CN113912861B - Preparation method and application of zirconium-based MOFs (metal-organic frameworks) material - Google Patents

Preparation method and application of zirconium-based MOFs (metal-organic frameworks) material Download PDF

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CN113912861B
CN113912861B CN202111348221.4A CN202111348221A CN113912861B CN 113912861 B CN113912861 B CN 113912861B CN 202111348221 A CN202111348221 A CN 202111348221A CN 113912861 B CN113912861 B CN 113912861B
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zirconium
mofs material
based mofs
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powder product
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CN113912861A (en
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邓伟
徐绍亮
陈善良
张双猛
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Foshan Southern China Institute For New Materials
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention discloses a preparation method and application of a zirconium-based MOFs material. The preparation method of the zirconium-based MOFs material comprises the steps of suspending ligand terephthalic acid and zirconium salt in a mixed solvent of water and acetic acid, and carrying out reflux heating to obtain a powder product; sequentially soaking and cleaning the powder product by using absolute ethyl alcohol and absolute dichloromethane at room temperature; and removing the anhydrous dichloromethane to obtain a sample, and drying the sample under a dynamic vacuum condition to obtain the MOFs material. The preparation method of the zirconium-based MOFs material has the advantages of simple operation process, short preparation time and low cost. The application of the zirconium-based MOFs material is to prepare hydrogen.

Description

Preparation method and application of zirconium-based MOFs (metal-organic frameworks) material
Technical Field
The invention relates to the field of new energy manufacturing, in particular to a preparation method and application of a zirconium-based MOFs material.
Background
In recent years, there has been encouraging research progress in the study of the piezoelectric catalytic technology, which is a process of directly decomposing water using mechanical vibration energy. As an emerging hybrid material, inorganic and Organic, the Metal Organic Framework (MOF) is a structure that is one, two or three dimensional, composed of Metal atoms or clusters of atoms coordinated by Organic ligands. In general, most studies on MOFs have focused on their applications in gas storage, separation, purification, and catalysis, while few reports have been made on mechanical properties, piezoelectric properties (ACS Applied Materials & Interfaces,2017 32202.). Metal Organic Frameworks (MOFs) have the unique advantages of both the chemical, thermal and mechanical stability of inorganic bulk materials and the easily customizable molecular structure of organic linkers. Compared with the traditional piezoelectric material, the MOFs can be synthesized by a simple and convenient method at a relatively low temperature. To date, MOF materials have made significant progress in developing polarities with good piezoelectric properties, showing potential in various applications such as vibrators, sensors and energy harvesting technologies (angelw. Chem. Int. Ed., 2020).
However, the existing preparation method of MOFs materials is troublesome in operation, long in preparation time and high in cost, and is not suitable for mass production.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of a zirconium-based MOFs material with simple operation, short operation time and low cost and an application thereof.
A preparation method of zirconium-based MOFs materials comprises the following steps:
suspending ligand terephthalic acid and zirconium salt in a mixed solvent of water and acetic acid, and performing reflux heating to obtain a powder product;
sequentially soaking and cleaning the powder product by using absolute ethyl alcohol and absolute dichloromethane at room temperature;
and removing the anhydrous dichloromethane to obtain a sample, and drying the sample under a dynamic vacuum condition to obtain the MOFs material.
Further preferably, the suspending the ligand terephthalic acid and zirconium salt in a mixed solvent of water and acetic acid comprises:
to a 300ml reactor equipped with a stirrer and a reflux condenser was added 50ml of a mixed solvent of water and acetic acid in a volume ratio of 3.
The use of a mixed solvent of water and acetic acid as a reaction solvent can facilitate the dissolution of the reactants. Since hydroxyl groups are present in acetic acid, they can form intermolecular hydrogen bonds with your coordination polymer, which is equivalent to forming a stable system in solution, and thus are easily dissolved. DMSO, DMF, chloroform, etc. do not have hydroxyl groups and do not form hydrogen bonds, so they are difficult to dissolve.
Further preferably, the ligand terephthalic acid is tetrafluoroterephthalic acid or dihydroxyterephthalic acid.
Further preferably, the zirconium salt is Zr (NO) 3 ) 4 Or ZrCl 4 。
Further preferably, the soaking and cleaning of the powder product with anhydrous ethanol and anhydrous dichloromethane sequentially at room temperature comprises the following steps:
soaking the powder product in 100ml of absolute ethyl alcohol at room temperature for three days, adding new absolute ethyl alcohol every day, and soaking the powder product soaked in the absolute ethyl alcohol in 100ml of absolute dichloromethane at room temperature for three days, and adding new absolute dichloromethane every day.
Anhydrous ethanol can rapidly activate the powder product. The powder is cleaned by using absolute ethyl alcohol and absolute dichloromethane as solvents, the cleaning time is short, the efficiency is high, and the deionized water is used for washing more than 8 times.
Further preferably, the removing of the anhydrous dichloromethane to obtain a sample, and the sample is dried under a dynamic vacuum condition to obtain the MOFs material, including:
washing away residual reagents (ligand terephthalic acid, acetic acid, methanol and anhydrous dichloromethane) on the surface of the sample by using deionized water, centrifuging by using a centrifugal machine, then separating out the anhydrous dichloromethane to obtain a sample, and drying the sample in a vacuum freeze dryer at-60 ℃ for 24 hours to obtain the zirconium-based MOFs material.
Freeze-drying is a process in which the dried material is rapidly frozen at low temperature and then frozen water molecules are directly sublimated to escape as water vapor under a suitable vacuum environment. Drying at low temperature results in little loss of some of the volatile components in the product. Since the drying is performed in a frozen state, the volume is almost unchanged, the original structure is maintained, and the shrinkage phenomenon does not occur, so that the material structure is not damaged.
Further preferably, the zirconium-based MOFs material is in the shape of nano octahedron or nano flower particles, the diameter of the nano octahedron is 100-200nm, and the diameter of the nano flower is about 150 nm.
According to the preparation method of the zirconium-based MOFs material, ligand terephthalic acid and zirconium salt are used as raw materials, a mixture of water and acetic acid is used as a solvent, and the zirconium-based MOFs material is finally obtained.
An application of zirconium-based MOFs material, which comprises the following steps:
and pouring water into an ultrasonic cleaning tank, adding the zirconium-based MOFs material prepared by the preparation method of the zirconium-based MOFs material, and decomposing the water under the ultrasonic condition to prepare hydrogen.
Further preferably, the ultrasonic frequency is 50-60kHz.
Further preferably, the mass fraction of the zirconium-based MOFs material is 15-20%.
Compared with the prior art, the application of the zirconium-based MOFs material applies ultrasonic external force to the piezoelectric MOFs material to generate active free radicals, so that water is catalytically decomposed to generate hydrogen, a new way is provided for efficient utilization of mechanical energy, and the reaction condition is mild. The performance of the hydrogen prepared by the method can reach 240 mu mol/g/h, and the method is environment-friendly, has high repeatability and is suitable for industrial production.
For a better understanding and practice, the present invention is described in detail below with reference to the accompanying drawings.
Drawings
FIG. 1 shows UiO66- (OH) prepared by the method for preparing zirconium-based MOFs material of the present invention 2 Electron micrograph of sample.
FIG. 2 is an electron microscope image of a UiO66-F4 sample prepared by the preparation method of the zirconium-based MOFs material.
FIG. 3 is UiO66- (OH) 2 And a UiO66-F4 hydrogen production performance diagram.
Detailed Description
The terms of orientation of up, down, left, right, front, back, top, bottom, and the like, referred to or may be referred to in this specification, are defined relative to their configuration, and are relative concepts. Therefore, it may be changed according to different positions and different use states. Therefore, these and other directional terms should not be construed as limiting terms.
The implementations described in the exemplary embodiments below are not intended to represent all implementations consistent with the present disclosure. Rather, they are merely examples of implementations consistent with certain aspects of the present disclosure.
The terminology used in the disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. As used in this disclosure, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
Example one
The preparation method of the zirconium-based MOFs material comprises the following steps:
s1: to a 300ml reactor equipped with a stirrer and a reflux condenser, 50ml of a mixed solvent of water and acetic acid at a volume ratio of 3 3 ) 4 Suspending the mixed solvent, heating to 80 ℃, refluxing, and heating for 24 hours to obtain a powder product;
s2: soaking the powder product in 100ml of absolute ethyl alcohol at room temperature for three days, adding new absolute ethyl alcohol every day, and soaking the powder product soaked in the absolute ethyl alcohol in 100ml of absolute dichloromethane at room temperature for three days, adding new absolute dichloromethane every day;
s3: washing off residual reagents (ligand terephthalic acid, acetic acid, methanol and anhydrous dichloromethane) on the surface of the sample by using deionized water, centrifuging by using a centrifugal machine, pouring out the anhydrous dichloromethane after pouring out to obtain a sample, and drying the sample in a vacuum freeze dryer at the temperature of-60 ℃ for 24 hours to obtain the zirconium-based MOFs material UiO66- (OH) 2 . As shown in fig. 1.
The application method of the zirconium-based MOFs material in the embodiment comprises the following steps:
100ml of pure water was put into the reactor and placed in an ultrasonic cleaning tank, and then 15mg of UiO66- (OH) was added 2 Subsequently, ultrasonic vibration was applied to the reactor at an ultrasonic frequency of 60kHz for 5 hours. The hydrogen produced was collected every 1 h.
Example two
The preparation method of the zirconium-based MOFs material comprises the following steps:
s1: to a 300ml reactor equipped with a stirrer and a reflux condenser, 50ml of a mixed solvent of water and acetic acid in a volume ratio of 3 4 Suspending the mixed solvent, heating to 80 ℃, refluxing, and heating for 24h to obtain a powder product;
s2: soaking the powder product in 100ml of absolute ethyl alcohol at room temperature for three days, adding new absolute ethyl alcohol every day, and soaking the powder product soaked in the absolute ethyl alcohol in 100ml of absolute dichloromethane at room temperature for three days, and adding new absolute dichloromethane every day;
s3: washing away residual reagents (ligand terephthalic acid, acetic acid, methanol and anhydrous dichloromethane) on the surface of the sample by using deionized water, centrifuging by using a centrifugal machine, then separating out the anhydrous dichloromethane to obtain a sample, and drying the sample in a vacuum freeze dryer at-60 ℃ for 24 hours to obtain the zirconium-based MOFs material UiO66-F4, as shown in figure 2.
The application method of the zirconium-based MOFs material in the embodiment comprises the following steps:
100ml of pure water was charged into the reactor and placed in an ultrasonic cleaning tank, and then 20mg of UiO66-F4 was added, followed by applying ultrasonic vibration to the reactor at an ultrasonic frequency of 50kHz for 5 hours, and collecting the generated hydrogen gas every 1 hour.
FIG. 3 is a graph comparing the hydrogen production from zirconium-based MOFs in example one and example two, showing that UiO66- (OH) in example one 2 Compared with UiO66-F4 in the second embodiment, the hydrogen can be prepared, and the performance of preparing the hydrogen is higher.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention.

Claims (9)

1. The application of the zirconium-based MOFs material is characterized in that: the application method comprises the following steps:
pouring water into an ultrasonic cleaning tank, adding the zirconium-based MOFs material prepared by the preparation method of the zirconium-based MOFs material, and decomposing the water under the ultrasonic condition to prepare hydrogen;
the preparation method of the zirconium-based MOFs material comprises the following steps:
suspending ligand terephthalic acid and zirconium salt in a mixed solvent of water and acetic acid, and performing reflux heating to obtain a powder product;
sequentially soaking and cleaning the powder product by using absolute ethyl alcohol and absolute dichloromethane at room temperature;
and removing the anhydrous dichloromethane to obtain a sample, and drying the sample under a dynamic vacuum condition to obtain the MOFs material.
2. Use of zirconium based MOFs material according to claim 1, wherein: the ligand terephthalic acid and zirconium salt are suspended in a mixed solvent of water and acetic acid, and the method comprises the following steps:
to a 300ml reactor equipped with a stirrer and a reflux condenser was added 50ml of a mixed solvent of water and acetic acid in a volume ratio of 3.
3. Use of zirconium-based MOFs material according to claim 1, wherein: the ligand terephthalic acid is tetrafluoroterephthalic acid or dihydroxyterephthalic acid.
4. Use of zirconium-based MOFs material according to claim 1, wherein: the zirconium salt is Zr (NO) 3 ) 4 Or ZrCl 4 。
5. Use of zirconium based MOFs material according to any of the claims 1 to 4, wherein: the powder product is soaked and cleaned by absolute ethyl alcohol and absolute dichloromethane at room temperature in sequence, and the method comprises the following steps:
soaking the powder product in 100ml of absolute ethyl alcohol at room temperature for three days, adding new absolute ethyl alcohol every day, and soaking the powder product soaked in the absolute ethyl alcohol in 100ml of absolute dichloromethane at room temperature for three days, adding new absolute dichloromethane every day.
6. Use of zirconium based MOFs material according to any of the claims 1 to 4, wherein: the method comprises the following steps of removing anhydrous dichloromethane to obtain a sample, and drying the sample under a dynamic vacuum condition to obtain the MOFs material, wherein the steps of the method comprise:
washing away residual reagents on the surface of the sample by using deionized water, centrifuging by using a centrifugal machine, then separating out anhydrous dichloromethane to obtain a sample, and drying the sample in a vacuum freeze dryer at-60 ℃ for 24 hours to obtain the zirconium-based MOFs material.
7. Use of zirconium based MOFs material according to any of the claims 1 to 4, wherein: the zirconium-based MOFs material is in the shape of nano octahedron or nano flower particles.
8. Use of zirconium-based MOFs material according to claim 1, wherein: the ultrasonic frequency is 50-60kHz.
9. Use of zirconium based MOFs material according to claim 1, wherein: the mass fraction of the zirconium-based MOFs material is 15-20%.
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CN103316714B (en) * 2013-06-28 2015-07-15 中国石油大学(北京) Catalyst for photo-catalytically decomposing water to produce hydrogen and preparation method of catalyst
CN107614097B (en) * 2015-05-27 2020-02-14 联邦科学与工业研究组织 Production of metal-organic frameworks
CN106589398B (en) * 2016-12-06 2019-05-07 首都师范大学 A kind of zirconium class organic framework materials and its preparation method and application
CN106750356A (en) * 2017-01-10 2017-05-31 北京大学 A kind of method that metal-organic framework materials of utilization UiO 66 purify selenium-containing wastewater
CN107163258B (en) * 2017-05-31 2020-08-18 同济大学 Preparation method of metal organic framework material UiO-66 in ethanol phase
CN109354696A (en) * 2018-10-08 2019-02-19 浙江大学 A kind of preparation method of Zr-MOFs material UiO-66 (nN) (n=1 ~ 4)

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