solution into an 80m L reaction kettle, sealing, placing in an oven, carrying out hydrothermal reaction at 110 ℃ for 12h to obtain a reaction product, carrying out centrifugal separation on the reaction product, washing, and drying at 80 ℃ for 4h to obtain the photochromic titanium oxyoxalate material, wherein the particle size of the photochromic titanium oxyoxalate material is 12 microns.
Referring to fig. 16 and 17, the novel photochromic titanyl oxalate material prepared in example 5 has polyhedral shape, good dispersibility, uniform shape, large particle size and complete particle growth.
Referring to FIG. 18, the photochromic titanium oxyoxalate material prepared in example 5 was irradiated by UV light for 2360cm-1The nearby surface functional groups are changed, wherein the change is mainly caused by water adsorbed on the surface of the sample, and the change does not influence the crystal structure of the photochromic titanyl oxalate material.
In conclusion, the preparation method of the novel photochromic titanyl oxalate material adopts a one-step hydrothermal method to prepare the photochromic titanyl oxalate material with polyhedral morphology, can obtain a better crystal phase without subsequent secondary treatment, and has simple and easily-controlled preparation process; meanwhile, the preparation method and the synthesis process of the photochromic titanyl oxalate material are limited, and the photochromic titanyl oxalate material is firstly used in the photochromic field, so that the synthesis of the photochromic titanyl oxalate material by a low-temperature method is firstly realized.
Furthermore, the photochromic titanium oxyoxalate material prepared by the preparation method of the photochromic titanium oxyoxalate material has excellent reversible photochromic performance, and the photochromic titanium oxyoxalate material in the application can be changed into a blue-gray second color state from a white first color state by 365nm ultraviolet irradiation, and the photochromic titanium oxyoxalate material in the second color state can be further changed into a white third color state from the blue-gray second color state after being irradiated by a 500W xenon lamp, and the first color state and the third color state have the same or approximately the same color state; can be used as a light reversible material in the fields of anti-counterfeiting, reversible color developing films, erasable 3D printing and the like.
While only the basic principles, essential features and advantages of the invention have been shown and described in the foregoing specification, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing embodiments, but is capable of other specific forms without departing from the spirit or essential features of the invention. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein, and any reference signs in the claims are not intended to be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A preparation method of a photochromic titanium oxyoxalate material is characterized by comprising the following steps:
s1: adding a certain amount of titanium potassium oxalate into deionized water, and stirring to obtain a titanium potassium oxalate solution with the concentration of 0.05-0.35M;
s2: adding hydrochloric acid with the concentration of 36 wt% -38 wt% into the titanium potassium oxalate solution obtained in the step S1, uniformly stirring to obtain a precursor solution, and carrying out hydrothermal treatment on the precursor solution to obtain a reaction product;
s3: and (4) centrifugally separating the reaction product obtained in the step (S2), washing, and drying at 60-80 ℃ for 3-5h to obtain the photochromic titanyl oxalate material.
2. The method as claimed in claim 1, wherein the step S1 is carried out by adding 0.53g, 1.06g, 2.12g, 2.65g, 3.18g, 3.71g or 4.24g of potassium titanium oxalate into 30m L of deionized water with pH of 6.
3. The method for preparing a photochromic titanyl oxalate material of claim 1 wherein: in the step S1, the heating temperature of the deionized water after the titanium potassium oxalate is added is 45 ± 5 ℃, and the mixture is stirred for 10-15min until the titanium potassium oxalate is completely dissolved, so as to obtain the titanium potassium oxalate solution.
4. The method for preparing a photochromic titanium oxyoxalate material according to claim 1, wherein the step S2 specifically comprises:
s21, stopping heating and stirring of the potassium titanium oxalate solution in the step S1, after the potassium titanium oxalate solution is cooled to 25 +/-1 ℃, rapidly adding hydrochloric acid with the concentration of 36-38 wt%, continuously stirring at 25 +/-1 ℃, and uniformly stirring to obtain a precursor solution;
and S22, transferring the precursor solution obtained in the step S21 into a reaction kettle, sealing the reaction kettle, and then placing the reaction kettle in an oven for hydrothermal treatment to obtain a reaction product.
5. The method of claim 4, wherein in step S21, the hydrochloric acid with a concentration of 36 wt% to 38 wt% is used in an amount of 3.0 + -0.2 m L.
6. The method for preparing a photochromic titanyl oxalate material of claim 4 wherein: and (S21) adding the hydrochloric acid, and stirring at 25 +/-1 ℃ for 10-15min until the hydrochloric acid and the titanium potassium oxalate solution are uniformly mixed.
7. The method for preparing a photochromic titanyl oxalate material of claim 1 wherein: in the step S2, the temperature of the hydrothermal treatment is 100-.
8. A photochromic titanyl oxalate material is characterized in that: the photochromic titanyl oxalate material is prepared by the preparation method of the photochromic titanyl oxalate material according to any one of claims 1-7; the photochromic titanyl oxalate material has a polyhedral shape and a particle size of 8-12 mu m.
9. The photochromic titanyl oxalate material of claim 8 wherein: the photochromic titanium oxyoxalate material has a first white color state, when 365nm ultraviolet light irradiates on the photochromic titanium oxyoxalate material in the first color state, the photochromic titanium oxyoxalate material is changed into a second blue-gray color state from the first white color state, and after the photochromic titanium oxyoxalate material in the second color state is irradiated by a 500W xenon lamp, the second blue-gray color state is changed into a third white color state again.
10. The photochromic titanyl oxalate material of claim 8 wherein: the UV-vis absorption spectrum of the photochromic titanyl oxalate material in the first color state has an absorption peak at 300-390nm, the UV-vis absorption spectrum of the photochromic titanyl oxalate material in the second color state has an absorption peak at 300-800nm, and the UV-vis absorption spectrum of the photochromic titanyl oxalate material in the third color state has an absorption peak at 300-390 nm; and the first color state and the third color state have a consistent intrinsic structure and the same apparent color.
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| JP2019077799A (en) * | 2017-10-25 | 2019-05-23 | 国立大学法人名古屋大学 | Photochromic material and method for producing the same |
| CN109794289A (en) * | 2019-01-31 | 2019-05-24 | 天津城建大学 | A kind of dish-like titanium oxyoxalate salt photochemical catalyst of hand and preparation method thereof |
| CN109794290A (en) * | 2019-01-31 | 2019-05-24 | 天津城建大学 | A kind of screw type titanium oxyoxalate salt photochemical catalyst and preparation method thereof |
| JP2019137796A (en) * | 2018-02-13 | 2019-08-22 | 国立大学法人山口大学 | Photochromic complex |
| CN110358526A (en) * | 2018-04-08 | 2019-10-22 | 中国科学技术大学 | Photochromic material and application thereof |
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| JP2019077799A (en) * | 2017-10-25 | 2019-05-23 | 国立大学法人名古屋大学 | Photochromic material and method for producing the same |
| JP2019137796A (en) * | 2018-02-13 | 2019-08-22 | 国立大学法人山口大学 | Photochromic complex |
| CN110358526A (en) * | 2018-04-08 | 2019-10-22 | 中国科学技术大学 | Photochromic material and application thereof |
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