CN114920949B - Preparation method and application of metal organic framework nano array material - Google Patents
Preparation method and application of metal organic framework nano array material Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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Abstract
The invention provides a preparation method and application of a soft nano brush guide metal organic framework nano array. The preparation method comprises the following steps: constructing a soft nano brush on the surface of a base material; (2) Repeatedly soaking the base material on which the soft nano brush grows in a precursor solution containing metal salt and an organic ligand to obtain a nano brush material attached with metal organic framework nano particles; (3) And processing the material by adopting a freeze drying technology to obtain the metal organic framework nano array. According to the invention, a flexible coordination mode of a pyridine functional group of a soft nano brush shell layer is utilized, and other functional nano particles are further introduced to obtain the metal-organic framework hybrid nano array. The invention can realize the flexible growth of the soft nanometer brush on the surfaces of various base materials based on the active crystallization driven self-assembly principle and successfully induce the highly controllable metal organic framework nanometer array. The metal organic framework nano array prepared by the invention shows excellent performance in the aspects of methanol catalytic oxidation and hydrogen sulfide sensing.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a preparation method and application of a metal organic framework nano array material, and especially relates to a metal organic framework nano array induced by taking a soft nano brush as a template, and a preparation method and application thereof.
Background
The nano array structure has attracted extensive attention in the fields of catalysis, sensing, energy, photoelectricity and the like due to the combination of the advantages of nano size, directional arrangement and the like. The nano-array material has excellent stability, high specific surface area, and free open space compared to the randomly stacked powder. A series of transition metal oxides and hydroxides were prepared in an array form in the early stage of the study. However, with the continuous and deep research on nano-array materials, the development of various applications is hindered by the problems of single composition, poor structural adjustability and the like of nano-arrays mainly made of metal oxides, and therefore, the search for novel nano-array materials is an inevitable trend of future development.
Metal Organic Frameworks (MOFs), which are porous crystalline materials constructed by Metal ions and Organic ligands, stand out from a large number of materials due to the advantages of various structures, adjustable performance and the like, and have potential application prospects in the fields of catalysis, separation, sensing, gas adsorption, storage and the like. With the continuous and intensive research on the MOFs materials, the MOFs in the form of crystal or powder are not suitable for practical applications. In order to better develop the application value of the MOFs, it is important to grow an MOFs array with a regular arrangement on the surface of a necessary substrate. The traditional methods for preparing the MOFs array comprise a solvothermal method, a hard template method, a thermal deposition method and the like, and although various MOFs nanometer arrays can be prepared by the methods to a certain extent, the preparation conditions are harsh and are mostly limited to MOFs with one-dimensional or two-dimensional crystal structures, so that the types of the MOFs nanometer arrays are greatly limited. At the same time, flexible manipulation of the height of MOFs nanoarrays and simultaneous introduction of complementary functional components remains a huge challenge.
The present application has been made for the above reasons.
Disclosure of Invention
The invention aims to solve the problems pointed out in the background art and the defects of the prior art and provides a method for directionally inducing the growth of an MOFs nano array by taking a soft nano brush as a template. The method has the advantages of mild and flexible preparation conditions and high precision controllability on MOFs nano arrays.
The purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of a metal organic framework nano array material, which comprises the following steps:
(1) Preparation of Nanobrush
Loading the columnar micelle seed crystal on the surface of the base material to obtain the base material loaded with the columnar micelle seed crystal; then soaking the substrate in a selective solvent a, dripping the block copolymer solution while oscillating, standing, aging, leaching and drying to obtain the substrate with the nano brush, namely the crystalline block copolymer nano brush;
(2) Preparation of MOFs nano array
And (2) respectively soaking the substrate on which the nano brush grows in a metal salt solution and an organic ligand solution for a plurality of times, cleaning the substrate after each soaking, and then soaking the obtained material in a selective solvent b for freeze drying to obtain the MOFs nano array, namely the metal organic framework nano array material.
Preferably, the columnar micelle seed in step (1) is prepared by the following method: dissolving the segmented copolymer in a selective solvent a, stirring to completely dissolve the segmented copolymer, and then standing and aging at room temperature to obtain long columnar micelles; and (3) placing the micelle in an ice water bath at 0 ℃, carrying out ultrasonic treatment to break the micelle, standing and aging to obtain the columnar micelle seed crystal with the length of 40-50 nm.
Preferably, in the preparation of the columnar micelle seed crystal, the concentration of the block copolymer in the selective solvent a is 0.5mg/mL; the ultrasonic treatment time is 0.25-2 h, and the ultrasonic intensity is 50-140W. Stirring is carried out at 80 ℃ for 30min. The standing and aging time is 1 day.
Preferably, the loading of the columnar micelle seed crystals on the surface of the substrate in the step (1) is specifically as follows: pretreating the base material, dripping the solution of the columnar micelle seed crystal on the base material, aging, leaching and drying to obtain the base material with the columnar micelle seed crystal loaded on the surface.
Preferably, the pretreatment specifically comprises: the base material was ultrasonically cleaned in acetone and water for 30min, dried under nitrogen atmosphere, and then oxygen-plasma treated for 10 min.
Preferably, the ratio of the solution of the columnar micelle seed to the size of the substrate at the time of dispensing is 20 μ L:1cm 2 . Aging is 1 day at room temperature. The leaching and drying are performed by leaching with isobutanol and drying in a nitrogen environment. Rinsing removes free copolymer and removes seeds that are incompletely bonded to the substrate.
Preferably, the selective solvent a in step (1) comprises one or more of water, methanol, ethanol, propanol and isopropanol.
Preferably, the substrate in step (1) comprises any one of silica, metal, glass, ceramic, nickel foam, plastic, and carbon nanotubes.
Preferably, the block copolymer in step (1) comprises PFS 24 -b-P2VP 314 、PFS 27 -b-P2VP 356 、PFS 44 -b-P2VP 526 Any one of them. The block copolymer subscript refers to the degree of polymerization of each block.
Preferably, the solvent of the block copolymer solution in the step (1) is tetrahydrofuran. The concentration of the solution formed by mixing the block copolymer and tetrahydrofuran is 1-20 mg/mL.
Preferably, the oscillation in step (1) is performed for 10s to 2h on an oscillator. The standing is carried out at room temperature for 0.5-48 h. The leaching is to place the substrate in isopropanol for leaching; drying was carried out under nitrogen atmosphere.
In the step (1), the nano brush is prepared, and the block polymer is dripped to initiate growth, the growth is driven by active crystals, the tail end of the nano brush still has the growth capability of the active crystals, and the accurate adjustment of the length of the nano brush and the design of a shell structure according to functional requirements can be realized. The length of the nanosush is here mainly controlled by the monomer addition, which is a critical factor.
Preferably, the metal salt in step (2) comprises any one of copper acetate, zinc acetate, copper nitrate and ferric trichloride.
Preferably, the organic ligand in step (2) includes any one of trimesic acid, imidazole, 1, 4-diazabicyclo [2, 2] octane, and 2, 7-naphthalenedicarboxylic acid. The cycle times are 2-10 times, and the reciprocating times can control the size of MOF particles.
Preferably, the solvent in the metal salt solution and the organic ligand solution in step (2) comprises any one of ethanol, methanol and isopropanol. The solvent is preferably ethanol.
Preferably, the concentration of the metal salt and the organic ligand in step (2) are both 2 to 10mM. The circulation times are 5-8 times;
preferably, the selective solvent b in step (2) comprises any one of isopropanol and tert-butanol.
Preferably, in the step (2), the freeze-drying time is 5-10 h. The volume of the selective solvent b is 0.5 to 1mL, as long as the substrate can be completely immersed therein. Before freeze drying, the selective solvent b is frozen in liquid nitrogen for 30 min-1 h.
Preferably, the washing in step (2) is washing with an ethanol solution. And the excess metal salt and organic ligand adhered to the surface of the nano brush can be removed by cleaning.
Preferably, the preparation method of the metal organic framework nano array material further comprises the following steps: functional nano particles are introduced into an MOFs nano array structure in a pre-doping mode, so that a functional hybrid metal organic framework nano array material is obtained. The pre-doping is specifically as follows: and (3) respectively soaking the base material with the nano brush grown in the step (2) in a functional polyoxometalate solution, a metal salt solution and an organic ligand solution for a plurality of times, cleaning the base material after each soaking, and then soaking the obtained material in a selective solvent b for freeze drying to obtain the functional nano particle doped MOF hybrid nano array. The substrate is soaked in the functional multi-metal cluster solution before being soaked in the metal salt solution and the organic ligand solution, so that pre-doping is realized. The functional nano-particle comprises any one of polymetal oxygen clusters. The polyoxometalate includes one of polymolybdate, phosphotungstate and polymolybdate.
Preferably, the solution solubility of the polyoxometallate cluster is 1-2 mol/L, and the soaking time of the polyoxometallate cluster solution is 10-15 min. Then, the metal salt and the organic ligand are circularly reacted for many times.
Preferably, the preparation method of the metal organic framework nano array material further comprises the following steps: functional nanoparticles are introduced into an MOFs nano array structure in a loading mode, so that a functional hybrid metal organic framework nano array material is obtained. The load is specifically as follows: and (3) soaking the MOF nano array obtained in the step (2) in a noble metal precursor aqueous solution to obtain a functional MOF hybrid nano array, namely a metal organic framework nano array material. The functional nanoparticles comprise any one of noble metal nanoparticles. The noble metal comprises one of Au, pd and Pt.
Preferably, the noble metal precursor concentration is 1 to 2mM. When soaking, oscillating for 2-4h at room temperature, adding NaBH 4 Water solution, and shaking the obtained material for 20-30min. And soaking the obtained material in isopropanol solution, and leaching with isopropanol to obtain the MOF nano array loaded with noble metal nano particles.
By utilizing the flexible coordination mode of the pyridine functional group of the soft nanometer brush shell layer, functional nanoparticles can be easily introduced into the MOF nanometer array. Compared with the traditional preparation method of the MOF nano-array, the method is more flexible and effective. Compared with a pure MOF nano array, the introduced functional nanoparticles and the MOF can have a synergistic effect, so that the performance of the MOF nano array can be further improved.
The invention also provides an application of the metal organic framework nano array material prepared by the method in methanol catalytic oxidation reaction.
The invention also provides an application of the metal organic framework nano array material prepared by the method in gas sensing.
The application in the catalytic oxidation reaction of the methanol is as follows: the method comprises the steps of utilizing an MOFs nano array as a catalyst, utilizing methanol as a substrate molecule, gasifying the methanol through high-temperature heating, contacting the gasified methanol with the MOFs nano array, then catalytically oxidizing the gasified methanol into products such as formaldehyde, methyl formate, dimethoxymethane, carbon dioxide and the like, and detecting the formaldehyde as a main product through in-situ gas chromatography.
The application in gas sensing is specifically as follows: the MOFs nano-array material is used as a sensor, is connected into a gas sensitive device after being aged at 150 ℃, and the response capability of the MOFs nano-array to gases such as methanol, ethanol, nitrogen dioxide, hydrogen sulfide, acetone, nitric oxide, toluene and methane is judged by observing the change of resistance values.
The soft nano brush provided by the invention can be stretched in a benign solvent as a template, and a large amount of metal ions and organic ligands in the solvent are combined, so that MOFs nano particles are constructed on the surface of the nano brush. As the pyridine functional group in the structure of the nano brush can be combined with various metal ions, the nano brush can induce various MOFs hybridized nano arrays, namely the soft nano brush is used as a template to directionally induce various MOFs nano arrays.
The invention provides a template guiding function of the soft nano brush, so that the soft nano brush can guide a multifunctional MOF array, and the adjustment of nano arrays with different heights can be realized on the basis. In addition, by utilizing the structural advantages of the nano brush, other functional nano particles are introduced while the MOF nano array is prepared, which is a step difficult to realize in the traditional preparation of the MOF nano array, so that the obtained multifunctional MOF hybrid array can realize various applications. Ceramic tubes have also been selected on the substrate, which provides a scenario for subsequent gas sensitive applications.
The preparation of various MOF nano arrays is very important, and the precise regulation and control of the height of the MOF nano arrays are realized in the preparation process, wherein the height change of the MOF nano arrays has obvious influence on the next catalytic application, and the higher the nano arrays are, the faster the conversion rate of methanol is. Furthermore, doping or loading functional nanoparticles into MOF nanoarrays is also a great innovation of this strategy, since it is difficult to achieve the simultaneous introduction of other nanoparticles in the traditional methods of making MOF nanoarrays. Wherein, the doped polyoxometalate has the function of promoting the selectivity of the catalytic oxidation of the methanol. And the loaded Pt nano particles can realize H-pair 2 And (4) rapidly desorbing S gas. The undoped MIL-100 nano array also has catalytic activity on methanol, but the performance is not outstanding enough in the aspect of selectivity, and therefore, a polyoxometalate with redox performance is introduced to further improve the selectivity.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention takes the soft nanometer brush with the characteristic of crystallization activity growth as a template, and flexibly and accurately controls the height of the obtained MOFs nanometer array.
(2) The nano brush disclosed by the invention can be combined with various metal ions, so that the types of MOFs nano arrays can be effectively expanded, and particularly, three-dimensional MOFs can be effectively expanded.
(3) The nanometer brush of the invention can grow on various functional base materials, which lays a foundation for the MOFs nanometer array to be widely applied to the fields of catalysis, sensing, separation, filtration and the like.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is an atomic force microscope image of a soft nano-brush obtained by adding 6. Mu.L of polymer in example 1;
FIG. 2 is a schematic diagram of the preparation of nanoarrays guided by nanosbrushes;
FIG. 3 is an SEM photograph of MIL-100 (Fe) prepared by adding 6. Mu.L of polymer to example 2;
FIG. 4 is an XRD pattern of a MIL-100 (Fe) nanoarray prepared by addition of 16 μ L of polymer in example 2;
FIG. 5 is a cross-sectional SEM photograph of MIL-100 (Fe) nanoarrays of varying heights prepared in example 2 and after their incorporation into MOF particles; wherein a is a section SEM picture of MIL-100 (Fe) nano-brushes prepared by dripping different amounts (2, 4, 6, 8 and 16 mu L), and b is a section SEM picture of an induced MIL-100 (Fe) nano-array;
FIG. 6 is an SEM image of growth of HKUST-1 nanoarrays on the surface of a ceramic tube by adding 16 μ L of polymer in example 3;
FIG. 7 is a linear plot of temperature and conversion for MIL-100 (Fe) nanoarray catalyzed oxidation of methanol prepared by the addition of 16 μ L of polymer in example 2;
FIG. 8 is a graph of the sensing response of the HKUST-1 nanoarray loaded with Pt nanoparticles of example 5 to gas.
Detailed Description
The invention is further explained in detail below with reference to the drawings and the embodiments. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific operations will be given to illustrate the invention, but the scope of the present invention is not limited to the following embodiments. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Preparation of Nanobrush
PFS Block copolymer 44 -b-P2VP 526 Dissolving in isopropanol to prepare a solution with a concentration of 0.5mg/mL, stirring at 80 deg.C for 30min to completely dissolve, and aging at room temperature for one day to obtain long column micelle. Placing the micelle in an ice water bath at 0 ℃, performing ultrasonic treatment for 0.5h by using a probe ultrasonic processor (80W) to break the micelle, standing and aging for one day, wherein the length of the columnar micelle seed crystal is about 50nm, and obtaining a columnar micelle seed crystal solution with a shorter column.
The silicon wafer (1 cm × 1 cm) was ultrasonically cleaned in acetone and water for 30min, dried under nitrogen atmosphere, and then oxygen-plasma treated for 10 min. And dripping 20 mu L of columnar micelle seed crystal solution on the silicon wafer, aging for one day at room temperature, leaching with isobutanol, and drying in a nitrogen environment to obtain the silicon wafer with the columnar micelle seed crystal loaded on the surface.
The micelle seed-loaded silicon wafer was placed in 1mL of isopropanol and different amounts (2, 4, 6, 8 and 16. Mu.L) of the polymer PFS were added dropwise 24 -b-P2VP 314 Then, the resulting solution (10 mg/mL) was shaken on a shaker for 30min and then allowed to stand at room temperature for 0.5h. And finally, placing the silicon wafer into isopropanol for leaching and drying under nitrogen atmosphere to obtain the silicon wafer with the uniform columnar nano brush loaded on the surface. To which 6. Mu.L of PFS-containing solution was added 24 -b-P2VP 314 The atomic force microscope image of the obtained nano-brush in tetrahydrofuran solution (10 mg/mL) is shown in FIG. 1, the average height is 58nm, and the nano-brush is densely distributed on the surface of the silicon wafer. The pure nanosrush could not stand up in the dry state as shown in figure 5 a. When the nanosush was combined with the MOF particles, the nanofilaments encapsulating the MOF particles were allowed to stand upright in the dry state due to the rigidity of the MOF particles, the height change of which is shown in fig. 5 b.
Example 2
Preparation of MOFs nano-array
The silicon wafer modified with the nano brush prepared in the example 1 is firstly placed in a 10mM ethanol solution of ferric trichloride for 10min, then is rinsed by the ethanol solution, is subsequently placed in a 10mM ethanol solution of trimesic acid for 10min, and is then rinsed by the ethanol solution, and the process is repeated five times to obtain the MIL-100 (Fe) nano particles coated on the surface of the nano brush. And soaking the obtained material in 0.5mL of isopropanol solution, freezing the obtained material by using liquid nitrogen until the obtained material is crystallized, and freeze-drying the obtained material in a freeze dryer for 5 hours to obtain the MIL-100 (Fe) nano array. The corresponding preparation process is shown in figure 2.
The MIL-100 (Fe) nanoarrays grown on silicon wafers prepared in example 2 above were tested using a Scanning Electron Microscope (SEM), as shown in fig. 3: as can be seen from the figure, dense nanorods grow on the silicon chip, and each nanorod has a large amount of tiny MOFs particles stacked thereon, and the nanorods are uniformly arranged to form the appearance of an array. The height of the MOF nanoarrays varies depending on the length of the nanosbrushes.
The MIL-100 (Fe) nanoarrays prepared in example 2 of the present invention and the MIL-100 (Fe) nanopowders prepared in example 2 were characterized by X-ray diffraction (XRD), and as shown in fig. 4, diffraction peaks of the MIL-100 (Fe) nanoarrays were completely matched compared to the simulation.
The different length nanopushes prepared in example 2 above were tested using SEM to induce MIL-100 (Fe) nanoarrays, as shown in fig. 5 b: with addition of 2, 4, 6, 8 and 16. Mu.L PFS 24 -b-P2VP 314 The tetrahydrofuran solution of the monomer, correspondingly the MIL-100 (Fe) nanoarray height, increases significantly from about 200nm to around 1100 nm.
Example 3
HKUST-1 nano array grown on surface of ceramic tube
The ceramic tube was washed in acetone and ethanol solutions for 30min, dried under nitrogen atmosphere and repeatedly soaked three times in the micelle seed solution prepared in example 1, aged for one day at room temperature, rinsed with isobutanol and dried under nitrogen atmosphere to obtain a ceramic tube with the surface loaded with columnar micelle seeds.
The ceramic tube loaded with micelle seeds was placed in 1mL of isopropanol and different amounts (2, 4, 6, 8 and 16. Mu.L) of polymer PFS were added dropwise 24 -b-P2VP 314 The tetrahydrofuran solution (10 mg/mL) was shaken on a shaker for 30min and then allowed to stand at room temperature for 0.5h. And finally, placing the ceramic tube in isopropanol to leach and dry the ceramic tube under nitrogen atmosphere to obtain the ceramic tube with the uniform columnar nano brush loaded on the surface.
The ceramic tube modified with the nano brush is firstly placed in an ethanol solution of 10mM copper acetate for 10min, then rinsed by the ethanol solution, then placed in an ethanol solution of 10mM trimesic acid for 10min, and then rinsed by the ethanol solution, and the HKUST-1 nano particles wrapped on the surface of the nano brush are obtained by repeating the process five times. And soaking the obtained material in 0.5mL of isopropanol solution, freezing with liquid nitrogen to crystallize, and freeze-drying in a freeze dryer for 5h to obtain the HKUST-1 nano array.
HKUST-1 nanoarrays grown on ceramic tubes prepared in example 3 above were tested by SEM as shown in FIG. 6: as can be seen from the figure, the ceramic tube is composed of a block of metal oxide, on which a plurality of nanorods with regular arrangement are grown, and the surface of each nanorod is formed by closely packing a plurality of small-sized particles.
Example 4
Preparation of polyacid-doped MIL-100 (Fe) nanoarrays
The silicon wafer modified with 6 μ L of the nano brush prepared in example 1 was first placed in a mixed solution (1. And soaking the obtained material in 0.5mL of isopropanol solution, freezing the obtained material by using liquid nitrogen until the obtained material is crystallized, and freeze-drying the obtained material in a freeze dryer for 5 hours to obtain the polyacid-doped MIL-100 (Fe) nano array.
Example 5
Preparation of HKUST-1 nano array loaded with Pt nano particles
The ceramic tube modified with 6 μ L of the nano brush prepared in example 3 was first placed in a 10mM ethanol solution of copper acetate for 10min, and then rinsed with the ethanol solution, and then placed in a 10mM ethanol solution of trimesic acid for 10min, and then rinsed with the ethanol solution, and the above process was repeated five times to obtain HKUST-1 nanoparticles coated on the surface of the nano brush. The resulting material was placed in 0.5mL of isopropanol, and then 0.001M aqueous solution (1. Mu.L) of sodium chloroplatinate was added thereto at room temperatureShaking for 3h, 3.75 μ L of NaBH was added 4 And (3) oscillating the aqueous solution for 30min, taking out, soaking in 0.5mL of isopropanol solution again, freezing with liquid nitrogen until crystallization, and freeze-drying in a freeze dryer for 5h to obtain the HKUST-1 nano array loaded with the Pt nano particles.
Application example 1
The MIL-100 (Fe) nanoarray prepared in example 2 above was used as a catalyst for catalytic oxidation of methanol.
Taking the MIL-100 (Fe) nano array prepared in example 2 as an example, the catalytic oxidation performance test method is as follows:
the silicon wafer (0.5 g) on which the MIL-100 (Fe) nano array and the MIL-100 (Fe) hybrid nano array doped with the poly-molybdenum vanadate respectively grow is crushed, then the silicon wafer and 0.5g of quartz sand are mixed and then are loaded into a high-temperature reaction tube, the initial temperature of the reaction device is set to be 120 ℃, the temperature rise rate is 10 ℃/min, the methanol injection rate is 0.002mL/min, and the reaction termination temperature is set to be 230 ℃. The products of the reaction were then detected using in situ connected gas chromatography for each 10 ℃ rise.
Application example 2
The HKUST-1 nano array which is prepared in the embodiment 5 and is loaded with Pt nano particles and grows on the surface of the ceramic tube is used as a sensor for gas sensing.
And (3) carrying out gas sensitivity detection on the prepared HKUST-1 nano array by using an MA1.0 gas-sensitive testing device. A ceramic tube with Au electrodes was used as the sensing substrate. The Ni-Cr alloy wire serves as a heater. The sensing material is provided with an adjustable working temperature by applying a certain voltage. The assembled sensor assembly was mounted on a PCB holder, a pair of electrodes was attached to the material and aged at 150 ℃ for two days to remove excess solvent molecules in the HKUST-1 structure. The target analyte is then passed into the gas sensor. The sensitivity of the material to gases is judged by observing the change in resistance.
Test results 1
FIG. 7 is a graph of the catalytic oxidation conversion rate of the MIL-100 (Fe) nanoarrays of example 2 to methanol at different temperatures, and it can be seen from FIG. 7 that the MIL-100 (Fe) nanoarrays have a significantly improved conversion rate to methanol compared to the MIL-100 (Fe) powder, and in addition, the higher the MIL-100 (Fe) nanoarrays, the faster the catalytic rate in the catalytic oxidation reaction of methanol is exhibited. Meanwhile, the MIL-100 (Fe) nano-array doped with poly-molybdenum vanadate shows almost the same conversion rate and has more outstanding selectivity to products, wherein the selectivity to formaldehyde is as high as 92.8%.
FIG. 8 is the sensitivity test results of the HKUST-1 nanoarrays loaded with Pt nanoparticles grown on the ceramic tubes in example 5 to different gases, and it can be seen from FIG. 8 that the HKUST-1 nanoarrays loaded with Pt nanoparticles have obvious response to hydrogen sulfide in a series of gases (methanol, ethanol, nitrogen dioxide, acetone, methane, hydrogen sulfide, etc.). Compared with a pure HKUST-1 nano array, the HKUST-1 nano array loaded with the Pt nano particles has excellent circulation stability to hydrogen sulfide.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (7)
1. The preparation method of the metal organic framework nano array material is characterized by comprising the following steps of:
(1) Preparation of Nanobrush
Loading the columnar micelle seed crystal on the surface of the base material to obtain the base material loaded with the columnar micelle seed crystal; then soaking the substrate in a selective solvent a, dripping a block copolymer solution while oscillating, standing for aging, leaching and drying to obtain the substrate with the nano brush, namely the crystalline block copolymer nano brush;
(2) Preparation of MOFs nano-array
Soaking the substrate with the nano brush in a metal salt solution and an organic ligand solution respectively for a plurality of times, cleaning the substrate after each soaking, and then soaking the obtained material in a selective solvent b for freeze drying to obtain an MOFs nano array, namely the metal organic framework nano array material;
the block copolymer in step (1) comprises PFS 24 -b-P2VP 314 、PFS 27 -b-P2VP 356 、PFS 44 -b-P2VP 526 Any one of the above;
the metal salt in the step (2) comprises any one of copper acetate, zinc acetate, copper nitrate and ferric trichloride; the organic ligand comprises any one of trimesic acid, imidazole, 1, 4-diazabicyclo [2, 2] octane and 2, 7-naphthalene dicarboxylic acid.
2. The method according to claim 1, wherein the selective solvent a in step (1) comprises one or more of water, methanol, ethanol, propanol, and isopropanol.
3. The method according to claim 1, wherein the substrate in step (1) comprises any one of silica, metal, glass, ceramic, nickel foam, plastic, and carbon nanotube.
4. The method according to claim 1, wherein the selective solvent b in step (2) comprises any one of isopropyl alcohol and tert-butyl alcohol.
5. The method of claim 1, wherein the method of preparing the metal-organic framework nanoarray material further comprises: functional nano particles are introduced into an MOFs nano array structure in a pre-doping mode, so that a functional hybrid metal organic framework nano array material is obtained.
6. The method of claim 1, wherein the method of preparing the metal-organic framework nanoarray material further comprises: functional nanoparticles are introduced into an MOFs nano array structure in a loading mode, so that a functional hybrid metal organic framework nano array material is obtained.
7. Use of the metal organic framework nano array material prepared by the method of any one of claims 1 to 6 in methanol catalytic oxidation reaction or gas sensing.
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