CN110183677A - The mesoporous Ru-MIL-125-NH prepared using supercritical fluid2Catalyst - Google Patents
The mesoporous Ru-MIL-125-NH prepared using supercritical fluid2Catalyst Download PDFInfo
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- CN110183677A CN110183677A CN201910479867.2A CN201910479867A CN110183677A CN 110183677 A CN110183677 A CN 110183677A CN 201910479867 A CN201910479867 A CN 201910479867A CN 110183677 A CN110183677 A CN 110183677A
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- 239000000463 material Substances 0.000 claims abstract description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000007146 photocatalysis Methods 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 14
- 229910019891 RuCl3 Inorganic materials 0.000 claims abstract description 13
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims abstract description 13
- 229910009112 xH2O Inorganic materials 0.000 claims abstract description 13
- 239000012530 fluid Substances 0.000 claims abstract description 9
- 239000012621 metal-organic framework Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 238000001291 vacuum drying Methods 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 description 10
- 238000002336 sorption--desorption measurement Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004773 frontier orbital Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- 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]
-
- B01J35/39—
-
- B01J35/617—
-
- B01J35/618—
-
- B01J35/635—
-
- B01J35/647—
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- 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
- B01J2531/46—Titanium
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a kind of mesoporous Ru-MIL-125-NH prepared using supercritical fluid2Catalyst.The mesoporous Ru-MIL-125-NH2Material is the MIL-125-NH by will prepare2And RuCl3·xH2O is added in methanol according to feed ratio, is stirred at room temperature to being uniformly mixed, is passed through the carbon dioxide of certain pressure, reacts 5 hours at 200 DEG C.After being cooled to room temperature, carbon dioxide in reaction kettle is removed by way of pressure release, with N, dinethylformamide (DMF) and methanol wash obtained precipitating, then the product that centrifugation obtains is placed in a vacuum drying oven to the DMF and methanol for removing remaining, drying temperature is 80 DEG C, obtains mesoporous Ru-MIL-125-NH after 24 hours dry2Catalyst material.The material has preferable catalytic activity to photocatalysis water-splitting.
Description
Technical field
The invention belongs to Material Fields, are related to a kind of mesoporous Ru-MIL-125-NH prepared using supercritical fluid2Catalysis
Agent.
Background technique
Metal-organic framework (MOFs) material is that a kind of metal ion or metal cluster are formed by connecting by organic ligand
One polyporous materials.This kind of compound has regulatable microstructure, higher porosity and biggish specific surface area etc. excellent
Good characteristic, these unique properties have it in terms of the fields such as gas storage, the purification separation of gas, heterogeneous catalysis
It is widely applied.Especially since it is with programmable metal oxygen cluster and organic ligand and its higher porosity, MOFs
There is relatively broad application prospect in terms of catalysis material.But the activity based on itself is lower, and MOFs material is as urging
The application aspect of agent nevertheless suffers from very big limitation.Generally, by the way that metal precursor is reduced into metal nanoparticle dispersion
This problem is solved in the outer surface of MOFs solid.But metal nanoparticle metal/MOFs composite catalyst surface not
Evitable to assemble, so as to cause the reduction of catalytic activity, the stability of catalyst is greatly reduced.In order to improve
The photocatalysis performance and stability of MOFs material need to have the metal-modified of catalytic activity in the inner hole of MOFs.However,
It is still a huge challenge since the pore size (~1nm) of MOF is very small.
Summary of the invention
The object of the present invention is to provide a kind of mesoporous Ru-MIL-125-NH prepared using supercritical fluid2Catalyst.
It is provided by the invention to prepare mesoporous Ru-MIL-125-NH2The method of material, comprising: be with MOF material and metal salt
Raw material is made using the method for supercritical fluid.
In the method for supercritical fluid described in the above method, reaction medium used is supercritical carbon dioxide；
The metal salt is RuCl3·xH2O；
The MOFs material is MIL-125-NH2。
In the method for the supercritical fluid, the mass ratio of the MOFs material and metal salt is 100:1-10；Specially
100:5；
Reaction temperature is 120-200 DEG C；Specially 200 DEG C；
Time is 1-9h；Specially 1,3,5,6 or 9 hour；
Reaction pressure is 1-6MPa；Specially 5.58MPa；
Solvent for use is selected from least one of methanol, ethyl alcohol and acetone.
In addition, the mesoporous Ru-MIL-125-NH being prepared according to the method described above2Material also belongs to protection of the invention
Range.
Above-mentioned mesoporous Ru-MIL-125-NH2The specific surface area of material is 900-1300m2g-1；Total pore volume is 0.5-
0.8cm3g-1；Mesoporous partial size is 3-10nm；Specially 3.8nm；The content of Ru is 0.95wt%-1.75wt%.
In addition, the mesoporous Ru-MIL-125-NH that aforementioned present invention provides2Application of the material as catalyst in photocatalysis
And contain the mesoporous Ru-MIL-125-NH2The catalyst of material, also belongs to protection scope of the present invention.
Wherein, concretely photocatalysis water-splitting is reacted for the photocatalysis；
In the photocatalysis water-splitting reaction, the wavelength of light source used is greater than 420nm；Power is 150-500W；Specially
300W；
Light source used is specially xenon lamp.
The catalyst is photochemical catalyst or the catalyst that photocatalysis water-splitting is reacted.
Mesoporous Ru-MIL-125-NH is prepared the present invention provides a kind of2Method.This method utilizes supercritical carbon dioxide
The characteristics of permeability with higher and water can form carbonic acid is prepared for high mesoporous in supercritical carbon dioxide reaction medium
Ru-MIL-125-NH2Material.By controlling the reaction time, it can effectively change Ru-MIL-125-NH2Ru's in material contains
Amount and Ru-MIL-125-NH2Specific surface area and pore volume.This method solve the low method of MOFs material catalytic effect,
Less amount of Ru element is introduced into the skeleton of MOF material by the effect of coordination, to improve its photocatalysis water-splitting
Reactivity.
The high mesoporous ruthenium coordination MOFs material of gained of the invention has the advantage that
1)Ru3+Ion interacts with the ligand in MOF, changes the energy and component of frontier molecular orbital, favorably
In the progress of photocatalysis water-splitting reaction；
2) visible light absorption capacity of MOF material is improved；
3) Ru-MOF material has high meso-hole structure, increases active site, while promoting the diffusion of substrate and product.
Therefore, which shows excellent catalytic activity in terms of photocatalysis water-splitting.
Detailed description of the invention
Fig. 1 is MIL-125-NH2(a, c) and Ru-MIL-125-NH2Scanning, transmission electron microscope and the XRD spectrum (f) of (b, d)；
Ru-MIL-125-NH2Distribution diagram of element (e).Scale: 1 μm, (c, d) 500nm, (e) 200nm of (a, b).
Fig. 2 is MIL-125-NH2And Ru-MIL-125-NH2N2Adsorption-desorption inhales thermoisopleth (a) and pore size distribution curve
(b)。
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The raw material can obtain unless otherwise instructed from public commercial source.
MIL-125-NH used in following embodiments2Synthetic method is as follows:
Synthesize MIL-125-NH2Material uses presoma for butyl titanate and 2- amino terephthalic acid (TPA), use it is molten
Agent is methanol and DMF.
Butyl titanate and 2- amino terephthalic acid (TPA) are added in reaction kettle according to molar ratio 1:2, stirred at room temperature
It mixes 30 minutes, will react 16 hours, be cooled to room temperature at a temperature of reaction kettle is placed in 150 DEG C later, distinguished with DMF and ethyl alcohol
It washes twice, centrifugation is precipitated, and the sediment that centrifugation obtains is placed in a vacuum drying oven, and drying temperature is 80 DEG C, dry
Yellow powdery solid material is obtained after 12 hours.
Embodiment 1
The mesoporous Ru-MIL-125-NH of height of the present embodiment2Synthetic method is as follows:
The high mesoporous Ru-MIL-125-NH of synthesis2The metal salt presoma used is RuCl3·xH2O, MOFs material are MIL-
125-NH2。
By MIL-125-NH2With RuCl3·xH2O is added in reaction kettle according to mass ratio 100:5, be stirred at room temperature to
It is uniformly mixed, is filled with the carbon dioxide of certain pressure (5.58MPa) later, reaction 5 is small under conditions of reaction temperature is 200 DEG C
When after, be cooled to room temperature, by way of pressure release by reaction kettle carbon dioxide remove, centrifugation obtain solid sediment,
Gained sediment is washed with DMF and methanol, then places it in vacuum oven and removes the solvent molecule of remaining, drying temperature
It is 80 DEG C, obtains Ru-MIL-125-NH after 12 hours dry2。
By MIL-125-NH2And high mesoporous Ru-MIL-125-NH obtained by the embodiment2It is scanned respectively, transmits electricity
Mirror, X-ray diffraction (XRD) and N2Adsorption/desorption characterization, as a result as shown in figures 1 and 2.
In Fig. 1, Gao Jiekong Ru-MIL-125-NH2Substantially original MIL-125-NH is kept2The hexahedron pattern of material, still
A breakage is appeared to have, cavitation phenomenon has occurred in inside.From distribution diagram of element, C, Ti and Ru is highly uniform is dispersed in
Ru-MIL-125-NH2On material.
In Fig. 2, Ru-MIL-125-NH2N2Adsorption-desorption isothermal curve is presented type I and type IV two types and inhales
The combination of desorption curve, type I and type IV respectively correspond adsorption curve caused by micropore and mesoporous material.MIL-125-
NH2Type I is presented in the adsorption-desorption curve of material, is typical poromerics.Due to mesoporous formation, Ru-MIL-125-
NH2Total pore volume is compared with MIL-125-NH2It increased.Ru-MIL-125-NH2Mesopore size is distributed in~3.8nm.Ru is in Ru-
MIL-125-NH2Content in material is 1.36wt%.
Embodiment 2
The mesoporous Ru-MIL-125-NH of the present embodiment2Synthetic method it is as follows:
Synthesising mesoporous Ru-MIL-125-NH2The metal salt presoma used is RuCl3·xH2O, MOFs material are MIL-
125-NH2。
By MIL-125-NH2With RuCl3·xH2O is added in reaction kettle according to mass ratio 100:5, be stirred at room temperature to
It is uniformly mixed, is filled with the carbon dioxide of certain pressure (5.58MPa) later, reaction 1 is small under conditions of reaction temperature is 200 DEG C
When after, be cooled to room temperature, by way of pressure release by reaction kettle carbon dioxide remove, centrifugation obtain solid sediment,
Gained sediment is washed with DMF and methanol, then places it in vacuum oven and removes the solvent molecule of remaining, drying temperature
It is 80 DEG C, obtains Ru-MIL-125-NH after 12 hours dry2。
Gained Ru-MIL-125-NH2It is scanned respectively, transmission electron microscope, X-ray diffraction (XRD) and N2Adsorption/desorption
Characterization, as a result with embodiment 1.
Embodiment 4
The mesoporous Ru-MIL-125-NH of the present embodiment2Synthetic method it is as follows:
Synthesising mesoporous Ru-MIL-125-NH2The metal salt presoma used is RuCl3·xH2O, MOFs material are MIL-
125-NH2。
By MIL-125-NH2With RuCl3·xH2O is added in reaction kettle according to mass ratio 100:5, be stirred at room temperature to
It is uniformly mixed, is filled with the carbon dioxide of certain pressure (5.58MPa) later, reaction 3 is small under conditions of reaction temperature is 200 DEG C
Shi Hou is cooled to room temperature, and is removed the carbon dioxide in reaction kettle by way of pressure release, and centrifugation obtains solid sediment, is used
DMF and methanol wash gained sediment, then place it in the solvent molecule that remaining is removed in vacuum oven, and drying temperature is
80 DEG C, Ru-MIL-125-NH is obtained after 12 hours dry2。
Gained Ru-MIL-125-NH2It is scanned respectively, transmission electron microscope, X-ray diffraction (XRD) and N2Adsorption/desorption
Characterization, as a result with embodiment 1.
Embodiment 5
The mesoporous Ru-MIL-125-NH of the present embodiment2Synthetic method it is as follows:
Synthesising mesoporous Ru-MIL-125-NH2The metal salt presoma used is RuCl3·xH2O, MOFs material are MIL-
125-NH2。
By MIL-125-NH2With RuCl3·xH2O is added in reaction kettle according to mass ratio 100:5, be stirred at room temperature to
It is uniformly mixed, is filled with the carbon dioxide of certain pressure (5.58MPa) later, reaction 9 is small under conditions of reaction temperature is 200 DEG C
When after, be cooled to room temperature, by way of pressure release by reaction kettle carbon dioxide remove, centrifugation obtain solid sediment,
Gained sediment is washed with DMF and methanol, then places it in vacuum oven and removes the solvent molecule of remaining, drying temperature
It is 80 DEG C, obtains Ru-MIL-125-NH after 12 hours dry2。
Gained Ru-MIL-125-NH2It is scanned respectively, transmission electron microscope, X-ray diffraction (XRD) and N2Adsorption/desorption
Characterization, as a result with embodiment 1.
Reference examples
The Ru/MIL-125-NH of the present embodiment2Synthetic method it is as follows:
Synthesize Ru/MIL-125-NH2The metal salt presoma used is RuCl3·xH2O, MOFs material are MIL-125-
NH2。
Specific implementation step are as follows: by MIL-125-NH2With RuCl3·xH2O is put into 5mL methanol according to mass ratio 100:5,
10mg NaBH is added later4Reducing agent as reducing metal ruthenium is stirred to react 6 hours at room temperature, and centrifugation obtains solid precipitating
Object washs gained sediment with DMF and methanol, then places it in vacuum oven and removes the solvent molecule of remaining, dry
Temperature is 80 DEG C, 12 hours dry, and Ru/MIL-125-NH can be obtained2。
Embodiment 7
By MIL-125-NH2And mesoporous Ru-MIL-125-NH obtained by previous embodiment2And Ru/MIL-125-NH2Material is made
For the catalyst of photocatalysis water-splitting.Specific implementation step are as follows:
By MIL-125-NH2With the mesoporous Ru-MIL-125-NH of the preparation gained of embodiment 12Gained Ru/ is prepared with reference examples
MIL-125-NH2Material is applied in the reaction of photocatalysis water-splitting.
A certain amount of photochemical catalyst, triethanolamine, acetonitrile and water are added in the round-bottomed flask of 100mL, nitrogen is passed through
Air in 30 minutes removing round-bottomed flasks, then seals, is placed in Photoreactor, and the xenon lamp for opening 300W starts light reaction
(wavelength is greater than 420nm), by the system water-bath temperature control at 25 DEG C, the rate of reaction is detected with gas-chromatography.As a result such as table 1
It is shown.
The test result that table 1, material light catalysis water-splitting are reacted
As shown in Table 1 with initial MIL-125-NH2And Ru/MIL-25-NH2Material is compared, provided by the invention mesoporous
Ru-MIL-25-NH2Photocatalysis water-splitting H2-producing capacity greatly promote.
Above content is only illustration made for the present invention.Those skilled in the art of the present invention can be right
Described embodiment is modified, supplements or is replaced, if being regarded as belonging to this hair without departing from conception range of the invention
Bright protection scope.
Claims (9)
1. a kind of prepare mesoporous Ru-MIL-125-NH2The method of material, comprising: using MOF material and metal salt as raw material, using super
The method of critical fluids is made.
2. according to the method described in claim 1, it is characterized by: in the method for the supercritical fluid, reaction medium used
For supercritical carbon dioxide；
The metal salt is RuCl3·xH2O；
The MOFs material is MIL-125-NH2。
3. method according to claim 1 or 2, it is characterised in that: in the method for the supercritical fluid, the MOFs material
The mass ratio of material and metal salt is 100:1-10；Specially 100:5；
Reaction temperature is 120-200 DEG C；
Time is 1-9h；
Reaction pressure is 1-6MPa；Specially 5.58MPa；
Solvent for use is selected from least one of methanol, ethyl alcohol and acetone.
4. the mesoporous Ru-MIL-125-NH that any the method for claim 1-3 is prepared2Material.
5. mesoporous Ru-MIL-125-NH according to claim 42Material, it is characterised in that: the mesoporous Ru-MIL-125-
NH2The specific surface area of material is 900-1300m2 g-1；Total pore volume is 0.5-0.8cm3 g-1；Mesoporous partial size is 3-10nm；Tool
Body is 3.8nm；The content of Ru is 0.95wt%-1.75wt%.
6. the mesoporous Ru-MIL-125-NH of claim 4 or 52Application of the material as catalyst in photocatalysis.
7. application according to claim 6, it is characterised in that: the photocatalysis is photocatalysis water-splitting reaction；
In the photocatalysis water-splitting reaction, the wavelength of light source used is greater than 420nm；Power is 150-500W；Specially 300W；
Light source used is specially xenon lamp.
8. containing the mesoporous Ru-MIL-125-NH of claim 4 or 52The catalyst of material.
9. catalyst according to claim 8, it is characterised in that: the catalyst is photochemical catalyst or photocatalysis water-splitting
The catalyst of reaction.
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| CN101780406A (en) * | 2009-01-19 | 2010-07-21 | 中国科学院化学研究所 | Nano metal catalyst and preparation method and application thereof |
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| US20130237412A1 (en) * | 2009-12-10 | 2013-09-12 | Northwestern University | Activation of Porous MOF Materials |
| CN107694521A (en) * | 2017-03-14 | 2018-02-16 | 中国石油大学(北京) | Step hole MOFs and preparation method thereof and the application as ultra-deep desulfurization agent |
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