CN115124727A - Preparation method of MOF film - Google Patents
Preparation method of MOF film Download PDFInfo
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Abstract
The invention belongs to the technical field of MOF films, and particularly relates to a preparation method of an MOF film. The invention provides a preparation method of an MOF film, which comprises the following steps: depositing a metal precursor and an organic precursor on the surface of a substrate by alternating pulse deposition by utilizing a molecular layer deposition technology to obtain an amorphous organic-inorganic hybrid film; and carrying out solvent-free gas phase ligand exchange crystallization on the amorphous organic-inorganic hybrid film and the organic ligand to obtain the MOF film. The molecular layer deposition technology is utilized to deposit on the surface of the substrate to obtain the amorphous organic-inorganic hybrid film, and the amorphous organic-inorganic hybrid film has a similar porous structure with MOF materials, so that large deformation and volume expansion cannot occur in the ligand exchange crystallization process. The method has no organic solvent in the process of preparing the MOF film, and avoids the problem of poor stability of the MOF film caused by the residual solvent molecules in the MOF film pore passages.
Description
Technical Field
The invention belongs to the technical field of MOF films, and particularly relates to a preparation method of an MOF film.
Background
The metal organic framework has the advantages of large porosity and surface area, strong functionality, strong size controllability and the like, so that the MOF material is subjected to functional regulation and modification according to specific requirements, and a new generation of membrane material, namely an MOF membrane, can be obtained. Compared with MOFs nanoparticles, the MOF film has the advantages of definite pore structure, adjustable thickness, large longitudinal and transverse dimensions and specific surface area, easiness in combination with other functional centers and the like, and shows special properties different from those of the traditional MOF particles in the frontier fields of electronic devices, gas separation, biological medicines, catalysis and the like.
Currently, MOF films are synthesized mainly by solvothermal and sacrificial template methods. The synthesis of the MOF film by the solvothermal method is based on homogeneous nucleation in a solution, and the obtained MOF film is mostly formed by stacking MOFs particles, so that the surface of the MOF film has high roughness, and a uniform film is difficult to obtain. In addition, solvothermal methods generally involve the participation of toxic organic solvent molecules, which can cause solvent molecules to remain in the MOF film pore channels, corroding the organic framework, and leading to poor stability of the MOF film. The sacrificial template method is characterized in that metal oxide is used as a template, the metal oxide and organic ligand are combined in a solvent to be converted into a porous MOF film through the combination of the dense metal oxide and the organic ligand, and the metal oxide expands in volume and becomes larger in shape in the process of being converted into the MOF film due to the great difference of the structures of the metal oxide and the MOF film, so that the MOF film has larger internal stress, poor film uniformity and high surface roughness. Meanwhile, when the metal oxide sacrificial template is thick, there is also a problem that the metal oxide template is not completely transformed due to the limited diffusion of ligand molecules. The MOF film obtained by the existing synthesis method has the problems of high surface roughness, poor film uniformity and the like, and a preparation technology for preparing a high-quality MOF film with uniform surface and sub-nanometer grade accurate and controllable thickness does not exist.
Disclosure of Invention
In view of the above, the invention provides a preparation method of an MOF film, and the MOF film obtained by the preparation method provided by the invention has good uniformity, smooth surface and precisely controllable sub-nanometer level thickness.
In order to solve the technical problem, the invention provides a preparation method of an MOF film, which comprises the following steps:
depositing the gas phase of a metal precursor and the gas phase of an organic precursor on the surface of a substrate by using a molecular layer deposition technology in an alternating pulse mode to obtain an amorphous organic-inorganic hybrid film;
and carrying out ligand exchange crystallization on the amorphous organic-inorganic hybrid film and the organic ligand to obtain the MOF film.
Preferably, the metal precursor is a metal salt;
the metal salt includes an organic metal salt or an inorganic metal salt.
Preferably, the pulse time of the gas phase for depositing the metal precursor is 0.01 to 1200 s.
Preferably, the organic precursor comprises ethylene glycol or glycerol.
Preferably, the pulse time for depositing the organic precursor is 0.015-800 s.
Preferably, the organic ligand comprises dimethylimidazole, diethylimidazole or terephthalic acid.
Preferably, the temperature of the ligand exchange crystallization is 30-300 ℃; the heat preservation time of the ligand exchange crystallization is 0.5-100 h.
Preferably, the matrix comprises a powder substrate or a non-porous substrate;
the powder substrate includes a metal oxide or a carbon material, the metal oxide including silicon dioxide nanowires, aluminum oxide, cerium oxide or titanium dioxide; the carbon material comprises graphene, carbon nanotubes, carbon helices or carbon black;
the non-porous substrate comprises a polymer film, a monocrystalline silicon wafer, or a silicon nanoarray.
Preferably, when the substrate is a powder substrate, before performing the deposition of the alternating pulses, the method further comprises: dispersing the powder substrate in an organic solvent to obtain a suspension; drying the suspension after coating the suspension on the surface of the carrier;
when the substrate is a non-porous substrate, before the deposition of the alternating pulses, the method further comprises: and sequentially carrying out purification treatment and drying on the non-porous substrate.
Preferably, the number of deposition times of the alternating pulses is 1-1000.
The invention provides a preparation method of an MOF film, which comprises the following steps: depositing the gas phase of a metal precursor and the gas phase of an organic precursor on the surface of a substrate by using a molecular layer deposition technology in an alternating pulse mode to obtain an amorphous organic-inorganic hybrid film; and carrying out ligand exchange crystallization on the amorphous organic-inorganic hybrid film and the organic ligand to obtain the MOF film. The amorphous organic-inorganic hybrid film is obtained by depositing on the surface of the substrate by utilizing a molecular layer deposition technology, and because the organic-inorganic hybrid film has a similar porous structure with an MOF material, compared with an MOF film prepared by taking a metal oxide film as a sacrificial template, the MOF film prepared by the method does not generate larger deformation and volume expansion in the process of ligand exchange crystallization, and has small surface roughness and good uniformity; in the process of preparing the MOF film by the method, no organic solvent is involved, so that the problem of poor stability of the MOF film caused by the corrosion of organic frameworks due to the residual solvent molecules in the MOF film pore channels is solved. Meanwhile, the MOF film prepared by the preparation method provided by the invention has excellent three-dimensional shape retention and can realize the sub-nanometer level precise regulation and control of the thickness of the MOF film.
Drawings
FIG. 1 is an infrared spectrum of a zinc-based amorphous organic-inorganic hybrid thin film and a ZIF-8 thin film in example 10;
FIG. 2 is nuclear magnetic spectra of zinc-based amorphous organic-inorganic hybrid thin film and ZIF-8 thin film in example 10;
FIG. 3 is an XRD spectrum of a ZIF-8 thin film obtained by the preparation of examples 2 to 5;
FIG. 4 is a TEM image of ZIF-8 thin films prepared in examples 7 to 10;
FIG. 5 is a TEM image of a thin film prepared in comparative example 1.
Detailed Description
The invention provides a preparation method of an MOF film, which comprises the following steps:
depositing the gas phase of a metal precursor and the gas phase of an organic precursor on the surface of a substrate by using a molecular layer deposition technology in an alternating pulse mode to obtain an amorphous organic-inorganic hybrid film;
and carrying out ligand exchange crystallization on the amorphous organic-inorganic hybrid film and the organic ligand to obtain the MOF film.
The invention utilizes molecular layer deposition technology to deposit the gas phase of metal precursor and the gas phase of organic precursor on the surface of the substrate by alternate pulse, thus obtaining the amorphous organic-inorganic hybrid film. In the present invention, it is a metal precursor or an organic precursor that is in direct contact with the substrate surface. In the present invention, when the metal precursor is in direct contact with the substrate, the alternating pulse deposition preferably comprises the steps of:
placing a substrate in a molecular layer deposition vacuum reaction cavity, and utilizing carrier gas to pulse the gas phase of a metal precursor to the molecular layer deposition vacuum reaction cavity so as to enable the gas phase of the metal precursor to be adsorbed on the surface of the substrate;
removing the gas phase of the unadsorbed metal precursor, and then utilizing carrier gas to pulse the gas phase of the organic precursor to a molecular layer deposition vacuum reaction cavity so as to enable the gas phase of the organic precursor and the metal precursor to perform a first half reaction;
removing the gas phase of the unreacted organic precursor, and then pulsing the gas phase of the metal precursor to a molecular layer deposition vacuum reaction cavity by using carrier gas to perform a second half reaction on the gas phase of the metal precursor and the organic precursor;
repeating the steps of the first half reaction and the second reaction to obtain the amorphous organic-inorganic hybrid film.
The substrate is placed in a molecular layer deposition vacuum reaction cavity, and the carrier gas is used for pulsing the gas phase of the metal precursor to the molecular layer deposition vacuum reaction cavity so that the gas phase of the metal precursor is adsorbed on the surface of the substrate. In the present invention, the substrate preferably comprises a powder substrate or a non-porous substrate; the powder substrate preferably comprises a metal oxide or a carbon material, the metal oxide preferably comprises silicon dioxide nanowires, aluminum oxide, cerium oxide or titanium dioxide, more preferably silicon dioxide nanowires; the carbon material preferably comprises graphene, carbon nanotubes, carbon helices or carbon black, more preferably graphene or carbon nanotubes. In the present invention, the non-porous substrate preferably comprises a polymer film, a monocrystalline silicon wafer or a silicon nanoarray, more preferably a monocrystalline silicon wafer or a silicon nanoarray. In the present invention, the silicon nano-array preferably comprises a silicon nano-wire array or a silicon nano-pillar array, and more preferably a silicon nano-pillar array.
The pre-treating of the substrate prior to placing the substrate in the molecular layer deposition vacuum reaction chamber according to the present invention preferably further comprises pre-treating the substrate. In the present invention, when the substrate is a powder substrate, the pretreatment preferably comprises the steps of: dispersing the powder substrate in an organic solvent to obtain a suspension; and drying the suspension after coating the suspension on the surface of the carrier. In the present invention, the organic solvent is preferably ethanol. In the present invention, the ratio of the mass of the powder base to the volume of the organic solvent is preferably 0.01g:0.8 to 1.2mL, and more preferably 0.01g:1.0 mL.
In the present invention, the support preferably comprises a glass sheet, preferably a quartz glass sheet. The invention has no special requirements on the coating mode and can adopt a conventional mode in the field. In the present invention, the drying is preferably carried out by subjecting the carrier coated with the suspension to natural air drying in the air. The present invention has no particular requirement for the air drying as long as the solvent in the suspension can be removed.
In the present invention, when the substrate is a non-porous substrate, the pretreatment preferably comprises the steps of: and sequentially carrying out purification treatment and drying on the non-porous substrate. In the present invention, the cleaning treatment is preferably performed by washing the non-porous substrate with a solvent; the solvent is preferably ethanol or water, more preferably ethanol. The present invention has no particular requirement on the manner of cleaning, as long as it is capable of removing the contaminants from the surface of the non-porous substrate. The present invention has no particular requirement for the drying as long as the solvent on the surface of the non-porous substrate can be removed. The invention can remove impurities on the surface of the non-porous substrate through purification treatment, and is beneficial to the growth of the amorphous organic-inorganic hybrid membrane.
In the present invention, the carrier gas preferably includes high-purity nitrogen, argon or helium, more preferably argon. In the present invention, the purity of the high-purity nitrogen gas is preferably 99.999%. In the invention, the volume ratio of the carrier gas to the molecular layer deposition vacuum reaction cavity is preferably 1/5-1/10, and more preferably 1/6-1/8. In the present invention, the flow rate of the carrier gas is preferably 45 to 55mL/min, and more preferably 50 mL/min.
In the present invention, the metal precursor is preferably a metal salt, and the metal salt preferably includes an organic metal salt or an inorganic metal salt; the organometallic salt preferably comprises dimethylzinc, diethylzinc, trimethylaluminum, titanium isopropoxide or zirconium tetra-tert-butoxide, more preferably diethylzinc or trimethylaluminum. In the present invention, the inorganic metal salt preferably includes titanium tetrachloride or zirconium chloride.
In the present invention, the pulse front preferably further comprises: heating the metal precursor; the heating temperature is preferably 10-200 ℃, and more preferably 20-120 ℃. In the present invention, the heating step provides the metal precursor with a certain vapor pressure.
In the invention, the temperature of the molecular layer deposition vacuum reaction cavity is preferably 100-300 ℃, and more preferably 140-180 ℃; the pressure of the molecular layer deposition vacuum reaction cavity is preferably 10-200 Pa, and more preferably 60-150 Pa. In the invention, the time of the pulse is preferably 0.015-1200 s, and more preferably 0.02-500 s; the time for holding breath after the pulse is preferably 5-3000 s, and more preferably 5-1000 s.
In the invention, the adsorption is chemical adsorption, and the metal precursor molecule and the surface of the substrate are subjected to chemical reaction to form a chemical bond.
After the adsorption is finished, the gas phase of the unadsorbed metal precursor is removed, the gas phase of the organic precursor is pulsed to the molecular layer deposition vacuum reaction cavity by using the carrier gas, and the gas phase of the organic precursor and the metal precursor are subjected to a first half reaction. In the present invention, the gas phase of the metal precursor which has not been adsorbed is preferably removed by evacuating the gas phase of the metal precursor which has not been reacted by means of a vacuum pump. In the invention, the air extraction time is preferably 5-3000 s, and more preferably 5-1000 s.
In the present invention, the carrier gas preferably includes high-purity nitrogen, argon or helium, more preferably argon. In the present invention, the purity of the high-purity nitrogen gas is preferably 99.999%. In the invention, the volume ratio of the carrier gas to the molecular layer deposition vacuum reaction cavity is preferably 1/5-1/10, and more preferably 1/6-1/8. In the present invention, the flow rate of the carrier gas is preferably 45 to 55mL/min, and more preferably 50 mL/min.
In the present invention, the organic precursor preferably includes ethylene glycol or glycerol, and more preferably ethylene glycol. In the present invention, when the organic precursor is in a non-gaseous state, it is preferable to heat the organic precursor so that it has a certain vapor pressure.
In the present invention, the pulse front preferably further comprises: heating the gas phase of the organic precursor; the heating temperature is preferably 10-200 ℃, and more preferably 20-120 ℃. In the present invention, the heating step provides the organic precursor with a certain vapor pressure.
In the invention, the temperature of the molecular layer deposition vacuum reaction cavity is preferably 100-300 ℃, and more preferably 140-180 ℃; the pressure of the molecular layer deposition vacuum reaction cavity is preferably 10-200 Pa, and more preferably 60-150 Pa. In the invention, the time of the pulse is preferably 0.015-1200 s, and more preferably 0.02-500 s; the first half reaction breath holding time is preferably 5-3000 s, and more preferably 5-1000 s.
After the first half reaction, the gas phase of the unreacted organic precursor is removed, and the gas phase of the metal precursor is pulsed to the molecular layer deposition vacuum reaction cavity by using the carrier gas, so that the gas phase of the metal precursor and the organic precursor are subjected to the second half reaction. In the present invention, it is preferable that the gas phase of the unreacted organic precursor is removed by evacuation using a vacuum pump. In the invention, the air extraction time is preferably 5-3000 s, and more preferably 5-1000 s.
In the present invention, the carrier gas preferably includes high-purity nitrogen, argon or helium, more preferably argon. In the present invention, the purity of the high-purity nitrogen gas is preferably 99.9999%. In the invention, the volume ratio of the carrier gas to the molecular layer deposition vacuum reaction cavity is preferably 1/5-1/10, and more preferably 1/6-1/8. In the present invention, the flow rate of the carrier gas is preferably 45 to 55mL/min, and more preferably 50 mL/min.
In the present invention, the metal precursor preferably includes zinc dimethyl, zinc diethyl, aluminum trimethyl, titanium isopropoxide, titanium tetrachloride, zirconium chloride or zirconium tetra-t-butoxide, more preferably zinc diethyl, zirconium chloride, aluminum trimethyl or titanium tetrachloride. In the present invention, when the metal precursor is non-gaseous, it is preferable to heat the metal precursor so that it has a certain vapor pressure.
In the present invention, the pulse front preferably further comprises: heating the gas phase of the metal precursor; the heating temperature is preferably 10-200 ℃, and more preferably 20-120 ℃.
In the invention, the temperature of the molecular layer deposition vacuum reaction cavity is preferably 100-300 ℃, and more preferably 140-180 ℃; the pressure of the molecular layer deposition vacuum reaction cavity is preferably 10-200 Pa, and more preferably 60-150 Pa. In the invention, the time of the pulse is preferably 0.015-1200 s, and more preferably 0.02-500 s; the second half reaction is preferably carried out for 5-3000 s, and more preferably for 5-1000 s.
The invention repeats the steps of the first half reaction and the second reaction to obtain the amorphous organic-inorganic hybrid film. In the present invention, the number of repetitions is preferably 1 to 1000, and more preferably 5 to 500.
In the present invention, the flow rate of the carrier gas is a fixed value during the deposition of alternating pulses.
In the present invention, the thickness of the amorphous organic-inorganic hybrid thin film is determined by the number of repetitions, and the present invention can control the thickness of the amorphous organic-inorganic hybrid thin film by adjusting the number of repetitions.
In the present invention, when the organic precursor directly contacts the substrate, the step of alternating pulse deposition is preferably the same as the step of alternating pulse deposition when the metal precursor directly contacts the substrate, except that the first deposition is to place the substrate in a molecular layer deposition vacuum reaction chamber, and pulse the gas phase of the organic precursor to the molecular layer deposition vacuum reaction chamber by using a carrier gas, so that the gas phase of the organic precursor is adsorbed on the surface of the substrate. For the sake of brevity, the present invention will not be repeated herein for the step of alternately pulsing deposition when the organic precursor is in direct contact with the substrate.
In the present invention, the deposition of the alternating pulses preferably further comprises: and taking out the product obtained by the alternate pulse deposition from the molecular layer deposition vacuum reaction cavity and then placing the product in a dryer for later use.
After the amorphous organic-inorganic hybrid film is obtained, the invention carries out ligand exchange crystallization on the amorphous organic-inorganic hybrid film and an organic ligand to obtain the MOF film. In the present invention, it is preferable to further include the following steps before the ligand exchange crystallization is performed:
placing the organic ligand in a beaker;
placing the amorphous organic-inorganic hybrid film in a quartz crucible filter element, and covering the quartz crucible filter element on the opening of the beaker to form a reaction system;
placing the reaction system in a reaction kettle for sealing;
and (3) placing the reaction kettle filled with the reaction system in a heating device.
In the present invention, the organic ligand preferably includes dimethylimidazole, diethylimidazole or terephthalic acid, more preferably dimethylimidazole or terephthalic acid.
In the invention, the cup mouth of the beaker is smaller than the bottom of the quartz crucible filter element.
In the invention, the reaction kettle preferably comprises a polytetrafluoroethylene inner container.
In the present invention, the heating means preferably comprises an oven.
In the invention, the temperature of the ligand exchange crystallization is preferably 30-300 ℃, and more preferably 50-280 ℃; the heating rate of heating to the temperature required by the ligand exchange crystallization is preferably 1-10 ℃/min, and more preferably 2-8 ℃/min; the heat preservation time of the ligand exchange crystallization is preferably 0.5-100 h, and more preferably 0.5-10 h.
In the present invention, the ligand exchange crystallization is preferably gas phase ligand exchange crystallization; and in the gas-phase ligand exchange crystallization process, organic ligands are exchanged with organic precursors in the amorphous organic-inorganic hybrid film, and the amorphous organic-inorganic hybrid film is transformed into an MOF film along with crystallization.
In the present invention, the ligand exchange crystallization preferably further comprises: cooling the ligand exchange crystallization system and taking out the membrane product;
and cleaning and drying the membrane product to obtain the MOF membrane.
In the invention, the temperature after cooling is preferably room temperature, and the temperature of the room temperature is preferably 20-35 ℃, and more preferably 25-30 ℃. In the present invention, the cooling is preferably natural cooling.
In the present invention, the cleaning solvent is preferably ethanol; the number of washing is preferably 2 to 4, and more preferably 3. In the present invention, the drying is preferably centrifugal drying.
In the present invention, the MOF film preferably includes a ZIF-8(Zn) film, a MAF-6(Zn) film, an MIL-53(Al) film, an MIL-125(Ti) film or a UiO-66(Zr) film, and more preferably a ZIF-8(Zn) film, an MIL-53(Al) film or a UiO-66(Zr) film.
In the invention, the thickness of the MOF film is preferably 0.5-2000 nm, and more preferably 5-1000 nm.
The invention utilizes molecular layer deposition technology (MLD) to deposit a metal-based amorphous organic-inorganic hybrid film on the surface of a substrate, and the amorphous organic-inorganic hybrid film and organic ligand molecules generate gas-phase ligand exchange and crystallization at a certain temperature, thereby realizing the preparation of the MOF film. Compared with the synthesis of the MOF film by taking metal oxide as a sacrificial template, the amorphous organic-inorganic hybrid film prepared by the molecular layer deposition technology avoids the stress caused by huge volume expansion and deformation in the crystal transformation process. In addition, the precursor is bonded with the surface of the substrate in a chemical adsorption mode in the MLD deposition process, so that the MOF film prepared by gas phase ligand exchange crystal transformation in the method has strong interaction with the substrate. Meanwhile, MLD is based on self-limiting reaction of precursor molecules and the surface of the substrate, so that the thickness of the organic-inorganic hybrid film can be accurately regulated and controlled by changing the number of MLD deposition cycles, and the thickness of the prepared MOF film can be accurately controlled. The inorganic part and the organic part of the amorphous organic-inorganic hybrid film prepared by MLD are adjustable, so that the inorganic part and the organic part can be changed to realize controllable synthesis of different MOF films. The method has good universality and can prepare various MOF films with high quality.
The preparation method provided by the invention is simple and easy to control, can be used for preparing various MOF films, has good uniformity and strong interaction force with the surface of a substrate, can be used for accurately regulating and controlling the thickness of the film in a nanoscale, and can realize conformal deposition on the surface of a carrier with a high aspect ratio.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
In the embodiment of the invention, when the substrate is silicon dioxide nanowire or aluminum oxide, the substrate needs to be dispersed in ethanol to obtain suspension; the suspension is coated on the surface of a quartz glass sheet and dried. When the substrate is a silicon nano-pillar array or a monocrystalline silicon wafer, the substrate is directly cleaned and then dried.
Example 1
1) Cleaning a monocrystalline silicon wafer by using ethanol, drying, placing the dried monocrystalline silicon wafer in a Molecular Layer Deposition (MLD) vacuum reaction cavity, wherein the temperature of the vacuum reaction cavity is 150 ℃, the pressure of the vacuum reaction cavity is 60Pa, argon is used as a carrier gas, the volume ratio of the carrier gas to the vacuum reaction cavity is 1/6, and the carrier gas flow is 50mL/min in the deposition process;
2) preparing an amorphous zinc-based organic-inorganic hybrid film by using a molecular layer deposition technology:
(a) the diethyl zinc precursor steam is pulsed into the MLD cavity to react with the surface of the monocrystalline silicon wafer, wherein the diethyl zinc precursor is kept at room temperature, the pulse time of the diethyl zinc precursor is 0.02s, and the gas holding time is 15 s; removing unadsorbed diethyl zinc precursor and physically adsorbed diethyl zinc precursor in the vacuum reaction cavity by vacuum pump air extraction for 50 s;
(b) performing half reaction on pulse ethylene glycol precursor steam and diethyl zinc chemically adsorbed on the surface of the monocrystalline silicon piece, wherein the ethylene glycol precursor is kept at 75 ℃ to provide enough steam pressure, the pulse time of the ethylene glycol precursor is 0.5s, and the gas holding time is 15 s; removing unreacted ethylene glycol precursor vapor in the vacuum reaction cavity by using a vacuum pump for pumping, wherein the pumping time is 25 s;
(c) repeating the step (a) and the step (b) in this way, and performing cyclic pulse deposition on the surface of the monocrystalline silicon wafer for 40 times;
(d) after MLD deposition is finished, taking the film out of the vacuum cavity to obtain a zinc-based amorphous organic-inorganic hybrid film;
3) preparing a ZIF-8 film by solvent-free gas-phase ligand exchange crystallization:
(a) placing the obtained zinc-based organic-inorganic hybrid film in a quartz crucible filter element, and placing 100mg of dimethyl imidazole ligand in a beaker;
(b) covering a quartz crucible filter element provided with a zinc-based organic-inorganic hybrid film sample on the mouth of a beaker provided with a dimethyl imidazole organic ligand, placing the beaker in a hydrothermal kettle with a polytetrafluoroethylene inner container, and sealing the hydrothermal kettle;
(c) placing the sealed hydrothermal kettle in an oven, and heating to 140 ℃ according to the heating rate of 5 ℃/min to perform gas phase ligand exchange crystallization for 6 hours;
(d) and naturally cooling to 25 ℃ after gas phase ligand exchange crystallization, taking out the film, washing for 2 times by using absolute ethyl alcohol, and drying to obtain the ZIF-8 film.
Example 2
A ZIF-8 film was prepared according to the method of example 1, except that the number of cyclic pulse depositions was 5, and the resulting ZIF-8 film, referred to as 5 ZIF-8/Si.
Example 3
A ZIF-8 film was prepared according to the method of example 1, except that the number of cyclic pulse depositions was 10, and the resulting ZIF-8 film, abbreviated as 10 ZIF-8/Si.
Example 4
A ZIF-8 film was prepared according to the method of example 1, except that the number of cyclic pulse depositions was 30, and the resulting ZIF-8 film, abbreviated as 30 ZIF-8/Si.
Example 5
A ZIF-8 film was prepared according to the method of example 1, except that the number of cyclic pulse depositions was 50, and the resulting ZIF-8 film, abbreviated as 50 ZIF-8/Si.
Example 6
A ZIF-8 thin film was prepared as in example 1, except that the silica nanowires were used as the substrate, and the pretreatment of the substrate was carried out using 20mg of SiO 2 The nano-wires are dispersed in ethanol to obtain suspension with the mass concentration of 0.01g/mL, the suspension is coated on the surface of a glass sheet, the glass sheet is naturally air-dried in the air and then placed in a molecular layer deposition vacuum reaction cavity, the temperature of the vacuum reaction cavity is 150 ℃, the pressure of the vacuum reaction cavity is 60Pa, high-purity nitrogen with the purity of 99.999 percent is used as carrier gas, the volume ratio of the carrier gas to the vacuum reaction cavity is 1/6, and the carrier gas flow is 50mL/min in the deposition process.
Example 7
ZIF-8 films were prepared as in example 6, except that the number of cyclic pulse depositions was 5, to obtain ZIF-8 films having a thickness of 2.7nm, abbreviated as 5ZIF-8/SiO 2 A nanowire.
Example 8
ZIF-8 thin films were prepared as in example 6, except that the number of cyclic pulse depositions was 10, and that ZIF-8 thin films having a thickness of 3.78nm, abbreviated as 10ZIF-8/SiO, were obtained 2 A nanowire.
Example 9
ZIF-8 films were prepared as in example 6, except that the number of cyclic pulse depositions was 30, to obtain ZIF-8 films having a thickness of 10.0nm, abbreviated as 30ZIF-8/SiO 2 A nanowire.
Example 10
A ZIF-8 film was prepared as in example 6, except that the number of deposition cycles was changed to50 times, obtaining a ZIF-8 film with the thickness of 21.82nm, which is called 50ZIF-8/SiO for short 2 A nanowire.
Example 11
A ZIF-8 thin film was prepared according to the method of example 6, except that the silica nanowires were replaced with spherical alumina; the number of deposition cycles was 10, and a ZIF-8 film having a thickness of 3.6nm was obtained.
Example 12
A ZIF-8 film was produced by the method of example 11, except that the number of cyclic pulse depositions was 30, to obtain a ZIF-8 film having a thickness of 9.9 nm.
Example 13
A ZIF-8 film was produced by the method of example 11, except that the number of cyclic pulse depositions was 50, to obtain a ZIF-8 film having a thickness of 21.2 nm.
Example 14
A ZIF-8 thin film was prepared as in example 6, except that the silicon dioxide nanowires were replaced with an array of high aspect ratio silicon nanopillars; the number of times of the cyclic pulse deposition is 10, and the silicon nano-pillar array conformally coated by the ZIF-8 film is obtained.
Example 15
A ZIF-8 film was prepared according to the method of example 14, except that the number of cyclic pulse depositions was 30, to obtain a ZIF-8 film conformally coated silicon nanopillar array.
Example 16
A ZIF-8 film was prepared according to the method of example 14, except that the number of cyclic pulse depositions was 50 times, to obtain a ZIF-8 film conformally coated silicon nanopillar array.
Example 17
An MOF film was prepared according to the method of example 6, except that diethylimidazole was used as the organic ligand, the temperature of ligand exchange crystallization was 80 ℃ and the holding time was 3 hours, and the obtained MOF film was a MAF-6 film.
Example 18
A MAF-6 film was prepared by the method of example 17 except that the number of deposition cycles was 5, to obtain a MAF-6 film having a thickness of 2.2 nm.
Example 19
A MAF-6 film was prepared by the method of example 17 except that the number of deposition cycles was 10 to obtain a MAF-6 film having a thickness of 6.9 nm.
Example 20
A MAF-6 film was prepared by the method of example 17 except that the number of deposition cycles was 30 to obtain a MAF-6 film having a thickness of 19.8 nm.
Example 21
A MAF-6 film was prepared by following the procedure of example 17 except that the number of deposition cycles of the pulse was 50 to obtain a MAF-6 film having a thickness of 32.4 nm.
Example 22
A MAF-6 film was prepared as in example 17, except that the silicon dioxide nanowires were replaced with an array of high aspect ratio silicon nanopillars; the number of times of cyclic pulse deposition is 10, and the silicon nano-pillar array coated with the MAF-6 film in a conformal mode is obtained.
Example 23
A MAF-6 film was prepared as in example 22, except that the number of cyclic pulse depositions was 30, giving a conformal coated silicon nanopillar array of MAF-6 film.
Example 24
A MAF-6 film was prepared as in example 22, except that the number of cyclic pulse depositions was 50 to obtain a conformal coated silicon nanopillar array of the MAF-6 film.
Example 25
A UiO-66 film was prepared according to the method of example 6, except that the metal precursor diethylzinc was replaced with zirconium tert-butoxide, wherein the heating temperature of the zirconium tert-butoxide precursor was 55 ℃, and the pulse, exposure, and hold-off times of the zirconium tert-butoxide precursor were 0.25s, 20s, and 25s, respectively; wherein the ethylene glycol precursor is kept at 75 ℃ to provide enough vapor pressure, and the pulse, gas hold and air extraction time of the ethylene glycol precursor are respectively 0.5s, 15s and 25 s; replacing organic ligand dimethyl imidazole with terephthalic acid; the temperature of ligand exchange crystallization is 180 ℃, and the heat preservation time is 5 h.
Example 26
A UiO-66 film was prepared by the method of example 25, except that the number of cyclic pulse depositions was 5, to obtain a UiO-66 film having a thickness of 1.8 nm.
Example 27
A UiO-66 film was prepared by the method of example 25, except that the number of cyclic pulse depositions was 10, to obtain a UiO-66 film having a thickness of 3.9 nm.
Example 28
A UiO-66 film was produced by the method of example 25, except that the number of cyclic pulse depositions was 30, to obtain a UiO-66 film having a thickness of 12.4 nm.
Example 29
A UiO-66 film was prepared by the method of example 25, except that the number of cyclic pulse depositions was 50, to obtain a UiO-66 film having a thickness of 24.3 nm.
Example 30
A UiO-66 film was prepared according to the method of example 25, except that the substrate was replaced with a high aspect ratio silicon nanopillar array and the number of cyclic pulse depositions was 10 times, resulting in a silicon nanopillar array conformally coated with the UiO-66 film.
Example 31
A UiO-66 film was prepared according to the method of example 30, except that the number of cyclic pulse depositions was 30 times, to obtain a silicon nanopillar array conformally coated with the UiO-66 film.
Example 32
A uo-66 thin film was prepared according to the method of example 30, except that the number of cyclic pulse depositions was 50 times, resulting in a silicon nanopillar array conformally coated with the uo-66 thin film.
Example 33
An MIL-53(Al) film was prepared as in example 25, except that the metal precursor, zirconium chloride, was replaced with trimethylaluminum, wherein the trimethylaluminum precursor was maintained at room temperature and the pulsing, gassing, and pumping times of the trimethylaluminum precursor were 0.1s, 20s, and 25s, respectively; wherein the ethylene glycol precursor is kept at 75 ℃ to provide enough vapor pressure, and the pulse, breath holding and air exhausting time of the ethylene glycol precursor is 0.5s, 15s and 25 s; the temperature of ligand exchange crystallization is 200 ℃, and the heat preservation time is 4 h.
Example 34
A MIL-53(Al) thin film was prepared as in example 33, except that the number of deposition cycles was 5, to obtain a MIL-53(Al) thin film having a thickness of 1.3 nm.
Example 35
A MIL-53(Al) thin film was prepared according to the method of example 33, except that the number of cyclic pulse depositions was 10 times, to obtain a MIL-53(Al) thin film having a thickness of 2.1 nm.
Example 36
A MIL-53(Al) thin film was prepared as in example 33, except that the number of deposition cycles was 30, to obtain a MIL-53(Al) thin film having a thickness of 6.4 nm.
Example 37
A MIL-53(Al) thin film was prepared as in example 33, except that the number of deposition cycles was 50, to obtain a MIL-53(Al) thin film having a thickness of 11.3 nm.
Example 38
A MIL-53(Al) thin film was prepared as in example 33, except that the substrate was replaced with a high aspect ratio silicon nanopillar array from silicon dioxide nanowires, and the number of cyclic pulse depositions was 10 times, resulting in a silicon nanopillar array conformally coated with the MIL-53(Al) thin film.
Example 39
MIL-53(Al) films were prepared according to the method of example 38, except that the number of cyclic pulse depositions was 30 times, resulting in a conformal coated silicon nanopillar array of MIL-53(Al) films.
Example 40
MIL-53(Al) films were prepared according to the method of example 38, except that the number of cyclic pulse depositions was 50, resulting in a conformal coated silicon nanopillar array of MIL-53(Al) films.
EXAMPLE 41
MIL-125(Ti) films were prepared as in example 25, except that the metal precursor, zirconium chloride, was replaced with titanium tetrachloride, wherein the titanium tetrachloride precursor was maintained at room temperature and the pulse, hold, and pump down times of the titanium tetrachloride precursor were 1s, 8s, and 25, respectively; wherein the ethylene glycol precursor is kept at 75 ℃ to provide enough vapor pressure, and the pulse, breath holding and air extraction time of the ethylene glycol precursor is respectively 0.5s, 15s and 25 s; the temperature of ligand exchange crystallization is 160 ℃, and the heat preservation time is 10 h.
Example 42
A MIL-125(Ti) thin film was prepared according to the method of example 41, except that the number of cyclic pulse depositions was 5 times, to obtain a MIL-125(Ti) thin film having a thickness of 2.4 nm.
Example 43
A MIL-125(Ti) thin film was prepared as in example 41, except that the number of deposition cycles was 10, to obtain a MIL-125(Ti) thin film having a thickness of 4.9 nm.
Example 44
A MIL-125(Ti) thin film was prepared as in example 41, except that the number of deposition cycles was 30, to obtain a MIL-125(Ti) thin film having a thickness of 15.8 nm.
Example 45
A MIL-125(Ti) thin film was prepared as in example 41, except that the number of deposition cycles was 50, to obtain a MIL-125(Ti) thin film having a thickness of 16.3 nm.
Example 46
An MIL-125(Ti) thin film was prepared as in example 41, except that the substrate silica nanowires were replaced with an array of high aspect ratio silicon nanopillars, and the number of cyclic pulse depositions was 10 times, resulting in an array of MIL-125(Ti) thin film conformally coated silicon nanopillars.
Example 47
MIL-125(Ti) films were prepared according to the method of example 46, except that the number of cyclic pulse depositions was 30 times, resulting in a silicon nanopillar array conformally coated with MIL-125(Ti) films.
Example 48
MIL-125(Ti) films were prepared according to the method of example 46, except that the number of cyclic pulse depositions was 50, resulting in a silicon nanopillar array conformally coated with MIL-125(Ti) films.
Comparative example 1
A ZIF-8 thin film was prepared as in example 6, except that the ethylene glycol precursor was replaced with water for 50 cyclical deposition times in Atomic Layer Deposition (ALD); the temperature of the distribution exchange crystallization is 140 ℃, the heat preservation time is 6h, and the prepared product is abbreviated as ALD50ZIF-8/SiO 2 A nanowire.
The zinc-based amorphous organic-inorganic hybrid film and the ZIF-8 film of example 10 were subjected to infrared detection to obtain an infrared spectrum, as shown in fig. 1. Comparing the infrared spectrograms of the zinc-based organic-inorganic hybrid film and the ZIF-8 film, it can be seen that the infrared spectrograms of the film are 3138cm respectively after gas-phase ligand exchange crystallization -1 And 2933cm -1 A stretching vibration absorption peak of methyl and imidazole C-H bonds appears, and 1145cm -1 And 990cm -1 A telescopic absorption peak of a C-N bond appears; and 3360cm -1 The vibrational peak of the hydroxyl group belonging to ethylene glycol disappeared. The method shows that through gas phase ligand exchange crystallization reaction, the dimethyl imidazole replaces glycol ligand in the original zinc-based organic-inorganic hybrid film, and generates a special dimethyl imidazole absorption peak.
The zinc-based amorphous organic-inorganic hybrid film and the ZIF-8 film of example 10 were subjected to solid nuclear magnetic detection, and the nuclear magnetic spectra were obtained as shown in fig. 2. As can be seen from FIG. 2, the film was deposited on SiO by molecular layer deposition 2 Forming amorphous organic-inorganic hybrid film on nanowire, forming amorphous organic-inorganic hybrid film on zinc base (Zn (C) 2 H 5 O 2 ) 2 /SiO 2 ) Wherein, the element C is distributed as shown in the structural formula a, which 13 Chemical shift of C is 63.92, after gas phase ligand exchange crystallization reaction of dimethyl imidazole, the structure of the dimethyl imidazole is changed into a structure shown as b, and 13 the chemical shift of C is changed into the characteristic shift of C of dimethyl imidazole, BProcess for preparing diols 13 The characteristic displacement of C disappears altogether. Since the acting force of N and Zn is stronger than that of O and Zn, it is considered that dimethylimidazole replaces the ethylene glycol bound to Zn in the amorphous organic-inorganic thin film during the ligand exchange crystallization reaction. Wherein after the dimethyl imidazole is combined with the Zn, 13 the chemical shifts of C are 150.68 for alpha, 123.71 for beta and 13.34 for gamma. And therefore, the ligand exchange crystallization reaction equation can be presumed to be shown as formula 1:
Zn(C 2 H 5 O 2 ) 2 +2C 2 H 6 N 2 →ZIF-8+2C 2 H 6 O 2 formula 1.
XRD detection is carried out on the ZIF-8 film prepared in the embodiment 2-5, and the XRD spectrogram is shown in figure 3. As can be seen from FIG. 3, XRD diffraction peaks of zinc-based organic-inorganic hybrid films deposited on the surface of monocrystalline silicon for 5 times, 10 times, 30 times and 50 times by MLD (multi-layer metal-oxide-semiconductor) cycle after gas-phase ligand exchange crystallization are consistent with ZIF-8XRD characteristic diffraction peaks, which indicates that highly crystalline ZIF-8 films are prepared in examples 2-5.
Transmission Electron Microscope (TEM) detection is performed on the ZIF-8 thin films prepared in examples 7-10, and a TEM image is obtained, as shown in FIG. 4. From FIG. 4, it can be seen that 2 The ZIF-8 film obtained by performing cyclic deposition on the surface of the nanowire for 5 times, 10 times, 30 times and 50 times and performing gas-phase ligand exchange crystallization on the zinc-based organic-inorganic hybrid film is uniformly and conformally coated on SiO 2 Surface of the nanowire, SiO not changed 2 A wire-like configuration of the nanowires. Meanwhile, the thickness of the ZIF-8 film is linearly increased along with the increase of the number of MLD deposition cycles, which shows that the MOF film prepared by the method can accurately regulate and control the thickness of the film at the sub-nanometer scale. In addition, no ZIF-8 film peeling phenomenon was observed in the figure, indicating that the MOF film prepared by the method has strong interaction with the substrate.
Comparative example 1 no organic-inorganic hybrid film was generated when preparing the ZIF-8 film, and the ZIF-8 film was directly generated by reacting zinc oxide with an organic ligand. The film obtained in comparative example 1 was examined by transmission electron microscopy to obtain a TEM image, as shown in FIG. 5. As can be seen from FIG. 5, the film prepared in comparative example 1 has a blocking phenomenon on the surface, and the thickness at different positions is very different and very non-uniform.
Although the present invention has been described in detail with reference to the above embodiments, it is only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments are included in the scope of the present invention.
Claims (10)
1. A method of making a MOF film comprising the steps of:
depositing the gas phase of a metal precursor and the gas phase of an organic precursor on the surface of a substrate by using a molecular layer deposition technology in an alternating pulse mode to obtain an amorphous organic-inorganic hybrid film;
and carrying out ligand exchange crystallization on the amorphous organic-inorganic hybrid film and the organic ligand to obtain the MOF film.
2. The method of making a MOF film according to claim 1, wherein the metal precursor is a metal salt;
the metal salt includes an organic metal salt or an inorganic metal salt.
3. The method for preparing the MOF film according to claim 1 or 2, wherein the pulse time for depositing the gas phase of the metal precursor is 0.01-1200 s.
4. A method of making a MOF film according to claim 1, wherein the organic precursor comprises ethylene glycol or glycerol.
5. The method for preparing the MOF film according to claim 1 or 4, wherein the pulse time for depositing the organic precursor is 0.015-800 s.
6. A process for the preparation of MOF film according to claim 1 wherein the organic ligand comprises dimethylimidazole, diethylimidazole or terephthalic acid.
7. The preparation method of the MOF film according to claim 1 or 6, wherein the temperature of the ligand exchange crystallization is 30-300 ℃; the heat preservation time of the ligand exchange crystallization is 0.5-100 h.
8. A method of making a MOF film according to claim 1 wherein the matrix comprises a powder substrate or a non-porous substrate;
the powder substrate includes a metal oxide or a carbon material, the metal oxide including silicon dioxide nanowires, aluminum oxide, cerium oxide or titanium dioxide; the carbon material comprises graphene, carbon nanotubes, carbon helices or carbon black;
the non-porous substrate comprises a polymer film, a monocrystalline silicon wafer, or a silicon nanoarray.
9. The method of making a MOF film according to claim 8, wherein when the substrate is a powdered substrate, the method further comprises prior to the depositing the alternating pulses: dispersing the powder substrate in an organic solvent to obtain a suspension; drying the suspension after coating the suspension on the surface of a carrier;
when the substrate is a non-porous substrate, before the deposition of the alternating pulses, the method further comprises: and sequentially carrying out purification treatment and drying on the non-porous substrate.
10. The method for preparing the MOF film according to claim 1, wherein the number of the alternate pulse deposition is 1-1000.
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