TW201009319A - Ammonia sensing material - Google Patents

Abstract

The invention provides an ammonia sensing material, which comprises a carrier comprising a meso-porous silicate with a specific surface area larger than 700m2/g, and a dye intercalated in the carrier, comprising an ammonia-sensitive indicator dye. When the ammonia sensing material is exposed to an atmosphere comprising ammonia, the ammonia-sensitive indicator dye produces a color change. The meso-porous silicates can be modified with a metal to provide another ammonia sensing material.

Description

201009319 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to an ammonia sensing material, and more particularly to an ammonia sensing material using a mesoporous material as a carrier. [Prior Art] Ammonia gas is a gas that is ubiquitous on the earth and has the characteristics of malodorous, irritating and corrosive. In China's air pollution control regulations, oxyfluoride is listed as a toxic pollutant, its regulatory standards Limit the perimeter concentration to no more than 1 ppm (Executive Council Environmental Protection Agency, 2003). Ammonia gas has a major impact on the human body and paint enamel. When the concentration of ammonia in the air is close to 7〇〇ppm, it will cause eye irritation and soreness. If the M5〇〇〇ppm is large, it will be in a short time. It is fatal inside, so the regulation of ammonia concentration is very important. Coupled with the rapid development of the high-tech industry, the air quality requirements in the production process are gradually tightened. Ammonia concentration not only affects the semiconductor process, but also causes damage to the machine and damage to the operator. Only the highly sensitive gas sensing system can provide the micro-polluted gas concentration change in the process environment in time, so that the air inside the machine meets the operation requirements, and then the yield of the product is improved. U.S. Patent No. 2003/0003589 proposes an ammonia gas sensor which uses polytetrafluoroethylene (PTFE) as a carrier and optionally detects an indicator of ammonia gas, by color change and spectral change of the dye. A brake ammonia. 5 201009319

The Malins research team prepared a sol-gel film containing a dye that used the dye to have a high absorbance and light stability in the visible range to detect ammonia. (Malins, C., Butler, T. M., MacCraith, B. D., Thin Solid Films, 368 (2000) 105-110) ^7

The Yimit research team attached the Ti02 film to the glass piece and attached it to the Ti02 film for arsenic detection using bromothymol blue. (Yimit, A., Itoh, K., Murabayashi, M., Sensors and Actuators B, 88 (2003) 239-245.) ^ Therefore, there is a need in the industry for a sensitive ammonia sensing material that specifically detects the environment. Medium and low concentration ammonia concentration to protect the human body and the environment in time. SUMMARY OF THE INVENTION The present invention provides an ammonia sensing material, comprising: a hole material in a dream acid salt having a specific surface area greater than · A. an agent, including an ammonia gas sensing coloring dye, wherein the ammonia gas sensing change = Into the carrier, when the ammonia sensitizing material is exposed to the ammonia gas, the gas sensing dying dye produces a color change. When the ammonia is used, the present invention further provides an ammonia sensing material, including: a metal-modified silicate salt material 'a carrier' package m2 / g; and - a dye, including ammonia gas sensing color change The area is greater than 7 〇〇 sensed color-changing dye embedded in the carrier, when the ammonia sensation & wherein the gas-reducing environment, the ammonia gas sensing color-changing agent production extension = material exposure to ammonia for the purpose of the present invention The above and other objects, features, and advantages. The following is a detailed description of the preferred embodiments, and the advantages and advantages can be more clearly described as follows: σ 々 々 , 作 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 The carrier comprises a pore material in the citrate, and the dye comprises an ammonia gas sensing coloring dye, wherein the ammonia sensing coloring dye is embedded in the carrier. In the present invention, the pore material is formed by the process of self-assembly of the inorganic cerium oxide and the organic surfactant to form a regularly arranged structure. Compared with the conventional polymer fiber carrier, it has a high specific surface area. The specific surface area is more than 700 m2/g, and the preferred range is 8〇〇m2/g~11〇〇m2/g, so that the detection sensitivity and the reaction rate can be improved to more effectively detect ammonia gas. In addition, the pore size of the mesoporous material is uniform, and the pore size distribution range is about 2.5 ηιη~3.5 nm °. The ammonia gas sensing dyeing agent used in the invention includes bromophenol blue and bromocreosol green. ), thymol blue, methyl crystal purple, chlorophenol red or bromocresol _ pmple. When the ammonia sensing material is exposed to the ammonia atmosphere, the ammonia gas sensing dye produces a color change, and the color development mechanism is described below. When the dye is embedded in the carrier material, the base of the carrier material (_〇H) gives the proton donator molecule 'in this case the dye molecule is protonated (pr〇t〇nafi〇n) state, if there is ammonia When the gas molecules are adsorbed on the surface of the material, the ammonia molecules will obtain protons from the dye molecules to form the amine salt (NH4+), and the dye becomes the deportonation color, and the color development mechanism is represented by a chemical equation. As follows: dye + (color of protonation state) + NH3 (gr ^ dye (deprotonation 7 201009319 state color) + NH4 + (aq). In one embodiment 'when the dye is cresol green When (br〇m〇cre〇s〇1 g·), the color change is deprotonated (4) blue by the orange (4) protonation state. In another embodiment, when the dye is bromophenol purple (bromocreosol purple) 'The color change is changed from the yellow state of the protonated state to the purple state of the protonated state. Therefore, the presence of ammonia can be detected by the color change of the dye. In addition, the ammonia sensing material after adsorption can be borrowed. Axillary by the regenerative (four) rod, including blowing ammonia gas sensing material with a blunt gas, letting ammonia Desorption, A is the use of heating method to regenerate 'the color of the dye molecules after regeneration will return to the original protonation state' can be detected again. The ammonia gas sensing material preparation method of the present invention Including (a) first preparing the starting solution, dissolving the desired metasilicate in deionized water, and then stirring the solution. (b) Then, a solution of a strong acid (e.g., sulfuric acid, hydrochloric acid) is slowly added dropwise to the above solution, and the pH of the solution is controlled to about 9 to 11, at which time the solution forms a gel. ' (c) Next, prepare a surfactant, such as cetyltrimethylammonium bromite (CTAB). The surfactant required for weighing is added to the deionized water and stirred slowly. In the step solution, when the surfactant is dropped, the solution may flocculate. The role of the surfactant is to provide a template for the material in the preparation. (d) After stirring for 3 hours, place the solution in a pressure cooker and place it in a bake 8 201009319 box to loot: ~200. (: hydrothermal method for about 25 to 40 hours of synthesis. (e) take out from the oven to be cooled, perform suction filtration, and repeat the rinse several times with deionized water, then take out the cake to be placed in (10) (two) order for the box to play = 6 hours, and finally placed in 4 thieves ~ 5 built high temperature furnace forging $ ^, you can get the hole material in the citrate. The wet dyeing method is used to embed the dye on the surface of the carrier, for example, ammonia : The dyeing agent and the Wei-perforation material are simultaneously dissolved in the "polar solvent", -C- or isopropanol)' after being scrambled at room temperature for 2 to 5 hours, and then ===. 1〇. . Drying in one box, state I, also provides an additional ammonia sensing material 'including carrier and dyeing greater than 70. Package 2 includes the metal-modified dream acid salt material's specific surface area including ammonia! : / §, the preferred range is _m2 / g ~ U ° Gm2 / g, and within the dye, measuring the color dyes 'Ammonia gas sensing color dye embedded in the carrier: sample by the above color development mechanism Measure the presence of ammonia. #表面^ In the present invention, the surface of the pore material is highly reactive, and it can be aluminum, molybdenum, and the metal is covalently bonded to the bismuth salt. The metal includes = two =: two - metal is good. #(1(10)add) position 'make the ammonia adsorption effect more like the metal modification of the hole material in the salt, the preparation method of the hole material in the square salt salt, the difference lies in the starting solution 9 201009319 except the addition of dodecanoic acid In addition to sodium, the addition of metallization to the mole ratio is based on Dream's dream atom and gold, nitric acid, and subsequent D (for example, molybdenum, copper or cobalt-containing sulphate preparation, except for calcination time) : "The same as the hole material in the bismuth citrate material, the hole material in the Wei salt is the same as 小时 = hour. The surface of the metal brocade is prepared, and finally the dye can be embedded by the wet impregnation method. Another ammonia sensing material. Concentration, no material through the continuous flow reactor debt measurement of ammonia gas is U mg / g ammonia gas sensing material for oxygen adsorption capacity about ammonia gas suction heart: last name. The metal-modified ammonia gas sensing material pair is at least higher, up to 4. 〇 〜 6.5 6.5, in addition to gas, and in addition, even in 3G seconds, the PPm grade of the ammonia-based hairpin I is measured in 20 minutes. Ammonia gas of PPb level is detected inside. Hole material C rides to have high The color change in the area of the sulphate, ί and the ammonia sensitizer can detect the low concentration of ammonia by the dye. This material has the following advantages: Sensitivity and speed by the material in the hole material The high specific surface area 'can improve the detection and speed' is more effective in detecting low-concentration ammonia gas. The saving of H improves the detection efficiency and reduces the amount of dye added, which can meet the environmental protection requirements. The hole material in the Utr metal 'because of increasing the position of the material' is more dangerous to improve the sensing ability of the ammonia gas. However, the λ gas sensing material can be reused by the regenerative process, which saves cost and conforms Environmental Protection Requirements 201009319 [Embodiment] Example 1 is made of citric acid in the Buddha! I ammonia material in the hole material of I. 21.2 g. Minutes, then prepare 4 N sulfuric acid (sulfurie aCld 98%) solution slowly drip, control the pH of the solution to 10.5, then the solution will form a gel. Then configure the surfactant cetyltrimethyl ^

Cetyltrimethylammonium bromite (CTAB), weigh CTAB 7.2 g and add 25 mL of deionized water to stir. After stirring, slowly drip into the pre-step solution. When the CTAB is dropped, the solution will flocculate. After stirring for 3 hours, the solution was placed in a pressure cooker and placed in an oven, and hydrothermally synthesized at 145 ° C for 36 hours. After the cold portion was taken out from the oven, suction filtration was performed, and the washing was repeated several times with deionized water, and then the filter cake was taken out and placed at 11 (drying for 6 hours at TC, and finally at 55 〇t for 6 hours).

Then weigh 0.1 g, 0.3 g and 〇.6g of the citrate hole material and o.ool g indicator bromocresyl green (bromocres 〇 1 green) and dissolve in 100 mL of solvent acetone, in the room After stirring for 3 hours at a temperature, the solution was poured into a crucible and placed in an oven at 10 ° C for drying, and finally a dye-modified ammonia gas sensing material was obtained. Example 2 Preparation of Ammonia Sensing Material Containing Aluminium Citrate Hole Material A method for synthesizing a hole material in an aluminosilicate having different bismuth/aluminum ratios, first weighing the desired sodium s(di-Um metasilicate) And add 80 mL of deionized water 'different bismuth/aluminum ratio required sodium citrate as shown in Table 1, then 201009319 所需 quantity of aluminum sulfate required to add 20 mL of deionized water, mix two After the solution was stirred for 30 minutes, the subsequent configuration was the same as the method for preparing the pore material in the citrate. The calcination time was changed to 1 hr. Table 1

矽/aluminum ratio added aluminum sulfate weight 25 0.684 50 0.342 75 0.228 100 0.171 150 0.114 Then weigh 0.3 g of different bismuth aluminum ratio of aluminosilicate hole material and 0.001 g of indicator Mojia 绿 green (broin〇 Cresol green) or bromocresol purple and dissolved in 1 mL of solvent acetone. After 3 hours of stirring at room temperature, pour the solution into the wrong place and place it in an oven for drying. Finally, a dye-modified ammonia gas sensing material can be obtained. Example 3: Ammonia sensing material for the pore material containing copper bismuth citrate The synthesis method of the pore material in the copper bismuth silicate with different bismuth/copper ratio, firstly weigh the required sodium metasilicate and Add 80 mL of deionized water 'different bismuth/copper ratio required sodium citrate as shown in Table 2, then weigh the required copper nitrate (Cu(N03)2) into 20 mL of deionized water, mix two After the solution was stirred for 30 minutes, the subsequent configuration was the same as the method for preparing the hole material in the phthalate 201009319, and the calcination time was changed to 10 hours. Table 2 Dream/Copper Ratio Added Copper Nitrate Heavy F 25 —-------- Vo/ 0.241 50 0.483 75 0.723 Then weigh 0.3 g of different copper-to-copper ratio in the copper carboxylate 0.001 g of the indicator was bromocresol green and dissolved in 100 mL of solvent acetone. After stirring at room temperature for 3 hours, the solution was poured into a hanging pot and placed at 11 Torr. Drying is carried out in a 〇 oven, and finally a dye-modified ammonia gas sensing material is obtained. »Example 4: The ammonia gas sensing material containing the hole material in the citrate is different from the 矽/cobalt ratio of the cobalt citrate in the synthesis of the pore material, firstly the amount of sodium metasilicate required. And add 80 mL of • deionized water 'different bismuth/cobalt ratio required for sodium metasilicate. See Table 3, then weigh the required cobalt nitrate (c〇(N〇3)2.6H2〇) Mixing the two solutions in 20 mL of deionized water and stirring for 3 minutes. The subsequent configuration is the same as the method of preparing the pore material in the acid salt. The calcination time is changed to 10 hours. Table 3 — Broken/start ratio added acid weight (g) 25 0.291 50 ~ one — 0.582 75 0.873 13 201009319 Then take the G'3 g different dreams of the dilute acid hole material and 0.001 g As the indicator xixi green (br〇m (10) to .] gran) and simultaneously dissolved in 100 must-have solvent acetone, stirred at room temperature for 3 hours, the solution was poured into the rhyme and placed in a not oven Drying, finally, a dye-modified ammonia gas sensation material can be obtained. Example 5 Ammonia gas suction experiment, ammonia gas sensor m method for continuous flow reaction for efficiency test β method: The reaction system is set in a strange temperature refrigerator, and the experiment is actually controlled at 25 C. The adsorption reaction tube of the system has an inner diameter of 0.8 cm, and the glass wool is used as a stage in the tube, and the ammonia gas sensation of the examples 2, 3, and 4 is filled on the stage through the mass flow controller. The concentration of ammonia gas required for control 'diluted ammonia concentration is 0.5, 5 Ppm, relative breadth is 55 ± 5%'. At a concentration of (10), the total gas flow is 1 〇〇〇 ccm ' and the concentration is At 〇5 ppm, the total gas flow rate is 2〇〇〇ccm, and the concentration change of ammonia gas is measured at the back of the system using an ammonia analyzer (SIR m〇dd-S5012, Spanish). Fig. 1 is a reaction time chart of ammonia gas sensing materials of Example 2 for different ammonia gas concentrations. When the ammonia gas concentration is 1 ppm, ammonia gas can be detected within 30 seconds. However, when the ammonia gas concentration is at 〇· At 5 ppm, it takes 20 minutes to detect ammonia. Table 4 shows the adsorption capacity of ammonia gas sensing material for ammonia gas of Example 1 to test the optimum sample filling amount for use in subsequent experiments, where 0.3 g was used as the optimum sample filling amount. While Table $ shows the ammonia gas of Example 2 14 201009319 The adsorption capacity of the material for ammonia gas is sensed. When the ratio of bismuth to aluminum is 50, the adsorption effect is the best, and the adsorption capacity value can reach 4.3 mg/g. Table 6 shows the adsorption capacity of the ammonia gas sensing material of Example 3 for ammonia gas. When the beryllium copper ratio is 50, the adsorption effect is the best, and the adsorption capacity value can reach 1.49 mg/g. Table 7 shows the adsorption capacity of the ammonia gas sensing material of Example 4 for ammonia gas. When the samarium-cobalt ratio is 50, the adsorption effect is the best, and the adsorption capacity value can reach 0.83 mg/g.

Table 4 Sample filling amount (g) Adsorption capacity (mg/g) 0.1 1.9 0.3 2.0 0.6 2.0 Table 5 矽/aluminum specific adsorption capacity (mg/g) 25 2.7 50 4.3 75 3.5 100 3.3 150 3.2 15 201009319 Table 6 Shi Xi /copper specific adsorption capacity (mg/g) 25 1.02 50 1.49 75 1.20 Table 7 Shixi/start specific adsorption capacity (mg/g) 25 0.71 50 0.83 75 0.79

While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and it is possible to make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims. 16 201009319 [Simplified description of the drawings] Fig. 1 is a graph showing the relationship between the concentration of different ammonia gases and the reaction time for explaining the reaction time for detecting ammonia gas in the embodiment of the present invention. [Main component symbol description] None.

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Claims (1)

201009319 X. Patent application scope: L An ammonia gas sensing material, comprising: a carrier 'including a hole in the acid salt, the specific surface area is greater than 7 〇〇 m 2 / g; and the dye 'including ammonia gas sensing color dyeing The agent, wherein the ammonia sensing coloring agent is immersed in the carrier. When the ammonia sensing material is exposed to an ammonia environment, the ammonia sensing coloring agent produces a color change. 2. The ammonia gas sensing material according to claim 1, wherein the mesoporous material has a specific surface area of about 800 m2/g to 1100 m2/g. 3. The ammonia gas sensing material according to claim 1, wherein the medium pore material has a pore diameter of 2.5 nm to 3.5 nm. 4. The ammonia gas sensing material according to claim 1, wherein the gas sensing coloring dye comprises bromophenol blue, bromocreosol green, and bristberry blue (thymol blue), methyl crystal purple, chlorophenol red or bromocresol purple. 5. The ammonia sensing material according to claim 1, wherein the ammonia sensing material has an adsorption capacity for ammonia of about 1.8 mg/g to 3.2 mg/g. 6. The ammonia gas sensing material of claim 1, wherein the ammonia sensing material is regenerated by a regeneration route. 7. The ammonia gas sensing material of claim 6, wherein the regeneration route comprises blowing the ammonia sensing material with a passive gas. 8. The ammonia gas sensing material according to item 6 of the patent application, wherein 201009319, the regeneration path includes heating the ammonia sensing material. 9. An ammonia sensing material comprising: a carrier comprising: a metal-modified acid surface having a surface area greater than 7 〇〇 m 2 /g; and a mesoporous material having a color than a wood agent comprising an ammonia gas sensing dye The dye is embedded in the carrier, and when the ammonia sensing material is gas-sensing, the ammonia-sensing color-changing dye produces a color change and is exposed to the environment 10. As described in claim 9 of the claim 5 Thereafter, the metal includes the combination of the material of the above-mentioned test material or the combination of the above-mentioned materials, wherein the ammonia gas sensing material described in item 9 of the sheet metal patent range, the hole material in the acid salt of the metal t-decoration in the pot, to a 矽Acid salt. The metal is bonded by a covalent bond. 12. The ammonia gas sensing material according to item n of the patent application, wherein the ratio of the (iv) of the Wei salt to the molar ratio of the metal is about 25 to 150. 13. The gas sensing material according to claim 9, wherein the medium hole material has a specific surface area of about 800 m2/g to 11 〇〇 m2/g. 14. The ammonia gas sensing material according to claim 9 wherein the pore material has a pore diameter of 2.5 nm to 3.5 nm. 15. The ammonia sensing material according to claim 9, wherein the gas sensing coloring dye comprises bromophenol blue, bromocreosol green, bromoquinol blue (thymol blue), methyl crystal purple, chlorophenol red or bromocresol purple. 16. The ammonia gas sensing material according to claim 9 of the patent application, wherein 19 201009319 has an adsorption capacity of the ammonia gas sensing material to ammonia gas of about 4.0 mg/g to 6.5 mg/g. 17. The ammonia sensing material according to claim 9, wherein the ammonia sensing material has a detection concentration of ammonia greater than 1 ppm. 18. The ammonia sensing material of claim 9, wherein the ammonia sensing material is regenerated by a regeneration route. 19. The ammonia gas sensing material of claim 18, wherein the regeneration path of φ comprises blowing the ammonia sensing material with a passive gas. 20. The ammonia sensing material of claim 18, wherein the regeneration pathway comprises heating the ammonia sensing material. 20