CN106256432A - A kind of water oxidation reaction catalyst based on metallic organic framework graphene oxide and preparation method thereof - Google Patents
A kind of water oxidation reaction catalyst based on metallic organic framework graphene oxide and preparation method thereof Download PDFInfo
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- CN106256432A CN106256432A CN201610626663.3A CN201610626663A CN106256432A CN 106256432 A CN106256432 A CN 106256432A CN 201610626663 A CN201610626663 A CN 201610626663A CN 106256432 A CN106256432 A CN 106256432A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 63
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000007809 chemical reaction catalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000013384 organic framework Substances 0.000 title abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- -1 2-amino p-phthalic acid Chemical compound 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 7
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 239000010953 base metal Substances 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 229910004882 Na2S2O8 Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000002508 compound effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- QVGXLLKOCUKJST-OUBTZVSYSA-N oxygen-17 atom Chemical compound [17O] QVGXLLKOCUKJST-OUBTZVSYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012876 topography Methods 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
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a kind of water oxidation reaction catalyst based on metallic organic framework graphene oxide and preparation method thereof, comprise the following steps: step 1, by graphene oxide ultrasonic disperse to N, in N dimethylformamide；Step 2, mixed liquor in step 1 add slaine and 2 amino p-phthalic acids, after mix homogeneously, proceeds to reactor；Step 3, reactor is put in baking oven and carry out constant temp. heating reaction, cool down after completion of the reaction, sucking filtration, washing, be dried, it is thus achieved that water oxidation reaction catalyst based on metallic organic framework graphene oxide.The present invention can realize the metal-organic framework materials of porous and the high efficiency composition of Graphene, brings the photocatalysis water oxidation susceptibility of excellence.
Description
Technical field
The invention belongs to chemical catalyst technical field, be specifically related to a kind of based on metallic organic framework-graphene oxide
Water oxidation reaction catalyst and preparation method thereof.
Background technology
Convert solar energy into chemical energy and the electric energy of cleaning, be the study hotspot tapped a new source of energy in world wide.Water
Oxidation reaction is still solar energy up to now and converts and the great restraining factors of correlation technique application, designs synthesizing efficient water
Oxidation catalyst, and be applied to visible ray drive water oxidation system at present become solve the problems referred to above potential approach.
But the catalyst that catalytic water oxidation effectiveness is good at present is many with noble metals such as Ru or Ir as catalytic active center, involves great expense；And
Catalyst effect with normal transition metals such as Mn or Co as active center is poor.At present, the modification of this type of photocatalyst
Method, the method such as including topography optimization, band gap regulation and control, wherein increase specific surface area and Graphene are combined is conventional two kind modifications
Method.On the other hand, the metal-organic framework materials that past 20 years developed rapidly is with the porous of its excellence, good warm
The advantage such as stability and chemical stability has obtained the concern of people.If can be by the porous character of metal-organic framework materials
Being combined with Graphene, the material obtained not only has the pore structure of excellence, and reduces the compound effect of light induced electron and hole
Rate, is conducive to improving ability and the efficiency of catalytic water oxidation reaction.
Summary of the invention
It is an object of the invention to improve the ability of water oxidation reaction and efficiency, propose a kind of novel organic based on metal
Water oxidation reaction catalyst of skeleton graphene oxide and preparation method thereof, it is achieved that Graphene and metallic organic framework activity
The high efficiency composition in site, enriches the kind of water oxidation reaction catalyst, has effectively facilitated the research of water oxidation reaction.
This catalyst is made up of metallic organic framework and the graphene oxide of porous, and its preparation method is by graphene oxide
It is distributed in metallic organic framework presoma carry out hydro-thermal reaction.The hole of metal-organic framework materials achieves avtive spot
Fully exposing, Graphene reduces the combined efficiency of light induced electron and hole, thus imparts this light meeting material excellent and urge
Change the performance of water oxidation reaction.The present invention enriches the kind of water oxidation reaction catalyst, and proposes a kind of effective compound
Material preparation method；The method is with low cost, effectively facilitates the research of water oxidation reaction and in the energy, environment and biological medicine
The application of aspect.
Technical scheme is as follows:
A kind of water oxidation reaction catalyst based on metallic organic framework-graphene oxide, described catalyst is by porous
Metallic organic framework and graphene oxide composition, the metal-organic framework materials of porous is evenly distributed on graphene oxide.
Further, the metal in described metal-organic framework materials be 3d transition metal such as: Fe, Co and Mn etc. and group of the lanthanides
Metal is such as: Eu and La；Organic ligand in described metal-organic framework materials is 2-amino p-phthalic acid.
Further, described metal-organic framework materials is 1:1～10 with the mass ratio of graphene oxide.
Further, described metal is 1～10:1 with the ratio of the amount of the material of 2-amino p-phthalic acid.
The preparation method of a kind of water oxidation reaction catalyst based on metallic organic framework-graphene oxide, including following
Step:
Step 1, by graphene oxide ultrasonic disperse to N,N-dimethylformamide (DMF)；
Step 2, mixed liquor in step 1 add slaine and 2-amino p-phthalic acid, proceeds to after mix homogeneously
Reactor；
Step 3, reactor is put in baking oven and carries out constant temp. heating reaction, cool down after completion of the reaction, sucking filtration, washing, be dried,
Obtain water oxidation reaction catalyst based on metallic organic framework-graphene oxide.
In step 1, described graphene oxide is 1mg:2～5mL with the amount ratio of DMF.
In step 2, described slaine is 1～10:1 with the ratio of the amount of the material of 2-amino p-phthalic acid.
In step 2, described slaine includes that 3d transition metal is: Fe, Co and Mn etc. and lanthanide series metal such as: Eu and La.
In step 2, described slaine is Fe, the nitrate of Co, Mn, Eu and La or chloride.
In step 3, the temperature of described constant temp. heating reaction is 80-150 DEG C, and the response time is 48～72h.
The invention have the benefit that the present invention can realize the metal-organic framework materials of porous and the efficient of Graphene
Compound, bring the photocatalysis water oxidation susceptibility of excellence；This that the pinhole of catalyst is effective with the band gap regulation and control of Graphene
The compound synthesis that strategy is composite provides new thinking, promotes preparation and the research of high activity composite catalyst；
The method technique is simple, with low cost, contributes to the research of water oxidation reaction and in terms of the energy, environment and biological medicine
Application.
Accompanying drawing explanation
Fig. 1 is the PXRD diffraction spectrogram of Eu Base Metal organic backbone-graphene oxide；
Fig. 2 is the FT-IR spectrogram of Eu Base Metal organic backbone-graphene oxide；
Fig. 3 is the uv atlas of Eu Base Metal organic backbone-graphene oxide；
Fig. 4 is the cyclic voltammetric spectrogram of Eu Base Metal organic backbone-graphene oxide；
Fig. 5 is the photocatalysis water oxidization condition of Eu Base Metal organic backbone-graphene oxide.
Detailed description of the invention
Below by by concrete example, the invention will be further described.
Embodiment 1:
The preparation of Eu Base Metal organic backbone Graphene
2mg graphene dispersion, in 4mL DMF, adds EuCl in backward dispersion liquid3.6H2O (25mg) and 2-amino are to benzene
Dioctyl phthalate (36.1mg), ultrasonic disperse, it is transferred to reactor after mix homogeneously.Reactor is put into the baking oven of 120 DEG C reacts 2
My god, cooling, sucking filtration, washing, it is dried, it is thus achieved that the water oxidation reaction catalyst of Eu Base Metal organic backbone Graphene.Its structure
As shown in Figures 1 to 3.Fig. 1 is the x-ray diffractogram of powder (PXRD) of composite, after showing to be combined with Graphene, does not affect
The structure of Eu Base Metal organic framework material, Fig. 2 is that the FT-IR spectral catalogue of composite understands the success of Eu Base Metal organic backbone
Load on Graphene；Demonstrate this material through uv atlas (see accompanying drawing 3) and visible ray is had absorption, can be as photocatalysis
Agent；Cyclic voltammetric spectrogram (see accompanying drawing 4) shows that this material possesses the ability of catalytic water oxidation.
Eu Base Metal organic backbone Graphene photocatalysis water oxidation susceptibility is evaluated
2mL buffer solution (is wherein contained 80mM Na2S2O8), the bipyridyl ruthenium aqueous solution of 200 μ l 0.01M is urged with 4mg
Agent puts in 25ml round-bottomed flask, is passed through nitrogen, by the air Ex-all in reaction bulb in round-bottomed flask.Air is eliminated in oneself
The reaction bulb equipped with reaction solution before plus the optical filter only allowed by visible ray, be close to optical filter with LED light source and irradiate
Reaction bulb, connects gas chromatogram, opens software and produces the volume of gas every 10 minutes records, no longer increases to producing gas volume
Till length.Oxygen 183 μm ol (see accompanying drawing 5) can be produced after testing.
Embodiment 2:
The preparation of La Base Metal organic backbone Graphene
2mg graphene dispersion, in 4mL DMF, adds La (NO in backward dispersion liquid3)3.6H2O (198mg) and 2-amino
P-phthalic acid (36.1mg), ultrasonic disperse, it is transferred to reactor after mix homogeneously.Reactor is put in the baking oven of 120 DEG C
React 2 days, cooling, sucking filtration, washing, be dried, it is thus achieved that the water oxidation reaction catalyst of La Base Metal organic backbone Graphene.Will
It is used as the catalyst of photocatalysis water oxidation, at bipyridyl ruthenium-Na2S2O8In system, oxygen 61 μm ol can be produced after testing.
Embodiment 3:
The preparation of Fe Base Metal organic backbone Graphene
2mg graphene dispersion, in 10mL DMF, adds FeCl in backward dispersion liquid3.6H2O (270mg) and 2-amino pair
Phthalic acid (180mg), ultrasonic disperse, it is transferred to reactor after mix homogeneously.Reactor is put in the baking oven of 150 DEG C and react
3 days, cooling, sucking filtration, washing, it is dried, it is thus achieved that the water oxidation reaction catalyst of Fe Base Metal organic backbone Graphene.Used
Make the catalyst of photocatalysis water oxidation, at bipyridyl ruthenium-Na2S2O8In system, oxygen 209 μm ol can be produced after testing.
Embodiment 4:
The preparation of Co Base Metal organic backbone Graphene
2mg graphene dispersion, in 10mL DMF, adds Co (NO in backward dispersion liquid3)2·6H2O (40mg) and 2-amino
P-phthalic acid (23mg), ultrasonic disperse, it is transferred to reactor after mix homogeneously.Reactor is put in the baking oven of 100 DEG C anti-
Answer 2 days, cooling, sucking filtration, washing, be dried, it is thus achieved that the water oxidation reaction catalyst of Co Base Metal organic backbone Graphene.By it
As the catalyst of photocatalysis water oxidation, at bipyridyl ruthenium-Na2S2O8In system, oxygen 172 μm ol can be produced after testing.
Embodiment 5:
The preparation of Mn Base Metal organic backbone Graphene
2mg graphene dispersion, in 10mL DMF, adds Mn (NO in backward dispersion liquid3)2·9H2O (0.9mmol) and 2-
Amino p-phthalic acid (14.5mg), ultrasonic disperse, it is transferred to reactor after mix homogeneously.Reactor is put into the baking of 120 DEG C
Case reacts 2 days, cooling, sucking filtration, washing, be dried, it is thus achieved that the water oxidation reaction catalysis of Co Base Metal organic backbone Graphene
Agent.It is used as the catalyst of photocatalysis water oxidation, at bipyridyl ruthenium-Na2S2O8In system, oxygen 17 μ can be produced after testing
mol。
Claims (10)
1. a water oxidation reaction catalyst based on metallic organic framework-graphene oxide, described catalyst is by the gold of porous
Belonging to organic backbone and graphene oxide composition, the metal-organic framework materials of porous is evenly distributed on graphene oxide.
A kind of water oxidation reaction catalyst based on metallic organic framework-graphene oxide the most according to claim 1, its
Being characterised by, the metal in described metal-organic framework materials is any one in Fe, Co, Mn, Eu and La；Described metal has
Organic ligand in machine framework material is 2-amino p-phthalic acid.
A kind of water oxidation reaction catalyst based on metallic organic framework-graphene oxide the most according to claim 1, its
Being characterised by, described metal-organic framework materials is 1:1～10 with the mass ratio of graphene oxide.
A kind of water oxidation reaction catalyst based on metallic organic framework-graphene oxide the most according to claim 1, its
Being characterised by, described metal is 1～10:1 with the ratio of the amount of the material of 2-amino p-phthalic acid.
5. the preparation method of a water oxidation reaction catalyst based on metallic organic framework-graphene oxide, it is characterised in that
Comprise the following steps:
Step 1, by graphene oxide ultrasonic disperse to N,N-dimethylformamide；
Step 2, mixed liquor in step 1 add slaine and 2-amino p-phthalic acid, after mix homogeneously, proceeds to reaction
Still；
Step 3, reactor is put in baking oven and carries out constant temp. heating reaction, cool down after completion of the reaction, sucking filtration, washing, be dried, it is thus achieved that
Water oxidation reaction catalyst based on metallic organic framework-graphene oxide.
A kind of water oxidation reaction catalyst based on metallic organic framework-graphene oxide the most according to claim 5
Preparation method, it is characterised in that in step 1, described graphene oxide is 1mg:2～5mL with the amount ratio of DMF.
A kind of water oxidation reaction catalyst based on metallic organic framework-graphene oxide the most according to claim 5
Preparation method, it is characterised in that in step 2, the ratio of described slaine and the amount of the material of 2-amino p-phthalic acid be 1～
10:1.
A kind of water oxidation reaction catalyst based on metallic organic framework-graphene oxide the most according to claim 5
Preparation method, it is characterised in that in step 2, described slaine is any one in Fe, Co, Mn, Eu and La.
A kind of water oxidation reaction catalyst based on metallic organic framework-graphene oxide the most according to claim 5
Preparation method, it is characterised in that in step 2, described slaine is Fe, the nitrate of Co, Mn, Eu and La or chloride.
A kind of water oxidation reaction catalyst based on metallic organic framework-graphene oxide the most according to claim 5
Preparation method, it is characterised in that in step 3, the temperature of described constant temp. heating reaction is 80-150 DEG C, the response time be 48～
72h。
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Cited By (12)
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| CN107029672A (en) * | 2017-05-10 | 2017-08-11 | 上海师范大学 | Based on the NH of UIO 662With the graphene synthesis adsorption photochemical catalysis composite of assembling altogether in situ |
| CN107158964A (en) * | 2017-07-04 | 2017-09-15 | 中国石油大学(华东) | A kind of composite film material based on metal organic framework nanometer sheet and graphene oxide, preparation method and the application in gas separation |
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| CN114957679A (en) * | 2022-02-22 | 2022-08-30 | 中国科学院苏州生物医学工程技术研究所 | Metal organic framework material fluorescent probe and pyridine dicarboxylic acid detection method |
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| CN109166733A (en) * | 2018-09-30 | 2019-01-08 | 北京印刷学院 | A kind of method that hydro-thermal method prepares Ni/Co base MOF material |
| CN109821573A (en) * | 2019-02-15 | 2019-05-31 | 江苏大学 | A kind of water oxidation catalyst and preparation method and purposes |
| CN109821573B (en) * | 2019-02-15 | 2022-02-15 | 江苏大学 | Water oxidation catalyst, preparation method and application |
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| CN111085275A (en) * | 2019-12-31 | 2020-05-01 | 华南理工大学 | Reductive graphene oxide/metal organic framework composite material and preparation method and application thereof |
| CN111151303A (en) * | 2020-01-07 | 2020-05-15 | 东北师范大学 | Application of novel MIL-53(Fe) -based catalyst in removal of antibiotics in water |
| CN111500175A (en) * | 2020-05-12 | 2020-08-07 | 黎哲华 | High-flame-retardant waterborne polyurethane coating and preparation method thereof |
| CN112679966A (en) * | 2020-12-23 | 2021-04-20 | 广东邦普循环科技有限公司 | Preparation method and application of composite material containing graphite and MOF |
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| CN112679966B (en) * | 2020-12-23 | 2023-08-11 | 广东邦普循环科技有限公司 | Preparation method and application of composite material containing graphite and MOF |
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| CN113663647A (en) * | 2021-07-26 | 2021-11-19 | 安徽大学 | Method for adsorbing and degrading metal organic framework material/graphene compound of organic pollutants |
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