CN115058731A - N, S doped porous carbon loaded Co composite material and preparation method and application thereof - Google Patents
N, S doped porous carbon loaded Co composite material and preparation method and application thereof Download PDFInfo
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 53
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 40
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000004640 Melamine resin Substances 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 239000002114 nanocomposite Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 11
- 239000012621 metal-organic framework Substances 0.000 claims description 10
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 2
- SBNQJAHLGZCHCA-UHFFFAOYSA-N [Co].CC=1NC=CN1 Chemical compound [Co].CC=1NC=CN1 SBNQJAHLGZCHCA-UHFFFAOYSA-N 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 15
- 238000005868 electrolysis reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 125000005842 heteroatom Chemical group 0.000 description 12
- 230000010287 polarization Effects 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 6
- 150000001868 cobalt Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KFKJUYCIGRHJCF-UHFFFAOYSA-N cobalt;ethanol Chemical compound [Co].CCO KFKJUYCIGRHJCF-UHFFFAOYSA-N 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- GANMEEJISNNTGT-UHFFFAOYSA-N ethanol;2-methyl-1h-imidazole Chemical compound CCO.CC1=NC=CN1 GANMEEJISNNTGT-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides an N, S doped porous carbon loaded Co composite material, a preparation method and application thereof, in particular to a nitrogen (N) and sulfur (S) doped porous carbon loaded Co nanocomposite material which is an electrochemical catalyst. The preparation method of the electrochemical catalyst comprises the following steps: synthesizing ZIF-67 in absolute ethyl alcohol, then growing melamine resin (MUF) synthesized by melamine, trithiocyanuric acid and glyoxylic acid on the surface of ZIF-67 in an in-situ polymerization manner to obtain a ZIF-67/MUF precursor, and calcining to obtain the C-ZIF-67/MUF nano composite material. The nano composite material provided by the invention has good oxygen evolution catalytic activity and stability. The preparation method has the advantages of simple and easy preparation process, cheap and easily obtained raw materials, easy operation and the like.
Description
Technical Field
The invention belongs to the field of materials and energy, and particularly relates to an N, S doped porous carbon loaded Co composite material and a preparation method and application thereof, in particular to a polymer-based N, S doped porous carbon loaded Co composite material and a preparation method and application thereof.
Background
The hydrogen energy is one of the most potential new energy sources due to high heat value and no pollution, and the catalytic electrolysis of water has important research significance for hydrogen production. However, the two half reactions of catalytic water electrolysis, namely Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER), have the problems of slow reaction kinetics and high overpotential, and generally require a catalyst to reduce the activation energy of the reaction. The heteroatom-doped porous carbon material has the advantages of large specific surface area, adjustable composition and performance, high stability and the like, and has good application prospect in the field of catalytic electrolysis of water.
Metal-organic frameworks (MOFs) are a new type of nanoporous materials with high specific surface area and tunable pore size. Wherein ZIF-67 is made of Co 2+ The MOFs material formed by coordination with 2-methylimidazole has the advantages of rich nitrogen atoms, higher specific surface area, excellent chemical stability, thermal stability and the like, and the N-doped porous carbon loaded Co nanoparticles prepared by carbonization of ZIF-67 are widely applied to the field of electrocatalytic decomposition of water. However, the electrolytic water catalyst prepared based on the carbonization of ZIF-67 still has the problems of high cost, low N doping amount, poor stability and the like, and has limited electrocatalytic activity.
There are two main methods of doping carbon materials with heteroatoms commonly used: post-treatment doping and in-situ doping. The post-treatment doping refers to post-treatment of a carbon material with a substance containing a heteroatom, and the heteroatom is chemically removed from the original substance at high temperature and high pressure and then enters the surface or the interior of the carbon material. In-situ doping refers to doping heteroatoms in the process of synthesizing the carbon material, and carbonizing a precursor containing the heteroatoms to dope the heteroatoms in a carbon skeleton. Compared with post-treatment doping, the doping amount of the heteroatoms doped in situ is higher, and the heteroatoms can be uniformly doped in the carbon material.
Therefore, by growing polymeric melamine resin (MUF) in situ on ZIF-67, nitrogen (N) and sulfur (S) heteroatoms are introduced to rearrange the electron cloud around the carbon, increase the active sites of the material and improve the electrical conductivity thereof, and simultaneously remove the volatile part by carbonization to improve the catalytic activity thereof.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a preparation method and application of a nitrogen (N) and sulfur (S) doped porous carbon loaded Co nanocomposite aiming at the defects, and solves the problems of high preparation cost, unstable structure and few active sites of the traditional MOFs catalyst, in particular to a high-efficiency cobalt-based electrochemical catalyst and a preparation method and application thereof.
The technical scheme is as follows: in order to achieve the purpose, the invention adopts the technical scheme that:
the first purpose of the invention is to provide an N, S doped porous carbon loaded Co composite material, wherein the N, S doped porous carbon loaded Co composite material is a porous carbon material C-ZIF-67/MUF containing Co, N and S doping, the ZIF-67 is a metal organic framework material formed by Co and 2-methylimidazole, and the melamine resin MUF grows on the surface of the ZIF-67 through in-situ polymerization.
The invention aims to synthesize a polymer-based MOFs-derived porous carbon electro-catalyst, in particular to a high-efficiency MOFs-derived cobalt-doped nitrogen and sulfur porous carbon electro-catalyst, which is a C-ZIF-67/MUF nano composite material and is a porous carbon material doped with cobalt (Co), nitrogen (N) and sulfur (S).
Furthermore, the mass ratio of the ZIF-67 to the melamine resin MUF is (1-4) to (10-50).
Further, the melamine resin MUF is synthesized by cyanamide oligomers and glyoxylic acid, and the cyanamide polymers are melamine and/or trithiocyanuric acid.
Further, when the cyanamide oligomer is melamine or trithiocyanuric acid, the molar ratio of the cyanamide oligomer to glyoxylic acid is (0-2): 1.
Further, when the cyanamide oligomer is melamine and trithiocyanuric acid, the molar ratio of the melamine to the trithiocyanuric acid to the glyoxylic acid is (0-2): (0-2): 1.
Furthermore, the mol ratio of the melamine, the trithiocyanuric acid to the glyoxylic acid is (0.5-1.5): (0.5-1.5): 1.
The third purpose of the invention is to provide an application of the N, S doped porous carbon supported Co composite material, in particular to a catalytic oxygen evolution reaction.
The second purpose of the invention is to provide a preparation method of N, S doped porous carbon loaded Co composite material, which comprises the steps of growing melamine resin (MUF) on the surface of ZIF-67 in situ to obtain a ZIF-67/MUF composite material, and preparing the nitrogen (N) and sulfur (S) doped Co-loaded C-ZIF-67/MUF nano composite material by a calcination method.
Furthermore, the ZIF-67 is synthesized by stirring 2-methylimidazole and cobalt salt in absolute ethyl alcohol, wherein the molar ratio of the 2-methylimidazole to the cobalt salt is 8: 1.
Specifically, the preparation method of the ZIF-67 comprises the following steps: respectively dissolving 2-methylimidazole and cobalt salt in absolute ethyl alcohol to obtain a 2-methylimidazole ethanol solution and a cobalt salt ethanol solution, slowly dripping the cobalt salt ethanol solution into the 2-methylimidazole ethanol solution, and placing the mixture in a magnetic stirrer at room temperature for stirring reaction.
Furthermore, the stirring time is 4-10 hours.
Further, the stirring time is 6 hours.
Further, the ZIF-67/MUF composite material obtained by in-situ polymerization growth of melamine resin MUF on the surface of ZIF-67 is as follows: dissolving cyanamide oligomer and glyoxylic acid in a ZIF-67 ethanol solution by stirring to obtain a solution; the cyanamide oligomer is melamine and/or trithiocyanuric acid.
Further, when the cyanamide oligomer is melamine and trithiocyanuric acid, the adding sequence of the trithiocyanuric acid, the glyoxylic acid and the melamine is as follows: dissolving trithiocyanuric acid and glyoxylic acid in a ZIF-67 ethanol solution by stirring, and then adding melamine to dissolve by stirring. The preferential addition of acid-containing monomers facilitates partial ligand exchange with ZIF-67 for subsequent polymer growth on the ZIF-67 surface.
Furthermore, the stirring time is 5-15 hours.
Further, the stirring time is 10 hours.
Further, when the cyanamide oligomer is melamine or trithiocyanuric acid, the molar ratio of the cyanamide oligomer to glyoxylic acid is (0-2): 1.
Further, when the cyanamide oligomer is melamine and trithiocyanuric acid, the molar ratio of the melamine to the trithiocyanuric acid to the glyoxylic acid is (0-2): (0-2): 1.
Furthermore, the mol ratio of the melamine, the trithiocyanuric acid to the glyoxylic acid is (0.5-1.5): (0.5-1.5): 1.
Further, in one embodiment of the present invention, the method for preparing the C-ZIF-67/MUF nanocomposite comprises the steps of;
(1) preparing ZIF-67 in an absolute ethanol solution by taking cobalt salt and 2-methylimidazole as raw materials;
(2) in the prepared ZIF-67 system, melamine, trithiocyanuric acid and glyoxylic acid are added in situ to prepare the ZIF-67/MUF composite material. (ii) a
(3) And (3) preparing the obtained ZIF-67/MUF composite material by a calcination method to obtain the nitrogen and sulfur doped porous carbon loaded Co nano composite material C-ZIF-67/MUF.
Further, the step (1) is specifically as follows: dissolving 0.67mol of 2-methylimidazole and 0.08mol of cobalt salt in 20mL of absolute ethanol and 3mL of absolute ethanol respectively, slowly dropwise adding the cobalt salt ethanol solution into the 2-methylimidazole ethanol solution, and placing the mixture in a magnetic stirrer at room temperature for stirring and reacting for 6 hours.
Further, the step (2) is specifically to stir trithiocyanuric acid and glyoxylic acid in the ZIF-67 system until the trithiocyanuric acid and the glyoxylic acid are completely dissolved to obtain a mixed solution, add melamine into the mixed solution, and place the mixed solution in a magnetic stirrer at room temperature for stirring and reacting for 10 hours.
Furthermore, the molar ratio of the melamine to the cyanuric acid to the glyoxylic acid is (02-20): 0-2): 1.
Furthermore, the mol ratio of the melamine, the trithiocyanuric acid to the glyoxylic acid is (0.5-1.5): (0.5-1.5): 1.
Furthermore, the calcining method in the step (3) is to prepare the C-ZIF-67/MUF nano composite material through centrifugation, washing, drying and calcining.
Further, the drying temperature is 50-80 ℃, and the drying time is 10-15 hours.
Further, the drying temperature is 60 ℃ and the drying time is 12 hours.
Further, the calcination is carried out at 650-700 ℃ for 2-5 hours in a nitrogen atmosphere, and the heating rate is controlled at 2-10 ℃/min.
Furthermore, the calcination is carried out at 650-700 ℃ for 3 hours in nitrogen atmosphere, and the heating rate is controlled at 5 ℃/min.
The third purpose of the invention is to provide the application of the polymer-based N, S doped porous carbon loaded Co nano composite material in catalysis of oxygen evolution reaction. The catalyst can efficiently catalyze the oxygen evolution reaction, and has higher OER catalytic activity compared with a commercial catalyst.
The invention has the advantages that:
(1) the C-ZIF-67/MUF nanocomposite is an N, S-doped porous carbon loaded Co nanocomposite, and the introduction of heteroatoms Co, N and S in the porous carbon can improve the catalytic activity of a hybrid system; the catalyst can efficiently catalyze the oxygen evolution reaction, and has higher OER catalytic activity and stability compared with a commercial catalyst;
(3) the materials used in the invention are all cheap and easily available;
(4) the preparation process is easy to operate, environment-friendly and efficient.
Drawings
FIG. 1 is an XRD spectrum of the material obtained after carbonization in example 4, example 1, example 2 and example 3;
FIG. 2 shows examples 4, 1, 2, 3, 5, 1, 2, 3 and 3, which gave (a) C-ZIF-67/MUF-1, (b) C-ZIF-67/MUF-2, (C) C-ZIF-67/MUF-3, (d) C-ZIF-67/MUF-4, (e) C-ZIF-67/MUF-5, (f) C-ZIF-67, (h) C-MUF-3 and (g) RuO 2 When used as anode catalyst for water electrolysisA plot of polarization of;
FIG. 3 shows examples 4, 1, 2, 3, 5, 1, 2, 3 and 3, which gave (a) C-ZIF-67/MUF-1, (b) C-ZIF-67/MUF-2, (C) C-ZIF-67/MUF-3, (d) C-ZIF-67/MUF-4, (e) C-ZIF-67/MUF-5, (f) C-ZIF-67, (h) C-MUF-3, (g) RuO 2 Tafel slope plot as anode catalyst for electrolysis of water.
Detailed Description
The invention is further described with reference to the following figures and specific examples, which are not to be construed as limiting the invention. The present invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims.
The invention provides an N, S doped porous carbon loaded Co composite material and a preparation method and application thereof, belonging to the technical field of energy and material preparation. According to the invention, melamine resin (MUF) grows in situ on the surface of ZIF-67, nitrogen (N) and sulfur (S) heteroatoms are introduced into Co-loaded MOFs, and C-ZIF-67/MUF is successfully prepared by high-temperature carbonization. The preparation method has the advantages of simple and feasible preparation process, only one-step calcination, green and environment-friendly process and the like.
The starting materials used in this example were all obtained commercially.
Example 1: C-ZIF-67/MUF-2, wherein the molar ratio of the cyanuric acid to the melamine to the glyoxylic acid is 1.5:0.5: 1.
(1)5.5g of 2-methylimidazole is completely dissolved in 20mL of absolute ethyl alcohol to prepare a solution 1; 0.45g Co (NO) 3 ) 2 ·6H 2 Completely dissolving O in 3mL of absolute ethyl alcohol to prepare a solution 2; and slowly dropwise adding the solution 2 into the solution 1 under the stirring state, and placing the mixture in a magnetic stirrer at room temperature to stir and react for 6 hours to prepare a ZIF-67 system.
(2) 1.064g (6mmol) of trithiocyanuric acid and 0.592g (4mmol) of glyoxylic acid are stirred and completely dissolved in a ZIF-67 system, then 0.252g (2mmol) of melamine is added into the mixed system, and the mixed system is placed in a magnetic stirrer at room temperature to be stirred and react for 10 hours to prepare ZIF-67/MUF-2.
(3) Centrifuging ZIF-67/MUF-2, washing with absolute ethanol for 5 times, drying at 60 ℃ for 12 hours, feeding into a tube furnace for calcination, setting a programmed temperature rise from room temperature under a nitrogen atmosphere, heating to 650 ℃ at a temperature rise rate of 5 ℃/min, keeping the temperature for 3 hours, naturally cooling to room temperature, taking out, washing with distilled water, and drying at 60 ℃ to finally obtain the C-ZIF-67/MUF-2.
The XRD of the obtained catalyst is shown in fig. 1, the polarization curve when the catalyst is used as an anode catalyst for electrolysis of water is shown in fig. 2(b), the tafel slope curve when the catalyst is used as an anode catalyst for electrolysis of water is shown in fig. 3(b), and the detailed analysis of the results is shown in the subsequent examples.
Example 2: C-ZIF-67/MUF-3, wherein the molar ratio of the cyanuric acid to the melamine to the glyoxylic acid is 1:1: 1.
An experiment was carried out in the same manner as in example 1 except that 0.709g (4mmol) of trithiocyanuric acid, 0.504g (4mmol) of melamine and 0.592g (4mmol) of glyoxylic acid were used to obtain C-ZIF-67/MUF-3.
The XRD of the obtained catalyst is shown in fig. 1, the polarization curve when the catalyst is used as an anode catalyst for electrolysis of water is shown in fig. 2(c), the tafel slope curve when the catalyst is used as an anode catalyst for electrolysis of water is shown in fig. 3(c), and the detailed analysis of the results is shown in the subsequent examples.
Example 3: C-ZIF-67/MUF-4, wherein the molar ratio of the cyanuric acid to the melamine to the glyoxylic acid is 0.5:1.5: 1.
An experiment was carried out in the same manner as in example 1 except that 0.355g (2mmol) of trithiocyanuric acid, 0.757g (4mmol) of melamine and 0.592g (6mmol) of glyoxylic acid were used to obtain C-ZIF-67/MUF-4.
The XRD of the obtained catalyst is shown in fig. 1, the polarization curve when the catalyst is used as an anode catalyst for electrolysis of water is shown in fig. 2(d), the tafel slope curve when the catalyst is used as an anode catalyst for electrolysis of water is shown in fig. 3(d), and the detailed analysis of the results is shown in the subsequent examples.
Example 4: C-ZIF-67/MUF-1, wherein the molar ratio of the cyanuric acid to the melamine to the glyoxylic acid is 2:0: 1.
(1) A ZIF-67 system was prepared as in example 1 (1).
(2) Adding 1.418g (8mmol) of trithiocyanuric acid and 0.592g (4mmol) of glyoxylic acid into a ZIF-67 system, and placing the mixture in a magnetic stirrer at room temperature to stir for 10 hours to react to prepare ZIF-67/MUF-1.
(3) ZIF-67/MUF-1 was calcined at high temperature to C-ZIF-67/MUF-1 in the same manner as in example 1 (3).
The XRD of the obtained catalyst is shown in fig. 1, the polarization curve when the catalyst is used as an anode catalyst for electrolysis of water is shown in fig. 2(a), the tafel slope curve when the catalyst is used as an anode catalyst for electrolysis of water is shown in fig. 3(a), and the detailed analysis of the results is shown in the results of the examples which follow.
Example 5: C-ZIF-67/MUF-5, wherein the molar ratio of the cyanuric acid to the melamine to the glyoxylic acid is 0:2: 1.
An experiment was carried out in the same manner as in comparative example 1 except that 1.009g (8mmol) of melamine and 0.592g (4mmol) of glyoxylic acid were used to obtain C-ZIF-67/MUF-5.
The polarization curve when the anode catalyst is electrolyzed with water is shown in FIG. 2(e), the tafel slope curve when the anode catalyst is electrolyzed with water is shown in FIG. 3(e), and the detailed results are analyzed in the examples which follow.
Comparative example 1: C-ZIF-67
ZIF-67 was synthesized in the same manner as in step (1) of example 1, and the calcination process was the same as in step (3) of example 1, whereby C-ZIF-67 was obtained.
The polarization curve when the anode catalyst was electrolyzed with water is shown in FIG. 2(f), the tafel slope curve when the anode catalyst was electrolyzed with water is shown in FIG. 3(f), and the detailed results of the analysis are shown in the results of the examples which follow.
Comparative example 2: C-MUF-3
MUF-3 was synthesized in the same manner as in step (2) of example 1, and the calcination process was the same as in step (3) of example 1, whereby C-MUF was obtained.
The polarization curve of the obtained catalyst as an anode catalyst for electrolyzed water is shown in FIG. 2(g), the tafel slope curve as an anode catalyst for electrolyzed water is shown in FIG. 3(g), and the detailed analysis of the results is shown in the subsequent examples.
Comparative example 3: commercial catalyst RuO 2 The polarization curve when the anode catalyst was electrolyzed with water is shown in fig. 2(h), the tafel slope curve when the anode catalyst was electrolyzed with water is shown in fig. 3(h), and the detailed results of the analysis are shown in the results of the examples which follow.
Example analysis of results:
first, determination of the external characteristics of the catalyst
XRD measurements were carried out on the products obtained in examples 1 to 4.
The XRD test results of fig. 1 show that the catalysts obtained in example 1, example 2 and example 3 all show diffraction peaks at 44.40 ° and 51.65 °, corresponding to the (111) and (200) crystal planes of elemental Co, respectively. The catalyst obtained in example 3 showed a diffraction peak significantly different from those of the catalysts obtained in examples 2 and 3, a diffraction peak corresponding to the crystal plane of CoN (111) appeared at 36.2 degrees, and a diffraction peak of graphitized carbon appeared at 23 degrees. Therefore, with the increase of the amount of melamine monomer in the precursor polymer, the Co monomer in the product is gradually converted into CoN, the catalytic activity of CoN is higher, the graphitization degree of the obtained carbon material is increased, the conductivity is enhanced, and the catalytic performance of the carbon material is promoted.
Second, a test of catalytic activity for oxygen evolution of a high efficiency electrolyzed water catalyst
The catalysts for high efficiency electrolysis of water obtained in examples 1 to 5 and comparative examples 1 to 3 were subjected to oxygen evolution catalytic activity test.
Oxygen evolution test conditions: 5mg of the catalyst obtained in each of the above examples and comparative examples was added to 490. mu.L of deionized water, 500. mu.L of absolute ethanol and 20. mu.L of a 0.5 wt% Nafion mixed solution, and the catalyst was uniformly dispersed in the solution by sonication. A glassy carbon electrode (diameter 5mm) was polished with 50nm alumina polishing powder until a smooth mirror surface was obtained. And dripping 6 mu L of the prepared catalyst dispersion liquid on the surface of the glassy carbon electrode for three times, and drying at room temperature to prepare the working electrode. Electrochemical tests were performed at an electrochemical workstation (CHI760E) using a three-electrode system, a graphite rod electrode as a counter electrode, Ag/AgCl as a reference electrode, and the prepared glassy carbon electrode as a working electrode, and in a 0.1M KOH electrolyte purified with nitrogen, the voltammetry curve and tafel slope were tested at room temperature.
The overpotential (. eta.) is used to evaluate the overall activity of the target electrocatalyst, typically at a specified current density of 10mA/cm 2 The corresponding overpotentials were used to compare the electrocatalytic activity of different catalysts. The current density of 10mAcm can be calculated from the cyclic voltammetry curve -2 Overpotential (η/mV): η ═ E-1.23 × 1000, and E represents electromotive force.
By converting the current density to a logarithmic value of 10 as the x-axis and the overpotential to a polarization curve as the y-axis, we can obtain a Tafel plot of the target catalyst, which shows the dependence of the steady-state current density (j) on the overpotential (η). Fitting by Tafel equation: η ═ a + b log j, where b is the Tafel slope and a is a constant determined by the exchange current density j0 and the Tafel slope. Among them, the Tafel slope is generally related to the electrochemical reaction mechanism, and represents the rate of increase of current density with increase of overpotential. That is, a smaller Tafel slope indicates that a greater current density is achieved with a much smaller overpotential change, exhibiting rapid electrocatalytic reaction kinetics.
Therefore, the smaller the overpotential, the smaller the Tafel slope, and the higher the electrocatalytic activity.
The obtained cyclic voltammograms for oxygen evolution of the high efficiency electrolyzed water catalyst are shown in FIG. 2, the Tafel slopes are shown by the solid lines in FIG. 3, and the results of the concrete data are shown in Table 1 as examples 4, 1, 2, 3, 5, 1, 2, and 3, and the results of the concrete data are shown in Table 1 as C-ZIF-67/MUF-1, (b) C-ZIF-67/MUF-2, (C) C-ZIF-67/MUF-3, (d) C-ZIF-67/MUF-4, (e) C-ZIF-67/MUF-5, (f) C-ZIF-67, (h) C-MUF-3, (g) RuO 2 When used as anode catalyst for water electrolysis, the catalyst is 10mA cm -2 Over-potential and tafel slope.
TABLE 1 test results for each material
As shown in FIG. 2 and Table 1, the catalysts obtained in example 1, example 2, example 3, example 4, example 5, comparative example 1, comparative example 2 and comparative example 3 were in the range of 10mA cm -2 The overpotentials of (a) were 254mV, 274mV, 268mV, 363 Mv, 414mV, 400mV, 349mV, 284mV, respectively, and it can be seen that examples 1-5, which employ the scheme of the present invention, all had lower overpotentials. In particular, in example 1, example 2 and example 3, the MUF material was prepared using tris-thiocyanic acid, melamine and glyoxylic acid together, and the obtained catalyst was compared to other catalysts and commercially available RuO 2 The material has lower overpotential, namely better oxygen precipitation catalytic activity, and illustrates the technical scheme of the embodiments 1-3 of the invention, and can be used as expensive RuO 2 An effective alternative to materials.
As shown in FIG. 3, the Tafel slopes of the catalysts obtained in example 1, example 2, example 3 and example 4, example 5, comparative example 1, comparative example 2, comparative example 3 were 86.4mV · dec, respectively -1 、91.9mV·dec -1 、89.7mV·dec -1 、110.4 mV·dec -1 、112.3mV·dec -1 、111.2mV·dec -1 、109.6mV·dec -1 、103.4mV·dec -1 It can be seen that examples 1-5, prepared according to the inventive protocol, all have a relatively low tafel slope. Especially, the target products in the embodiments 1, 2 and 3 have smaller tafel slope and lower overpotential under the same environment, show faster catalytic reaction kinetics and have good catalytic activity. RuO compared with noble metal catalyst 2 By adopting the scheme of the embodiment of the invention, the Tafel slope is lower under the same environment, the reaction kinetics of catalyzing OER is faster, the catalytic activity is better, and the technical schemes of the embodiments 1 to 3 of the invention are explained again, so that the RuO can be used as the RuO with high price 2 An effective alternative to materials.
In conclusion, the melamine resin (MUF) grows on the surface of the ZIF-67 in situ, nitrogen (N) and sulfur (S) heteroatoms are introduced into the MOFs material loaded with Co, and the C-ZIF-67/MUF is successfully prepared through high-temperature carbonization, so that the catalyst can be used as an ideal high-efficiency electrolytic water catalyst and has lower overpotential and smaller Tafel slope, and the catalyst prepared by the method can efficiently catalyze an oxygen evolution reaction.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. The N, S doped porous carbon loaded Co composite material is characterized in that the N, S doped porous carbon loaded Co composite material is a C-ZIF-67/MUF doped porous carbon material containing Co, N and S, the C-ZIF-67/MUF is obtained by carbonizing a precursor ZIF-67/MUF, wherein the ZIF-67 is a metal organic framework material formed by metal Co and 2-methylimidazole, and the melamine resin MUF grows on the surface of the ZIF-67 in an in-situ polymerization manner.
2. The N, S doped porous carbon-loaded Co nanocomposite material of claim 1, wherein the mass ratio of ZIF-67 to melamine resin MUF is (1-4): (10-50).
3. The N, S doped porous carbon-loaded Co composite material of claim 1, wherein the melamine resin MUF is synthesized from cyanamide oligomers and glyoxylic acid, the cyanamide oligomers being melamine and/or trithiocyanuric acid.
4. The N, S doped porous carbon-loaded Co composite material as claimed in claim 3, wherein when the cyanamide oligomer is melamine or cyanuric acid, the molar ratio of the cyanamide oligomer to glyoxylic acid is (0-2) to 1;
when the cyanamide oligomer is melamine and trithiocyanuric acid, the molar ratio of the melamine to the trithiocyanuric acid to the glyoxylic acid is (0-2) to 1.
5. The preparation method of N, S doped porous carbon loaded Co composite material according to any one of claims 1-4, wherein the ZIF-67/MUF composite material is prepared by growing melamine resin MUF on the surface of ZIF-67 through in-situ polymerization, and calcining the ZIF-67/MUF composite material.
6. The method as claimed in claim 5, wherein the ZIF-67 is prepared by stirring 2-methylimidazole cobalt salt in absolute ethanol, and the molar ratio of 2-methylimidazole cobalt salt is 8: 1.
7. The method as claimed in claim 5, wherein the in-situ polymerization growth of the melamine resin MUF on the surface of the ZIF-67 to obtain the ZIF-67/MUF composite material is as follows: dissolving cyanamide oligomer and glyoxylic acid in ZIF-67 ethanol solution by stirring to obtain the mixture;
the cyanamide oligomer is melamine and/or trithiocyanuric acid, and when the cyanamide oligomer is melamine and trithiocyanuric acid, the addition sequence of the trithiocyanuric acid, the glyoxylic acid and the melamine is as follows: dissolving trithiocyanuric acid and glyoxylic acid in ZIF-67 ethanol solution under stirring, adding melamine, and dissolving under stirring.
8. The method according to claim 7, wherein when the cyanamide oligomer is melamine or trithiocyanuric acid, the molar ratio of the cyanamide polymer to the glyoxylic acid is (0-2) to 1;
when the cyanamide oligomer is melamine and trithiocyanuric acid, the molar ratio of the melamine to the trithiocyanuric acid to the glyoxylic acid is (0-2): (0-2) to 1.
9. The method of claim 5, wherein the calcination process comprises centrifuging, washing, drying, and calcining to obtain the C-ZIF-67/MUF nanocomposite, and the calcination process comprises maintaining the temperature at 650-700 ℃ for 2-5 hours in a nitrogen atmosphere, wherein the temperature is increased at a rate of about 2-10 ℃/min.
10. Use of N, S doped porous carbon loaded Co composite material, the composite material being according to any one of claims 1 to 4 or prepared according to any one of claims 5 to 9, for electrocatalytic oxygen evolution reactions.
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