CN106423279A - Preparation method of graphene-supported Fe2Co metal-organic framework material - Google Patents
Preparation method of graphene-supported Fe2Co metal-organic framework material Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 81
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 69
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims description 134
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 229910021389 graphene Inorganic materials 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 26
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- 238000004519 manufacturing process Methods 0.000 abstract description 27
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- 230000001699 photocatalysis Effects 0.000 abstract description 15
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- 238000002484 cyclic voltammetry Methods 0.000 abstract description 6
- 238000002411 thermogravimetry Methods 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
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- 238000012360 testing method Methods 0.000 description 64
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- 238000007146 photocatalysis Methods 0.000 description 12
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- 239000012476 oxidizable substance Substances 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- NQFUSWIGRKFAHK-KEMUHUQJSA-N α-pinene-oxide Chemical compound CC12OC1C[C@H]1C(C)(C)[C@@H]2C1 NQFUSWIGRKFAHK-KEMUHUQJSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
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- 238000001514 detection method Methods 0.000 description 3
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- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
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- 229910002804 graphite Inorganic materials 0.000 description 2
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- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005588 protonation Effects 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
- 230000005855 radiation Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- 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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a graphene-supported Fe2Co metal-organic framework material, relates to a preparation method of a metal-organic framework material, and aims at solving the problem that the hydrogen production efficiency of an existing material for producing hydrogen by photocatalytically splitting water is low. The method comprises the steps of 1 preparation of a Fe2Co-MOF material and 2 preparation of a Go/Fe2Co-MOF material. The oxidation potential energy level value 0.42 eV is obtained through cyclic voltammetry, then the reduction potential energy level value 1.23 eV can be calculated and is more negative than the energy level value generated when hydrogen is produced through hydrogen ion reduction, and therefore the material achieves the photocatalytic hydrogen production capability. The stability of the Go/Fe2Co-MOF material prepared through the method is studied by adopting thermogravimetric analysis (TGA), and a result shows that the Go/Fe2Co-MOF material prepared through the method has the very good stability when the temperature is lower than 400 DEG C.
Description
Technical field
The present invention relates to a kind of preparation method of metal-organic framework materials.
Background technology
Since 21st century, energy shortage and environmental pollution become the problem of whole world people's facing, new forms of energy
Exploitation also become the topic kept away not open, solar energy, the resource such as wind energy by continuous exploitation, utilize, and Hydrogen Energy stores because of it
Amount is big, and quantity of heat production is up to two times of fossil fuel, the excellent characteristic such as cleanliness without any pollution and obtain concern and the research of people.Hydrogen
The way of production of energy has many kinds, for example：Organic waste hydrogen manufacturing, continue a large amount of hydrogen manufacturing using microalgae, to come from plant former
Material hydrogen manufacturing and photocatalysis hydrogen production etc., wherein utilize solar energy, and water is most commonly seen by the method for photocatalysis hydrogen production.Using too
Sun can become the optimal method obtaining Hydrogen Energy, receive domestic and international researcher to obtain the photocatalysis technology of Hydrogen Energy
Favor.Wherein Japanese scholars Fujishima and Honda research finds to work as illumination n-type semiconductor TiO2During electrode, may result in
Water decomposition, makes people recognize the feasibility using solar energy photocatalytic hydrogen manufacturing.But because of it during photocatalysis hydrogen production light
The shortcomings of give birth to electronics and hole-recombination rate height, can only respond ultraviolet light, limits its development.Therefore develop a kind of new light to urge
Agent is extremely urgent.
Metal-organic framework materials are centered on metal ion or metal cluster, with organic ligand through coordinate bond self assembly
The coordination polymer becoming.As a kind of material of hybrid inorganic-organic, have that many traditional materials do not have is excellent for MOFs material
Good characteristic, such as diversity, higher specific surface area and the porosity of component and structure, it is convenient etc. to synthesize；Make its numerous areas
Have broad application prospects, such as in catalysis, gas storage, fluorescence detection etc..Because MOFs material has semiconductor in itself
Property, recent years, increasing research had been verified that MOFs material can absorb sunshine, can produce photoproduction after exciting
Electronics, such that it is able to be applied to photocatalysis hydrogen production.
The fast development of metal-organic framework materials is the important breakthrough that recent two decades carry out domain of inorganic chemistry.MOFs material
Material is as central point by metal center or metal cluster.It is formed by connecting by coordinate bond self assembly with organic ligand, there is height
Periodically network crystalline complex, also referred to as metal coordinating polymer[7].
The unique texture feature of this hybrid inorganic-organic of MOFs and the bore hole size of its Nano grade, make it one
One or more catalytic site are provided, this is that other materials institute is irrealizable in individual cavity.Therefore MOFs material has many
Tempting feature：First, MOFs material has component diversity, by selecting different metal ions and different parts, just
Miscellaneous MOFs material can be synthesized.The structure of second, MOFs material has performance-adjustable, with designed, designed and can close
Become wanted structure, and the functionalization of MOF material can be realized by the modification of functional material.3rd, MOFs material
There is loose structure of uniform size, larger specific surface area.4th, MOFs material has good heat endurance and chemistry
Stability.5th, simple synthetic method, simple to operate.
In the research of nearly 30 years, MOFs material develops with surprising rapidity.In many chemical periodicals, with regard to MOFs
Paper or summary exponentially increase, it is light that so fast development speed also illustrate that this material has act foot in field of scientific study
The status of weight.So far, researchers oneself through having synthesized novel, the of good performance MOFs material of substantial amounts of structure, obtain
Numerous scientific research effects highly visible.
MOFs booming two during the decade, the researchers from countries in the world join in this field, constantly
Synthesize various structures expand its application in every field.The Many researchers of recent year are in this field
Achieve certain achievement, also there is far-reaching influence in the world.
But existing MOFs material photolysis water hydrogen is inefficient, needs further to be probed into, develop a kind of photocatalytic water
The high material of hydrogen production efficiency.
Content of the invention
The invention aims to solving the problems, such as that the material hydrogen production efficiency being currently used for photolysis water hydrogen is not high, and provide
A kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials.
A kind of graphene-supported Fe of the present invention2The preparation method of Co metal-organic framework materials is to complete according to the following steps
's：
First, Fe2The preparation of Co-MOF material：To Fe2DMF I and glacial acetic acid is added, in supersonic frequency in Co
Rate is ultrasonically treated 4min～6min under conditions of 35KHz～45KHz, is subsequently adding 3,3 ', 5,5 '-azo benzene tertacarbonic acid,
Supersonic frequency is ultrasonically treated 25min～35min under conditions of 35KHz～45KHz, then reaction vessel is put into reactor
In, then reactor is placed in reaction 2h～12h in the baking oven that temperature is 130～150 DEG C, obtain Fe2Co-MOF material；
N,N-dimethylformamide I described in step one is 2 with the volume ratio of glacial acetic acid:(0.5～1.5)；
The volume of N,N-dimethylformamide I described in step one and Fe2The ratio of the quality of Co is 2mL:(10～40) mg；
Fe described in step one2Co and 3,3 ', the mass ratio of 5,5 '-azo benzene tertacarbonic acid is 1:(1～2) mg；
2nd, Go/Fe2The preparation of Co-MOF material：1. Graphene is dissolved in DMF II, in supersonic frequency
Rate is ultrasonically treated 50min～70min under conditions of 35KHz～45KHz, obtains mixed solution；2. 1. step 2 is obtained
The Fe that mixed solution and step one obtain2Put in reactor after the mixing of Co-MOF material, then reactor is placed in temperature for 130
React 3h～5h in～150 DEG C of baking oven, obtain Go/Fe2Co-MOF material, i.e. graphene-supported Fe2Co metallic organic framework material
Material；
1. the quality of described Graphene and the ratio of the volume of N,N-dimethylformamide II are (0.2～0.3) mg to step 2:
2mL；
The Fe that in the step 2 mixed solution that 2. 1. described step 2 obtains, the quality of Graphene is obtained with step one2Co-
The mass ratio of MOF material is (0.025～0.25):25.
Part of the present invention 3,3 ', 5,5 '-azo benzene tertacarbonic acid press《Catalytic science and technology, iron (III), metal is organic
Framework isomerization to australene readily oxidizable substance as solid Lewis acid, 2012》Described in method preparation.
Beneficial effects of the present invention
The present invention passes through hydro-thermal (solvent heat) method by part 3,3 ', 5,5 '-azo benzene tertacarbonic acid's (3,3 ', 5,5 '-azobenzene
Tetrabasic carboxylic acid, H4abtc) and Fe2Co reaction generates Fe2Co-MOF；And using infrared, X-ray single crystal diffraction to obtained MOFs
Material has carried out structural characterization, and testing result shows to successfully synthesize the Fe of more pure phase2Co-MOF material.Then exist
Fe2Co-MOF material load Graphene, obtains the Go/Fe of different graphene-supported amounts2Co-MOF material, by solid ultraviolet-can
See that the analysis of spectrum that diffuses (UV-Vis) test result shows：Fe2The Co-MOF and GO/Fe of 0.25% graphene-supported amount2Co-
The edge energy of MOF material oxidation current potential-reduction potential is respectively 1.65eV, 1.55eV；Oxidizing potential is obtained by cyclic voltammetry
Energy level value is 0.42eV, and then can calculate reduction potential energy level value for -1.23eV, than the energy level value of reducing hydrogen ions hydrogen
More negative, therefore possess the ability of photocatalysis hydrogen production, the Go/Fe using thermogravimetric analysis (TGA) being prepared by the present invention2Co-MOF material
Stability probed into, result show the present invention preparation Go/Fe2Co-MOF material has when temperature is less than 400 DEG C
Stability well.
Brief description
Fig. 1 is the Go/Fe of different graphene-supported amounts2Co-MOF and part 3,3 ', 5,5 '-azo benzene tertacarbonic acid's is red
External spectrum figure；
Fig. 2 is the Go/Fe of different graphene-supported amounts2The X-ray powder diffraction characterization result of Co-MOF and its monocrystalline solution
Analysis simulation drawing；
Fig. 3 is the Go/Fe of test two preparation2The SEM figure of Co-MOF；
Fig. 4 is the Go/Fe of test three preparation2The SEM figure of Co-MOF；
Fig. 5 is the Go/Fe of test four preparation2The SEM figure of Co-MOF；
Fig. 6 is the Go/Fe of test five preparation2The SEM figure of Co-MOF；
Fig. 7 is the Fe of test three step one preparation2The uv-visible absorption spectrum figure of Co-MOF；
Fig. 8 is the Go/Fe of test three preparation2The uv-visible absorption spectrum figure of Co-MOF is such as；
Fig. 9 is the Go/Fe of test three preparation2The cyclic voltammetry test chart of Co-MOF；
Figure 10 is the Go/Fe of test three preparation2The thermogravimetric curve figure of Co-MOF；
The canonical plotting that Figure 11 tests for gas chromatograph hydrogen manufacturing；
Figure 12 is the GO/Fe of different graphene-supported amounts2The hydrogen output curve map of Co-MOF.
Specific embodiment
Specific embodiment one：A kind of graphene-supported Fe of present embodiment2The preparation of Co metal-organic framework materials
Method completes according to the following steps：
First, Fe2The preparation of Co-MOF material：To Fe2DMF I and glacial acetic acid is added, in supersonic frequency in Co
Rate is ultrasonically treated 4min～6min under conditions of 35KHz～45KHz, is subsequently adding 3,3 ', 5,5 '-azo benzene tertacarbonic acid,
Supersonic frequency is ultrasonically treated 25min～35min under conditions of 35KHz～45KHz, then reaction vessel is put into reactor
In, then reactor is placed in reaction 2h～12h in the baking oven that temperature is 130～150 DEG C, obtain Fe2Co-MOF material；
N,N-dimethylformamide I described in step one is 2 with the volume ratio of glacial acetic acid:(0.5～1.5)；
The volume of N,N-dimethylformamide I described in step one and Fe2The ratio of the quality of Co is 2mL:(10～40) mg；
Fe described in step one2Co and 3,3 ', the mass ratio of 5,5 '-azo benzene tertacarbonic acid is 1:(1～2) mg；
2nd, Go/Fe2The preparation of Co-MOF material：1. Graphene is dissolved in DMF II, in supersonic frequency
Rate is ultrasonically treated 50min～70min under conditions of 35KHz～45KHz, obtains mixed solution；2. 1. step 2 is obtained
The Fe that mixed solution and step one obtain2Put in reactor after the mixing of Co-MOF material, then reactor is placed in temperature for 130
React 3h～5h in～150 DEG C of baking oven, obtain Go/Fe2Co-MOF material, i.e. graphene-supported Fe2Co metallic organic framework material
Material；
1. the quality of described Graphene and the ratio of the volume of N,N-dimethylformamide II are (0.2～0.3) mg to step 2:
2mL；
The Fe that in the step 2 mixed solution that 2. 1. described step 2 obtains, the quality of Graphene is obtained with step one2Co-
The mass ratio of MOF material is (0.025～0.25):25.
Described in present embodiment, part 3,3 ', 5,5 '-azo benzene tertacarbonic acid presses《Catalytic science and technology, iron (III), metal
Organic frame isomerization to australene readily oxidizable substance as solid Lewis acid, 2012》(Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) described in method preparation.
Present embodiment pass through hydro-thermal (solvent heat) method by part 3,3 ', 5,5 '-azo benzene tertacarbonic acid (3,3 ', 5,5 '-even
Pyridine tetrabasic carboxylic acid, H4abtc) and Fe2Co reaction generates Fe2Co-MOF；And using infrared, X-ray single crystal diffraction to obtained
MOFs material has carried out structural characterization, and testing result shows to successfully synthesize the Fe of more pure phase2Co-MOF material.Then exist
Fe2Co-MOF material load Graphene, obtains the Go/Fe of different graphene-supported amounts2Co-MOF material, by solid ultraviolet-can
See that the analysis of spectrum that diffuses (UV-Vis) test result shows：Fe2The Co-MOF and GO/Fe of 0.25% graphene-supported amount2Co-
The edge energy of MOF material oxidation current potential-reduction potential is respectively 1.65eV, 1.55eV；Oxidizing potential is obtained by cyclic voltammetry
Energy level value is 0.42eV, and then can calculate reduction potential energy level value for -1.23eV, than the energy level value of reducing hydrogen ions hydrogen
More negative, therefore possess the ability of photocatalysis hydrogen production, the Go/Fe using thermogravimetric analysis (TGA) being prepared by the present invention2Co-MOF material
Stability probed into, result show present embodiment preparation Go/Fe2Co-MOF material is when temperature is less than 400 DEG C
There is good stability.
Specific embodiment two：Present embodiment from unlike specific embodiment one：N described in step one, N- bis-
NMF I is 2 with the volume ratio of glacial acetic acid:0.9.Other steps and parameter are identical with specific embodiment one.
Specific embodiment three：Present embodiment from unlike specific embodiment one or two：N described in step one,
The volume of dinethylformamide I and Fe2The ratio of the quality of Co is 2mL：(20～30) mg.Other steps and parameter and specifically reality
Apply mode one or two identical.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：Institute in step one
State Fe2Co and 3,3 ', the ratio of the quality of 5,5 '-azo benzene tertacarbonic acid is 1:1.5mg.Other steps and parameter and specific embodiment party
One of formula one to three is identical.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：In step one to
Fe2Addition DMF I and glacial acetic acid in Co, ultrasonically treated 5min under conditions of supersonic frequency is for 40KHz, so
Addition 3,3 ', 5 afterwards, 5 '-azo benzene tertacarbonic acid, ultrasonically treated 30min under conditions of supersonic frequency is for 40KHz.Other steps
And one of parameter and specific embodiment one to four are identical.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：Will in step one
Reaction vessel is put in reactor, then reactor is placed in reaction 4h in the baking oven that temperature is 140 DEG C, obtains Fe2Co-MOF material
Material.One of other steps and parameter and specific embodiment one to five are identical.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Step 2 1. institute
The ratio of the quality and the volume of N,N-dimethylformamide II of stating Graphene is 0.25mg:2mL.Other steps and parameter with concrete
One of embodiment one to six is identical.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：Step 2 2. institute
State the Fe that in the mixed solution that 1. step 2 obtains, the quality of Graphene and step one obtain2The mass ratio of Co-MOF material is
0.0625:25.One of other steps and parameter and specific embodiment one to the Seventh Five-Year Plan are identical.
Specific embodiment nine：Unlike one of present embodiment and specific embodiment one to eight：Step 2 1. in
Graphene is dissolved in DMF II, ultrasonically treated under conditions of supersonic frequency is for 35KHz～45KHz
60min, obtains mixed solution.One of other steps and parameter and specific embodiment one to eight are identical.
Specific embodiment ten：Unlike one of present embodiment and specific embodiment one to nine：Step 2 2. in
The Fe that the mixed solution that 1. step 2 is obtained is obtained with step one2Put in reactor after the mixing of Co-MOF material, then will be anti-
React 4h in answer kettle to be placed in baking oven that temperature is 140 DEG C, obtain Go/Fe2Co-MOF material, i.e. graphene-supported Fe2Co metal has
Machine framework material.One of other steps and parameter and specific embodiment one to nine are identical.
Verify beneficial effects of the present invention with tests below
Test one, a kind of graphene-supported Fe of this experiment2The preparation method of Co metal-organic framework materials presses following step
Suddenly carry out：
First, Fe2The preparation of Co-MOF material：Fe to 40mg2N,N-dimethylformamide I He of 2mL is added in Co
The glacial acetic acid of 0.9mL, ultrasonically treated 5min under conditions of supersonic frequency is for 40KHz, it is subsequently adding the 3 of 60mg, 3 ', 5,5 '-
Azo benzene tertacarbonic acid, under conditions of supersonic frequency is for 40KHz, then reaction vessel is put into reactor by ultrasonically treated 30min
In, then reactor is placed in reaction 4h in the baking oven that temperature is 140 DEG C, obtain Fe2Co-MOF material；
2nd, Go/Fe2The preparation of Co-MOF material：1. 0.1mg Graphene is dissolved in the N,N-dimethylformamide II of 2mL
In, under conditions of supersonic frequency is for 40KHz, ultrasonically treated 60min, obtains mixed solution；2. the mixing 1. step 2 being obtained
The Fe that solution and step one obtain2The mixing of Co-MOF material is put in reactor, then reactor is placed in the baking that temperature is 140 DEG C
React 4h in case, obtain Go/Fe2Co-MOF material, i.e. graphene-supported Fe2Co metal-organic framework materials；
In this test, the load capacity of Graphene is 0.1% in parts by weight.
This test described part 3,3 ', 5,5 '-azo benzene tertacarbonic acid press《Catalytic science and technology, iron (III), metal is organic
Framework isomerization to australene readily oxidizable substance as solid Lewis acid, 2012》(Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) described in method preparation.
Test two, a kind of graphene-supported Fe of this experiment2The preparation method of Co metal-organic framework materials presses following step
Suddenly carry out：
First, Fe2The preparation of Co-MOF material：Fe to 40mg2N,N-dimethylformamide I He of 2mL is added in Co
The glacial acetic acid of 0.9mL, ultrasonically treated 5min under conditions of supersonic frequency is for 40KHz, it is subsequently adding the 3 of 60mg, 3 ', 5,5 '-
Azo benzene tertacarbonic acid, under conditions of supersonic frequency is for 40KHz, then reaction vessel is put into reactor by ultrasonically treated 30min
In, then reactor is placed in reaction 4h in the baking oven that temperature is 140 DEG C, obtain Fe2Co-MOF material；
2nd, Go/Fe2The preparation of Co-MOF material：1. 0.2mg Graphene is dissolved in the N,N-dimethylformamide II of 2mL
In, under conditions of supersonic frequency is for 40KHz, ultrasonically treated 60min, obtains mixed solution；2. the mixing 1. step 2 being obtained
The Fe that solution and step one obtain2The mixing of Co-MOF material is put in reactor, then reactor is placed in the baking that temperature is 140 DEG C
React 4h in case, obtain Go/Fe2Co-MOF material, i.e. graphene-supported Fe2Co metal-organic framework materials；
In this test, the load capacity of Graphene is 0.2% in parts by weight.
This test described part 3,3 ', 5,5 '-azo benzene tertacarbonic acid press《Catalytic science and technology, iron (III), metal is organic
Framework isomerization to australene readily oxidizable substance as solid Lewis acid, 2012》(Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) described in method preparation.
Test three, a kind of graphene-supported Fe of this experiment2The preparation method of Co metal-organic framework materials presses following step
Suddenly carry out：
First, Fe2The preparation of Co-MOF material：Fe to 40mg2N,N-dimethylformamide I He of 2mL is added in Co
The glacial acetic acid of 0.9mL, ultrasonically treated 5min under conditions of supersonic frequency is for 40KHz, it is subsequently adding the 3 of 60mg, 3 ', 5,5 '-
Azo benzene tertacarbonic acid, under conditions of supersonic frequency is for 40KHz, then reaction vessel is put into reactor by ultrasonically treated 30min
In, then reactor is placed in reaction 4h in the baking oven that temperature is 140 DEG C, obtain Fe2Co-MOF material；
2nd, Go/Fe2The preparation of Co-MOF material：1. 0.25mg Graphene is dissolved in the N,N-dimethylformamide II of 2mL
In, under conditions of supersonic frequency is for 40KHz, ultrasonically treated 60min, obtains mixed solution；2. the mixing 1. step 2 being obtained
The Fe that solution and step one obtain2The mixing of Co-MOF material is put in reactor, then reactor is placed in the baking that temperature is 140 DEG C
React 4h in case, obtain Go/Fe2Co-MOF material, i.e. graphene-supported Fe2Co metal-organic framework materials；
In this test, the load capacity of Graphene is 0.25% in parts by weight.
This test described part 3,3 ', 5,5 '-azo benzene tertacarbonic acid press《Catalytic science and technology, iron (III), metal is organic
Framework isomerization to australene readily oxidizable substance as solid Lewis acid, 2012》(Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) described in method preparation.
Test four, a kind of graphene-supported Fe of this experiment2The preparation method of Co metal-organic framework materials presses following step
Suddenly carry out：
First, Fe2The preparation of Co-MOF material：Fe to 40mg2N,N-dimethylformamide I He of 2mL is added in Co
The glacial acetic acid of 0.9mL, ultrasonically treated 5min under conditions of supersonic frequency is for 40KHz, it is subsequently adding the 3 of 60mg, 3 ', 5,5 '-
Azo benzene tertacarbonic acid, under conditions of supersonic frequency is for 40KHz, then reaction vessel is put into reactor by ultrasonically treated 30min
In, then reactor is placed in reaction 4h in the baking oven that temperature is 140 DEG C, obtain Fe2Co-MOF material；
2nd, Go/Fe2The preparation of Co-MOF material：1. 0.5mg Graphene is dissolved in the N,N-dimethylformamide II of 2mL
In, under conditions of supersonic frequency is for 40KHz, ultrasonically treated 60min, obtains mixed solution；2. the mixing 1. step 2 being obtained
The Fe that solution and step one obtain2The mixing of Co-MOF material is put in reactor, then reactor is placed in the baking that temperature is 140 DEG C
React 4h in case, obtain Go/Fe2Co-MOF material, i.e. graphene-supported Fe2Co metal-organic framework materials；
In this test, the load capacity of Graphene is 0.5% in parts by weight.
This test described part 3,3 ', 5,5 '-azo benzene tertacarbonic acid press《Catalytic science and technology, iron (III), metal is organic
Framework isomerization to australene readily oxidizable substance as solid Lewis acid, 2012》(Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) described in method preparation.
Test five, a kind of graphene-supported Fe of this experiment2The preparation method of Co metal-organic framework materials presses following step
Suddenly carry out：
First, Fe2The preparation of Co-MOF material：Fe to 40mg2N,N-dimethylformamide I He of 2mL is added in Co
The glacial acetic acid of 0.9mL, ultrasonically treated 5min under conditions of supersonic frequency is for 40KHz, it is subsequently adding the 3 of 60mg, 3 ', 5,5 '-
Azo benzene tertacarbonic acid, under conditions of supersonic frequency is for 40KHz, then reaction vessel is put into reactor by ultrasonically treated 30min
In, then reactor is placed in reaction 4h in the baking oven that temperature is 140 DEG C, obtain Fe2Co-MOF material；
2nd, Go/Fe2The preparation of Co-MOF material：1. 1mg Graphene is dissolved in the DMF II of 2mL,
Under conditions of supersonic frequency is for 40KHz, ultrasonically treated 60min, obtains mixed solution；2. the mixing 1. obtaining step 2 is molten
The Fe that liquid and step one obtain2The mixing of Co-MOF material is put in reactor, then reactor is placed in the baking oven that temperature is 140 DEG C
Middle reaction 4h, obtains Go/Fe2Co-MOF material, i.e. graphene-supported Fe2Co metal-organic framework materials；
In this test, the load capacity of Graphene is 1% in parts by weight.
This test described part 3,3 ', 5,5 '-azo benzene tertacarbonic acid press《Catalytic science and technology, iron (III), metal is organic
Framework isomerization to australene readily oxidizable substance as solid Lewis acid, 2012》(Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) described in method preparation.
(1) Go/Fe that test one is obtained to test five2The phenetic analysis of Co-MOF：
1. infrared spectrum analysis
Go/Fe to test one, the graphene-supported amount of difference to test five preparation for the test three2Co-MOF and part 3,
3 ', 5,5 '-azo benzene tertacarbonic acid detected, obtains the Go/Fe of different graphene-supported amounts2Co-MOF and part 3,3 ',
The infrared spectrum of 5,5 '-azo benzene tertacarbonic acid is as shown in Figure 1；The Go/Fe that wherein 1 is 0% for graphene-supported amount2Co-MOF
(i.e. Fe2Co-MOF curve), the Go/Fe that 2 is 0.1% for graphene-supported amount2The curve of Co-MOF, 3 is graphene-supported amount
Go/Fe for 0.25%2The curve of Co-MOF, the Go/Fe that 4 is 0.5% for graphene-supported amount2The curve of Co-MOF, 5 is stone
Black alkene load capacity is 1% Go/Fe2The curve of Co-MOF, 6 is part 3,3 ', 5, the curve of 5 '-azo benzene tertacarbonic acid.By Fig. 1
Understand, Fe2Co-MOF and GO/Fe2Co-MOF material is in 1652cm-1The stretching vibration peak of carbonyl in place, with ligand 1 696cm-1
The carbonyl peak that place occurs is compared and be there occurs obvious displacement；And in 1696cm-1The absworption peak of carboxyl in place, shows in part
Carboxyl all there is protonation reaction, and and metallic ion coordination.Thus can determine whether, Fe2+Ion be there occurs with ketonic oxygen
Bridging.
2. X-ray powder diffraction analysis
Go/Fe to the graphene-supported amount of difference to test five preparation for the test one2Co-MOF carries out X-ray detection, with
Cu target (λ=0.15418nm) is x-ray source, and sets the tube voltage of 45kV, the sweep speed of 8 °/min, 0.02 ° of scanning step
Long, 5 °～50 ° of 2 θ scopes.Obtain testing the Go/Fe of a graphene-supported amount of difference to test five preparation2The X- of Co-MOF
Ray powder diffraction characterization result is as shown in Figure 2 with its monocrystalline analytic simulation figure；Wherein 1 is Go/Fe2The simulation of Co-MOF is bent
Line, the Go/Fe that 2 is 0.1% for graphene-supported amount2The curve of Co-MOF, the Go/ that 3 is 0.2% for graphene-supported amount
Fe2The curve of Co-MOF, the Go/Fe that 4 is 0.25% for graphene-supported amount2The curve of Co-MOF, 5 for graphene-supported amount are
0.5% Go/Fe2The curve of Co-MOF, the Go/Fe that 6 is 1% for graphene-supported amount2The curve of Co-MOF.As shown in Figure 2,
Go/Fe for different graphene-supported amounts2For Co-MOF, these peaks are all preferable with the standard spectrogram degree of agreement of sample,
Illustrate all to have obtained the Go/Fe of more pure phase2Co-MOF material, but the Go/Fe when the load capacity of Graphene is 0.25%2Co-
No matter the XRD of MOF goodness of fit compared with standard spectrogram preferably, significantly main characteristic peak respectively at 8.2 °, 11.3 °
Main characteristic peak or miscellaneous peak, can be corresponding well with simulation drawing, explanation obtained crystal formation preferably and also purer Go/
Fe2Co-MOF.
3. scanning electron microscope analysis
Go/Fe to the graphene-supported amount of difference to test five preparation for the test two2Co-MOF is scanned electron microscopic
Microscopy is surveyed, and obtains testing the Go/Fe of two preparations2The SEM of Co-MOF schemes as shown in figure 3, obtaining testing the Go/Fe of three preparations2Co-
The SEM of MOF schemes as shown in figure 4, obtaining testing the Go/Fe of four preparations2The SEM of Co-MOF schemes as shown in figure 5, obtaining testing five systems
Standby Go/Fe2The SEM of Co-MOF schemes as shown in fig. 6, from Fig. 3～6, load capacity is excessive to cause excessive Graphene to cover
On plane of crystal, and there is agglomeration, load capacity is too small to cause Graphene covering on crystal uneven；When load capacity is
0.25% (the Go/Fe of test three preparation2When Co-MOF), the degree that Graphene is combined with metal-organic framework materials is best.
4. uv-visible absorption spectra analysis
Go/Fe to test three preparation2Prepared by Co-MOF (graphene-supported amount is 0.25%) and test three steps one
Fe2Co-MOF carries out uv-visible absorption spectra analysis, method of testing：Use the UV- of HIT's production
3010 type ultraviolet-uisible spectrophotometers, the experiment condition of test is：Between 200～800nm, sweep spacing is sweep limits
2s, with BaSO4Standard white plate is reference.Obtain testing the Fe of three step one preparations2The uv-visible absorption spectrum figure of Co-MOF
As shown in fig. 7, obtaining testing the Go/Fe of three preparations2The uv-visible absorption spectrum figure of Co-MOF is as shown in figure 8, can by Fig. 7
To find out, maximum to the absorption intensity of light at 310nm, also there is stronger absorption in the visible-range interior focusing of 400-600nm,
The a length of 750nm of maximum absorption wave；As seen from Figure 8, GO/Fe2Co-MOF testing of materials result (b) is at 330nm to light
Absorption intensity is maximum, a length of 800nm of maximum absorption wave；It follows that bi-material is all stronger to the responding ability of light,
And after having loaded Graphene, the absorbing wavelength of light is substantially increased, oxidizing potential-reduction electricity can be calculated by spectrogram simultaneously
Edge energy between position is respectively 1.65eV, 1.55eV.
5. cyclic voltammetry analysis
Go/Fe to test three preparation2Co-MOF (graphene-supported amount is 0.25%) is circulated Voltammetric detection, test
Method：Using three-electrode system, wherein comprise carbon paste working electrode, platinum is to electrode and Ag/AgCl reference electrode.Using 1mol/L
H2SO4Solution is electrolyte, the sweep limits of 0.2～1.0V, the sweep speed of 50mV/s.
The method wherein making carbon paste electrode is as follows：By graphite and Fe2Co-MOF or GO/Fe2Co-MOF material mixes (matter
Amount 4/1), mortar is fully ground 30min, to guarantee that the two mixes, then with glue head dropper dropping atoleine, is placed in
In glass tube, insert copper wire, make carbon paste electrode.
Obtain the Go/Fe of test three preparation as shown in Figure 92The cyclic voltammetry test chart of Co-MOF.
H+/H2Energy level value be zero, when the reduction potential energy level value of metal-organic framework materials is more negative than zero, then permissible
Judge that this material has photocatalysis hydrogen production performance, on the contrary, then there is no photocatalysis hydrogen production performance.And reduction potential energy level value can be by
The mathematic interpolation of oxidizing potential edge energy and oxidizing potential-reduction potential energy level value obtains, so only needing to obtain oxidizing potential
Energy level value just can calculate reduction potential energy level value, and then judges whether with photocatalysis hydrogen production performance.
As seen from Figure 9, the Go/Fe of test three preparation2The energy level value of the oxidizing potential of Co-MOF is 0.42eV, therefore
Can obtain testing the Go/Fe of three preparations2The reduction potential energy level value of Co-MOF is -1.23eV, than reducing hydrogen ions hydrogen
Energy level value is more negative, therefore may determine that the Go/Fe of test three preparation2Co-MOF has photocatalysis hydrogen production performance.
6. thermogravimetric spectrum analysis
Go/Fe to test three preparation2Co-MOF (graphene-supported amount is 0.25%) carries out heat endurance curve, obtains
The Go/Fe of test three preparation as shown in Figure 102The thermogravimetric curve figure of Co-MOF, as can be seen from Figure 10：At 30～200 DEG C
Interior, the Go/Fe of test three preparation2Co-MOF gradually loses the hydrone of free solvent molecule and coordination；When temperature reaches
When 400 DEG C, skeleton starts to cave in, when more than 600 DEG C, the Go/Fe of test three preparation2The skeleton of Co-MOF caves in completely.
(2) with the Go/Fe of test three preparation2Co-MOF photolysis water hydrogen
1. the formulation of calibration curve
Respectively gas chromatographic analysis is carried out to the pure hydrogen of different volumes, obtained the standard of gas chromatograph hydrogen manufacturing experiment
As shown in figure 11, calibration curve equation is y=7645.4x-24057, R to curve map2=0.996.
2. the GO/Fe of different graphene-supported amounts2The impact to hydrogen-producing speed for the Co-MOF
The experiment of photolysis water hydrogen is to carry out in airtight quartz reactor；Add the Fe of 50mg2Co-MOF or GO/
Fe2Co-MOF catalyst, 15mL triethanolamine, 85ml distilled water；Device for producing hydrogen leads to afterwards the operation of nitrogen through first vacuumizing,
Reciprocation cycle three times, to remove the air containing in solution and other foreign gas；Radiation of visible light in the simulation of 300W xenon lamp
Under conditions of react, adopt a sample every 1h, sample 7 times altogether, and carry out the mensure of hydrogen content by gas chromatograph.
Reaction condition is：Catalyst (the Go/Fe of test one to test five preparation2Co-MOF input amount) is 50mg,
15mL triethanolamine, 85mL distilled water, carry out photocatalysis hydrogen production reaction under the xenon lamp of 300W, adopt a sample within every 1 hour, survey altogether
7 times, and carry out the mensure of hydrogen content by gas chromatograph.
As follows using the chromatographic condition determination of chromatogram：With N2For carrier gas, adopt 5Molecular sieve filling, TCD detector；
Setting 40 DEG C is initial temperature, 80 DEG C of column temperatures, 80 DEG C of detection room temperatures, 80A electric current.
Obtain the GO/Fe of different graphene-supported amounts2The hydrogen output curve map of Co-MOF is as shown in figure 12；Wherein 1 is stone
Black alkene load capacity is 0% Go/Fe2Co-MOF (i.e. Fe2Co-MOF curve), the Go/ that 2 is 0.1% for graphene-supported amount
Fe2The curve of Co-MOF, the Go/Fe that 3 is 0.2% for graphene-supported amount2The curve of Co-MOF, 4 for graphene-supported amount are
0.25% Go/Fe2The curve of Co-MOF, the Go/Fe that 5 is 0.5% for graphene-supported amount2The curve of Co-MOF, 6 is graphite
Alkene load capacity is 1% Go/Fe2The curve of Co-MOF.As can be seen from Figure 12：Fe2The increase in time of the hydrogen manufacturing amount of Co-MOF
Present and first increase the trend subtracting afterwards, the Fe of load Graphene2Co-MOF and single Fe2Co-MOF compares, and hydrogen manufacturing amount increases relatively；
The Fe of different graphene-supported amounts2Co-MOF compares, and when graphene-supported amount is 0.25%, hydrogen manufacturing amount reaches maximum 16 μ L/
(g·h).
Claims (10)
1. a kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials is it is characterised in that one kind is graphene-supported
Fe2The preparation method of Co metal-organic framework materials is carried out according to the following steps：
First, Fe2The preparation of Co-MOF material：To Fe2Add DMF I and glacial acetic acid in Co, in supersonic frequency be
Ultrasonically treated 4min～6min under conditions of 35KHz～45KHz, is subsequently adding 3,3 ', 5,5 '-azo benzene tertacarbonic acid, ultrasonic
Frequency is ultrasonically treated 25min～35min under conditions of 35KHz～45KHz, then puts into reaction vessel in reactor, then
Reactor is placed in reaction 2h～12h in the baking oven that temperature is 130～150 DEG C, obtains Fe2Co-MOF material；
N,N-dimethylformamide I described in step one is 2 with the volume ratio of glacial acetic acid:(0.5～1.5)；
The volume of N,N-dimethylformamide I described in step one and Fe2The ratio of the quality of Co is 2mL:(10～40) mg；
Fe described in step one2Co and 3,3 ', the mass ratio of 5,5 '-azo benzene tertacarbonic acid is 1:(1～2) mg；
2nd, Go/Fe2The preparation of Co-MOF material：1. Graphene is dissolved in DMF II, in supersonic frequency is
Under conditions of 35KHz～45KHz, ultrasonically treated 50min～70min, obtains mixed solution；2. the mixing 1. step 2 being obtained
The Fe that solution and step one obtain2Co-MOF material mixing after put in reactor, then by reactor be placed in temperature be 130～
React 3h～5h in 150 DEG C of baking oven, obtain Go/Fe2Co-MOF material, i.e. graphene-supported Fe2Co metallic organic framework material
Material；
1. the quality of described Graphene and the ratio of the volume of N,N-dimethylformamide II are (0.2～0.3) mg to step 2:2mL；
The Fe that in the step 2 mixed solution that 2. 1. described step 2 obtains, the quality of Graphene is obtained with step one2Co-MOF material
The mass ratio of material is (0.025～0.25):25.
2. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, its feature
It is that N,N-dimethylformamide I described in step one is 2 with the volume ratio of glacial acetic acid:0.9.
3. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, its feature
It is volume and the Fe of N,N-dimethylformamide I described in step one2The ratio of the quality of Co is 2mL:(20～30) mg.
4. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, its feature
It is Fe described in step one2Co and 3,3 ', the ratio of the quality of 5,5 '-azo benzene tertacarbonic acid is 1:1.5mg.
5. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, its feature
It is in step one to Fe2DMF I and glacial acetic acid is added, under conditions of supersonic frequency is for 40KHz in Co
Ultrasonically treated 5min, is subsequently adding 3,3 ', 5, and 5 '-azo benzene tertacarbonic acid is ultrasonically treated under conditions of supersonic frequency is for 40KHz
30min.
6. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, its feature
It is to put in reactor by reaction vessel in step one, then reactor is placed in reaction 4h in the baking oven that temperature is 140 DEG C, obtain
To Fe2Co-MOF material.
7. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, its feature
It is that 1. the quality of described Graphene and the ratio of the volume of N,N-dimethylformamide II are 0.25mg to step 2:2mL.
8. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, its feature
It is the Fe that the quality of Graphene in the step 2 mixed solution that 2. 1. described step 2 obtains is obtained with step one2Co-MOF material
The mass ratio of material is 0.0625:25.
9. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, its feature
In being step 2 1., Graphene is dissolved in DMF II, in the condition for 35KHz～45KHz for the supersonic frequency
Under ultrasonically treated 60min, obtain mixed solution.
10. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, its feature
The Fe in being step 2 2., the mixed solution that 1. step 2 obtains being obtained with step one2Put into anti-after the mixing of Co-MOF material
Answer in kettle, then reactor is placed in reaction 4h in the baking oven that temperature is 140 DEG C, obtain Go/Fe2Co-MOF material, i.e. Graphene
Load Fe2Co metal-organic framework materials.
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| CN107703195A (en) * | 2017-08-16 | 2018-02-16 | 商丘师范学院 | A kind of preparation method of graphene metal organic frame composite modified electrode |
| CN108559097A (en) * | 2018-04-28 | 2018-09-21 | 中北大学 | 3,3 ', 5,5 '-azoxy benzene tetracarboxylic acid europiums（III）Metal coordinating polymer and its synthetic method and application |
| CN109529932A (en) * | 2018-12-04 | 2019-03-29 | 三峡大学 | The preparation method and applications of petal-shaped metal-organic framework material |
| WO2021007990A1 (en) * | 2019-07-18 | 2021-01-21 | 华南理工大学 | Tea leaf dregs graphene-cucemof-pvb composite material and preparation method and application therefor |
| CN113368902A (en) * | 2021-06-22 | 2021-09-10 | 哈尔滨理工大学 | Fe2Co-MOFs loaded with ionic liquid CO2Preparation of reduced photocatalyst |
| CN114989447A (en) * | 2022-08-02 | 2022-09-02 | 广东工业大学 | Water-stable mixed-valence MOF material, preparation method thereof and application thereof in photocatalytic water decomposition |
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| CN107703195B (en) * | 2017-08-16 | 2019-08-30 | 商丘师范学院 | A kind of preparation method of graphene-metal organic frame composite material modified electrode |
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| CN108559097B (en) * | 2018-04-28 | 2020-10-02 | 中北大学 | 3,3',5,5' -azoxybenzenetetracarboxylic acid europium (III) metal coordination polymer and synthetic method and application thereof |
| CN109529932A (en) * | 2018-12-04 | 2019-03-29 | 三峡大学 | The preparation method and applications of petal-shaped metal-organic framework material |
| CN109529932B (en) * | 2018-12-04 | 2021-09-21 | 三峡大学 | Preparation method and application of petal-shaped metal organic framework material |
| WO2021007990A1 (en) * | 2019-07-18 | 2021-01-21 | 华南理工大学 | Tea leaf dregs graphene-cucemof-pvb composite material and preparation method and application therefor |
| CN113368902A (en) * | 2021-06-22 | 2021-09-10 | 哈尔滨理工大学 | Fe2Co-MOFs loaded with ionic liquid CO2Preparation of reduced photocatalyst |
| CN114989447A (en) * | 2022-08-02 | 2022-09-02 | 广东工业大学 | Water-stable mixed-valence MOF material, preparation method thereof and application thereof in photocatalytic water decomposition |
| CN114989447B (en) * | 2022-08-02 | 2022-12-09 | 广东工业大学 | Water-stable mixed-valence MOF material, preparation method thereof and application thereof in photocatalytic water decomposition |
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