CN112063183A - Three-dimensional ordered structure with semiconductor and MOF framework space complementary, and preparation method and application thereof - Google Patents
Three-dimensional ordered structure with semiconductor and MOF framework space complementary, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of development of three-dimensional ordered structures with complementary semiconductor and MOF framework spaces, and particularly relates to a three-dimensional ordered structure with complementary semiconductor and MOF framework spaces, and a preparation method and application thereof. The three-dimensional ordered structure with the semiconductor and the MOF framework being complementary in space comprises the MOF and the semiconductor filled in an MOF pore passage, the semiconductor in the MOF pore passage is periodically arranged in space and is uniform in size, the particle size of the semiconductor is not larger than the diameter of the corresponding pore passage in an MOF crystal lattice, and the semiconductor and the MOF framework are complementary in space and are accurately spliced with the inner wall of the MOF pore passage. The semiconductor and MOF framework of the invention has a complementary three-dimensional ordered structure, the semiconductor material has uniform size, the arrangement periodicity is consistent with mesoporous pore canals, and a three-dimensional stacking mode which cannot be obtained by other traditional methods can be constructed, so that the composite material with extremely high activity can be prepared more easily.
Description
Technical Field
The invention belongs to the technical field of development of a three-dimensional ordered structure with a semiconductor and an MOF framework being complementary in space, and particularly relates to a three-dimensional ordered structure with a semiconductor and an MOF framework being complementary in space, a preparation method and an application thereof, wherein the semiconductor and the MOF framework are precisely spliced with the inner wall of a three-dimensional pore passage of the MOF on the premise of not damaging the original framework connection mode and local structure of the MOF.
Background
Metal-organic frameworks (MOFs), also known as metal-organic frameworks or metal-organic frameworks, are a class of inorganic porous materials formed by bonding inorganic metal nodes and organic molecules through coordination bonds. The MOF has rich pore topological structure and large specific surface area, is commonly used for loading functional guest molecules, and has important application in the fields of biology, catalysis, gas separation, drug release and the like. Due to its unique physical and chemical properties, functional nanomaterials have attracted extensive attention in the fields of photocatalysis, electrocatalysis, magnetic response, etc. The functional expression of the nanometer functional material depends on the ordered arrangement degree of the functional nanometer material in the three-dimensional space, for example, the periodically arranged magnets in the three-dimensional space can generate a strong magnetic field effect, but the nanometer functional material prepared by the traditional method has large particles, nonuniform size and disordered three-dimensional space arrangement, thereby greatly limiting the development of the functional nanometer material in the field. In view of this, if the functional nanomaterial is introduced into the porous material pore channel, a three-dimensional topological structure complementary to the porous material skeleton structure is prepared, and the potential of the functional nanomaterial can be further excavated and exerted.
Currently, there are two structures for binding functional nanomaterials to MOFs: 1) coating the functional nano material on the MOF surface; 2) functional nanomaterials are loaded randomly inside the MOF pore channels. The first method produces a structured, functional nanomaterial (TiO)2Semiconductors) are easy to agglomerate on the outer surface of the MOF, the arrangement of the nanometer functional materials on a three-dimensional space is still disordered, and the agglomerated functional nanometer materials are easy to agglomerateBlocking the internal pore structure of the MOF (r.li, j.jiang, q.zhang, y.j.xiong et al, adv.mater.2014,26,28.) which originally has low utilization rate; in the second method, although functional nano materials can be filled into three-dimensional pore channels of the MOF, the distribution of the nano functional materials in the three-dimensional pore channel space is random, each mesoporous pore channel with a proper pore diameter of the MOF cannot be fully utilized, and the particle size of the prepared nano functional materials is often larger than the pore channel size corresponding to the MOF crystal lattice, so that the original skeleton connection mode and the local structure of the MOF are damaged; for example, the metal clusters are directly deposited into the MOF pore channels by using an Atomic Layer Deposition (ALD) method, but the ALD deposition is a process that the nanometer functional material is changed from small to large, and the connection mode of the original MOF framework is easily broken, so that the obvious increase of the half-peak width of XRD can be observed (l.y.wu, m.zhang, t.b.lu et al, angelw.chem.int.ed.2019, 58,9491); or the metal ions are introduced into the interior of the pore channels in advance by utilizing the adsorption capacity of the MOF pore channels, and then another reactant or reactants are introduced into the interior of the pore channels to react to prepare the final product. Due to the strong mobility of metal ions, it is difficult to maintain a limited range in the pore canal for a long time, so that the content of the correspondingly obtained functional nano material is low, and the continuous adjustment of the loading capacity is extremely difficult to realize. The migration efficiency of the corresponding reactant in different pore canals is inconsistent, so that the functional nano material cannot grow in all mesopores with proper pore diameter. And the chemical reaction rate of the metal ions and the corresponding reactants in the pores depends on the concentration, thermodynamic and kinetic constants of the two reactants, and the original framework connection mode of MOF can be damaged by some carelessness (J.E. Mondloch, Omar K.Farha, Joseph T.Hupp et al, J.Am.chem.Soc.2013,135, 10294.). The two methods adopt a synthesis strategy of 'bottom-up', and a functional nano material grows in a pore channel, but the prepared functional nano material cannot be complementarily spliced with a mesopore with a proper pore diameter on the molecular scale on the premise of not damaging a local structure and a connection mode of an MOF pore channel, so that the further development of the functional nano material in the fields of biology, catalysis, gas separation, drug release and the like is limited.
Disclosure of Invention
One of the purposes of the invention is to provide a three-dimensional ordered structure with a semiconductor and a MOF framework which are complementary in space, wherein the semiconductor is accurately spliced in mesopores corresponding to MOF crystal lattices, so that the three-dimensional ordered structure has the characteristics of uniform size, high periodicity and the like.
The second purpose of the invention is to provide a preparation method of a three-dimensional ordered structure with a semiconductor and MOF framework space complementary, which has simple and convenient preparation process and easy adjustment.
The invention also aims to provide application of a three-dimensional ordered structure of a semiconductor and a MOF framework which are complementary in space.
The scheme adopted by the invention for realizing one of the purposes is as follows: a three-dimensional ordered structure with a semiconductor and an MOF framework being complementary in space comprises an MOF and a semiconductor filled in an MOF pore passage, the semiconductor in the MOF pore passage is periodically arranged in space and is uniform in size, the particle size of the semiconductor is not larger than the diameter of a corresponding pore passage in an MOF crystal lattice, and the semiconductor and the MOF framework are complementary in space and are accurately spliced with the inner wall of the MOF pore passage.
Preferably, the MOF is a mesoporous MOF material.
Preferably, the mesoporous MOF material comprises MIL-101-Cr and MIL-101-Cr-NO2、MIL-101-Cr-NH2、MIL-101-Al-NH2MIL-101-Fe, MIL-100-Fe, MIL-101-Cr.
Preferably, the semiconductor is TiO2、WO3、ZnO、CuO、Cu2At least one of O.
Preferably, the molecular formula of the three-dimensional ordered structure is x% of Semiconductor-in-MOF, wherein x% is the mass fraction of the Semiconductor in the whole three-dimensional ordered structure, and x is more than or equal to 5 and less than or equal to 50.
The second scheme adopted by the invention for achieving the purpose is as follows: a method for preparing a three-dimensional ordered structure with a semiconductor and MOF framework being complementary in space comprises the following steps:
(1) according to the type of a semiconductor, under the condition of 10-40 ℃, selecting a proper inorganic or organic precursor to prepare a metal precursor solution, adding the metal precursor solution into a solvent, preparing a metal precursor solution with the metal concentration of 1-300mM and the solution pH value of 3-7, and uniformly mixing to prepare a sol with the metal sol precursor particle size of 0.5-1.2 nm;
(2) mixing the sol prepared in the step (1) with a certain volume with a certain amount of MOF, stirring at a constant temperature of 0-40 ℃ for 5-30h, and then pumping the solution to obtain a three-dimensional ordered structure of a solidified semiconductor intermediate product and an MOF framework which are complementary;
(3) performing constant-temperature aging at 80-200 ℃ and supercritical CO at 80-150 ℃ on the three-dimensional ordered structure of the solidified semiconductor intermediate product prepared in the step (2) and the MOF framework which are complementary2Activating for 10-24h to obtain a semiconductor three-dimensional ordered structure which is complementary with the MOF framework space.
Preferably, in the steps (1) to (3), the semiconductor material can be one or more, when the semiconductor material is multiple, multiple metal precursor solutions are respectively prepared in the step (1), the step (2) is to mix the MOF and the semiconductor I sol to prepare a three-dimensional ordered structure of the solidified semiconductor I intermediate product complementary to the MOF framework, and in the step (3), the three-dimensional ordered structure of the solidified semiconductor I intermediate product complementary to the MOF framework is prepared and subjected to constant temperature aging and supercritical CO2And (3) mixing the sol of the semiconductor II with the composite material I to obtain a three-dimensional ordered structure of the semiconductor I-II and the MOF framework, and repeating the steps (2) and (3) until a three-dimensional ordered structure of the semiconductor I-II … … -N and the MOF framework is obtained.
Preferably, in the step (1), the semiconductor is TiO2、WO3、ZnO、CuO、Cu2At least one of O.
Preferably, when the semiconductor material is TiO2The preparation of the precursor sol comprises the following steps: adding tetrabutyl titanate and nitric acid into an ethanol solution at the temperature of 15-30 ℃, keeping the concentration of titanium in the solution at 1-15mM and the volume ratio of concentrated nitric acid to ethanol at 0.001-0.01, uniformly mixing, keeping the temperature at 15-30 ℃, and uniformly stirring to obtain precursor sol;
when the semiconductor material is WO3The preparation of the precursor sol comprises the following steps: adding tungstic acid into 30 percent of hydrogen peroxide solution at the temperature of 15-30 ℃, wherein the concentration of tungsten is 60-300mM, and preserving the temperature of the mixed solution at the temperature of 40-100 ℃ for 10-48h to prepare precursor sol;
when the semiconductor material is CuO, the precursor sol is prepared, and the method comprises the following steps: preparing 1-24mM copper nitrate aqueous solution at 10-40 ℃, and marking as solution I; preparing an ethanol solution of dodecylamine with the concentration of 0.15-0.45M, marking as a solution II, uniformly mixing the solution I and the solution II according to a certain volume ratio, adding n-hexane, and continuously stirring until the solution is uniform to prepare precursor sol, wherein the volume ratio of the solution I to the solution II to the n-hexane is 1: (1-3).
The scheme adopted by the invention for realizing the third purpose is as follows: the three-dimensional ordered structure with the semiconductor and MOF framework being complementary in space is applied to the fields of photocatalysis, electrocatalysis and magnetic response materials.
The principle of the preparation method of the invention is as follows: the metal precursor sol is introduced into all mesopores of the MOF by adopting a bottom-up strategy in the process of introducing the metal precursor sol with the particle size within the range of a mesopore window, the sol precursors in pore channels are further fused and grown along with the stirring, but the surface tension of the sol precursors is limited, so that the three-dimensional ordered structure of the sol precursors which is complementary with the MOF framework space can be obtained on the premise of not damaging the original framework connection mode of the MOF; after loading the precursor sol, adopting a top-down aging strategy to convert the precursor sol with larger volume into solid particles with small volume in situ inside the pore channel, thereby obtaining a semiconductor three-dimensional ordered structure which is complementary with the MOF framework space. In the three-dimensional ordered structure, semiconductors are accurately spliced in mesopores corresponding to MOF lattices, so that the three-dimensional ordered structure has the characteristics of uniform size, high periodicity and the like.
The invention has the following advantages and beneficial effects:
1. the semiconductor and MOF framework of the invention have a complementary three-dimensional ordered structure, the semiconductor material has uniform size, and the arrangement periodicity is consistent with mesoporous pore canals.
2. The three-dimensional ordered structure of the semiconductor and the MOF framework which are complementary in space is limited by the topological structure of the MOF pore passage, and the three-dimensional stacking mode which cannot be obtained by other traditional methods can be constructed, so that the composite material with extremely high activity can be prepared more easily.
3. The three-dimensional ordered structure with high periodicity, all sizes and continuously adjustable content can be used for exploring the influence of semiconductors in different pore channels on the photocatalysis effect, and a new thought is brought for improving the effect of artificial photosynthesis.
4. The preparation method is mild, has no damage to the MOF framework, has various related semiconductors and MOFs, basically covers all the MOFs with mesoporous scales and classical semiconductors with full-spectrum response, and has strong universality.
5. According to the preparation method, the semiconductor can be accurately spliced with the hole wall in the MOF hole channel on the premise of not damaging the original skeleton connection mode and local structure of the MOF by simply and simply controlling the conditions of temperature, precursor concentration and the like, the content is continuously adjustable, and no residue is left on the MOF surface.
Drawings
FIG. 1 shows TiO in example 12An XRD pattern of a three-dimensional ordered structure that is spatially complementary to the MOF framework;
FIG. 2 shows TiO in example 12A graph comparing unit cell parameters (a) and half peak widths of diffraction peaks (b) for three-dimensional ordered structures that are spatially complementary to MOF frameworks;
FIG. 3 shows TiO in example 12SEM images (scale 200nm) of three-dimensional ordered structures that are spatially complementary to the MOF framework;
FIG. 4 shows 42% TiO in example 12The HAAD-STEM plots of MIL-101-Cr and MIL-101-Cr (scale 20 nm);
FIG. 5 shows TiO in example 12-MIL-101-Cr series charge differential density map;
FIG. 6 is WO of example 23-XRD pattern of sample of MIL-101-Cr series;
FIG. 7 shows 42% TiO in example 42-MIL-101-Cr-NO2TiO with different pore channels2Comparative graph of photocatalytic reduction performance.
Detailed Description
The following examples are provided to further illustrate the present invention for better understanding, but the present invention is not limited to the following examples.
Example 1.
TiO2The preparation and molecular scale characterization of the three-dimensional ordered structure complementary to the MOF framework space specifically comprises the following steps:
1): weighing 120ml ethanol, placing in a250 ml round bottom flask, adding 0.14ml concentrated nitric acid under 20 deg.C (15-25 deg.C, preferably 20 deg.C), stirring well, rapidly adding 0.2ml tetrabutyl titanate, and continuing stirring for 5 min.
2): in a 100ml long-necked round-bottomed flask, 20mg of MIL-101-Cr and 30ml of the mixed solution in step 1 were charged. And after the sample is added, sealing the flask by using a sealing film, and carrying out ultrasonic treatment for 2min until the MOF particles are uniformly dispersed in the titanium sol precursor.
3): and (3) placing the mixed solution filled with the MOF and the titanium sol precursor in the step 2 in a water bath constant temperature device with the temperature of 22 ℃ (10-25 ℃, preferably 22 ℃) for reaction for 10 hours. During the constant temperature period, the rotating speed is controlled to be 100 revolutions per minute, and the magnetic particle model is A250.
4): and 3, transferring the mixed solution which is subjected to constant temperature reaction for 10 hours in the step 3 into a beaker of 100ml, then transferring the whole into a double-row pipe, and draining the solution under the condition of keeping the pressure of 90Pa (50-90Pa, preferably 90Pa) to obtain the three-dimensional ordered structure spliced by the titanium gel and the MOF framework.
5): transferring the three-dimensional ordered structure in the step 4 into a sand bath, keeping the temperature of 80 ℃ (50-80 ℃, preferably 80 ℃) for 2h (1-5h, preferably 2h), and then respectively placing the sample in a vacuum drying oven and supercritical CO2Activating at 80 deg.C (80-120 deg.C, preferably 80 deg.C) for 12 hr (10-15 hr, preferably 12 hr) to obtain TiO 42%2-in-MIL-101-Cr.
6): changing the mass of the MOF and the volume of the titanium sol precursor in the step 2, and repeating the steps 2-5 to respectively prepare TiO with the loading amounts of 13%, 23%, 37%, 42% and 47%2A three-dimensional ordered structure spliced with the MOF framework.
7): changing the type of MOF in the step 2, and repeating the steps 2-5 to prepare TiO with different loading amounts2Three-dimensional ordered structures spliced with different MOF frameworks.
8): testing different loadings of TiO2XRD pattern of (1), TiO was obtained by Fourier subtraction2The periodic arrangement and the accurate measurement of the content of the TiO in the specific pore canal type are respectively measured to obtain the loading amounts of 13 percent, 23 percent, 37 percent, 42 percent and 47 percent, and the TiO in the specific pore canal type is researched2The maximum loading amount of the loading device is 47 percent, and is consistent with the calculation result according to the charging ratio.
9): observation of TiO in Steps 5-7 Using Low Damage STEM technique2TiO in three-dimensional ordered structure complementary to MOF framework space2Precise distribution within the corresponding individual channels of the MOF lattice.
Synthesis of TiO2Carrying out X-ray powder diffraction analysis on a three-dimensional ordered structure which is complementary with the MOF framework space to obtain a diffraction pattern shown in figure 1, wherein the pattern can be known as follows: TiO 22The loading of the MOF does not change the position of the diffraction peak of the MOF, which indicates that the original connection mode and local structure of the MOF are not damaged, and meanwhile, TiO with different contents2The intensity of the diffraction peak of MOF is changed regularly after loading, which indicates that TiO2The particles were successfully loaded into the MOF channels. Analysis of the half-width results of further diffraction peaks showed (fig. 2): different contents of TiO2The MOF porous pipe is accurately spliced with the inner wall of the MOF porous pipe, and the original crystal structure of the MOF is not damaged. FIG. 3 is a SEM comparison of composite materials of different loadings with pure MOF, from which it can be seen that the prepared composite material has a smooth surface with no residue, and further TEM results show (FIG. 4), even at TiO2At a content of up to 42%, TiO2The particles are uniformly distributed in the channels corresponding to the MOF lattice. FIG. 5 is a graph of the charge differential density of samples of different loadings, from which it is evident that when TiO is used2When the content is lower, filling the mesoporous titanium oxide in a smaller mesopore (component II) first, and when the content is lower, filling TiO in the mesoporous titanium oxide in the smaller mesopore (component II)2After the content is higher than 37%, the filling of larger mesopores (component I) is started, and TiO2Inside two kinds of pore canalsThe arrangement of (A) is different, and the growth is concentrated in the component II as the center, and is attached to the wall in the component I.
Example 2
WO3The preparation and molecular scale characterization of the three-dimensional ordered structure spliced with the MOF framework specifically comprises the following steps:
1): 2g (2-4g, preferably 2g) of H2WO4Adding into 20mL (10-50mL, preferably 20mL) of 30% H2O2Heating and stirring the solution at 70 deg.C (40-100 deg.C, preferably 70 deg.C) for 24 hr (10-24 hr, preferably 24 hr) until the solid powder is completely dissolved, cooling, and diluting with ultrapure water to 50mL to obtain H2WO4A precursor liquid.
2): adding 50mg of MIL-100(Fe) powder crystals subjected to degassing activation treatment into a beaker containing 2mL (2-10mL, preferably 2mL) of absolute ethyl alcohol, adding 150 muL (50-1100 muL, preferably 150 muL) of tungstic acid precursor solution, performing ultrasonic dispersion for 5min, stirring for 12h (10-24h, preferably 12h) at 30 ℃ (10-40 ℃, preferably 30 ℃), then transferring the whole into a double-row pipe, and pumping the solution under the condition of keeping the pressure of 60Pa (50-90Pa, preferably 60Pa), thus obtaining the three-dimensional ordered structure formed by splicing the tungsten trioxide containing the crystal water and the MOF framework.
3): and (3) placing the three-dimensional ordered structure formed by splicing the tungsten trioxide containing the crystal water and the MOF framework in the step (2) into a reaction kettle with a 30mL polytetrafluoroethylene lining, adding 5mL (5-10mL, preferably 5mL) of anhydrous ethanol, sealing, heating for 12h (10-24h, preferably 12h) at 200 ℃ (150 ℃ and 200 ℃, preferably 200 ℃), cooling, and performing vacuum drying to remove the solvent to obtain the three-dimensional ordered structure with 10% of tungsten trioxide and MOF framework being complementary in space.
4): changing the mass of the MOF and the volume of the tungsten sol precursor in the step 2, and repeating the steps 2-3 to respectively prepare WO with different loading amounts3A three-dimensional ordered structure spliced with the MOF framework.
5): respectively placing the three-dimensional ordered structures in the steps 3 and 4 in a vacuum drying oven and supercritical CO2Activating at 120 deg.C (80-120 deg.C, preferably 120 deg.C) for 10h (10-15h, preferably 10h) to obtain WO with molecular formula of x%3-three-dimensional ordered structure of in-MIL-100-Fe, wherein the value of x% 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, respectively.
6): testing of different loadings of WO3By Fourier subtraction to obtain WO3The loading amount of the periodic arrangement and the accurate measurement of the content of the periodic arrangement in the specific type of the pore channels is respectively measured to be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% and 50%, and the WO in the specific type of the pore channels is measured3The maximum loading amount of the reactor is 50 percent, which is consistent with the calculation according to the result of the charge ratio.
Synthesis of WO3The three-dimensional ordered structure which is complementary with the MOF framework space is subjected to X-ray powder diffraction analysis to obtain a diffraction pattern shown in figure 6, and the pattern shows that: WO3The loading of the MOF does not change the position of the diffraction peak of the MOF, which indicates that the original connection mode and local structure of the MOF are not damaged, and meanwhile, different contents of WO3The intensity of the diffraction peak of MOF is changed regularly after loading, which shows that WO3The particles were successfully loaded into the MOF channels.
Example 3
TiO2-WO3The preparation and molecular scale characterization of the three-dimensional ordered structure spliced with the MOF framework specifically comprises the following steps:
step 1): weighing 120ml ethanol, placing in a250 ml round bottom flask, adding 0.3ml concentrated nitric acid under 20 deg.C (15-25 deg.C, preferably 20 deg.C), stirring well, rapidly adding 0.1ml tetrabutyl titanate, and continuing stirring for 10 min.
Step 2): into a 100ml long-necked round-bottomed flask, 40mg of MIL-101-Cr and 60ml of the mixed solution in step 1 were charged. And after the sample is added, sealing the flask by using a sealing film, and carrying out ultrasonic treatment for 5min until the MOF particles are uniformly dispersed in the titanium sol precursor.
Step 3): and (3) placing the mixed solution filled with the MOF and the titanium sol precursor in the step 2 in a water bath constant temperature device with the temperature of 17 ℃ (10-25 ℃, preferably 17 ℃) for reaction for 15 hours. During the constant temperature period, the rotating speed is controlled to be 100 revolutions per minute, and the magnetic particle model is A250.
Step 4): and (3) transferring the mixed solution which is subjected to constant temperature reaction for 15 hours in the step 3 into a beaker of 100ml, then transferring the whole into a double-row pipe, and draining the solution under the condition of keeping the pressure of 70Pa (50-90Pa, preferably 70Pa) to obtain the three-dimensional ordered structure of the titanium gel entering the pore channels in the MOF.
Step 5): transferring the solid sample in step 4 into a sand bath, keeping the temperature of 80 deg.C (50-80 deg.C, preferably 80 deg.C) for 1h (1-5h, preferably 1h), and respectively placing the sample in a vacuum drying oven and supercritical CO2Activating at 80 deg.C (80-120 deg.C, preferably 80 deg.C) for 12h (10-15h, preferably 12h) to obtain 23% TiO2-in-MIL-101-Cr samples.
Step 6): 360 mu L of tungstic acid precursor solution in example 2 and 23 percent of TiO in step 5255mg of the in-MIL-101-Cr sample was mixed, dispersed by sonication for 5min, stirred at 30 ℃ (10-40 ℃, preferably 30 ℃) for 12h (10-24h, preferably 12h), and then the whole was transferred to a double row pipe, and the solution was drained while maintaining the pressure at 60Pa (50-90Pa, preferably 60 Pa).
Step 7): transferring the solid sample obtained in step 6 into a sand bath, keeping the temperature of 80 deg.C (50-80 deg.C, preferably 80 deg.C) for 1h (1-5h, preferably 1h), and respectively placing the sample in a vacuum drying oven and supercritical CO2Activating at 120 deg.C (80-120 deg.C, preferably 120 deg.C) for 15h (10-15h, preferably 15h) to obtain 23% TiO2-22％WO3-in-MIL-101-Cr.
Example 4
Weighing 1mg of composite material, dispersing in 0.5ml of water, ultrasonically dispersing uniformly, placing the mixed solution on a glass slide by using a dripping method, drying, and carrying out photocatalysis CO2Reduction test, test conditions were as follows: reactor volume 500ml, ultrapure water 1ml, CO2Xe lamp illumination at a pressure of 80KPa, 300W; sampling interval: 0.5 h/needle; the sampling mode is as follows: and (6) automatic sample injection. FIG. 7 shows TiO in different pore channels2Comparing the TOF value of the TiO in the pore canal, and finding out that the TiO in the pore canal2TiO with activity far higher than that of the agglomerated state or attached on the MOF surface2(ii) a At the same time, TiO in different pore channels2There was also a large difference in activity, up to 45-fold difference.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A three-dimensional ordered structure of a semiconductor that is spatially complementary to a MOF framework, comprising: the MOF/MOF.
2. The three-dimensional ordered structure of a semiconductor spatially complementary to a MOF framework of claim 1, wherein: the MOF is a mesoporous MOF material.
3. A three-dimensional ordered structure of a semiconductor spatially complementary to a MOF framework according to claim 2, wherein: the mesoporous MOF material comprises any one of MIL-101-Cr, MIL-101-Al, MIL-101-Fe, MIL-101-V, MIL-100-Fe, MIL-100-Cr, MIL-100-Al, MIL-100-Ti, MIL-100-Ni, MIL-100-Sc, MIL-100-V, MIL-100-Mn, PCN-332-Fe, PCN-332-V, PCN-332-Sc, PCN-332-Al, PCN-332-In, PCN-333-Fe, PCN-333-Sc and derivative functional groups thereof.
4. The three-dimensional ordered structure of a semiconductor spatially complementary to a MOF framework of claim 1, wherein: the semiconductor is TiO2、WO3、ZnO、CuO、Cu2O、CdO、Cr2O3、FeO、Fe2O3、Fe3O4、Ga2O3、In2O3、CdS、CuS、CdSe、C3N4、MoS2At least one of InP, ZnS, CuInS, BiOCl, BiOBr and BiOI.
5. The three-dimensional ordered structure of a semiconductor spatially complementary to a MOF framework of claim 1, wherein: the molecular formula of the three-dimensional ordered structure is x% of Semiconductor-in-MOF, wherein x% is the mass fraction of the Semiconductor in the whole three-dimensional ordered structure, and x is more than or equal to 5 and less than or equal to 50.
6. A method of preparing a three-dimensional ordered structure of a semiconductor of any of claims 1-5 that is sterically complementary to a MOF framework, comprising the steps of:
(1) according to the type of a semiconductor, under the condition of 10-40 ℃, selecting a proper inorganic or organic precursor to prepare a metal precursor solution, adding the metal precursor solution into a solvent, preparing a metal precursor solution with the metal concentration of 1-300mM and the solution pH value of 3-7, and uniformly mixing to prepare a sol with the metal sol precursor particle size of 0.5-1.2 nm;
(2) mixing the sol prepared in the step (1) with a certain volume with a certain amount of MOF, stirring at a constant temperature of 0-40 ℃ for 5-30h, and then pumping the solution to obtain a three-dimensional ordered structure of a solidified semiconductor intermediate product and an MOF framework which are complementary;
(3) performing constant-temperature aging at 80-200 ℃ and supercritical CO at 80-150 ℃ on the three-dimensional ordered structure of the solidified semiconductor intermediate product prepared in the step (2) and the MOF framework which are complementary2Activating for 10-24h to obtain a semiconductor three-dimensional ordered structure which is complementary with the MOF framework space.
7. A method of preparing a three-dimensional ordered structure of a semiconductor that is sterically complementary to a MOF framework according to claim 6, wherein: in the steps (1) to (3), the semiconductor material can be one or more, when the semiconductor material is multiple, multiple metal precursor solutions are respectively prepared in the step (1), in the step (2), the MOF and the semiconductor I sol are mixed to prepare a three-dimensional ordered structure of a solidified semiconductor I intermediate product complementary to an MOF framework, and in the step (3), the prepared three-dimensional ordered structure of the solidified semiconductor I intermediate product complementary to the MOF framework is subjected to constant-temperature aging and supercritical CO2Activating to obtain the framework hollow with the MOFAnd (3) mixing the sol of the semiconductor II with the composite material I to obtain a three-dimensional ordered structure of the semiconductor I-II and the MOF framework, and repeating the steps (2) and (3) until a three-dimensional ordered structure of the semiconductor I-II … … -N and the MOF framework is obtained.
8. A method of preparing a three-dimensional ordered structure of a semiconductor that is sterically complementary to a MOF framework according to claim 6, wherein: in the step (1), the semiconductor is TiO2、WO3、ZnO、CuO、Cu2At least one of O.
9. A method of preparing a three-dimensional ordered structure of a semiconductor that is sterically complementary to a MOF framework according to claim 8, wherein: when the semiconductor material is TiO2The preparation of the precursor sol comprises the following steps: adding tetrabutyl titanate and nitric acid into an ethanol solution at the temperature of 15-30 ℃, keeping the concentration of titanium in the solution at 1-15mM and the volume ratio of concentrated nitric acid to ethanol at 0.001-0.01, uniformly mixing, keeping the temperature at 15-30 ℃, and uniformly stirring to obtain precursor sol;
when the semiconductor material is WO3The preparation of the precursor sol comprises the following steps: adding tungstic acid into 30 percent of hydrogen peroxide solution at the temperature of 15-30 ℃, wherein the concentration of tungsten is 60-300mM, and preserving the temperature of the mixed solution at the temperature of 40-100 ℃ for 10-48h to prepare precursor sol;
when the semiconductor material is CuO, the precursor sol is prepared, and the method comprises the following steps: preparing 1-24mM copper nitrate aqueous solution at 10-40 ℃, and marking as solution I; preparing an ethanol solution of dodecylamine with the concentration of 0.15-0.45M, marking as a solution II, uniformly mixing the solution I and the solution II according to a certain volume ratio, adding n-hexane, and continuously stirring until the solution is uniform to prepare precursor sol, wherein the volume ratio of the solution I to the solution II to the n-hexane is 1: (1-3).
10. The three-dimensional ordered structure of the semiconductor and the MOF framework which are complementary in space and prepared by the preparation method of any one of claims 1 to 5 or the three-dimensional ordered structure of the semiconductor and the MOF framework which are complementary in space and prepared by the preparation method of any one of claims 6 to 9 are applied to the fields of photocatalysis, electrocatalysis and magnetic response materials.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254461A (en) * | 2020-01-19 | 2020-06-09 | 安徽大学 | Tungsten oxide/bismuth oxyiodide heterojunction material for photo-reduction of carbon dioxide and preparation method and application thereof |
| CN114054063A (en) * | 2021-10-26 | 2022-02-18 | 北京化工大学 | Method for synthesizing monatomic catalytic material with asymmetric double-ligand structure through in-situ coating-pyrolysis of nanocrystalline |
| CN115888833A (en) * | 2022-10-31 | 2023-04-04 | 淮北师范大学 | CdS/Mn-MOF composite photocatalyst and preparation method and application thereof |
| CN116440924A (en) * | 2023-03-13 | 2023-07-18 | 华南理工大学 | Preparation method of single-atom copper-based catalyst and application of single-atom copper-based catalyst in photocatalytic methane oxidation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881155A (en) * | 2016-12-29 | 2017-06-23 | 广州凯耀资产管理有限公司 | A kind of Au/TiO2/ metal organic framework composite photo-catalyst and preparation method and application |
| CN108126756A (en) * | 2017-12-12 | 2018-06-08 | 上海大学 | Bismuth tungstate-MIL-53 (Al) composite material, preparation method and application |
-
2020
- 2020-08-14 CN CN202010822546.0A patent/CN112063183B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106881155A (en) * | 2016-12-29 | 2017-06-23 | 广州凯耀资产管理有限公司 | A kind of Au/TiO2/ metal organic framework composite photo-catalyst and preparation method and application |
| CN108126756A (en) * | 2017-12-12 | 2018-06-08 | 上海大学 | Bismuth tungstate-MIL-53 (Al) composite material, preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| DING DENG等: "Impregnation of semiconductor CdS NPs in MOFs cavities via double solvent method for effective photocatalytic CO2 conversion", 《JOURNAL OF CATALYSIS》 * |
| HU JUANMIN等: "In situ fabrication of amorphous TiO2/NH2-MIL-125(Ti) for enhanced photocatalytic CO2 into CH4 with H2O under visible-light irradiation", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| JIANG ZHUO等: "Filling metal–organic framework mesopores with TiO2 for CO2 photoreduction", 《NATURE》 * |
| 江卓: "含钛光催化剂合成及其活性研究", 《中国博士学位论文全文数据库工程科技I辑》 * |
| 韩雪: "金属有机框架 MIL-125(Ti)复合材料的制备及其光催化性能研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
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|---|---|---|---|---|
| CN111254461A (en) * | 2020-01-19 | 2020-06-09 | 安徽大学 | Tungsten oxide/bismuth oxyiodide heterojunction material for photo-reduction of carbon dioxide and preparation method and application thereof |
| CN111254461B (en) * | 2020-01-19 | 2021-08-27 | 安徽大学 | Tungsten oxide/bismuth oxyiodide heterojunction material for photo-reduction of carbon dioxide and preparation method and application thereof |
| CN114054063A (en) * | 2021-10-26 | 2022-02-18 | 北京化工大学 | Method for synthesizing monatomic catalytic material with asymmetric double-ligand structure through in-situ coating-pyrolysis of nanocrystalline |
| CN114054063B (en) * | 2021-10-26 | 2023-11-21 | 北京化工大学 | Method for synthesizing monoatomic catalytic material with asymmetric double-ligand structure by nanocrystalline in-situ cladding-pyrolysis |
| CN115888833A (en) * | 2022-10-31 | 2023-04-04 | 淮北师范大学 | CdS/Mn-MOF composite photocatalyst and preparation method and application thereof |
| CN115888833B (en) * | 2022-10-31 | 2024-02-27 | 淮北师范大学 | CdS/Mn-MOF composite photocatalyst and preparation method and application thereof |
| CN116440924A (en) * | 2023-03-13 | 2023-07-18 | 华南理工大学 | Preparation method of single-atom copper-based catalyst and application of single-atom copper-based catalyst in photocatalytic methane oxidation |
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