CN101386427B - Method for preparing photochromic WO3 film induced by malic acid - Google Patents
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Abstract
本发明公开了一种制备光致变色WO3薄膜的方法,特别是在诱导剂苹果酸作用下光致变色WO3薄膜的制备方法。该方法包括以下步骤:配制钨酸盐溶液;离子交换合成钨酸;调整体系pH值;加入稳定剂和成膜剂;加入诱导剂;镀膜及干燥;热处理。本发明方法简单,制得的WO3薄膜在低功率的激发光源条件下能产生良好的变色效果,同时在无光的条件下WO3薄膜能够实现褪色,从而实现了利用诱导剂苹果酸制备具有良好光致变色性能的WO3薄膜。The invention discloses a method for preparing a photochromic WO 3 film, in particular a method for preparing a photochromic WO 3 film under the action of an inducer malic acid. The method comprises the following steps: preparing tungstate solution; synthesizing tungstic acid by ion exchange; adjusting the pH value of the system; adding a stabilizer and a film-forming agent; adding an inducer; coating and drying; heat treatment. The method of the present invention is simple, and the prepared WO3 film can produce a good discoloration effect under the condition of a low-power excitation light source, and at the same time, the WO3 film can realize discoloration under the condition of no light, thereby realizing the preparation of the WO3 film with an inducer malic acid. WO 3 film with good photochromic properties.
Description
技术领域technical field
本发明涉及一种制备光致变色WO3薄膜的方法,特别是在诱导剂苹果酸作用下制备光致变色WO3薄膜的方法。 The invention relates to a method for preparing a photochromic WO 3 film, in particular to a method for preparing a photochromic WO 3 film under the action of an inducer malic acid.
背景技术Background technique
在外界激发源的作用下,一种物质或一个体系发生颜色明显变化的现象称为变色性。光致变色是指一种化合物A受到一定波长的光照射时,可发生光化学反应得到产物B,A和B的颜色(即对光的吸收)明显不同。B在另外一束光的照射下或经加热又可恢复到原来的形式A。光致变色的材料早在1867年就有所报道,在这之后的20多年的时间里,科学家开始逐渐进入该领域研究,但直至1956年Hirshberg提出光致变色材料应用于光记录存储的可能性之后,才引起了广泛的注意。近年来,将光致变色材料用于光信息存储、光调控、光开关、光学器件材料、光信息基因材料、修饰基因芯片材料等领域已受到全球范围内的广泛关注。 Under the action of an external excitation source, the phenomenon that a substance or a system undergoes a significant change in color is called discoloration. Photochromism means that when a compound A is irradiated by light of a certain wavelength, a photochemical reaction can occur to obtain a product B, and the colors of A and B (that is, the absorption of light) are obviously different. B can be restored to its original form A under the irradiation of another beam of light or by heating. Photochromic materials were reported as early as 1867. In the following 20 years, scientists began to gradually enter the field of research, but it was not until 1956 that Hirshberg proposed the possibility of photochromic materials being applied to optical recording and storage. After that, it attracted widespread attention. In recent years, the use of photochromic materials in optical information storage, optical regulation, optical switches, optical device materials, optical information genetic materials, modified gene chip materials and other fields has attracted widespread attention worldwide. the
纳米氧化钨是重要的新型半导体材料,由于颗粒实现超微离子化,因此热学、电学、磁学和光学性质表现出奇异性质,其中氧化钨薄膜在光、电、气致变色、催化降解、以及光解水制氢电极材料等领域有着重要的应用。在氧化钨薄膜变色性能的研究中,电致变色已获得较为广泛地应用,如应用于建筑物和汽车的玻璃上,制造节约能源、调节光线和控制热负荷的智能窗等。而气致变色器件由于结构简单,光学调节范围较广,使其更具有市场潜力,因而成为近期氧化钨薄膜致色材料应用研究的热点之一,但是对于光致变色的成果则鲜见报道,在较少的光致变色研究报道中,存在着光致变色激发光源要求苛刻以及变色效果缺乏明确表征的不足。 Nano-tungsten oxide is an important new semiconductor material. Due to the ultra-fine ionization of the particles, the thermal, electrical, magnetic and optical properties show singular properties. It has important applications in fields such as photolysis of water to hydrogen production electrode materials. In the study of the discoloration properties of tungsten oxide thin films, electrochromism has been widely used, such as applied to the glass of buildings and automobiles, to manufacture smart windows that save energy, adjust light and control heat load, etc. The gasochromic device has more market potential due to its simple structure and wide optical adjustment range, so it has become one of the hotspots in the application research of tungsten oxide thin film chromogenic materials in the near future, but the results of photochromism are rarely reported. In the few research reports on photochromism, there are deficiencies in that the photochromic excitation light source is demanding and the color changing effect is lack of clear characterization. the
发明内容Contents of the invention
本发明的目的就是针对现有光致变色WO3薄膜研究的不足之处,利用苹果酸为诱导剂制备了在低功率激发光源条件下具有良好光致变色效果的WO3薄膜,并定量的表征了WO3薄膜的光致变色效果。 The purpose of the present invention is to address the deficiencies of existing photochromic WO 3 film research, using malic acid as an inducer to prepare a WO 3 film with good photochromic effect under the condition of low-power excitation light source, and quantitatively characterize The photochromic effect of WO 3 film.
本发明的目的是这样实现的:一种利用苹果酸诱导制备光致变色WO3薄膜的方法通过以下步骤制得:The object of the present invention is achieved like this: a kind of method that utilizes malic acid induction to prepare photochromic WO 3 film is made through the following steps:
(1)配制0.05~3mol/L钨酸盐溶液; (1) Prepare 0.05~3mol/L tungstate solution;
(2)离子交换合成钨酸; (2) Synthesis of tungstic acid by ion exchange;
(3)用浓盐酸调整体系pH值至0.8~2.0; (3) Adjust the pH value of the system to 0.8-2.0 with concentrated hydrochloric acid;
(4)按钨酸盐溶液与稳定剂及成膜剂的体积比为1.0∶0.1~1.0∶0.1~2.0。加入稳定剂和成膜剂; (4) The volume ratio of the tungstate solution to the stabilizer and film-forming agent is 1.0:0.1-1.0:0.1-2.0. Add stabilizers and film formers;
(5)按钨酸盐溶液与苹果酸的体积比为1.0∶0.5~2.0加入1~5mol/L的诱导剂苹果酸溶液; (5) According to the volume ratio of tungstate solution and malic acid is 1.0:0.5~2.0, add 1~5mol/L inducer malic acid solution;
(6)镀膜及干燥; (6) Coating and drying;
(7)热处理。 (7) Heat treatment. the
上述第(1)步所说的配制钨酸盐溶液是指浓度为0.05~3mol/L的钨酸盐溶液,且所用钨酸盐的阳离子的强酸盐也易溶于水。第(2)步所说的离子交换合成钨酸是指将钨酸盐溶液通过阳离子交换树脂得到钨酸溶液。第(3)步所说的调整体系pH值是用质量百分比浓度为37~38%浓盐酸调节溶液的pH值为0.8~2.0。第(4)步所说的加入稳定剂和成膜剂是指在磁力搅拌器以200~600r/min的速度搅拌下逐滴加入稳定剂和成膜剂,所用稳定剂为正丙醇、丙三醇、丙酮或乙酰丙酮,所用成膜剂为分子量在2000~5000,可与水互溶、在300℃以下分解的聚合物,如聚丙烯酸。其中钨酸盐溶液与稳定剂及成膜剂的体积比为钨酸盐溶液∶稳定剂∶成膜剂=1.0∶0.1~1.0∶0.1~2.0。第(5)步所说的加入诱导剂是指使用磁力搅拌器以200~600r/min的速度搅拌下将浓度为1~5mol/L的苹果酸溶液逐滴加入到溶液中,搅拌2~6h后放至暗处静置12~48h,其中钨酸盐溶液与诱导剂的体积比为钨酸盐溶液∶诱导剂=1.0∶0.5~2.0。第(6)步所说的镀膜及干燥是指用浸渍提拉法提拉速度为15~25mm/s,镀膜时间为80~200s,在玻璃基片上镀膜并在40~60℃干燥。第(7)步所说的热处理是指置于真空干燥箱中,在真空度为0.05~0.1、温度为150~200℃条件下保温1~3h。 The preparation of the tungstate solution mentioned in the above step (1) refers to the tungstate solution with a concentration of 0.05-3mol/L, and the strong salt of the tungstate cation used is also easily soluble in water. The said ion-exchange synthesis of tungstic acid in the step (2) refers to passing the tungstate solution through a cation exchange resin to obtain a tungstic acid solution. The said adjusting system pH value in the step (3) is to adjust the pH value of the solution to 0.8-2.0 with a mass percentage concentration of 37-38% concentrated hydrochloric acid. The said addition of stabilizer and film-forming agent in step (4) refers to the addition of stabilizer and film-forming agent dropwise under magnetic stirrer stirring at a speed of 200 to 600r/min. The stabilizer used is n-propanol, propanol, Triol, acetone or acetylacetone, the film-forming agent used is a polymer with a molecular weight of 2000-5000, miscible with water, and decomposed below 300°C, such as polyacrylic acid. Wherein the volume ratio of the tungstate solution, the stabilizer and the film-forming agent is tungstate solution:stabilizer:film-forming agent=1.0:0.1-1.0:0.1-2.0. Adding the inducer in the step (5) refers to adding the malic acid solution with a concentration of 1 to 5 mol/L dropwise into the solution under stirring at a speed of 200 to 600 r/min using a magnetic stirrer, and stirring for 2 to 6 hours Then put it in a dark place and let it stand for 12-48 hours, wherein the volume ratio of tungstate solution to inducer is tungstate solution: inducer=1.0:0.5-2.0. The said coating and drying of the step (6) means that the pulling speed is 15-25mm/s by dipping and pulling method, and the coating time is 80-200s, and the coating is performed on the glass substrate and dried at 40-60°C. The heat treatment mentioned in the step (7) refers to placing in a vacuum oven, keeping the heat for 1-3 hours at a vacuum degree of 0.05-0.1 and a temperature of 150-200°C. the
本发明具有以下有益效果: The present invention has the following beneficial effects:
本发明采用溶胶凝胶-浸渍提拉法制备苹果酸诱导WO3薄膜,由于钨酸易于有机小分子络合,而苹果酸中的羧基与钨酸中的阴离子WOn -易形成氢键,生成了钨酸和有机小分子的交联结构,抑制了钨酸的聚集,使得钨酸沉积在玻璃基体上生成单分散WO3晶体,因而增大了WO3晶体的比表面积,同时增强了WO3薄膜表面 晶体对光源的吸收能力,从而提高了薄膜光致变色反应活性,使所制备的WO3薄膜在低功率的激发光源条件下能产生良好的变色效果,同时在无光的条件下WO3薄膜能够实现褪色。从而实现了利用诱导剂苹果酸制备具有良好光致变色性能的WO3薄膜。 The present invention adopts sol-gel-dipping and pulling method to prepare malic acid-induced WO 3 film, because tungstic acid is easy to complex small organic molecules, and the carboxyl group in malic acid and the anion WO n - in tungstic acid are easy to form hydrogen bonds, forming The cross-linked structure of tungstic acid and organic small molecules is suppressed, and the aggregation of tungstic acid is inhibited, so that tungstic acid is deposited on the glass substrate to form monodisperse WO 3 crystals, thus increasing the specific surface area of WO 3 crystals and enhancing WO 3 The absorption ability of the crystals on the surface of the film to the light source improves the photochromic reaction activity of the film, so that the prepared WO 3 film can produce a good discoloration effect under the condition of low-power excitation light source, and at the same time, the WO 3 film can be produced under the condition of no light The film is capable of fading. Thus, the preparation of WO 3 films with good photochromic properties by using the inducer malic acid was realized.
具体实施方式Detailed ways
实施例1 Example 1
首先,配制0.2mol/L的Na2WO4溶液25ml,将Na2WO4溶液通过阳离子交换树脂后用质量百分比浓度为36%的浓盐酸调节pH值为1.0,在磁力搅拌器以400r/min的速度搅拌下,逐滴加入正丙醇10ml和聚丙烯酸15ml,之后逐滴加入3mol/L的诱导剂苹果酸溶液25ml,然后将反应体系搅拌均化4个小时后放至暗处静置24h,随后用浸渍提拉法(提拉速度为20mm/s,镀膜时间为120s)镀膜并在50℃干燥。最后,将镀膜后的玻片放入真空干燥箱中在真空度为0.085、温度为150℃的条件下保温1h,即得光致变色WO3薄膜。利用SC-80C全自动色差计(北京康光仪器有限公司)测得薄膜色度为12.47;将WO3薄膜放入Z-F-20C暗箱式紫外分析仪(上海宝山顾村电光仪器厂制造,功率为6W,选择的紫外光波长为365nm。WO3薄膜距光源10cm),反应温度为室温,光照时间5h,测得其色度值为13.75。说明利用苹果酸诱导后的WO3薄膜在紫外光照射下受激变色。将变色的WO3薄膜移入无光处,2h后WO3薄膜褪色,测得其色度值为12.47,说明苹果酸诱导制备的WO3薄膜在无光条件下褪色。 First, prepare 25ml of 0.2mol/L Na 2 WO 4 solution, pass the Na 2 WO 4 solution through the cation exchange resin and adjust the pH value to 1.0 with concentrated hydrochloric acid with a concentration of 36% by mass percentage. Under stirring at a high speed, add 10ml of n-propanol and 15ml of polyacrylic acid dropwise, then add 25ml of 3mol/L inducer malic acid solution dropwise, then stir and homogenize the reaction system for 4 hours, then put it in a dark place for 24h , followed by dipping and pulling method (pulling speed is 20mm/s, coating time is 120s) coating and drying at 50°C. Finally, put the coated glass slide into a vacuum drying oven and keep it warm for 1 hour under the conditions of a vacuum degree of 0.085 and a temperature of 150° C. to obtain a photochromic WO 3 film. Utilize SC-80C full-automatic colorimeter (Beijing Kangguang Instrument Co., Ltd.) to measure film chromaticity to be 12.47; WO 3 film is put into ZF-20C dark box type ultraviolet analyzer (manufactured by Shanghai Baoshan Gucun Electro-optic Instrument Factory, power is 6W , the selected wavelength of ultraviolet light is 365nm. The WO 3 film is 10cm away from the light source), the reaction temperature is room temperature, and the light time is 5h. The measured chromaticity value is 13.75. It shows that the WO 3 film induced by malic acid changes color under ultraviolet light irradiation. The discolored WO 3 film was moved into a dark place, and the WO 3 film faded after 2 hours, and its chromaticity value was measured to be 12.47, indicating that the WO 3 film prepared by malic acid faded under dark conditions.
实施例2 Example 2
本实施例加入的苹果酸溶液的量为实施例1所用量的0.5倍即加入12.5ml苹果酸溶液,其他条件同实施例1,制取光致变色WO3薄膜,测得薄膜的色度值为12.45,紫外灯照射5h后,其色度值为13.30,移入暗处2h后褪色,其色度值为12.44。 The amount of the malic acid solution added in this embodiment is 0.5 times of the amount used in Example 1, that is, add 12.5ml of the malic acid solution, and other conditions are the same as in Example 1 to prepare the photochromic WO 3 film, and measure the chromaticity value of the film After being irradiated with ultraviolet light for 5 hours, its chromaticity value is 13.30, and after moving into a dark place for 2 hours, it fades, and its chromaticity value is 12.44.
实施例3 Example 3
取实施例1制得的光致变色WO3薄膜样品在南方地区夏季晴天中午12点到14点间测试其光致变色性能,其光照2h后色度值为13.15,移入暗处2h后褪色,其色度值为12.45。Get the photochromic WO 3 film sample that embodiment 1 makes and test its photochromic performance between 12:00 noon to 14:00 on a sunny summer day in southern China, its chromaticity value is 13.15 after 2 hours of light, and fades after moving into a dark place for 2 hours. Its chroma value is 12.45.
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