CN108892783A - A kind of metal-organic framework materials and preparation method thereof of the visible optical drive hydrogen manufacturing based on eosin - Google Patents
A kind of metal-organic framework materials and preparation method thereof of the visible optical drive hydrogen manufacturing based on eosin Download PDFInfo
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- CN108892783A CN108892783A CN201810419193.2A CN201810419193A CN108892783A CN 108892783 A CN108892783 A CN 108892783A CN 201810419193 A CN201810419193 A CN 201810419193A CN 108892783 A CN108892783 A CN 108892783A
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- 239000000463 material Substances 0.000 title claims abstract description 54
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 39
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000001257 hydrogen Substances 0.000 title claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000003287 optical effect Effects 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003446 ligand Substances 0.000 claims abstract description 14
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 2
- 230000031700 light absorption Effects 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000005424 photoluminescence Methods 0.000 abstract description 3
- 238000006303 photolysis reaction Methods 0.000 abstract description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000013265 porous functional material Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/27—Cadmium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The metal-organic framework materials and preparation method thereof for the visible optical drive hydrogen manufacturing based on eosin that the invention discloses a kind of.The metal-organic framework materials are with eosin for main ligand, and 4,4'- bipyridyls are assistant ligand, are prepared with the soluble-salt of cadmium by hydro-thermal reaction, the chemical formula of the material is：[Mm(L1)n(L2)b(H2O)·(H2O)q], in formula, L1For eosin, L2For 4,4'- bipyridyl, M is Metal Ions Cd2+, m=1, n=1, b=0.5, q=4.Material provided by the invention has excellent stability of photoluminescence, high chemical resistance and efficient catalytic performance, can be used for the photolysis water hydrogen of visible optical drive；Preparation process of the invention is simple, environmental-friendly, at low cost, is easy to large scale preparation.
Description
Technical field
The invention belongs to field of photocatalytic material, are related to a kind of metal-organic framework materials for visible light catalytic, tool
Body is related to a kind of metal-organic framework materials and preparation method thereof of visible optical drive hydrogen manufacturing based on eosin.
Background technique
Hydrogen is a kind of sustainable clean energy resource, can be with substitute fossil fuels.Photolysis water hydrogen is considered as that one kind has
The hydrogen production technology of feasibility, it is therefore an objective to convert chemical fuel energy for solar energy abundant on the earth.However, most of light
Catalyst is reacted under ultraviolet light irradiation, and the 3%-5% of solar spectrum is only accounted for.Therefore, efficient photochemical catalyst should be developed
To improve the utilization rate to visible light to the maximum extent.
However, it is a great challenge that design, which synthesizes the catalysis material with efficient light utilization ratio for hydrogen manufacturing,
Project.Some metal-organic dyestuff such as Ru, Pt and Ir base complex sensitization catalyst have been used for developing visible-light response type light
Catalyst, but it is expensive, and there is toxicity and recuperability difference to limit it and widely apply.By metal ion and organic
Connector is formed by metal-organic framework materials (Metal-organic Frameworks, MOFs) by Coordinate self-assembly,
It can promote the mass transport in light-catalyzed reaction with highly crystalline and bone porous stability and improve electron-hole
Isolated efficiency, so that making MOFs become excellent photochemical catalyst becomes potentially possible for photolysis water hydrogen.But at present
The MOFs material of research will be really applied in efficient visible optical drive hydrogen manufacturing, and scientific worker also needs to solve the problems, such as follows：
1. most metal-organic dyestuff are based on the compound of Ru, Pt and Ir there are expensive, there is toxicity, recyclability
The problem of difference；
2. traditional MOFs generally has low visible light utilization efficiency, higher cost and lower work as photochemical catalyst
Property, it is seen that the photocatalytic activity MOFs in light SPECTRAL REGION is still relatively fewer.
Therefore, it is most important to develop a kind of cheap, environmental-friendly, with visible light photocatalysis performance MOFs.
Summary of the invention
An object of the present invention is to provide a kind of metal-organic framework material of visible optical drive hydrogen manufacturing based on eosin
Material, cheap, environmental-friendly, stability of photoluminescence is good.
The second object of the present invention is to provide a kind of metal organic frame of above-mentioned visible optical drive hydrogen manufacturing based on eosin
The preparation method of material, simple process can be mass-produced.
One of to achieve the above object, the technical solution adopted by the present invention is that：A kind of visible optical drive system based on eosin
The metal-organic framework materials of hydrogen, with Metal Ions Cd2+For node, with Eosin Y (eosin) for the main ligand of organic linking and light
Absorptive unit, 4,4'- bipyridyls are assistant ligand, and the metal-organic framework with three-dimensional net structure is obtained by hydro-thermal method
Material C d-EY；
The chemical formula of Cd-EY is：[Mm(L1)n(L2)b(H2O)·(H2O)q], in formula,
L1For the main ligand Eosin Y of organic linking, structural formula is shown in formula I；
L2For assistant ligand bpy, structural formula is shown in formula II；
M is Metal Ions Cd2+；
M, n, b and q are respectively metal ion, the main ligand of organic linking (Eosin Y), assistant ligand (bpy) and hydrone
Number, wherein m=1, n=1, b=0.5, q=4.
To achieve the above object two, the technical solution adopted by the present invention is that：A kind of visible optical drive system based on eosin
The preparation method of the metal-organic framework materials of hydrogen, includes the following steps：
S1, according to molar ratio (1~1.2)：(1~1.1)：(1.3~1.5) weigh eosin (Eosin Y), 4,4'- respectively
The soluble-salt of bipyridyl (bpy) and cadmium, are placed in glass sample bottle, and water is added and methanol volume ratio is 1:1 mixing is molten
Agent, and stir evenly；
S2, glass sample bottle is placed in hydrothermal synthesis reaction kettle, under the conditions of 75 DEG C~85 DEG C insulation reaction 22h~
26h；
S3, to after reaction, cooling obtains red bulk crystals, then is successively filtered, washed, is dried, i.e.,
The metal-organic framework materials of visible optical drive hydrogen manufacturing are made.
Preferably, the molar ratio of the soluble-salt of the eosin, 4,4'- bipyridyl and cadmium is 1：1：1.3.
Preferably, the soluble-salt of the cadmium is four nitric hydrate cadmiums.
In step S3, the temperature of the drying is 80 DEG C~100 DEG C, and the time of the drying is 5h~8h.
The chemical equation for preparing Cd-EY is as follows：
Metal-organic framework materials provided by the invention can be used as visible-light-responsive photocatalyst, be applied to photocatalytic water
Hydrogen manufacturing.
The present invention is using cheap, environmentally friendly dyestuff eosin as main ligand and light absorption units, 4,4'- connection
Pyridine is as time ligand, and with cadmium ion by a step hydro-thermal reaction, obtaining an example, there is the metal-of three-dimensional net structure to have machine frame
Frame material.The solid uv-visible absorption spectra of the material shows the broad absorption band within the scope of 373-650nm, shows this
Material has response in visible-range, provides premise for the utilization rate of realization raising visible light and the high efficiency of photochemical catalyst,
And material can be stabilized in the aqueous solution of pH=10.5 and 5.6, show excellent stability of photoluminescence and Gao Naihua
The property learned provides the foundation for optical drive liberation of hydrogen in aqueous solution.
When introducing organic linker of the eosin as MOF, it is seen that the liberation of hydrogen effect of optical drive greatly enhances, and highest is living
Property is that TON (hydrogen output of unit mol catalyst) reaches 13920.It is detailed research shows that its efficient catalytic performance can attribution
In the redox site in frame space and the effective photo induced electron transfer process occurred between photosensitizer.
The beneficial effects of the invention are as follows：The starting material eosin (Eosin Y) and 4,4'- bipyridyl that the present invention uses
(bpy) cheap, environmental-friendly, it does not need additionally to synthesize；And target material is synthesized by a step hydro-thermal reaction, yield is high
And chemical property is stablized, and preparation process is simple, and it is at low cost, it is easy to large scale preparation.Method provided by the invention is development and system
Standby wide spectrum with visible absorption and cheap novel porous functional material opened up a new way.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of metal-organic framework materials prepared by the embodiment of the present invention 1；
Fig. 2 is the PXRD stability test figure of metal-organic framework materials prepared by the embodiment of the present invention 1；
Fig. 3 is the solid uv-visible absorption spectra of metal-organic framework materials prepared by the embodiment of the present invention 1；
Fig. 4 is optimum condition figure of the metal-organic framework materials of the preparation of the embodiment of the present invention 1 as photochemical catalyst；
Fig. 5 is the metal-organic framework materials of the preparation of the embodiment of the present invention 1 to [Co (bpy)3]Cl2Fluorescence titration figure.
Specific embodiment
The present invention is further described in the following with reference to the drawings and specific embodiments.
Embodiment 1
Weigh 18.7mg eosin, 4.2mg 4,4'- bipyridyl and 10.8mg Cd (NO3)2·4H2O is placed in the glass of 10mL
In sample bottle, 5mL water and methanol (volume ratio 1 is added:1) mixed solvent, is then placed in hydrothermal synthesis for glass sample bottle
In reaction kettle, then hydrothermal synthesis reaction kettle is placed in electric drying oven with forced convection, 80 DEG C of constant temperature, reaction for 24 hours, to the end of reacting
Afterwards, cooling obtains red bulk crystals, is filtered, washed, 100 DEG C of dry 5h, and metal-organic framework materials are made.Its crystal knot
Structure has a biggish duct, as shown in Figure 1, as can be seen from the figure eosin unit is uniformly distributed to carry out its photocatalytic water
Hydrogen manufacturing performance research lays the foundation.
The stability test of material
Material C d-the EY in 2 parts of embodiments 1 is weighed, is added separately in the aqueous solution that pH value is 5.6 and 10.5, stirring
24 hours, filtering tested its PXRD after normal-temperature vacuum is dry respectively, and test results are shown in figure 2, it can be seen that material is in pH=
It can be stabilized in 10.5 and 5.6 aqueous solution, provide support for the stability of material.
The solid uv-visible absorption spectra of material is tested
Material C d-EY dress the sample in 10mg embodiment 1 is weighed, the test outside solid violet is carried out.Test result such as Fig. 3 institute
Showing, it can be seen that broad absorption band of the Cd-EY within the scope of 373-650nm shows that the material has response in visible-range,
Premise is provided for the utilization rate of realization raising visible light and the high efficiency of photochemical catalyst.
The Photocatalytic Performance Study of material
Guarantee steady temperature, using Cd-EY as photosensitizer, [Co (bpy) using circulation3]Cl2It is urged for proton reduction
Agent, TEA are electronics sacrificial body, are put into volume ratio 1:1 ethyl alcohol and the in the mixed solvent of water are carried out real with xenon source irradiation
It tests.The hydrogen of generation is detected with gas-chromatography, and carrier gas is nitrogen.The results are shown in attached figure 4, it can be seen that with light application time
It carries out, hydrogen generating quantity gradually increases, reacts 5 hours TON and reach 13920.
Material is to [Co (bpy)3]Cl2Fluorescence titration test
Material C d-the EY in embodiment 1 is weighed, the standard suspension of the water of 0.17mM is configured to, takes the above-mentioned suspension of 2mL
In quartz colorimetric utensil, then [the Co (bpy) of 0.02M is gradually added dropwise thereto3]Cl2Aqueous solution, until fluorescence intensity no longer occurs
Until variation, amounts to and [Co (bpy) is added3]Cl2Concentration is 0.24mM, excitation wavelength 452nm, records it in the fluorescence of 558nm
Emission peak.As a result as shown in Figure 5, it can be seen that with [Co (bpy)3]Cl2The fluorescence generation of the increase of amount, Cd-EY is significantly quenched
It goes out, shows effectively to occur Photoinduced Electron from Cd-EY excitation state to [Co (bpy)3]Cl2Transmitting.
Embodiment 2
Weigh 18.7mg eosin, 4.2mg 4,4'- bipyridyl and 12.5mg Cd (NO3)2·4H2O is placed in the glass of 10mL
In sample bottle, 7mL water and methanol (volume ratio 1 is added:1) mixed solvent, is then placed in hydrothermal synthesis for glass sample bottle
In reaction kettle, then hydrothermal synthesis reaction kettle is placed in electric drying oven with forced convection, 75 DEG C of constant temperature, reaction for 24 hours, to the end of reacting
Afterwards, cooling obtains red bulk crystals, is filtered, washed, 90 DEG C of dry 6h, and metal-organic framework materials are made.
Embodiment 3
Weigh 22.4mg eosin, 4.2mg 4,4'- bipyridyl and 10.8mg Cd (NO3)2·4H2O is placed in the glass of 10mL
In sample bottle, 10mL water and methanol (volume ratio 1 is added:1) mixed solvent, is then placed in hydrothermal synthesis for glass sample bottle
In reaction kettle, then hydrothermal synthesis reaction kettle is placed in electric drying oven with forced convection, 75 DEG C of constant temperature, 26h reacted, to the end of reacting
Afterwards, cooling obtains red bulk crystals, is filtered, washed, 100 DEG C of dry 6h, and metal-organic framework materials are made.
Embodiment 4
Weigh 22.4mg eosin, 4.6mg 4,4'- bipyridyl and 10.8mg Cd (NO3)2·4H2O is placed in the glass of 10mL
In sample bottle, 10mL water and methanol (volume ratio 1 is added:1) mixed solvent, is then placed in hydrothermal synthesis for glass sample bottle
In reaction kettle, then hydrothermal synthesis reaction kettle is placed in electric drying oven with forced convection, 80 DEG C of constant temperature, 22h reacted, to the end of reacting
Afterwards, cooling obtains red bulk crystals, is filtered, washed, 80 DEG C of dry 8h, and metal-organic framework materials are made.
Embodiment 5
Weigh 22.4mg eosin, 4.2mg 4,4'- bipyridyl and 12.5mg Cd (NO3)2·4H2O is placed in the glass of 10mL
In sample bottle, 10mL water and methanol (volume ratio 1 is added:1) mixed solvent, is then placed in hydrothermal synthesis for glass sample bottle
In reaction kettle, then hydrothermal synthesis reaction kettle is placed in electric drying oven with forced convection, 80 DEG C of constant temperature, 26h reacted, to the end of reacting
Afterwards, cooling obtains red bulk crystals, is filtered, washed, 100 DEG C of dry 5h, and metal-organic framework materials are made.
Embodiment 6
Weigh 22.4mg eosin, 4.6mg 4,4'- bipyridyl and 12.5mg Cd (NO3)2·4H2O is placed in the glass of 10mL
In sample bottle, 10mL water and methanol (volume ratio 1 is added:1) mixed solvent, is then placed in hydrothermal synthesis for glass sample bottle
In reaction kettle, then hydrothermal synthesis reaction kettle is placed in electric drying oven with forced convection, 85 DEG C of constant temperature, reaction for 24 hours, to the end of reacting
Afterwards, cooling obtains red bulk crystals, is filtered, washed, 90 DEG C of dry 5h, and metal-organic framework materials are made.
Claims (6)
1. a kind of metal-organic framework materials of the visible optical drive hydrogen manufacturing based on eosin, it is characterised in that：The material is with gold
Belong to ion Cd2+For node, using eosin as the main ligand of organic linking and light absorption units, 4,4'- bipyridyls are assistant ligand, are passed through
Hydro-thermal method is made；The chemical formula of the material is：[Mm(L1)n(L2)b(H2O)·(H2O)q], in formula, L1For eosin, L2For 4,4'-
Bipyridyl, M are Metal Ions Cd2+；M, n, b and q are respectively metal ion, the main ligand of organic linking, assistant ligand and hydrone
Number, wherein m=1, n=1, b=0.5, q=4.
2. a kind of system of the metal-organic framework materials of the visible optical drive hydrogen manufacturing according to claim 1 based on eosin
Preparation Method, it is characterised in that：Include the following steps：
S1, according to molar ratio (1~1.2)：(1~1.1)：What (1.3~1.5) weighed eosin, 4,4'- bipyridyl and cadmium respectively can
Soluble is placed in glass sample bottle, and water is added and methanol volume ratio is 1:1 mixed solvent, and stir evenly；
S2, glass sample bottle is placed in hydrothermal synthesis reaction kettle, insulation reaction 22h~26h under the conditions of 75 DEG C~85 DEG C；
S3, to after reaction, cooling obtains red bulk crystals, then is successively filtered, washed, is dried, and obtains
It can be seen that the metal-organic framework materials of optical drive hydrogen manufacturing.
3. the preparation side of the metal-organic framework materials of the visible optical drive hydrogen manufacturing according to claim 2 based on eosin
Method, it is characterised in that：The molar ratio of the soluble-salt of the eosin, 4,4'- bipyridyl and cadmium is 1：1：1.3.
4. the preparation side of the metal-organic framework materials of the visible optical drive hydrogen manufacturing according to claim 2 based on eosin
Method, it is characterised in that：The soluble-salt of the cadmium is four nitric hydrate cadmiums.
5. the preparation side of the metal-organic framework materials of the visible optical drive hydrogen manufacturing according to claim 2 based on eosin
Method, it is characterised in that：In step S3, the temperature of the drying is 80 DEG C~100 DEG C, and the time of the drying is 5h~8h.
6. the metal-organic framework materials of the visible optical drive hydrogen manufacturing according to claim 1 based on eosin can in preparation
Application in light-exposed responsive photocatalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810419193.2A CN108892783B (en) | 2018-05-04 | 2018-05-04 | Visible light driven hydrogen production metal-organic framework material based on eosin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810419193.2A CN108892783B (en) | 2018-05-04 | 2018-05-04 | Visible light driven hydrogen production metal-organic framework material based on eosin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108892783A true CN108892783A (en) | 2018-11-27 |
| CN108892783B CN108892783B (en) | 2021-03-12 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111921559A (en) * | 2020-08-16 | 2020-11-13 | 复旦大学 | Single-site transition metal covalent organic framework photocatalyst and preparation method thereof |
| CN113289687A (en) * | 2021-05-26 | 2021-08-24 | 华东师范大学 | Zirconium-based MOF visible light catalyst for treating hexavalent chromium wastewater and preparation method and application thereof |
| CN114308125A (en) * | 2021-12-13 | 2022-04-12 | 大连理工大学 | Preparation method and application of eosin Y-based metal organic framework with function of activating inert C-H bond |
| CN115385799A (en) * | 2022-10-26 | 2022-11-25 | 广东工业大学 | Organic ligand, triphenylene alkynyl functionalized organic framework material, and preparation method and application thereof |
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| CN105879885A (en) * | 2016-05-04 | 2016-08-24 | 上海大学 | Catalyst for photocatalytic decomposition of water into hydrogen by visible light and method for preparing catalyst |
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| CN105879885A (en) * | 2016-05-04 | 2016-08-24 | 上海大学 | Catalyst for photocatalytic decomposition of water into hydrogen by visible light and method for preparing catalyst |
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| XU XIAO-WU等: "Two New Coordination Complexes Based on Eosin Y Dye Ligand: Syntheses, Crystal Structures and Magnetic Properties", 《CHINESE J. STRUCT. CHEM.》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111921559A (en) * | 2020-08-16 | 2020-11-13 | 复旦大学 | Single-site transition metal covalent organic framework photocatalyst and preparation method thereof |
| CN111921559B (en) * | 2020-08-16 | 2023-04-07 | 复旦大学 | Single-site transition metal covalent organic framework photocatalyst and preparation method thereof |
| CN113289687A (en) * | 2021-05-26 | 2021-08-24 | 华东师范大学 | Zirconium-based MOF visible light catalyst for treating hexavalent chromium wastewater and preparation method and application thereof |
| CN114308125A (en) * | 2021-12-13 | 2022-04-12 | 大连理工大学 | Preparation method and application of eosin Y-based metal organic framework with function of activating inert C-H bond |
| CN115385799A (en) * | 2022-10-26 | 2022-11-25 | 广东工业大学 | Organic ligand, triphenylene alkynyl functionalized organic framework material, and preparation method and application thereof |
| CN115385799B (en) * | 2022-10-26 | 2023-03-14 | 广东工业大学 | Organic ligand, triphenylene alkynyl functionalized organic framework material, and preparation method and application thereof |
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