CN108607512A - The method of the sulfide modified MOF materials of molybdenum base - Google Patents
The method of the sulfide modified MOF materials of molybdenum base Download PDFInfo
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- CN108607512A CN108607512A CN201810299276.2A CN201810299276A CN108607512A CN 108607512 A CN108607512 A CN 108607512A CN 201810299276 A CN201810299276 A CN 201810299276A CN 108607512 A CN108607512 A CN 108607512A
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- molybdenum base
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- sulfide
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- 239000000463 material Substances 0.000 title claims abstract description 57
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 46
- 239000011733 molybdenum Substances 0.000 title claims abstract description 46
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000013110 organic ligand Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- -1 thio ammonium molybdate Chemical compound 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical class CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 claims 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 49
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 37
- 239000001569 carbon dioxide Substances 0.000 abstract description 23
- 238000001179 sorption measurement Methods 0.000 abstract description 20
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- 239000011148 porous material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 32
- 229960004424 carbon dioxide Drugs 0.000 description 20
- 239000013136 MOF-253 Substances 0.000 description 11
- 239000013208 UiO-67 Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000004088 simulation Methods 0.000 description 6
- 229910003185 MoSx Inorganic materials 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910019964 (NH4)2MoS4 Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 125000000101 thioether group Chemical group 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910007932 ZrCl4 Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013310 covalent-organic framework Substances 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/204—Metal organic frameworks (MOF's)
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of methods of the sulfide modified MOF materials of molybdenum base, belong to the preparing technical field of Inorganic-organic Hybrid Material.The method is that immobilized molybdenum base sulfide obtains the modification MOF materials containing monodisperse molybdenum base sulfide active center on MOF skeletons.In obtained modified MOF materials, molybdenum base sulfide is immobilized on by coordination on MOF skeletons, is in monodisperse status, is effectively increased chemical adsorption capacity and selectivity of the MOF materials to carbon dioxide, have higher chemisorption energy in low pressure range.The sulfide modified method of molybdenum base of the present invention has the versatility for porous material, while improving the adsorption capacity of carbon dioxide, the chemisorption energy for enhancing carbon dioxide has industrialization prospect in the associated catalytic conversion field of gas absorption separation and carbon dioxide.
Description
Technical field
The present invention relates to a kind of modified CO for improving MOF2The method of absorption property, belongs to Inorganic-Organic Hybrid Material
Preparing technical field.
Background technology
The trapping and utilization of carbon dioxide are control CO2Discharge, reduces the important means of greenhouse effects.It is arranged as carbon in China
Amplify state, how to reduce CO2Emission problem seems particularly urgent.Reduce CO2Discharge mainly passes through two class technical solutions, Yi Leishi
CO2Trapping and Plugging Technology Applied (carbon capture and storage, CCS) will be generated by carbon trapping in industrial production
CO2 detach and seal up for safekeeping；Another kind of is CO2Trapping and using technology (carbon capture and utilization,
CCU), CO separation and collection gone out2Carbon source is further used as to prepare industrial chemicals and high valuable chemicals.Both technologies
In scheme, to CO2It is premise to carry out effective trapping.Absorption method trapping separation CO2It is the method for relatively inexpensive property, and improves material
Material is to CO2Adsorbance and adsorption energy be crucial.In recent years, the appearance of some novel porous materials such as MOFs and COFs materials is big
CO is widened greatly2The range of choice of adsorbent, this porous polymer material have aperture adjustable, and large specific surface area is easy to repair
The advantages of decorations.For CO2Adsorption applications can be improved by improving the specific surface area of MOFs and COFs materials to CO2High pressure
Adsorbance, however this method is to the CO under lower pressure2No clear superiority is adsorbed, introducing suitable active group can have
Effect is improved to CO2Selective absorption effect, it is common such as amido, the groups such as mercaptan.
MoS2Material has extensive research in fields such as battery, lubrication and catalysis, have theoretical calculation recently studies have shown that
Single layer MoS with defects2It is good absorbable substrate, has higher chemisorption to carbon dioxide
(Phys.Chem.Chem.Phys.,2015,17,11700-11704)。(NH4)2MoS4It is to prepare MoS2Precursor, in two-dimensional layer
Have in shape plane and MoS2Similar structure, seminar of Northwestern Univ USA is by molybdenum base sulfide (NH4)2MoS4Gel is made
MoSx, after supercritical carbon dioxide exchanges, its specific surface area can be improved to 370m2/ g, at 273K, the CO of MoSx gels2
Adsorbance is about 0.7mmol/g, to CO under zero coverage rate2Heat of adsorption QstAbout 13kJ/mol
(J.Am.Chem.Soc.2015,137,13943-13948).Heat of adsorption is evaluation material to the important of carbon dioxide adsorption performance
The more strong then heat of adsorption of the active force of index, material and carbon dioxide is bigger.
Invention content
The present invention is to improve porous material to CO2Absorption property for the purpose of, it is desirable to provide a kind of side of modified MOF materials
Method is simultaneously further obtained with excellent CO2Absorption property material.
Present invention firstly provides a kind of method of the sulfide modified MOF materials of molybdenum base, this method is immobilized on MOF skeletons
Molybdenum base sulfide obtains the modification MOF materials containing monodisperse molybdenum base sulfide active center.This method can effectively improve MOF
The chemisorption of material and carbon dioxide.And the method for modifying of the present invention has certain universality, preparation method letter
Single flexible, the carbon dioxide adsorption of the modified MOF materials containing azacyclo- can increase.
On the other hand, the present invention provides a kind of MOF materials that the molybdenum base prepared by the above method is sulfide modified.Through upper
The modified MOF materials of method are stated, specific surface area is 200~2500m2/ g, Mo/MOF molar ratio are 0.15~3, Ke Yigao
Effect ground absorption carbon dioxide.
Therefore, the sulfide modified MOF materials of the molybdenum base of another aspect of the present invention offer aforementioned present invention are in carbon dioxide
Application in absorption.
Description of the drawings
Fig. 1 is Example 1 and Example 2 of the present invention preparation-obtained MOF-253 and MOF-253-MoS4X-ray spread out
The xrd spectrograms for penetrating spectrogram and standard MOF-253 structural simulations compare.
Fig. 2 is 4 preparation-obtained UiO-67 and UiO-67-MoS of the embodiment of the present invention 3 and embodiment4X-ray diffraction
The xrd spectrograms of spectrogram and standard UiO-67 structural simulations compare.
Fig. 3 is COs of MOF-253 under the conditions of 273K in the embodiment of the present invention 5 before and after immobilized MoSx components2Absorption etc.
Warm line.
Fig. 4 is COs of UiO-67 under the conditions of 273K in the embodiment of the present invention 5 before and after immobilized MoSx components2Adsorption isotherm
Line.
Fig. 5 is suction of the carbon dioxide on the UiO-67 and MOF-253 before and after immobilized MoSx components in the embodiment of the present invention 5
The attached hot variation with adsorbance.
Specific implementation mode
The present invention provides a kind of method of the sulfide modified MOF materials of molybdenum base, and this method is the immobilized molybdenum base on MOF skeletons
Sulfide obtains the modification MOF materials containing monodisperse molybdenum base sulfide active center.
In specific embodiment, the method for aforementioned present invention includes the steps that preparing MOF materials, material liquid with material liquid
In contain organic ligand and metal salt, molybdenum base sulphide precursor used in modified MOF materials can mix MOF and prepare material liquid
In, the form that can also be later modified after the completion of MOF materials synthesis is modified MOF materials.I.e. above-mentioned with raw material
Liquid was prepared in the step of MOF materials, further included the operation of following a or b：
A. molybdenum base sulphide precursor is added into the material liquid, alternatively,
B. the MOF materials synthesized are contacted with molybdenum base sulphide precursor.
In the specific technical solution of any one of the above, the molybdenum base sulphide precursor is four thio ammonium molybdate.
In the above-mentioned modified operation to MOF materials, the organic ligand in MOF synthesis material liquid specifically can be selected from comprising such as formula
The 2 of I, the chelate structure of 2 '-bipyridyls, wherein R1And R2Respectively it is individually selected from-COOH ,-CN ,-OH ,-B (OH)2,-CHO ,-
PO(OH)2Or-NH2；Metal salt in MOF synthesis material liquid specifically can be selected from the salt of transition metal, boron family's metal and lanthanide series metal
Class, preferably zirconates, aluminium salt, gallium salt or molysite.
More specifically in embodiment, the operation of synthesis and the modification of MOF materials is completed above by one-step synthesis
In, that is, include the step a technical solution in, the molar ratio of the molybdenum base sulphide precursor and organic ligand is 0.05~
1.The technical solution can further be specifically described as the method included the following steps：By molybdenum base sulphide precursor, organic ligand
And metal salt ultrasonic disperse is in organic solvent, in 110~160 DEG C of 8~120h of confined reaction；Reaction system is cooled to room temperature
Afterwards, it filters, washing obtains powder sample；With organic solvent dispersion, 40~80 DEG C are stirred 1~3 hour, then through Soxhlet extractor
Extracting 12-24 hours；Products therefrom drying activation；Wherein the organic solvent is selected from N,N-dimethylformamide (DMF), N,
Or mixtures thereof N- diethylformamides (DEF), DMAC N,N' dimethyl acetamide (DMA), dioxane, dimethyl sulfoxide (DMSO)；It is described
Solvent used in Soxhlet extractor is methanol or ethyl alcohol.
In another specific embodiment, above by first synthesizing in the then operation of modification of MOF materials, that is, include
In the technical solution of the step b, the molar ratio of the molybdenum base sulphide precursor and organic ligand is 0.1~1.The technical side
Case can further be specifically described as the method included the following steps：By organic ligand and metal salt ultrasonic disperse in organic solvent
In, in 110~160 DEG C of 8~120h of confined reaction；It after reaction system is cooled to room temperature, filters, washing obtains powder sample；It will
Gained powder sample is scattered in molybdenum base sulphide precursor solution, and 40~80 DEG C of heating stirrings 1~3 hour are filtered, washed and do
Dry activation；Wherein the solvent of the molybdenum base sulphide precursor solution is selected from water, dichloromethane or chloroform.
The modification MOF materials obtained by above-mentioned technical proposal, after measured, provable molybdenum base sulfide are successfully embedded in
Into crystalline framework, do not change crystal structure；And it is proved by adsorptivity testing experiment, it is sulfide modified effectively by molybdenum base
The chemisorption improved between adsorbent and carbon dioxide, substantially increase adsorbance.
Beneficial effects of the present invention are further described with reference to specific embodiment, but should not be construed as to this hair
The bright any type of restriction of content.
Embodiment 1
A kind of metal-organic framework materials MOF-253, preparation method are as follows：
AlCl3·6H2O (0.5g), H2Bpydc (0.5g), DEF (50mL).Above-mentioned drug is weighed to be added in 150mL flasks,
Magnetic agitation 30min at room temperature, 140 DEG C of oil bath heatings are for 24 hours.It is cooled to room temperature, filters, DMF is washed three times.100 DEG C of air blast are dry
Dry, for 24 hours, it is MOF-253 to collect white solid to obtained solid Soxhlet extraction.Pass through xray diffraction characterization and and single-crystal x
The standard spectrogram of ray diffraction data simulation compares, it was demonstrated that synthesizes successfully (Fig. 1).Low temperature nitrogen physical absorption measures its BET ratio
Surface area is as shown in table 1, is 1363m2/g。
Table 1
Embodiment 2
A kind of MOF-253 materials that molybdenum base is sulfide modified, preparation method are as follows：
Weigh four thio ammonium molybdate ((NH4)2MoS4) 0.1g, it is dissolved in 50ml dichloromethane, is added made from embodiment 1
MOF-2530.5g, 50 degree of lower constant temperature stir 3h.1 is cooled to room temperature, and filtering, DMF is washed three times.100 DEG C of forced air dryings are collected
Brown solid is denoted as MOF-253-MoS4.Pass through xray diffraction characterization and the mark with single-crystal x x ray diffraction digital simulation
Quasi- spectrogram compares, it was demonstrated that molybdenum base sulfide is successfully embedded into crystalline framework, does not change crystal structure (Fig. 1).Low temperature nitrogen object
It is as shown in table 1 that reason absorption measures its BET specific surface area, is 546m2/g。
Embodiment 3
A kind of metal-organic framework materials UiO-67, preparation method are as follows：Weigh 0.245g ZrCl4It is added to 150ml
In round-bottomed flask, 50ml N ' dinethylformamides (DMF), ultrasound to ZrCl is then added4It is completely dissolved.Then it is added
0.26g 2,2 '-bipyridyls -5,5 '-dioctyl phthalate (H2Bpydc), ultrasonic 20min, the lower 120 DEG C of oil baths reaction of magnetic agitation is for 24 hours.
It is cooled to room temperature, centrifuges, take solid product, 50ml DMF, the lower 80 DEG C of reactions 3h of stirring is added.It is cooled to room temperature, centrifuges, with nothing
Water-ethanol washs (3 × 10ml), and 100 DEG C are dried overnight, and UIO-67 is made.It is characterized by xray diffraction and is penetrated with single-crystal x
The standard spectrogram of line diffraction data simulation compares, it was demonstrated that synthesizes successfully (Fig. 2).Low temperature nitrogen physical absorption measures its BET and compares table
Area is as shown in table 1, is 1900m2/g。
Embodiment 4
A kind of UiO-67 materials that molybdenum base is sulfide modified, preparation method are as follows：Weigh 0.1g ZrCl4、
0.1gH2Bpydc, 0.05g four thio ammonium molybdate ((NH4)2MoS4), be added 10ml DMF, ultrasonic dissolution disperse 20min, will mix
It closes object to be transferred in reaction kettle, stands heating 72h at 130 DEG C after closed, obtained dark brown solid uses DMF and anhydrous respectively
Ethyl alcohol washes twice, and is dried overnight at 100 DEG C, and the sulfide modified UiO-67 materials of molybdenum base are made, are denoted as UiO-67-MoS4。
Characterized by xray diffraction and compared with the standard spectrogram of single-crystal x x ray diffraction digital simulation, it was demonstrated that molybdenum base sulfide at
Work(is embedded into crystalline framework, does not change crystal structure (Fig. 2).Low temperature nitrogen physical absorption measures its BET specific surface area such as table 1
It is shown, it is 734m2/g。
Embodiment 5
Test object of the present invention is MOF-253, MOF-253-MoS prepared by Claims 1 to 44, UiO-67 and UiO-
67-MoS4。
The adsorption assessment device of carbon dioxide is the physical adsorption appearance (Autosorb-1) of Kang Ta companies of the U.S. in the present invention,
Sample is fully activated to after deaerating (120 DEG C vacuumize overnight), is passed through pure carbon dioxide gas under the conditions of 273K and 298K respectively
Body measures the variation of pressure in sample cell, is used to the isothermal adsorption capacity of pure gas to obtain adsorbent under different partial pressures
Langmuir-Freundlich models are fitted the adsorption isotherm data of carbon dioxide at different temperatures, and by two
Variation between carbonoxide heat of adsorption on the sorbent and equilibrium adsorption capacity is associated.
As shown in Figure 3 and Figure 4, the immobilized molybdenum base sulfur-containing compounds of MOF-253 and UiO-67 are measured using surface analysis instrument
The front and back carbon dioxide gas adsorption property at 273K, in low pressure stage, MOF-253 and UiO-67 are sulfide modified through molybdenum base
Afterwards, the adsorbance of carbon dioxide increases significantly, wherein MOF-253-MoS4Unit area adsorbance is improved to improve to changing
2.2 times before property, UiO-67-MoS4Unit area adsorbance is improved to 1.4 times before modified.Using Langmuir-
Freundlich models calculate before modified after carbon dioxide heat of adsorption (Fig. 5) on the adsorbent material, the results showed that dioxy
Change carbon in MOF-253-MoS4And UiO-67-MoS4Heat of adsorption on material is above MOF-253 and UiO-67 before modified,
Middle MOF-253-MoS4The heat of adsorption for adsorbing carbon dioxide is maximum.Illustrate that immobilized sulfur-containing compound can effectively improve adsorbent
Chemisorption between carbon dioxide.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. the method for the sulfide modified MOF materials of molybdenum base, which is characterized in that be that immobilized molybdenum base sulfide obtains on MOF skeletons
Modification MOF materials containing monodisperse molybdenum base sulfide active center.
2. according to the method described in claim 1, including the steps that preparing MOF materials with material liquid, contain in material liquid organic
Ligand and metal salt, which is characterized in that further include following step：
A. molybdenum base sulphide precursor is added into the material liquid, alternatively,
B. the MOF materials synthesized are contacted with molybdenum base sulphide precursor.
3. according to the method described in claim 2, it is characterized in that, the molybdenum base sulphide precursor is four thio ammonium molybdate.
4. according to the method described in claim 2, it is characterized in that, the organic ligand includes 2, the 2 '-bipyridyls such as Formulas I
Chelate structure, wherein R1And R2Respectively it is individually selected from-COOH ,-CN ,-OH ,-B (OH)2,-CHO ,-PO (OH)2Or-NH2。
5. according to the method described in claim 2, it is characterized in that, the metal salt be selected from transition metal, boron family's metal and
The salt of lanthanide series metal.
6. according to the method described in claim 2, it is characterized in that, molybdenum base sulphide precursor is matched with organic in the step a
The molar ratio of body is 0.05~1.
7. according to the method described in claim 6, it is characterised in that it includes following steps：By molybdenum base sulphide precursor, You Jipei
Body and metal salt ultrasonic disperse are in organic solvent, in 110~160 DEG C of 8~120h of confined reaction；Reaction system is cooled to room temperature
Afterwards, it filters, washing obtains powder sample；With organic solvent dispersion, 40~80 DEG C are stirred 1~3 hour, then through Soxhlet extractor
Extracting 12-24 hours；Products therefrom drying activation；
Wherein the organic solvent is selected from N,N-dimethylformamide (DMF), N, N- diethylformamides (DEF), N, N- bis-
Or mixtures thereof methylacetamide (DMA), dioxane, dimethyl sulfoxide (DMSO)；
Solvent used in the Soxhlet extractor is methanol or ethyl alcohol.
8. according to the method described in claim 2, it is characterized in that, molybdenum base sulphide precursor is matched with organic in the step b
The molar ratio of body is 0.1~1.
9. according to the method described in claim 8, it is characterised in that it includes following steps：By organic ligand and metal salt ultrasound
It is scattered in organic solvent, in 110~160 DEG C of 8~120h of confined reaction；It after reaction system is cooled to room temperature, filters, wash
To powder sample；Gained powder sample is scattered in molybdenum base sulphide precursor solution, 40~80 DEG C of heating stirrings 1~3 hour,
It filters, wash and drying activates；
Wherein the solvent of the molybdenum base sulphide precursor solution is selected from water, dichloromethane or chloroform.
10. the sulfide modified MOF materials of the molybdenum base of method preparation described in claim 1.
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