CN105738338B - A kind of water sensitive fluorescent capillary pipe and its preparation method and application based on amino silane zinc oxide - Google Patents

A kind of water sensitive fluorescent capillary pipe and its preparation method and application based on amino silane zinc oxide Download PDF

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CN105738338B
CN105738338B CN201610125053.5A CN201610125053A CN105738338B CN 105738338 B CN105738338 B CN 105738338B CN 201610125053 A CN201610125053 A CN 201610125053A CN 105738338 B CN105738338 B CN 105738338B
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capillary
water sensitive
aps
zno
moisture
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CN201610125053.5A
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CN105738338A (en
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王桦
李淑英
郑滢亭
鲁叶
白玉龙
张营
窦晓萌
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曲阜师范大学
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Abstract

The invention discloses a kind of water sensitive fluorescent capillary pipe and its preparation method and application based on Aminosilylation nano zine oxide, water sensitive fluorescent capillary pipe is by capillary and solidification in the Aminosilylation nano zine oxide of capillary inner surface(APS‑ZnO)It constitutes.By preparing a kind of silanization nano-zinc oxide sol with fluorescent characteristic and water sensitive, and is cured and fluorescence APS ZnO water sensitive capillaries are made in capillary substrate material surface, by the capillarity automatic sucking sample solution of capillary itself, and using ZnO fluorescent quenching performances caused by the hydrolysis of APS ZnO materials, moisture in organic sample is judged according to fluorescence intensity.Agents useful for same of the present invention is safe and non-toxic, easy to operate, you can qualitative analysis can also quantitative determine;It is not related to complicated instrumentation, has the characteristics that cheap, portable, presentation integrated design, the intuitive quick, high sensitivity of quantitative manner;Have many advantages, such as quick detection, sensitivity, automation, milligram ammonia, live speed facilitated to survey application.

Description

It is a kind of based on the water sensitive fluorescent capillary pipe of amino silane zinc oxide and its preparation side Method and application

Technical field

The invention belongs to derived energy chemical detection fields, and it is glimmering to be related to a kind of water sensitive based on Aminosilylation nano zine oxide Light capillary and preparation method thereof can be applied to the quick detection of moisture in oil plant.

Background technology

Some moisture are often mixed in oil and products thereof, these moisture in storage and transport process other than it may introduce, stone Oil itself also has a degree of water imbibition, and can absorb in the contact from air or with water and dissolve a part of water.In oil Substantially there are three types of forms for the presence of water, including:Suspension moisture, is more common in crude oil and residual fuel oil;Emulsifying moisture, with Superfine microballon is dispersed in oil, and separation is difficult;Dissolved form moisture, is generally present in aviation fuel.In particular, these Moisture present in oil be easy to cause the different degrees of harm of fuel oil instrument, is all deposited in communications and transportation, aerospace etc. In huge hidden danger, or even cause disaster.For example, the moisture in light-end products can be such that combustion process deteriorates, carbon deposit is generated, is increased The abrasion of cylinder;Water is easy to freeze under altitude low temperature in aviation fuels, blocks fuel conductor and filter;Lubricate W/O meeting Cause the corrosion, etc. of engine part.Therefore, determination of moisture in oil plant becomes the oil products such as crude oil, oil and edible oil Qualified one of important indicator.In addition, the organic reagents such as ethyl alcohol also need a kind of simple and effective moisture detecting method, to protect Demonstrate,prove product quality and production safety.

Currently, mainly there is the method for determination of moisture in organic reagent:Condistillation method, Karl_Fischer method and gas chromatography. Condistillation method is that the moisture in oil product is taken out of to oil sample and same volume solvent such as toluene condistillation, the latter accounts for former examination by toluene The volume ratio of the sample i.e. moisture of the sample, this method evaluated error is larger, is only suitable for the measurement of constant moisture;Karl Fischer Assay method of the method as moisture in common oil plant, titrating solution are related to using substances such as iodine, sulfur dioxide, pyridine, methanol, easily Side reaction occurs, when measuring low content water, naked eyes judge that terminal is not sharp, poor reproducibility, which is suitble to measure micro-moisture, but There are karrs that is troublesome in poeration, using.The shortcomings such as C.Fischer is mostly toxic, accuracy is poor, minute length;Gas phase Chromatography is although easy to operate, is suitable for gross sample and measures, but instrument is huge, expensive, measure and take, environmental requirement is high, no Conducive to the process control of Site Detection and product.Therefore, a kind of easy, nontoxic, cheap, sensitive, fast survey of portable moisture is established Method, realization are of great significance the fast measuring tool of moisture in the organic reagents such as oil plant.

Invention content

For disadvantages mentioned above of the existing technology, the present invention has developed a kind of based on Aminosilylation nano zine oxide Water sensitive fluorescent capillary pipe and preparation method thereof, wherein Aminosilylation nano zine oxide can be indicated with APS-ZnO, base of the present invention It can be used for the quick of moisture in the organic reagents sample such as oil plant in the water sensitive fluorescent capillary pipe of Aminosilylation nano zine oxide Detection.

Technical solution of the present invention is as follows:

A kind of water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide, by capillary and solidification in capillary The Aminosilylation nano zine oxide of inner surface(APS-ZnO)It constituting, the APS-ZnO load capacity of capillary inner surface is 0.02~ 0.05 mg/mm2;The APS-ZnO is colourless bright colloidal sol, and 3~5nm of size, the capillary is water white transparency, two The glass material capillary of end opening, internal diameter are 0.99~1.0 mm, and thickness is 0.05~0.10 mm, and length is 10.0 cm;

The water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide, priming color is water white transparency Shape.

The preparation method of the above-mentioned water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide, including following step Suddenly:

1)Prepare fluorescence APS-ZnO water sensitive Nano sols:By Zn (AC)2·2H2O is dissolved in absolute ethyl alcohol, and dissolving is dense Degree is 0.066 g/mL, and 10 min of ultrasound, are then added LiOHH at room temperature2O continues ultrasound to whole dissolvings, obtains nano oxygen Change Zinc material, Aminosilylation reagent is then added into nano zinc oxide material, sealing is protected from light, 24 h are stirred at room temperature, obtains glimmering Light APS-ZnO water sensitive Nano sols;

2)The silicic acid anhydride of capillary:Capillary substrate material is impregnated into 12 h in Piranha solution, is then used clear Water cleans the acid on surface, and 20 min in the ethanol solution of hydrophobic silanization reagent are soaked in after dry, and taking-up is dried spare;

3)Prepare APS-ZnO water sensitive fluorescent capillary pipes:Take step 1)The fluorescence APS-ZnO water sensitive nanometers of preparation are molten Glue is added isometric absolute ethyl alcohol and dilutes 2 times, step 2 is then added)Capillary after silicic acid anhydride impregnates, capillary Drying is taken out, the water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide is made.

Step 1)In, the Zn (AC)2·2H2O and LiOHH2The ratio of the amount of the substance of O is 1.4~1.0.

Step 1)In, a concentration of 0.050~0.080mol/ L of zinc oxide in the nano zinc oxide material.

Step 1)In, the Aminosilylation reagent and the ratio of the amount of the substance of zinc oxide in nano zinc oxide material are 1 :40~60.

Step 1)In, the aminosilane reagents are 3- aminopropyl triethoxysilanes (APS).

Step 2)In, the Piranha solution is volume ratio 7:3 concentrated sulfuric acid and hydrogen peroxide mixed solution.

Step 2)In, the volume ratio of the silylating reagent and ethyl alcohol is 1:5~10.

Step 2)In, the hydrophobic silanization reagent is hexadecyl trimethoxy silane.

Step 3)In, the immersion, the time is 2 h.

The application of the above-mentioned water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide, can be used for organic reagent sample The quick detection of moisture in product, the organic reagent sample to be measured include:Aviation gasoline, automobile gasoline, ethyl alcohol, machine oil and food Use salad oil.

The application, step include:

1)It establishes standard fluorescence and compares pipe control collection of illustrative plates:The organic reagent standard solution of moisture graded is prepared, Water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide is inserted into the standard solution prepared, insertion depth 3.0 ~5.0 mm, solidification, which is hydrolyzed in the APS-ZnO materials of capillary inner surface with the moisture in sucking capillary, reacts, and stands 30S, after the reaction was complete, taking-up is dried, and obtains a series of organic reagent standard fluorescence capillary of moisture gradeds, into And Portable ultraviolet is used to transmit platform, and under 310 nm wavelength, the graded of the fluorescence response of record standard fluorescent capillary pipe, And corresponded with standard solution moisture, it establishes standard fluorescence and compares pipe control collection of illustrative plates;

2)Sample detection:Water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide is inserted into organic reagent In sample, 3.0~5.0 mm of insertion depth cures the APS-ZnO materials in capillary inner surface and the water in sucking capillary Divide and reaction is hydrolyzed, stands 30S, after the reaction was complete, taking-up is dried, using Portable fluorescence radiation instrument, in 310 nm wavelength Under, the fluorescence response intensity of fluorescent capillary pipe is recorded, its measurement result with standard fluorescence is compared into pipe compares collection of illustrative plates and compare, determination The concentration of moisture in organic reagent sample.

The water sensitive fluorescent capillary pipe of the application, Aminosilylation nano zine oxide is limited to the lowest detection of moisture 0.01 % of volume fraction.

The present invention has unique texture and water-sensitive using normal capillary pipe host material cheap and easy to get as carrier, by preparation Feel the amino silane zinc oxide fluorescent nano material of characteristic, and then introduces silylating reagent and surface-functionalized place is carried out to it Reason, and be allowed to derive corresponding functional group(Such as amino), obtain the Aminosilylation nano zine oxide of high water phase sensitivity(APS- ZnO), then, the fluorescence APS-ZnO nano materials with water sensitive characteristic are cured in capillary tube inner wall, in capillary wall On load capacity be 0.010 mg mm-2, the APS-ZnO fluorescent capillary pipes of water sensitive are made;The capillary is directly immersed in be measured In sample, by the capillarity automatic sucking sample solution of capillary itself, and using caused by the hydrolysis of APS-ZnO materials ZnO fluorescent quenching performances, and then according to the fluorescent quenching degree of capillary under Portable fluorescence radiation instrument, analysis has different water Divide the sample solution of content, the moisture of obtained fluorescence intensity change, different content that APS-ZnO fluorescent capillary pipes can be caused to present Go out the distinguishable fluorescence graded of naked eyes, and be compared with the fluorescence intensity of standard fluorescence capillary, judges that oil plant etc. has Moisture in machine reagent sample.

Technical solution of the present invention advantageous effect is:

(1)Prepare a kind of fluorescent silane nano zine oxide with fluorescent characteristic and water sensitive(APS-ZnO) material, And cured in capillary substrate material surface, load capacity is 0.010 mg mm-2, prepare fluorescence APS-ZnO water sensitive capillarys Pipe, combined type portable fluorescence radiation instrument quickly detect moisture in organic reagent.

(2)Have the characteristics that cheap, portable and integrated design is presented;The capillarity automatic sucking sample of capillary itself Product solution, does not need extrinsic power;Complicated instrumentation it is not related to, quantitative manner is intuitive, quick, by visual observation, you can sees The variation of fluorescence power is surveyed, agents useful for same is safe and non-toxic, easy to operate, you can qualitative analysis can also quantitative determine, and have preferable Application prospect.

(3)It is easy to operate, detection time is short, high sensitivity when capillary of the present invention is used for water content detection(Detection limit down to 0.01 % of volume fraction), detecting system it is portable, suitable for in the organic reagents sample such as oils moisture it is quick, sensitive, from Dynamicization, milligram ammonia, can field application speed survey;Testing result is consistent with the classical quantitative result of Karl_Fischer method.

Description of the drawings

Fig. 1 is the quick test device based on APS-ZnO fluorescent capillary pipes(Portable ultraviolet transmits platform);

Fig. 2 is ZnO fluorescent materials(Before adding 3% moisture oils sample A, after B), APS-ZnO(Add 3% moisture oily Before class sample C, after D)Fluorescence intensity change;

Fig. 3 is influence of the APS concentration to APS-ZnO materials:A translucency, B fluorescence uniformities(Concentration is more than 20%, colloidal sol Bright state is presented);

Fig. 4 is that 4 standard fluorescence of embodiment compares pipe control collection of illustrative plates;

Fig. 5 is the fluorescence response intensity of embodiment 4-8 fluorescent capillaries.

Specific implementation mode

By describing the present invention in conjunction with specific embodiments, without departing from the idea case in the present invention described above, according to this The various replacements or change that field ordinary technical knowledge and customary means are made, are included within the scope of the present invention.

Embodiment 1

A kind of water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide, by capillary and solidification in capillary The Aminosilylation nano zine oxide of inner surface(APS-ZnO)It constitutes, the APS-ZnO load capacity of capillary inner surface is 0.03mg/mm2;The APS-ZnO is colourless bright shape colloidal sol.

The capillary is the glass material capillary of water white transparency, both ends open, and internal diameter is 1.0 mm, and thickness is 0.08mm, length 10.0cm.

The water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide, priming color is water white transparency Shape, size is in 3nm or so.

Preparation method includes the following steps:

1)Prepare fluorescence APS-ZnO water sensitive Nano sols:By Zn (AC)2·2H2O is dissolved in absolute ethyl alcohol, and dissolving is dense Degree is 0.066 g/mL, and 10 min of ultrasound, are then added LiOHH at room temperature2O, Zn (AC)2·2H2O and LiOHH2The object of O The ratio of the amount of matter is 1.2, continues ultrasound to whole dissolvings, obtains nano zinc oxide material, zinc oxide is dense in nano zinc oxide material Degree is 0.050mol/ L, and 3- aminopropyl triethoxysilanes, three ethoxy of 3- aminopropyls are then added into nano zinc oxide material Base silane and the ratio of the amount of the substance of zinc oxide in nano zinc oxide material are 1:50, sealing is protected from light, is stirred overnight at room temperature, obtains Fluorescence APS-ZnO water sensitive Nano sols, the colloidal sol is sensitive to moisture responsive, is added after isometric water, and fluorescence moment is sudden It goes out(Fig. 2).By changing APS concentration, find, when APS concentration is higher than 20%, water white transparency colloidal sol can be obtained(Fig. 3);

2)The silicic acid anhydride of capillary:By capillary substrate material in volume ratio 7:3 concentrated sulfuric acid and hydrogen peroxide mixing 12 h are impregnated in solution, the acid of excess surface are washed away with clear water, and introduce hydroxyl on surface, cetyl three is soaked in after dry The volume ratio of 20 min in the ethanol solution of methoxy silane, silylating reagent and ethyl alcohol is 1:10, taking-up is dried spare;

3)Prepare APS-ZnO water sensitive fluorescent capillary pipes:Take step 1)The fluorescence APS-ZnO water sensitive nanometers of preparation are molten Glue dilutes 2 times with absolute ethyl alcohol, step 2 is then added)Capillary after silicic acid anhydride impregnates 2 h, and capillary takes out dry It is dry, the water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide is made.

Embodiment 2

1)Prepare fluorescence APS-ZnO water sensitive Nano sols:By Zn (AC)2·2H2O is dissolved in absolute ethyl alcohol, and dissolving is dense Degree is 0.033 g/mL, and 10 min of ultrasound, are then added LiOHH at room temperature2O, Zn (AC)2·2H2O and LiOHH2The object of O The ratio of the amount of matter is 1.0, continues ultrasound to whole dissolvings, obtains nano zinc oxide material, zinc oxide is dense in nano zinc oxide material Degree is 0.050mol/ L, and 3- aminopropyl triethoxysilanes, three ethoxy of 3- aminopropyls are then added into nano zinc oxide material Base silane and the ratio of the amount of the substance of zinc oxide in nano zinc oxide material are 1:40, sealing is protected from light, is stirred overnight at room temperature, obtains Fluorescence APS-ZnO water sensitive Nano sols;

2)The silicic acid anhydride of capillary:By capillary substrate material in volume ratio 7:3 concentrated sulfuric acid and hydrogen peroxide mixing 12 h are impregnated in solution, the acid of excess surface are washed away with clear water, and introduce hydroxyl on surface, cetyl three is soaked in after dry The volume ratio of 20 min in the ethanol solution of methoxy silane, silylating reagent and ethyl alcohol is 1:5, taking-up is dried spare;

3)Prepare APS-ZnO water sensitive fluorescent capillary pipes:Take step 1)The fluorescence APS-ZnO water sensitive nanometers of preparation are molten Glue dilutes 2 times with absolute ethyl alcohol, step 2 is then added)Capillary after silicic acid anhydride impregnates 2 h, dry, is made and is based on The water sensitive fluorescent capillary pipe of Aminosilylation nano zine oxide, this proportioning present fluorescence present blue, it is not easy to identify, effect compared with Embodiment 1 is poor.

Embodiment 3

1)Prepare fluorescence APS-ZnO water sensitive Nano sols:By Zn (AC)2·2H2O is dissolved in absolute ethyl alcohol, and dissolving is dense Degree is 0.011 g/mL, and 10 min of ultrasound, are then added LiOHH at room temperature2O, Zn (AC)2·2H2O and LiOHH2The object of O The ratio of the amount of matter is 1.4, continues ultrasound to whole dissolvings, obtains nano zinc oxide material, zinc oxide is dense in nano zinc oxide material Degree is 0.050mol/ L, and 3- aminopropyl triethoxysilanes, three ethoxy of 3- aminopropyls are then added into nano zinc oxide material Base silane and the ratio of the amount of the substance of zinc oxide in nano zinc oxide material are 1:60, sealing is protected from light, is stirred overnight at room temperature, obtains Fluorescence APS-ZnO water sensitive Nano sols;

2)The silicic acid anhydride of capillary:By capillary substrate material in volume ratio 7:3 concentrated sulfuric acid and hydrogen peroxide mixing 12 h are impregnated in solution, the acid of excess surface are washed away with clear water, and introduce hydroxyl on surface, cetyl three is soaked in after dry The volume ratio of 20 min in the ethanol solution of methoxy silane, silylating reagent and ethyl alcohol is 1:5, taking-up is dried spare;

3)Prepare APS-ZnO water sensitive fluorescent capillary pipes:Take step 1)The fluorescence APS-ZnO water sensitive nanometers of preparation are molten Glue dilutes 2 times with absolute ethyl alcohol, step 2 is then added)Capillary after silicic acid anhydride impregnates 2 h, dry, is made and is based on The water sensitive fluorescent capillary pipe of Aminosilylation nano zine oxide, this proportioning water sensitive fluorescent capillary pipe fluorescence are weak compared with embodiment 1.

Embodiment 4:The speed of moisture is surveyed in aviation gasoline

1)It establishes standard fluorescence and compares pipe control collection of illustrative plates(As shown in Figure 4):Prepare the aviation vapour of moisture graded Oil standard solution, moisture are followed successively by 0.01 %, 0.05 %, 0.2 %, 1.0 %, 5.0 %, 10.0 %, will be based on amino silicone The water sensitive fluorescent capillary pipe of alkanisation nano zine oxide is inserted into the standard solution prepared, 3.0~5.0 mm of insertion depth, solidification It is hydrolyzed and reacts with the moisture in sucking capillary in the APS-ZnO materials of capillary inner surface, stand 30S, the reaction was complete Afterwards, taking-up is dried, and obtains a series of aviation gasoline standard fluorescence capillary of moisture gradeds, and then using portable Ultraviolet transmission platform(Fig. 1), under 310 nm wavelength, the graded of the fluorescence response of record standard fluorescent capillary pipe, and with The aviation gasoline standard solution moisture of system corresponds, and the standard fluorescence for establishing aviation gasoline compares pipe control collection of illustrative plates;

2)Sample detection:Water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide is inserted into and contains unknown water Point aviation gasoline sample in, 3.0~5.0 mm of insertion depth stands 30S, takes out after the reaction was complete, removed with blotting paper in Portion's solution, dries, and then uses Portable fluorescence radiation instrument, under 310 nm wavelength, records the fluorescence response of fluorescent capillary pipe Intensity(As shown in Figure 5), its measurement result with standard fluorescence compared into pipe compare collection of illustrative plates and compare, determine water in aviation gasoline sample The concentration divided.

Test in the aviation gasoline sample of embodiment 4 moisture be 0.01 %.It is verified using Karl_Fischer method, karr Moisture is 0.0096 % in the aviation gasoline sample of Fei Xiufa measurement embodiments 4, as a result almost the same, shows base of the present invention It accurately can be used to detect the moisture in aviation gasoline in the water sensitive fluorescent capillary pipe of Aminosilylation nano zine oxide.

Embodiment 5:The speed of moisture is surveyed in general-utility car gasoline

1)It establishes standard fluorescence and compares pipe control collection of illustrative plates:Method is the same as embodiment 4;

2)Sample detection:APS-ZnO water sensitive fluorescent capillary pipes prepared by embodiment 1 are soaked in automobile gasoline, are inserted It is taken out after entering depth 3.0~5.0 mm, 30 s, removes internal solution with blotting paper, dry, dry in the air to 3~4 s, then by just Take the fluorescence intensity that formula fluorescence radiation instrument detects the fluorescent capillary pipe(As shown in Figure 5), and compare pipe compares figure with standard fluorescence The fluorescence intensity of spectrum compares, and determines moisture in general-utility car gasoline.

Test in the general-utility car gasoline of embodiment 5 moisture be 0.01 %.It is verified using Karl_Fischer method, karr Moisture is 0.0099 % in the general-utility car gasoline of Fei Xiufa measurement embodiments 5, as a result almost the same, shows base of the present invention It accurately can be used to detect the moisture in general-utility car gasoline in the water sensitive fluorescent capillary pipe of Aminosilylation nano zine oxide Content.

Embodiment 6:The speed of moisture is surveyed in machine oil

1)It establishes standard fluorescence and compares pipe control collection of illustrative plates:Method is the same as embodiment 4;

2)Sample detection:APS-ZnO water sensitive fluorescent capillary pipes prepared by embodiment are soaked in machine oil, insertion depth It is taken out after 3.0~5.0 mm, 30 s, removes internal solution with blotting paper, dry, dry in the air to 3~4 s, then by portable glimmering Light radiation instrument detects the fluorescence intensity of the fluorescent capillary pipe(As shown in Figure 5), and compare pipe with standard fluorescence and compare the glimmering of collection of illustrative plates Light strength ratio pair determines moisture in machine oil.

Test in the machine oil of embodiment 6 moisture be 0.05 %.It is verified using Karl_Fischer method, Karl_Fischer method is surveyed It is 0.048 % to determine moisture in the machine oil of embodiment 6, as a result almost the same, shows that the present invention is based on Aminosilylation nanometers The water sensitive fluorescent capillary pipe of zinc oxide accurately can be used to detect the moisture in machine oil.

Embodiment 7:The speed of moisture is surveyed in salad oil

1)It establishes standard fluorescence and compares pipe control collection of illustrative plates:Method is the same as embodiment 4;

2)Sample detection:APS-ZnO water sensitive fluorescent capillary pipes prepared by embodiment 2 are soaked in salad oil, are inserted into It is taken out after depth 3.0~5.0 mm, 30 s, removes internal solution with blotting paper, dry, dry in the air to 3~4 s, then by portable Formula fluorescence radiation instrument detects the fluorescence intensity of the fluorescent capillary pipe(As shown in Figure 5), and compare pipe with standard fluorescence and compare collection of illustrative plates Fluorescence intensity compare, determine moisture in salad oil.

Test in the salad oil of embodiment 7 moisture be 0.2 %.It is verified using Karl_Fischer method, Karl_Fischer method It is 0.205 % to measure moisture in the salad oil of embodiment 7, as a result almost the same, shows that the present invention is based on Aminosilylations The water sensitive fluorescent capillary pipe of nano zine oxide accurately can be used to detect the moisture in salad oil.

Embodiment 8:The speed of moisture is surveyed in 95 ethyl alcohol

1)It establishes standard fluorescence and compares pipe control collection of illustrative plates:Method is the same as embodiment 4;

2)Sample detection:APS-ZnO water sensitive fluorescent capillary pipes prepared by embodiment 3 are soaked in 95 ethyl alcohol, are inserted into It is taken out after depth 3.0~5.0 mm, 30 s, removes internal solution with blotting paper, dry, dry in the air to 3~4 s, then by portable Formula fluorescence radiation instrument detects the fluorescence intensity of the fluorescent capillary pipe(As shown in Figure 5), and compare pipe with standard fluorescence and compare collection of illustrative plates Fluorescence intensity compare, determine moisture in 95 ethyl alcohol.

Test in the salad oil of embodiment 8 moisture be 5.0 %.It is verified using gas chromatography, gas chromatography It is 5.12 % to measure moisture in 95 ethyl alcohol of embodiment 8, as a result almost the same, shows that the present invention is based on Aminosilylations to receive The water sensitive fluorescent capillary pipe of rice zinc oxide can accurately be used to detect the moisture in 95 ethyl alcohol.

Above-described embodiment 4-8 uses APS-ZnO fluorescence water sensitive capillary test sample moisture result and error, sees Table 1.

Table 1

Claims (9)

1. a kind of preparation method of the water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide, which is characterized in that packet Include following steps:
1)Prepare fluorescence APS-ZnO water sensitive Nano sols:By Zn (AC)2·2H2O is dissolved in absolute ethyl alcohol, and concentration of ordinary dissolution is 0.066 g/mL, 10 min of ultrasound, are then added LiOHH at room temperature2O continues ultrasound to whole dissolvings, obtains nano zine oxide Material, is then added Aminosilylation reagent into nano zinc oxide material, and sealing is protected from light, 24 h are stirred at room temperature, obtain fluorescence APS-ZnO water sensitive Nano sols;
2)The silicic acid anhydride of capillary:Capillary substrate material is impregnated into 12 h in Piranha solution, is then washed with clear water The acid on net surface, is soaked in 20 min in the ethanol solution of hydrophobic silanization reagent after dry, taking-up is dried spare;
3)Prepare APS-ZnO water sensitive fluorescent capillary pipes:Take step 1)The fluorescence APS-ZnO water sensitive Nano sols of preparation, add Enter isometric absolute ethyl alcohol and dilute 2 times, step 2 is then added)Capillary after silicic acid anhydride impregnates, and capillary takes out dry It is dry, the water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide is made;
It is described by capillary and to be cured in table in capillary based on the water sensitive fluorescent capillary pipe of Aminosilylation nano zine oxide The Aminosilylation nano zine oxide in face is constituted, and the APS-ZnO load capacity of capillary inner surface is 0.02~0.05 mg/mm2; The APS-ZnO is colourless bright colloidal sol, and 3~5nm of size, the capillary is the glass of water white transparency, both ends open Material capillary, internal diameter are 0.99~1.0 mm, and thickness is 0.05~0.10 mm, and length is 10.0 cm;It is described based on ammonia The water sensitive fluorescent capillary pipe of base silane nano zine oxide, priming color are colorless and transparent.
2. preparation method according to claim 1, it is characterised in that:Step 1)In, the Zn (AC)2·2H2O with LiOH·H2The ratio of the amount of the substance of O is 1.0~1.4;Zinc oxide a concentration of 0.050 in the nano zinc oxide material~ 0.080mol/ L;The Aminosilylation reagent and the ratio of the amount of the substance of zinc oxide in nano zinc oxide material are 1:40 ~60.
3. preparation method according to claim 1, it is characterised in that:Step 1)In, the aminosilane reagents are 3- Aminopropyl triethoxysilane.
4. preparation method according to claim 1, it is characterised in that:Step 2)In, the Piranha solution is volume Than 7:3 concentrated sulfuric acid and hydrogen peroxide mixed solution;The volume ratio of the silylating reagent and ethyl alcohol is 1:5~10.
5. preparation method according to claim 1, it is characterised in that:Step 2)In, the hydrophobic silanization reagent is Hexadecyl trimethoxy silane.
6. preparation method according to claim 1, it is characterised in that:Step 3)In, the immersion, time 2h.
7. a kind of application of the water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide prepared such as claim 1, It is characterized in that:It can be used for the quick detection of moisture in organic reagent sample, the organic reagent sample includes:Aviation vapour Oil, automobile gasoline, ethyl alcohol, machine oil and edible salad oil.
8. application according to claim 7, which is characterized in that step includes:
1)It establishes standard fluorescence and compares pipe control collection of illustrative plates:The organic reagent standard solution for preparing moisture graded, by base It is inserted into the standard solution prepared in the water sensitive fluorescent capillary pipe of Aminosilylation nano zine oxide, insertion depth 3.0~ 5.0mm, solidification, which is hydrolyzed in the APS-ZnO materials of capillary inner surface with the moisture in sucking capillary, reacts, and stands 30S, after the reaction was complete, taking-up is dried, and obtains a series of organic reagent standard fluorescence capillary of moisture gradeds, into And Portable ultraviolet is used to transmit platform, and under 310nm wavelength, the graded of the fluorescence response of record standard fluorescent capillary pipe, And corresponded with standard solution moisture, it establishes standard fluorescence and compares pipe control collection of illustrative plates;
2)Sample detection:Water sensitive fluorescent capillary pipe based on Aminosilylation nano zine oxide is inserted into organic reagent sample In, 3.0~5.0mm of insertion depth, the APS-ZnO materials cured in capillary inner surface are carried out with the moisture in sucking capillary Hydrolysis stands 30S, and after the reaction was complete, taking-up is dried, using Portable fluorescence radiation instrument, under 310nm wavelength, and record The fluorescence response intensity of fluorescent capillary pipe, with standard fluorescence compares pipe by its measurement result and compares collection of illustrative plates and compare, and determines organic examination The concentration of moisture in agent sample.
9. application according to claim 7, it is characterised in that:Volume fraction 0.01% is limited to the lowest detection of moisture.
CN201610125053.5A 2016-03-04 2016-03-04 A kind of water sensitive fluorescent capillary pipe and its preparation method and application based on amino silane zinc oxide CN105738338B (en)

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US7708944B1 (en) * 2006-06-13 2010-05-04 Research Foundation Of State University Of New York Ultra-sensitive, portable capillary sensor
CN103018462B (en) * 2012-12-18 2016-05-18 西南大学 Nano oxidized Zinc modified immune capillary and its preparation method and application
CN105241859B (en) * 2015-10-30 2018-03-30 曲阜师范大学 A kind of CTS ZnO fluorescent test papers and its preparation method and application

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