CN115124727B - Preparation method of MOF film - Google Patents
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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: alternately pulse-depositing a metal precursor and an organic precursor on the surface of a substrate by utilizing a molecular layer deposition technology to obtain an amorphous organic-inorganic hybrid film; and carrying out solvent-free gas 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 deposited on the surface of the substrate by utilizing a molecular layer deposition technology, and the amorphous organic-inorganic hybrid film has a similar porous structure with the MOF material, so that larger deformation and volume expansion can not occur in the ligand exchange crystallization process, and the MOF film prepared by the method has small surface roughness and good uniformity. The method has no participation of organic solvent in the process of preparing the MOF film, and avoids the problem of poor stability of the MOF film caused by residual solvent molecules in the pore canal of the MOF film.
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 nano particles, the MOF film has the advantages of clear pore channel structure, adjustable thickness, large longitudinal and transverse dimensions, large specific surface area, easiness in compounding with other functional centers and the like, and shows special properties different from those of the traditional MOF particles in the front fields of electronic devices, gas separation, biological medicines, catalysis and the like.
Currently, MOF films are synthesized primarily by solvothermal and sacrificial template methods. The synthesis of MOF films by solvothermal method is based on homogeneous nucleation in solution, and the obtained MOF films are mostly formed by stacking MOFs particles, so that the surfaces of the MOF films have high roughness, and uniform films are difficult to obtain. In addition, solvothermal methods generally involve the participation of toxic organic solvent molecules, which can cause the solvent molecules to remain in the pores of the MOF film and corrode the organic framework, resulting in poor stability of the MOF film. The sacrificial template method uses metal oxide as a template, and converts the metal oxide into a porous MOF film through the combination of compact metal oxide and an organic ligand in a solvent, and the metal oxide expands and deforms greatly in the process of converting the metal oxide into the MOF film due to the great difference of the metal oxide and the MOF film in the structural aspect, so that the internal stress of the MOF film is larger, the uniformity of the film is poor, and the surface roughness is high. Meanwhile, when the metal oxide sacrificial template is thicker, there is also a problem that the metal oxide template is not completely transformed due to the diffusion limitation of the 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 the high-quality MOF film with uniform surface and accurate and controllable thickness at a sub-nanometer level is not available.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a MOF film, and the MOF film obtained by the preparation method provided by the invention has good uniformity, smooth surface and accurate and controllable thickness in sub-nanometer level.
In order to solve the technical problems, the invention provides a preparation method of an MOF film, which comprises the following steps:
depositing the gas phase of the metal precursor and the gas phase of the organic precursor on the surface of the substrate by using a molecular layer deposition technology in an alternating pulse manner 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 for depositing the gas phase of the metal precursor is 0.01 to 1200s.
Preferably, the organic precursor comprises ethylene glycol or glycerol.
Preferably, the pulse time for depositing the organic precursor is 0.015 to 800 seconds.
Preferably, the organic ligand comprises dimethyl imidazole, diethyl imidazole or terephthalic acid.
Preferably, the temperature of ligand exchange crystallization is 30-300 ℃; the heat preservation time of ligand exchange crystallization is 0.5-100 h.
Preferably, the matrix comprises a powder substrate or a non-porous substrate;
the powder substrate comprises a metal oxide or carbon material, the metal oxide comprising silica nanowires, aluminum oxide, cerium oxide, or titanium dioxide; the carbon material comprises graphene, carbon nanotubes, carbon spirals 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, the method further comprises, before performing the alternate pulse deposition: dispersing the powder substrate in an organic solvent to obtain a suspension; coating the suspension on the surface of a carrier and drying;
when the substrate is a non-porous substrate, the method further comprises the following steps before the alternate pulse deposition: and sequentially carrying out purification treatment and drying on the non-porous substrate.
Preferably, the number of times of the alternate pulse deposition is 1 to 1000 times.
The invention provides a preparation method of an MOF film, which comprises the following steps: depositing the gas phase of the metal precursor and the gas phase of the organic precursor on the surface of the substrate by using a molecular layer deposition technology in an alternating pulse manner 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. According to the invention, the amorphous organic-inorganic hybrid film is deposited on the surface of the substrate by utilizing a molecular layer deposition technology, and because the organic-inorganic hybrid film and the MOF material have similar porous structures, compared with the MOF film prepared by taking the metal oxide film as a sacrificial template, the MOF film prepared by the method has the advantages that larger deformation and volume expansion cannot occur in the ligand exchange crystallization process, the surface roughness of the MOF film prepared by the method is small, and the uniformity of the MOF film is good; in the process of preparing the MOF film, no organic solvent participates, so that the problems of poor stability of the MOF film caused by residual solvent molecules in the pore canal of the MOF film and corrosion of an organic framework are avoided. Meanwhile, the MOF film prepared by the preparation method provided by the invention has excellent three-dimensional shape retention, and can realize accurate regulation and control of the thickness of the MOF film at a sub-nanometer level.
Drawings
FIG. 1 is an infrared spectrum of a zinc-based amorphous organic-inorganic hybrid film and a ZIF-8 film in example 10;
FIG. 2 is a nuclear magnetic resonance spectrum of a zinc-based amorphous organic-inorganic hybrid film and a ZIF-8 film in example 10;
FIG. 3 is an XRD spectrum of ZIF-8 films prepared in examples 2 to 5;
FIG. 4 is a TEM image of ZIF-8 films prepared in examples 7 to 10;
FIG. 5 is a TEM image of the 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 the metal precursor and the gas phase of the organic precursor on the surface of the substrate by using a molecular layer deposition technology in an alternating pulse manner 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 a molecular layer deposition technology to alternately pulse the gas phase of the metal precursor and the gas phase of the organic precursor on the surface of the substrate, thus obtaining the amorphous organic-inorganic hybrid film. In the present invention, the metal precursor or the organic precursor 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 includes the steps of:
placing a substrate in a molecular layer deposition vacuum reaction cavity, and utilizing carrier gas to pulse 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;
after removing the gas phase of the unadsorbed metal precursor, utilizing carrier gas to pulse the gas phase of the organic precursor to the molecular layer deposition vacuum reaction cavity, so that the gas phase of the organic precursor and the metal precursor perform a first half reaction;
after removing the gas phase of the unreacted organic precursor, pulsing the gas phase of the metal precursor to the molecular layer deposition vacuum reaction cavity by using carrier gas, so that the gas phase of the metal precursor and the organic precursor perform a second half reaction;
repeating the steps of the first half reaction and the second reaction to obtain the amorphous organic-inorganic hybrid film.
The method comprises the steps of placing a substrate in a molecular layer deposition vacuum reaction cavity, and utilizing carrier gas to pulse 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. In the present invention, the substrate preferably includes a powder substrate or a non-porous substrate; the powder substrate preferably comprises a metal oxide or carbon material, preferably comprising silica nanowires, alumina, ceria or titania, more preferably silica 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 includes a polymer film, a monocrystalline silicon wafer, or a silicon nano-array, more preferably a monocrystalline silicon wafer or a silicon nano-array. In the present invention, the silicon nano-array preferably includes a silicon nanowire array or a silicon nano-pillar array, more preferably a silicon nano-pillar array.
The method for placing the substrate in the molecular layer deposition vacuum reaction cavity also preferably comprises the step of preprocessing the substrate. In the present invention, when the substrate is a powder substrate, the pretreatment preferably includes the steps of: dispersing the powder substrate in an organic solvent to obtain a suspension; the suspension is applied to the surface of the support and dried. 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, more preferably 0.01g:1.0mL.
In the present invention, the carrier preferably comprises a glass sheet, preferably a quartz glass sheet. The invention has no special requirements on the coating mode, and can be realized by adopting a mode conventional in the field. In the present invention, the drying is preferably natural air-drying the carrier coated with the suspension in air. The invention has no special requirement on 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 includes 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 a cleaning of the non-porous substrate with a solvent; the solvent is preferably ethanol or water, more preferably ethanol. The method of the present invention is not particularly limited as long as the dirt on the surface of the non-porous substrate can be removed. The present invention has no special 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 by purification treatment, which is beneficial to the growth of the amorphous organic-inorganic hybrid film.
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 present invention, the volume ratio of the carrier gas to the molecular layer deposition vacuum reaction chamber is preferably 1/5 to 1/10, more preferably 1/6 to 1/8. In the present invention, the flow rate of the carrier gas is preferably 45 to 55mL/min, more preferably 50mL/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 dimethyl zinc, diethyl zinc, trimethylaluminum, titanium isopropoxide or zirconium tetra-tert-butoxide, more preferably diethyl zinc or trimethylaluminum. In the present invention, the inorganic metal salt preferably includes titanium tetrachloride or zirconium chloride.
In the present invention, the pre-pulse further preferably includes: heating the metal precursor; the heating temperature is preferably 10 to 200 ℃, more preferably 20 to 120 ℃. In the present invention, the heating step imparts a certain vapor pressure to the metal precursor.
In the invention, the temperature of the molecular layer deposition vacuum reaction cavity is preferably 100-300 ℃, more preferably 140-180 ℃; the pressure of the molecular layer deposition vacuum reaction chamber is preferably 10 to 200Pa, more preferably 60 to 150Pa. In the present invention, the time of the pulse is preferably 0.015 to 1200s, more preferably 0.02 to 500s; the time for the post-pulse breath hold is preferably 5 to 3000s, more preferably 5 to 1000s.
In the invention, the adsorption is chemical adsorption, and the metal precursor molecules react with the surface of the substrate chemically to form chemical bonds.
After the adsorption is finished, the gas phase of the non-adsorbed metal precursor is removed, and then the gas phase of the organic precursor is pulsed to the molecular layer deposition vacuum reaction cavity by using carrier gas, so that the gas phase of the organic precursor and the metal precursor perform a first half reaction. In the present invention, the method of removing the gas phase of the non-adsorbed metal precursor is preferably to remove the gas phase of the non-reacted metal precursor by pumping with a vacuum pump. In the present invention, the time for the evacuation is preferably 5 to 3000 seconds, more preferably 5 to 1000 seconds.
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 present invention, the volume ratio of the carrier gas to the molecular layer deposition vacuum reaction chamber is preferably 1/5 to 1/10, more preferably 1/6 to 1/8. In the present invention, the flow rate of the carrier gas is preferably 45 to 55mL/min, more preferably 50mL/min.
In the present invention, the organic precursor preferably includes ethylene glycol or glycerol, 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 as to have a certain vapor pressure.
In the present invention, the pre-pulse further preferably includes: heating the gas phase of the organic precursor; the heating temperature is preferably 10 to 200 ℃, more preferably 20 to 120 ℃. In the present invention, the heating step imparts a vapor pressure to the organic precursor.
In the invention, the temperature of the molecular layer deposition vacuum reaction cavity is preferably 100-300 ℃, more preferably 140-180 ℃; the pressure of the molecular layer deposition vacuum reaction chamber is preferably 10 to 200Pa, more preferably 60 to 150Pa. In the present invention, the time of the pulse is preferably 0.015 to 1200s, more preferably 0.02 to 500s; the first half reaction is preferably carried out for a period of time of 5 to 3000 seconds, more preferably 5 to 1000 seconds.
After the first half reaction, the invention removes the gas phase of the unreacted organic precursor, and then utilizes the carrier gas to pulse the gas phase of the metal precursor to the molecular layer deposition vacuum reaction cavity, so that the gas phase of the metal precursor and the organic precursor are subjected to the second half reaction. In the present invention, the mode of removing the gas phase of the unreacted organic precursor is preferably to pump out the gas phase of the unreacted organic precursor by a vacuum pump. In the present invention, the time for the evacuation is preferably 5 to 3000 seconds, more preferably 5 to 1000 seconds.
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 present invention, the volume ratio of the carrier gas to the molecular layer deposition vacuum reaction chamber is preferably 1/5 to 1/10, more preferably 1/6 to 1/8. In the present invention, the flow rate of the carrier gas is preferably 45 to 55mL/min, more preferably 50mL/min.
In the present invention, the metal precursor preferably includes dimethyl zinc, diethyl zinc, trimethylaluminum, titanium isopropoxide, titanium tetrachloride, zirconium chloride or zirconium tetra-tert-butoxide, more preferably diethyl zinc, zirconium chloride, trimethylaluminum or titanium tetrachloride. In the present invention, when the metal precursor is in a non-gaseous state, it is preferable to heat the metal precursor so as to have a certain vapor pressure.
In the present invention, the pre-pulse further preferably includes: heating the gas phase of the metal precursor; the heating temperature is preferably 10 to 200 ℃, more preferably 20 to 120 ℃.
In the invention, the temperature of the molecular layer deposition vacuum reaction cavity is preferably 100-300 ℃, more preferably 140-180 ℃; the pressure of the molecular layer deposition vacuum reaction chamber is preferably 10 to 200Pa, more preferably 60 to 150Pa. In the present invention, the time of the pulse is preferably 0.015 to 1200s, more preferably 0.02 to 500s; the second half reaction is preferably carried out for 5 to 3000 seconds, more preferably 5 to 1000 seconds.
The present invention repeats the steps of the first half reaction and the second reaction to obtain an amorphous organic-inorganic hybrid film. In the present invention, the number of repetitions is preferably 1 to 1000, more preferably 5 to 500.
In the invention, the flow rate of the carrier gas is a fixed value in the alternate pulse deposition process.
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 is directly contacted with the substrate, the step of alternately pulse depositing is preferably consistent with the step of alternately pulse depositing when the metal precursor is directly contacted with the substrate, except that the first depositing is to place the substrate in the molecular layer deposition vacuum reaction chamber, and the gas phase of the organic precursor is pulsed to the molecular layer deposition vacuum reaction chamber by using the carrier gas, so that the gas phase of the organic precursor is adsorbed on the surface of the substrate. For brevity, the invention is not repeated here for the step of alternating pulse deposition when the organic precursor is in direct contact with the substrate.
In the present invention, the alternate pulse deposition preferably further comprises: and taking out the product obtained by alternate pulse deposition from the molecular layer deposition vacuum reaction cavity, and placing the product in a dryer for standby.
After the amorphous organic-inorganic hybrid film is obtained, the invention carries out ligand exchange crystallization on the amorphous organic-inorganic hybrid film and the organic ligand to obtain the MOF film. In the present invention, the ligand exchange crystallization is preferably preceded by the steps of:
placing an 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 beaker cup opening to form a reaction system;
placing the reaction system in a reaction kettle for sealing;
the reaction vessel containing the reaction system was placed in a heating apparatus.
In the present invention, the organic ligand preferably includes dimethyl imidazole, diethyl imidazole or terephthalic acid, more preferably dimethyl imidazole or terephthalic acid.
In the invention, the beaker cup opening is smaller than the bottom of the quartz crucible filter element.
In the invention, the reaction kettle preferably comprises a polytetrafluoroethylene liner.
In the present invention, the heating means preferably comprises an oven.
In the present invention, the temperature of the ligand exchange crystallization is preferably 30 to 300 ℃, more preferably 50 to 280 ℃; the heating rate to the temperature required for ligand exchange crystallization is preferably 1-10 ℃/min, more preferably 2-8 ℃/min; the heat preservation time of the ligand exchange crystallization is preferably 0.5 to 100 hours, more preferably 0.5 to 10 hours.
In the present invention, the ligand exchange crystallization is preferably gas ligand exchange crystallization; the organic ligand is exchanged with the organic precursor in the amorphous organic-inorganic hybrid film during the gas phase ligand exchange crystallization process, and is converted into the MOF film along with the crystallization of the amorphous organic-inorganic hybrid film.
In the present invention, the ligand exchange crystallization further preferably includes: cooling the ligand exchange crystallization system and then taking out a membrane product;
and cleaning and drying the membrane product to obtain the MOF membrane.
In the present invention, the temperature after cooling is preferably room temperature, and the temperature of the room temperature is preferably 20 to 35 ℃, more preferably 25 to 30 ℃. In the present invention, the cooling is preferably natural cooling.
In the present invention, the cleaning solvent is preferably ethanol; the number of times of the washing is preferably 2 to 4 times, more preferably 3 times. 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, a MIL-53 (Al) film, a MIL-125 (Ti) film or a UiO-66 (Zr) film, more preferably a ZIF-8 (Zn) film, a MIL-53 (Al) film or a UiO-66 (Zr) film.
In the present invention, the thickness of the MOF film is preferably 0.5 to 2000nm, more preferably 5 to 1000nm.
The invention utilizes a Molecular Layer Deposition (MLD) technology to deposit a metal-based amorphous organic-inorganic hybrid film on the surface of a substrate, and the amorphous organic-inorganic hybrid film and an organic ligand molecule generate gas ligand exchange and crystallization at a certain temperature, thereby realizing the preparation of the MOF film. Compared with the metal oxide used as a sacrificial template to synthesize the MOF film, the amorphous organic-inorganic hybrid film prepared by the molecular layer deposition technology avoids the huge volume expansion and stress caused by deformation in the crystal transformation process. In addition, since the precursor is chemically bonded to the substrate surface during the MLD deposition, the MOF film prepared by the gas-ligand exchange flip-chip method has a strong interaction with the substrate. Meanwhile, since the MLD is based on self-limiting reaction of precursor molecules and the surface of the substrate, the thickness of the organic-inorganic hybrid film can be accurately regulated and controlled by changing the deposition cycle number of the MLD, 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 using MLD are adjustable, so that the controllable synthesis of different MOF films can be realized by changing the inorganic part and the organic part. The method has good universality and can prepare various high-quality MOF films.
The preparation method provided by the invention is simple and easy to control, can prepare MOF films of various types, has good uniformity and strong interaction force with the surface of a substrate, can accurately regulate and control the thickness of the film on a nano scale, and can realize conformal deposition on the surface of a carrier with a high aspect ratio.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
In the embodiment of the invention, when the substrate is silica nanowires or aluminum oxide, the substrate is required to be dispersed in ethanol to obtain a 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) Washing 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 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) Pulse diethyl zinc precursor steam into the MLD cavity to enable the diethyl zinc precursor steam to react with the surface of the monocrystalline silicon wafer, wherein the diethyl zinc precursor is kept at a room temperature state, the pulse time of the diethyl zinc precursor is 0.02s, and the breath holding time is 15s; removing unadsorbed diethyl zinc precursor and physically adsorbed diethyl zinc precursor in the vacuum reaction cavity by using a vacuum pump, wherein the pumping time is 50s;
(b) The pulse ethylene glycol precursor vapor and diethyl zinc chemically adsorbed on the surface of the monocrystalline silicon piece are subjected to half reaction, wherein the ethylene glycol precursor is kept at 75 ℃ to provide enough vapor pressure, the pulse time of the ethylene glycol precursor is 0.5s, and the holding time is 15s; removing unreacted glycol precursor steam in the vacuum reaction cavity by utilizing a vacuum pump, wherein the air extracting time is 25s;
(c) Repeating the steps (a) and (b) for 40 times on the surface of the monocrystalline silicon piece by cyclic pulse deposition;
(d) After the MLD deposition is finished, taking the film out of the vacuum cavity to obtain a zinc-based amorphous organic-inorganic hybrid film;
3) ZIF-8 film is prepared by solvent-free gas ligand exchange crystallization:
(a) Placing the obtained zinc-based organic-inorganic hybrid film in a quartz crucible filter core, and placing 100mg of dimethyl imidazole ligand in a beaker;
(b) Covering a quartz crucible filter core filled with a zinc-based organic-inorganic hybrid film sample on the opening of a beaker provided with a dimethylimidazole organic ligand, and then placing the quartz crucible filter core in a hydrothermal kettle containing a polytetrafluoroethylene liner and sealing;
(c) Placing the sealed hydrothermal kettle in an oven, and heating to 140 ℃ according to the heating rate of 5 ℃/min for gas-phase exchange crystallization for 6 hours;
(d) And naturally cooling to 25 ℃ after gas-phase ligand exchange crystallization, taking out the film, washing with absolute ethyl alcohol for 2 times, and drying to obtain the ZIF-8 film.
Example 2
A ZIF-8 film was prepared in the same manner as in example 1 except that the number of cyclic pulse depositions was 5, and the resulting ZIF-8 film was abbreviated as 5ZIF-8/Si.
Example 3
A ZIF-8 film was prepared in the same manner as in example 1 except that the number of cyclic pulse depositions was 10, and the resulting ZIF-8 film was abbreviated as 10ZIF-8/Si.
Example 4
A ZIF-8 film was prepared in the same manner as in example 1 except that the number of cyclic pulse depositions was 30, and the resulting ZIF-8 film was abbreviated as 30ZIF-8/Si.
Example 5
A ZIF-8 film was prepared in the same manner as in example 1 except that the number of cyclic pulse depositions was 50, and the resulting ZIF-8 film was abbreviated as 50ZIF-8/Si.
Example 6
A ZIF-8 film was prepared as in example 1, except that the silicon dioxide nanowires were used as the substrate, and the substrate was pretreated with 20mg of SiO 2 Dispersing the nanowires in ethanol to obtain a suspension with the mass concentration of 0.01g/mL, coating the suspension on the surface of a glass sheet, naturally airing in air, placing the glass sheet in a molecular layer deposition vacuum reaction cavity, wherein 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% 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
A ZIF-8 film was prepared in the same manner as in example 6 except that the number of cyclic pulse depositions was 5 to obtain a ZIF-8 film having a thickness of 2.7nm, abbreviated as 5ZIF-8/SiO 2 A nanowire.
Example 8
A ZIF-8 film was prepared in the same manner as in example 6 except that the number of cyclic pulse depositions was 10, giving a ZIF-8 film thickness of 3.78nm, abbreviated as 10ZIF-8/SiO 2 A nanowire.
Example 9
A ZIF-8 film was prepared in the same manner as in example 6 except that the number of cyclic pulse depositions was 30 to obtain a ZIF-8 film having a thickness of 10.0nm, abbreviated as 30ZIF-8/SiO 2 A nanowire.
Example 10
A ZIF-8 film was prepared in the same manner as in example 6 except that the number of cyclic pulse depositions was 50 to obtain a ZIF-8 film of 21.82nm in thickness, abbreviated as 50ZIF-8/SiO 2 A nanowire.
Example 11
A ZIF-8 film was prepared as in example 6, except that the silica nanowires were replaced with spherical aluminum oxide; the number of deposition times of the cyclic pulse is 10, and the ZIF-8 film with the thickness of 3.6nm is obtained.
Example 12
A ZIF-8 film was prepared in the same manner as in example 11 except that the number of deposition of cyclic pulses was 30, to obtain a ZIF-8 film having a thickness of 9.9 nm.
Example 13
A ZIF-8 film was prepared in the same manner as in 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 film was prepared as in example 6, except that the silicon dioxide nanowires were replaced with arrays of high aspect ratio silicon nanopillars; and the number of the cyclic pulse deposition is 10, so as to obtain the silicon nano-pillar array conformally coated by the ZIF-8 film.
Example 15
A ZIF-8 film was prepared as in example 14, except that the number of cyclic pulse depositions was 30, resulting in a ZIF-8 film conformally coated silicon nanopillar array.
Example 16
A ZIF-8 film was prepared as in example 14, except that the number of cyclic pulse depositions was 50, resulting in a ZIF-8 film conformally coated silicon nanopillar array.
Example 17
A MOF film was prepared according to the method of example 6, except that diethylimidazole was used as an organic ligand, the temperature of ligand exchange crystallization was 80℃and the heat-preservation time was 3 hours, and the obtained MOF film was a MAF-6 film.
Example 18
A MAF-6 film was prepared in the same manner as in example 17 except that the number of deposition of cyclic pulses was 5, to obtain a MAF-6 film having a thickness of 2.2 nm.
Example 19
A MAF-6 film was prepared in the same manner as in example 17 except that the number of deposition of cyclic pulses was 10, to obtain a MAF-6 film having a thickness of 6.9 nm.
Example 20
A MAF-6 film was prepared in the same manner as in example 17 except that the number of deposition of cyclic pulses was 30, to obtain a MAF-6 film having a thickness of 19.8 nm.
Example 21
A MAF-6 film was prepared in the same manner as in example 17 except that the number of deposition of cyclic pulses was 50, to obtain a MAF-6 film having a thickness of 32.4 nm.
Example 22
MAF-6 films were prepared as in example 17, except that the silicon dioxide nanowires were replaced with arrays of high aspect ratio silicon nanopillars; and the number of times of cyclic pulse deposition is 10, so that the silicon nano-pillar array conformally coated by the MAF-6 film is obtained.
Example 23
A MAF-6 film was prepared as in example 22, except that the number of cyclic pulse depositions was 30, resulting in a MAF-6 film conformally coated silicon nanopillar array.
Example 24
A MAF-6 film was prepared as in example 22, except that the number of cyclic pulse depositions was 50, resulting in a MAF-6 film conformally coated silicon nanopillar array.
Example 25
A thin film of UiO-66 was prepared as in example 6, except that the metal precursor diethyl zinc was replaced with zirconium tert-butoxide, wherein the heating temperature of the zirconium tert-butoxide precursor was 55deg.C, and the pulse, exposure, and hold-down 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 sufficient vapor pressure, and the pulse, the holding time and the pumping time of the ethylene glycol precursor are respectively 0.5s, 15s and 25s; and the organic ligand dimethyl imidazole is replaced by terephthalic acid; the temperature of ligand exchange crystallization is 180 ℃, and the heat preservation time is 5h.
Example 26
A thin film of UiO-66 was prepared as in example 25, except that the number of cyclic pulse depositions was 5, giving a thin film of UiO-66 with a thickness of 1.8 nm.
Example 27
A thin film of UiO-66 was prepared as in example 25, except that the number of deposition of cyclic pulses was 10, giving a thin film of UiO-66 with a thickness of 3.9 nm.
Example 28
A thin film of UiO-66 was prepared as in example 25, except that the number of deposition of cyclic pulses was 30, giving a thin film of UiO-66 with a thickness of 12.4 nm.
Example 29
A thin film of UiO-66 was prepared as in example 25, except that the number of deposition of cyclic pulses was 50, giving a thin film of UiO-66 with a thickness of 24.3 nm.
Example 30
A thin film of UiO-66 was prepared as in example 25, except that the substrate was replaced with an array of high aspect ratio silicon nanopillars, and the number of cyclic pulse depositions was 10, resulting in an array of silicon nanopillars conformally coated with the thin film of UiO-66.
Example 31
A thin film of UiO-66 was prepared as in example 30, except that the number of cyclic pulse depositions was 30, resulting in a silicon nanopillar array conformally coated with the thin film of UiO-66.
Example 32
A thin film of UiO-66 was prepared as in example 30, except that the number of cyclic pulse depositions was 50, resulting in a silicon nanopillar array conformally coated with the thin film of UiO-66.
Example 33
MIL-53 (Al) film was prepared according to the method of example 25, except that zirconium chloride, a metal precursor, was replaced with trimethylaluminum, wherein the trimethylaluminum precursor was kept at ambient temperature, and the pulse, hold-down, and pump-down times of the trimethylaluminum precursor were 0.1s, 20s, and 25s, respectively; wherein the ethylene glycol precursor is kept at 75 ℃ to provide sufficient vapor pressure, and the pulse, the holding time and the pumping time of the ethylene glycol precursor are 0.5s, 15s and 25s; the temperature of ligand exchange crystallization is 200 ℃, and the heat preservation time is 4 hours.
Example 34
MIL-53 (Al) film was prepared in the same manner as in example 33 except that the number of deposition of cyclic pulses was 5, to obtain MIL-53 (Al) film having a thickness of 1.3 nm.
Example 35
MIL-53 (Al) film was prepared in the same manner as in example 33 except that the number of deposition of cyclic pulses was 10, to obtain MIL-53 (Al) film having a thickness of 2.1 nm.
Example 36
MIL-53 (Al) film was prepared in the same manner as in example 33 except that the number of deposition of cyclic pulses was 30, to obtain a MIL-53 (Al) film having a thickness of 6.4 nm.
Example 37
MIL-53 (Al) film was prepared in the same manner as in example 33 except that the number of deposition of cyclic pulses was 50, to obtain MIL-53 (Al) film having a thickness of 11.3 nm.
Example 38
MILs-53 (Al) films were prepared according to the method of example 33, except that the substrate was replaced with an array of high aspect ratio silicon nanopillars from silicon dioxide nanowires, and the number of cyclic pulse depositions was 10, resulting in an array of MILs-53 (Al) film conformally coated silicon nanopillars.
Example 39
MIL-53 (Al) films were prepared as in example 38, except that the number of cyclic pulse depositions was 30, resulting in MIL-53 (Al) film conformally coated silicon nanopillar arrays.
Example 40
MIL-53 (Al) films were prepared as in example 38, except that the number of cyclic pulse depositions was 50, resulting in MIL-53 (Al) film conformally coated silicon nanopillar arrays.
Example 41
MIL-125 (Ti) film was prepared according to the method of example 25, except that the metal precursor zirconium chloride was replaced with titanium tetrachloride, wherein the titanium tetrachloride precursor was kept at room temperature, and the pulse, hold-down, 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 sufficient vapor pressure, and the pulse, the holding time and the pumping time of the ethylene glycol precursor are respectively 0.5s, 15s and 25s; the temperature of ligand exchange crystallization is 160 ℃, and the heat preservation time is 10 hours.
Example 42
MIL-125 (Ti) film was prepared according to the method of example 41, except that the number of cyclic pulse depositions was 5, to obtain MIL-125 (Ti) film having a thickness of 2.4 nm.
Example 43
MIL-125 (Ti) film was prepared according to the method of example 41, except that the number of cyclic pulse depositions was 10, to obtain MIL-125 (Ti) film having a thickness of 4.9 nm.
Example 44
MIL-125 (Ti) film was prepared according to the method of example 41, except that the number of cyclic pulse depositions was 30, to obtain MIL-125 (Ti) film having a thickness of 15.8 nm.
Example 45
MIL-125 (Ti) film was prepared according to the method of example 41, except that the number of cyclic pulse depositions was 50, to obtain MIL-125 (Ti) film having a thickness of 16.3 nm.
Example 46
MILs-125 (Ti) films were prepared according to the method of example 41, except that the base silicon dioxide nanowires were replaced with high aspect ratio arrays of silicon nanopillars, and the number of cyclic pulse depositions was 10, resulting in MILs-125 (Ti) film conformal-coated arrays of silicon nanopillars.
Example 47
MIL-125 (Ti) film was prepared according to the method of example 46, except that the number of cyclic pulse depositions was 30, resulting in a MIL-125 (Ti) film conformally coated silicon nanopillar array.
Example 48
MIL-125 (Ti) film was prepared according to the method of example 46, except that the number of cyclic pulse depositions was 50, resulting in a MIL-125 (Ti) film conformally coated silicon nanopillar array.
Comparative example 1
A ZIF-8 film was prepared as in example 6, except that the ethylene glycol precursor was replaced with water, the number of cyclical depositions was 50, and the deposition was Atomic Layer Deposition (ALD); the temperature of ration exchange crystallization is 140 ℃, the heat preservation time is 6 hours, and the prepared product is called ALD50ZIF-8/SiO for short 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 infrared spectra, 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 gas phase ligand is exchanged and crystallized at 3138cm respectively -1 And 2933cm -1 The telescopic vibration absorption peak of the C-H bond of methyl and imidazole appears, and 1145cm -1 And 990cm -1 The telescopic absorption peak of the C-N bond appears; and 3360cm -1 The hydroxyl vibrational peak belonging to ethylene glycol disappeared. It shows that dimethyl imidazole replaces glycol ligand in the original zinc-based organic-inorganic hybrid film through gas ligand exchange crystallization reaction, and a specific dimethyl imidazole absorption peak is generated.
The solid nuclear magnetic resonance examination was performed on the zinc-based amorphous organic-inorganic hybrid film and the ZIF-8 film of example 10, and the nuclear magnetic resonance spectrum is shown in FIG. 2. As can be seen from FIG. 2, the molecular layer is deposited on SiO 2 An amorphous organic-inorganic hybrid film was formed on the nanowires, and a zinc-based amorphous organic-inorganic hybrid film (Zn (C) 2 H 5 O 2 ) 2 /SiO 2 ) Wherein the distribution of the C element is shown as a structural formula a 13 The chemical shift of C is 63.92, and after the reaction of gas-phase ligand exchange crystallization of dimethylimidazole, the structure of the material is changed into the structure shown as b, and 13 the chemical shift of C is obviously changed into the characteristic shift of C of dimethylimidazole, and glycol 13 The characteristic displacement of C is completely disappeared. Because the acting force of N and Zn is stronger than that of O and Zn, dimethyl imidazole can be considered to replace ethylene glycol combined with Zn in the amorphous organic-inorganic unique film in the ligand exchange crystallization reaction process. Wherein after the dimethylimidazole is combined with Zn, 13 the chemical shift of C is 150.68 for α, 123.71 for β and 13.34 for γ. And it can be deduced from this that the ligand exchange crystallization reaction equation is shown in 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 was performed on the ZIF-8 films prepared in examples 2 to 5, and XRD spectra were shown in FIG. 3. As can be seen from FIG. 3, XRD diffraction peaks of zinc-based organic-inorganic hybrid films deposited on the surface of single crystal silicon for 5 times, 10 times, 30 times and 50 times by using MLD circulation are consistent with those of ZIF-8XRD characteristic diffraction peaks after gas phase exchange crystallization, which shows that the ZIF-8 films with high crystallinity are prepared in examples 2 to 5.
For the embodimentAnd 7-10, performing transmission electron microscopy detection on the ZIF-8 film prepared by the method, and obtaining a TEM image, as shown in figure 4. As can be seen from FIG. 4, the SiO is formed in the following 2 The ZIF-8 film obtained by circularly depositing zinc-based organic-inorganic hybrid films for 5 times, 10 times, 30 times and 50 times on the surface of the nanowire through gas ligand exchange crystallization is uniformly and conformally coated on SiO 2 The surface of the nanowire is not changed with SiO 2 A wire-like configuration of nanowires. Meanwhile, the thickness of the ZIF-8 film is linearly increased along with the increase of the MLD deposition cycle number, which shows that the MOF film prepared by the method can accurately regulate and control the thickness of the film in a sub-nanometer scale. In addition, the ZIF-8 film is not observed to fall off in the figure, which indicates that the MOF film prepared by the method has strong interaction with the substrate.
Comparative example 1 the ZIF-8 film was produced without producing an organic-inorganic hybrid film by directly reacting zinc oxide with an organic ligand. The film obtained in comparative example 1 was subjected to 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 exhibited a blocking phenomenon on the surface, and the thickness was greatly different at different positions, and was very uneven.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (7)
1. A method of preparing a MOF film comprising the steps of:
depositing the gas phase of the metal precursor and the gas phase of the organic precursor on the surface of the substrate by using a molecular layer deposition technology in an alternating pulse manner to obtain an amorphous organic-inorganic hybrid film; the organic precursor comprises ethylene glycol or glycerol; the metal precursor is diethyl zinc, zirconium tert-butoxide, trimethylaluminum, zirconium chloride or titanium tetrachloride;
carrying out ligand exchange crystallization on the amorphous organic-inorganic hybrid film and an organic ligand to obtain an MOF film; the organic ligand is dimethyl imidazole, diethyl imidazole or terephthalic acid.
2. The method of claim 1, wherein the pulse time for depositing the vapor phase of the metal precursor is 0.01 to 1200 seconds.
3. The method of claim 1, wherein the pulse time for depositing the organic precursor is 0.015 to 800 seconds.
4. The method for preparing a MOF film according to claim 1, wherein the temperature of the ligand exchange crystallization is 30 to 300 ℃; the heat preservation time of ligand exchange crystallization is 0.5-100 h.
5. The method of preparing a MOF film according to claim 1, wherein the substrate comprises a powder substrate or a non-porous substrate;
the powder substrate comprises a metal oxide or carbon material, the metal oxide comprising silica nanowires 、 Alumina, ceria or titania; the carbon material comprises graphene, carbon nanotubes, carbon spirals or carbon black;
the non-porous substrate comprises a polymer film, a monocrystalline silicon wafer, or a silicon nanoarray.
6. The method of claim 5, wherein when the substrate is a powder substrate, further comprising, prior to performing the alternating pulse deposition: dispersing the powder substrate in an organic solvent to obtain a suspension; coating the suspension on the surface of a carrier and drying;
when the substrate is a non-porous substrate, the method further comprises the following steps before the alternate pulse deposition: and sequentially carrying out purification treatment and drying on the non-porous substrate.
7. The method of claim 1, wherein the number of alternating pulse depositions is 1 to 1000.
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