CN106589398B - A kind of zirconium class organic framework materials and its preparation method and application - Google Patents
A kind of zirconium class organic framework materials and its preparation method and application Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- 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 the application of a kind of new function UiO-66 system zirconium organic frame catalyst material and preparation method thereof and the catalyst material in terms of visible light catalytic cracks aquatic products hydrogen.The preparation method of the zirconium class organic framework materials is comprising steps of the 1) preparation of ligand 2,5- dimethyl sulfide terephthalic acid (TPA)；With 2) zirconium class organic frame catalyst material (UiO-66 (Zr)-(SCH3)2) preparation.Preparation method according to the present invention is simple, stablizes.Obtained zirconium metal organic frame catalyst material stable structure, can be used for the optoelectronic pole material that optical electro-chemistry decomposes aquatic products hydrogen, and performance is better than the metal-organic framework material that aquatic products hydrogen is decomposed for optical electro-chemistry reported.The material can also be used for visible light catalytic and produce hydrogen, have excellent performance, and be conducive to the application in clean energy resource and environment sustainable development.
Description
Technical field
The present invention relates to the field of chemical synthesis, especially orgnometallic catalyst field, specifically, being a kind of novel function
UiO-66 system zirconium organic frame catalyst material and preparation method thereof and the catalyst material can be changed to crack in visible light catalytic
Application in terms of aquatic products hydrogen.
Background technique
Metal organic frame (metal-organic framework (MOF)) material is a kind of porous cooperation polymer, should
Class complex is by using metal ion as node, organic ligand is the frame material that skeletal support is formed.It is this kind of porous and have
The complex material of crystallographic property is because having many performances better than traditional complex to cause the extensive concern of people.The material allusion quotation
The structure feature of type and key is that have the porosity and specific surface area of superelevation.Meanwhile their structure is easy to pass through with function
Different metal ion and organic ligand is selected to be designed and regulate and control, so the material can expire and artificially designing synthesis
The various application-specific demands of foot are stored in gas, sensed, be catalyzed, led to show the controllable special performance of intelligence
Electric material etc. has great application prospect.
The advantages of UiO-66 series metal organic framework materials be it is highly stable, in water, in acid solution and high temperature
The stabilization of structure can be kept down, and therefore, which is a kind of photochemical catalyst for having great potential, has been had at present using UiO-
66 series metal organic framework materials are ground with the application after other metals or compound (photosensitizer) heterozygosis as photochemical catalyst
Study carefully, such as in document " Water Stable Zr-Benzenedicarboxylate Metal-Organic Frameworks
As Photocatalysts for Hydrogen Generation " (Claudia et al., Chem.Eur.J., 2010,16,
A kind of compound UiO-66 (NH of Zr is reported in 11133-11138)2) series metal organic framework materials, have ultraviolet
The lower ability for decomposing aquatic products hydrogen of light irradiation.
However the metal-organic framework material in currently available technology often can only be effective in ultraviolet wavelength region, and
It is weaker that water hydrogen production potential is decomposed in visible-range, or even cannot decompose water completely, and in addition metal in the prior art has machine frame
The performance of the decomposition water of frame material at any time often gradually decreases, i.e., decays at any time.
Therefore, there is still a need for exploitation decomposition water hydrogen production potential in visible-range is strong, and performance is stablized, and does not decline at any time
The novel metal-organic framework material subtracted.
Summary of the invention
In view of the above-mentioned problems of the prior art, zirconium organic frame catalyst material according to the present invention is using new
Ligand, obtain a new class of UiO-66 catalyst series material as ligand by using 2,5- dimethyl sulfide terephthalic acid (TPA)
Material, with broader optical response range, can effectively absorb visible light, to reach the mesh for improving the material light catalysis property
's.
According to an aspect of the present invention, it is an object of the present invention to provide a kind of zirconium class organic framework materials
(UiO-66(Zr)-(SCH3)2), method preparation is prepared as follows in the zirconium class organic framework materials, and the preparation method includes
Step:
1) preparation of ligand 2,5- dimethyl sulfide terephthalic acid (TPA)
By weight, 2,5- dialkyl group sulfydryl terephthalic acid (TPA) shown in 4 to 70 parts of following structural formulas (1) is weighed in anti-
It answers in device, 4 to 80 parts of acetone is then added, 80 to 250 parts of K are added after stirring2CO3With 0.3 to 2.0 part of CH3I.It stirs to face
Color from it is orange become thick yellow-white when revolving, obtain white solid, white solid be then dissolved in deionized water, be placed in ice water
It is 1 to 2 that concentrated hydrochloric acid is added dropwise in bath to reaction system pH, a large amount of yellow mercury oxides occurs, finally filters and obtain yellow solid, then with greatly
Measure deionization washing.Obtained yellow sample is placed in vacuum tank dry.
Wherein substituent R is selected from the alkyl of C1 to C6, preferably methyl, ethyl or propyl, more preferably methyl.
2) zirconium class organic frame catalyst material (UiO-66 (Zr)-(SCH3)2) preparation
By weight, 3-80 parts of zirconium chlorides, 0.1-2.0 parts of glacial acetic acid, 20 parts of N, N '-dimethyl formamide are taken
(DMF) in reactor, ultrasonic disperse to zirconium chloride dissolves, and is in colourless transparent solution.Then preparation in step 1) is weighed
Ligand 2,4-80 parts of 5- dimethyl sulfide terephthalic acid (TPA), puts among this solution, N2Protection, is put into 80-150 DEG C for reactor
Oil bath in heat 5-30h.After reaction, mixed liquor is moved in centrifuge tube, is centrifuged, obtain yellow UiO-66
(Zr)-(SCH3)2Crude product is washed with DMF, is washed again with methylene chloride after washing, and UiO-66 (Zr)-is obtained after centrifugation
(SCH3)2Naturally dry.
Selectively, the step 2) may be carried out as follows:
By weight, take 3-80 parts of zirconium chlorides, 0.1-2.0 parts of glacial acetic acid, 20 parts of DMF in stainless steel cauldron liner
In, ultrasonic disperse to zirconium chloride dissolves, and is in colourless transparent solution, is then transferred into the polytetrafluoroethylene (PTFE) bottle of solvent thermal reaction kettle
In.Then the ligand 2 prepared in step 1) is weighed, 4-80 parts of 5- dimethyl sulfide terephthalic acid (TPA) puts into stainless steel cauldron
In liner, N2Polytetrafluoro liner equipped with above-mentioned solution is packed into reaction kettle set, tightens kettle cover, be put into baking oven by protection
100-180 DEG C of reaction 5-30h.After reaction, reaction kettle is taken out, natural cooling.After cooling, mixed liquor is moved into centrifuge tube
In, it is centrifuged, obtains yellow UiO-66 (Zr)-(SCH3)2Crude product is washed with DMF, uses methylene chloride after washing again
Washing, obtains UiO-66 (Zr)-(SCH after centrifugation3)2Naturally dry.
Preferably, by weight, 2, the 5- dialkyl group mercapto in the step (1) in preparation method according to the present invention
Base terephthalic acid (TPA) is 50-70 parts, K2CO3It is 180-220 parts, CH3I is 0.7-0.9 parts；
Preferably, by weight, the zirconium chloride in the step 2) in preparation method according to the present invention is 50-
70 parts, glacial acetic acid be 1.4-1.7 parts, ligand 2,5- dialkyl sulfide terephthalic acid (TPA) is 50-70 parts；
Preferably, oil bath temperature is preferred 100-130 DEG C in the step 2) in preparation method according to the present invention, instead
Preferred 20-25h between seasonable；
Preferably, preferred 110-150 DEG C of oven temperature in the step 2) in preparation method according to the present invention, reaction
Time preferred 24-26h, the preferred 20-50ml of stainless steel cauldron liner volume.
According to another aspect of the present invention, it is an object of the present invention to provide a kind of zirconium metal organic frames to urge
Agent material.
According to another aspect of the present invention, it is an object of the present invention to provide the zirconium metal organic frames to urge
Purposes of the agent material in terms of visible light catalytic produces hydrogen.
Beneficial effect
Preparation method of the invention is simple, stablizes.Obtained zirconium metal organic frame catalyst material stable structure, can use
The optoelectronic pole material of aquatic products hydrogen is decomposed in optical electro-chemistry, performance is better than the metal that aquatic products hydrogen is decomposed for optical electro-chemistry reported
Organic framework materials.The material can also be used for visible light catalytic and produce hydrogen, have excellent performance, and being conducive to can in clean energy resource and environment
Application in sustainable development.
Detailed description of the invention
Fig. 1 is the X-ray powder diffraction figure of UiO-66 structure obtained according to embodiments of the present invention 1 and UiO-66 knot
The simulation X-ray powder diffraction figure of structure.
Fig. 2 is the X-ray powder diffraction figure of UiO-66 structure obtained according to embodiments of the present invention 2 and UiO-66 knot
The simulation X-ray powder diffraction figure of structure.
Fig. 3 be in embodiment 1 metal-organic framework material for preparing in the case that have light and it is two kinds unglazed photoelectric current it is close
Spend the comparison diagram of size.
Fig. 4 is the current time figure of the metal-organic framework material prepared in embodiment 1.
Fig. 5 is the ultraviolet-visible absorption figure of the metal-organic framework material prepared in embodiment 1.
Fig. 6 is the hydrogen output figure at any time of the metal-organic framework material prepared in embodiment 1.
Specific embodiment
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims used in term should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with technical aspect of the invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence and design of the invention each falls within the present invention
Protection scope.
Specific experimental section is as follows: for obtained sample, being characterized respectively with following instrument/technology: Rigaku
D/Max 2200PC x-ray powder diffraction instrument, 600 nuclear magnetic resonance spectroscopy of Bruker AVANCE III, electrochemical workstation
(CHI 660D), ultraviolet-uisible spectrophotometer (Cary 500scan spectrophotometers, Varian.USA) (beauty
500 scanning spectrophotometers in state's Varian card).Unless stated otherwise, the reagent used in following embodiment be it is commercially available can
Obtain product.
Embodiment 1
(1) synthesis of ligand 2,5- dimethyl sulfide terephthalic acid (TPA)
57.5mg 2 is weighed, then 5- dimercapto terephthalic acid (TPA) is added 20.0ml acetone, stirs in 50ml single-necked flask
207mg K is added after mixing2CO3, 0.5ml CH is finally added dropwise while stirring3I liquid.Stirring becomes thick to color from orange
It is rotated when yellow-white, obtains white solid, white solid is then dissolved in deionized water, be placed in ice-water bath and concentrated hydrochloric acid is added dropwise extremely
There are a large amount of yellow mercury oxides in pH=1, finally filters and obtains yellow solid, then is washed till pH=7 with a large amount of deionized waters.It will obtain
Yellow sample be placed in 60 DEG C of dryings in vacuum tank.
The nucleus magnetic hydrogen spectrum data of obtained 2,5- dimethyl sulfide terephthalic acid (TPA) are as follows:
1H NMR (400MHz, deuterated DMSO): 7.74 (s, 2H, CHAr), 2.40 (s, 6H, CH3)
It is the hydrogen on phenyl ring at 7.74, the hydrogen at 2.40 on peak position methyl, ratio 1:3, the compound illustrated
Structure is the structure of 2,5- dimethyl sulfide terephthalic acid (TPA).
(2)UiO-66(Zr)-(SCH3)2Preparation
Take zirconium chloride 58.25mg, glacial acetic acid 1.5ml, DMF 15ml in 50ml twoport flask, ultrasonic disperse to tetrachloro
Change zirconium dissolution, is in colourless transparent solution.Then weigh ligand 2,5- dimethyl sulfide terephthalic acid (TPA) 61mg, put into this solution it
In, N2Protection, flask is put into the oil bath for be preheating in advance 120 DEG C and is heated for 24 hours.After reaction, mixed liquor is moved into centrifuge tube
In, it is centrifuged, obtains yellow UiO-66 (Zr)-(SCH3)2Crude product is washed with DMF, uses dichloro again after washing three times
Methane wash centrifugation obtains UiO-66 (Zr)-(SCH afterwards three times3)2Naturally dry.
Product UiO-66 (Zr)-(SCH3)2X-ray powder diffraction figure as shown in Figure 1, wherein above curve according to
Product UiO-66 (Zr)-(SCH manufactured in the present embodiment3)2X-ray powder diffraction curve, following curve is UiO-66 structure
Simulation X-ray powder diffraction curve illustrate the product in the present embodiment from figure 1 it appears that two Curve Matchings are intact
UiO-66(Zr)-(SCH3)2With UiO-66 structure.
Embodiment 2
(1) synthesis of ligand 2,5- dimethyl sulfide terephthalic acid (TPA)
57.5mg 2 is weighed, then 5- dimercapto terephthalic acid (TPA) is added 20.0ml acetone, stirs in 50ml single-necked flask
207mg K is added after mixing2CO3, 0.5ml CH is finally added dropwise while stirring3I liquid.Stirring becomes thick to color from orange
It is rotated when yellow-white, obtains white solid, white solid is then dissolved in deionized water, be placed in ice-water bath and concentrated hydrochloric acid is added dropwise extremely
There are a large amount of yellow mercury oxides in PH=1, finally filters and obtains yellow solid, then is washed till PH=7 with a large amount of deionized waters.It will obtain
Yellow sample be placed in 60 DEG C of dryings in vacuum tank.
(2)UiO-66(Zr)-(SCH3)2Preparation
Take zirconium chloride 58.25mg, glacial acetic acid 1.5ml, DMF 15ml in 50ml flask, ultrasonic disperse to zirconium chloride
Dissolution is in colourless transparent solution, is then transferred into the polytetrafluoroethylene (PTFE) bottle of solvent thermal reaction kettle.Then ligand 2,5- bis- is weighed
Dimethyl sulfide terephthalic acid (TPA) 61mg is put into stainless steel cauldron liner, N2Protection, will be in the polytetrafluoro equipped with above-mentioned solution
Lining is packed into reaction kettle set, tightens kettle cover, is put into baking oven and is reacted for 24 hours for 120 DEG C.After reaction, reaction kettle is taken out, it is naturally cold
But.After cooling, mixed liquor is moved in centrifuge tube, is centrifuged, yellow UiO-66 (Zr)-(SCH is obtained3)2Crude product uses DMF
It is washed, is washed three times with methylene chloride again after washing three times, UiO-66 (Zr)-(SCH is obtained after centrifugation3)2Naturally dry.
Product UiO-66 (Zr)-(SCH3)2X-ray powder diffraction figure as shown in Fig. 2, wherein above curve according to
Product UiO-66 (Zr)-(SCH manufactured in the present embodiment3)2X-ray powder diffraction curve, following curve is UiO-66 structure
Simulation X-ray powder diffraction curve illustrate the product in the present embodiment from figure 2 it can be seen that two Curve Matchings are intact
UiO-66(Zr)-(SCH3)2With UiO-66 structure.
Testing example:
1, optical electro-chemistry decomposes the reaction of water
(1) preparation of working electrode:
At room temperature, by tin oxide transparent conductive glass (FTO) substrate of Fluorin doped (length is 2 centimetres, and width is 1 centimetre)
It is cleaned with acetone and deionized water, later by FTO substrate with being dried with nitrogen.
The metal-organic framework material 10mg prepared in embodiment 1 is distributed in 1ml ethyl alcohol, suspension is formed.With drop
Pipe draws above-mentioned suspension, is added drop-wise on FTO substrate conducting surface, FTO substrate is placed in 60 degree of baking ovens and is dried, and repeats the above step
Suddenly three times.
(2) measurement of PhotoelectrochemicalProperties Properties:
Optical electro-chemistry produces hydrogen by electrochemical workstation (CHI 660D) in 0.5M H2SO4(pH=0) it is surveyed in aqueous solution
Density of photocurrent is measured to carry out.Photoelectric current is stronger, illustrates that the efficiency for decomposing aquatic products hydrogen is higher.During the test, by above-mentioned steps
1) the FTO substrate prepared in is used as working electrode, gauze platinum electrode to electrode, and mercury-mercurous sulfate electrode is as reference electrode.
In experimentation, with 350W xenon lamp provide illumination light source (400-800 nanometers of wavelength, intensity 50mW/cm2), then carry out electricity
The linear voltammetric scan of chemistry.
Fig. 3 is the metal-organic framework material (UiO-66 (Zr)-(SCH prepared in embodiment 13)2) there are light and unglazed two
The comparison diagram of the size of density of photocurrent in the case of kind.From comparison it can be seen that the metal prepared under illumination condition has machine frame
Frame material can effectively generate photoelectric current.
Fig. 4 is the current time figure of the metal-organic framework material prepared in embodiment 1, and switching in every 20 seconds has light in test
And no light condition, to measure the variation of electric current, as can be seen from the figure the material can generate stable photoelectric current, not at any time
Decaying, illustrates photoelectric properties excellent in stability.
Fig. 5 is the ultraviolet-visible absorption figure of metal-organic framework material prepared in embodiment 1, compared to reporting in document
The material of the amino in road has stronger absorption in visible region.
2, Photocatalyzed Hydrogen Production reacts
It disperses the metal-organic framework material prepared in 50mg embodiment 1 in 80ml aqueous solution (containing CH3OH
H 20vol%) is added2PtCl6(Pt 1.0wt%)；It is cold under 77K liquid nitrogen temperature to remove dissolved oxygen；6 DEG C of recirculated water coolings keep temperature
Degree；Stirring；With 350W xenon lamp provide illumination light source (400-800 nanometers of wavelength, intensity 50mW/cm2)；Hydrogen output test makes
With GC real-time monitoring, using argon gas as carrier gas.
Fig. 6 is the hydrogen output figure at any time of the metal-organic framework material prepared in embodiment 1, wherein produces hydrogen speed
Rate is about 19 μm of ol/g/h.And under similarity condition, document " Water Stable Zr-Benzenedicarboxylate
Metal-Organic Frameworks as Photocatalysts for Hydrogen Generation " (Claudia etc.
People, Chem.Eur.J., 2010,16,11133-11138) in report amino modified metal-organic framework material in visible light
Under can not generate hydrogen.This is primarily due to be used in the present invention sulfydryl terephthalic acid (TPA) as ligand, and the prior art is adopted
Use amino terephthalic acid (TPA) as ligand, the sulfydryl terephthalic acid (TPA) as ligand may be to the band gap of metal-organic framework material
It causes to change, therefore causes different in the absorbability of visible light.
Claims (10)
1. a kind of zirconium class organic framework materials UiO-66 (Zr)-(SCH3)2Preparation method, the preparation method comprising steps of
1) preparation of ligand 2,5- dimethyl sulfide terephthalic acid (TPA)
By weight, 2,5- dialkyl group sulfydryl terephthalic acid (TPA) shown in 4 to 70 parts of following structural formulas (1) is weighed in reactor
In, 4 to 80 parts of acetone are then added, 80 to 250 parts of K are added after stirring2CO3With 0.3 to 2.0 part of CH3I, stirring to color by
It is orange to become revolving when thick yellow-white, white solid is obtained, white solid is then dissolved in deionized water, is placed in ice-water bath
It is 1 to 2 that concentrated hydrochloric acid, which is added dropwise, to reaction system pH, a large amount of yellow mercury oxides occurs, finally filters and obtain yellow solid, then with largely going
Obtained yellow sample is placed in drying in vacuum tank by ion washing,
Wherein substituent R is selected from the alkyl of C1 to C6；
2) zirconium class organic frame catalyst material UiO-66 (Zr)-(SCH3)2Preparation
By weight, take 3-80 parts of zirconium chlorides, 0.1-2.0 parts of glacial acetic acid, 20 parts of N, N '-dimethyl formamide (DMF) in
In reactor, ultrasonic disperse to zirconium chloride dissolves, and is in colourless transparent solution, then weighs the ligand 2,5- prepared in step 1)
It 4-80 parts of dimethyl sulfide terephthalic acid (TPA), puts among this solution, N2Protection, reactor is put into 80-150 DEG C of oil bath
Heating 5-30h after reaction moves to mixed liquor in centrifuge tube, is centrifuged, obtains yellow UiO-66 (Zr)-(SCH3)2
Crude product is washed with DMF, is washed again with methylene chloride after washing, and UiO-66 (Zr)-(SCH is obtained after centrifugation3)2Naturally it dries in the air
It is dry.
2. the preparation method of zirconium class organic framework materials according to claim 1, which is characterized in that in structural formula (1)
Substituent R is methyl, ethyl or propyl.
3. the preparation method of zirconium class organic framework materials according to claim 1, which is characterized in that in structural formula (1)
Substituent R is methyl.
4. the preparation method of zirconium class organic framework materials according to claim 1, which is characterized in that the step 2) is as follows
It carries out:
By weight, take 3-80 parts of zirconium chlorides, 0.1-2.0 parts of glacial acetic acid, 20 parts of DMF in stainless steel cauldron liner,
Ultrasonic disperse to zirconium chloride dissolves, and is in colourless transparent solution, is then transferred into the polytetrafluoroethylene (PTFE) bottle of solvent thermal reaction kettle.
Then the ligand 2 prepared in step 1) is weighed, 4-80 parts of 5- dimethyl sulfide terephthalic acid (TPA) puts into stainless steel cauldron liner
In, N2Polytetrafluoro liner equipped with above-mentioned solution is packed into reaction kettle set, tightens kettle cover, be put into 100-180 in baking oven by protection
DEG C reaction 5-30h after reaction takes out reaction kettle, and natural cooling moves to mixed liquor in centrifuge tube after cooling, carries out
Centrifugation, obtains yellow UiO-66 (Zr)-(SCH3)2Crude product is washed with DMF, is washed again with methylene chloride after washing, from
UiO-66 (Zr)-(SCH is obtained after the heart3)2Naturally dry.
5. the preparation method of zirconium class organic framework materials according to claim 1, which is characterized in that by weight, institute
Stating 2, the 5- dialkyl group sulfydryl terephthalic acid (TPA) in step (1) is 50-70 parts, K2CO3It is 180-220 parts, CH3I is 0.7-0.9
Part.
6. the preparation method of zirconium class organic framework materials according to claim 1, which is characterized in that by weight, institute
State that the zirconium chloride in step 2) is 50-70 parts, glacial acetic acid is 1.4-1.7 parts, ligand 2,5- dialkyl sulfide terephthalic acid (TPA)
It is 50-70 parts.
7. the preparation method of zirconium class organic framework materials according to claim 1, which is characterized in that oily in the step 2)
Bath temperature is 100-130 DEG C, reaction time 20-25h.
8. the preparation method of zirconium class organic framework materials according to claim 1, which is characterized in that dried in the step 2)
Box temperature degree is 110-150 DEG C, reaction time 24-26h, reactor volume 20-50ml.
9. a kind of zirconium metal organic frame catalyst material, which is characterized in that the zirconium metal organic frame catalyst material root
It is prepared according to preparation method described in any one of claim 1 to 8.
10. the purposes that the zirconium metal organic frame catalyst material according to claim 9 produces hydrogen in visible light catalytic.
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| CN109096498B (en) * | 2018-08-27 | 2021-08-13 | 广东工业大学 | Two-dimensional conductive metal organic framework material and preparation method thereof |
| CN109265702B (en) * | 2018-11-01 | 2020-11-13 | 广东工业大学 | Sulfonic acid functionalized zirconium-based metal organic framework material, and preparation method and application thereof |
| CN109731602A (en) * | 2019-01-15 | 2019-05-10 | 宁德师范学院 | Surfactant/UiO-66-NH2Composite photo-catalyst and preparation method thereof |
| CN110560172A (en) * | 2019-09-17 | 2019-12-13 | 南开大学 | Zirconium metal organic framework heterojunction material with photocatalytic performance and preparation method thereof |
| CN111019147A (en) * | 2019-09-29 | 2020-04-17 | 昆明理工大学 | Metal organic framework adsorbent, one-step preparation method and application thereof |
| CN111056530B (en) * | 2019-12-27 | 2021-10-22 | 武汉大学 | Method for producing hydrogen by photocatalytic nitrogen-containing heterocyclic compound |
| CN113036161A (en) * | 2021-02-07 | 2021-06-25 | 同济大学 | MOF-based platinum monatomic catalyst, preparation and application |
| CN113019458A (en) * | 2021-03-22 | 2021-06-25 | 上海师范大学 | Preparation method and application of UV-Vis-NIR wide spectral response functionalized MOF catalyst |
| CN113912861B (en) * | 2021-11-15 | 2023-04-11 | 佛山(华南)新材料研究院 | Preparation method and application of zirconium-based MOFs (metal-organic frameworks) material |
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| CN104857988A (en) * | 2015-05-07 | 2015-08-26 | 盐城工学院 | Heteropolyacid-modified Zr-MOF catalyst as well as preparation method and application thereof |
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