CN114797798B - Preparation method and application of MOF/corn stalk composite material and device - Google Patents

Preparation method and application of MOF/corn stalk composite material and device Download PDF

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CN114797798B
CN114797798B CN202210390327.9A CN202210390327A CN114797798B CN 114797798 B CN114797798 B CN 114797798B CN 202210390327 A CN202210390327 A CN 202210390327A CN 114797798 B CN114797798 B CN 114797798B
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mof
corn
straw
precursor
composite material
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CN114797798A (en
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王光辉
李德昌
张潜
张珊
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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Qingdao Institute of Bioenergy and Bioprocess Technology of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3285—Coating or impregnation layers comprising different type of functional groups or interactions, e.g. different ligands in various parts of the sorbent, mixed mode, dual zone, bimodal, multimodal, ionic or hydrophobic, cationic or anionic, hydrophilic or hydrophobic
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
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  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract

The invention relates to a preparation method and application of a MOF/corn stalk composite material and a device. According to the invention, corn straw with honeycomb ordered macropores is used as a carrier, MOFs are uniformly grown on the surfaces of straw cells, so that the MOFs/corn straw composite material with the straw biological structure is obtained, and the introduction of the corn straw carrier is beneficial to mass transfer and exposure of active sites. The composite material can be further assembled into devices for application fields such as adsorption, separation, catalysis and the like due to good mechanical properties of the corn stalks. The method has the advantages of low preparation cost, simple process, wide universality, green and sustainable property and good large-scale application prospect.

Description

Preparation method and application of MOF/corn stalk composite material and device
Technical Field
The invention relates to the technical field of biomass functional materials, in particular to a MOF/corn straw composite material, a preparation method and application of a device.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
In recent years, MOF materials are attracting attention in the fields of pollutant adsorption, heterogeneous catalysis, gas separation and the like, and the performance advantages and the feasibility of industrial application of the MOF materials are widely demonstrated. However, MOFs are usually in powder form, and in order to facilitate separation recovery or reduce the pressure drop of a fixed bed, the industry often shapes the powder material by means of high pressure compaction or the addition of binders, which greatly affects mass transfer and active site exposure, thereby greatly inhibiting the exertion of intrinsic properties.
The MOF and the formed carrier material are compounded, so that the composite material which not only maintains the original property and function of the MOF, but also has the structure and characteristics of the carrier is developed, and the MOF powder forming method is an effective way for solving the MOF powder forming problem.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a MOF/corn straw composite material and a device, wherein corn straw is used as a carrier to controllably load MOF, the biological structure of the corn straw is utilized to improve mass transfer and exposure of active sites in the composite material, so that the exertion of the intrinsic performance of MOF is promoted, the problems that the conventional MOF material is difficult to recover, difficult to process and poor in operability are solved, and the recycling of waste straw is realized.
In a first aspect of the invention, a method for preparing a MOF/corn stalk composite material is provided, comprising the steps of:
(1) Pretreating corn stalks;
(2) Introducing the MOF precursor into the corn straw to obtain corn straw containing the MOF precursor;
(3) Transferring corn stalks containing MOF precursors into a reactor, and raising the temperature to a certain reaction temperature to perform nucleation and growth of MOFs;
(4) And washing and drying the reacted material to obtain the MOF/corn stalk composite material.
Further, the pretreatment comprises the steps of peeling, cutting, washing, drying and the like.
Further, in step (2), the method of introducing the MOF precursor into the corn stover includes dipping and vapor deposition;
further, the dipping method is to dissolve a precursor of MOF in a solvent, soak corn straw in the solution, fill the interior of the corn straw with the solution through negative pressure treatment, then separate solid from liquid and dry; preferably, the solvent is selected from the group consisting of water, ethanol, methanol, N-Dimethylformamide (DMF), isopropanol, ethylene glycol, glycerol, and the like.
Further, the vapor deposition method is to place corn stalk and MOF precursor in a reaction container, heat up the reaction container to make the MOF precursor become gaseous and adsorb and deposit on the surface of stalk duct; it should be noted that depending on the nature of the reaction of the MOF precursor, the MOF precursor may be introduced into the interior of the straw stepwise or simultaneously, or the impregnation method may be applied to the loading of the MOF in combination with the vapor deposition method.
Further, the MOF precursor includes a metal salt, an organic ligand, and a structure modulator.
The metal salt is selected from nitrate, sulfate, acetylacetonate, halide, acetate, metal salt or organic complex of Mg, ni, co, zn, zr, sn, in, cu, ce, al, fe, cr, mn and other metals; the organic ligand is terephthalic acid, 2-X-1, 4-terephthalic acid (X is-NH) 2 ,-NO 2 -OH, -COOH, -Cl, -Br or-I), trimesic acid, pyromellitic acid, 2-methylimidazole, imidazole or porphyrin, etc.; the structure regulator is acetic acid, hydrochloric acid, sulfuric acid or nitric acid.
In the step (2), the concentration of the metal ions of the metal salt is 0.01-5mol/L, preferably 0.05-0.15mol/L; the molar ratio of organic ligand to metal ion in metal salt is 20:1-1:1, preferably 8:1-1:1; the volume percentage of the structure modifier in the precursor solution is 0-20%, preferably 8-12%.
In the step (2), the dosage ratio of the corn stalk to the MOF precursor solution is 5-20g/L, preferably 10-15g/L.
Further, in the step (3), the reaction temperature is 20-200 ℃, and is selected according to the boiling point of the organic ligand; the reaction time is 1 to 24 hours, preferably 6 to 12 hours.
In a second aspect of the invention, the MOF/corn straw composite material prepared by the preparation method is provided.
Further, the MOFs include Zr-MOFs, zn-MOFs, fe-MOFs, co-MOFs, ni-MOFs, cu-MOFs, al-MOFs, mg-MOFs, ti-MOFs, cr-MOFs, ce-MOFs, sn-MOFs, in-MOFs, mn-MOFs, and the like.
In a third aspect of the present invention, there is provided a device, the method of making comprising the steps of:
and (3) after the MOF/corn stalk composite material is subjected to physical cutting, splicing, bonding and other treatments, the MOF/corn stalk composite material is put into a reactor with a certain size, and the MOF/corn stalk device is obtained after sealing and pipeline connection.
In a fourth aspect of the invention there is provided the use of the device described above in the fields of adsorption, separation, catalysis and the like.
The beneficial effects of the invention are as follows:
(1) The corn straw is a traditional agricultural waste, has large yield and green sustainability, and has economic benefit and environmental benefit when being used in value-added mode; therefore, the method can solve the problems of expensive preparation cost, unsustainable preparation and the like of the traditional MOF composite material.
(2) The corn straw is used as a mass transfer channel and a supporting framework for corn growth, has rich porosity, oxygen-containing groups and good structural stability, and is an ideal three-dimensional carrier material; the corn stalk is selected as the MOF carrier, so that the problems of difficult separation and recovery of MOF powder, large pressure drop, poor operability and the like can be solved, and the problem of activity reduction caused by mass transfer limitation in the traditional MOF forming process is effectively solved.
(3) In the MOF/corn straw composite material, MOFs are uniformly distributed on the cell walls of the straw, so that agglomeration of MOF particles is effectively inhibited, and full exposure of active sites is ensured;
(4) The corn stalk has certain elasticity and mechanical strength, this facilitates customization of the composite material and assembly of the device, meeting practical requirements; the method has wide universality for different MOFs, is simple, has low cost, is easy to produce in an amplified manner, and has good large-scale application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute an undue limitation to the application.
Fig. 1: a is a photograph of corn stalks and UIO-66/corn stalks; b is a photograph of the interior of UiO-66/corn stover (example 1);
FIG. 2 SEM pictures of UiO-66/corn stover made at different Zr precursor concentrations (examples 1,2, 3);
FIG. 3 a) is an XRD pattern of a sample illustrating the formation of UiO-66; b) N of sample 2 Adsorption and desorption isotherms; example 1 comparative examples 1,2
FIG. 4 SEM image of ZIF-67/straw; example 4
FIG. 5 shows the results of adsorption kinetics experiments on phosphate; example 7
FIG. 6 shows the adsorption isotherm test results of the sample on phosphate; example 8
FIG. 7 is a photograph and schematic illustration of the operation of a single MOF/corn stover device; example 5
FIG. 8 is a schematic diagram of the operation of a tandem MOF/corn stover device; example 5
FIG. 9 shows the results of an adsorption column experiment of a single MOF/corn stalk device on phosphate; example 9
FIG. 10 shows the results of phosphate treatment with tandem MOF/corn stover devices at different sample injection fluxes; example 10
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
At present, the conventional molding MOF has the problems of low mass transfer efficiency, insufficient exposure of active sites, high preparation cost, poor application performance and the like, and therefore, the invention provides a preparation method and application of the MOF/corn stalk composite material and a device.
In one embodiment of the invention, a method for preparing a MOF/corn stalk composite comprises:
(1): pretreating corn stalks, including: peeling, cutting, washing, drying and the like;
(2): introducing precursor components such as metal salt, organic ligand, structure regulator and the like required by synthesizing MOF into the corn stalk;
(3): transferring corn stalks containing MOF precursors into a reactor, and raising the temperature to a certain reaction temperature to perform nucleation and growth of MOFs;
(4) And washing and drying the reacted material to obtain the MOF/corn straw composite material.
In some embodiments, the corn stover is pre-treated prior to use of the corn stover; the corn stalk pretreatment comprises: peeling corn stalk, cutting, washing with acid solution, washing with water to neutrality, and drying; or, the acid is selected from one or more of hydrochloric acid, sulfuric acid and nitric acid, and is preferably hydrochloric acid. By preprocessing the corn stalks, the influence of background metal in the corn stalks on MOF growth can be eliminated.
In some specific embodiments, in step (2), the method of introducing the MOF precursor into the corn stover comprises an impregnation process and a vapor deposition process; the dipping method is to dissolve precursor of MOF in solvent, soak corn stalk in the solution, fill the corn stalk with the solution through negative pressure treatment, then solid-liquid separation and drying; the solvent is selected from water, ethanol, methanol, N-Dimethylformamide (DMF), isopropanol, ethylene glycol, glycerol and the like; the vapor deposition method is to place corn stalk and MOF precursor in a reaction container, heat up the reaction container to make the MOF precursor become gaseous and adsorb and deposit on the surface of stalk duct; it should be noted that depending on the nature of the reaction of the MOF precursor, the MOF precursor may be introduced into the interior of the straw either stepwise or simultaneously, or a dipping process may be used in conjunction with a vapor deposition process to load the MOF.
In some specific embodiments, in step (2), the metal salt is selected from the group consisting of nitrate, sulfate, acetylacetonate, halide, acetate, metallate, and organic complex of a metal such as Mg, ni, co, zn, zr, sn, in, cu, ce, al, fe, cr, mn; the organic ligand is terephthalic acid, 2-X-1, 4-terephthalic acid (X is-NH) 2 ,-NO 2 -OH, -COOH, -Cl, -Br or-I), trimesic acid, pyromellitic acid, 2-methylimidazole, imidazole or porphyrin, etc.; the structure regulator is acetic acid, hydrochloric acid, sulfuric acid or nitric acid;
in some specific embodiments, in step (2), the concentration of the metal salt is between 0.01 and 5mol/L, preferably between 0.05 and 0.15mol/L; or, in step (2), the molar ratio of the organic ligand to the metal is between 20:1 and 1:10, preferably between 8:1 and 1:1.
In some embodiments, in step (3), the reaction temperature is between 20 and 200 ℃ selected according to the boiling point of the organic ligand; the reaction time is between 1 and 24 hours, preferably between 6 and 12 hours.
In one embodiment of the invention, the MOF/corn stalk composite material is prepared by the preparation method.
In one embodiment of the invention, a device is made based on the MOF/corn stover composite. And (3) physically cutting, splicing, bonding and the like the MOF/corn stalk composite material prepared by the preparation method, loading the MOF/corn stalk composite material into a reactor with a certain size, and obtaining the MOF/corn stalk device after sealing and pipeline connection. The material of the reactor can be plastic, metal, glass, organic glass and the like.
In one embodiment of the invention, the MOF/corn stalk composite or device is used in the fields of adsorption, separation, catalysis and the like. The MOF/corn stalk composite or device of the present invention has advantages in mass transfer and active site exposure compared to conventional homogeneous molding materials, and thus has potential advantages in many application scenarios. For example, the UiO-66 MOF/corn stalk composite material prepared by the invention has excellent adsorption performance in phosphate in water, and the adsorbent can be used in the forms of particles, fixed beds, devices and the like due to the physical characteristics of stalk.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Implementation of the embodiments example 1
MOF/corn stalk composite material:
a) Pretreating corn stalks, peeling the corn stalks, cutting the corn stalks into segments, washing the corn stalks with 1M dilute hydrochloric acid for 3 times, washing the corn stalks with water until the corn stalks are neutral, and drying the corn stalks to obtain pretreated corn stalks;
b) 4mmol ZrCl 4 4mmol terephthalic acid, 10mL glacial acetic acid are dissolved in 80mL N, N-dimethylformamide; 1g of corn straw is taken to be soaked in the solution, and vacuum is pumped/removed for 3 times to saturate the corn straw;
c) Transferring the straws filled with the MOF precursor solution into a hydrothermal kettle, and raising the temperature to 120 ℃ for 24 hours; and then the obtained product is washed with DMF and water for a plurality of times, the residual reactant is removed, and the product is dried, so that the UiO-66/straw composite material with the biological structure of the corn straw maintained is obtained. As shown in fig. 1, a is a photograph of corn stalks and UiO-66/corn stalks; and b, an internal photo of the UiO-66/corn straw. As can be seen from fig. 2e-f, the MOFs are uniformly distributed on the surface of the straw, and are closely arranged to form a film. FIG. 3 shows that the XRD spectrum of UiO-66/corn straw has a peak of UiO-66, and the nitrogen adsorption and desorption curve also shows that the prepared product has the micropore characteristic of MOF, thus proving the formation of UiO-66.
Example 2
MOF/corn stalk composite material:
a) Pretreating corn stalks, peeling the corn stalks, cutting the corn stalks into segments, washing the corn stalks with 1M dilute hydrochloric acid for 3 times, washing the corn stalks with water until the corn stalks are neutral, and drying the corn stalks to obtain pretreated corn stalks;
b) 2mmol ZrCl 4 2mmol terephthalic acid, 5mL glacial acetic acid are dissolved in 80mL N, N-dimethylformamide; 1g of corn straw is taken to be soaked in the solution, and vacuum is pumped/removed for 3 times to saturate the corn straw;
c) Transferring the straws filled with the MOF precursor solution into a hydrothermal kettle, and raising the temperature to 120 ℃ for 24 hours; and then the obtained product is washed with DMF and water for several times, the residual reactant is removed, and the product is dried, so that the UiO-66/straw composite material with lower load is obtained.
As shown in fig. 2a-b, at lower precursor concentrations, the MOF particles were discretely distributed on the straw surface and no film was formed.
Example 3
MOF/corn stalk composite material:
a) Pretreating corn stalks, peeling the corn stalks, cutting the corn stalks into segments, washing the corn stalks with 1M dilute hydrochloric acid for 3 times, washing the corn stalks with water until the corn stalks are neutral, and drying the corn stalks to obtain pretreated corn stalks;
b) 8mmol ZrCl 4 8mmol terephthalic acid, 10mL glacial acetic acid are dissolved in 80mL N, N-dimethylformamide; 1g of corn straw is taken to be soaked in the solution, and vacuum is pumped/removed for 3 times to saturate the corn straw;
c) Transferring the straws filled with the MOF precursor solution into a hydrothermal kettle, and raising the temperature to 120 ℃ for 24 hours; and then the obtained product is washed with DMF and water for a plurality of times, the residual reactant is removed, and the product is dried, so that the UiO-66/straw composite material with higher loading capacity is obtained.
As shown in fig. 2a-b, at higher precursor concentrations, excess MOF particles are dissociated outside the MOF membrane.
Example 4
Preparing the MOF/corn stalk composite material by a vapor deposition method:
a) Peeling corn stalk, cutting, washing with 1M diluted hydrochloric acid for 3 times, washing with water to neutrality, and drying;
b) 6mmol Co (NO) 3 ) 2 ·6H 2 O, 24mmol urea was dissolved in 20mL water+60 mL ethanol;
c) 1g of corn straw is taken to be immersed in the solution, vacuumizing for 3 times to saturate the corn straw;
d) Transferring the straw filled with the solution into a hydrothermal kettle, and heating to 100 ℃ and keeping for 24 hours; washing the obtained product with water for several times, removing residual reactants, and drying;
e) Placing 0.3g of the Co metal loaded straw and 0.3g of 2-methylimidazole into a sealed quartz tube, vacuumizing, maintaining at 160 ℃ for 24 hours, and cooling to obtain ZIF-67/straw;
as shown in FIG. 4, the ZIF-67/straw obtained had a layer of particles formed on the surface.
Example 5
Preparing a MOF/corn stalk device:
cutting corn stalks with the diameter of about 14cm to the length of 5cm, preparing UIO-66/stalk according to the method described in the embodiment 1, coating vacuum silicone grease on the surface of a cylindrical sample, wrapping a sealing belt, and coating the vacuum silicone grease on the surface of the sealing belt; then, the sample is plugged into a glass tube with the length of 10cm and the diameter of 14cm, and the two ends of the glass tube are connected with threaded joints to prepare an MOF/corn stalk device (shown in figure 7); multiple devices were connected in series to obtain a tandem MOF/corn straw device (as shown in fig. 8).
Example 6
Preparing a MOF/corn stalk device:
corn stalks are cut to 10cm in length, uiO-66/stalks are prepared according to the method described in example 1, a plurality of cylindrical samples are filled in parallel into plastic pipes with the diameter of 15cm, gaps between the samples and the plastic pipes are filled with resin, after the resin is solidified, two ends of the plastic pipes are sealed, and joints are connected, so that a group of parallel MOF/corn stalk devices are prepared.
Example 7
Granular MOF/corn straw is used for adsorbing phosphate in water body:
80mg of UiO-66/straw particles prepared in example 1 were weighed, placed in a 50mL separation tube, 40mL of potassium dihydrogen phosphate solution with an initial P concentration of 30ppm was added, the initial pH was adjusted to 5.0, and the mixture was subjected to rotary adsorption reaction on a rotary bed, and sampling and testing were performed at regular intervals. The same quality of UiO-66 granules (comparative example 1) obtained by high pressure compression molding was used as a control group, and performance test was conducted under the same conditions.
As shown in fig. 5, the adsorption rate of UiO-66/straw with straw biological structure to P is significantly better than that of the high-pressure compression molded UiO-66 particles, supporting the expectation that the biological structure of corn straw promotes mass transfer and active site exposure.
Example 8
Granular MOF/corn stover for adsorption of water phosphate (adsorption isotherm):
80mg of UiO-66/straw particles prepared in example 1 were weighed, placed in 50mL of a separation tube, 40mL of a potassium dihydrogen phosphate solution with an initial P concentration of 10/30/50/100/200/300/500/750/1000ppm was added respectively, the initial pH was adjusted to 5.0, a rotary adsorption reaction was performed on a rotary bed, and after 7 days, samples were taken to test the P adsorption amount. The samples obtained in comparative examples 1 and 2 were tested under the same conditions for control.
As shown in FIG. 6, the adsorption capacity of P by straw was almost 0, and the adsorption capacity of P by UiO-66/straw was as high as 270 mg.g -1 The preparation method is obviously superior to the UiO-66 granules formed by high-pressure compression, and supports the expectation that the biological structure of the corn straw promotes mass transfer and active site exposure.
Example 9
The MOF/corn stalk device is used for continuous flow adsorption of water phosphate:
the UiO-66/straw device prepared in example 5 was connected to a microscale pump at 6.5 L.m -2 ·h -1 Is pumped into potassium dihydrogen phosphate solution with initial P concentration of 3ppm, and is sampled and tested at intervals.
As a result, as shown in FIG. 9, after running 35BV of phosphate solution, the P concentration in the effluent still meets the first-level standard specification of the national sewage discharge standard (GB 8978-2002).
Example 10
The tandem MOF/corn stalk device is used for continuous flow adsorption of water phosphate:
four UiO-66/straw devices prepared in example 5 are connected in series, one end of each device is connected with a microsyringe pump, and the thickness of each device is 6.5-800 L.m -2 ·h -1 And (3) modulating the sample injection flux in a range, and examining the relation between the flux and the P removal efficiency.
As shown in FIG. 10, when the sample injection flux is lower than 300 L.m -2 ·h -1 When the P concentration of the effluent meets the first-level standard of national sewage discharge standard<0.5 ppm); when the sample injection flux is close to 800 L.m -2 ·h -1 When the P concentration of the effluent still meets the secondary standard of national sewage discharge standard<1.0 ppm), indicating that the UiO-66/straw filter has great practical application potential.
Comparative example 1
Tabletting method is used for preparing UiO-66 formed particles:
4mmol ZrCl 4 4mmol of terephthalic acid,10mL of glacial acetic acid was dissolved in 80mL of N, N-dimethylformamide; transferring the solution into a hydrothermal kettle, and raising the temperature to 120 ℃ and keeping for 24 hours; the precipitate was then isolated by suction filtration, washed several times with DMF and water, the remaining reactants removed and dried to give UiO-66 powder.
The obtained UiO-66 powder is placed in a tablet press and pressed and molded under the pressure of 5MPa, so as to obtain the UiO-66 particles. As can be seen from FIG. 3, the UiO-66 particles retain the microporous character of the UiO-66.
For a pair of proportion 2
Corn stalks not loaded with UiO-66:
a) Pretreating corn stalks, peeling the corn stalks, cutting the corn stalks into segments, washing the corn stalks with 1M dilute hydrochloric acid for 3 times, washing the corn stalks with water until the corn stalks are neutral, and drying the corn stalks to obtain pretreated corn stalks;
b) 1g of corn straw is immersed in 80mL of N, N-dimethylformamide, and vacuum is pumped/removed for 3 times to saturate the corn straw;
c) Transferring the straws filled with the solvent into a hydrothermal kettle, and heating to 120 ℃ and keeping for 24 hours; and then drying the obtained product for a plurality of times by using DMF and water to obtain a corn stalk control group without carrying UiO-66.
As can be seen from FIG. 3, the corn stover without UiO-66 loading contains very few micropores and mesopores, which are negligible.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims (16)

1. The preparation method of the MOF/corn stalk composite material is characterized by comprising the following steps:
(1) Pretreating corn stalks;
(2) Introducing the MOF precursor into the corn straw to obtain corn straw containing the MOF precursor;
(3) Transferring corn stalks containing MOF precursors into a reactor, and raising the temperature to a certain reaction temperature to perform nucleation and growth of MOFs;
(4) Washing and drying the reacted material to obtain the MOF/corn straw composite material with the straw biological structure;
the pretreatment comprises peeling, cutting, washing and drying;
the MOF precursor includes a metal salt, an organic ligand, and a structure modifier;
the metal salt is selected from nitrate, sulfate, acetylacetonate, halide, acetate, metal salt or organic complex of Mg, ni, co, zn, zr, sn, in, cu, ce, al, fe, cr, mn; the organic ligand is one or more of terephthalic acid, 2-X-1, 4-terephthalic acid, trimesic acid, pyromellitic acid, 2-methylimidazole, imidazole or porphyrin; the structure regulator is acetic acid, hydrochloric acid, sulfuric acid or nitric acid; wherein X is-NH 2 , -NO 2 -OH, -COOH, -Cl, -Br or-I;
in the step (2), the concentration of metal ions of the metal salt is 0.01-5 mol/L; the molar ratio of the organic ligand to the metal ions in the metal salt is 20:1-1:1; the volume percentage of the structure regulator in the precursor solution is 0-20%; the dosage ratio of the corn stalk to the MOF precursor solution is 5-20 g/L.
2. The method of claim 1, wherein in step (2), the MOF precursor is introduced into the corn stover by a process comprising dipping and vapor deposition.
3. The method according to claim 2, wherein the dipping method is to dissolve the MOF precursor in a solvent to obtain a solution, dip the corn stalk in the solution, fill the corn stalk with the solution by a negative pressure treatment, then separate solid and liquid, and dry.
4. The method according to claim 3, wherein the solvent is one or more selected from the group consisting of water, ethanol, methanol, N-dimethylformamide, isopropanol, ethylene glycol, and glycerol.
5. The method according to claim 2, wherein the vapor deposition method is to place corn stalk and MOF precursor in a reaction vessel, heat up the mixture to make the MOF precursor become gaseous and adsorb and deposit on the surface of stalk duct.
6. The method according to claim 1, wherein in the step (2), the impregnation method is applied together with the vapor deposition method to the MOF load.
7. The method according to claim 1, wherein in the step (2), the concentration of the metal ion of the metal salt is 0.05 to 0.15mol/L; the molar ratio of the organic ligand to the metal ions in the metal salt is 8:1-1:1; the volume percentage of the structure regulator in the precursor solution is 8-12%; the dosage ratio of the corn stalk to the MOF precursor solution is 10-15g/L.
8. The method according to claim 1, wherein in the step (3), the reaction temperature is 20 to 200 ℃; the reaction time is 1-24 and h.
9. The method according to claim 8, wherein in the step (3), the reaction time is 6 to 12h.
10. A MOF/corn stover composite material prepared according to the method of any one of the preceding claims.
11. The MOF/corn stover composite of claim 10, wherein the MOF comprises one or more of Zr-MOF, zn-MOF, fe-MOF, co-MOF, ni-MOF, cu-MOF, al-MOF, mg-MOF, cr-MOF, ce-MOF, sn-MOF, in-MOF, mn-MOF.
12. The preparation method of the MOF/corn stalk device is characterized by comprising the following steps of:
the MOF/corn stalk composite material of claim 10 or 11 is subjected to physical cutting, splicing or bonding treatment, then is put into a reactor, and is subjected to sealing and pipeline connection to obtain the MOF/corn stalk device.
13. The MOF/corn stover device of claim 12, wherein the reactor is plastic, metal or glass.
14. The MOF/corn stover device of claim 13, wherein the plastic is plexiglas.
15. Use of the MOF/corn stalk device according to claim 12 in the fields of adsorption, separation, catalysis.
16. Use according to claim 15, in the adsorption of phosphate in a body of water.
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