CN114505058B - 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 nanomaterial and a preparation method thereof. The hydrogen concentration of the low-concentration hydrogen on the surface of the nano material is improved by coating the micro-pores, open metal sites and the like in the MOF on the surface of the nano material to perform limited-enrichment on hydrogen molecules, so that the sensitivity of the material to hydrogen and the hydrogen electrochromic rate of the material are improved, and the material can realize quick response under 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 nanomaterial and a preparation method thereof.
Background
Hydrogen is colorless and odorless gas, is easy to generate hydrogen embrittlement, is easy to leak and is not easy to be perceived during application, and the popularization and application of hydrogen energy are limited to a certain extent. Therefore, in order to realize safe and efficient utilization of hydrogen energy and avoid accidents, development of a rapid, accurate and high-sensitivity hydrogen detection mode is needed to monitor leakage of hydrogen so as to ensure safety of hydrogen in the processes of storage, transportation and use.
Against this background, a visual hydrogen-induced electrochromic material is the opportunity to solve the problem, which material contacts H 2 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, intuitively, effectively and safely, a visual solving way is provided for solving the problem of hydrogen leakage, and early warning can be performed in advance.
In patent literatureIn the donation, chinese patent CN108072497 is based on WO 3 The hydrogen-based electrochromic material is characterized in that a layer of polymer is coated on the surface of the material to improve the stability of the material and is used for isolating the influence of oxygen and water molecules in air on the material, and the polymer can not influence the diffusion of hydrogen, but the added diffusion layer prolongs the diffusion path of the hydrogen, so that the hydrogen is not beneficial to the detection of hydrogen with low concentration and low flow rate, and particularly the hydrogen concentration is extremely low and difficult to detect in the early stage of hydrogen leakage.
In the current hydrogen use process, the hydrogen leakage detection time is positively correlated with the safety coefficient, so that the response sensitivity of the material hydrogen electrochromic process is improved, and the response time is shortened.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art, and 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:
the metal organic framework material-assisted high-sensitivity hydrogen detection nanomaterial comprises a nanomaterial, wherein the surface of the nanomaterial 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 of: the method comprises the following steps:
step 1, dissolving 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 MOF synthetic mother liquor;
step 4, adding WO to the MOF synthesis mother liquor 3 Nano material, stirring uniformly, then making thermal reaction, cooling, filtering, washing and drying so as to obtain the invented material A.
Step 5: and (3) selecting a noble metal compound, depositing noble metal nano particles on the surface of the material A 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 metal organic framework material-assisted high-sensitivity hydrogen detection nano material.
A preparation method of a metal organic framework material-assisted high-sensitivity hydrogen detection nano material is characterized by comprising the following steps of: the method comprises the following steps:
step 1, selecting a noble metal compound, and depositing noble metal nano particles on WO (WO) by using the noble metal compound through atomic layer deposition, chemical reduction deposition, ultraviolet reduction deposition and other chemical reduction methods or a physical sputtering method of magnetron sputtering 3 The material B is obtained on the surface of the nano material.
step 3, dissolving an organic ligand in a solvent to prepare a solution B;
step 4: 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 MOF synthetic mother liquor;
and 5, adding the material B into the MOF synthesis mother solution, uniformly stirring, performing thermal reaction, and then cooling, filtering, washing and drying to obtain the high-sensitivity hydrogen detection nano material with the assistance of the metal organic framework material.
Preferably, the molar ratio of the metal element in the metal salt to the organic ligand 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 element in the metal salt to the solvent is 0.01-1:10-100, the molar ratio of ligand to solvent b is 0.01-1:10-100.
Preferably, the organic ligand in the step 2 is one or more of 1, 4-terephthalic acid, fumaric acid, 2, 5-dihydroxyterephthalic acid, 4 4' -biphthalic acid, azobenzene-4, 4-dicarboxylic acid, 2' -bipyridine-5, 5' -dicarboxylic acid, 1,3, 5-trimesic acid and 3,3', 5' -biphenyl tetracarboxylic 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 is reacted at 80-220 ℃ for 30min-75 h.
Preferably, the crystalline phase of the nanomaterial is one of a monoclinic phase, a triclinic phase, a hexagonal phase or an rhombohedral phase;
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;
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 carried out by the method disclosed in the conventional WO 3 The surface of the base hydrogen electrochromic material is coated with a metal organic framework material, the limiting-enriching effect of micropores, open metal sites and the like in the metal organic framework material on hydrogen molecules is utilized, the capture of the hydrogen molecules is realized under the condition of low hydrogen concentration, and then the hydrogen enriching-supplying effect of the metal organic framework material is utilized to accelerate WO 3 The dissociation process of hydrogen on the outer surface of the base hydrogen electrochromic material shortens the response time and improves the sensitivity of the material.
Compared with the traditional WO 3 The hydrogen-based electrochromic material utilizes the self structural specificity of the metal organic framework material to realize the enrichment-supply of hydrogen under the condition of low hydrogen concentration, thereby not only improving the hydrogen-based electrochromic materialThe color development rate can also increase the contrast of color development, and is more suitable for hydrogen leakage monitoring under low flow rate and low concentration. Therefore, the hydrogen chromic material prepared by the method can be used for reducing H 2 The preparation method has the advantages that the quick response to hydrogen in a short time is visible in the naked eye under the conditions of low concentration and low gas flow rate, and the preparation process is simple in condition and easy to operate in a large scale.
Drawings
FIG. 1 shows Pt/WO prepared in example 1 3 X-ray powder diffraction Pattern (PXRD) of MOF material;
FIG. 2 shows the Pt/WO prepared in example 1 3 Scanning Electron Microscope (SEM) images of MOF materials;
FIG. 3 shows the Pt/WO prepared in example 1 3 Transmission Electron Microscopy (TEM) images of the @ MOF material;
FIG. 4 shows the Pt/WO prepared in example 1 3 Low temperature nitrogen adsorption and desorption curve graph and pore size distribution graph of MOF material;
FIG. 5 shows Pt/WO prepared in example 2 3 Scanning Electron Microscope (SEM) images of MOF materials;
FIG. 6 shows Pt/WO prepared in example 2 3 Transmission Electron Microscopy (TEM) image of MOF material.
Detailed Description
The invention is further illustrated below in conjunction with specific embodiments and figures, but the invention is not limited thereto. The test methods described in the examples below, unless otherwise specified, are all conventional; the apparatus and materials are commercially available unless otherwise specified.
Example 1:
the metal-organic framework material of the embodiment assists the high sensitivity WO 3 The preparation method of the base hydrogen electrochromic material comprises the following steps:
(1) 0.028 g of zirconium tetrachloride was dissolved in 8 ml of N, N-Dimethylformamide (DMF) solvent to obtain solution A; 0.021 g of 1, 4-terephthalic acid is weighed and dissolved 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;
(2) Adding WO to the MOF mother liquor 3 And (3) after fully stirring the nanorods, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 3 hours at 120 ℃, centrifugally separating a product, cleaning the product with DMF and ethanol for three times, and drying the product in a vacuum drying oven to obtain a material A.
(3) 0.500g of material A 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, excess newly configured NaBH 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 drying to obtain Pt/WO 3 @mof hydrochromic material.
Pt/WO thus obtained 3 As can be seen from FIG. 1, the X-ray powder diffraction pattern of the MOF hydrochromic material is shown in FIG. 1, and the product obtained in this example is WO 3 Complex phase with MOF.
As shown in FIG. 2 and FIG. 3, a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) show that the obtained hydrogen electrochromic material is shown in WO 2 and FIG. 3 3 The outer surface is uniformly coated with MOF nano particles.
As can be seen from the low-temperature nitrogen adsorption and desorption isotherm and the pore diameter distribution diagram of the material in FIG. 4, the hydrogen-induced color material has a multi-stage pore structure, micropores occupy relatively high, and the specific surface area of the obtained material is 103 m 2 Per gram, micropore specific surface area of 68.7m 2 /g。
Micropores are mainly derived from MOF materials, and mesopores are derived from stacking holes formed by the nanorods, so that the promotion of the hydrogen electrochromic performance is facilitated.
Example 2:
the metal-organic framework material of the embodiment assists the high sensitivity WO 3 The preparation method of the base hydrogen electrochromic material comprises the following steps:
(1) Weigh 0.500g WO 3 Dispersing the nanorods in 60mL deionized water, and stirring for 30min; 13.6mL of a chloroplatinic acid solution with the concentration of 1g/L is added dropwise into the suspension; under ice bath, excess newly configured NaBH 4 The aqueous solution is added into the suspension drop by drop, stirring is continued for 0.5. 0.5 h, standing is carried out for half an hour, suction filtration is carried out, deionized water is used for washing for three times, and drying is carried out, thus obtaining the material B.
(2) 0.014 g of zirconium tetrachloride was weighed out and dissolved in 8 ml of N, N-Dimethylformamide (DMF) solvent to obtain solution A; 0.011 g of 1, 4-terephthalic acid is weighed and dissolved 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 material B into MOF mother liquor, stirring thoroughly, transferring the suspension into a high-pressure reaction kettle with polytetrafluoroethylene lining, reacting at 120deg.C for 3 hr, centrifuging, cleaning with DMF and ethanol for three times, and vacuum drying in a vacuum drying oven to obtain Pt/WO 3 @mof hydrochromic material.
Pt/WO made in this example 3 SEM and TEM images of the MOF hydrochromic material are shown in FIGS. 5 and 6, and it can be seen from the figures that MOF particles are uniformly coated in WO 3 The nanowire surface was similar to example 1.
Example 3:
the metal-organic framework material of the embodiment assists the high sensitivity WO 3 The preparation method of the base hydrogen electrochromic material comprises the following steps:
(1) Weigh 0.500g WO 3 Dispersing the nano-sheets in 30mL deionized water, and stirring for 30min; 4.7mL of a 1g/L palladium chloride solution was added dropwise to the suspension; and (3) exposing the suspension for 7 hours under an ultraviolet lamp, filtering, washing with deionized water for three times, and drying to obtain a material B.
(2) 0.028 g of aluminum nitrate is weighed and dissolved in 10 ml of deionized water to obtain solution A; weighing 0.021 g of 1, 4-terephthalic acid and dissolving in 10 ml of methanol solvent to obtain solution B; weighing and mixing the solution A and the solution B, 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 solution, fully stirring, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 4 hours at 210 DEG CDuring the process, the product is centrifugally separated, washed three times by ethanol and deionized water, and dried to obtain Pd/WO 3 @mof hydrochromic material.
Example 4:
the metal-organic framework material of the embodiment assists the high sensitivity WO 3 The preparation method of the base hydrogen electrochromic material comprises the following steps:
(1) 0.031 g of magnesium nitrate dissolved in 5 ml of a mixed solution of N, N-dimethylformamide, ethanol and water (V N, N-dimethylformamide ：V Ethanol ：V Water and its preparation method =15: 1: 1) Obtaining a solution A; 0.024 g of 2, 5-dihydroxyterephthalic acid was weighed out in 5 ml of a mixed solution of N, N-dimethylformamide, ethanol and water (V N, N-dimethylformamide ：V Ethanol ：V Water and its preparation method =15: 1: 1) Obtaining 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) Adding WO to the MOF mother liquor 3 After the nanoflower is fully stirred, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 5 hours at 125 ℃, centrifugally separating the product, cleaning the product with ethanol and deionized water for three times, and drying the product in a vacuum drying oven to obtain a material A.
(3) 0.500g of material A is weighed and dispersed in 50 mL deionized water, and stirred for 30min; dropwise adding 1.05 mL chloroauric acid solution with concentration of 1g/100mL into the suspension, adding 0.15g urea into the suspension, heating to 80deg.C, stirring in dark for 12 h, cooling to room temperature, centrifuging, washing with deionized water, and vacuum drying to obtain Au-WO 3 @mof hydrochromic material.
Example 5:
the metal-organic framework material of the embodiment assists the high sensitivity WO 3 The preparation method of the base hydrogen electrochromic material comprises the following steps:
1) 0.035 g of zinc nitrate was weighed and dissolved in 6ml of N, N-dimethylformamide to obtain a solution A; 0.021 g of 1, 4-terephthalic acid is weighed and dissolved in 6ml of N, N-dimethylformamide to obtain a solution B; mixing the solution A and the solution B, and then fully stirring the mixture, and uniformly stirring the mixture to obtain MOF mother liquor;
(2) Ir-WO is added into the MOF mother solution 3 And (3) after the nanowires are fully stirred, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 3 hours at 105 ℃, centrifugally separating the product, cleaning the product with DMF 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, performing 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, ozone is used as an oxidant, and 15 cycles of deposition are performed to obtain Pt-WO 3 @mof hydrochromic material.
Example 6:
the metal-organic framework material of the embodiment assists the high sensitivity WO 3 The preparation method of the base hydrogen electrochromic material comprises the following steps:
1) 0.028 g of aluminum chloride is weighed and dissolved in 5 ml of deionized water to obtain solution A, and 0.013 g of 1,3, 5-trimesic acid is dissolved in 6ml of ethanol to obtain solution B; mixing the solution A and the solution B, and fully stirring to obtain MOF mother liquor;
(2) Adding WO to the MOF mother liquor 3 And (3) after the nanospheres are fully stirred, transferring the suspension into a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 10 hours at 200 ℃, centrifugally separating the product, cleaning the product with deionized water and ethanol for three times, and drying the product in a vacuum drying oven to obtain the material A.
(3) 0.500g of material A is weighed and dispersed in 30mL of deionized water, and stirred for 30min; dropwise adding 1.25 mL potassium chloroiridium acid solution with the concentration of 1g/100mL into the suspension, and continuously stirring for 3 h; dropwise adding a newly prepared NaBH4 aqueous solution into the suspension under ice bath, continuously stirring for 0.5. 0.5 h, standing for half an hour, filtering, washing with deionized water for three times, and drying to obtain Ir-WO 3 @mof hydrochromic material.
Experimental example 1:
to further verify the effect of the metal organic framework material on the hydrogen electrochromic properties and rates, taking example 1 as an example, the effect of different metal organic framework material coating ratios on the hydrogen electrochromic sensitivity was compared, the steps were as follows:
(1) Weighing a certain mass of zirconium tetrachloride and dissolving in 8 ml of N, N-Dimethylformamide (DMF) solvent to obtain solution A, and weighing 1, 4-terephthalic acid with corresponding mass 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;
(2) Addition of Pt-WO to the above MOF mother liquor 3 And (3) transferring the suspension to a high-pressure reaction kettle with a polytetrafluoroethylene lining after fully stirring the nanorods, reacting for 3 hours at 120 ℃, centrifugally separating the product, cleaning the product with DMF and ethanol for three times, and drying the product by a vacuum drying oven to obtain a material A.
(3) 0.500g of material A 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, an excessive amount of newly configured NaBH is added 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 drying to obtain Pt/WO 3 @mof hydrochromic material.
(4) Hydrogen-induced color property test:
Pt/WO prepared in this example 3 The hydrogen electrochromic material of the MOF is subjected to hydrogen electrochromic performance evaluation under the conditions of low hydrogen concentration and low mixed gas flow, and the specific operation is as follows: weigh 0.1 gram of fully dried Pt/WO 3 The @ MOF sample was uniformly spread in the sample cell and compacted into a flat surface, the sample cell was enclosed inside an opaque gas cell and sealed. 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.
Pt/WO prepared in this example 3 @MOF hydrogen electrochromic materialThe hydrogen sensitive performance test results are shown in Table 1.
TABLE 1 Pt/WO 3 @MOF hydrogen electrochromic material and hydrogen sensitivity performance test result thereof
As can be seen from the above results, pt/WO with uncoated MOF 3 Compared with the hydrogen-induced color change material, the Pt/WO of the invention 3 The hydrogen enrichment-supply capability of the MOF material is gradually enhanced along with the improvement of the MOF coating proportion, the hydrogen electrochromic time of the material is shortened, and the sensitivity of the hydrogen electrochromic material under the conditions of low hydrogen concentration and low gas flow is improved.
In addition, in WO 3 The MOF material is coated on the surface, and meanwhile, the high-dispersion noble metal center is loaded, which is equivalent to the preparation of hydrogen storage sites around the noble metal sites, so that hydrogen can be timely enriched and supplied to the noble metal center, the response time and the color development degree of the material under the condition of low hydrogen concentration are improved, and the timely monitoring of the tiny leakage point is more facilitated.
Through the sequence of coating the MOF material and then depositing the noble metal, the coverage of the noble metal center in the MOF coating process can be effectively avoided, the overflow distance of activated hydrogen is effectively shortened, the utilization efficiency of the noble metal is improved, and the action and effect of the MOF hydrogen storage site are further ensured.
The above examples 1 to 7 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 teachings of examples 1-7.
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 (6)
1. A preparation method of a metal organic framework material-assisted high-sensitivity hydrogen detection nano material is characterized by comprising the following steps of: the surface of the nano material is coated with a metal organic framework material with a hydrogen molecular confinement effect;
the preparation method comprises the following steps:
step 1, dissolving metal salt in a solvent to prepare a solution A;
step 2, dissolving an organic ligand in a solvent to prepare a solution B, wherein the molar ratio of metal elements in the metal salt to the organic ligand is 0.1-5:1, a step of;
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 MOF synthetic mother liquor;
step 4, adding WO to the MOF synthesis mother liquor 3 Nano material, stirring uniformly, then carrying out thermal reaction, and then cooling, filtering, washing and drying to obtain a material A;
step 5: a noble metal compound is selected, noble metal nano particles are deposited on the surface of a material A by a chemical reduction method or a physical sputtering method, and finally, a high-sensitivity hydrogen detection nano material assisted by a metal organic framework material is obtained after drying;
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;
the organic ligand in the step 2 is one or more of 1, 4-terephthalic acid, fumaric acid, 2, 5-dihydroxyterephthalic acid, 4 4' -biphthalic acid, azobenzene-4, 4-dicarboxylic acid, 2' -bipyridine-5, 5' -dicarboxylic acid, 1,3, 5-trimesic acid and 3,3', 5' -biphenyl tetracarboxylic acid;
the metal of the noble metal compound is one or more of gold, silver, palladium, platinum, rhodium and iridium.
2. A preparation method of a metal organic framework material-assisted high-sensitivity hydrogen detection nano material is characterized by comprising the following steps of: the surface of the nano material is coated with a metal organic framework material with a hydrogen molecular confinement effect;
the preparation method comprises the following steps:
step 1, selecting a noble metal compound, and depositing noble metal nano particles on WO (WO) by a chemical reduction method or a physical sputtering method by the noble metal compound 3 The surface of the nano material is provided with a material B;
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, wherein the molar ratio of metal elements in the metal salt to the organic ligand is 0.1-5:1, a step of;
step 4: 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 MOF synthetic mother liquor;
step 5, adding the material B into the MOF synthesis mother liquor, uniformly stirring, performing thermal reaction, and then cooling, filtering, washing and drying to obtain the high-sensitivity hydrogen detection nano material with the assistance of the metal organic framework material;
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;
the organic ligand in the step 2 is one or more of 1, 4-terephthalic acid, fumaric acid, 2, 5-dihydroxyterephthalic acid, 4 4' -biphthalic acid, azobenzene-4, 4-dicarboxylic acid, 2' -bipyridine-5, 5' -dicarboxylic acid, 1,3, 5-trimesic acid and 3,3', 5' -biphenyl tetracarboxylic acid;
the metal of the noble metal compound is one or more of gold, silver, palladium, platinum, rhodium and iridium.
3. The method for preparing the metal-organic framework material-assisted high-sensitivity hydrogen detection nanomaterial according to claim 1 or 2, wherein the method comprises the following steps of: the solvent is one or more of deionized water, absolute ethyl alcohol, methanol and N, N-dimethylformamide, and the molar ratio of metal elements in the metal salt to the solvent is 0.01-1:10-100, the molar ratio of ligand to solvent b is 0.01-1:10-100.
4. The method for preparing the metal-organic framework material-assisted high-sensitivity hydrogen detection nanomaterial according to claim 1 or 2, wherein the method comprises the following steps of: 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, wherein the pH regulator is non-zero.
5. The method for preparing the metal-organic framework material-assisted high-sensitivity hydrogen detection nanomaterial according to claim 1 or 2, wherein the method comprises the following steps of: the thermal reaction in the step 4 is that the system reacts for 30min-75 h at 80-220 ℃.
6. The method for preparing the metal-organic framework material-assisted high-sensitivity hydrogen detection nanomaterial according to claim 1 or 2, wherein the method comprises the following steps of: the crystal phase of the nano material is one of a monoclinic phase, a triclinic phase, a hexagonal phase or an rhombic phase;
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.
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| CN113310917B (en) * | 2021-05-26 | 2022-06-07 | 燕山大学 | Hydrogen sensor based on Fabry-Perot interference |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN113860374A (en) * | 2021-09-30 | 2021-12-31 | 郑州轻工业大学 | In-situ free-growing flower-shaped nano WO3Gas-sensitive material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Oxygen vacancy-assisted hydrogen evolution reaction of the Pt/WO3 electrocatalyst;Han Tian;J. Mater. Chem. A;第7卷;第6285页 * |
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