CN114570922B - Nanometer material capable of rapidly and repeatedly detecting hydrogen and preparation method thereof - Google Patents

Nanometer material capable of rapidly and repeatedly detecting hydrogen and preparation method thereof Download PDF

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CN114570922B
CN114570922B CN202210263738.1A CN202210263738A CN114570922B CN 114570922 B CN114570922 B CN 114570922B CN 202210263738 A CN202210263738 A CN 202210263738A CN 114570922 B CN114570922 B CN 114570922B
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CN114570922A (en
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刘丹丹
韩爱艳
耿资恒
柳云骐
潘原
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China University of Petroleum East China
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F9/00—Making metallic powder or suspensions thereof
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    • G01M3/20—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using special tracer materials, e.g. dye, fluorescent material, radioactive material
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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Abstract

The invention relates to the technical field of hydrogen detection, in particular to a nano material capable of rapidly and repeatedly detecting hydrogen and a preparation method thereof. The nano material has metal oxide nano islands of activated oxygen molecules on the surface and is loaded with noble metal nano particles. The adsorption-activation effect of the metal oxide nano islands on oxygen molecules in the air is utilized to assist in accelerating the adsorption and dissociation of oxygen in the recovery process of noble metal centers, so that the rate control step in the material recovery process is accelerated, the recovery time is shortened, and the rapid recovery of the colored material under the room temperature condition is realized. In addition, when the material prepared by the method contacts low-concentration hydrogen, visual color change can be generated, and after a hydrogen source is cut off, the material can be restored to an initial state after being contacted with air at room temperature, so that the hydrogen electrochromic property of the material can be restored, the effect of quick recycling can be achieved, and the popularization of the material in practical application is facilitated.

Description

Nanometer material capable of rapidly and repeatedly detecting hydrogen and preparation method thereof
Technical Field
The invention relates to the technical field of hydrogen detection, in particular to a nano material capable of rapidly and repeatedly detecting hydrogen and a preparation method thereof.
Background
At present, a visual hydrogen electrochromic-restoring material becomes a focus of attention, and the material can generate macroscopic color change after contacting H2, and can realize detection at low hydrogen concentration, so that the hydrogen leakage condition can be fed back quickly, intuitively, effectively and safely; after the discolored material encounters O2, the color of the material can be restored to the original color of the material, so that the repeated use of the material is realized.
By using the visualized hydrogen-induced color material, not only can the leakage of hydrogen be determined, but also the hydrogen leakage site can be accurately positioned, thereby achieving the effect of early warning of the micro leakage of hydrogen, saving time and labor, and also being capable of being repeatedly used and saving cost.
In the aspect of patent literature, chinese patent CN108593637 proposes a label ribbon for detecting hydrogen by taking a molybdenum oxide nanowire as a substrate and modifying noble metal quantum dots and a preparation method thereof, and after the hydrogen-sensitive material prepared by the patent reacts with the hydrogen, a series of optical signals such as reflectivity, transmissivity, wavelength and the like can be changed.
However, the following problems are difficult to overcome in the detection material:
(1) The color-changed material needs to be placed in a muffle furnace and heated at a high temperature of 200 ℃ for 2 hours to recover the color for reuse, and if the color can be recovered in a room temperature environment generally at least for 12 hours, the recycling efficiency is low, and the material has certain limitation in popularization and application.
(2) The color-changing response of the material in the color-developing process is slow or not color-changing when the material contacts low-concentration and low-flow hydrogen, and the visual contrast is not obvious enough, so that the material cannot be used in the low-concentration and low-flow environment.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art, and provides a nano material capable of rapidly and repeatedly detecting hydrogen and a preparation method thereof.
The technical scheme of the invention is as follows:
a nanomaterial capable of rapidly and repeatedly detecting hydrogen, comprising a nanomaterial, the surface of which has a metal oxide of an activated oxygen molecule in the form of a nanoisland and is also loaded with noble metal nanoparticles.
A preparation method of a nano material capable of rapidly and repeatedly detecting hydrogen comprises the following steps:
step 1: selecting a metal salt precursor with oxygen activating capacity, dissolving the metal salt precursor in a solvent, and fully stirring and dissolving to obtain a solution A;
step 2: WO is added to solution A 3 The nano material is fully stirred to form a suspension, and then the solvent is slowly evaporated at the temperature of 30-90 ℃ to obtain a material B;
step 3: carrying out heat treatment on the material B to obtain a material C;
step 4: and (3) selecting a noble metal compound, depositing noble metal nano particles on the surface of the material C by using a chemical reduction method such as atomic layer deposition, chemical reduction deposition, ultraviolet light reduction deposition and the like or a physical sputtering method such as magnetron sputtering, and finally drying to obtain the material capable of rapidly and repeatedly detecting hydrogen.
Preferably, the molar ratio of the metal element to the solvent in the metal salt in the step 1 is 0.01-60:1000.
preferably, the solvent in the step 1 is one or more of deionized water, absolute ethyl alcohol and methanol.
Preferably, the metal in the metal salt in the step 1 is one or more of zirconium, bismuth, cerium, titanium or zinc.
Preferably, the metal salt in the step 1 is one or more of nitrate, acetate, sulfate or chloride.
Preferably, WO in said step 2 3 The crystalline phase of the nanomaterial is one of a monoclinic phase, a triclinic phase, a hexagonal phase or an rhombohedral phase.
Preferably, WO in said step 2 3 The shape of the nano material is one of a nano sheet, a nano rod, a nano ball, a nano wire, a nano belt and a nano three-dimensional structure assembled based on the structural unitsOr several kinds of three-dimensional nanometer structures including nanometer flower, nanometer sea urchin, nanometer array, etc.
Preferably, the metal of the noble metal compound in the step 4 is one or more of gold, silver, palladium, platinum, rhodium and iridium.
Preferably, the temperature of the heat treatment is 150-400 ℃, the temperature rising rate is 1-10 ℃/min, and the heat treatment is carried out at constant temperature for 30-12 h.
Compared with the prior art, the invention has the following advantages:
the invention is carried out by the method disclosed in the conventional WO 3 The surface of the base hydrogen electrochromic material is modified with a metal oxide nano island with an oxygen activating effect, and the WO is accelerated on the basis of not influencing the response time and the color development degree of the hydrogen electrochromic performance by utilizing the adsorption-activation effect of the metal oxide nano island on oxygen molecules in the air 3 The process of dissociating hydrogen on the outer surface of the base hydrogen electrochromic material assists the noble metal center to enhance the response of the nano material to oxygen, improves the recovery rate of the colored material to an initial state in air at normal temperature, shortens the response-recovery period of the material, and is beneficial to popularization and application of the material in practical application scenes. The hydrogen color material prepared by the invention can be used in low H 2 Under the concentration, the hydrogen can be quickly responded to the naked eyes in a short time, the initial state can be quickly recovered in the air, and the material has reversibility and can be repeatedly used. The preparation process has simple conditions and is easy to operate in a large scale.
By controlling the volatilization rate of the metal salt solution and its pyrolysis process during the impregnation process, in WO 3 The surface of the base hydrogen electrochromic material is modified with a metal oxide nano island with an oxygen activating effect, and WO is accelerated through the adsorption-activating effect of the metal oxide nano island on oxygen molecules in air 3 And in the process of dissociating oxygen on the outer surface of the base hydrogen electrochromic material, the noble metal center is assisted to strengthen the response of the nano material to oxygen, the recovery rate of the colored material to an initial state in air at normal temperature is improved, and the response-recovery period of the material is shortened.
Currently conventional hydrogen-chromic materials, although alsoInvolving the introduction of a second metal oxide, but by bulk doping during the preparation, and the purpose of this is to use the metal oxide with WO 3 The synergistic effect of (2) intensifies the hydrogen-induced discoloration process without promoting its recovery process.
Therefore, the conventional methods disclosed are essentially different from the present patent in terms of the selection, introduction manner, and addition purpose of the second metal oxide.
The introduction of the metal oxide nano islands can also serve as a physical grid effect while improving the oxygen activating capability of the material, so that the high dispersion of noble metal centers is realized, and the aggregation of the noble metal centers is inhibited, thereby improving the hydrogen dissociation rate of the material and enabling the hydrogen-induced color change material to be low in H 2 Under the concentration, the hydrogen can be quickly responded to the naked eyes in a short time, the service life of the material can be prolonged, and the sensitivity of the material can be ensured.
Drawings
FIG. 1 is an X-ray powder diffraction Pattern (PXRD) of the hydrochromic-restoration material prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the hydrogen electrochromic-restorative material prepared in example 1;
FIG. 3 is a Transmission Electron Microscope (TEM) image of the hydrogen electrochromic-restorative material obtained in example 1;
FIG. 4 is an EDS diagram of the hydrogen electrochromic-restorative material prepared in example 1;
FIG. 5 is an X-ray powder diffraction Pattern (PXRD) of the hydrochromic-restoration material prepared in example 2;
FIG. 6 is a Scanning Electron Microscope (SEM) image of the hydrogen electrochromic-restorative material prepared in example 2;
FIG. 7 is a Transmission Electron Microscope (TEM) image of the hydrogen electrochromic-restoring material prepared in example 2;
FIG. 8 is an EDS diagram of the hydrogen electrochromic-restorative material prepared in example 2;
FIG. 9 is a spectrum of the hydrogen discoloration-recovering material prepared in example 1 before and after discoloration;
FIG. 10 is a graph showing the discoloration-recovery cycle of the hydrogen discoloration-recovery materials prepared in example 1 and example 2 and comparative example 1;
FIG. 11 shows example 1 in series 1%H 2 Multi-cycle hydrochromic-recovery cycle diagram with/Ar and air switching.
Detailed Description
The invention is further illustrated by the following examples in connection with the accompanying drawings.
The present invention is further illustrated below with reference to specific embodiments and the accompanying drawings, but the present invention is not limited thereto, and the embodiments described below are some, but not all embodiments of the present invention, and are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The test methods described in the following examples were performed under conventional conditions or manufacturer-suggested conditions, where no specific conditions were noted in the examples; the apparatus and materials are commercially available unless otherwise specified.
It should be noted that the hydrogen content in this document is described as volume fraction.
Example 1:
the preparation method of the reversible tungsten oxide-based hydrochromic-restoring material for multi-cycle repeated use comprises the following steps:
(1) 0.0106g ZrOCl was weighed out 2 ·8H 2 O was dissolved in 10mL deionized water with a molar ratio of zirconium to deionized water in the metal source of 0.06:1000, stirring continuously for 30min to obtain a solution A;
(2) To solution A0.4 g of WO was added 3 The nanowire is fully stirred for 30min, the suspension is transferred into a 60 ℃ oven for slowly evaporating the solvent, and after 12h of complete drying, the sample is collected to obtain a material B;
(3) Placing the material B in a muffle furnace, heating to 300 ℃ at a speed of 2 ℃/min, maintaining for 3 hours, and cooling to room temperature to obtain the metal oxide modified WO 3 Nanowires, denoted material C;
(4) Weigh 0.500gDispersing the material C in 60mL deionized water, and stirring for 30min; to the suspension, a chloroplatinic acid solution having a concentration of 1g/L of 13.6. 13.6mL was added dropwise; under ice bath, 6.5 mLNaBH 4 The aqueous solution is added into the suspension drop by drop, and the suspension is continuously stirred for 0.5 to h, kept stand for half an hour, filtered by suction, washed by deionized water for three times, and dried, thus obtaining the quick response-recovery hydrogen electrochromic material.
ZrO obtained by the preparation of this example 2 Nanometer island modified WO 3 X-ray powder diffraction (XRD), scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) patterns of the nanowire-supported platinum-hydrogen electrochromic material are shown in FIGS. 1-3, respectively. WO prepared in this example 3 No ZrO is observed in the nanowire hydrochromic material 2 And Pt phase. To further demonstrate the success of the modification of ZrO at the example surface 2 The nano islands, which were obtained by EDS analysis of the prepared material, were shown in FIG. 4, in which ZrO was uniformly modified on the surface of the example 2 。
Example 2:
referring to fig. 2 to 8, the preparation method of the reversible tungsten oxide-based electrochromic-restoring material for multi-cycle repeated use according to the embodiment comprises the following steps:
(1) Weigh 0.0084gBi (NO) 3 ) 3 ·5H 2 O is dissolved in 10mL deionized water, and the molar ratio of bismuth element in the metal source to deionized water is 0.03:1000, stirring continuously for 30min to obtain a solution A;
(2) Adding 0.4. 0.4gWO to solution A 3 The nanowire is fully stirred for 30min, the suspension is transferred into a 60 ℃ oven for slowly evaporating the solvent, and after 12h of complete drying, the sample is collected to obtain a material B;
(3) Placing the material B in a muffle furnace, heating to 300 ℃ at a speed of 2 ℃/min, maintaining for 3 hours, and cooling to room temperature to obtain the metal oxide modified WO 3 Nanowires, denoted material C;
(4) 0.500g of material C is weighed and dispersed in 60mL of deionized water, and stirred for 30min; 13.6mL of a chloroplatinic acid solution with the concentration of 1g/L is added dropwise into the suspension; under ice bath, 6.5 mLNaBH 4 The aqueous solution is added dropwise into the suspensionContinuously stirring for 0.5 to h, standing for half an hour, filtering, washing with deionized water for three times, and drying to obtain the quick-response-recovery hydrogen electrochromic material.
Bi prepared in this example 2 O 3 Nanometer island modified WO 3 X-ray powder diffraction (XRD), scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) patterns of the nanowire-supported platinum-hydrogen electrochromic material are shown in FIGS. 5-7, respectively. WO prepared in this example 3 No Bi is observed in the nanowire hydrochromic material 2 O 3 And Pt phase. To further demonstrate the successful modification of Bi at the example surface 2 O 3 The nano islands were subjected to EDS analysis of the prepared material, and the result is shown in FIG. 8, from which it can be seen that Bi was uniformly modified on the surface of the present example 2 O 3 . It is demonstrated that this method can produce highly dispersed metal oxide nanoislands similar to example 1.
Example 3:
the preparation method of the reversible tungsten oxide-based hydrochromic-restoring material for multi-cycle repeated use comprises the following steps:
(1) Weigh 0.0108gCe (NO) 3 ) 3 ·6H 2 O is dissolved in 10mL deionized water, and the molar ratio of cerium element in the metal source to deionized water is 0.025:1000, stirring continuously for 30min to obtain a solution A;
(2) Adding 0.4. 0.4gWO to solution A 3 The nanowire is fully stirred for 30min, the suspension is transferred into a 60 ℃ oven for slowly evaporating the solvent, and after 12h of complete drying, the sample is collected to obtain a material B;
(3) Placing the material B in a muffle furnace, heating to 300 ℃ at a speed of 2 ℃/min, maintaining for 3 hours, and cooling to room temperature to obtain the metal oxide modified WO 3 Nanowires, denoted material C;
(4) 0.500g of material C is weighed and dispersed in 60mL deionized water, and stirred for 30min; to the suspension, a chloroplatinic acid solution having a concentration of 1g/L of 13.6. 13.6mL was added dropwise; 6.5 mL NaBH was added under ice bath 4 Dropwise adding the aqueous solution into the suspension, continuously stirring for 0.5. 0.5 h, standing for half an hour, filtering, washing with deionized water for three times, and dryingDrying to obtain the quick response-recovery hydrogen chromic material.
Example 4:
the preparation method of the reversible tungsten oxide-based hydrochromic-restoring material for multi-cycle repeated use comprises the following steps:
(1) 0.0047g TiCl was weighed out 4 Dissolved in 10mL deionized water, the molar ratio of titanium element to deionized water in the metal source was 0.045:1000, stirring continuously for 30min to obtain a solution A;
(2) To solution A0.4 g of WO was added 3 The nanoflower is fully stirred for 30min, the suspension is transferred into a 50 ℃ oven for slowly evaporating the solvent, and the sample is collected after 14h of complete drying, so as to obtain a material B;
(3) Placing the material B in a muffle furnace, heating to 300 ℃ at a speed of 2 ℃/min, maintaining for 3 hours, and cooling to room temperature to obtain the metal oxide modified WO 3 Nano flowers, which are marked as a material C;
(4) 0.500g of material C is weighed and dispersed in 30mL of deionized water, and stirred for 30min; 4.7mL of a 1g/L palladium chloride solution was added dropwise to the suspension; and exposing the suspension for 7 hours under an ultraviolet lamp, filtering, washing with deionized water for three times, and drying to obtain the quick-response-recovery hydrogen electrochromic material.
Example 5:
the preparation method of the reversible tungsten oxide-based hydrochromic-restoring material for multi-cycle repeated use comprises the following steps:
(1) Weigh 0.0074gZn (NO) 3 ) 3 ·6H 2 O was dissolved in 10mL deionized water with a molar ratio of zinc metal to deionized water of 0.045:1000, stirring continuously for 30min to obtain a solution A;
(2) To solution A0.4 g of WO was added 3 The nanowire is fully stirred for 30min, the suspension is transferred into an oven at 80 ℃ to slowly evaporate the solvent, and after 10h of complete drying, the sample is collected to obtain a material B;
(3) Placing the material B in a muffle furnace, heating to 300 ℃ at a speed of 2 ℃/min, maintaining the temperature to 3h, and cooling to room temperature to obtain the metal oxide modified materialWO of (2) 3 Nanowires, denoted material C;
(4) Dispersing a certain amount of material C on a high-temperature-resistant quartz glass plate, performing a deposition reaction in a deposition reactor of an Atomic Layer Deposition (ALD) system, wherein a precursor for ALD deposition of Pt nano particles is trimethylcyclopentadienyl platinum, and depositing for 5 cycles by taking precursor ozone as an oxidant to obtain the hydrogen-induced color material capable of rapidly responding and recovering.
Example 6:
the preparation method of the reversible tungsten oxide-based hydrochromic-restoring material for multi-cycle repeated use comprises the following steps:
(1) Weighing 0.0106g ZrOCl.8H 2 O was dissolved in 10mL deionized water with a molar ratio of zirconium to deionized water in the metal source of 0.06:1000, stirring continuously for 30min to obtain a solution A;
(2) Adding 0.4. 0.4gWO to solution A 3 The nano belt is fully stirred for 30min, the suspension is transferred into a 60 ℃ oven for slowly evaporating the solvent, and after 12h of complete drying, the sample is collected to obtain a material B;
(3) Placing the material B in a muffle furnace, heating to 300 ℃ at a speed of 2 ℃/min, maintaining the temperature to 3h, and cooling to room temperature to obtain the metal oxide modified WO 3 A nanoribbon, denoted material C;
(4) 0.100 of g material C is weighed and dispersed in a mixed solution of 48 mL glycol and water (V ethylene glycol: V water=5:1), and stirred for 30min; and (3) dropwise adding 15mL of 1g/L chloroplatinic acid solution into the suspension, stirring for 2 hours, transferring into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting at 120 ℃ for 2h, centrifugally separating the product, filtering, washing with deionized water for three times, and drying to obtain the quick-response-recovery hydrogen-induced color material.
Experimental example 1:
see fig. 9-11 for further description of WO 3 Influence of surface Metal oxide nanoislands on the recovery Properties of Hydrogen-induced color change Material in WO with example 1, example 2 and distinction of unmodified Metal oxide nanoislands only 3 Platinum-carrying Material as comparative example 1, the material was tested for Hydrogen color change-recovery periodThe difference of the performances is compared with the influence of the modification of the metal oxide nanometer islands on the recovery performance of the hydrogen-induced color change material.
The test method is as follows:
weighing 0.1 g of fully dried sample, uniformly spreading the sample in a sample tank, compacting the sample tank into a plane, sealing the sample tank in an opaque air chamber, and sealing the sample tank. The light source of the optical fiber spectrometer is vertically irradiated to the surface of the sample, then the reflection spectrum of the surface of the sample is collected from the signal collector at the center of the probe, and after the spectrum is stabilized, 1% of H is introduced 2 The flow rate of the Ar mixture was 30mL/min, and then the change in reflectance spectrum of the sample was observed, and the change in reflectance at 750nm over time was recorded. After the sample reaches the final coloring state and is maintained for 5 min, the atmosphere is switched to air, the change of the reflection spectrum of the sample is observed, and the change curve of the reflectivity at 750nm along with time is continuously recorded.
The results of the test are shown in FIGS. 9-10, FIG. 9 is the reflectance spectra of example 1 before and after contact with 1% hydrogen by volume, FIG. 10 is WO modified with different metal oxides 3 The hydrogen sensitivity performance test results of the platinum-carrying hydrogen electrochromic material with the change curve of the reflectivity at 750nm along with time are shown in table 1.
Table 1: pt/MO x -WO 3 Hydrochromic material and results of a hydrochromic-recovery Performance test
Figure 202511DEST_PATH_IMAGE001
From the above results, it can be seen that the reflectance spectrum of example 1 changes significantly after contact with hydrogen, indicating that the color of the sample changed.
Examples and comparative example 1 after exposure to hydrogen, the color of the material changed from light to dark, and the reflectance decreased rapidly, indicating that a significant color change was seen with the naked eye in a short period of time.
After the examples and comparative example 1 reached the final colored state, air was introduced at room temperature, and the reflectance of the material was recovered in real time, indicating that the material began to fade and gradually recovered to the original state over time. As can be seen from the data of comparative examples and comparative example 1, the modification of the metal oxide nano islands does not have a significant effect on the hydrogen electrochromic properties, but the recovery time of the material after hydrogen electrochromic is significantly shortened, and the recovery rate is improved.
Experimental example 2:
to further illustrate that the hydrogen electrochromic material of the present invention has excellent reversibility, taking example 1 as an example, the hydrogen electrochromic material prepared in example 1 is tested according to the test method of experimental example 1, the same hydrogen concentration is adopted at room temperature, the reflectivity of the material is continuously, reciprocally and continuously changed, and the test result is shown in fig. 11.
From the graph, after the material with hydrogen color reaches the final coloring state, air is introduced at room temperature, the color can be restored to the initial state, the response of the restored material to hydrogen can be restored in real time, and the performance is hardly changed after continuous circulation for many times, so that the material has excellent circulation reversibility.
The above examples 1-6 and experimental examples 1-2 are not limiting, and in the actual production process, the process parameters and the ratio thereof may be amplified by a multiple to satisfy the production requirements. Other combinations not illustrated will be apparent to those skilled in the art from the above description of examples 1-6 and examples 1-2.
It is noted that any equivalent or obvious modification made by those skilled in the art under the teachings of this specification shall fall within the scope of this invention.

Claims (8)

1. A preparation method of a nano material capable of rapidly and repeatedly detecting hydrogen is characterized by comprising the following steps of: the surface of the nanomaterial is provided with a metal oxide of activated oxygen molecules in the form of nanometer islands and is also loaded with noble metal nanoparticles;
the preparation method comprises the following steps:
step 1: selecting a metal salt precursor with oxygen activating capacity, dissolving the metal salt precursor in a solvent, and fully stirring and dissolving to obtain a solution A;
step 2: WO is added to solution A 3 The nano material is fully stirred to form a suspension, and then the solvent is slowly evaporated at the temperature of 30-90 ℃ to obtain a material B;
step 3: carrying out heat treatment on the material B to obtain a material C, wherein the temperature of the heat treatment is 150-400 ℃, the heating rate is 1-10 ℃/min, and the heat treatment is carried out for 30-12 h at constant temperature;
step 4: and (3) selecting a noble metal compound, depositing noble metal nano particles on the surface of the material C by a chemical reduction method and a physical sputtering method, and finally drying to obtain the material capable of rapidly and repeatedly detecting hydrogen.
2. The method for preparing the nanomaterial capable of rapidly and repeatedly detecting hydrogen according to claim 1, wherein the method comprises the following steps: the molar ratio of the metal element to the solvent in the metal salt in the step 1 is 0.01-60:1000.
3. the method for preparing the nanomaterial capable of rapidly and repeatedly detecting hydrogen according to claim 1, wherein the method comprises the following steps: the solvent in the step 1 is one or more of deionized water, absolute ethyl alcohol and methanol.
4. The method for preparing the nanomaterial capable of rapidly and repeatedly detecting hydrogen according to claim 1, wherein the method comprises the following steps: the metal in the metal salt in the step 1 is one or more of zirconium, bismuth, cerium, titanium or zinc.
5. The method for preparing the nanomaterial capable of rapidly and repeatedly detecting hydrogen according to claim 1, wherein the method comprises the following steps: the metal salt in the step 1 is one or more of nitrate, acetate, sulfate or chloride.
6. The method for preparing the nanomaterial capable of rapidly and repeatedly detecting hydrogen according to claim 1, wherein the method comprises the following steps: WO in said step 2 3 The crystal phase of the nano material is singleOne of a rhombic phase, a triclinic phase, a hexagonal phase or a rhombic phase.
7. The method for preparing the nanomaterial capable of rapidly and repeatedly detecting hydrogen according to claim 6, wherein the method comprises the following steps: WO in said step 2 3 The shape of the nano material is one or more of a nano sheet, a nano rod, a nano ball, a nano wire, a nano belt and a nano three-dimensional structure assembled based on the structural units.
8. The method for preparing the nanomaterial capable of rapidly and repeatedly detecting hydrogen according to claim 1, wherein the method comprises the following steps: the metal of the noble metal compound in the step 4 is one or more of gold, silver, palladium, platinum, rhodium and iridium.
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