CN114505058A - Metal organic framework material assisted high-sensitivity hydrogen detection nano material and preparation method thereof - Google Patents
Metal organic framework material assisted high-sensitivity hydrogen detection nano material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of hydrogen detection materials, in particular to a metal organic framework material-assisted high-sensitivity hydrogen detection nano material and a preparation method thereof. And the hydrogen with low concentration is enriched on the surface of the nano material by the confinement-enrichment effect of micropores, open metal sites and the like in the MOF coated on the surface of the nano material on hydrogen molecules, so that the hydrogen concentration on the surface of the material is improved, the sensitivity of the material to the hydrogen and the hydrogen-induced discoloration rate of the material are further improved, and the material can realize quick response in the environment with low hydrogen concentration and low flow rate.
Description
Technical Field
The invention relates to the technical field of hydrogen detection materials, in particular to a metal organic framework material-assisted high-sensitivity hydrogen detection nano material and a preparation method thereof.
Background
The hydrogen is a colorless and tasteless gas, and is easy to generate hydrogen embrittlement phenomenon, and is easy to leak and not easy to be perceived when in application, so that the popularization and application of hydrogen energy are limited to a certain extent. Therefore, in order to realize the safe and efficient utilization of hydrogen energy and avoid accidents, the leakage of hydrogen needs to be monitored by developing a quick, accurate and high-sensitivity hydrogen detection mode, so that the safety of hydrogen in the processes of storage, transportation and use is ensured.
Against this background, a visual hydrogen-induced discoloration material, which is brought into contact with H, becomes the trigger for solving the problem2And then, the obvious color change which can be distinguished by naked eyes can be generated, so that the leakage condition of the hydrogen can be fed back quickly, visually, effectively and safely, a visual solution is provided for solving the problem of hydrogen leakage, and early warning can be performed in advance.
In the patent literature, chinese patent CN108072497 is based on WO3The hydrogen-induced color-changing material is characterized in that a layer of polymer is coated on the surface of the material for improving the stability of the material, and is used for isolating the influence of oxygen and water molecules in the air on the material.
At present, in the hydrogen use process, the hydrogen leakage detection time is in positive correlation with the safety factor, so that the response sensitivity of the material in the hydrogen discoloration process is improved, and the response time is shortened.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a metal-organic framework material assisted high-sensitivity hydrogen detection nano material and a preparation method thereof.
The technical scheme of the invention is as follows:
a metal organic framework material assisted high-sensitivity hydrogen detection nano material comprises a nano material, wherein the surface of the nano material is coated with the metal organic framework material with a hydrogen molecule confinement effect.
A preparation method of a metal organic framework material assisted high-sensitivity hydrogen detection nano material is characterized by comprising the following steps: the method comprises the following steps:
step 1, dissolving a metal salt in a solvent to prepare a solution A;
step 3, mixing the solution A and the solution B, fully stirring to obtain a mixed solution, adding a pH regulator into the mixed solution, and uniformly stirring to obtain an MOF synthesis mother liquor;
step 4, adding WO into MOF synthesis mother liquor3And (3) uniformly stirring the nano materials, carrying out thermal reaction, and then cooling, filtering, washing and drying to obtain a material A.
And 5: selecting a noble metal compound, depositing noble metal nanoparticles on the surface of the material A by using a chemical reduction method such as atomic layer deposition, chemical reduction deposition, ultraviolet light reduction method deposition and the like or a physical sputtering method of magnetron sputtering of the noble metal compound, and finally drying to obtain the high-sensitivity hydrogen detection nanomaterial assisted by the metal organic framework material.
A preparation method of a metal organic framework material assisted high-sensitivity hydrogen detection nano material is characterized by comprising the following steps: the method comprises the following steps:
step 1, selecting a noble metal compound, and depositing noble metal nanoparticles on WO by using the noble metal compound through a chemical reduction method such as atomic layer deposition, chemical reduction deposition, ultraviolet light reduction method deposition and the like or a physical sputtering method of magnetron sputtering3And (5) obtaining a material B on the surface of the nano material.
step 3, dissolving an organic ligand in a solvent to prepare a solution B;
and 4, step 4: fully stirring the solution A and the solution B to obtain a mixed solution, adding a pH regulator into the mixed solution, and uniformly stirring to obtain an MOF synthetic mother liquor;
and 5, adding the material B into the MOF synthesis mother liquor, uniformly stirring, carrying out thermal reaction, cooling, filtering, washing and drying to obtain the high-sensitivity hydrogen detection nano material assisted by the metal organic framework material.
Preferably, the molar ratio of the metal element to the organic ligand in the metal salt is 0.1-5: 1.
preferably, the metal salt is one or more of nitrate, acetate, sulfate or chloride, and the metal element in the metal salt is one or more of aluminum, zinc, zirconium and magnesium.
Preferably, the solvent is one or more of deionized water, absolute ethyl alcohol, methanol and N, N-dimethylformamide, and the molar ratio of the metal elements in the metal salt to the solvent is 0.01-1: 10-100, the molar ratio of the ligand to the solvent b is 0.01-1: 10-100.
Preferably, the organic ligand in step 2 is one or more of 1, 4-terephthalic acid, fumaric acid, 2, 5-dihydroxyterephthalic acid, 44 ' -biphenyldicarboxylic acid, azobenzene-4, 4-dicarboxylic acid, 2 ' -bipyridine-5, 5' -dicarboxylic acid, 1,3, 5-trimesic acid, and 3,3',5,5' -biphenyltetracarboxylic acid.
Preferably, the regulator is one or more of hydrochloric acid, nitric acid, hydrofluoric acid, formic acid and acetic acid, and the volume ratio of the pH regulator to the mixed solution is 0-1: 10-50. .
Preferably, the thermal reaction in the step 4 is that the system reacts for 30min-75 h at 80-220 ℃.
Preferably, the crystalline phase of the nanomaterial is one of a monoclinic phase, a triclinic phase, a hexagonal phase or an orthorhombic phase;
the shape of the nano material is one or more of nano sheets, nano rods, nano spheres, nano wires, nano belts and nano three-dimensional structures assembled based on the structural units;
the metal of the noble metal compound is one or more of gold, silver, palladium, platinum, rhodium and iridium.
Compared with the prior art, the invention has the following advantages:
the invention is realized by the conventional WO3Radical hydrogen induced changeThe surface of the color material is coated with a metal organic framework material, the hydrogen molecules are captured under low hydrogen concentration by utilizing the domain-limiting and enriching action of micropores, open metal sites and the like in the metal organic framework material on the hydrogen molecules, and then the hydrogen enrichment-supply action of the metal organic framework material is utilized to accelerate WO3The dissociation process of the hydrogen on the outer surface of the hydrogen-based allochroic material shortens the response time and improves the sensitivity of the material.
Compared with the traditional WO3The hydrogen-induced color-changing material utilizes the particularity of the structure of the metal organic framework material to realize enrichment-supply of hydrogen under low hydrogen concentration, thereby not only improving the color development rate of the hydrogen-induced color-changing material, but also increasing the contrast of color development, and being more suitable for monitoring hydrogen leakage under low flow rate and low concentration. Therefore, the hydrogen-induced color-changing material prepared by the method can be in low H2Under the conditions of concentration and low gas flow rate, macroscopic quick response is generated to hydrogen in a short time, and the preparation process has simpler conditions and is easy to operate on a large scale.
Drawings
FIG. 1 shows Pt/WO obtained in example 13X-ray powder diffraction Pattern (PXRD) of @ MOF material;
FIG. 2 shows Pt/WO obtained in example 13A Scanning Electron Microscope (SEM) picture of the @ MOF material;
FIG. 3 shows Pt/WO obtained in example 13A Transmission Electron Microscope (TEM) image of the @ MOF material;
FIG. 4 shows Pt/WO obtained in example 13The low-temperature nitrogen adsorption and desorption curve diagram and the pore size distribution diagram of the @ MOF material;
FIG. 5 shows Pt/WO obtained in example 23A Scanning Electron Microscope (SEM) picture of the @ MOF material;
FIG. 6 shows Pt/WO obtained in example 23Transmission Electron Microscope (TEM) images of the @ MOF material.
Detailed Description
The invention will be further explained below with reference to specific embodiments and the drawing, to which, however, the invention is not restricted. The test methods described in the following examples are all conventional methods unless otherwise specified; the apparatus and materials are commercially available, unless otherwise specified.
Example 1:
high sensitivity WO assisted by a Metal organic framework Material as described in this example3The preparation method of the hydrogen-based allochroic material comprises the following steps:
(1) weighing 0.028 g of zirconium tetrachloride, and dissolving in 8 ml of N, N-Dimethylformamide (DMF) solvent to obtain a solution A; weighing 0.021 g of 1, 4-terephthalic acid, and dissolving in 8 ml of N, N-Dimethylformamide (DMF) solvent to obtain a solution B; mixing the solution A and the solution B, fully stirring, adding 0.5 ml of acetic acid, and uniformly stirring to obtain MOF mother liquor;
(2) addition of WO to the MOF mother liquor described above3And (3) fully stirring the nano rods, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 3 hours at 120 ℃, centrifugally separating a product, cleaning with DMF (dimethyl formamide) and ethanol for three times, and drying by a vacuum drying oven to obtain a material A.
(3) Weighing 0.500g of the material A, dispersing in 60mL of deionized water, and stirring for 30 min; 13.6mL of chloroplatinic acid solution with the concentration of 1g/L is added into the suspension drop by drop; under ice bath, the excessive newly prepared NaBH4Dropwise adding the aqueous solution into the suspension, continuously stirring for 0.5 h, standing for half an hour, performing suction filtration, washing with deionized water for three times, and drying to obtain Pt/WO3@ MOF Hydrochromic material.
Obtained Pt/WO3The X-ray powder diffraction pattern of the @ MOF hydrochromic material is shown in FIG. 1, and it can be seen from FIG. 1 that the product obtained by the preparation of the example is WO3A composite phase with MOF.
As shown in FIGS. 2 and 3, the Scanning Electron Microscope (SEM) and the Transmission Electron Microscope (TEM) showed that the obtained hydrogen-induced discoloration material was obtained in WO 2 and 33The outer surface is evenly coated with MOF nano particles.
As can be seen from the low-temperature nitrogen adsorption and desorption isotherm and the pore size distribution diagram of the material in FIG. 4, the hydrogen-induced discoloration material has a hierarchical pore structure and a high micropore ratio, and the specific surface area of the obtained material is 103 m2Per g, specific surface area of micropores 68.7m2/g。
Micropores mainly come from MOF materials, and mesopores come from stacking holes formed by nanorods, which are all helpful to the improvement of hydrogen discoloration performance.
Example 2:
high sensitivity WO assisted by a Metal organic framework Material as described in this example3The preparation method of the hydrogen-based allochroic material comprises the following steps:
(1) 0.500g of WO is weighed out3Dispersing the nano rods in 60mL of deionized water, and stirring for 30 min; 13.6mL of chloroplatinic acid solution with the concentration of 1g/L is added into the suspension drop by drop; under ice bath, the excessive newly prepared NaBH4And dropwise adding the aqueous solution into the suspension, continuously stirring for 0.5 h, standing for half an hour, performing suction filtration, washing with deionized water for three times, and drying to obtain a material B.
(2) Weighing 0.014 g of zirconium tetrachloride, and dissolving in 8 ml of N, N-Dimethylformamide (DMF) solvent to obtain a solution A; weighing 0.011 g of 1, 4-terephthalic acid and dissolving in 8 ml of N, N-Dimethylformamide (DMF) solvent to obtain solution B; mixing the solution A and the solution B, fully stirring, adding 0.5 ml of acetic acid, and uniformly stirring to obtain MOF mother liquor;
(3) adding the material B into the MOF mother liquor, fully stirring, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 3 hours at 120 ℃, centrifugally separating the product, washing with DMF (dimethyl formamide) and ethanol for three times, and drying by a vacuum drying oven to obtain Pt/WO (platinum/tungsten oxide)3@ MOF Hydrochromic material.
Pt/WO obtained in this example3SEM and TEM images of the @ MOF hydrochromic material are shown in FIGS. 5 and 6, and it can be seen from the images that the MOF particles are uniformly coated on WO3Nanowire surface, similar to example 1.
Example 3:
high sensitivity WO assisted by a Metal organic framework Material as described in this example3The preparation method of the hydrogen-based allochroic material comprises the following steps:
(1) 0.500g of WO is weighed out3Dispersing the nano-sheets in 30mL of deionized water, and stirring for 30 min; 4.7mL of 1g/L palladium chloride solution was added dropwise to the suspensionLiquid; and (3) exposing the suspension for 7 hours under an ultraviolet lamp, performing suction filtration, washing with deionized water for three times, and drying to obtain a material B.
(2) Weighing 0.028 g of aluminum nitrate and dissolving in 10 ml of deionized water to obtain a solution A; weighing 0.021 g of 1, 4-terephthalic acid and dissolving in 10 ml of methanol solvent to obtain solution B; weighing the solution A and the solution B, mixing, fully stirring, adding 0.05 ml of nitric acid, and uniformly stirring to obtain MOF mother liquor;
(3) adding the material B into the MOF mother liquor, fully stirring, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 4 hours at 210 ℃, centrifugally separating the product, cleaning with ethanol and deionized water for three times, and drying to obtain the Pd/WO3@ MOF Hydrochromic material.
Example 4:
high sensitivity WO assisted by a Metal organic framework Material as described in this example3The preparation method of the hydrogen-based allochroic material comprises the following steps:
(1) 0.031 g of magnesium nitrate is dissolved in 5 ml of a mixed solution of N, N-dimethylformamide, ethanol and water (V)N, N-dimethylformamide：VEthanol：VWater (W)= 15: 1: 1) to obtain a solution A; 0.024 g of 2, 5-dihydroxyterephthalic acid was weighed and dissolved in 5 ml of a mixed solution of N, N-dimethylformamide, ethanol and water (V)N, N-dimethylformamide：VEthanol：VWater (W)= 15: 1: 1) to obtain a solution B; mixing the solution A and the solution B, fully stirring, adding 0.2 ml of acetic acid, and uniformly stirring to obtain MOF mother liquor;
(2) addition of WO to the MOF mother liquor described above3And (3) stirring the nanoflower completely, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 5 hours at 125 ℃, centrifugally separating a product, washing with ethanol and deionized water for three times, and drying in a vacuum drying oven to obtain a material A.
(3) Weighing 0.500g of the material A, dispersing in 50 mL of deionized water, and stirring for 30 min; adding 1.05 mL chloroauric acid solution with concentration of 1g/100mL into the suspension dropwise, adding 0.15g urea into the suspension, and raising temperature to 80 deg.C in darkStirring for 12 h, cooling to room temperature, centrifuging, washing with deionized water, and vacuum drying to obtain Au-WO3@ MOF Hydrochromic material.
Example 5:
high sensitivity WO assisted by a Metal organic framework Material as described in this example3The preparation method of the hydrogen-based allochroic material comprises the following steps:
1) weighing 0.035 g of zinc nitrate, and dissolving in 6ml of N, N-dimethylformamide to obtain a solution A; weighing 0.021 g of 1, 4-terephthalic acid, and dissolving in 6ml of N, N-dimethylformamide to obtain a solution B; mixing the solution A and the solution B, fully stirring, and uniformly stirring to obtain MOF mother liquor;
(2) adding Ir-WO to the MOF mother liquor3And (3) fully stirring the nanowires, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 3 hours at 105 ℃, centrifugally separating a product, cleaning the product with DMF (dimethyl formamide) and ethanol for three times, and drying the product in a vacuum drying oven to obtain a material A.
(3) Dispersing a certain amount of material A on a high-temperature-resistant quartz glass plate, carrying out deposition reaction in a deposition reactor of an Atomic Layer Deposition (ALD) system, depositing 15 cycles to obtain Pt-WO (platinum-tungsten oxide) by taking trimethyl methylcyclopentadienyl platinum as a precursor for ALD deposition of Pt nanoparticles and ozone as an oxidant3@ MOF Hydrochromic material.
Example 6:
high sensitivity WO assisted by a Metal organic framework Material as described in this example3The preparation method of the hydrogen-based allochroic material comprises the following steps:
1) weighing 0.028 g of aluminum chloride, dissolving the aluminum chloride in 5 ml of deionized water to obtain a solution A, and dissolving 0.013 g of 1,3, 5-trimesic acid in 6ml of ethanol to obtain a solution B; mixing the solution A and the solution B, and then fully stirring to obtain MOF mother liquor;
(2) addition of WO to the MOF mother liquor described above3And (3) fully stirring the nanospheres, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 10 hours at 200 ℃, centrifugally separating a product, washing with deionized water and ethanol for three times, and drying in a vacuum drying oven to obtain a material A.
(3) Weighing 0.500g of the material A, dispersing the material A in 30mL of deionized water, and stirring for 30 min; dropwise adding 1.25 mL of 1g/100mL potassium chloroiridate solution into the suspension, and continuously stirring for 3 h; dropwise adding the newly-prepared NaBH4 aqueous solution into the suspension under ice bath, continuously stirring for 0.5 h, standing for half an hour, performing suction filtration, washing with deionized water for three times, and drying to obtain Ir-WO3@ MOF Hydrochromic material.
Experimental example 1:
to further verify the influence of the metal organic framework material on the hydrogen discoloration performance and rate, taking example 1 as an example, the influence of coating proportion of different metal organic framework materials on the hydrogen discoloration sensitivity is compared, and the steps are as follows:
(1) weighing a certain mass of zirconium tetrachloride, dissolving the zirconium tetrachloride in 8 ml of N, N-Dimethylformamide (DMF) solvent to obtain a solution A, weighing 1, 4-terephthalic acid with corresponding mass, and dissolving the 1, 4-terephthalic acid in 8 ml of N, N-Dimethylformamide (DMF) solvent to obtain a solution B; mixing the solution A and the solution B, fully stirring, adding 0.5 ml of acetic acid, and uniformly stirring to obtain MOF mother liquor;
(2) adding Pt-WO to the MOF mother liquor3And (3) fully stirring the nano rods, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 3 hours at 120 ℃, centrifugally separating a product, washing with DMF (dimethyl formamide) and ethanol for three times, and drying by a vacuum drying oven to obtain a material A.
(3) Weighing 0.500g of the material A, dispersing the material A in 60mL of deionized water, and stirring for 30 min; 13.6mL of chloroplatinic acid solution with the concentration of 1g/L is added into the suspension drop by drop; under ice-bath, excess newly-configured NaBH will be added4Dropwise adding the aqueous solution into the suspension, continuously stirring for 0.5 h, standing for half an hour, performing suction filtration, washing with deionized water for three times, and drying to obtain Pt/WO3@ MOF Hydrochromic material.
(4) Hydrogen induced discoloration performance test:
Pt/WO prepared in this example3The @ MOF hydrogen-induced discoloration material is subjected to hydrogen-induced discoloration performance evaluation under the conditions of low hydrogen concentration and low mixed gas flow, and the specific operation is as follows: 0.1 g of fully dried Pt/WO was weighed3The @ MOF sample is evenly laid in the sample cell and compacted into a plane, and the sample cell is sealed inside an opaque gas cell and sealed. Vertically irradiating a light source of a fiber optic spectrometer to the surface of a sample, then collecting a reflection spectrum of the surface of the sample from a signal collector at the center of a probe, and introducing 1% of H after the spectrum is stabilized2The flow rate of the/Ar mixed gas is 30mL/min, and then the change of the reflection spectrum of the sample is observed, and the change curve of the reflectivity at 750nm along with the time is recorded.
Pt/WO prepared in this example3The results of the hydrogen sensitive performance test of the @ MOF hydrogen-allochroic material are shown in Table 1.
TABLE 1 Pt/WO3@ MOF hydrogen-induced color-changing material and hydrogen sensitivity performance test result thereof
From the above results, it can be seen that the catalyst is compatible with the non-MOF coated Pt/WO3Compared with a hydrogen-induced color-changing material, the Pt/WO of the invention3The @ MOF material is gradually enhanced in hydrogen enrichment-supply capacity along with the improvement of the MOF coating proportion, so that the hydrogen discoloration time of the material is shortened, and the sensitivity of the hydrogen discoloration material under low hydrogen concentration and low gas flow is improved.
In addition, in WO3When the MOF material is coated on the surface, the highly dispersed noble metal center is loaded, namely the hydrogen storage sites are arranged around the noble metal sites, so that hydrogen can be enriched in time and supplied to the noble metal center, the response time and the color development degree of the material under low hydrogen concentration are improved, and the timely monitoring of the micro leakage point is facilitated.
Through coating the MOF material firstly and then depositing the noble metal, the covering of the noble metal center in the MOF coating process can be effectively avoided, the overflow distance of the activated hydrogen is effectively shortened, the utilization efficiency of the noble metal is improved, and the action and the effect of the MOF hydrogen storage site are further ensured.
The above examples 1-7 are not intended to limit the present invention, and the process parameters and ratios can be scaled up by a factor to meet the production requirements during the actual production process. Other combinations not exemplified will be apparent to those skilled in the art from the foregoing guidance of examples 1-7.
It is intended that any equivalents, or obvious variations, which may be made by those skilled in the art in light of the teachings herein, be within the scope of the present invention.
Claims (10)
1. A metal organic framework material assisted high-sensitivity hydrogen detection nanometer material is characterized in that: the hydrogen-based organic composite material comprises a nano material, wherein the surface of the nano material is coated with a metal organic framework material with a hydrogen molecular confinement effect.
2. The preparation method of the metal organic framework material-assisted high-sensitivity hydrogen detection nanomaterial according to claim 1, characterized by comprising the following steps: the method comprises the following steps:
step 1, dissolving a metal salt in a solvent to prepare a solution A;
step 2, dissolving an organic ligand in a solvent to prepare a solution B;
step 3, mixing the solution A and the solution B, fully stirring to obtain a mixed solution, adding a pH regulator into the mixed solution, and uniformly stirring to obtain an MOF synthesis mother liquor;
step 4, adding WO into MOF synthesis mother liquor3And (3) uniformly stirring the nano materials, carrying out thermal reaction, and then cooling, filtering, washing and drying to obtain a material A.
And 5: selecting a noble metal compound, depositing noble metal nano particles on the surface of the material A by the noble metal compound through a chemical reduction method or a physical sputtering method, and finally drying to obtain the metal organic framework material assisted high-sensitivity hydrogen detection nano material.
3. The preparation method of the metal organic framework material-assisted high-sensitivity hydrogen detection nanomaterial according to claim 1, characterized in that: the method comprises the following steps:
step 1, selecting a noble metal compound, and mixing the noble metal compound with the noble metalThe compound is prepared by depositing noble metal nano particles to WO by a chemical reduction method or a physical sputtering method3And (5) obtaining a material B on the surface of the nano material.
Step 2, dissolving metal salt in a solvent to prepare a solution A;
step 3, dissolving an organic ligand in a solvent to prepare a solution B;
and 4, step 4: fully stirring the solution A and the solution B to obtain a mixed solution, adding a pH regulator into the mixed solution, and uniformly stirring to obtain an MOF synthetic mother liquor;
and 5, adding the material B into the MOF synthesis mother liquor, uniformly stirring, carrying out thermal reaction, cooling, filtering, washing and drying to obtain the high-sensitivity hydrogen detection nano material assisted by the metal organic framework material.
4. The preparation method of the metal organic framework material assisted high-sensitivity hydrogen detection nanomaterial according to claim 2 or 3, characterized by comprising the following steps: the molar ratio of the metal element in the metal salt to the organic ligand is 0.1-5: 1.
5. the preparation method of the metal organic framework material assisted high-sensitivity hydrogen detection nanomaterial according to claim 2 or 3, characterized by comprising the following steps: the metal salt is one or more of nitrate, acetate, sulfate or chloride, and the metal element in the metal salt is one or more of aluminum, zinc, zirconium and magnesium.
6. The preparation method of the metal organic framework material assisted high-sensitivity hydrogen detection nanomaterial according to claim 2 or 3, characterized by comprising the following steps: the solvent is one or more of deionized water, absolute ethyl alcohol, methanol and N, N-dimethylformamide, and the molar ratio of the metal elements in the metal salt to the solvent is 0.01-1: 10-100, the molar ratio of the ligand to the solvent b is 0.01-1: 10-100.
7. The preparation method of the metal organic framework material assisted high-sensitivity hydrogen detection nanomaterial according to claim 2 or 3, characterized by comprising the following steps: the organic ligand in the step 2 is one or more of 1, 4-terephthalic acid, fumaric acid, 2, 5-dihydroxyterephthalic acid, 44 ' -biphenyldicarboxylic acid, azobenzene-4, 4-dicarboxylic acid, 2 ' -bipyridine-5, 5' -dicarboxylic acid, 1,3, 5-trimesic acid and 3,3',5,5' -biphenyltetracarboxylic acid.
8. The preparation method of the metal organic framework material assisted high-sensitivity hydrogen detection nanomaterial according to claim 2 or 3, characterized by comprising the following steps: the regulator is one or more of hydrochloric acid, nitric acid, hydrofluoric acid, formic acid and acetic acid, and the volume ratio of the pH regulator to the mixed solution is 0-1: 10-50.
9. The preparation method of the metal organic framework material assisted high-sensitivity hydrogen detection nanomaterial according to claim 2 or 3, characterized by comprising the following steps: the thermal reaction in the step 4 is that the system reacts for 30min-75 h at the temperature of 80-220 ℃.
10. The preparation method of the metal organic framework material assisted high-sensitivity hydrogen detection nanomaterial according to claim 2 or 3, characterized by comprising the following steps: the crystalline phase of the nano material is one of monoclinic phase, triclinic phase, hexagonal phase or rhombic phase;
the shape of the nano material is one or more of nano sheets, nano rods, nano spheres, nano wires, nano belts and nano three-dimensional structures assembled based on the structural units;
the metal of the noble metal compound is one or more of gold, silver, palladium, platinum, rhodium and iridium.
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