Ag @ Pt nanocrystal and preparation method thereof, and formaldehyde sensor based on Ag @ Pt nanocrystal and preparation method and application thereof
阅读说明：本技术 Ag@Pt纳米晶及制备方法、基于Ag@Pt纳米晶的甲醛传感器及制备方法和应用 (Ag @ Pt nanocrystal and preparation method thereof, and formaldehyde sensor based on Ag @ Pt nanocrystal and preparation method and application thereof ) 是由 郑丹 许鹏程 徐东升 孙辉文 丁培 于 2019-10-31 设计创作，主要内容包括：本发明涉及一种Ag@Pt纳米晶及制备方法、基于Ag@Pt纳米晶的甲醛传感器及制备方法和应用,该甲醛传感器包括有金属氧化物敏感材料,金属氧化物敏感材料的表面负载有Ag@Pt纳米晶颗粒。与现有技术相比,本发明能够增强甲醛传感器检测甲醛的灵敏度,实现协同催化作用,其制备方法简单成熟、易于操作、价格低廉,用途先进、具有现实的应用意义,对有毒有害气体的检测等有着积极的意义。(The invention relates to an Ag @ Pt nanocrystal and a preparation method thereof, a formaldehyde sensor based on the Ag @ Pt nanocrystal and a preparation method and application thereof. Compared with the prior art, the formaldehyde sensor disclosed by the invention can enhance the sensitivity of detecting formaldehyde by the formaldehyde sensor and realize a synergistic catalytic effect, and the preparation method is simple and mature, easy to operate, low in price, advanced in application, practical in application significance and positive in detection of toxic and harmful gases and the like.)
1. A preparation method of Ag @ Pt nanocrystal is characterized by comprising the following steps:
(1) preheating oleylamine, and then adding platinum chloride and silver nitrate for heat preservation to obtain oleylamine system solution;
(2) and (2) heating the oleylamine system solution obtained in the step (1), cooling, and centrifugally cleaning to obtain the Ag @ Pt nanocrystal.
2. The method for preparing Ag @ Pt nanocrystals according to claim 1, wherein the step (1) comprises any one or more of the following conditions:
(1-1) the preheating time of the oleylamine is 10-15 min;
(1-2) the preheating temperature of the oleylamine is 110-130 ℃;
(1-3) the ratio of the volume of the added oleylamine to the total mole number of the added platinum chloride and silver nitrate is 9-11 mL:0.2 mmol;
(1-5) the molar ratio of the silver nitrate to the platinum chloride is 1: 4-5: 1;
(1-6) the heat preservation time is 10-15 min.
3. The method for preparing Ag @ Pt nanocrystals according to claim 1, wherein the step (2) comprises any one or more of the following conditions:
(2-1) the temperature raising program is: heating to 155-;
(2-2) the conditions of the centrifugal washing are as follows: the centrifugation rate is 10000-;
(2-3) the centrifugal cleaning is performed for 2-4 times.
4. Ag @ Pt nanocrystal characterized by being obtained by the preparation method according to any one of claims 1 to 3.
5. The Ag @ Pt nanocrystal of claim 4, wherein the Ag @ Pt nanocrystal has a pentagram-shaped micro morphology, and the atomic ratio of Ag element to Pt element in the Ag @ Pt nanocrystal is 1:4 to 5: 1.
6. A formaldehyde sensor based on Ag @ Pt nanocrystals comprises a metal oxide sensitive material, and is characterized in that the surface of the metal oxide sensitive material is loaded with the Ag @ Pt nanocrystal particles as in any one of claims 4 to 5.
7. The Ag @ Pt nanocrystal-based formaldehyde sensor according to claim 6, wherein the metal oxide sensitive material is selected from ZnO and SnO2、In2O3And WO3Any one of the above; the Ag @ Pt nanocrystal accounts for 0.1-1 wt% of the metal oxide sensitive material.
8. The method for preparing the Ag @ Pt nanocrystal-based formaldehyde sensor according to claim 6 or 7, comprising the steps of:
(A) dispersing the Ag @ Pt nanocrystal into a solvent to obtain an Ag @ Pt nanocrystal dispersion solution;
(B) mixing the Ag @ Pt nanocrystal dispersion solution obtained in the step (A) with a metal oxide sensitive material and then carrying out ultrasonic treatment to obtain a formaldehyde sensitive material modified by Ag @ Pt nanocrystals;
(C) and (C) coating the formaldehyde sensitive material obtained in the step (B) on comb electrodes of a sensor chip to obtain the Ag @ Pt nanocrystal-based formaldehyde sensor.
9. The method of making a Ag @ Pt nanocrystal-based formaldehyde sensor as claimed in claim 8, comprising any one or more of the following conditions:
(3-1) in the step (A), the ratio of the added mass of the Ag @ Pt nanocrystal to the added volume of the solvent is 0.012-0.030 g: 5-60 mL;
(3-2) in the step (A), the solvent is selected from one of n-hexane, ethanol and toluene;
(3-3) in the step (B), the ratio of the volume of the Ag @ Pt nanocrystal dispersion solution to the mass of the metal oxide sensitive material is 1-2 mL: 0.02-0.15 g;
(3-4) in the step (B), the mixing is stirring and mixing, and the mixing time is 0.5-1.5 min;
and (3-5) in the step (B), the ultrasonic time is 50-70 s.
10. Use of a Ag @ Pt nanocrystal-based formaldehyde sensor according to claim 6 or 7 in formaldehyde detection.
Technical Field
The invention belongs to the technical field of gas sensors, relates to a novel formaldehyde sensor and a preparation method thereof, and particularly relates to an Ag @ Pt nanocrystal and a preparation method thereof, a formaldehyde sensor based on the Ag @ Pt nanocrystal and a preparation method and application thereof.
Background
Formaldehyde is an important chemical product and is widely applied to industries such as food corrosion prevention, household materials, synthetic resins, rubber, leather, medicines and the like. However, formaldehyde is a typical Volatile Organic Compound (VOC) and is colorless and toxic, and the possibility of diseases such as myelogenous leukemia and the like can be obviously increased by long-term exposure to formaldehyde. Currently, various methods have been developed for the detection of formaldehyde, including spectrophotometry, chromatography, and gas sensor methods.
Since formaldehyde is toxic and widely distributed, frequent field testing is required, and thus, a high-performance portable formaldehyde sensor needs to be developed. In a traditional semiconductor type formaldehyde sensor, although a metal oxide sensitive material (such as zinc oxide) has certain sensitivity to formaldehyde, the sensitivity, selectivity and stability of the traditional semiconductor type formaldehyde sensor still cannot meet the requirement of formaldehyde detection in an actual detection environment. The system is greatly influenced by the outside world, and under the conditions of lack of regular calibration and magnitude traceability, test data are unreliable, and the system can seriously mislead the disposal of the home environment space.
Silver catalysts are often used to improve the formaldehyde sensitivity of the sensing material. But a single metallic silver catalyst is easily poisoned and thus loses activity.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an Ag @ Pt nanocrystal and a preparation method thereof, a formaldehyde sensor based on the Ag @ Pt nanocrystal and a preparation method and application of the formaldehyde sensor. The method is used for improving the efficiency and the sensitivity of formaldehyde detection.
The purpose of the invention can be realized by the following technical scheme:
one aspect of the invention provides a preparation method of Ag @ Pt nanocrystal, which comprises the following steps:
(1) preheating oleylamine, and then adding platinum chloride and silver nitrate for heat preservation to obtain oleylamine system solution;
(2) and (2) heating the oleylamine system solution obtained in the step (1), cooling, and centrifugally cleaning to obtain the Ag @ Pt nanocrystal.
Preferably, in the step (1), the preheating time of the oleylamine is 10-15 min.
Preferably, in the step (1), the preheating temperature of the oleylamine is 110-130 ℃.
Preferably, in the step (1), the ratio of the volume of the added oleylamine to the total mole number of the added platinum chloride and silver nitrate is 9-11 mL:0.2 mmol. It is further preferred that the ratio of the volume of oleylamine added to the total moles of platinum chloride and silver nitrate added is 10: 0.2.
Preferably, in the step (1), the ratio of the added mole number of the silver nitrate to the platinum chloride is 1: 4-5: 1.
Preferably, in the step (1), the heat preservation time is 10-15 min.
Specifically, in the step (1), the CAS number of the oleylamine is 112-90-3.
Specifically, in the step (1), the platinum chloride is platinum chloride powder.
Specifically, in the step (1), the silver nitrate is silver nitrate powder.
Preferably, in step (2), the temperature raising procedure is: the temperature is raised to 155-. Further preferably, the temperature raising program is: heating to 160 ℃ and preserving heat for 15-25 min, and then heating to 200 ℃ and preserving heat for 15-25 min.
Preferably, in step (2), the centrifugal washing conditions are as follows: the centrifugation rate is 10000-;
preferably, in the step (2), the number of times of centrifugal cleaning is 2-4 times.
The invention provides Ag @ Pt nanocrystalline obtained by the preparation method.
Preferably, the microscopic morphology of the Ag @ Pt nanocrystal is pentagram-shaped, and the atomic ratio of Ag element to Pt element (Ag/Pt) in the Ag @ Pt nanocrystal is 1: 4-5: 1. Further preferably, the atomic ratio of the Ag element to the Pt element (Ag/Pt) in the Ag @ Pt nanocrystal is 2: 3-5: 1. Further preferably, the atomic ratio of the Ag element to the Pt element (Ag/Pt) in the Ag @ Pt nanocrystal is 1: 1-5: 1.
The invention provides a formaldehyde sensor based on Ag @ Pt nanocrystalline, which comprises a metal oxide sensitive material, wherein Ag @ Pt nanocrystalline particles are loaded on the surface of the metal oxide sensitive material.
Preferably, the metal oxide sensitive material is selected from ZnO and SnO2、In2O3And WO3Any one of them. It is further preferred that the metal oxide sensitive material is selected from ZnO and SnO2And In2O3Any one of them. It is further preferred that the metal oxide sensitive material is ZnO.
Preferably, the Ag @ Pt nanocrystal accounts for 0.1-1 wt% of the metal oxide sensitive material.
In the invention, the Ag @ Pt nanocrystal is a sensitization material in the formaldehyde sensor.
The formaldehyde sensor is a conventionally used semiconductor type sensor. Specifically, the semiconductor sensor is a resistance semiconductor sensor, also called a metal oxide semiconductor formaldehyde sensor. The working principle is as follows: after formaldehyde is adsorbed, the formaldehyde is combined with oxygen ions in the metal oxide surface adsorption layer to release electrons, so that the carrier concentration of the metal oxide semiconductor is changed, and a certain functional relationship exists between the change value and the volume fraction of the formaldehyde. The Ag @ Pt core-shell structure nanocrystal provided by the invention is used as a sensitizing material, can increase the sensing activity of a metal oxide semiconductor, and improves the detection sensitivity and selectivity of the nanocrystal to formaldehyde molecules.
In the formaldehyde sensor, the metal oxide sensitive material is used as an electrode of the formaldehyde sensor. Specifically, the metal oxide sensitive material is used as a comb electrode material of a formaldehyde sensor chip.
The Ag @ Pt core-shell structure nanocrystalline is loaded on the surface of the metal oxide sensitive material, namely the Ag @ Pt core-shell structure nanocrystalline particles are modified on the surface of the metal oxide sensitive material.
The invention provides a preparation method of a formaldehyde sensor based on Ag @ Pt nanocrystals, which comprises the following steps:
(A) dispersing the Ag @ Pt nanocrystal into a solvent to obtain an Ag @ Pt nanocrystal dispersion solution;
(B) mixing the Ag @ Pt nanocrystal dispersion solution obtained in the step (A) with a metal oxide sensitive material and then carrying out ultrasonic treatment to obtain a formaldehyde sensitive material modified by Ag @ Pt nanocrystals;
(C) and (C) coating the formaldehyde sensitive material obtained in the step (B) on comb electrodes of a sensor chip to obtain the Ag @ Pt nanocrystal-based formaldehyde sensor.
Preferably, in the step (a), the ratio of the added mass of the Ag @ Pt nanocrystals to the added volume of the solvent is 0.012-0.030 g: 5-60 mL. Further preferably, the ratio of the added mass of the Ag @ Pt nanocrystal to the added volume of the solvent is 0.012-0.030 g: 10-50 mL.
Preferably, in the step (a), the solvent is selected from one of n-hexane, ethanol and toluene. More preferably, the solvent is n-hexane.
Preferably, in the step (B), the ratio of the volume of the Ag @ Pt nanocrystal dispersion solution to the mass of the metal oxide sensitive material is 1 to 2 mL: 0.02-0.15 g. Further preferably, the ratio of the volume of the Ag @ Pt nanocrystal dispersion solution to the mass of the metal oxide sensitive material is 1-2 mL: 0.05 to 0.10 g.
Preferably, in the step (B), the mixing is stirring mixing, and the mixing time is 0.5-1.5 min. More preferably, the mixing time is 1 min.
Preferably, in the step (B), the time of the ultrasonic treatment is 50-70 s. Further preferably, the time for the sonication is 60 s.
Preferably, in the step (B), the power of the ultrasound is 50-200W. Further preferably, the power of the ultrasound is 100W.
Preferably, in step (C), the sensor chip is a silicon chip of a formaldehyde sensor which is conventionally used. The comb teeth electrode of the sensor chip is a comb teeth electrode of a silicon chip of a formaldehyde sensor which is used conventionally.
The fifth aspect of the invention provides application of a formaldehyde sensor based on Ag @ Pt nanocrystals in formaldehyde detection.
As mentioned above, the pentagram-shaped Ag @ Pt nanocrystalline-based formaldehyde sensor and the preparation method thereof provided by the invention improve the existing formaldehyde sensor, load the pentagram-shaped Ag @ Pt core-shell structure nanocrystalline particles on the surface of a semiconductor metal oxide by adopting an ultrasonic method to obtain the pentagram-shaped Ag @ Pt core-shell structure nanocrystalline modified formaldehyde sensitive material, and further coat the sensitive material on a comb electrode of a microsensor chip to obtain the required resistance-type formaldehyde sensor. As shown in figure 1, oxygen anions on the surface of the pentagram-shaped Ag @ Pt core-shell structure nanocrystal can react with formaldehyde molecules and release electrons, and the process causes the resistance of a sensing material to be reduced, so that the detection of formaldehyde is realized. The addition of the Ag @ Pt core-shell structure sensitization material can change the adsorption state of formaldehyde molecules on the surface of the sensing material and adjust the activation energy required by the catalytic reaction. When Pt and Ag in the pentagram-shaped Ag @ Pt core-shell structure nanocrystal modified on the formaldehyde sensor are kept in a certain proportion, the response of the semiconductor metal oxide formaldehyde sensor is maximum, and the synergistic effect of Ag @ Pt is most obvious. The formaldehyde sensor can detect the formaldehyde with the lowest sensitivity reaching 120ppb, thereby enhancing the sensitivity of the formaldehyde sensor in detecting the formaldehyde.
The formaldehyde sensor based on the pentagram-shaped Ag @ Pt nanocrystal is applied to the detection of formaldehyde, wherein the pentagram-shaped Ag @ Pt core-shell structure nanocrystal modified formaldehyde sensor plays a role of a catalyst in the reaction of semiconductor metal oxide nanowires and formaldehyde. The composite structure nano material generates a new higher-level complex structure system by different functionalized nano elements through a certain assembly arrangement mode, and shows flexible and changeable synergetic catalysis in heterogeneous catalysis.
Compared with the prior art, the pentagram-shaped Ag @ Pt nanocrystal-based formaldehyde sensor provided by the invention has theoretical research significance, long-term consideration on application, simple and mature preparation, easy operation, low price, advanced application, practical application significance and positive significance for detection of toxic and harmful gases and the like.
Drawings
FIG. 1 shows scanning electron micrographs of formaldehyde sensors prepared as pentacle-shaped Ag @ Pt nanocrystalline particles/zinc oxide composites in examples 1 and 2.
FIG. 2 shows a TEM photograph of pentacle-shaped Ag @ Pt nanocrystalline particles prepared in example 1.
FIG. 3 shows a TEM micrograph of pentacooid Ag @ Pt nanocrystalline particles/zinc oxide composite prepared in example 1.
FIG. 4 is a graph showing a comparison of the responses of the formaldehyde sensor # 1 and the zinc oxide formaldehyde sensor of example 1 to detect formaldehyde.
Detailed Description
A preparation method of Ag @ Pt nanocrystal comprises the following steps:
(1) preheating oleylamine, and then adding platinum chloride and silver nitrate for heat preservation to obtain oleylamine system solution;
(2) and (2) heating the oleylamine system solution obtained in the step (1), cooling, and centrifugally cleaning to obtain the Ag @ Pt nanocrystal.
Preferably, in the step (1), the preheating time of the oleylamine is 10-15 min.
Preferably, in the step (1), the preheating temperature of the oleylamine is 110-130 ℃.
Preferably, in the step (1), the ratio of the volume of the added oleylamine to the total mole number of the added platinum chloride and silver nitrate is 9-11 mL:0.2 mmol. It is further preferred that the ratio of the volume of oleylamine added to the total moles of platinum chloride and silver nitrate added is 10: 0.2.
Preferably, in the step (1), the ratio of the added mole number of the silver nitrate to the platinum chloride is 1: 4-5: 1.
Preferably, in the step (1), the heat preservation time is 10-15 min.
Specifically, in the step (1), the CAS number of the oleylamine is 112-90-3.
Specifically, in the step (1), the platinum chloride is platinum chloride powder.
Specifically, in the step (1), the silver nitrate is silver nitrate powder.
Preferably, in step (2), the temperature raising procedure is: the temperature is raised to 155-. Further preferably, the temperature raising program is: heating to 160 ℃ and preserving heat for 15-25 min, and then heating to 200 ℃ and preserving heat for 15-25 min.
Preferably, in step (2), the centrifugal washing conditions are as follows: the centrifugation rate is 10000-;
preferably, in the step (2), the number of times of centrifugal cleaning is 2-4 times.
The Ag @ Pt nanocrystal is obtained by the preparation method.
Preferably, the microscopic morphology of the Ag @ Pt nanocrystal is pentagram-shaped, and the atomic ratio of Ag element to Pt element (Ag/Pt) in the Ag @ Pt nanocrystal is 1: 4-5: 1. Further preferably, the atomic ratio of the Ag element to the Pt element (Ag/Pt) in the Ag @ Pt nanocrystal is 2: 3-5: 1. Further preferably, the atomic ratio of the Ag element to the Pt element (Ag/Pt) in the Ag @ Pt nanocrystal is 1: 1-5: 1.
The formaldehyde sensor based on the Ag @ Pt nanocrystal comprises a metal oxide sensitive material, wherein the surface of the metal oxide sensitive material is loaded with the Ag @ Pt nanocrystal particles.
Preferably, the metal oxide sensitive material is selected from ZnO and SnO2、In2O3And WO3Any one of them. It is further preferred that the metal oxide sensitive material is selected from ZnO and SnO2And In2O3Any one of them. It is further preferred that the metal oxide sensitive material is ZnO.
Preferably, the Ag @ Pt nanocrystal accounts for 0.1-1 wt% of the metal oxide sensitive material.
In the invention, the Ag @ Pt nanocrystal is a sensitization material in the formaldehyde sensor.
The formaldehyde sensor is a conventionally used semiconductor type sensor. Specifically, the semiconductor sensor is a resistance semiconductor sensor, also called a metal oxide semiconductor formaldehyde sensor. The working principle is as follows: after formaldehyde is adsorbed, the formaldehyde is combined with oxygen ions in the metal oxide surface adsorption layer to release electrons, so that the carrier concentration of the metal oxide semiconductor is changed, and a certain functional relationship exists between the change value and the volume fraction of the formaldehyde. The Ag @ Pt core-shell structure nanocrystal provided by the invention is used as a sensitizing material, can increase the sensing activity of a metal oxide semiconductor, and improves the detection sensitivity and selectivity of the nanocrystal to formaldehyde molecules.
In the formaldehyde sensor, the metal oxide sensitive material is used as an electrode of the formaldehyde sensor. Specifically, the metal oxide sensitive material is used as a comb electrode material of a formaldehyde sensor chip.
The Ag @ Pt core-shell structure nanocrystalline is loaded on the surface of the metal oxide sensitive material, namely the Ag @ Pt core-shell structure nanocrystalline particles are modified on the surface of the metal oxide sensitive material.
The preparation method of the formaldehyde sensor based on the Ag @ Pt nanocrystal comprises the following steps:
(A) dispersing the Ag @ Pt nanocrystal into a solvent to obtain an Ag @ Pt nanocrystal dispersion solution;
(B) mixing the Ag @ Pt nanocrystal dispersion solution obtained in the step (A) with a metal oxide sensitive material and then carrying out ultrasonic treatment to obtain a formaldehyde sensitive material modified by Ag @ Pt nanocrystals;
(C) and (C) coating the formaldehyde sensitive material obtained in the step (B) on comb electrodes of a sensor chip to obtain the Ag @ Pt nanocrystal-based formaldehyde sensor.
Preferably, in the step (a), the ratio of the added mass of the Ag @ Pt nanocrystals to the added volume of the solvent is 0.012-0.030 g: 5-60 mL. Further preferably, the ratio of the added mass of the Ag @ Pt nanocrystal to the added volume of the solvent is 0.012-0.030 g: 10-50 mL.
Preferably, in the step (a), the solvent is selected from one of n-hexane, ethanol and toluene. More preferably, the solvent is n-hexane.
Preferably, in the step (B), the ratio of the volume of the Ag @ Pt nanocrystal dispersion solution to the mass of the metal oxide sensitive material is 1 to 2 mL: 0.02-0.15 g. Further preferably, the ratio of the volume of the Ag @ Pt nanocrystal dispersion solution to the mass of the metal oxide sensitive material is 1-2 mL: 0.05 to 0.10 g.
Preferably, in the step (B), the mixing is stirring mixing, and the mixing time is 0.5-1.5 min. More preferably, the mixing time is 1 min.
Preferably, in the step (B), the time of the ultrasonic treatment is 50-70 s. Further preferably, the time for the sonication is 60 s.
Preferably, in the step (B), the power of the ultrasound is 50-200W. Further preferably, the power of the ultrasound is 100W.
Preferably, in step (C), the sensor chip is a silicon chip of a formaldehyde sensor which is conventionally used. The comb teeth electrode of the sensor chip is a comb teeth electrode of a silicon chip of a formaldehyde sensor which is used conventionally.
The formaldehyde sensor based on the Ag @ Pt nanocrystal can be applied to formaldehyde detection.
The invention is described in detail below with reference to the figures and specific embodiments. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It should be understood that the processing equipment or devices not specifically mentioned in the following examples are conventional in the art; all pressure values and ranges refer to relative pressures.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.