CN113866243A - Hydrogen sensor based on MOS @ MOF, pore regulation and preparation method - Google Patents
Hydrogen sensor based on MOS @ MOF, pore regulation and preparation method Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses a hydrogen sensor based on MOS @ MOF.A noble metal particle is embedded in the pore diameter of an MOF coating layer in a particle form, so that a gas passing channel is further reduced, most other interfering gases are blocked, and the selectivity of the MOS @ MOF to hydrogen is obviously improved; meanwhile, the catalytic action of the embedded noble metal particles can reduce the activation energy of hydrogen in the reaction on the surface of the MOS and promote the reaction of hydrogen and adsorbed oxygen ions, so that the response performance of the MOS @ MOF is effectively enhanced, and the composite material hydrogen sensor with high selectivity and high sensitivity is developed. The synergistic effect of the MOF coating layer and the embedded metal particles plays a key role in improving the performance of the prepared hydrogen sensor. The active regulation and control of the pore space are further provided in a mode of regulating and controlling the shape and size of the embedded metal nanoparticles, the gas sieving performance shows the adjustable and controllable gas sensitivity selectivity of the material, and a new general idea is provided for designing MOF molecular sieve materials and MOS @ MOF gas sensors.
Description
Technical Field
The invention belongs to the field of semiconductor gas sensors, relates to a hydrogen sensor with high selectivity and high sensitivity and a preparation method thereof, and particularly relates to a hydrogen sensor based on MOS @ MOF, and a pore regulation and preparation method thereof.
Background
Hydrogen has important application in the industrial field, but because of the danger of flammability, explosiveness and the like, the high-precision real-time monitoring in the development, storage, transportation and use processes of hydrogen is very important. The hydrogen sensor based on Metal Oxide Semiconductor (MOS) is widely researched and applied due to the characteristics of high sensitivity, convenience in operation, low cost and the like, but environmental gas still causes great interference on the MOS-based sensor and influences the selective response of the sensor to hydrogen.
A Metal Organic Framework (MOF) material is a typical porous material, and the prior art CN109954481A discloses a silver-doped ZnO @ ZIF-8, wherein AgOH is doped between ZnO molecules to form AgOH-doped ZnO nanoflower intermediate products serving as cores, and the surfaces of the cores are coated with ZIF-8; although the MOF shell is coated on the surface of the inner core, the MOF porous structure is utilized to separate part of macromolecular gas, and the interference is reduced to a certain extent, hydrogen is gas with the minimum molecular weight, the pore size of the MOF is not small enough no matter what MOF is adopted at present, other gases which are not hydrogen can form interference all the time, and the selectivity to hydrogen is still limited and needs to be further improved.
Disclosure of Invention
Aiming at least one of the defects or the improvement requirements in the prior art, the invention provides a hydrogen sensor based on MOS @ MOF and a preparation method thereof, wherein MOF is coated on the surface of an MOS nanorod to prepare an MOS @ MOF composite structure, so that macromolecular interference gas in the environment can be preliminarily screened out, and the selectivity of MOS to hydrogen is enhanced; moreover, noble metal particles are embedded in the pore diameter of the MOF coating layer in a particle form, so that a gas passing channel is further reduced, most other interfering gases are blocked, and the selectivity of MOS @ MOF to hydrogen is obviously improved; meanwhile, the embedded noble metal particles can also effectively enhance the response performance of MOS @ MOF, so that a composite material hydrogen sensor with high selectivity and high sensitivity is developed.
In order to achieve the above object, according to one aspect of the present invention, there is provided a MOS @ MOF based hydrogen sensor, comprising a MOS @ MOF composite structure sensitive material, wherein the MOS of the core is a hydrogen gas sensitive material, wherein:
and constructing the metal nano-materials in the pore structures of the coating MOF in a manner that the metal nano-materials are embedded in the pore structures of the MOF, wherein the metal nano-materials are in the form of metal nano-particles.
Further preferably, the MOS is a MOS nanorod array. The oxygen ions adsorbed on the surface are combined with the hydrogen, so that the carrier concentration of the MOS is changed, and the resistance of the sensitive material is influenced. The change in resistance is specifically correlated with the volume fraction of hydrogen gas, thereby detecting hydrogen gas.
Further preferably, the MOS is ZnO, WO3、SnO2Any one of them.
Further preferably, the MOS is grown in situ on the front side of the sensor substrate.
Further preferably, the sensor substrate is Al2O3And (5) ceramic plates. The front surface of the ceramic wafer is printed with a gold electrode, the back surface of the ceramic wafer is printed with a heating electrode and a heating base material, and the heating base material comprises but is not limited to ruthenium oxide, platinum and nickel.
Further preferably, the MOS nanorod array grows on the surface of the sensor substrate in situ, namely the MOS nanorod array is printed with the gold electrode Al2O3The front surface of the ceramic plate.
Further preferably, the thickness of the MOF layer is 50-70 nm.
Further preferably, the embedded metal nanoparticles are any one of Ag, Pt, and Au.
Further preferably, the sensor substrate loaded with the sensitive material is welded to a hexagonal base for connecting the sensor substrate and the test chamber. More preferably, the hexagonal base is of a plastic structure, 6 electrode columns are uniformly distributed on the hexagonal base, and the heating electrode and the testing electrode of the sensor substrate are welded to 4 specific electrode columns respectively.
In order to achieve the above object, according to another aspect of the present invention, there is also provided a method for regulating pores of a MOS @ MOF based hydrogen sensor, wherein:
the size of pores is regulated by embedding the same metal nanoparticle in different MOFs, wherein the different MOFs have different intrinsic pore diameters, and the morphological sizes of the same metal nanoparticle are approximately the same;
alternatively, the pore size can be tailored by embedding different metal nanoparticles in the same MOF, where the different metal nanoparticles have different morphological sizes.
In order to achieve the above object, according to another aspect of the present invention, there is also provided a method for regulating pores of a MOS @ MOF based hydrogen sensor, wherein:
regardless of the MOF intrinsic pore size, and regardless of the type of metal nanoparticles, the size of the pores is regulated in a manner that regulates the size of the morphological dimensions of the metal nanoparticles embedded in the pore structure of the MOF.
In order to achieve the above object, according to another aspect of the present invention, there is also provided a method for preparing a MOS @ MOF based hydrogen sensor, comprising the steps of:
(1) coating MOF on the surface of the MOS to form a MOS @ MOF composite structure sensitive material;
(2) preprocessing a device: dissolving impurities in a cavity of the MOS @ MOF composite structure sensitive material, and drying;
(3) the method comprises the following steps of (1) enabling a metal nano material to penetrate into holes of a MOS @ MOF composite structure sensitive material in a metal ion mode;
(4) reducing metal ions into metal nanoparticles, and embedding the metal nanoparticles into holes of the MOS @ MOF composite structure sensitive material in situ;
(5) by obtaining MOS @ MOF
The hydrogen sensor is assembled by metal nanoparticles, namely MOS @ MOF composite structure sensitive materials embedded with the metal nanoparticles.
Further preferably, step (3) includes:
preparing a target metal ion source and alcohol solvent mixed solution by a heating and dissolving method, taking methanol to immerse the product obtained in the step (2), dripping the target metal ion source and alcohol solvent mixed solution under the stirring condition to avoid the accumulation of high-concentration solutes, and then continuously stirring at room temperature under the light-shielding condition to ensure that metal ions fully enter holes of the MOS @ MOF composite structure sensitive material.
Further preferably, step (4) comprises:
and (3) preparing a reducing agent in the process of waiting for permeation in the step (3), immediately dropwise adding the reducing agent after the step (3) is finished, keeping stirring for a preset time period to fully reduce metal ions, and embedding the metal ions into holes of the MOS @ MOF composite structure sensitive material in situ.
Further preferably, in the step (1), the MOS is ZnO or WO3、SnO2Any one of them.
Further preferably, in the step (3), the metal nanomaterial is any one of Ag, Pt, and Au.
In order to achieve the above object, according to another aspect of the present invention, there is also provided a method for preparing a pore-tunable hydrogen sensor based on MOS @ MOF, wherein:
in the step (3) of the preparation method of the MOS @ MOF-based hydrogen sensor, the content of metal ions permeating into the MOF holes is controlled in a mode of adjusting the concentration of the metal ions to be permeated, so that the sizes of the holes are regulated, and finally the hydrogen sensors with different hole sizes are prepared.
In order to achieve the above object, according to another aspect of the present invention, there is also provided a method for preparing a pore-tunable hydrogen sensor based on MOS @ MOF, wherein:
in the step (3) of the preparation method of the MOS @ MOF-based hydrogen sensor, the content of metal ions permeating into pores of the MOF is controlled in a manner of adjusting the permeation duration of the metal ions, so that the sizes of the pores are regulated, and finally the hydrogen sensors with different pore sizes are prepared.
In order to achieve the above object, according to another aspect of the present invention, there is also provided a method for preparing a pore-tunable hydrogen sensor based on MOS @ MOF, wherein:
in the step (3) of the preparation method of the MOS @ MOF-based hydrogen sensor, the content of the metal ions permeating into the pores of the MOF is controlled in a manner of adjusting the concentration of the metal ions to be permeated and adjusting the permeation duration of the metal ions, so that the sizes of the pores are adjusted and controlled, and finally the hydrogen sensors with different pore sizes are prepared.
The above-described preferred features may be combined with each other as long as they do not conflict with each other.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
1. according to the hydrogen sensor based on the MOS @ MOF, the surface of the hydrogen sensitive material MOS nanorod is coated with the porous MOF to prepare the MOS @ MOF composite structure, so that macromolecular interference gas in the environment can be preliminarily screened out, and the selectivity of the MOS to micromolecular hydrogen is enhanced; moreover, noble metal particles are embedded in the pore diameter of the MOF coating layer in a particle form, so that a gas passing channel is further reduced, most other interfering gases are blocked, and the selectivity of MOS @ MOF to hydrogen is obviously improved; meanwhile, the catalytic action of the embedded noble metal particles can reduce the activation energy of hydrogen in the reaction on the surface of the MOS, promote the reaction of hydrogen and adsorbed oxygen ions, and effectively enhance the response performance of the MOS @ MOF, so that the composite material hydrogen sensor with high selectivity and high sensitivity is developed.
2. The synergistic effect of the MOF coating layer and the embedded metal particles plays a key role in improving the performance of the prepared hydrogen sensor. MOS @ MOF based hydrogen sensors exhibit the highest sensitivity with a lower detection limit of up to 100ppb when the permeant ion is maintained at a certain concentration.
3. Compared with the prior art, the hydrogen sensor provided by the invention has stronger interference resistance, and shows better selectivity and higher sensitivity to hydrogen. Meanwhile, the preparation method provided by the invention does not depend on precise equipment and complex reaction conditions, the technical scheme is simple, and the raw materials are low in cost and easy to obtain.
4. The invention is in MOS @ MOF
On the basis that metal nanoparticles, namely MOF pores are embedded into the metal nanoparticles to reduce the pores and improve the selectivity, active regulation and control of the pores are further provided, and various technical means are provided, wherein one is that the sizes of the pores are regulated and controlled by embedding the same metal nanoparticles into different MOFs, wherein the different MOFs have different intrinsic pores, and the morphological sizes of the same metal nanoparticles are approximately the same; secondly, the sizes of pores are regulated by embedding different metal nanoparticles in the same MOF, wherein the different metal nanoparticles have different morphological sizes; and thirdly, regulating the size of pores in a mode of regulating the morphological size of metal nanoparticles embedded in the pore structure of the MOF, no matter how the intrinsic pore diameter of the MOF is or the type of the metal nanoparticles is, specifically, controlling the content of metal ions permeated into the pores of the MOF in a mode of regulating the concentration of metal ions to be permeated and/or regulating the permeation duration of the metal ions in the permeation process of a target metal ion source to regulate the size of the pores, and finally preparing the hydrogen sensors with different pore sizes. Therefore, the gas sieving performance of the invention shows the adjustable and controllable gas sensitivity selectivity of the material, and provides a new general idea for designing MOF molecular sieve materials and MOS @ MOF gas sensors.
Drawings
FIG. 1 is a schematic view of a process for preparing a ZnO nanorod array in example 1 of the present invention;
FIG. 2 is a schematic view showing Ag nanoparticle intercalation performed by the infiltration-reduction method in example 1 of the present invention;
FIG. 3a is a ZnO nanorod array prepared in example 1 of the present invention;
FIG. 3b is a SEM photograph of ZnO @ ZIF-71 prepared in example 1 of the present invention;
FIG. 4 is a TEM photograph of ZnO @ ZIF-71 prepared in example 1 of the present invention;
FIG. 5a is a transmission electron micrograph of ZnO @ ZIF-71Ag, at 10nm scale, prepared in example 1 of the present invention.
FIG. 5b is a 5nm stage TEM image of ZnO @ ZIF-71Ag prepared in example 1 of the present invention.
FIG. 6 is an XRD pattern of ZnO @ ZIF-71Ag prepared in example 1 of the present invention before and after the intercalation of Ag nanoparticles.
FIG. 7 is a graph showing the selective response of ZnO @ ZIF-71Ag and ZnO @ ZIF-71 prepared in example 1 of the present invention to different gases.
FIG. 8 shows the response of ZnO @ ZIF-71Ag prepared in example 1 of the present invention to 0.1-2 ppm hydrogen.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other. The present invention will be described in further detail with reference to specific embodiments.
According to one aspect of the invention, the MOS @ MOF-based hydrogen sensor comprises an MOS @ MOF composite structure sensitive material, wherein MOS of an inner core is a hydrogen gas sensitive material, and the hydrogen gas sensitive material comprises:
and constructing the metal nano-materials in the pore structures of the coating MOF in a manner that the metal nano-materials are embedded in the pore structures of the MOF, wherein the metal nano-materials are in the form of metal nano-particles.
Further preferably, the MOS is a MOS nanorod array. The oxygen ions adsorbed on the surface are combined with the hydrogen, so that the carrier concentration of the MOS is changed, and the resistance of the sensitive material is influenced. The change in resistance is specifically correlated with the volume fraction of hydrogen gas, thereby detecting hydrogen gas.
Further preferably, the MOS is ZnO, WO3、SnO2Any one of them.
Further preferably, the MOS is grown in situ on the front side of the sensor substrate.
Go toPreferably, the sensor substrate is Al2O3And (5) ceramic plates. The front surface of the ceramic wafer is printed with a gold electrode, the back surface of the ceramic wafer is printed with a heating electrode and a heating base material, and the heating base material comprises but is not limited to ruthenium oxide, platinum and nickel.
Further preferably, the MOS nanorod array grows on the surface of the sensor substrate in situ, namely the MOS nanorod array is printed with the gold electrode Al2O3The front surface of the ceramic plate.
Further preferably, the thickness of the MOF layer is 50-70 nm.
Further preferably, the embedded metal nanoparticles are any one of Ag, Pt, and Au.
Further preferably, it is loaded with MOS @ MOF
The sensor substrate of metal particles is welded to the hexagonal base, and the hexagonal base is used for connecting the sensor substrate and the test cavity. More preferably, the hexagonal base is of a plastic structure, 6 electrode columns are uniformly distributed on the hexagonal base, and the heating electrode and the testing electrode of the sensor substrate are welded to 4 specific electrode columns respectively.
In order to achieve the above object, according to another aspect of the present invention, there is also provided a method for preparing a MOS @ MOF based hydrogen sensor, comprising the steps of:
(1) coating MOF on the surface of the MOS to form a MOS @ MOF composite structure sensitive material;
(2) preprocessing a device: dissolving impurities in a cavity of the MOS @ MOF composite structure sensitive material, and drying;
(3) the method comprises the following steps of (1) enabling a metal nano material to penetrate into holes of a MOS @ MOF composite structure sensitive material in a metal ion mode;
(4) reducing metal ions into metal nanoparticles, and embedding the metal nanoparticles into holes of the MOS @ MOF composite structure sensitive material in situ;
(5) by obtaining MOS @ MOF
Metallic nanoparticles, i.e. intercalationA hydrogen sensor is assembled by MOS @ MOF composite structure sensitive materials of metal nano particles.
Further preferably, step (3) includes:
preparing a target metal ion source and alcohol solvent mixed solution by a heating and dissolving method, taking methanol to immerse the product obtained in the step (2), dripping the target metal ion source and alcohol solvent mixed solution under the stirring condition to avoid the accumulation of high-concentration solutes, and then continuously stirring at room temperature under the light-shielding condition to ensure that metal ions fully enter holes of the MOS @ MOF composite structure sensitive material.
Further preferably, step (4) comprises:
and (3) preparing a reducing agent in the process of waiting for permeation in the step (3), immediately dropwise adding the reducing agent after the step (3) is finished, keeping stirring for a preset time period to fully reduce metal ions, and embedding the metal ions into holes of the MOS @ MOF composite structure sensitive material in situ.
Further preferably, in the step (1), the MOS is ZnO or WO3、SnO2Any one of them.
Further preferably, in the step (3), the metal nanomaterial is any one of Ag, Pt, and Au.
Example 1
As shown in fig. 1 to 8, the following description will be made by taking a product and a method of coating the surface of the ZnO nanorod array with ZIF-71 and embedding Ag particles as an example, and the preparation method thereof includes the following steps:
(1) preparing zinc oxide seed crystal:
using methanol as a solvent, respectively preparing a sodium hydroxide solution and a zinc acetate solution with certain concentrations, and dropwise adding the sodium hydroxide solution into the zinc acetate solution under magnetic stirring and heating conditions to obtain a milky crystal seed suspension;
(2) the seed crystal solution was spin coated on the front side of the ceramic wafer with the gold electrode printed.
A suitable number of small electrode pieces are fixed on a ceramic wafer of a suitable size by a heat-resistant adhesive tape, and the ceramic wafer is adsorbed on a suction cup of a spin coater. Spin-coating for 30-60 s at a certain rotation speed, drying, repeating for several times to make the seed crystal layer reach the target thickness, and finally annealing at 200-300 ℃ for 1 h;
(3) and (5) growing the ZnO nanorod array.
Dissolving a certain amount of hexamethylenetetramine and zinc nitrate hydrate in deionized water, keeping the front side of the electrode plate coated with the seed crystal layer upward, putting the electrode plate into the solution, and then reacting for 5-10 hours at 80-100 ℃ to obtain a ZnO nanorod array;
(4) preparing a ZIF-71 precursor.
Mixing deionized water with DMF according to the ratio of 1-2: 3-10 parts of the mixture is added into a polytetrafluoroethylene lining of a stainless steel high-temperature reaction kettle with the capacity of 50mL, the mixture is stirred properly and mixed uniformly, and then 0.05-0.15 g of 4, 5-dichloroimidazole is added;
(5) ZIF-71 is coated on the surface of ZnO.
Putting the electrode plate with the grown ZnO nano-rod into a reaction kettle, putting the reaction kettle into a muffle furnace at 50-100 ℃, heating for 2-8 hours, cooling, and repeatedly washing with methanol to complete ZIF-71 coating;
(6) and (5) preprocessing the device.
Soaking the ZnO @ ZIF-71 nanorod array obtained in the step (5) in methanol for 2 to 5 days to fully dissolve impurities in the cavity, and then carrying out vacuum drying at 60 ℃ for 10 hours;
(7) and Ag ions permeate.
Preparing a certain amount of 0.02-0.05M AgNO by a heating dissolution method3Taking a small amount of methanol to immerse the electrode plate obtained in the step (6), and then dripping AgNO into the electrode plate under vigorous stirring3Methanol solution to avoid the build-up of high concentrations of solutes. Stirring at room temperature for 120min to obtain Ag+Fully enter the ZIF-71 hole.
(8) Reduction of Ag ions and intercalation of Ag nanoparticles.
And (3) dissolving 0.05-0.15 g of sodium borohydride in 10mL of methanol, immediately dropwise adding the sodium borohydride solution after the step (7) is finished, and keeping vigorous stirring for 10-20 minutes to ensure that Ag ions are fully reduced and embedded into holes of ZIF-71 in situ. The resulting device was then washed repeatedly with methanol and dried.
(9) And (5) welding the device.
Welding the electrode slice obtained in the step (8) onto a hexagonal base by using a spot welding device to obtain the electrode slice based on
The hydrogen sensor of (1).
Preferably, the nanorod array may be replaced with WO3、SnO2The embedded nano particles can be replaced by any other metal particles including Pt and Au, and the target metal source involved in the ion infiltration is replaced by chloroplatinic acid and chloroauric acid solution with certain concentration.
More specifically, the detailed process of embedding Ag nanoparticles into ZnO @ ZIF-71 pore structure is as follows.
(1) And (5) growing the ZnO nanorod array.
Zinc oxide seed crystals are first prepared.
Taking methanol as a solvent, respectively preparing 20mL of 0.03M sodium hydroxide solution and 20mL of 0.01M zinc acetate solution, dropwise adding the sodium hydroxide solution into the zinc acetate solution, and stirring at a certain rotation speed for 2 hours at 60 ℃ to obtain milky suspension, namely completing the preparation of the seed crystal.
And then spin-coating the seed crystal solution on the front surface of the ceramic chip printed with the metal electrode by a spin-coating method.
A ceramic sheet with a proper size is taken, and a proper number of small electrode sheets are fixed on the ceramic sheet by a heat-resistant adhesive tape. Then spin coating for 30s at a certain rotation speed, drying at 60 deg.C, and repeating several times to reach the target seed crystal thickness. In order to make the crystallinity and adhesion of the seed crystal better, annealing is carried out for 1h at the temperature of 200 ℃.
And finally finishing the growth of the zinc oxide nano rod.
0.0015mol of hexamethylenetetramine and zinc nitrate hexahydrate are taken and added into 30ml of deionized water, the electrode plate and the large ceramic chip are added after the materials are dissolved, and the front side of the electrode plate is kept downward. Followed by hydrothermal reaction at 80 ℃ for 6 hours. And obtaining the ZnO nanorod array growing on the electrode plate.
(2) The surface is coated with ZIF-71.
Firstly, preparing a solvent with proper pH value, preparing 32mL of the solution by using deionized water and DMF according to the ratio of 1:2, putting the solution into a polytetrafluoroethylene lining of a stainless steel high-temperature reaction kettle with the capacity of 50mL, and stirring the solution properly to mix the solution fully and uniformly.
Thereafter, 0.12g of 4, 5-dichloroimidazole was added thereto and sufficiently dissolved using ultrasound. And putting the electrode plate with the ZnO nano-rod into a reaction kettle with the surface facing downwards. The stainless steel shell of the reaction kettle is screwed, and the reaction kettle is placed in an oven and heated at the temperature of 70 ℃. And then, washing with methanol for three times, and removing redundant impurities to finish the ZIF-71 coating.
(3) Ag nanoparticles are embedded.
The intercalation process of Ag nanoparticles is completed by means of infiltration-reduction method based on the above. The method is characterized in that metal ions are pressed into a cavity of the porous material by means of osmotic pressure, and then the metal ions are reduced in the cavity under the action of a reducing agent. Therefore, in order to ensure osmotic pressure, the ZnO @ ZIF-71 nanorod array needs to be pretreated before metal loading, and the prepared device is soaked in methanol for 48 hours, so that impurities in the cavity are fully dissolved. Then a vacuum oven is used for vacuumizing for 10 hours at the temperature of 60 ℃, so that impurities are removed.
After treatment, AgNO was prepared at a concentration of 0.05M by a process of heating to 30 ℃ to assist dissolution322ml of methanol solution is reserved. Firstly, putting a sample into 6mL of methanol to ensure that an electrode plate is immersed in the methanol, and then, dropwise adding AgNO prepared before under vigorous stirring3The solution avoids the accumulation of solute with too high concentration on the surface. Stirring at room temperature for 120min to obtain Ag+Fully into the ZIF-71 pore structure.
And preparing a reducing agent in the waiting process. 0.1g of NaBH4Added to 10mL of methanol and stirred to dissolve NaBH4Is more active and can be used as soon as possible after the preparation is finished. When the stirring time reaches 2 hours, the reducing agent which is just prepared is added dropwise, and the vigorous stirring is continuously kept for 10 minutes to ensure that the Ag+Complete reduction is obtained. Finally, the prepared sample was soaked in a pure methanol solutionWashed for 30 minutes to remove excess impurities and oven dried at 60 ℃.
(4) And (6) assembling the sensor.
And respectively welding the heating electrode and the testing electrode of the electrode slice prepared by the steps to an electrode column of a hexagonal base to obtain the hydrogen sensor taking ZnO @ ZIF-71Ag as a sensitive material.
Example 1 demonstrates that the intercalation of Ag nanoparticles successfully modulates the pore size of the MOF layer, thereby enhancing the selectivity of ZnO @ ZIF-71 to hydrogen, as shown in fig. 1-8. However, the above solution is not limited to the development of the hydrogen sensor, and in fact, the gas sensor can be extended to target gases of other sizes.
The invention also relates to the MOS @ MOF
On the basis that metal nanoparticles, namely MOF pores, are embedded into the metal nanoparticles to reduce the pores and improve the selectivity, active regulation and control of the pores are further provided, and various implementation modes are provided.
Example 2
The invention provides a pore regulation method of a hydrogen sensor based on MOS @ MOF, wherein the pore regulation method comprises the following steps: the size of the pores is regulated by embedding the same metal nanoparticles in different MOFs, wherein the different MOFs have different intrinsic pore sizes and the morphological size of the same metal nanoparticles is approximately the same.
Different MOFs such as ZIF-71 and ZIF-8 have different intrinsic pore diameters, are embedded in the same metal nanoparticle such as one of Ag, Pt and Au, have approximately the same morphological size, and can form different pores so as to regulate and control the size of the pores.
Example 3
The invention provides a pore regulation method of a hydrogen sensor based on MOS @ MOF, wherein the pore regulation method comprises the following steps: the pore size is regulated by embedding different metal nanoparticles in the same MOF, wherein the different metal nanoparticles have different morphological sizes.
The same MOF, such as ZIF-71, has the same intrinsic pore diameter, is embedded with one of different metal nano particles, such as Ag, Pt and Au, and has different morphological sizes, so that different pores can be formed, and the size of the pores can be regulated.
Example 4
The invention also provides a pore regulation method of the MOS @ MOF-based hydrogen sensor, wherein the pore regulation method comprises the following steps: regardless of the MOF intrinsic pore size, and regardless of the type of metal nanoparticles, the size of the pores is regulated in a manner that regulates the size of the morphological dimensions of the metal nanoparticles embedded in the pore structure of the MOF.
No matter whether the MOF adopts ZIF-71 or ZIF-8 or other metal nanoparticles such as Ag, Pt or Au, different pores can be formed by regulating the size of the morphological size of the metal nanoparticles embedded in the pore structure of the MOF, so that the size of the pores can be regulated.
Example 5
The invention also provides a preparation method of the hydrogen sensor with adjustable pores based on MOS @ MOF, wherein the preparation method comprises the following steps: in the step (3) of the preparation method of the MOS @ MOF-based hydrogen sensor (other steps are basically kept consistent), the content of metal ions permeating into pores of the MOF is controlled in a mode of adjusting the concentration of the metal ions to be permeated, so that the sizes of the pores are regulated, and finally the hydrogen sensors with different pore sizes are prepared.
For example, by increasing or decreasing AgNO during Ag ion infiltration of example 13By increasing or decreasing the content of Ag ions that penetrate into the pores of the MOF and the size of the final particles, the size of the voids decreases or increases accordingly, thereby controlling the size of the pores.
Example 6
The invention also provides a preparation method of the hydrogen sensor with adjustable pores based on MOS @ MOF, wherein the preparation method comprises the following steps: in the step (3) of the preparation method of the MOS @ MOF-based hydrogen sensor (other steps are basically kept consistent), the content of metal ions permeating into MOF pores is controlled in a mode of adjusting the permeation time of the metal ions, so that the sizes of the pores are regulated, and finally the hydrogen sensors with different pore sizes are prepared.
For example, by increasing or decreasing Ag during the Ag ion infiltration of example 1+The infiltration time, and the content of Ag ions that infiltrate into the MOF pores and the size of the final particles, are increased or decreased accordingly, the size of the voids is decreased or increased accordingly, thereby regulating the size of the pores.
Example 7
The invention also provides a preparation method of the hydrogen sensor with adjustable pores based on MOS @ MOF, wherein the preparation method comprises the following steps: in the step (3) of the preparation method of the MOS @ MOF-based hydrogen sensor (other steps are basically kept consistent), the content of the metal ions permeating into the pores of the MOF is controlled in a mode of adjusting the concentration of the metal ions to be permeated and adjusting the permeation duration of the metal ions, so that the sizes of the pores are adjusted and controlled, and finally the hydrogen sensors with different pore sizes are prepared.
For example, by reducing AgNO during Ag ion infiltration of example 13Concentration of (3) reduces Ag+The infiltration time, and consequently the content of Ag ions that penetrate into the MOF pores and the size of the final particles, are reduced, the size of the voids is increased accordingly, thereby controlling the size of the pores. It is worth to be noted that adjusting the concentration of the metal ions to be infiltrated and adjusting the infiltration duration of the metal ions are two separate variables, which do not necessarily all point to the same regulation direction (e.g., both increase the pores), but may also be opposite, and in short, the stepless regulation of the pores can be achieved by the two variables.
The method specifically comprises the following steps: the Zn @ ZIF-71 nanorod array prepared in example 1 is taken for standby. AgNO with concentration of 0.022M is prepared by a method of heating to 30 ℃ to assist dissolution322ml of methanol solution is reserved. Firstly, putting a sample into 6mL of methanol to ensure that an electrode plate is immersed in the methanol, and then, dropwise adding AgNO prepared before under vigorous stirring3The solution avoids the accumulation of solute with too high concentration on the surface. Stirring at room temperature for 45min in dark condition to allow Ag to precipitate+Fully into the ZIF-71 pore structure. The remaining steps are in accordance with example 1, by reducing Ag+Concentration and osmosisAnd (3) obtaining the Ag nano particles with smaller particle size after the addition of time. Accordingly, after the Ag nanoparticles are embedded, ZIF-71 will leave larger pores for the gas to pass through, and vice versa. The size difference of the Ag nanoparticles and the pore difference of ZnO @ ZIF-71 are confirmed by transmission electron microscopy and N2 desorption characterization, respectively.
In summary, compared with the prior art, the scheme of the invention has the following significant advantages:
according to the hydrogen sensor based on the MOS @ MOF, the surface of the hydrogen sensitive material MOS nanorod is coated with the porous MOF to prepare the MOS @ MOF composite structure, so that macromolecular interference gas in the environment can be preliminarily screened out, and the selectivity of the MOS to micromolecular hydrogen is enhanced; moreover, noble metal particles are embedded in the pore diameter of the MOF coating layer in a particle form, so that a gas passing channel is further reduced, most other interfering gases are blocked, and the selectivity of MOS @ MOF to hydrogen is obviously improved; meanwhile, the catalytic action of the embedded noble metal particles can reduce the activation energy of hydrogen in the reaction on the surface of the MOS, promote the reaction of hydrogen and adsorbed oxygen ions, and effectively enhance the response performance of the MOS @ MOF, so that the composite material hydrogen sensor with high selectivity and high sensitivity is developed.
The synergistic effect of the MOF coating layer and the embedded metal particles plays a key role in improving the performance of the prepared hydrogen sensor. MOS @ MOF based hydrogen sensors exhibit the highest sensitivity with a lower detection limit of up to 100ppb when the permeant ion is maintained at a certain concentration.
Compared with the prior art, the hydrogen sensor provided by the invention has stronger interference resistance, and shows better selectivity and higher sensitivity to hydrogen. Meanwhile, the preparation method provided by the invention does not depend on precise equipment and complex reaction conditions, the technical scheme is simple, and the raw materials are low in cost and easy to obtain.
The invention is in MOS @ MOF
Based on the metal nanoparticles, namely MOF pores are embedded with the metal nanoparticles to reduce the pores and improve the selectivity, the method further providesThe pore size is regulated and controlled by embedding the same metal nano-particles into different MOFs, wherein the different MOFs have different intrinsic pore diameters, and the morphological sizes of the same metal nano-particles are approximately the same; secondly, the sizes of pores are regulated by embedding different metal nanoparticles in the same MOF, wherein the different metal nanoparticles have different morphological sizes; and thirdly, regulating the size of pores in a mode of regulating the morphological size of metal nanoparticles embedded in the pore structure of the MOF, no matter how the intrinsic pore diameter of the MOF is or the type of the metal nanoparticles is, specifically, controlling the content of metal ions permeated into the pores of the MOF in a mode of regulating the concentration of metal ions to be permeated and/or regulating the permeation duration of the metal ions in the permeation process of a target metal ion source to regulate the size of the pores, and finally preparing the hydrogen sensors with different pore sizes. Therefore, the gas sieving performance of the invention shows the adjustable and controllable gas sensitivity selectivity of the material, and provides a new general idea for designing MOF molecular sieve materials and MOS @ MOF gas sensors.
It will be appreciated that the embodiments of the system described above are merely illustrative, in that elements illustrated as separate components may or may not be physically separate, may be located in one place, or may be distributed over different network elements. Some or all of the modules can be selected according to actual needs to achieve the purpose of the scheme of the embodiment. One of ordinary skill in the art can understand and implement it without inventive effort.
In addition, it should be understood by those skilled in the art that in the specification of the embodiments of the present invention, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
In the description of the embodiments of the invention, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some instances, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description. Similarly, it should be appreciated that in the foregoing description of exemplary embodiments of the invention, various features of the embodiments of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects.
However, the disclosed method should not be interpreted as reflecting an intention that: that is, the claimed embodiments of the invention require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of an embodiment of this invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the embodiments of the present invention, and not to limit the same; although embodiments of the present invention have been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (13)
1. The utility model provides a hydrogen sensor based on MOS @ MOF, includes MOS @ MOF composite construction sensitive material, its characterized in that:
and constructing the metal nano-materials in the pore structures of the MOF in a manner that the metal nano-materials are embedded in the pore structures of the MOF, wherein the metal nano-materials are in the form of metal nano-particles.
2. The MOS @ MOF based hydrogen sensor of claim 1, wherein:
the MOS is an MOS nanorod array.
3. The MOS @ MOF based hydrogen sensor of claim 1, wherein:
the MOS is ZnO or WO3、SnO2Any one of them.
4. The MOS @ MOF based hydrogen sensor of claim 1, wherein:
the embedded metal nanoparticles are any one of Ag, Pt and Au.
5. A method of pore modulation for a MOS @ MOF based hydrogen sensor as claimed in claims 1-4, wherein:
the size of pores is regulated by embedding the same metal nanoparticle in different MOFs, wherein the different MOFs have different intrinsic pore diameters, and the morphological sizes of the same metal nanoparticle are approximately the same;
alternatively, the pore size can be tailored by embedding different metal nanoparticles in the same MOF, where the different metal nanoparticles have different morphological sizes.
6. A method of pore modulation for a MOS @ MOF based hydrogen sensor as claimed in claims 1-4, wherein:
the size of the pores is regulated in a manner that regulates the size of the morphological dimensions of the metal nanoparticles embedded in the pore structure of the MOF.
7. A preparation method of a hydrogen sensor based on MOS @ MOF is characterized by comprising the following steps:
(1) coating MOF on the surface of the MOS to form a MOS @ MOF composite structure sensitive material;
(2) preprocessing a device: dissolving impurities in a cavity of the MOS @ MOF composite structure sensitive material, and drying;
(3) the method comprises the following steps of (1) enabling a metal nano material to penetrate into holes of a MOS @ MOF composite structure sensitive material in a metal ion mode;
(4) reducing metal ions into metal nanoparticles, and embedding the metal nanoparticles into holes of the MOS @ MOF composite structure sensitive material in situ;
(5) by obtaining
Namely, the hydrogen sensor is assembled by the MOS @ MOF composite structure sensitive material embedded with the metal nano particles.
8. The method of making a MOS @ MOF based hydrogen sensor of claim 7, wherein:
the step (3) comprises the following steps:
preparing an alcohol solvent of a target metal ion source, taking the alcohol solvent to immerse the product obtained in the step (2), dripping the alcohol solvent of the target metal ion source under the stirring condition to avoid the accumulation of solutes, and then continuously stirring for a preset time at room temperature under the dark condition to ensure that metal ions fully enter pores of the MOS @ MOF composite structure sensitive material.
9. The method of making a MOS @ MOF based hydrogen sensor of claim 7, wherein:
the step (4) comprises the following steps:
and (3) preparing a reducing agent in the process of waiting for permeation in the step (3), immediately dropwise adding the reducing agent after the step (3) is finished, keeping stirring for a preset time period to fully reduce metal ions, and embedding the metal ions into holes of the MOS @ MOF composite structure sensitive material in situ.
10. The method of making a MOS @ MOF based hydrogen sensor of claim 7, wherein:
in the step (1), the MOS is ZnO or WO3、SnO2Any one of them.
11. The method of making a MOS @ MOF based hydrogen sensor of claim 7, wherein:
in the step (3), the metal nano material is any one of Ag, Pt and Au.
12. A preparation method of a hydrogen sensor with adjustable pores based on MOS @ MOF is characterized by comprising the following steps:
in the step (3) of the preparation method of the MOS @ MOF-based hydrogen sensor, according to claim 7, the content of the metal ions permeating into the pores of the MOF is controlled in a manner of adjusting the concentration of the metal ions to be permeated, so as to regulate the sizes of the pores, and finally, the hydrogen sensors with different pore sizes are prepared.
13. A preparation method of a hydrogen sensor with adjustable pores based on MOS @ MOF is characterized by comprising the following steps:
in the step (3) of the preparation method of the MOS @ MOF-based hydrogen sensor, according to claim 7, the content of the metal ions permeating into the pores of the MOF is controlled in a manner of adjusting the permeation time of the metal ions, so as to regulate the sizes of the pores, and finally, the hydrogen sensors with different pore sizes are prepared.
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