CN114459943A - Quartz crystal microbalance sensor and preparation method thereof - Google Patents
Quartz crystal microbalance sensor and preparation method thereof Download PDFInfo
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- 238000003380 quartz crystal microbalance Methods 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000000243 solution Substances 0.000 claims abstract description 69
- 239000002114 nanocomposite Substances 0.000 claims abstract description 56
- 239000013078 crystal Substances 0.000 claims abstract description 45
- 238000004140 cleaning Methods 0.000 claims abstract description 35
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 25
- 239000012528 membrane Substances 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 52
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 29
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 18
- 238000005119 centrifugation Methods 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 10
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 230000003068 static effect Effects 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- PZUPAGRIHCRVKN-UHFFFAOYSA-N 5-[5-[3,4-dihydroxy-6-[(3,4,5-trihydroxyoxan-2-yl)oxymethyl]-5-[3,4,5-trihydroxy-6-[(3,4,5-trihydroxyoxan-2-yl)oxymethyl]oxan-2-yl]oxyoxan-2-yl]oxy-3,4-dihydroxy-6-[(3,4,5-trihydroxyoxan-2-yl)oxymethyl]oxan-2-yl]oxy-6-(hydroxymethyl)oxane-2,3,4-triol Chemical compound OCC1OC(O)C(O)C(O)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(COC4C(C(O)C(O)CO4)O)O3)O)C(COC3C(C(O)C(O)CO3)O)O2)O)C(COC2C(C(O)C(O)CO2)O)O1 PZUPAGRIHCRVKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 230000004043 responsiveness Effects 0.000 abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 239000010936 titanium Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 229960004011 methenamine Drugs 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 230000002035 prolonged effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01G—WEIGHING
- G01G3/00—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances
- G01G3/12—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances wherein the weighing element is in the form of a solid body stressed by pressure or tension during weighing
- G01G3/16—Weighing apparatus characterised by the use of elastically-deformable members, e.g. spring balances wherein the weighing element is in the form of a solid body stressed by pressure or tension during weighing measuring variations of frequency of oscillations of the body
Abstract
The invention relates to a quartz crystal microbalance sensor and a preparation method thereof, wherein the preparation method comprises the following steps: s1, immersing the crystal oscillator electrode into a MnO solution and taking out, repeating for 3-4 times, drying and annealing to obtain an electrode coated with MnO seeds; s2, disposing Mn (NO)3)2Immersing the electrode coated with the MnO seed into the mixed solution to prepare an electrode coated with the MnO nano composite membrane; s3, dissolving titanium dioxide powder in deionized water, performing ultrasonic dispersion treatment, and centrifuging to remove insoluble particulate matters to obtain a suspension containing titanium dioxide; s4, immersing the electrode coated with the MnO nano composite membrane into titanium dioxideDrying at room temperature to obtain the modified MnO/TiO2An electrode of a nanocomposite film. According to the technical scheme, the sensor with high responsiveness, high sensitivity and high stability is obtained; the self-cleaning coating can be modified on the surface of the crystal oscillator electrode, and self-cleaning can be realized.
Description
Technical Field
The invention relates to the technical field of sensor detection, in particular to a quartz crystal microbalance sensor and a preparation method thereof.
Background
The Quartz Crystal Microbalance (QCM) as a sensor based on mass change has the advantages of low cost, simple operation, good specificity, high sensitivity and the like, and is widely applied to the fields of chemistry, physics, surface science, biomedicine and the like. In liquid phase detection, whether the electrode surface of the QCM crystal oscillator is clean or not has great influence on the detection result. At present, the electrode is cleaned by soaking the electrode in cleaning liquid, and a plurality of cleaning liquids are usually corrosive, so that the electrode detection performance of the QCM crystal oscillator is greatly influenced, and the service life is greatly shortened.
Disclosure of Invention
The invention aims to provide a preparation method of a quartz crystal microbalance sensor, which is used for obtaining a sensor with high responsiveness, high sensitivity and high stability; the self-cleaning coating can be modified on the surface of the crystal oscillator electrode in the quartz crystal microbalance sensor, self-cleaning can be realized without putting the crystal oscillator electrode into cleaning liquid for soaking, and the service life of the crystal oscillator electrode can be effectively prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a quartz crystal microbalance sensor, wherein the quartz crystal microbalance sensor comprises a crystal oscillator, and the preparation method comprises the following steps:
s1, immersing the crystal oscillator electrode into MnO solution and taking out, repeating for 3-4 times, drying and annealing to obtain an electrode coated with MnO seeds;
s2, preparing Mn (NO)3)2Immersing the electrode coated with MnO seeds in the mixed solution of hexamethylenetetramine and cyclic heptasaccharide to prepare the electrode coated with the MnO nano composite film;
s3, dissolving titanium dioxide P25 powder in deionized water, performing ultrasonic dispersion treatment, and centrifuging to remove insoluble particulate matters to obtain a suspension containing titanium dioxide P25;
s4, immersing the electrode coated with the MnO nano composite membrane into the suspension containing titanium dioxide P25, drying at room temperature to obtain the MnO/TiO modified2An electrode of a nanocomposite film.
Preferably, step S1 includes: immersing the electrode of the crystal oscillator into MnO solution, taking out, repeating for 3-4 times, and drying; and then annealing at the temperature of 260-280 ℃ for 0.5-1 h, and then annealing at the temperature of 460-490 ℃ for 0.5-1 h to prepare the electrode coated with the MnO seeds.
Preferably, step S2 includes: configuration 0.03E0.045mol/L Mn(NO3)20.03-0.045 mol/L hexamethylenetetramine and 3-5 g/L cycloheptasaccharide are mixed to obtain a mixed solution, and the electrode coated with the MnO seeds is immersed in the mixed solution to obtain the electrode coated with the MnO nano composite membrane.
Preferably, the ultrasonic dispersion time in step S3 is 15min, the centrifugation speed is 1500rpm, and the centrifugation time is 20 min.
Preferably, the immersion time in step S1 is 3min, the take-out speed is 3cm/min, and the drying time is 8 min.
Preferably, before step S1, the preparation method further includes preparing a MnO solution, the steps being as follows:
weighing Mn (CH) in the same amount3COO)2·2H2O and HO (CH)2)2NH2And respectively dissolved in equal amounts of C4H10O2In the (III), uniformly stirring to obtain HO (CH)2)2NH2Solution with Mn (CH)3COO)2·2H2O solution;
the obtained Mn (CH)3COO)2·2H2O solution was added slowly to HO (CH)2)2NH2Stirring the solution uniformly to prepare MnO gel; then adding polyethylene glycol to prepare MnO solution, and statically aging for later use.
Preferably, 0.06-0.09 mol of Mn (CH) is weighed3COO)2·2H2O and 0.06-0.09 mol of HO (CH)2)2NH2And dissolved in 60ul of C respectively4H10O2Stirring to obtain HO (CH)2)2NH2Solution with Mn (CH)3COO)2·2H2O solution; the obtained Mn (CH)3COO)2·2H2O solution was added slowly to HO (CH)2)2NH2Stirring the solution uniformly to prepare MnO gel; and then adding 0.3-0.6 g of polyethylene glycol to prepare a MnO solution, and statically aging for later use.
Preferably, HO (CH) is prepared2)2NH2Solution with Mn (CH)3COO)2·2H2In the step of O solution, the stirring temperature is 70 ℃, and the stirring time is 25 min; in the step of preparing MnO gel, the stirring temperature is 70 ℃, the stirring time is 1.5h, and the static aging time is 20 h.
The invention also provides a quartz crystal microbalance sensor which is prepared by applying the preparation method; the quartz crystal microbalance sensor comprises a crystal oscillator, wherein a self-cleaning coating is modified on the surface of an electrode of the crystal oscillator and comprises MnO/TiO2A nanocomposite film.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the quartz crystal microbalance sensor, MnO is used as a seed layer of a crystal oscillator to prepare the electrode coated with the MnO nano composite film, and the electrode coated with the MnO nano composite film is immersed in a suspension containing titanium dioxide to finally prepare the sensor modified with MnO/TiO2The sensor with high responsiveness, high sensitivity and high stability is obtained by using the electrode of the nano composite film; in addition, MnO/TiO is modified on the surface of the crystal oscillator electrode2Nanocomposite membrane electrode based on MnO/TiO2Self-cleaning is realized by the excellent hydrophobicity of the nano composite film and the self-cleaning performance under ultraviolet irradiation, a crystal oscillator electrode does not need to be soaked into cleaning liquid for cleaning, and the service life of the nano composite film can be prolonged while accurate measurement is facilitated.
Detailed Description
In the following, for a better understanding of the present invention, the contents of the present invention will be further described with reference to some examples. The various embodiments may be combined with each other to form other embodiments not shown in the following description.
The invention provides a preparation method of a quartz crystal microbalance sensor, which comprises the following steps:
s1, immersing the crystal oscillator electrode into MnO solution and taking out, repeating for 3-4 times, drying and annealing to obtain an electrode coated with MnO seeds;
s2, preparing Mn (NO)3)2A mixed solution of hexamethylene tetramine and cyclo heptasaccharide,immersing the electrode coated with the MnO seed into the mixed solution to prepare an electrode coated with the MnO nano composite film;
s3, dissolving titanium dioxide P25 powder in deionized water, performing ultrasonic dispersion treatment, and centrifuging to remove insoluble particulate matters to obtain a suspension containing titanium dioxide P25;
s4, immersing the electrode coated with the MnO nano composite membrane into the suspension containing titanium dioxide P25, drying at room temperature to obtain the MnO/TiO modified2An electrode of a nanocomposite film.
It can be understood that MnO is adopted as a seed layer of the crystal oscillator to prepare the electrode coated with the MnO nano composite film, and then the electrode coated with the MnO nano composite film is immersed into the suspension containing titanium dioxide to finally prepare the MnO/TiO modified2The sensor with high responsiveness, high sensitivity and high stability is obtained by using the electrode of the nano composite film; in addition, MnO/TiO is modified on the surface of the crystal oscillator electrode2Nanocomposite membrane electrode based on MnO/TiO2Self-cleaning is realized by the excellent hydrophobicity of the nano composite film and the self-cleaning performance under ultraviolet irradiation, a crystal oscillator electrode does not need to be soaked into cleaning liquid for cleaning, and the service life of the nano composite film can be prolonged while accurate measurement is facilitated.
The self-cleaning process of the MnO/TiO2 nano composite film can be briefly described as follows: under the irradiation of ultraviolet light, MnO and TiO2 in the MnO/TiO2 nano composite film absorb photons, electrons in a valence band are excited to a conduction band, and an electron-hole pair is generated; the electron-hole pairs migrate to the surface of the MnO/TiO2 nano composite film to participate in redox reaction, so that organic pollutants on the surface of the MnO/TiO2 nano composite film can be degraded, and the aim of self-cleaning is fulfilled.
Specifically, step S1 includes: immersing the electrode of the crystal oscillator into MnO solution for 3min, taking out, repeating for 3-4 times at the taking-out speed of 3cm/min, and drying for 8 min; and then annealing at the temperature of 260-280 ℃ for 0.5-1 h, and then annealing at the temperature of 460-490 ℃ for 0.5-1 h to prepare the electrode coated with the MnO seeds.
Step S2 includes: 0.03 to 0.045mol/LMn (NO) is disposed3)20.03 to 0.045mol/L hexamethyleneAnd mixing tetramine and 3-5 g/L cycloheptasaccharide to obtain a mixed solution, and immersing the electrode coated with the MnO seeds into the mixed solution to obtain the electrode coated with the MnO nano composite membrane.
The ultrasonic dispersion time in step S3 was 15min, the centrifugation speed was 1500rpm, and the centrifugation time was 20 min.
In one embodiment, to prepare the MnO solution, before step S1, the preparation method further includes the steps of:
weighing 0.06-0.09 mol of Mn (CH)3COO)2·2H2O and 0.06-0.09 mol of HO (CH)2)2NH2And respectively dissolved in 60ulC4H10O2In the (III), uniformly stirring to obtain HO (CH)2)2NH2Solution with Mn (CH)3COO)2·2H2O solution, wherein the stirring temperature is 70 ℃, and the stirring time is 25 min;
the obtained Mn (CH)3COO)2·2H2O solution was added slowly to HO (CH)2)2NH2Uniformly stirring the solution to prepare MnO gel, wherein the stirring temperature is 70 ℃, and the stirring time is 1.5 h; and then adding 0.3-0.6 g of polyethylene glycol to prepare a MnO solution, and statically aging for later use, wherein the static aging time is 20 hours.
The invention also provides a quartz crystal microbalance sensor which is prepared by applying the preparation method; the quartz crystal microbalance sensor comprises a crystal oscillator, wherein a self-cleaning coating is modified on the surface of an electrode of the crystal oscillator and comprises MnO/TiO2Nanocomposite film by MnO/TiO2Self-cleaning is realized by the excellent hydrophobicity of the nano composite film and the self-cleaning performance under ultraviolet irradiation, a crystal oscillator electrode does not need to be soaked into cleaning liquid for cleaning, and the service life of the nano composite film can be prolonged while accurate measurement is facilitated.
Example one
The quartz crystal microbalance sensor provided by the embodiment comprises a crystal oscillator, wherein the surface of an electrode of the crystal oscillator is modified with a self-cleaning coating, and the self-cleaning coating is MnO/TiO2A nanocomposite film.
The preparation method of the quartz crystal microbalance sensor comprises the following steps:
0.06mol of Mn (CH) is weighed3COO)2·2H2O and 0.06mol of HO (CH)2)2NH2And respectively dissolved in 60ulC4H10O2In the (III), uniformly stirring to obtain HO (CH)2)2NH2Solution with Mn (CH)3COO)2·2H2O solution, wherein the stirring temperature is 70 ℃, and the stirring time is 25 min;
the obtained Mn (CH)3COO)2·2H2O solution was added slowly to HO (CH)2)2NH2Uniformly stirring the solution to prepare MnO gel, wherein the stirring temperature is 70 ℃, and the stirring time is 1.5 h; then adding 0.3g of polyethylene glycol to prepare MnO solution, and statically aging for later use, wherein the static aging time is 20 hours;
immersing the electrode of the crystal oscillator into MnO solution, taking out, repeating for 3 times, and drying for 10 min; then annealing at 230 ℃ for 0.3h, then annealing at 430 ℃ for 0.8h and annealing to obtain an electrode coated with MnO seeds;
configuration of 0.03mol/LMn (NO)3)2Soaking the electrode coated with MnO seeds in the mixed solution of 0.03mol/L hexamethylenetetramine and 3g/L cycloheptasaccharide for 4 hours at the reaction temperature of 85 ℃ to prepare the electrode coated with the MnO nano composite membrane;
dissolving titanium dioxide P25 powder in deionized water, performing ultrasonic dispersion treatment for 15min, centrifuging to remove insoluble particulate matters, wherein the centrifugation speed is 1500rpm, and the centrifugation time is 20min to obtain a suspension containing titanium dioxide P25;
immersing the prepared electrode coated with the MnO nano composite membrane into a suspension containing titanium dioxide P25, and drying at room temperature to prepare the modified MnO/TiO2An electrode of a nanocomposite film; wherein the immersion time is 30min, the reaction temperature is 90 ℃, the taking-out speed is 2cm/min, and the drying time is 24 hours.
Example two
The embodiment provides a stoneThe quartz crystal microbalance sensor comprises a crystal oscillator, wherein the surface of an electrode of the crystal oscillator is modified with a self-cleaning coating which is MnO/TiO2A nanocomposite film.
The preparation method of the quartz crystal microbalance sensor comprises the following steps:
0.09mol of Mn (CH) is weighed3COO)2·2H2O and 0.09mol of HO (CH)2)2NH2And respectively dissolved in 60ulC4H10O2In the (III), uniformly stirring to obtain HO (CH)2)2NH2Solution with Mn (CH)3COO)2·2H2O solution, wherein the stirring temperature is 70 ℃, and the stirring time is 25 min;
the obtained Mn (CH)3COO)2·2H2O solution was added slowly to HO (CH)2)2NH2Uniformly stirring the solution to prepare MnO gel, wherein the stirring temperature is 70 ℃, and the stirring time is 1.5 h; then adding 0.6g of polyethylene glycol to prepare MnO solution, and statically aging for later use, wherein the static aging time is 20 hours;
immersing the electrode of the crystal oscillator into MnO solution, taking out, repeating for 4 times, and drying for 10 min; then annealing at 230 ℃ for 1.3h, then annealing at 430 ℃ for 2h, and annealing to obtain an electrode coated with MnO seeds;
0.045mol/LMn (NO) is configured3)20.045mol/L hexamethylenetetramine and 5g/L cycloheptasaccharide, and immersing the electrode coated with the MnO seeds in the mixed solution for 4 hours at the reaction temperature of 85 ℃ to prepare the electrode coated with the MnO nano composite membrane;
dissolving titanium dioxide P25 powder in deionized water, performing ultrasonic dispersion treatment for 15min, centrifuging to remove insoluble particulate matters, wherein the centrifugation speed is 1500rpm, and the centrifugation time is 20min to obtain a suspension containing titanium dioxide P25;
immersing the prepared electrode coated with the MnO nano composite membrane into a suspension containing titanium dioxide P25, and drying at room temperature to prepare the modified MnO/TiO2An electrode of a nanocomposite film; wherein the immersion time is 30min, the reaction temperature is 90 deg.C, and collectingThe discharge speed was 2cm/min and the drying time was 24 hours.
EXAMPLE III
The quartz crystal microbalance sensor provided by the embodiment comprises a crystal oscillator, wherein the surface of an electrode of the crystal oscillator is modified with a self-cleaning coating, and the self-cleaning coating is MnO/TiO2A nanocomposite film.
The preparation method of the quartz crystal microbalance sensor comprises the following steps:
0.07mol of Mn (CH) is weighed3COO)2·2H2O and 0.07mol of HO (CH)2)2NH2And respectively dissolved in 60ulC4H10O2In the above-mentioned step, uniformly stirring them to obtain HO (CH)2)2NH2Solution with Mn (CH)3COO)2·2H2O solution, wherein the stirring temperature is 70 ℃, and the stirring time is 25 min;
the obtained Mn (CH)3COO)2·2H2O solution was added slowly to HO (CH)2)2NH2Uniformly stirring the solution to prepare MnO gel, wherein the stirring temperature is 70 ℃, and the stirring time is 1.5 h; then adding 0.5g of polyethylene glycol to prepare MnO solution, and statically aging for later use, wherein the static aging time is 20 hours;
immersing the electrode of the crystal oscillator into MnO solution, taking out, repeating for 4 times, and drying for 10 min; then annealing at 230 ℃ for 01h, then annealing at 430 ℃ for 1.5h and annealing to prepare an electrode coated with MnO seeds;
configuration of 0.04mol/LMn (NO)3)2Immersing the electrode coated with MnO seeds in the mixed solution of 0.04mol/L hexamethylenetetramine and 4g/L cycloheptasaccharide for 4 hours at the reaction temperature of 85 ℃ to prepare the electrode coated with the MnO nano composite membrane;
dissolving titanium dioxide P25 powder in deionized water, performing ultrasonic dispersion treatment for 15min, centrifuging to remove insoluble particulate matters, wherein the centrifugation speed is 1500rpm, and the centrifugation time is 20min to obtain a suspension containing titanium dioxide P25;
immersing the prepared electrode coated with MnO nano composite film into the dioxygen-containingDrying the titanium oxide P25 suspension at room temperature to obtain the modified MnO/TiO2An electrode of a nanocomposite film; wherein the immersion time is 30min, the reaction temperature is 90 ℃, the taking-out speed is 2cm/min, and the drying time is 24 hours.
Comparative example 1
The quartz crystal microbalance sensor comprises a crystal oscillator, wherein the electrode surface of the crystal oscillator is modified with a self-cleaning coating which is MnO/TiO2A nanocomposite film.
The preparation method of the quartz crystal microbalance sensor comprises the following steps:
0.04mol of Mn (CH) is weighed3COO)2·2H2O and 0.04mol of HO (CH)2)2NH2And respectively dissolved in 60ulC4H10O2In the (III), uniformly stirring to obtain HO (CH)2)2NH2Solution with Mn (CH)3COO)2·2H2O solution, wherein the stirring temperature is 70 ℃, and the stirring time is 25 min;
the obtained Mn (CH)3COO)2·2H2O solution was added slowly to HO (CH)2)2NH2Uniformly stirring the solution to prepare MnO gel, wherein the stirring temperature is 70 ℃, and the stirring time is 1.5 h; then adding 0.5g of polyethylene glycol to prepare MnO solution, and statically aging for later use, wherein the static aging time is 20 hours;
immersing the electrode of the crystal oscillator into MnO solution, taking out, repeating for 4 times, and drying for 10 min; then annealing at 230 ℃ for 01h, then annealing at 430 ℃ for 1.5h and annealing to prepare an electrode coated with MnO seeds;
configuration of 0.01mol/LMn (NO)3)20.01mol/L of hexamethylenetetramine and 1g/L of cycloheptasaccharide, and immersing the electrode coated with the MnO seeds in the mixed solution for 4 hours at the reaction temperature of 85 ℃ to prepare the electrode coated with the MnO nano composite membrane;
dissolving titanium dioxide P25 powder in deionized water, performing ultrasonic dispersion treatment for 15min, centrifuging to remove insoluble particulate matters, wherein the centrifugation speed is 1500rpm, and the centrifugation time is 20min to obtain a suspension containing titanium dioxide P25;
immersing the prepared electrode coated with the MnO nano composite membrane into a suspension containing titanium dioxide P25, and drying at room temperature to prepare the modified MnO/TiO2An electrode of a nanocomposite film; wherein the immersion time is 30min, the reaction temperature is 90 ℃, the taking-out speed is 2cm/min, and the drying time is 24 hours.
Comparative example 2
The quartz crystal microbalance sensor comprises a crystal oscillator, wherein the electrode surface of the crystal oscillator is modified with a self-cleaning coating which is MnO/TiO2A nanocomposite film.
The preparation method of the quartz crystal microbalance sensor comprises the following steps:
0.15mol of Mn (CH) is weighed3COO)2·2H2O and 0.15mol of HO (CH)2)2NH2And respectively dissolved in 60ulC4H10O2In the (III), uniformly stirring to obtain HO (CH)2)2NH2Solution with Mn (CH)3COO)2·2H2O solution, wherein the stirring temperature is 70 ℃, and the stirring time is 25 min;
the obtained Mn (CH)3COO)2·2H2O solution was added slowly to HO (CH)2)2NH2Uniformly stirring the solution to prepare MnO gel, wherein the stirring temperature is 70 ℃, and the stirring time is 1.5 h; then adding 0.5g of polyethylene glycol to prepare MnO solution, and statically aging for later use, wherein the static aging time is 20 hours;
immersing the electrode of the crystal oscillator into MnO solution, taking out, repeating for 4 times, and drying for 10 min; then annealing at 230 ℃ for 01h, then annealing at 430 ℃ for 1.5h and annealing to prepare an electrode coated with MnO seeds;
configuration of 0.06mol/LMn (NO)3)20.06mol/L hexamethylenetetramine and 7g/L cycloheptasaccharide, and immersing the electrode coated with the MnO seeds in the mixed solution for 4 hours at the reaction temperature of 85 ℃ to prepare the electrode coated with the MnO nano composite membrane;
dissolving titanium dioxide P25 powder in deionized water, performing ultrasonic dispersion treatment for 15min, centrifuging to remove insoluble particulate matters, wherein the centrifugation speed is 1500rpm, and the centrifugation time is 20min to obtain a suspension containing titanium dioxide P25;
immersing the prepared electrode coated with the MnO nano composite membrane into a suspension containing titanium dioxide P25, and drying at room temperature to prepare the modified MnO/TiO2An electrode of a nanocomposite film; wherein the immersion time is 30min, the reaction temperature is 90 ℃, the taking-out speed is 2cm/min, and the drying time is 24 hours.
The quartz crystal microbalance sensors prepared in examples 1 to 3 and comparative examples 1 to 2 above were tested, respectively, and the test results are shown in the following table:
| test example | Responsiveness of | Sensitivity of the probe | Stability of | Self-cleaning performance | Service life |
| Example 1 | Is higher than | Is higher than | Is higher than | Is preferably used | Is longer |
| Example 2 | Is higher than | Is higher than | Is higher than | Is preferably used | Is longer |
| Example 3 | Is higher than | Is higher than | Is higher than | Is better | Is longer |
| Comparative example 1 | Is poor | Heavy weight | Is poor | Is poor | Is shorter |
| Comparative example 2 | Is poor | Heavy weight | Is poor | Is poor | Is shorter |
As can be seen from the above test results, regardless of whether comparative example was compared, or compared to comparative example 2; the quartz crystal microbalance sensor obtained by the preparation method of the quartz crystal microbalance sensor provided in the embodiments 1 to 3 of the present application has a sensor with high responsiveness, high sensitivity and high stability, and meanwhile, since the surface of the crystal oscillator electrode in the quartz crystal microbalance sensor is modified with the self-cleaning coating, the self-cleaning can be realized without putting the crystal oscillator electrode into the cleaning solution for soaking, and the service life of the quartz crystal microbalance sensor can be effectively prolonged.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (9)
1. A preparation method of a quartz crystal microbalance sensor is characterized in that the quartz crystal microbalance sensor comprises a crystal oscillator, and the preparation method comprises the following steps:
s1, immersing the crystal oscillator electrode into MnO solution and taking out, repeating for 3-4 times, drying and annealing to obtain an electrode coated with MnO seeds;
s2, preparing Mn (NO)3)2Immersing the electrode coated with MnO seeds in the mixed solution of hexamethylenetetramine and cyclic heptasaccharide to prepare the electrode coated with the MnO nano composite film;
s3, dissolving titanium dioxide P25 powder in deionized water, performing ultrasonic dispersion treatment, and centrifuging to remove insoluble particulate matters to obtain a suspension containing titanium dioxide P25;
s4, immersing the electrode coated with the MnO nano composite membrane into the suspension containing titanium dioxide P25, drying at room temperature to obtain the MnO/TiO modified2An electrode of a nanocomposite film.
2. The method for manufacturing a quartz crystal microbalance sensor according to claim 1, wherein the step S1 includes: immersing the electrode of the crystal oscillator into MnO solution, taking out, repeating for 3-4 times, and drying; and then annealing at the temperature of 260-280 ℃ for 0.5-1 h, and then annealing at the temperature of 460-490 ℃ for 0.5-1 h to prepare the electrode coated with the MnO seeds.
3. The method for manufacturing a quartz crystal microbalance sensor according to claim 1, wherein the step S2 includes: the amount of Mn (NO) is 0.03-0.045 mol/L3)2、0.03～0.0And mixing 45mol/L hexamethylenetetramine and 3-5 g/L cycloheptasaccharide to obtain a mixed solution, and immersing the electrode coated with the MnO seeds into the mixed solution to obtain the electrode coated with the MnO nano composite membrane.
4. The method of claim 1, wherein the ultrasonic dispersion time in step S3 is 15min, the centrifugation speed is 1500rpm, and the centrifugation time is 20 min.
5. The method according to claim 1, wherein the immersion time in step S1 is 3min, the taking-out speed is 3cm/min, and the drying time is 8 min.
6. The method of claim 1, wherein prior to step S1, the method further comprises preparing a MnO solution comprising the steps of:
weighing Mn (CH) in the same amount3COO)2·2H2O and HO (CH)2)2NH2And respectively dissolved in equal amounts of C4H10O2In the above-mentioned step, uniformly stirring them to obtain HO (CH)2)2NH2Solution with Mn (CH)3COO)2·2H2O solution;
the obtained Mn (CH)3COO)2·2H2O solution was added slowly to HO (CH)2)2NH2Stirring the solution uniformly to prepare MnO gel; then adding polyethylene glycol to prepare MnO solution, and statically aging for later use.
7. The method according to claim 6, wherein 0.06-0.09 mol of Mn (CH) is weighed3COO)2·2H2O and 0.06-0.09 mol of HO (CH)2)2NH2And dissolved in 60ul of C respectively4H10O2Stirring to obtain HO (CH)2)2NH2Solution with Mn (CH)3COO)2·2H2O solution; the obtained Mn (CH)3COO)2·2H2Slow release of O solutionSlow addition to HO (CH)2)2NH2Stirring the solution uniformly to prepare MnO gel; and then adding 0.3-0.6 g of polyethylene glycol to prepare a MnO solution, and statically aging for later use.
8. The method of claim 6, wherein HO (CH) is produced2)2NH2Solution with Mn (CH)3COO)2·2H2In the step of O solution, the stirring temperature is 70 ℃, and the stirring time is 25 min; in the step of preparing MnO gel, the stirring temperature is 70 ℃, the stirring time is 1.5h, and the static aging time is 20 h.
9. A quartz crystal microbalance sensor, characterized by being produced by the production method according to any one of claims 1 to 8; the quartz crystal microbalance sensor comprises a crystal oscillator, wherein a self-cleaning coating is modified on the surface of an electrode of the crystal oscillator and comprises MnO/TiO2A nanocomposite film.
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| CN103372379A (en) * | 2013-07-14 | 2013-10-30 | 浙江大学 | Preparation method of molecular sieve composite membrane by taking metallic oxide as carrier |
| CN105092646A (en) * | 2015-08-19 | 2015-11-25 | 电子科技大学 | Graphene/metal oxide composite film gas sensor and preparation method |
| CN112858471A (en) * | 2021-01-07 | 2021-05-28 | 杭州诺蒙微晶生物科技有限公司 | Quartz crystal microbalance sensor, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103372379A (en) * | 2013-07-14 | 2013-10-30 | 浙江大学 | Preparation method of molecular sieve composite membrane by taking metallic oxide as carrier |
| CN105092646A (en) * | 2015-08-19 | 2015-11-25 | 电子科技大学 | Graphene/metal oxide composite film gas sensor and preparation method |
| CN112858471A (en) * | 2021-01-07 | 2021-05-28 | 杭州诺蒙微晶生物科技有限公司 | Quartz crystal microbalance sensor, preparation method and application thereof |
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