CN106423279B - A kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials - Google Patents
A kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials Download PDFInfo
- Publication number
- CN106423279B CN106423279B CN201610817843.XA CN201610817843A CN106423279B CN 106423279 B CN106423279 B CN 106423279B CN 201610817843 A CN201610817843 A CN 201610817843A CN 106423279 B CN106423279 B CN 106423279B
- Authority
- CN
- China
- Prior art keywords
- graphene
- preparation
- metal
- mof
- supported
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 141
- 238000002360 preparation method Methods 0.000 title claims abstract description 71
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 68
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 138
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 94
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 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
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 16
- 229960000583 acetic acid Drugs 0.000 claims description 15
- 239000012362 glacial acetic acid Substances 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 8
- 229910000705 Fe2N Inorganic materials 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 46
- 238000004519 manufacturing process Methods 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 15
- 230000001699 photocatalysis Effects 0.000 abstract description 15
- 238000007146 photocatalysis Methods 0.000 abstract description 13
- 238000005381 potential energy Methods 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 238000002484 cyclic voltammetry Methods 0.000 abstract description 6
- 238000002411 thermogravimetry Methods 0.000 abstract description 6
- 238000006303 photolysis reaction Methods 0.000 abstract description 5
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 5
- -1 hydrogen ions hydrogen Chemical class 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 185
- 238000012360 testing method Methods 0.000 description 63
- 239000003446 ligand Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 14
- 239000002841 Lewis acid Substances 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 13
- 238000006317 isomerization reaction Methods 0.000 description 13
- 150000007517 lewis acids Chemical class 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000012476 oxidizable substance Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 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
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000010183 spectrum analysis Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 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
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-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
- 238000011088 calibration curve Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 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
- 238000000386 microscopy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 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
- 230000000737 periodic effect Effects 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
- 230000006798 recombination Effects 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
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004154 testing of material Methods 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
- B01J31/22—Organic complexes
-
- B01J35/39—
-
- 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
Abstract
A kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials.The present invention relates to a kind of preparation methods of metal-organic framework materials.The invention aims to solve the problems, such as that the material hydrogen production efficiency for being currently used for photolysis water hydrogen is not high.Method: one, Fe2The preparation of Co-MOF material；Two, Go/Fe2The preparation of Co-MOF material.Obtaining oxidizing potential energy level value by cyclic voltammetry is 0.42eV, and then can calculate reduction potential energy level value is -1.23eV, it is more negative than the energy level value of reducing hydrogen ions hydrogen, therefore have the ability of photocatalysis hydrogen production, using thermogravimetric analysis (TGA) to Go/Fe prepared by the present invention2The stability of Co-MOF material is probed into, as the result is shown Go/Fe prepared by the present invention2Co-MOF material has good stability when temperature is lower than 400 DEG C.
Description
Technical field
The present invention relates to a kind of preparation methods of metal-organic framework materials.
Background technique
Since 21st century, the problem of energy shortage and environmental pollution become whole world people facing, new energy
Exploitation also become the topic kept away not open, solar energy, the resources such as wind energy by continuous exploitation, utilize, and Hydrogen Energy is because of its storage
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 the concern and research of people.Hydrogen
There are many kinds of the way of production of energy, such as: organic waste hydrogen manufacturing is continued a large amount of hydrogen manufacturing using microalgae, is former derived from plant
Expect hydrogen manufacturing and photocatalysis hydrogen production etc., wherein solar energy is utilized, water is most commonly seen by the method for photocatalysis hydrogen production.Using too
Sun can obtain the photocatalysis technology of Hydrogen Energy, become the optimal method for obtaining Hydrogen Energy, receive domestic and international researcher
Favor.Wherein illumination n-type semiconductor TiO is worked as in Japanese scholars Fujishima and Honda research discovery2When electrode, it can lead to
Water decomposition, make it was recognized that using solar energy photocatalytic hydrogen manufacturing feasibility.But because its during photocatalysis hydrogen production light
Raw electrons and holes recombination rate is high, can only respond the disadvantages of ultraviolet light, limits its development.Therefore the novel light of one kind is developed to urge
Agent is extremely urgent.
Metal-organic framework materials be centered on metal ion or metal cluster, with organic ligand through coordinate bond self assembly and
At coordination polymer.A kind of material of the MOFs material as hybrid inorganic-organic there are many traditional materials not have excellent
Good characteristic, such as the diversity of component and structure, higher specific surface area and porosity, synthesis facilitate；So that its numerous areas
It has broad application prospects, such as in catalysis, gas storage, fluorescence detection.Since MOFs material itself has semiconductor
Property is more and more studied and has been verified that sunlight can be absorbed in MOFs material, can produce photoproduction after excitation recent years
Electronics, so as to be applied to photocatalysis hydrogen production.
The fast development of metal-organic framework materials is the important breakthrough of domain of inorganic chemistry in the latest 20 years.MOFs material
Material is by point centered on metal center or metal cluster.It is formed by connecting with organic ligand by coordinate bond self assembly, there is height
Periodic network crystalline complex, also referred to as metal coordinating polymer[7]。
The bore hole size of the unique texture feature of this hybrid inorganic-organic of MOFs and its Nano grade, makes it one
One or more catalytic sites are provided in a cavity, this is that other materials institute is irrealizable.Therefore MOFs material has many
Tempting feature: first, MOFs material have component diversity, by selecting different metal ions and different ligands, just
Miscellaneous MOFs material can be synthesized.The structure of second, MOFs material has performance-adjustable, with designed, designed and can close
At wanted structure, and the modification of functional material, the functionalization of Lai Shixian MOF material can be passed through.Third, MOFs material
With porous structure of uniform size, biggish specific surface area.4th, MOFs material have good thermal stability and chemistry
Stability.5th, it is simple synthetic method, easy to operate.
In nearly research in 30 years, MOFs material develops at an amazing speed.In many chemical periodicals, about MOFs
Paper or summary exponentially increase, so fast development speed also illustrates that this material has that lift foot light in field of scientific study
The status of weight.So far, researchers oneself synthesized a large amount of structure novel, MOFs material of good performance, 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
The various structures of synthesis and expand it in the application of every field.Domestic Many researchers are in the field in recent years
Certain achievement is achieved, also there is far-reaching influence in the world.
However existing MOFs material photolysis water hydrogen is inefficient, needs further to be probed into, develops a kind of photocatalytic water
The high material of hydrogen production efficiency.
Summary of the invention
The invention aims to solve the problems, such as that the material hydrogen production efficiency for 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 invention2The preparation method of Co metal-organic framework materials is to complete according to the following steps
:
One, Fe2The preparation of Co-MOF material: to Fe2N,N-Dimethylformamide I and glacial acetic acid are added in Co, in supersonic frequency
Rate is ultrasonically treated 4min~6min under conditions of being 35KHz~45KHz, and 3,3 ', 5,5 '-azo benzene tertacarbonic acids are then added,
Supersonic frequency is ultrasonically treated 25min~35min under conditions of being 35KHz~45KHz, and reaction vessel is then put into reaction kettle
In, then reaction kettle is placed in the baking oven that temperature is 130~150 DEG C and reacts 2h~12h, obtain Fe2Co-MOF material；
The volume ratio of N,N-dimethylformamide I described in step 1 and glacial acetic acid is 2:(0.5~1.5)；
The volume and Fe of N,N-dimethylformamide I described in step 12The ratio of the quality of Co is 2mL:(10~40) mg；
Fe described in step 12Co and 3,3 ', the mass ratio of 5,5 '-azo benzene tertacarbonic acids are 1:(1~2) mg；
Two, Go/Fe2The preparation of Co-MOF material: 1. graphene is dissolved in n,N-Dimethylformamide II, in supersonic frequency
Rate is ultrasonically treated 50min~70min under conditions of being 35KHz~45KHz, obtains mixed solution；2. 1. step 2 is obtained
The Fe that mixed solution and step 1 obtain2It is put into reaction kettle after the mixing of Co-MOF material, then it is 130 that reaction kettle, which is placed in temperature,
3h~5h is reacted in~150 DEG C of baking oven, obtains Go/Fe2Co-MOF material, i.e., graphene-supported Fe2Co metal organic framework material
Material；
1. the ratio of the quality of the graphene and the volume of N,N-dimethylformamide II is (0.2~0.3) mg to step 2:
2mL；
The Fe that the quality Yu step 1 of graphene obtain in the step 2 mixed solution that 2. 1. the step 2 obtains2Co-
The mass ratio of MOF material is (0.025~0.25): 25.
3,3 ', 5,5 '-azo benzene tertacarbonic acid of ligand of the present invention is by " catalytic science and technology, iron (III), metal is organic
Isomerization of the frame as solid Lewis acid to australene readily oxidizable substance, 2012 " the method preparation recorded in.
Beneficial effects of the present invention
The present invention passes through hydro-thermal (solvent heat) method for 3,3 ', 5,5 '-azo of ligand benzene tertacarbonic acid's (3,3 ', 5,5 '-azobenzenes
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 have successfully synthesized 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 violet outside-can
See that the spectrum analysis that diffuses (UV-Vis) test result shows: Fe2The GO/Fe of the graphene-supported amount of Co-MOF and 0.25%2Co-
MOF material oxidation current potential-reduction potential edge energy 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 is -1.23eV, than the energy level value of reducing hydrogen ions hydrogen
It is more negative, therefore have the ability of photocatalysis hydrogen production, using thermogravimetric analysis (TGA) to Go/Fe prepared by the present invention2Co-MOF material
Stability probed into, Go/Fe prepared by the present invention as the result is shown2Co-MOF material has when temperature is lower than 400 DEG C
Good stability.
Detailed description of the invention
Fig. 1 is the Go/Fe of different graphene-supported amounts2Co-MOF and ligand 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
Analyse simulation drawing；
Fig. 3 is the Go/Fe for testing two preparations2The SEM of Co-MOF schemes；
Fig. 4 is the Go/Fe for testing three preparations2The SEM of Co-MOF schemes；
Fig. 5 is the Go/Fe for testing four preparations2The SEM of Co-MOF schemes；
Fig. 6 is the Go/Fe for testing five preparations2The SEM of Co-MOF schemes；
Fig. 7 is the Fe for testing the preparation of three step 12The uv-visible absorption spectrum figure of Co-MOF；
Fig. 8 is the Go/Fe for testing three preparations2The uv-visible absorption spectrum figure of Co-MOF is such as；
Fig. 9 is the Go/Fe for testing three preparations2The cyclic voltammetry test chart of Co-MOF；
Figure 10 is the Go/Fe for testing three preparations2The thermogravimetric curve figure of Co-MOF；
Figure 11 is the canonical plotting of gas chromatograph hydrogen manufacturing experiment；
Figure 12 is the GO/Fe of different graphene-supported amounts2The hydrogen output curve graph of Co-MOF.
Specific embodiment
Specific embodiment 1: a kind of graphene-supported Fe of present embodiment2The preparation of Co metal-organic framework materials
Method is completed by the following steps:
One, Fe2The preparation of Co-MOF material: to Fe2N,N-Dimethylformamide I and glacial acetic acid are added in Co, in supersonic frequency
Rate is ultrasonically treated 4min~6min under conditions of being 35KHz~45KHz, and 3,3 ', 5,5 '-azo benzene tertacarbonic acids are then added,
Supersonic frequency is ultrasonically treated 25min~35min under conditions of being 35KHz~45KHz, and reaction vessel is then put into reaction kettle
In, then reaction kettle is placed in the baking oven that temperature is 130~150 DEG C and reacts 2h~12h, obtain Fe2Co-MOF material；
The volume ratio of N,N-dimethylformamide I described in step 1 and glacial acetic acid is 2:(0.5~1.5)；
The volume and Fe of N,N-dimethylformamide I described in step 12The ratio of the quality of Co is 2mL:(10~40) mg；
Fe described in step 12Co and 3,3 ', the mass ratio of 5,5 '-azo benzene tertacarbonic acids are 1:(1~2) mg；
Two, Go/Fe2The preparation of Co-MOF material: 1. graphene is dissolved in n,N-Dimethylformamide II, in supersonic frequency
Rate is ultrasonically treated 50min~70min under conditions of being 35KHz~45KHz, obtains mixed solution；2. 1. step 2 is obtained
The Fe that mixed solution and step 1 obtain2It is put into reaction kettle after the mixing of Co-MOF material, then it is 130 that reaction kettle, which is placed in temperature,
3h~5h is reacted in~150 DEG C of baking oven, obtains Go/Fe2Co-MOF material, i.e., graphene-supported Fe2Co metal organic framework material
Material；
1. the ratio of the quality of the graphene and the volume of N,N-dimethylformamide II is (0.2~0.3) mg to step 2:
2mL；
The Fe that the quality Yu step 1 of graphene obtain in the step 2 mixed solution that 2. 1. the step 2 obtains2Co-
The mass ratio of MOF material is (0.025~0.25): 25.
Ligand 3 described in present embodiment, 3 ', 5,5 '-azo benzene tertacarbonic acids press " catalytic science and technology, iron (III), metal
Isomerization of the organic frame as solid Lewis acid to australene readily oxidizable substance, 2012 " (Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) in record method preparation.
By 3,3 ', 5,5 '-azo of ligand benzene tertacarbonic acid, (3,3 ', 5,5 '-is even by hydro-thermal (solvent heat) method for present embodiment
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 have successfully synthesized 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 violet outside-can
See that the spectrum analysis that diffuses (UV-Vis) test result shows: Fe2The GO/Fe of the graphene-supported amount of Co-MOF and 0.25%2Co-
MOF material oxidation current potential-reduction potential edge energy 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 is -1.23eV, than the energy level value of reducing hydrogen ions hydrogen
It is more negative, therefore have the ability of photocatalysis hydrogen production, using thermogravimetric analysis (TGA) to Go/Fe prepared by the present invention2Co-MOF material
Stability probed into, as the result is shown present embodiment preparation Go/Fe2Co-MOF material is when temperature is lower than 400 DEG C
With good stability.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: N described in step 1, N- bis-
Methylformamide I and the volume ratio of glacial acetic acid are 2:0.9.Other steps and parameter are same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: N described in step 1,
The volume and Fe of dinethylformamide I2The ratio of the quality of Co is 2mL:(20~30) mg.Other steps and parameter and specific reality
It is identical to apply mode one or two.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: institute in step 1
State Fe2Co and 3,3 ', the ratio of the quality of 5,5 '-azo benzene tertacarbonic acids are 1:1.5mg.Other steps and parameter and specific embodiment party
One of formula one to three is identical.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: in step 1 to
Fe2N,N-Dimethylformamide I and glacial acetic acid are added in Co, is ultrasonically treated 5min under conditions of supersonic frequency is 40KHz, so
After 3,3 ', 5,5 '-azo benzene tertacarbonic acids are added, supersonic frequency be 40KHz under conditions of be ultrasonically treated 30min.Other steps
And parameter is identical as one of specific embodiment one to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: will in step 1
Reaction vessel is put into reaction kettle, then reaction kettle is placed in the baking oven that temperature is 140 DEG C and reacts 4h, obtains Fe2Co-MOF material
Material.Other steps and parameter are identical as one of specific embodiment one to five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: step 2 1. institute
The ratio for stating the quality of graphene and the volume of N,N-dimethylformamide II is 0.25mg:2mL.Other steps and parameter and specific
One of embodiment one to six is identical.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: step 2 2. institute
State the Fe that the quality Yu step 1 of graphene in 1. mixed solution that step 2 obtains obtain2The mass ratio of Co-MOF material is
0.0625:25.Other steps and parameter are identical as one of specific embodiment one to the Seventh Five-Year Plan.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: step 2 1. in
Graphene is dissolved in n,N-Dimethylformamide II, is ultrasonically treated under conditions of supersonic frequency is 35KHz~45KHz
60min obtains mixed solution.Other steps and parameter are identical as one of specific embodiment one to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine: step 2 2. in
By 1. mixed solution that step 2 obtains and the Fe that step 1 obtains2It is put into reaction kettle after the mixing of Co-MOF material, then will be anti-
It answers kettle to be placed in the baking oven that temperature is 140 DEG C and reacts 4h, obtain Go/Fe2Co-MOF material, i.e., graphene-supported Fe2Co metal has
Machine framework material.Other steps and parameter are identical as one of specific embodiment one to nine.
Beneficial effects of the present invention are verified with following tests
A kind of graphene-supported Fe of test one, this experiment2The preparation method of Co metal-organic framework materials presses following step
It is rapid to carry out:
One, Fe2The preparation of Co-MOF material: to the Fe of 40mg2I He of N,N-dimethylformamide of 2mL is added in Co
The glacial acetic acid of 0.9mL is ultrasonically treated 5min under conditions of supersonic frequency is 40KHz, is then added 3,3 ', 5, the 5 '-of 60mg
Azo benzene tertacarbonic acid is ultrasonically treated 30min under conditions of supersonic frequency is 40KHz, reaction vessel is then put into reaction kettle
In, then reaction kettle is placed in the baking oven that temperature is 140 DEG C and reacts 4h, obtain Fe2Co-MOF material；
Two, Go/Fe2The preparation of Co-MOF material: 1. 0.1mg graphene is dissolved in 2mL N,N-dimethylformamide II
In, it is ultrasonically treated 60min under conditions of supersonic frequency is 40KHz, obtains mixed solution；2. 1. mixing that step 2 is obtained
The Fe that solution and step 1 obtain2The mixing of Co-MOF material is put into reaction kettle, then reaction kettle is placed in the baking that temperature is 140 DEG C
4h is reacted in case, obtains Go/Fe2Co-MOF material, i.e., graphene-supported Fe2Co metal-organic framework materials；
The load capacity of graphene is 0.1% as mass fraction in this test.
This test 3,3 ', 5,5 '-azo benzene tertacarbonic acid of ligand is by " catalytic science and technology, iron (III), metal is organic
Isomerization of the frame as solid Lewis acid to australene readily oxidizable substance, 2012 " (Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) in record method preparation.
A kind of graphene-supported Fe of test two, this experiment2The preparation method of Co metal-organic framework materials presses following step
It is rapid to carry out:
One, Fe2The preparation of Co-MOF material: to the Fe of 40mg2I He of N,N-dimethylformamide of 2mL is added in Co
The glacial acetic acid of 0.9mL is ultrasonically treated 5min under conditions of supersonic frequency is 40KHz, is then added 3,3 ', 5, the 5 '-of 60mg
Azo benzene tertacarbonic acid is ultrasonically treated 30min under conditions of supersonic frequency is 40KHz, reaction vessel is then put into reaction kettle
In, then reaction kettle is placed in the baking oven that temperature is 140 DEG C and reacts 4h, obtain Fe2Co-MOF material；
Two, Go/Fe2The preparation of Co-MOF material: 1. 0.2mg graphene is dissolved in 2mL N,N-dimethylformamide II
In, it is ultrasonically treated 60min under conditions of supersonic frequency is 40KHz, obtains mixed solution；2. 1. mixing that step 2 is obtained
The Fe that solution and step 1 obtain2The mixing of Co-MOF material is put into reaction kettle, then reaction kettle is placed in the baking that temperature is 140 DEG C
4h is reacted in case, obtains Go/Fe2Co-MOF material, i.e., graphene-supported Fe2Co metal-organic framework materials；
The load capacity of graphene is 0.2% as mass fraction in this test.
This test 3,3 ', 5,5 '-azo benzene tertacarbonic acid of ligand is by " catalytic science and technology, iron (III), metal is organic
Isomerization of the frame as solid Lewis acid to australene readily oxidizable substance, 2012 " (Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) in record method preparation.
A kind of graphene-supported Fe of test three, this experiment2The preparation method of Co metal-organic framework materials presses following step
It is rapid to carry out:
One, Fe2The preparation of Co-MOF material: to the Fe of 40mg2I He of N,N-dimethylformamide of 2mL is added in Co
The glacial acetic acid of 0.9mL is ultrasonically treated 5min under conditions of supersonic frequency is 40KHz, is then added 3,3 ', 5, the 5 '-of 60mg
Azo benzene tertacarbonic acid is ultrasonically treated 30min under conditions of supersonic frequency is 40KHz, reaction vessel is then put into reaction kettle
In, then reaction kettle is placed in the baking oven that temperature is 140 DEG C and reacts 4h, obtain Fe2Co-MOF material；
Two, Go/Fe2The preparation of Co-MOF material: 1. 0.25mg graphene is dissolved in 2mL N,N-dimethylformamide II
In, it is ultrasonically treated 60min under conditions of supersonic frequency is 40KHz, obtains mixed solution；2. 1. mixing that step 2 is obtained
The Fe that solution and step 1 obtain2The mixing of Co-MOF material is put into reaction kettle, then reaction kettle is placed in the baking that temperature is 140 DEG C
4h is reacted in case, obtains Go/Fe2Co-MOF material, i.e., graphene-supported Fe2Co metal-organic framework materials；
The load capacity of graphene is 0.25% as mass fraction in this test.
This test 3,3 ', 5,5 '-azo benzene tertacarbonic acid of ligand is by " catalytic science and technology, iron (III), metal is organic
Isomerization of the frame as solid Lewis acid to australene readily oxidizable substance, 2012 " (Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) in record method preparation.
A kind of graphene-supported Fe of test four, this experiment2The preparation method of Co metal-organic framework materials presses following step
It is rapid to carry out:
One, Fe2The preparation of Co-MOF material: to the Fe of 40mg2I He of N,N-dimethylformamide of 2mL is added in Co
The glacial acetic acid of 0.9mL is ultrasonically treated 5min under conditions of supersonic frequency is 40KHz, is then added 3,3 ', 5, the 5 '-of 60mg
Azo benzene tertacarbonic acid is ultrasonically treated 30min under conditions of supersonic frequency is 40KHz, reaction vessel is then put into reaction kettle
In, then reaction kettle is placed in the baking oven that temperature is 140 DEG C and reacts 4h, obtain Fe2Co-MOF material；
Two, Go/Fe2The preparation of Co-MOF material: 1. 0.5mg graphene is dissolved in 2mL N,N-dimethylformamide II
In, it is ultrasonically treated 60min under conditions of supersonic frequency is 40KHz, obtains mixed solution；2. 1. mixing that step 2 is obtained
The Fe that solution and step 1 obtain2The mixing of Co-MOF material is put into reaction kettle, then reaction kettle is placed in the baking that temperature is 140 DEG C
4h is reacted in case, obtains Go/Fe2Co-MOF material, i.e., graphene-supported Fe2Co metal-organic framework materials；
The load capacity of graphene is 0.5% as mass fraction in this test.
This test 3,3 ', 5,5 '-azo benzene tertacarbonic acid of ligand is by " catalytic science and technology, iron (III), metal is organic
Isomerization of the frame as solid Lewis acid to australene readily oxidizable substance, 2012 " (Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) in record method preparation.
A kind of graphene-supported Fe of test five, this experiment2The preparation method of Co metal-organic framework materials presses following step
It is rapid to carry out:
One, Fe2The preparation of Co-MOF material: to the Fe of 40mg2I He of N,N-dimethylformamide of 2mL is added in Co
The glacial acetic acid of 0.9mL is ultrasonically treated 5min under conditions of supersonic frequency is 40KHz, is then added 3,3 ', 5, the 5 '-of 60mg
Azo benzene tertacarbonic acid is ultrasonically treated 30min under conditions of supersonic frequency is 40KHz, reaction vessel is then put into reaction kettle
In, then reaction kettle is placed in the baking oven that temperature is 140 DEG C and reacts 4h, obtain Fe2Co-MOF material；
Two, Go/Fe21mg graphene: being 1. dissolved in the n,N-Dimethylformamide II of 2mL by the preparation of Co-MOF material,
It is ultrasonically treated 60min under conditions of supersonic frequency is 40KHz, obtains mixed solution；2. 1. mixing that step 2 is obtained is molten
The Fe that liquid and step 1 obtain2The mixing of Co-MOF material is put into reaction kettle, then reaction kettle 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；
The load capacity of graphene is 1% as mass fraction in this test.
This test 3,3 ', 5,5 '-azo benzene tertacarbonic acid of ligand is by " catalytic science and technology, iron (III), metal is organic
Isomerization of the frame as solid Lewis acid to australene readily oxidizable substance, 2012 " (Catalysis Science&
Technology Iron(III)metal–organic frameworks as solid Lewis acids for the
Isomerization of a-pinene oxide 2012) in record method preparation.
(1) Go/Fe that test one is obtained to test five2The phenetic analysis of Co-MOF:
1. infrared spectrum analysis
To the Go/Fe of the graphene-supported amount of difference prepared by test one, test three to test five2Co-MOF and ligand 3,
3 ', 5,5 '-azo benzene tertacarbonic acids detect, and obtain the Go/Fe of different graphene-supported amounts2Co-MOF and ligand 3,3 ',
The infrared spectroscopy of 5,5 '-azo benzene tertacarbonic acids is as shown in Figure 1；Wherein 1 for graphene-supported amount be 0% Go/Fe2Co-MOF
(i.e. Fe2Co-MOF curve), 2 be the Go/Fe that graphene-supported amount is 0.1%2The curve of Co-MOF, 3 be graphene-supported amount
For 0.25% Go/Fe2The curve of Co-MOF, 4 be the Go/Fe that graphene-supported amount is 0.5%2The curve of Co-MOF, 5 be stone
The Go/Fe that black alkene load capacity is 1%2The curve of Co-MOF, 6 be the curve of 3,3 ', 5,5 '-azo benzene tertacarbonic acid of ligand.By Fig. 1
It is found that Fe2Co-MOF and GO/Fe2Co-MOF material is in 1652cm-1There is the stretching vibration peak of carbonyl in place, with ligand 1 696cm-1
The carbonyl peak that place occurs is compared and apparent displacement has occurred；And in 1696cm-1Place does not occur the absorption peak of carboxyl, shows in ligand
Carboxyl protonation reaction, and and metallic ion coordination all occur.Thus it can determine whether, Fe2+Ion has occurred with ketonic oxygen
Bridging.
2. X-ray powder diffraction is analyzed
To the Go/Fe of the graphene-supported amount of difference prepared by test one to test five2Co-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
Length, 5 °~50 ° of 2 θ ranges.Obtain the Go/Fe of the graphene-supported amount of difference prepared by test one to test five2The X- of Co-MOF
Ray powder diffraction characterization result and its monocrystalline analytic simulation figure are as shown in Figure 2；Wherein 1 is Go/Fe2The simulation of Co-MOF is bent
Line, 2 be the Go/Fe that graphene-supported amount is 0.1%2The curve of Co-MOF, 3 be the Go/ that graphene-supported amount is 0.2%
Fe2The curve of Co-MOF, 4 be the Go/Fe that graphene-supported amount is 0.25%2The curve of Co-MOF, 5 are for graphene-supported amount
0.5% Go/Fe2The curve of Co-MOF, 6 be the Go/Fe that graphene-supported amount is 1%2The curve of Co-MOF.As shown in Figure 2,
For the Go/Fe of different graphene-supported amounts2For Co-MOF, these peaks are preferable with the standard spectrogram degree of agreement of sample,
Illustrate the Go/Fe for having obtained more pure phase2Co-MOF material, but the Go/Fe when the load capacity of graphene is 0.25%2Co-
The XRD diagram of MOF goodness of fit compared with standard spectrogram is best, no matter occurs apparent main characteristic peak at 8.2 °, 11.3 ° respectively
It is main characteristic peak or miscellaneous peak, can be corresponding well with simulation drawing, explanation has obtained the preferable and purer Go/ of crystal form
Fe2Co-MOF。
3. scanning electron microscope analysis
To the Go/Fe of the graphene-supported amount of difference prepared by test two to test five2Co-MOF is scanned electron microscopic
Microscopy is surveyed, and the Go/Fe of two preparation of test is obtained2The SEM of Co-MOF schemes as shown in figure 3, obtaining the Go/Fe of three preparation of test2Co-
The SEM of MOF schemes as shown in figure 4, obtaining the Go/Fe of four preparation of test2The SEM of Co-MOF schemes as shown in figure 5, obtaining five system of test
Standby Go/Fe2The SEM of Co-MOF schemes as shown in fig. 6, causing excessive graphene to cover it is found that load capacity is excessive by Fig. 3~6
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 three preparation of test2When Co-MOF), the graphene degree compound with metal-organic framework materials is best.
4. uv-visible absorption spectra is analyzed
Go/Fe prepared by test three2Co-MOF (graphene-supported amount is 0.25%) and test three step 1 preparation
Fe2Co-MOF carries out uv-visible absorption spectra analysis, test method: the UV- produced using Hitachi, Japan
3010 type ultraviolet-uisible spectrophotometers, the experiment condition of test are as follows: between 200~800nm, sweep spacing is scanning range
2s, with BaSO4Standard white plate is reference.Obtain the Fe of test three step 1 preparation2The uv-visible absorption spectrum figure of Co-MOF
As shown in fig. 7, obtaining the Go/Fe of three preparation of test2The uv-visible absorption spectrum figure of Co-MOF is as shown in figure 8, can by Fig. 7
It is maximum to the absorption intensity of light at 310nm to find out, 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 two kinds of materials are all stronger to the responding ability of light,
And the absorbing wavelength of light is obviously increased after having loaded graphene, while oxidizing potential-reduction electricity can be calculated by spectrogram
Edge energy between position is respectively 1.65eV, 1.55eV.
5. cyclic voltammetry is analyzed
Go/Fe prepared by test three2Co-MOF (graphene-supported amount is 0.25%) carries out cyclic voltammetric detection, test
Method: using three-electrode system, wherein including carbon paste working electrode, platinum is to electrode and Ag/AgCl reference electrode.Using 1mol/L
H2SO4Solution is electrolyte, the scanning range of 0.2~1.0V, the scanning speed of 50mV/s.
The method for wherein making carbon paste electrode is as follows: by graphite and Fe2Co-MOF or GO/Fe2Co-MOF material mixes (matter
4/1) amount, is fully ground 30min in mortar, to ensure that the two is uniformly mixed, then atoleine is added dropwise with rubber head dropper, is placed in
In glass tube, it is inserted into copper wire, carbon paste electrode is made.
Obtain Go/Fe prepared by test three as shown in Figure 92The cyclic voltammetry test chart of Co-MOF.
H+/H2Energy level value be zero, then can be with when the reduction potential energy level value of metal-organic framework materials is more negative than zero
Determine that the material has photocatalysis hydrogen production performance, on the contrary, not having photocatalysis hydrogen production performance then.And reduction potential energy level value can be by
Oxidizing potential edge energy and oxidizing potential-reduction potential energy level value difference are calculated, so only needing to obtain oxidizing potential
Energy level value can calculate reduction potential energy level value, and then judge whether with photocatalysis hydrogen production performance.
As seen from Figure 9, the Go/Fe of three preparation of test2The energy level value of the oxidizing potential of Co-MOF is 0.42eV, therefore
The Go/Fe of available three preparation of test2The 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 three preparation of test2Co-MOF has photocatalysis hydrogen production performance.
6. thermogravimetric spectrum analysis
Go/Fe prepared by test three2Co-MOF (graphene-supported amount is 0.25%) carries out thermal stability curve, obtains
Go/Fe prepared by test three as shown in Figure 102The thermogravimetric curve figure of Co-MOF, as can be seen from Figure 10: at 30~200 DEG C
It is interior, the Go/Fe of three preparation of test2Co-MOF gradually loses the hydrone of free solvent molecule and coordination；When temperature reaches
Skeleton starts to collapse at 400 DEG C, at 600 DEG C or more, the Go/Fe of three preparation of test2The skeleton of Co-MOF collapses completely.
(2) with the Go/Fe of three preparation of test2Co-MOF photolysis water hydrogen
1. the formulation of standard curve
Gas chromatographic analysis has been carried out to the pure hydrogen of different volumes respectively, has obtained the standard of gas chromatograph hydrogen manufacturing experiment
Curve graph is as shown in figure 11, calibration curve equation y=7645.4x-24057, R2=0.996.
2. the GO/Fe of different graphene-supported amounts2Influence of the Co-MOF to hydrogen-producing speed
The experiment of photolysis water hydrogen is carried out in closed quartz reactor；The Fe of 50mg is added2Co-MOF or GO/
Fe2Co-MOF catalyst, 15mL triethanolamine, 85ml distilled water；Device for producing hydrogen by first vacuumize afterwards lead to the operation of nitrogen,
Reciprocation cycle three times, to remove the air contained in solution and other foreign gases；In the radiation of visible light of 300W xenon lamp simulation
Under conditions of react, adopt a sample every 1h, altogether sample 7 times, and by gas chromatograph progress hydrogen content measurement.
Reaction condition are as follows: catalyst (Go/Fe prepared by test one to test five2Co-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 pass through the measurement of gas chromatograph progress hydrogen content.
Use the chromatographic determination condition of chromatography as follows: with N2For carrier gas, using 5Molecular sieve filling, TCD detector；
40 DEG C of setting are 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 graph of Co-MOF is as shown in figure 12；Wherein 1 is stone
The Go/Fe that black alkene load capacity is 0%2Co-MOF (i.e. Fe2Co-MOF curve), 2 be the Go/ that graphene-supported amount is 0.1%
Fe2The curve of Co-MOF, 3 be the Go/Fe that graphene-supported amount is 0.2%2The curve of Co-MOF, 4 are for graphene-supported amount
0.25% Go/Fe2The curve of Co-MOF, 5 be the Go/Fe that graphene-supported amount is 0.5%2The curve of Co-MOF, 6 be graphite
The Go/Fe that alkene load capacity is 1%2The curve of Co-MOF.As can be seen from Figure 12: Fe2The increase of the hydrogen manufacturing amount of Co-MOF at any time
Presentation first increases the trend subtracted afterwards, loads the Fe of graphene2Co-MOF and individual Fe2Co-MOF is compared, and hydrogen manufacturing amount is opposite to be increased；
The Fe of different graphene-supported amounts2Co-MOF is compared, and when graphene-supported amount is 0.25%, hydrogen manufacturing amount reaches 16 μ L/ of maximum
(g·h)。
Claims (10)
1. a kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials, it is characterised in that a kind of graphene-supported
Fe2The preparation method of Co metal-organic framework materials sequentially includes the following steps:
One, Fe2The preparation of Co-MOF material: to Fe2N,N-Dimethylformamide I and glacial acetic acid are added in Co, is in supersonic frequency
It is ultrasonically treated 4min~6min under conditions of 35KHz~45KHz, 3,3 ', 5,5 '-azo benzene tertacarbonic acids are then added, in ultrasound
Frequency is ultrasonically treated 25min~35min under conditions of being 35KHz~45KHz, and then reaction vessel is put into reaction kettle, then
Reaction kettle is placed in the baking oven that temperature is 130~150 DEG C and reacts 2h~12h, obtains Fe2Co-MOF material；
The volume ratio of N,N-dimethylformamide I described in step 1 and glacial acetic acid is 2:(0.5~1.5)；
The volume and Fe of N,N-dimethylformamide I described in step 12The ratio of the quality of Co is 2mL:(10~40) mg；
Fe described in step 12Co and 3,3 ', the mass ratio of 5,5 '-azo benzene tertacarbonic acids are 1:(1~2) mg；
Two, Go/Fe2Graphene: being 1. dissolved in n,N-Dimethylformamide II by the preparation of Co-MOF material, is in supersonic frequency
It is ultrasonically treated 50min~70min under conditions of 35KHz~45KHz, obtains mixed solution；2. 1. mixing that step 2 is obtained
The Fe that solution and step 1 obtain2Co-MOF material mixing after be put into reaction kettle, then by reaction kettle be placed in temperature be 130~
3h~5h is reacted in 150 DEG C of baking oven, obtains Go/Fe2Co-MOF material, i.e., graphene-supported Fe2Co metal organic framework material
Material；
1. the ratio of the quality of the graphene and the volume of N,N-dimethylformamide II is (0.2~0.3) mg:2mL to step 2；
The Fe that the quality Yu step 1 of graphene obtain in the step 2 mixed solution that 2. 1. the step 2 obtains2Co-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, feature
The volume ratio for being N,N-dimethylformamide I described in step 1 and glacial acetic acid is 2:0.9.
3. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, feature
It is the volume and Fe of N,N-dimethylformamide I described in step 12The 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, feature
It is Fe described in step 12Co and 3,3 ', the ratio of the quality of 5,5 '-azo benzene tertacarbonic acids are 1:1.5mg.
5. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, feature
It is in step 1 to Fe2N,N-Dimethylformamide I and glacial acetic acid are added in Co, under conditions of supersonic frequency is 40KHz
It is ultrasonically treated 5min, 3,3 ', 5,5 '-azo benzene tertacarbonic acids are then added, is ultrasonically treated under conditions of supersonic frequency is 40KHz
30min。
6. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, feature
It is that reaction vessel is put into reaction kettle in step 1, then reaction kettle is placed in the baking oven that temperature is 140 DEG C and reacts 4h, obtains
To Fe2Co-MOF material.
7. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, feature
It is that 1. the ratio of the quality of the graphene and the volume of N,N-dimethylformamide II is 0.25mg:2mL to step 2.
8. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, feature
It is the Fe that the quality Yu step 1 of graphene in the step 2 mixed solution that 2. 1. the step 2 obtains obtain2Co-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, feature
Graphene is dissolved in n,N-Dimethylformamide II in being step 2 1., in the condition that supersonic frequency is 35KHz~45KHz
Lower ultrasonic treatment 60min, obtains mixed solution.
10. a kind of graphene-supported Fe according to claim 12The preparation method of Co metal-organic framework materials, feature
By 1. mixed solution that step 2 obtains and the Fe that step 1 obtains in being step 2 2.2It is put into after the mixing of Co-MOF material anti-
It answers in kettle, then reaction kettle is placed in the baking oven that temperature is 140 DEG C and reacts 4h, obtain Go/Fe2Co-MOF material, i.e. graphene
Load Fe2Co metal-organic framework materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610817843.XA CN106423279B (en) | 2016-09-12 | 2016-09-12 | A kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610817843.XA CN106423279B (en) | 2016-09-12 | 2016-09-12 | A kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106423279A CN106423279A (en) | 2017-02-22 |
| CN106423279B true CN106423279B (en) | 2019-04-09 |
Family
ID=58169302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610817843.XA Expired - Fee Related CN106423279B (en) | 2016-09-12 | 2016-09-12 | A kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423279B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN109529932B (en) * | 2018-12-04 | 2021-09-21 | 三峡大学 | Preparation method and application of petal-shaped metal organic framework material |
| CN110387099A (en) * | 2019-07-18 | 2019-10-29 | 华南理工大学 | A kind of tealeaf residue graphene-CuCeMOF-PVB composite material and preparation method and application |
| 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 |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165916A (en) * | 2013-03-01 | 2013-06-19 | 北京化工大学常州先进材料研究院 | High-stability Pt-M/MOFs-graphene electro-catalytic agents and preparation method thereof |
| KR20130106463A (en) * | 2012-03-19 | 2013-09-30 | 인하대학교 산학협력단 | Manufacturing method of novel hybrid composites composed with metal-loaded graphene oxide and metal-organic frameworks for hydrogen storage |
| CN103432982A (en) * | 2013-08-05 | 2013-12-11 | 华南理工大学 | Preparation method of metal organic framework-graphite oxide composite |
| CN105355873A (en) * | 2015-10-29 | 2016-02-24 | 中国科学院宁波材料技术与工程研究所 | Iron based metal organic framework compound / graphene composite and application thereof |
-
2016
- 2016-09-12 CN CN201610817843.XA patent/CN106423279B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130106463A (en) * | 2012-03-19 | 2013-09-30 | 인하대학교 산학협력단 | Manufacturing method of novel hybrid composites composed with metal-loaded graphene oxide and metal-organic frameworks for hydrogen storage |
| CN103165916A (en) * | 2013-03-01 | 2013-06-19 | 北京化工大学常州先进材料研究院 | High-stability Pt-M/MOFs-graphene electro-catalytic agents and preparation method thereof |
| CN103432982A (en) * | 2013-08-05 | 2013-12-11 | 华南理工大学 | Preparation method of metal organic framework-graphite oxide composite |
| CN105355873A (en) * | 2015-10-29 | 2016-02-24 | 中国科学院宁波材料技术与工程研究所 | Iron based metal organic framework compound / graphene composite and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106423279A (en) | 2017-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106423279B (en) | A kind of graphene-supported Fe2The preparation method of Co metal-organic framework materials | |
| Cao et al. | Sensitive detection of glyphosate based on a Cu-BTC MOF/g-C3N4 nanosheet photoelectrochemical sensor | |
| Zeng et al. | A core–satellite structured Z-scheme catalyst Cd 0.5 Zn 0.5 S/BiVO 4 for highly efficient and stable photocatalytic water splitting | |
| CN112551571B (en) | Preparation and application of ultrathin nanosheet micro-unit hollow indium zinc sulfide nano cage | |
| CN106076364B (en) | A kind of efficient CdS-CdIn2S4The preparation method of superstructure photochemical catalyst | |
| Gao et al. | 2D/2D covalent organic framework/CdS Z-scheme heterojunction for enhanced photocatalytic H2 evolution: Insights into interfacial charge transfer mechanism | |
| Chang et al. | Photo-enhanced electrocatalysis of sea-urchin shaped Ni 3 (VO 4) 2 for the hydrogen evolution reaction | |
| CN107749483A (en) | A kind of catalyst for hydrogen-air fuel cell cathode material and preparation method thereof | |
| CN108866561A (en) | A kind of preparation method and applications of electro-catalysis carbon dioxide reduction electrode | |
| CN106711468B (en) | Carbon material with catalytic performance for oxygen reduction reaction, and preparation method and application thereof | |
| Li et al. | Novel CuBr-assisted graphdiyne synthesis strategy and application for efficient photocatalytic hydrogen evolution | |
| CN102107909A (en) | Method for preparing mesoporous nano manganese dioxide | |
| CN111558375A (en) | High-activity monatomic iron modified TiO2Preparation method of hollow microspheres and application of hollow microspheres in photocatalytic oxidation of NO | |
| She et al. | Preparation of Zn0. 5Cd0. 5S/nickel acetate hydroxide composite for ameliorated water splitting performance under visible light | |
| CN112500579A (en) | Magnetically-recyclable cerium complex/GO/Fe3O4Ternary complex, preparation method and application | |
| Zhang et al. | Facile and robust construction of a 3D-hierarchical NaNbO 3-nanorod/ZnIn 2 S 4 heterojunction towards ultra-high photocatalytic H 2 production | |
| Wei et al. | Integrating Co (OH) 2 nanosheet arrays on graphene for efficient noble-metal-free EY-sensitized photocatalytic H 2 evolution | |
| Kim et al. | Co-catalytic effects of Bi-based metal-organic framework on BiVO4 photoanodes for photoelectrochemical water oxidation | |
| Tan et al. | In situ fabrication of MIL-68 (In)@ ZnIn 2 S 4 heterojunction for enhanced photocatalytic hydrogen production | |
| Liu et al. | Dual Localized Surface Plasmon Resonance effect enhances Nb2AlC/Nb2C MXene thermally coupled photocatalytic reduction of CO2 hydrogenation activity | |
| CN110180594B (en) | Preparation method of electrocatalyst | |
| Huang et al. | In situ construction of a 2D CoTiO 3/gC 3 N 4 photocatalyst with an S-scheme heterojunction and its excellent performance for CO 2 reduction | |
| CN104409220B (en) | Preparation method of manganese dioxide nanowire material and application of manganese dioxide nanowire material as electrode material of supercapacitor | |
| CN114210315B (en) | Preparation and application of rare earth erbium modified pollen carbon composite photocatalyst | |
| CN109985642A (en) | Ni-Te-S complex carbon material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190409 Termination date: 20200912 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |