CN114920298B - Crystalline two-dimensional porous CuO/WO 3 Nanosheets, preparation method thereof and application of nanosheets as acetoin sensor - Google Patents
Crystalline two-dimensional porous CuO/WO 3 Nanosheets, preparation method thereof and application of nanosheets as acetoin sensor Download PDFInfo
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Abstract
The invention discloses a crystalline two-dimensional porous CuO/WO 3 Nanosheets synthesized by a spatially self-limited domain assembly strategy, cuO in the form of nanoparticles uniformly dispersed in crystalline porous WO, methods of preparation thereof and use as acetoin sensors 3 The surface of the nano-sheet. Dissolving inorganic salt, tungsten compound and copper compound in water, freezing the mixed solution at low temperature, obtaining precursor under the condition of freeze drying to obtain sample, calcining the sample under high temperature to crystallize the sample at high temperature, washing salt template with deionized water, and drying to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet. The invention is described in WO 3 The CuO nano particles are compounded on the basis of the preparation method, the selectivity and stability of the acetoin are improved, the acetoin is better in selectivity when the working temperature is 100 ℃, the sensitivity of the acetoin to 50ppm reaches 588.67, the response-recovery time is quick, the stability is high, and the moisture resistance is good.
Description
Technical Field
The invention relates to a crystalline two-dimensional porous CuO/WO 3 The preparation of the nano-sheet and the application of the nano-sheet in the acetoin sensor.
Background
Listeria Monocytogenes (LMs) is an infectious food pathogen that causes a variety of diseases, including localized enteritis and systemic infection in immunocompromised and immunocompromised individuals with a mortality rate of 20-30%. However, LMs are widely distributed in fruits, vegetables or other foods and exhibit high low-temperature reproductive ability, which makes it extremely difficult to prevent the spread of LMs. Therefore, it is of great importance to accurately and quantitatively detect LMs. Currently, various methods including nucleic acid detection, immunodetection and microbiological studies have been explored for the detection of LMs. Despite significant advances, these techniques still present complex and costly problems, and therefore it would be highly desirable to develop a low cost and convenient method for monitoring pathogenic microorganisms in food products. In particular, microbial Volatile Organic Compounds (MVOCs) are an important component of microbial metabolites. Acetoin (3-hydroxy-2-butanone) is reported to be the predominant exhaled gas (32.2% abundance) in LMs volatile metabolites, the concentration of which is related to the growth of LMs. Acetoin can thus be regarded as a biomarker for the detection of LMs. Literature reports that by constructing ordered cobalt-doped zinc oxide ultrafine particles (sensor. Act. B-chem., 358, 2022,131482) using MOF as a template, the prepared sensor has a higher optimal temperature response to acetoin and poor long-term stability. Literature reports that three-dimensional sea urchin-like WO is synthesized by adopting a hydrothermal method 3 (Mat. Sci. Semiconductor. Proc., 137, 2022, 106120), three-dimensional sea urchin-like WO 3 The sensor has a mesoporous structure composed of mutually connected nano rods, is favorable for the diffusion of gas molecules, has quick response-recovery time to acetoin, has low detection limit, but has higher operation temperature and low sensitivity. The existing acetoin sensor still has the defects of complicated preparation method, high operation temperature, poor stability, low sensitivity and the like. Therefore, it is necessary to develop a high sensitivity, a low operating temperature,Low cost and stable acetoin gas sensor.
Disclosure of Invention
Aiming at the defects of low sensitivity, high working temperature, poor stability and the like of an acetoin sensor, the invention provides a crystalline two-dimensional porous CuO/WO with high sensitivity, low power consumption and excellent selectivity for acetoin gas 3 A nano-sheet and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
crystalline two-dimensional porous CuO/WO of the invention 3 The nano-sheets are synthesized by a space self-limiting domain assembly strategy, and CuO nano-particles are uniformly distributed in crystalline two-dimensional porous WO 3 The surface of the nano-sheet.
Crystalline two-dimensional porous CuO/WO of the invention 3 The preparation method of the nano-sheet comprises the following steps: firstly, dissolving inorganic salt, tungsten compound and copper compound in water, ultrasonically dissolving, then pre-freezing the mixed solution under the condition of low temperature, obtaining a precursor under the condition of freeze drying to obtain a sample, calcining the sample under the condition of high temperature to crystallize the sample under the high temperature, washing a salt template by using deionized water, and drying in an oven to obtain the crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
The crystalline two-dimensional porous CuO/WO of the invention 3 The preparation method of the nano-sheet comprises the following specific steps:
crystalline two-dimensional porous CuO/WO 3 Nanoplatelets, the crystalline two-dimensional porous CuO/WO 3 The nano-sheets are synthesized by a space self-limiting domain assembly strategy, and CuO nano-particles are uniformly distributed in crystalline two-dimensional porous WO 3 The surface of the nano-sheet.
The crystalline two-dimensional porous CuO/WO of the invention 3 The preparation method of the nano-sheet comprises the following steps:
(1) Preparing an inorganic salt solution: dissolving inorganic salt in water, and stirring until the inorganic salt is transparent and clear to obtain an inorganic salt solution;
(2) Preparation of CuO/WO 3 Precursor: dissolving copper compound and tungsten compound in inorganic salt solution, ultrasonic stirring to completely disperse to obtain mixed solution, and making the mixed solution be lowPre-freezing at a temperature, and then freeze-drying in a freeze dryer to obtain CuO/WO 3 A precursor;
(3) Preparation of crystalline two-dimensional porous CuO/WO 3 Nanosheets: the CuO/WO prepared in the step (2) is used for preparing 3 Calcining the precursor in a muffle furnace to crystallize at high temperature, then fully washing the inorganic salt template with deionized water, and drying at 60 ℃ to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
Further, the inorganic salt in the step (1) is one or more of sodium chloride, potassium sulfate, potassium chloride, ammonium nitrate, potassium bromide, sodium sulfate or sodium nitrate, and the concentration of the inorganic salt solution is 0.05 g/mL-2 g/mL.
Further, the copper compound in the step (2) is CuCl 2 、CuSO 4 、CuSO 4 ·5H 2 O or Cu (NO) 3 ) 2 One or more of the following; the tungsten compound is Na 2 WO 4 ·2H 2 O、K 2 WO 4 、(NH 4 ) 6 H 2 W 12 O 40 ·XH 2 O、H 4 [Si(W 3 O 10 ) 4 ]·xH 2 O、WCl 6 One or more of the following.
Further, in the step (2), the mass ratio of the tungsten compound to the copper compound is 1:0.005-1:0.05; the total concentration of the tungsten compound and the copper compound in the mixed solution is 0.01-g/mL to 0.42g/mL.
Further, in the step (2), the mass ratio of the inorganic salt to the tungsten compound is 1:0.01-1:0.5.
Further, the pre-freezing temperature in the step (2) is-18-28 ℃, the pre-freezing time is 12-24 hours, the freeze drying temperature is-50 to-65 ℃, and the freeze drying time is 24-48 hours.
Further, in the step (3), the calcination temperature is 400-800 ℃, the heating rate is 2-5 ℃ per minute, and the calcination time is 1-2 h.
Further, in the step (3), the drying temperature is 60 ℃ and the drying time is 4-6h.
The key point of the innovation of the invention is to prepare crystalline two-dimensional porous CuO/WO 3 Nanometer scaleAnd (3) a sheet. Many materials for acetoin sensors are prepared, but the preparation method is complex, the operation temperature is high, the stability is poor and the sensitivity is low. The crystalline two-dimensional porous CuO/WO of the invention 3 Application of nano-sheet as gas sensor in high-sensitivity acetoin sensor, and crystalline two-dimensional porous CuO/WO (CuO/WO) when working temperature is 100 DEG C 3 The nano-sheet has better selectivity to acetoin as a gas sensor and has sensitivity to 50ppm of acetoin reaching 588.67.
The invention has the beneficial effects that: the invention is described in WO 3 The CuO nano particles are compounded on the basis of the nano sheets, so that the sensitivity and selectivity to acetoin gas are improved, and the stability is good; the sensitivity of 100 ℃ working temperature to 50ppm acetoin gas is 588.67, and the working temperature is reduced compared with the working temperature of the existing acetoin sensor. The method has the advantages of innovativeness, high yield and low preparation cost; the shape and the size of the material are uniform; has higher response to acetoin gas and is easy to realize industrialization.
Drawings
FIG. 1 is a crystalline two-dimensional porous CuO/WO prepared in example 8 3 XRD pattern of nanoplatelets.
FIG. 2 is a crystalline two-dimensional porous CuO/WO prepared in example 8 3 Scanning Electron Microscope (SEM) images of nanoplatelets.
FIG. 3 is a crystalline two-dimensional porous CuO/WO prepared in example 8 3 Transmission Electron Microscope (TEM) images of the nanoplatelets.
FIG. 4 is a crystalline two-dimensional porous CuO/WO prepared in example 8 3 Response value of nanoplatelets to 50ppm acetoin at 60-160 ℃.
FIG. 5 is a crystalline two-dimensional porous CuO/WO prepared in example 8 3 Long-term stability test of nanoplatelets against 50ppm acetoin within 30 days.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that numerous insubstantial modifications and adaptations can be made by those skilled in the art in light of the foregoing disclosure.
Example 1
The crystalline two-dimensional porous CuO/WO of this example 3 The preparation method of the nano-sheet comprises the following steps:
(1) 1g of potassium chloride is weighed, 10ml water is added, and ultrasonic stirring is carried out for 5min to form uniform and stable transparent clear solution;
(2) 200mg of Na was slowly added to the salt solution of (1) 2 WO 4 ·2H 2 O and 2mg CuCl 2 Pre-freezing at-18deg.C for 6 hr after dissolving for 10min under ultrasonic stirring, and lyophilizing at-50deg.C for 24 hr to obtain CuO/WO 3 A precursor;
(3) CuO/WO 3 The precursor is put into a muffle furnace to be heated to 400 ℃ at a heating rate of 2 ℃ per minute, and the temperature is kept for 2 hours. Washing the obtained product with distilled water for 3 times and absolute ethyl alcohol for 1 time, and drying in a 60 ℃ oven for 6 hours to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
Example 2
The crystalline two-dimensional porous CuO/WO of this example 3 The preparation method of the nano-sheet comprises the following steps:
(1) 1g of sodium chloride is weighed, 20ml of water is added, and ultrasonic stirring is carried out for dissolving for 10min, so that a uniform and stable transparent clear solution is formed;
(2) 400mg Na was slowly added to the (1) salt solution 2 WO 4 ·2H 2 O and 2mg CuCl 2 Pre-freezing at-18deg.C for 12 hr after dissolving for 20min under ultrasonic stirring, and lyophilizing at-54 deg.C for 32 hr to obtain CuO/WO 3 A precursor;
(3) CuO/WO 3 The precursor is put into a muffle furnace to be heated to 470 ℃ at a heating rate of 1.5 ℃ per min, and the temperature is kept for 2 hours. Washing the obtained product with distilled water for 4 times and absolute ethyl alcohol for 1 time, and drying in a 60 ℃ oven for 5 hours to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
Example 3
The crystalline two-dimensional porous CuO/WO of this example 3 The preparation method of the nano-sheet comprises the following steps:
(1) Weighing 2g of sodium sulfate, adding 10ml of water, and stirring and dissolving for 8min by ultrasonic to form uniform and stable transparent clear solution;
(2) To the salt solution of (1) 500mg K was slowly added 2 WO 4 And 25mg CuSO 4 ·5H 2 Dissolving O by ultrasonic stirring for 15min, pre-freezing at-18deg.C for 24 hr, and freeze-drying at-60deg.C for 36 hr to obtain CuO/WO 3 A precursor;
(3) CuO/WO 3 The precursor is put into a muffle furnace to be heated to 450 ℃ at a temperature rising rate of 5 ℃ per minute, and the temperature is kept for 1h. Washing the obtained product with distilled water for 4 times and absolute ethyl alcohol for 1 time, and drying in a 60 ℃ oven for 4 hours to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
Example 4
The crystalline two-dimensional porous CuO/WO of this example 3 The preparation method of the nano-sheet comprises the following steps:
(1) Weighing 500mg of potassium bromide and 500mg of ammonium nitrate, adding 10ml of water, and stirring ultrasonically to dissolve for 12min to form a uniform and stable transparent clear solution;
(2) 400mg (NH) of the salt solution (1) was slowly added thereto 4 ) 6 H 2 W 12 O 40 ·XH 2 O and 20mg CuCl 2 Pre-freezing at-18deg.C for 16 hr after dissolving for 25min under ultrasonic stirring, and lyophilizing at-60deg.C for 24 hr to obtain CuO/WO 3 A precursor;
(3) CuO/WO 3 The precursor is put into a muffle furnace to be heated to 500 ℃ at a temperature rising rate of 4 ℃ per minute, and the temperature is kept for 1.2h. Washing the obtained product with distilled water for 3 times and absolute ethyl alcohol for 1 time, and drying in a 60 ℃ oven for 4 hours to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
Example 5
The crystalline two-dimensional porous CuO/WO of this example 3 The preparation method of the nano-sheet comprises the following steps:
(1) Weighing 500mg of sodium sulfate and 500mg of potassium chloride, adding 12ml of water, and stirring ultrasonically to dissolve for 8min to form a uniform and stable transparent clear solution;
(2) To the salt solution of (1) was slowly added 100mg K 2 WO 4 And 10mg Cu (NO) 3 ) 2 Pre-freezing at-18deg.C for 18 hr after dissolving for 10min under ultrasonic stirring, and lyophilizing at-52deg.C in a lyophilizer for 12 hr to obtain CuO/WO 3 A precursor;
(3) CuO/WO 3 The precursor is put into a muffle furnace to be heated to 400 ℃ at a heating rate of 2.5 ℃ per minute, and the temperature is kept for 2 hours. Washing the obtained product with distilled water for 4 times and absolute ethyl alcohol for 1 time, and drying in a 60 ℃ oven for 4 hours to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
Example 6
The crystalline two-dimensional porous CuO/WO of this example 3 The preparation method of the nano-sheet comprises the following steps:
(1) Weighing 2g of sodium sulfate, adding 15ml of water, and stirring and dissolving for 10min by ultrasonic to form uniform and stable transparent clear solution;
(2) 150mg of H are slowly added to the salt solution of (1) 4 [Si(W 3 O 10 ) 4 ]·xH 2 O and 15mg CuSO 4 ·5H 2 Dissolving O by ultrasonic stirring for 30min, pre-freezing at-18deg.C for 16 hr, and freeze-drying at-48deg.C for 24 hr to obtain CuO/WO 3 A precursor;
(3) CuO/WO 3 The precursor is put into a muffle furnace to be heated to 440 ℃ at a heating rate of 2 ℃ per min, and the temperature is kept for 1h. Washing the obtained product with distilled water for 3 times and absolute ethyl alcohol for 1 time, and drying in a 60 ℃ oven for 6 hours to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
Example 7
The crystalline two-dimensional porous CuO/WO of this example 3 The preparation method of the nano-sheet comprises the following steps:
(1) 1g of sodium sulfate and 1g of potassium chloride are weighed, 20ml of water is added, and ultrasonic stirring is carried out for dissolving for 15min, so that a uniform and stable transparent clear solution is formed;
(2) 400mg WCl are slowly added to the salt solution of (1) 6 And 20mg CuSO 4 ·5H 2 Dissolving O with ultrasonic stirring for 10min, pre-freezing at-18deg.C for 14 hr, and freeze-drying at-56deg.C for 24 hrTo CuO/WO 3 A precursor;
(3) CuO/WO 3 The precursor is put into a muffle furnace to be heated to 600 ℃ at a heating rate of 2 ℃ per min, and the temperature is kept for 1.5h. Washing the obtained product with distilled water for 3 times and absolute ethyl alcohol for 1 time, and drying in a 60 ℃ oven for 5 hours to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
Example 8
The crystalline two-dimensional porous CuO/WO of this example 3 The preparation method of the nano-sheet comprises the following steps:
(1) 1g of sodium chloride is weighed, 10ml of water is added, and ultrasonic stirring is carried out for dissolving for 10min, so that a uniform and stable transparent clear solution is formed;
(2) 200mg of H was slowly added to the salt solution of (1) 4 [Si(W 3 O 10 ) 4 ]·xH 2 O and 10mg CuCl 2 Pre-freezing at-20deg.C for 20 hr after dissolving under ultrasonic stirring for 10min, and lyophilizing at-52deg.C for 24 hr to obtain CuO/WO 3 A precursor;
(3) CuO/WO 3 The precursor is put into a muffle furnace to be heated to 400 ℃ at a heating rate of 2 ℃ per min, and the temperature is kept for 1h. Washing the obtained product with distilled water for 3 times and absolute ethyl alcohol for 1 time, and drying in a 60 ℃ oven for 4 hours to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
FIG. 1 shows the crystalline two-dimensional porous CuO/WO obtained in this example 3 XRD spectra of nanoplatelets, the products are CuO and WO 3 But since the CuO loading is too low, no diffraction peak of CuO occurs. FIG. 2 is an SEM photograph of a material, cuO/WO 3 In the composite material, cuO nano particles are uniformly dispersed in two-dimensional porous WO 3 On the nanoplatelets. FIG. 3 shows the crystalline two-dimensional porous CuO/WO obtained in this example 3 TEM image of nanoplatelets, it can be seen that crystalline two-dimensional porous CuO/WO 3 The nanoplatelets are very thin, taking on a porous form.
FIG. 4 shows the crystalline two-dimensional porous CuO/WO obtained in this example 3 The response value of the nanosheets to 50ppm acetoin at 60-160 ℃ can be seen as CuO/WO at 100 DEG C 3 Response to 50ppm acetoin is highest, response value588.67, 100 ℃ is defined as the optimum operating temperature. FIG. 5 shows the crystalline two-dimensional porous CuO/WO obtained in this example 3 The long-term stability of the nano-sheet within 30 days can be seen that the response value does not change greatly, which indicates that the crystalline two-dimensional porous CuO/WO 3 The stability of the nano-sheet is better.
Example 9
The crystalline two-dimensional porous CuO/WO of this example 3 The preparation method of the nano-sheet comprises the following steps:
(1) Weighing 2g of sodium chloride, adding 20ml of water, and stirring and dissolving for 20min by ultrasonic to form uniform and stable transparent clear solution;
(2) To the salt solution of (1), 500mg of H was slowly added 4 [Si(W 3 O 10 ) 4 ]·xH 2 O and 5mg Cu (NO) 3 ) 2 Pre-freezing at-18deg.C for 18 hr after dissolving for 10min under ultrasonic stirring, and lyophilizing at-50deg.C for 24 hr to obtain CuO/WO 3 A precursor;
(3) CuO/WO 3 The precursor is put into a muffle furnace to be heated to 400 ℃ at a heating rate of 1 ℃ per minute, and the temperature is kept for 2 hours. Washing the obtained product with distilled water for 3 times and absolute ethyl alcohol for 1 time, and drying in a 60 ℃ oven for 5 hours to obtain crystalline two-dimensional porous CuO/WO 3 A nano-sheet.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. Crystalline two-dimensional porous CuO/WO 3 The preparation method of the nano-sheet is characterized by comprising the following steps:
(1) Preparing an inorganic salt solution: dissolving inorganic salt in water, and stirring until the inorganic salt is transparent and clear to obtain an inorganic salt solution;
(2) Preparation of CuO/WO 3 Precursor: dissolving copper compound and tungsten compound in inorganic salt solution, stirring with ultrasound until completely dispersed to obtain mixed solution, pre-freezing the mixed solution at low temperature, and freeze drying in a freeze dryer to obtain CuO/WO 3 A precursor;
(3) Preparation of crystalline two-dimensional porous CuO/WO 3 Nanosheets: the CuO/WO prepared in the step (2) is used for preparing 3 Calcining the precursor in a muffle furnace to crystallize at high temperature, then fully washing out an inorganic salt template with deionized water, and drying to obtain crystallized two-dimensional porous CuO/WO 3 A nanosheet;
the crystalline two-dimensional porous CuO/WO 3 The nano-sheets are synthesized by a space self-limiting domain assembly strategy, and CuO nano-particles are uniformly distributed in crystalline two-dimensional porous WO 3 The surface of the nano-sheet.
2. The crystalline two-dimensional porous CuO/WO according to claim 1 3 The preparation method of the nano-sheet is characterized in that: the inorganic salt in the step (1) is one or more of sodium chloride, potassium sulfate, potassium chloride, ammonium nitrate, potassium bromide, sodium sulfate or sodium nitrate, and the concentration of the inorganic salt solution is 0.05 g/mL-2 g/mL.
3. The crystalline two-dimensional porous CuO/WO according to claim 1 3 The preparation method of the nano-sheet is characterized in that: the copper compound in the step (2) is CuCl 2 、CuSO 4 、CuSO 4 ·5H 2 O or Cu (NO) 3 ) 2 One or more of the following; the tungsten compound is Na 2 WO 4 ·2H 2 O、K 2 WO 4 、(NH 4 ) 6 H 2 W 12 O 40 ·XH 2 O、H 4 [Si(W 3 O 10 ) 4 ]·xH 2 O、WCl 6 One or more of the following.
4. The crystalline two-dimensional porous CuO/WO according to claim 1 3 The preparation method of the nano-sheet is characterized in that: the mass ratio of the tungsten compound to the copper compound in the step (2) is 1:0.005-1:0.05; the total concentration of the tungsten compound and the copper compound in the mixed solution is 0.01 g/mL-0.42 g/mL.
5. The crystalline two-dimensional porous CuO/WO according to claim 1 3 The preparation method of the nano-sheet is characterized in that: in the step (2), the mass ratio of the inorganic salt to the tungsten compound is 1:0.01-1:0.5.
6. The crystalline two-dimensional porous CuO/WO according to claim 1 3 The preparation method of the nano-sheet is characterized in that: the pre-freezing temperature in the step (2) is-18-28 ℃, the pre-freezing time is 12-24h, the freeze drying temperature is-50 to-65 ℃, and the freeze drying time is 24-48h.
7. The crystalline two-dimensional porous CuO/WO according to claim 1 3 The preparation method of the nano-sheet is characterized in that: the calcining temperature in the step (3) is 400-800 ℃, the heating rate is 2-5 ℃/min, and the calcining time is 1-2 h.
8. Crystalline two-dimensional porous CuO/WO prepared by the preparation method according to any one of claims 1 to 7 3 The application of the nano-sheet as a gas sensor in the aspect of a high-sensitivity acetoin sensor is characterized in that: at a working temperature of 100 ℃, crystalline two-dimensional porous CuO/WO 3 The nano-sheet has better selectivity to acetoin as a gas sensor and has sensitivity to 50ppm of acetoin reaching 588.67.
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