CN108102108B - Preparation method of copper-based metal organic framework material and application of copper-based metal organic framework material in electro-catalysis hydrogen production - Google Patents
Preparation method of copper-based metal organic framework material and application of copper-based metal organic framework material in electro-catalysis hydrogen production Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 20
- 239000001257 hydrogen Substances 0.000 title claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000013084 copper-based metal-organic framework Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 title abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- RZTVGQJFNWMNPB-UHFFFAOYSA-N 4-[6-(2,4-dicarboxyphenyl)pyridin-2-yl]benzene-1,3-dicarboxylic acid Chemical compound OC(=O)c1ccc(-c2cccc(n2)-c2ccc(cc2C(O)=O)C(O)=O)c(c1)C(O)=O RZTVGQJFNWMNPB-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000002178 crystalline material Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 238000000227 grinding Methods 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000010411 electrocatalyst Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
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Abstract
The invention relates to a baseA preparation method of a copper-based metal organic framework material and application thereof in hydrogen production by electrocatalytic decomposition of water. The method uses copper nitrate, 2, 6-di (2', 4' -dicarboxyphenyl) pyridine (H)4L), DMF, ethanol and water are prepared into blue blocky crystals under the condition of hydrothermal synthesis, and the electrocatalytic material [ Cu ] is obtained by grinding and refining the blue crystals3(HL)2(H2O)2]n. The preparation method of the electrocatalytic material is relatively simple, the obtained electrocatalytic material has better capability of electrolyzing water to generate hydrogen, the Tafel slope can reach 90mV/decade, and the current density is 10mA/cm2The time-evolution hydrogen potential is 145mV, and the catalyst is an ideal high-performance catalyst material and can be used in the field of new energy resources such as electro-catalysis hydrogen production and the like.
Description
Technical Field
The invention belongs to the technical field of synthesis and application of catalysts, and particularly relates to a preparation method of a copper-based metal organic framework material with electrocatalytic performance and application of the copper-based metal organic framework material in the aspect of hydrogen production through electrocatalytic decomposition of water.
Background
The problems of energy shortage and environmental pollution have become key global problems, so the development of clean, renewable energy is an extremely urgent issue facing the world today. In order to solve the problems from the root, the green energy source is not thick, so that the dependence of people on the traditional fossil energy sources can be reduced, and the problem of environmental pollution caused by consumption of the traditional fossil energy sources can be obviously improved. Hydrogen has become the focus of attention because of its superior properties such as high calorific value, cleanliness, safety, convenient transportation, renewability, and the like. How to obtain hydrogen through a simple and efficient way. The electrolysis of water can produce pure hydrogen and oxygen, but consumes a part of the electric energy. It is known that the water splitting reaction does not proceed spontaneously, and its theoretical Gibbs free energy is 237kJ/mol, but the energy required for the reaction actually exceeds 482kJ/mol due to the reaction kinetics and the like. Therefore, the decomposition of water by applying an external voltage is one of the main ways of decomposing water at present. The difference between this applied voltage and the theoretical voltage required for the reaction is called the overpotential or overpotential. How to reduce the potential barrier of the reaction and improve the energy conversion efficiency is a basic scientific problem to be solved by electrocatalysis water decomposition hydrogen production. The recent emerging Metal-Organic Frameworks (MOFs) are one of such catalyst materials, which are crystalline porous materials with periodic network structure formed by connecting inorganic Metal centers (Metal ions or Metal clusters) and bridged Organic ligands with each other through self-assembly. Therefore, the research on the development and synthesis of novel MOFs materials and the application of the MOFs materials in the electrocatalytic hydrogen evolution is increasingly receiving attention.
Disclosure of Invention
The invention aims to provide a preparation method and application of a Cu-MOF electro-catalysis material which is obtained by assembling 2, 6-di (2', 4' -dicarboxyphenyl) pyridine and copper metal ions, aiming at the application of novel MOFs in the field of electro-catalysis hydrogen production.
The invention aims to realize the technical scheme that the hydrothermal method for preparing the copper-based metal organic framework electrocatalytic material with the stability in 0.5M sulfuric acid solution comprises the following steps
(1) Putting a copper source, 2, 6-bis (2', 4' -dicarboxyphenyl) pyridine, DMF, ethanol and water into a container, and performing ultrasonic treatment and dispersion to obtain a mixed solution;
(2) transferring the mixed solution obtained in the step (1) to a polytetrafluoroethylene reaction kettle for hydrothermal reaction;
(3) placing the reaction kettle filled with the mixed solution into a constant-temperature oven for reaction, and then slowly cooling to room temperature to obtain blue blocky crystals;
(4) and cleaning the obtained blue blocky crystal by using ethanol, and drying at 50-65 ℃ to obtain the electro-catalytic material.
The copper source is copper nitrate. The molar ratio of the copper source to the 2, 6-bis (2', 4' -dicarboxyphenyl) pyridine is 1:0.5-1.2, and the volume ratio of DMF, ethanol and water is 1:1-2: 0.3-0.8.
More preferably, the molar ratio of the copper source to 2, 6-bis (2', 4' -dicarboxyphenyl) pyridine is 1:1, and the volume ratio of DMF, ethanol and water is 1:1.5: 0.5.
The hydrothermal reaction temperature of the step (3) is 80-120 ℃, the reaction time is 40-50h, and the cooling time is 10-15 h. The Cu-MOF metal organic framework material is applied to electrocatalytic hydrogen production.
And (3) carrying out an electrolytic water hydrogen evolution test in 0.5M sulfuric acid by using the Cu-MOF material prepared in the steps as an electrocatalytic hydrogen production catalyst.
The invention has the following advantages:
1) the product prepared by the invention has the structural formula of [ Cu3(HL)2(H2O)2]n, the preparation method is relatively simple and has strong controllability;
2) the catalyst material prepared by the invention is a blocky crystal which has good crystallinity, can obtain accurate three-dimensional structure information through single crystal structure analysis, and is easy to separate and clean;
3) the catalyst material prepared by the invention has excellent capability of electrocatalytic decomposition of water and hydrogen evolution;
4) the raw materials used in the invention are relatively cheap and easily available, the cost of the catalyst can be effectively reduced, and the method is beneficial to large-scale production;
5) the preparation method disclosed by the invention is common equipment in a laboratory, special equipment is not required, and the process flow is simple.
Drawings
FIG. 1 shows [ Cu ] prepared according to the present invention (example 2)3(HL)2(H2O)2]nAnd (3) a coordination environment diagram of metal ions in the electrocatalyst.
FIG. 2 shows [ Cu ] prepared according to the present invention (example 2)3(HL)2(H2O)2]nTwo-dimensional layer of electrocatalyst materialAnd (4) a shape diagram.
FIG. 3 shows [ Cu ] prepared according to the present invention (example 2)3(HL)2(H2O)2]nThe X-ray powder diffraction (XRD) pattern of the electrocatalyst shows that the pattern obtained by the experiment is basically consistent with the theoretical simulation pattern.
FIG. 4 shows [ Cu ] prepared according to the present invention (example 2)3(HL)2(H2O)2]nElectrocatalyst materials at 0.5M H2SO4The linear scanning cyclic voltammogram in the formula (I) can obtain the current density of the material at 10mA/cm2The time-evolution hydrogen potential is 145 mV.
FIG. 5 shows [ Cu ] prepared according to the present invention (example 2)3(HL)2(H2O)2]nElectrocatalyst materials at 0.5M H2SO4The Tafel plot in (1) can obtain that the Tafel slope is 90 mV/decade.
Detailed Description
Example 1
0.02mmol of 2, 6-bis (2', 4' -dicarboxyphenyl) pyridine and 0.02mmol of copper nitrate trihydrate were put into a beaker, and DMF (1mL), H, was added thereto2O (1.5mL), ethanol (0.5mL), and placed in an ultrasonic machine for uniform sonication. Transferring the prepared uniform solution into a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into a constant-temperature oven at 80 ℃ for reaction for 48 hours, cooling the reaction kettle to room temperature for 12 hours to obtain blue blocky crystals, washing the materials with absolute ethyl alcohol, and putting the materials into a drying oven at 60 ℃ for drying to obtain the electrocatalyst of the invention, specifically [ Cu3(HL)2(H2O)2]n。
Example 2
0.02mmol of 2, 6-bis (2', 4' -dicarboxyphenyl) pyridine and 0.02mmol of copper nitrate trihydrate were put into a beaker, and DMF (1mL), H, was added thereto2O (1.5mL), ethanol (0.5mL), and placed in an ultrasonic machine for uniform sonication. Transferring the prepared uniform solution into a polytetrafluoroethylene reaction kettle, putting the reaction kettle into a constant-temperature oven at 100 ℃ for reaction for 48 hours, then cooling to room temperature for 12 hours to obtain blue blocky crystals, and adding absolute ethyl alcohol to the blocky crystalsThe material is put into a drying oven at 60 ℃ after being washed and dried to obtain the electrocatalyst of the invention, specifically [ Cu3(HL)2(H2O)2]n。
Example 3
0.02mmol of 2, 6-bis (2', 4' -dicarboxyphenyl) pyridine and 0.02mmol of copper nitrate trihydrate were put into a beaker, and DMF (1mL), H, was added thereto2O (1.5mL), ethanol (0.5mL), and placed in an ultrasonic machine for uniform sonication. Transferring the prepared uniform solution into a polytetrafluoroethylene reaction kettle, putting the polytetrafluoroethylene reaction kettle into a constant-temperature oven at 120 ℃ for reaction for 48 hours, cooling the reaction kettle to room temperature for 12 hours to obtain blue blocky crystals, washing the materials with absolute ethyl alcohol, and putting the materials into a drying oven at 60 ℃ for drying to obtain the electrocatalyst of the invention, specifically [ Cu3(HL)2(H2O)2]n。
Example 4
The obtained Cu-MOF electrocatalytic material is put into a 2mL sample tube, 5% by mass of perfluorosulfonic acid-polytetrafluoroethylene copolymer (Nafion) water and 1-propanol solution (0.1mL), ethanol (0.2mL) and water (0.5mL) are added into the sample tube, ultrasonic waves are carried out for homogenization, then 4 muL of sample is dropped on a glassy carbon electrode with the diameter of 3mm, and the electrode is placed on 0.5mol/L H2SO4The electrocatalytic hydrogen evolution test is carried out.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. Any changes, substitutions and alterations that can be easily made by those skilled in the art without departing from the spirit and principles of this invention are intended to be within the scope of the invention.
Claims (5)
1. A preparation method of a copper-based metal organic framework material is characterized in that (1) a copper source, 2, 6-bis (2', 4' -dicarboxyphenyl) pyridine, DMF, ethanol and water are put into a container, and a mixed solution is obtained through ultrasonic treatment and dispersion;
(2) transferring the mixed solution obtained in the step (1) toTransferring the mixture into a polytetrafluoroethylene reaction kettle for hydrothermal reaction at the temperature of 80-120 DEG CoC, the reaction time is 40-50h, and the cooling time is 10-15 h;
(3) placing the reaction kettle filled with the mixed solution into a constant-temperature oven for reaction, and then slowly cooling to room temperature to obtain blue blocky crystals;
(4) cleaning the obtained blue blocky crystal with ethanol, and drying at 50-65 ℃ to obtain the copper-based metal organic framework material with the structural formula of [ Cu [ ]3(HL)2(H2O)2]nHL is 2, 6-di (2', 4' -dicarboxyphenyl) pyridine, belongs to a monoclinic crystalline material and has a space group ofI2/mThe unit cell parameters are a =11.7901(4) Å, b =16.2618(5) Å, c =13.6342(5) Å,α=90°，β= 110.253(4)，γ=90°。
2. the method of claim 1, wherein the copper source is copper nitrate.
3. The method for preparing a copper-based metal organic framework material according to claim 1, wherein the molar ratio of the copper source to the 2, 6-bis (2', 4' -dicarboxyphenyl) pyridine is 1: 0.5-2, wherein the volume ratio of DMF, ethanol and water is 1:1-2: 0.3-0.8.
4. The method for preparing a copper-based metal organic framework material according to claim 1, wherein the molar ratio of the copper source to the 2, 6-bis (2', 4' -dicarboxyphenyl) pyridine is 1:1, wherein the volume ratio of DMF, ethanol and water is 1:1.5: 0.5.
5. the application of the copper-based metal organic framework material prepared by the method according to any one of claims 1 to 4 in electrocatalytic hydrogen production.
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| CN109433261B (en) * | 2018-11-29 | 2021-01-29 | 哈尔滨工业大学 | Preparation method of Ru/C nano assembly |
| CN111662320B (en) * | 2020-06-03 | 2023-05-09 | 陕西科技大学 | Pb-MOF integrated fluorescence sensor and preparation method thereof |
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| WO2013177223A1 (en) * | 2012-05-21 | 2013-11-28 | The Administrators Of The Tulane Educational Fund | Tuned synthetic dendrimer calibrants for mass spectrometry |
| CN105669729A (en) * | 2016-03-09 | 2016-06-15 | 三峡大学 | Dissimilar metal organic framework material of 2,2'-dipyridyl-3,3'-dicarboxylic acid and synthesis method thereof |
| CN105906817A (en) * | 2016-06-08 | 2016-08-31 | 南方医科大学 | Amphoteric carboxylic acid hexanuclear copper metal coordination polymer and preparation method thereof |
| CN106589397A (en) * | 2016-11-17 | 2017-04-26 | 中国科学院福建物质结构研究所 | Crystal material, synthesizing method thereof, and application of crystal material as fluorescent crystal material |
| CN107501088A (en) * | 2017-08-04 | 2017-12-22 | 三峡大学 | A kind of preparation and its application of copper base metal organic framework materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013177223A1 (en) * | 2012-05-21 | 2013-11-28 | The Administrators Of The Tulane Educational Fund | Tuned synthetic dendrimer calibrants for mass spectrometry |
| CN105669729A (en) * | 2016-03-09 | 2016-06-15 | 三峡大学 | Dissimilar metal organic framework material of 2,2'-dipyridyl-3,3'-dicarboxylic acid and synthesis method thereof |
| CN105906817A (en) * | 2016-06-08 | 2016-08-31 | 南方医科大学 | Amphoteric carboxylic acid hexanuclear copper metal coordination polymer and preparation method thereof |
| CN106589397A (en) * | 2016-11-17 | 2017-04-26 | 中国科学院福建物质结构研究所 | Crystal material, synthesizing method thereof, and application of crystal material as fluorescent crystal material |
| CN107501088A (en) * | 2017-08-04 | 2017-12-22 | 三峡大学 | A kind of preparation and its application of copper base metal organic framework materials |
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