CN114166898A - Amorphous noble metal RuOxPreparation method of/ZnO MEMS hydrogen sensor - Google Patents
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 28
- 239000001257 hydrogen Substances 0.000 title claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 18
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims abstract 4
- 238000000034 method Methods 0.000 title description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000007789 gas Substances 0.000 claims abstract description 32
- 229910019897 RuOx Inorganic materials 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000012360 testing method Methods 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002244 precipitate Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000002135 nanosheet Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 5
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000002114 nanocomposite Substances 0.000 description 4
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 4
- 229910019891 RuCl3 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910009112 xH2O Inorganic materials 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 208000035475 disorder Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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Abstract
The invention relates to the technical field of hydrogen sensors, in particular to amorphous noble metal RuOxFirstly, synthesizing amorphous noble metal RuOxThe RuO is regulated and controlled by compounding the RuO on a ZnO nano-chip through self-assemblyxThe amount of (A) is synthesized to form the amorphous noble metal RuO with different fractionsxGas sensitive material, mixing the material and ethanol in agate mortar to paste, coating on Pt electrode, drying to obtain resistance type sensor MEMS sensor, placing the sensor on a base with heating electrode and test electrode, heating voltage is 1.5V, and lasting for 24 hrxModifying ZnO surface by self-assembly with small amount of RuOxAfter ZnO is modified, the sensor shows a very high response value and an ultra-low detection limit (as low as 1ppm) to hydrogen, and has a wide application prospect in the aspect of manufacturing a novel efficient gas sensor.
Description
Technical Field
The invention relates to the technical field of hydrogen sensors, in particular to amorphous noble metal RuOxA preparation method of a/ZnO MEMS hydrogen sensor.
Background
H2Is a colorless and odorless gas, is considered to be an attractive alternative energy source and sustainable energy carrier due to its relatively low environmental impact, however, H2Leakage of molecules above a certain critical concentration can cause serious explosions and extreme fatalities, and suitable sensors have been developed to determine and control H during production, transport, storage and utilization2The content becomes more and more important and urgent.
Conventional gas sensors are generally prepared by combining a noble metal (such as Pd, Au, Rh, Ru, etc.) with MOS, which exhibits unique characteristics due to specific chemical and electronic sensitization characteristics, but the scarcity and the expense of noble metals greatly hinder their wide application, so that it is required to construct a highly active noble metal catalyst by increasing the number of active sites or optimizing intrinsic activity, and since the adsorption/desorption kinetics of gas-sensitive reactions are very dependent on the surface structure of the catalyst, constructing the surface structure of the catalyst, particularly at the atomic level, has become an effective and successful strategy for further improving the catalytic performance of noble metals, wherein, unlike crystalline materials having translational periodicity, the inherent disorder of amorphous materials can generate a large number of "dangling bonds" and defects in the loosely combined atomic free volume region, which can provide more active sites, therefore, the catalytic activity is improved, in addition, the amorphous material shows more excellent performance in the performance level, the amorphous noble metal has many applications in the catalytic field, but the application as a sensitizer in the field of gas sensors is very rare, and in the prior art, only an amorphous Pd layer (am-Pd/ZnO NRs) covering ZnO nanorods is synthesized, and compared with ZnO nanorod sensors decorated by crystalline Pd nanoparticles, am-Pd/ZnO NRs sensors show remarkable sensing response (Sensor Actuators B: Chemical 2018,262, 460-468). However, Ru-based amorphous noble metals as sensitizers have not been studied in the field of resistive gas sensors.
Therefore, it is necessary to design an amorphous noble metal RuOxPreparation method of/ZnO MEMS hydrogen sensor and prepared RuOxthe/ZnO composite gas-sensitive material has good sensitivity to hydrogen and has wide application prospect in the aspect of manufacturing novel efficient gas sensors.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an amorphous noble metal RuOxPreparation method of/ZnO MEMS hydrogen sensor and prepared RuOxthe/ZnO composite gas-sensitive material has good sensitivity to hydrogen and has wide application prospect in the aspect of manufacturing novel efficient gas sensors.
In order to achieve the above object, the present invention provides an amorphous noble metal RuOxThe preparation method of the/ZnO MEMS hydrogen sensor comprises the following steps:
s1: mixing the prepared composite gas-sensitive material and ethanol in an agate mortar, and grinding into paste;
s2: coating the paste on a Pt interdigital electrode, and naturally drying at room temperature to obtain a resistance type sensor MEMS sensor;
s3: placing a resistance type sensor MEMS sensor on a base with a heating electrode and a testing electrode, and then setting the heating voltage of the sensor to 1.5V for 24 hours;
the preparation method of the composite gas-sensitive material comprises the following steps:
s10: under the condition of electromagnetic stirring, 250 mg-300 mg RuCl is added3·xH2Dissolving O hydrate in 5ml of deionized water, and then adding 4-5 g of LiOH & H2Forming a solution after O;
s20: heating the solution to 85-90 ℃ under stirring to evaporate water, and calcining the solid product obtained after evaporation in static air at 350-410 ℃ for 2 hours;
s30: the catalyst was obtained after thorough washing of the solid product with deionized water and ethanol and drying overnight at 60 ℃ and was labelled RuOx；
S40: adding 8-15 mmol of Zn (CH)3COO)2·2H2Dissolving O, 5-12 mmol of Hexamethyltetramine (HMT) and 5mmol of Sodium Dodecyl Sulfate (SDS) in 20mL of distilled water, stirring vigorously for 30 minutes, transferring the solution into a 50mL high-pressure kettle, and keeping the high-pressure kettle at 160-200 ℃ for 9-12 hours;
s50: cooling the autoclave to room temperature, centrifuging the white precipitate, washing with ethanol and distilled water for several times, and drying at 60 ℃ overnight;
s60: calcining the precipitate at 500 ℃ for 2 hours at a heating rate of 2 ℃/min in an air atmosphere to obtain a ZnO nanosheet;
s70: RuO obtained in S30x(0.5-2 mg) is dispersed in 20mL of ethanol and mixed with ZnO (100mg) to form a mixture;
s80: treating the mixture with ultrasonic waves for 1 hour, and then drying the mixture for 8 hours at the temperature of 60-80 ℃ to finally obtain RuOxModified ZnO.
Compared with the prior art, the invention successfully synthesizes the amorphous noble metal (RuO) based on Ru by annealing the mixture of ruthenium chloride and lithium hydroxidex) ZnO, a typical n-type metal oxide semiconductor with a wide bandgap energy of 3.37eV, is one of the most studied sensing materials, and then RuO was usedxModification of ZnO surface by self-assembly with small amount of RuOxAfter modification of ZnO, RuOxthe/ZnO sensor shows a very high response value and an ultra-low detection limit (as low as 1ppm) to hydrogen, and has a wide application prospect in the aspect of manufacturing novel efficient gas sensors.
Drawings
FIG. 1 shows the RuO of amorphous noble metal prepared by the present inventionxXRD pattern of (a).
FIG. 2 is a display diagram of a scanning electron microscope and a transmission electron microscope for the microstructure of the porous ZnO nanosheet prepared in the present invention.
FIG. 3 shows RuO with 0.5% mass fraction of amorphous noble metal Ru according to the inventionxHigh resolution display of/Zn-O nanocomposites.
FIG. 4 shows the RuO of the present inventionxRuO content of 1%xThe sensitivity curve of the/ZnO nano composite at 280 ℃ to hydrogen with different concentrations is shown.
FIG. 5 shows the amorphous noble metal RuO of the present inventionxRuO content of 1.2%xThe sensitivity curve of the/ZnO nanocomposite at 280 ℃ to 1ppm of hydrogen is shown.
Detailed Description
The invention will now be further described with reference to the accompanying drawings.
Referring to FIGS. 1-5, the present invention provides an amorphous noble metal RuOxThe preparation method of the/ZnO MEMS hydrogen sensor comprises the following steps:
s1: mixing the prepared composite gas-sensitive material and ethanol in an agate mortar, and grinding into paste;
s2: coating the paste on a Pt interdigital electrode, and naturally drying at room temperature to obtain a resistance type sensor MEMS sensor;
s3: placing a resistance type sensor MEMS sensor on a base with a heating electrode and a testing electrode, and then setting the heating voltage of the sensor to 1.5V for 24 hours;
the preparation method of the composite gas-sensitive material comprises the following steps:
s10: under the condition of electromagnetic stirring, 250 mg-300 mg RuCl is added3·xH2Dissolving O hydrate in 5ml of deionized water, and then adding 4-5 g of LiOH & H2Forming a solution after O;
s20: heating the solution to 85-90 ℃ under stirring to evaporate water, and calcining the solid product obtained after evaporation in static air at 350-410 ℃ for 2 hours;
s30: the catalyst was obtained after thorough washing of the solid product with deionized water and ethanol and drying overnight at 60 ℃ and was labelled RuOx；
S40: adding 8-15 mmol of Zn (CH)3COO)2·2H2Dissolving O, 5-12 mmol of Hexamethyltetramine (HMT) and 5mmol of Sodium Dodecyl Sulfate (SDS) in 20mL of distilled water, stirring vigorously for 30 minutes, transferring the solution into a 50mL high-pressure kettle, and keeping the high-pressure kettle at 160-200 ℃ for 9-12 hours;
s50: cooling the autoclave to room temperature, centrifuging the white precipitate, washing with ethanol and distilled water for several times, and drying at 60 ℃ overnight;
s60: calcining the precipitate at 500 ℃ for 2 hours at a heating rate of 2 ℃/min in an air atmosphere to obtain a ZnO nanosheet;
s70: RuO obtained in S30x(0.5-2 mg) is dispersed in 20mL of ethanol and mixed with ZnO (100mg) to form a mixture;
s80: treating the mixture with ultrasonic waves for 1 hour, and then drying the mixture for 8 hours at the temperature of 60-80 ℃ to finally obtain RuOxModified ZnO.
Example 1:
under electromagnetic stirring, 250mg of RuCl3·xH2O hydrate was dissolved in 5ml of deionized water, thenThen 4.0g of LiOH H are added2O, heating the solution to 85 ℃ with stirring to evaporate the distilled water and calcining the resulting solid in static air at 350 ℃ for 2h, after which the sample is thoroughly washed with deionized water and ethanol and dried at 60 ℃ overnight, the sample being labelled RuOxThe XRD spectrum is shown in figure 1, and no diffraction peak is obvious in XRD, so that the synthesis of the amorphous material is proved. Adding 10mmol of Zn (CH)3COO)2·2H2Dissolving O, 10mmol of Hexamethyltetramine (HMT) and 5mmol of Sodium Dodecyl Sulfate (SDS) in 20mL of distilled water, stirring vigorously for 30 minutes, transferring the solution into a 50mL high-pressure kettle, keeping the temperature at 160 ℃ and 200 ℃ for 9 hours, cooling the high-pressure kettle to room temperature, centrifuging a white precipitate, washing the white precipitate with ethanol and distilled water for several times, drying the white precipitate at 60 ℃ overnight, and finally calcining the precipitate at 500 ℃ for 2 hours at a heating rate of 2 ℃/min in an air atmosphere to obtain ZnO nanosheets, wherein the microstructure scanning electron microscope photos and the transmission electron microscope photos of the prepared porous ZnO nanosheets can observe that ZnO is porous nanosheets. Finally, 0.5mg of RuO will be obtainedxDispersed in 20mL ethanol and mixed with ZnO (100mg), the mixture was sonicated for 1 hour and then dried at 60 ℃ for 8 hours to finally obtain RuOx/ZnO。
The prepared composite gas-sensitive material RuOxMixing ZnO and ethanol in an agate mortar, grinding into paste, coating the paste on a Pt interdigital electrode, naturally drying at room temperature to obtain a resistance type sensor MEMS sensor, placing the sensor on a base with a heating electrode and a test electrode, setting the heating voltage of the sensor to be 1.5V, and finishing the aging process after the sensor lasts for 24 hours. The gas sensitive test employs a static gas dispensing method, during which a micro-syringe is used to inject the desired amount of target gas into the test chamber. The gas sensing results are shown in FIG. 4, and the gas sensing test results show that the response value of the sensor at 280 ℃ is along with H2The increase of gas concentration shows that the MEMS sensor prepared by the method can detect extremely low H2And can quickly detect H2Is present.
Example 2:
under electromagnetic stirring, 300mg of RuCl3·xH2O hydrate was dissolved in 5ml of deionized water, and 5.0g of LiOH. H was added2O, heating the solution to 85 ℃ with stirring to evaporate the distilled water and calcining the resulting solid in static air at 410 ℃ for 2h, the sample being thoroughly washed with deionized water and ethanol and dried at 60 ℃ overnight, the sample being labelled RuOxAdding 8mmol of Zn (CH)3COO)2·2H2Dissolving O, 5mmol of Hexamethyltetramine (HMT) and 5mmol of Sodium Dodecyl Sulfate (SDS) in 20mL of distilled water, stirring vigorously for 30 minutes, transferring the solution to a 50mL autoclave, keeping the temperature at 180 ℃ for 9 hours, cooling the autoclave to room temperature, centrifuging a white precipitate, washing the white precipitate with ethanol and distilled water for several times, drying the white precipitate at 60 ℃ overnight, calcining the precipitate in an air atmosphere at 500 ℃ for 2 hours at a heating rate of 2 ℃/min to obtain ZnO nanosheets, and finally obtaining 1mg of RuOxDispersed in 20mL ethanol and mixed with ZnO (100mg), the mixture was sonicated for 1 hour and then dried at 60 ℃ for 8 hours to finally obtain RuOx/ZnO。
The prepared composite gas-sensitive material RuOxMixing ZnO and ethanol in an agate mortar, grinding into paste, coating the paste on a Pt interdigital electrode, naturally drying at room temperature to obtain a resistance type sensor MEMS sensor, placing the sensor on a base with a heating electrode and a test electrode, setting the heating voltage of the sensor to be 1.5V, and continuing for 24 hours to finish the process.
RuO prepared by testing the gas sensitivity Performance in example 1xThe result of the/ZnO nanocomposite gas-sensitive material is shown in FIG. 5, and the sensitivity of the material to 1ppm hydrogen at 280 ℃ is 1.1, and the response value shown in FIG. 5 is similar to that of example 1.
Example 3:
under electromagnetic stirring, 300mg of RuCl3·xH2O hydrate was dissolved in 5ml of deionized water, and 5.0g of LiOH. H was added2O, heating the solution to 90 ℃ with stirring to evaporate the distilled water and calcining the resulting solid in static air at 400 ℃ for 2h, the sample being thoroughly washed with deionized water and ethanol and dried at 60 ℃At night, the resulting sample was labeled as RuOx15mmol of Zn (CH)3COO)2·2H2Dissolving O, 12mmol of Hexamethyltetramine (HMT) and 5mmol of Sodium Dodecyl Sulfate (SDS) in 20mL of distilled water, stirring vigorously for 30 minutes, transferring the solution to a 50mL autoclave, keeping the temperature at 160 ℃ for 9 hours, cooling the autoclave to room temperature, centrifuging the white precipitate, washing the white precipitate with ethanol and distilled water for several times, drying the white precipitate at 60 ℃ overnight, calcining the precipitate in an air atmosphere at 500 ℃ for 2 hours at a heating rate of 2 ℃/min to obtain ZnO nanosheets, and finally obtaining 1mg of RuOxDispersed in 20mL ethanol and mixed with ZnO (100mg), the mixture was sonicated for 1 hour and then dried at 60 ℃ for 8 hours to finally obtain RuOx[ ZnO ], RuO in FIG. 3xTransmission diagram of/ZnO, clearly showing the amorphous noble metal RuOxWas successfully loaded onto the surface of ZnO.
The prepared composite gas-sensitive material RuOxMixing ZnO and ethanol in an agate mortar, grinding into paste, coating the paste on a Pt interdigital electrode, naturally drying at room temperature to obtain a resistance type sensor MEMS sensor, placing the sensor on a base with a heating electrode and a test electrode, setting the heating voltage of the sensor to be 1.5V, and finishing the aging process after the sensor lasts for 24 hours.
The above is only a preferred embodiment of the present invention, and is only used to help understand the method and the core idea of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
The invention integrally solves the problem that the application of amorphous noble metal in the field of resistance type gas sensors is not available in the prior art, and the amorphous noble metal RuO is synthesizedxThe nano-particles are compounded on a ZnO nano-chip by a self-assembly method, and the amorphous noble metal RuO is regulated and controlledxCan synthesize amorphous with different mass fractionsNoble metal RuOxGas sensitive material by control of amorphous noble metal RuOxLiOH & H in the synthesis process2The content of O can effectively control the synthesis of amorphous noble metal, and the surface of the amorphous noble metal Ru has a large amount of coordination unsaturated points and dangling bonds and has excellent sensitivity enhancement property, so that the prepared composite material is coated on an MEMS chip, a high-sensitivity low-power-consumption hydrogen sensor can be prepared, and the application prospect in the aspect of manufacturing novel high-efficiency gas sensors is wide.
Claims (1)
1. Amorphous noble metal RuOxThe preparation method of the/ZnO MEMS hydrogen sensor is characterized by comprising the following steps:
s1: mixing the prepared composite gas-sensitive material and ethanol in an agate mortar, and grinding into paste;
s2: coating the paste on a Pt interdigital electrode, and naturally drying at room temperature to obtain a resistance type sensor MEMS sensor;
s3: placing the resistance type sensor MEMS sensor on a base with a heating electrode and a testing electrode, and then setting the heating voltage of the sensor to 1.5V for 24 hours;
the preparation method of the composite gas-sensitive material comprises the following steps:
s10: under the condition of electromagnetic stirring, 250 mg-300 mg RuCl is added3·xH2Dissolving O hydrate in 5ml of deionized water, and then adding 4-5 g of LiOH & H2Forming a solution after O;
s20: heating the solution to 85-90 ℃ under stirring to evaporate water, and calcining the solid product obtained after evaporation in static air at 350-410 ℃ for 2 hours;
s30: the solid product was thoroughly washed with deionized water and ethanol and dried at 60 ℃ overnight to obtain the catalyst and labeled as RuOx；
S40: adding 8-15 mmol of Zn (CH)3COO)2·2H2Dissolving O, 5-12 mmol of Hexamethyltetramine (HMT) and 5mmol of Sodium Dodecyl Sulfate (SDS) in 20ml of distilled water, stirring vigorously for 30 minutes, and then dissolving the solutionTransferring the mixture into a 50mL autoclave, and keeping the temperature at 160-200 ℃ for 9-12 hours;
s50: cooling the autoclave to room temperature, centrifuging the white precipitate, washing with ethanol and distilled water for several times, and drying at 60 ℃ overnight;
s60: calcining the precipitate in air atmosphere at a heating rate of 2 ℃/min at 500 ℃ for 2 hours to obtain ZnO nanosheets;
s70: subjecting the RuO obtained in S30x(0.5-2 mg) is dispersed in 20mL of ethanol and mixed with the ZnO (100mg) to form a mixture;
s80: treating the mixture with ultrasonic waves for 1 hour, and then drying the mixture for 8 hours at the temperature of 60-80 ℃ to finally obtain RuOxModified ZnO.
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