CN109174188B - Preparation of heteroatom doped carbon material/Ni-MOF composite electrocatalyst - Google Patents
Preparation of heteroatom doped carbon material/Ni-MOF composite electrocatalyst Download PDFInfo
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 42
- 239000013099 nickel-based metal-organic framework Substances 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 13
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910001868 water Inorganic materials 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 6
- 239000008103 glucose Substances 0.000 claims abstract description 6
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 6
- 239000011592 zinc chloride Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 4
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- 239000000203 mixture Substances 0.000 claims description 18
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000012621 metal-organic framework Substances 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 3
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- 230000002195 synergetic effect Effects 0.000 abstract description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
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- 229910021645 metal ion Inorganic materials 0.000 description 2
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- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- 238000010257 thawing 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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Abstract
The invention belongs to the technical field of novel energy, and particularly relates to a preparation method of a heteroatom doped carbon material/Ni-MOF composite electrocatalyst. According to the invention, the charge density of adjacent carbon atoms is changed by utilizing the synergistic effect of N, S element codoping, so that the spin density in the matrix material is redistributed, rich active sites are formed in the prepared composite catalyst material, the catalytic reaction is facilitated, and the catalytic performance of the MOF-based material is improved. Glucose is used as a carbon source, thiourea is used as a sulfur source and a nitrogen source, zinc chloride is used as a structure directing agent, a hydrothermal method is adopted to preliminarily synthesize a carbon material, dezincification treatment is carried out, the carbon material is dried at 110 ℃ after washing, and then high-temperature carbonization is carried out in a tube furnace, so that the sulfur-nitrogen doped porous carbon (SNPC) material is obtained. And then, preparing a composite electrocatalyst (SNPC/Ni-MOF) of the heteroatom doped carbon material and the Ni-MOF by a hydrothermal method, and testing shows that the electrolytic water performance of the composite material is obviously improved.
Description
Technical Field
The invention belongs to the technical field of novel energy, and relates to preparation of a heteroatom doped carbon material/Ni-MOF composite electrocatalyst.
Background
Human beings have already stepped into the 21 st century, the civilization degree is greatly improved, the environmental awareness of human beings is increasing day by day, but how to realize harmonious coexistence of human beings and nature and sustainable development of economy is still a big problem. At present, people mainly use fossil fuels, and due to the rapid development of science and technology, the energy demand is increased day by day, which leads to the rapid exhaustion of the available fossil fuels, and the living environment of human beings is greatly damaged, such as global warming, glacier thawing, sea level rising and the like. Hydrogen energy is considered to be the most environmentally friendly energy source, primarily because of the products obtained when it is burned as an energy-providing substanceIs H2O is expected to replace fossil energy and becomes the leading energy in the future. However, both the Hydrogen Evolution Reaction (HER) and the Oxygen Evolution Reaction (OER) in electrochemical hydrogen production require the assistance of a catalyst. At present, most of the main HER and OER catalysts are platinum-based catalysts, but due to the defects of very limited practical storage amount of platinum, abnormally high price and the like, large-scale commercial application cannot be carried out, so that the search and search for the catalyst which can replace platinum and has excellent catalytic effect and low price has important practical significance.
The MOF material (metal-organic framework material) is a novel porous material formed by connecting rigid organic ligands (mainly providing lone electron pairs) and metal ions or metal clusters (mainly serving as core components and providing empty orbitals) in a coordination bond mode, and has an infinite network pore channel structure, so that the MOF material has high porosity and large specific surface area. Meanwhile, the material not only can adjust the size and change the appearance and has rich structure, but also has simple and easily obtained raw materials, simple and various synthesis methods, and most importantly, can carry out various chemical modifications according to experimental requirements. Therefore, MOFs have been widely studied and applied in the field of catalysis in recent years. The carbon material formed by a single carbon element has various properties, the physical property and the chemical property of the material can be adjusted by doping atoms (such as N, S, P, B and other atoms) into the carbon material, more active sites can be obtained, the process can not only improve the adsorption performance of the carbon material to atoms or molecules to enable the carbon material to perform catalytic reaction, the performance of the carbon material in the aspect of electrocatalysis is improved, but also the electrical conductivity of the carbon material cannot be reduced. The heteroatom-doped carbon-based material is low in price and excellent in catalytic effect, and is expected to become an ideal material for replacing a platinum-based catalyst. More importantly, these heteroatom-doped structures provide a platform for the research and development of lower cost catalysts with better catalytic activity and longer service life. The S, N heteroatom doped carbon material is adopted, the charge density of adjacent carbon atoms can be changed by mainly utilizing the synergistic effect of the two, so that the spin density in the matrix material is redistributed, then rich active sites are formed in the material, the catalytic reaction is facilitated, and the catalytic performance of the single metal organic framework material is improved.
Disclosure of Invention
The invention aims to enable the composite catalyst to have more and richer catalytic active sites through S, N heteroatom co-doped carbon materials, and facilitate the catalytic reaction, so that the preparation of the heteroatom doped carbon material/Ni-MOF composite electrocatalyst is provided.
The idea of the invention is as follows: anhydrous glucose (Panreac) and thiourea are used as raw materials, zinc chloride is added as a structure guiding agent, a hydrothermal method and a high-temperature calcination carbonization method are firstly used for synthesizing the sulfur-nitrogen doped porous carbon material, then the synthesized heteroatom-doped carbon material, metal ion salt and organic ligand are uniformly mixed and then are placed into a reaction kettle, and the heteroatom-doped carbon material/Ni-MOF composite electrocatalyst is prepared by a hydrothermal method again.
The method specifically comprises the following steps:
(1) weighing glucose and thiourea according to a certain molar ratio, adding 4.5g of zinc chloride, placing the mixture into a beaker, adding 16mL of deionized water, stirring the mixture by using a glass rod until the mixture is dissolved, placing the mixture into a hydrothermal reaction kettle to react for a certain time at a certain temperature, repeatedly carrying out suction filtration and washing on ethanol and water, drying the mixture in a drying oven at the temperature of 110 ℃, and then placing the dried mixture into a tubular furnace to carbonize at a certain temperature for a certain time under an inert atmosphere to obtain a heteroatom-doped porous carbon material, wherein the label;
(2)C4H6NiO4·4H2o and trimesic acid (H)3BTC) is weighed according to a certain molar ratio, a certain amount of sulfur and nitrogen doped porous carbon material (SNPC) is added, then 32mL of DMF and 20mL of ethanol are added, magnetic stirring is carried out for about 1 hour until the solution is uniformly dispersed, the solution is put into a hydrothermal reaction kettle to react for a certain time at a certain temperature, the obtained sample is repeatedly washed for many times, and the sample is dried at 60 ℃, and the sample is marked as SNPC/Ni-MOF.
The positive progress effects obtained by the invention are as follows: (1) the N, S heteroatom is doped in the carbon material, so that the physical property and the chemical property of the material can be adjusted, the electronic structure and the distribution of the material are changed by substituting the positions of certain carbon atoms in a carbon skeleton, the exposure of a large number of active sites is facilitated, the adsorption performance of the carbon material on atoms or molecules is improved, the catalytic reaction is carried out on the carbon material, and the activity of the material in the aspect of electrocatalysis is also improved. (2) The MOF-based material loaded by the carbon material with excellent conductivity as the carrier can well adjust and improve the overall conductivity of the composite catalyst, and is beneficial to improving the activity of electrolyzed water. (3) Through tests, the water electrolysis performance of the SNPC/Ni-MOF composite catalyst is obviously improved, and the experiments show that the heteroatom-doped carbon-based material is low in price and excellent in catalytic effect, and is expected to become an ideal material for replacing a platinum-based catalyst.
Drawings
FIG. 1 is a scanning electron micrograph of Ni-MOF.
FIG. 2 is a scanning electron micrograph of SNPC/Ni-MOF.
Detailed Description
The first embodiment is as follows: the preparation method of the heteroatom doped carbon material/Ni-MOF composite electrocatalyst is carried out according to the following steps:
(1) weighing glucose and thiourea according to a certain molar ratio, adding 4.5g of zinc chloride, placing the mixture into a beaker, adding 16mL of deionized water, stirring the mixture by using a glass rod until the mixture is dissolved, placing the mixture into a hydrothermal reaction kettle to react for a certain time at a certain temperature, repeatedly carrying out suction filtration and washing on ethanol and water, drying the mixture in a drying oven at the temperature of 110 ℃, and then placing the dried mixture into a tubular furnace to carbonize at a certain temperature for a certain time under an inert atmosphere to obtain a heteroatom-doped porous carbon material, wherein the label;
(2)C4H6NiO4·4H2o and trimesic acid (H)3BTC) is weighed according to a certain molar ratio, a certain amount of sulfur and nitrogen doped porous carbon material (SNPC) is added, then 32mL of DMF and 20mL of ethanol are added, magnetic stirring is carried out for about 1 hour until the solution is uniformly dispersed, the solution is put into a hydrothermal reaction kettle to react for a certain time at a certain temperature, the obtained sample is repeatedly washed for many times, and the sample is dried at 60 ℃, and the sample is marked as SNPC/Ni-MOF.
The second embodiment is as follows: the difference between the embodiment and the specific embodiment is that in the step (1), glucose and thiourea are weighed according to the molar ratio of 3:1, are subjected to hydrothermal reaction at 140 ℃ for 10 hours, and are carbonized at 700 ℃ for 2 hours. The rest is the same as the first embodiment.
The third concrete implementation mode: the difference between the embodiment mode and the embodiment mode I or II is that the step (2) is weighed according to the molar ratio of 2:1, 5mg of SNPC is added, and the hydrothermal reaction is carried out for 10 hours at 180 ℃. The others are the same as in the first or second embodiment.
The preparation of a heteroatom-doped carbon material/Ni-MOF composite electrocatalyst is specifically illustrated by the following examples and comparative examples.
The first embodiment is as follows:
(1) weighing glucose and thiourea according to a molar ratio of 3:1, adding 4.5g of zinc chloride, placing the mixture into a beaker, adding 16mL of deionized water, stirring the mixture by a glass rod until the mixture is dissolved, placing the mixture into a hydrothermal reaction kettle for hydrothermal reaction for 10 hours at 140 ℃, repeatedly carrying out suction filtration and washing on ethanol and water, drying an oven at 110 ℃, and then placing the dried oven into a tubular furnace for carbonization for 2 hours at 700 ℃ under an inert atmosphere to obtain a heteroatom-doped porous carbon material, wherein the label is SNPC;
(2)C4H6NiO4·4H2o and trimesic acid (H)3BTC) is weighed according to the molar ratio of 2:1, 5mg of sulfur-nitrogen doped porous carbon material (SNPC) is added, 32mL of DMF and 20mL of ethanol are added, magnetic stirring is carried out for about 1h until the solution is uniformly dispersed, the solution is put into a hydrothermal reaction kettle for hydrothermal reaction at 180 ℃ for 10h, the obtained sample is repeatedly washed for many times, and the sample is dried at 60 ℃, and is marked as SNPC/Ni-MOF.
FIG. 1 is a scanning electron microscope image of Ni-MOF, wherein the pure Ni-MOF material prepared by a hydrothermal method is in a uniform-shape cube structure, and the size of the pure Ni-MOF material is about 2-8 μm. The obvious pore structure can be seen on the surface of the material, which is the characteristic of the metal organic framework material and is also the main reason for the wide application of the material in the field of catalysis.
FIG. 2 is a scanning electron microscope image of SNPC/Ni-MOF, after the heteroatom doped carbon material is added, the surface of the square body of the MOF material is loaded with a plurality of spherical carbon materials, the surface is changed from flat and smooth to rough, and the pore diameter is increased compared with the former, the structure is beneficial to providing more catalytic active sites, being beneficial to the contact of a catalyst and an electrolyte, and improving the electrocatalytic performance of the composite material; the carbon material covered on the surface reduces the resistance of the composite material, namely, the conductivity of the catalyst is increased, and the catalytic activity of the composite material is favorably improved in the process of electrolyzing water.
Comparative example one:
C4H6NiO4·4H2o and trimesic acid (H)3BTC) is weighed according to the molar ratio of 2:1, then 32mL of DMF and 20mL of ethanol are added, magnetic stirring is carried out for about 1 hour until the solution is uniformly dispersed, the solution is put into a hydrothermal reaction kettle for hydrothermal reaction for 10 hours at 180 ℃, the obtained sample is repeatedly washed and dried at 60 ℃, and the sample is marked as Ni-MOF.
Claims (2)
1. The preparation method of the heteroatom doped carbon material/Ni-MOF composite electrocatalyst is characterized in that the catalyst is prepared by the following steps:
(1) weighing glucose and thiourea according to a molar ratio of 3:1, adding 4.5g of zinc chloride, placing the mixture into a beaker, adding 16mL of deionized water, stirring the mixture by a glass rod until the mixture is dissolved, placing the mixture into a hydrothermal reaction kettle for hydrothermal reaction for 10 hours at 140 ℃, repeatedly carrying out suction filtration and washing on ethanol and water, drying an oven at 110 ℃, placing the dried oven in a tubular furnace at 700 ℃ for high-temperature carbonization for 2 hours in an inert atmosphere to obtain a sulfur and nitrogen heteroatom doped porous carbon material, and marking the porous carbon material as SNPC;
（2）C4H6NiO4•4H2o and trimesic acid (H)3BTC) is weighed according to the molar ratio of 2:1, 5mg of heteroatom-doped porous carbon material (SNPC) is added, 32mL of DMF and 20mL of ethanol are added, magnetic stirring is carried out for 1 hour until the solution is uniformly dispersed, the solution is put into a hydrothermal reaction kettle, hydrothermal reaction is carried out for 10 hours at 180 ℃, the obtained sample is repeatedly washed for many times, and drying is carried out at 60 ℃ to obtain the heteroatom-doped carbon material/Ni-MOF composite electrocatalyst which is marked as SNPC/Ni-MOF.
2. The preparation method of the heteroatom doped carbon material/Ni-MOF composite electrocatalyst according to claim 1, characterized in that the prepared SNPC/Ni-MOF composite electrocatalyst has significantly improved water electrolysis performance.
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Application publication date: 20190111 Assignee: Changzhou Zhuoyida Machinery Co.,Ltd. Assignor: CHANGZHOU University Contract record no.: X2023980053835 Denomination of invention: Preparation of a heteroatom doped carbon material/Ni MOF composite electrocatalyst Granted publication date: 20200214 License type: Common License Record date: 20231225 |
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