CN115058731B - 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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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 27
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 69
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 57
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 44
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004640 Melamine resin Substances 0.000 claims abstract description 14
- 238000001354 calcination Methods 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
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 11
- 239000012621 metal-organic framework Substances 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011593 sulfur Substances 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 238000004458 analytical method Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 125000005842 heteroatom Chemical group 0.000 description 14
- 238000005868 electrolysis reaction Methods 0.000 description 13
- 230000010287 polarization Effects 0.000 description 10
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 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
- 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
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation 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
- 239000005539 carbonized material Substances 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
- 239000012153 distilled water Substances 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
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 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
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 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
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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 a 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: firstly, ZIF-67 is synthesized in absolute ethyl alcohol, then melamine resin (MF) synthesized by melamine, cyanuric acid and glyoxylic acid is polymerized and grown on the surface of the ZIF-67 in situ, a ZIF-67/MF precursor is obtained, and the C-ZIF-67/MF nanocomposite is obtained through calcination. The nanocomposite provided by the invention has good oxygen evolution catalytic activity and stability. The preparation method has the advantages of simple and easy preparation process, low-cost and easily available raw materials, easy operation and the like.
Description
Technical Field
The invention belongs to the field of materials and energy sources, and particularly relates to a 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 novel 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, hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER), have the problems of slow reaction kinetics and high overpotential, and a catalyst is generally required 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 novel nanoporous materials with high specific surface area and adjustable pore size. Wherein ZIF-67 is Co 2+ MOFs material formed by coordination of 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 nano particles prepared by carbonization of ZIF-67 are widely applied to the field of electrocatalytic decomposition of water. However, the electrolyzed water catalyst prepared by carbonization based on ZIF-67 still has the problems of high cost, low N doping amount, poor stability and the like, and has limited electrocatalytic activity.
The methods of doping carbon materials with heteroatoms commonly used are mainly two: post-processing doping and in-situ doping. Post-treatment doping refers to post-treatment of a carbon material with a heteroatom-containing substance, and under high temperature and high pressure, the heteroatom is separated from the original substance by chemical reaction and enters the surface or the interior of the carbon material, but generally the heteroatom doping amount is low. 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 in-situ doping of the hetero atoms has higher doping amount, and simultaneously, the hetero atoms can be uniformly doped in the carbon material.
Therefore, by growing polymeric melamine resin (MF) in situ in ZIF-67, introducing nitrogen (N) and sulfur (S) heteroatoms, electron clouds around carbon are rearranged, active sites of the material are increased, conductivity of the material is improved, and volatile parts are removed through carbonization, so that catalytic activity of the material is improved.
Disclosure of Invention
Technical problems: 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 above purpose, the invention adopts the following technical scheme:
the first object of the invention is to provide a 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/MF containing cobalt Co, N and S, the ZIF-67 is a metal organic framework material formed by Co and 2-methylimidazole, and the melamine resin MF is polymerized and grown on the surface of the ZIF-67 in situ.
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-sulfur porous carbon electro-chemical catalyst which is a C-ZIF-67/MF nanocomposite material and is a porous carbon material doped with cobalt (Co), nitrogen (N) and sulfur (S).
Further, the mass ratio of ZIF-67 to melamine resin MF is (1-4) (10-50).
Further, the melamine resin MF is synthesized by melamine oligomers and glyoxalic acid, and the melamine polymers are melamine and/or cyanuric acid.
Further, when the melamine oligomer is melamine or cyanuric acid, the molar ratio of the melamine oligomer to glyoxylic acid is (0-2): 1.
Further, when the cyanamide oligomer is melamine and cyanuric acid, the molar ratio of the melamine, the cyanuric acid and the glyoxylic acid is (0-2): 1.
Further, the mole ratio of melamine, cyanuric acid and glyoxylic acid is (0.5-1.5): 1.
The third object of the present invention is to provide an application of the N, S doped porous carbon loaded Co composite material, specifically for catalyzing oxygen evolution reaction.
The second object of the invention is to provide a preparation method of a N, S doped porous carbon loaded Co composite material, wherein melamine resin (MF) is grown on the surface of ZIF-67 in situ to obtain a ZIF-67/MF composite material, and the ZIF-67/MF composite material is prepared into a nitrogen (N) and sulfur (S) doped Co loaded C-ZIF-67/MF nano composite material by a calcination method.
Further, 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.
Further, the stirring time is 4 to 10 hours.
Still further, the stirring time was 6 hours.
Further, the in-situ polymerization growth of melamine resin MF on the surface of the ZIF-67 to obtain the ZIF-67/MF composite material comprises the following steps: stirring and dissolving cyanamide oligomer and glyoxylate in ZIF-67 ethanol solution to obtain the catalyst; the cyanamide oligomer is melamine and/or cyanuric acid.
Further, when the cyanamide oligomer is melamine and cyanuric acid, the addition sequence of cyanuric acid, glyoxylic acid and melamine is as follows: dissolving cyanuric acid and glyoxylic acid in ZIF-67 ethanol solution under stirring, and adding melamine and stirring. The preferential addition of the acid-containing monomer facilitates partial ligand exchange with ZIF-67 for subsequent polymer growth on the surface of ZIF-67.
Further, the stirring time is 5 to 15 hours.
Still further, the stirring time was 10 hours.
Further, when the melamine oligomer is melamine or cyanuric acid, the molar ratio of the melamine oligomer to glyoxylic acid is (0-2): 1.
Further, when the cyanamide oligomer is melamine and cyanuric acid, the molar ratio of the melamine, the cyanuric acid and the glyoxylic acid is (0-2): 1.
Further, the mole ratio of melamine, cyanuric acid and glyoxylic acid is (0.5-1.5): 1.
Further, in one embodiment of the present invention, the preparation method of the C-ZIF-67/MF nanocomposite material includes the steps of;
(1) Preparing ZIF-67 in absolute ethanol solution by taking cobalt salt and 2-methylimidazole as raw materials;
(2) In-situ adding melamine, cyanuric acid and glyoxylic acid into the prepared ZIF-67 system to prepare the ZIF-67/MF composite material. The method comprises the steps of carrying out a first treatment on the surface of the
(3) And preparing the obtained ZIF-67/MF composite material by a calcination method to obtain the nitrogen-sulfur doped porous carbon loaded Co nanocomposite material C-ZIF-67/MF.
Further, the step (1) specifically comprises: 0.67mol of 2-methylimidazole and 0.08mol of cobalt salt are respectively dissolved in 20mL of absolute ethyl alcohol and 3mL of absolute ethyl alcohol, and the cobalt salt ethanol solution is slowly added dropwise to the 2-methylimidazole ethanol solution, and the mixture is placed in a magnetic stirrer at room temperature for stirring reaction for 6 hours.
And (2) stirring the cyanuric acid and the glyoxylic acid in the ZIF-67 system until the cyanuric acid and the glyoxylic acid are completely dissolved to obtain a mixed solution, adding melamine into the mixed solution, and stirring and reacting for 10 hours at room temperature by a magnetic stirrer.
Further, the mole ratio of melamine, cyanuric acid and glyoxylic acid is (0.2-2.0): 0-2): 1.
Further, the mole ratio of melamine, cyanuric acid and glyoxylic acid is (0.5-1.5): 1.
And (3) preparing the C-ZIF-67/MF nanocomposite by centrifuging, washing, drying and calcining.
Further, the drying temperature is 50-80 ℃ and the drying time is 10-15 hours.
Further, the drying temperature was 60℃for 12 hours.
Further, the calcination is carried out for 2-5 hours at 650-700 ℃ under nitrogen atmosphere, and the temperature rising rate is controlled at 2-10 ℃/min.
Further, the calcination is carried out by keeping the temperature at 650-700 ℃ for 3 hours under the nitrogen atmosphere, and the temperature rising rate is controlled at 5 ℃/min.
A third object of the present invention is to provide an application of a polymer-based N, S doped porous carbon-loaded Co nanocomposite for catalysis of oxygen evolution reactions. 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/MF nanocomposite is a N, S doped porous carbon loaded Co nanocomposite, and the introduction of hetero atoms Co, N and S in the porous carbon can improve the catalytic activity of a hybridization system; the catalyst can efficiently catalyze the oxygen evolution reaction, and has higher OER catalytic activity and stability compared with commercial catalysts;
(3) The materials used in the invention are cheap and easily available;
(4) The preparation process of the invention is easy to operate, environment-friendly and efficient.
Drawings
FIG. 1 is an XRD pattern of the carbonized material obtained in example 4, example 1, example 2 and example 3;
FIG. 2 shows that examples 4, 1, 2, 3, 5, 1, 2, and 3 give (a) C-ZIF-67/MF-1, (b) C-ZIF-67/MF-2, (C) C-ZIF-67/MF-3, (d) C-ZIF-67/MF-4, (e) C-ZIF-67/MF-5, (f) C-ZIF-67, (h) C-MF-3, (g) RuO 2 A polarization curve graph when used as an anode catalyst for electrolyzing water;
FIG. 3 shows that examples 4, 1, 2, 3, 5, 1, 2, and 3 give (a) C-ZIF-67/MF-1, (b) C-ZIF-67/MF-2, (C) C-ZIF-67/MF-3, (d) C-ZIF-67/MF-4, and (e) C-ZIF-67/MF-5、(f)C-ZIF-67、(h)C-MF-3、(g)RuO 2 Tafil slope plot as an electrolyzed water anode catalyst.
Detailed Description
The invention is further described below with reference to the drawings and specific examples, which are not to be construed as limiting the invention. The invention will be better understood from the following examples. However, it will be readily understood by those skilled in the art that the specific material ratios, process conditions and results thereof described in the examples are illustrative of the present invention and should not be construed as limiting the invention described in detail in the claims.
The invention provides a N, S doped porous carbon loaded Co composite material and a preparation method and application thereof, and belongs to the technical field of energy and material preparation. In the invention, melamine resin (MF) grows on the surface of ZIF-67 in situ, nitrogen (N) and sulfur (S) heteroatoms are introduced into Co-loaded MOFs material, and C-ZIF-67/MF is successfully prepared through high-temperature carbonization. The preparation method has the advantages of simple and easy preparation process, only one-step calcination, green and environment-friendly process and the like.
The raw materials used in this example were all obtained commercially.
Example 1: the molar ratio of the C-ZIF-67/MF-2 to the cyanuric acid, the melamine and 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 O is completely dissolved in 3mL of absolute ethyl alcohol to prepare solution 2; slowly dripping the solution 2 into the solution 1 in a stirring state, and placing the solution in a magnetic stirrer at room temperature to stir and react for 6 hours to prepare the ZIF-67 system.
(2) 1.064g (6 mmol) of cyanuric acid and 0.592g (4 mmol) of glyoxylic acid are stirred and completely dissolved in a ZIF-67 system, 0.252g (2 mmol) of melamine is added into the mixed system, and the mixture is placed in a magnetic stirrer at room temperature for stirring and reacting for 10 hours, so as to prepare the ZIF-67/MF-2.
(3) And (3) centrifuging ZIF-67/MF-2, washing with absolute ethanol for 5 times, drying at 60 ℃ for 12 hours, sending into a tube furnace for calcination, setting a programmed temperature to be higher than room temperature under nitrogen atmosphere, heating to 650 ℃ at a temperature rising rate of 5 ℃/min, preserving heat 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/MF-2.
XRD of the obtained catalyst is shown in figure 1, a polarization curve of the catalyst serving as an electrolyzed water anode catalyst is shown in figure 2 (b), a Tafil slope curve of the catalyst serving as an electrolyzed water anode catalyst is shown in figure 3 (b), and detailed analysis of the results is shown in the analysis of the results of the following examples.
Example 2: the molar ratio of the C-ZIF-67/MF-3 to the cyanuric acid to the melamine to the glyoxylic acid is 1:1:1.
An experiment was performed according to 0.709g (4 mmol) of cyanuric acid, 0.504g (4 mmol) of melamine and 0.592g (4 mmol) of glyoxylate, with the remainder of example 1, to give C-ZIF-67/MF-3.
XRD of the obtained catalyst is shown in figure 1, a polarization curve of the catalyst serving as an electrolyzed water anode catalyst is shown in figure 2 (c), a Tafil slope curve of the catalyst serving as an electrolyzed water anode catalyst is shown in figure 3 (c), and detailed analysis of the results is shown in the analysis of the results of the following examples.
Example 3: the molar ratio of the C-ZIF-67/MF-4 to the cyanuric acid, the melamine and the glyoxylic acid is 0.5:1.5:1.
An experiment was performed according to 0.355g (2 mmol) of cyanuric acid, 0.757g (4 mmol) of melamine and 0.592g (6 mmol) of glyoxylate, with the remainder of example 1, to give C-ZIF-67/MF-4.
XRD of the obtained catalyst is shown in figure 1, a polarization curve of the catalyst serving as an electrolyzed water anode catalyst is shown in figure 2 (d), a Tafil slope curve of the catalyst serving as an electrolyzed water anode catalyst is shown in figure 3 (d), and detailed analysis of the results is shown in the analysis of the results of the following examples.
Example 4: the molar ratio of the C-ZIF-67/MF-1 to 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) 1.418g (8 mmol) of cyanuric acid and 0.592g (4 mmol) of glyoxylic acid were added to the ZIF-67 system, and the mixture was stirred at room temperature by a magnetic stirrer to react for 10 hours, thereby obtaining ZIF-67/MF-1.
(3) ZIF-67/MF-1 was calcined to C-ZIF-67/MF-1 at high temperature, as in example 1 (3).
XRD of the obtained catalyst is shown in figure 1, a polarization curve of the catalyst serving as an electrolytic water anode catalyst is shown in figure 2 (a), a Tafil slope curve of the catalyst serving as an electrolytic water anode catalyst is shown in figure 3 (a), and specific result analysis is shown in the subsequent example.
Example 5: the molar ratio of the C-ZIF-67/MF-5 to the cyanuric acid to the melamine to the glyoxylic acid is 0:2:1.
Experiments were performed according to 1.009g (8 mmol) of melamine and 0.592g (4 mmol) of glyoxylate, the remainder being the same as in comparative example 1, giving C-ZIF-67/MF-5.
The polarization curve as the water-splitting anode catalyst is shown in fig. 2 (e), the tafel slope curve as the water-splitting anode catalyst is shown in fig. 3 (e), and the detailed analysis of the results is shown in the analysis of the results of the subsequent examples.
Comparative example 1: C-ZIF-67
ZIF-67 was synthesized in the same manner as in the step (1) of example 1, and the calcination process was the same as in the step (3) of example 1, to obtain C-ZIF-67.
The polarization curve as the water-electrolysis anode catalyst is shown in fig. 2 (f), the tafel slope curve as the water-electrolysis anode catalyst is shown in fig. 3 (f), and the detailed analysis of the results is shown in the analysis of the results of the subsequent examples.
Comparative example 2: C-MF-3
The MF-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, to obtain C-MF.
The polarization curve of the obtained catalyst as the water electrolysis anode catalyst is shown in fig. 2 (g), the tafel slope curve of the catalyst as the water electrolysis anode catalyst is shown in fig. 3 (g), and the detailed analysis of the results is shown in the analysis of the results of the subsequent examples.
Comparative example 3: commercial catalyst RuO 2 The polarization curve as the water-electrolysis anode catalyst is shown in FIG. 2 (h), the Tafil slope curve as the water-electrolysis anode catalyst is shown in FIG. 3 (h), and the detailed analysis of the results is shown in the followingExample results analysis.
Example results analysis:
first, determination of external characteristics of catalyst
XRD testing was performed on the products obtained in examples 1-4.
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 the catalysts obtained in example 2 and example 3, a diffraction peak corresponding to the CoN (111) crystal plane at 36.2℃and a diffraction peak of graphitized carbon at 23 ℃. Therefore, along with the increase of the melamine monomer amount in the precursor polymer, the simple substance Co in the product is gradually converted into CoN, the catalytic activity of the 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 to be improved.
Second, catalytic activity test for oxygen evolution of 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 an 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 a mixed solution of 490. Mu.L of deionized water, 500. Mu.L of absolute ethanol and 20. Mu.L of 0.5wt% Nafion, and the catalyst was uniformly dispersed in the solution by ultrasonic waves. The glassy carbon electrode (diameter 5 mm) was polished with an alumina polishing powder of 50nm until a smooth mirror surface was obtained. And (3) taking 6 mu L of the prepared catalyst dispersion liquid, dripping the 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 testing was performed at an electrochemical workstation (CHI 760E) using a three electrode system with a graphite rod electrode as the counter electrode, ag/AgCl as the reference electrode, and the glassy carbon electrode prepared as described above as the working electrode, and the voltammetric characteristic and tafel slope were tested at room temperature in a 0.1M KOH electrolyte purified with nitrogen.
The overpotential (. Eta.) was used to evaluate the overall activity of the target electrocatalyst, typically at a specified current density of 10mA/cm 2 Corresponding overpotential for comparison ofElectrocatalytic activity of the different catalysts. From the cyclic voltammogram, a current density of 10mA cm can be calculated -2 Is (η/mV): η= (E-1.23) ×1000, E represents an electromotive force.
By converting the current density to a 10 logarithmic value as the x-axis and the overpotential as the y-axis to a polarization curve we can obtain Tafel plot of the target catalyst showing the dependence of steady state current density (j) on overpotential (η). Fitting by Tafel equation: η=a+blog j, where b is the Tafel slope and a is a constant determined by the switching current density j0 and the Tafel slope. Among them, tafel slope is generally related to electrochemical reaction mechanism, representing the rate of increase of current density with increasing overpotential. That is, a smaller Tafel slope indicates that a larger current density is achieved with a much smaller overpotential change, exhibiting rapid electrocatalytic reaction kinetics.
Thus, the smaller the overpotential, the smaller the Tafel slope and the higher the electrocatalytic activity.
The cyclic voltammogram obtained for oxygen evolution of the high-efficiency electrolytic water catalyst is shown in FIG. 2, the Taphil slope is shown in solid line in FIG. 3, and the specific data results are shown in Table 1 as example 4, example 1, example 2, example 3, example 5, comparative example 1, comparative example 2, comparative example 3 to give (a) C-ZIF-67/MF-1, (b) C-ZIF-67/MF-2, (C) C-ZIF-67/MF-3, (d) C-ZIF-67/MF-4, (e) C-ZIF-67/MF-5, (f) C-ZIF-67, (h) C-MF-3, (g) RuO 2 When used as an anode catalyst for water electrolysis, the catalyst can be used for water electrolysis at a concentration of 10mA cm -2 Is used for the overvoltage 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 measured at 10mA cm -2 The overpotential of (a) was 254mV, 274mV, 268mV, 363mV, 414mV, 400mV, 349mV, 284mV, respectively, it can be seen that the scheme of the present invention was employedExamples 1-5 all have lower overpotential. In particular, in the three examples of example 1 and example 2, example 3, the use of cyanuric acid, melamine and glyoxylic acid together for the preparation of the MF material gives a catalyst which is comparable to other catalysts and to the commercially available RuO 2 The material has lower overpotential, i.e. better oxygen evolution catalytic activity, which illustrates the technical proposal of the embodiment 1-3 of the invention, and can be used as the RuO with high price 2 An effective alternative to materials.
As shown in FIG. 3, the catalyst obtained in example 1, example 2, example 3 and example 4, example 5, comparative example 1, comparative example 2 and comparative example 3 had a Tafil slope of 86.4 mV.dec, respectively -1 、91.9mV·dec -1 、89.7mV·dec -1 、110.4mV·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, which were prepared using the inventive protocol, all had a small tafel slope. In particular, the target products in the examples 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. Compared with a noble metal catalyst RuO 2 By adopting the scheme of the embodiment of the invention, the catalyst has lower Tafil slope under the same environment, faster catalytic OER reaction kinetics and better catalytic activity, and the technical scheme of the embodiment 1-3 of the invention is illustrated again and can be used as high-cost RuO 2 An effective alternative to materials.
In conclusion, the invention introduces nitrogen (N) and sulfur (S) heteroatoms into MOFs material loaded with Co by growing melamine resin (MF) on the surface of ZIF-67 in situ, and successfully prepares C-ZIF-67/MF by high-temperature carbonization, thus being capable of being used as an ideal high-efficiency water electrolysis catalyst, and having lower overpotential and smaller Tafil slope, so that the catalyst prepared by the invention can efficiently catalyze oxygen evolution reaction.
The foregoing is only a preferred embodiment of the invention, it being 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 present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (7)
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 porous carbon material C-ZIF-67/MF doped with cobalt Co, N and S, wherein the C-ZIF-67/MF is obtained by carbonizing a precursor ZIF-67/MF, the ZIF-67 is a metal organic framework material formed by cobalt salt and 2-methylimidazole, and melamine resin MF is polymerized and grown on the surface of the ZIF-67 in situ;
the mass ratio of the ZIF-67 to the melamine resin MF is (1-4) (10-50);
the melamine resin MF is synthesized by melamine oligomers and glyoxalic acid, the melamine oligomers are melamine and cyanuric acid,
the mole ratio of melamine, cyanuric acid and glyoxylic acid is (0.5-1.5): 1.
2. The method for preparing the N, S doped porous carbon loaded Co composite material according to claim 1, wherein the method is characterized in that melamine resin MF is polymerized and grown on the surface of ZIF-67 in situ to obtain the ZIF-67/MF composite material, and the C-ZIF-67/MF nanocomposite material is prepared by a calcination method.
3. The method according to claim 2, wherein the ZIF-67 is synthesized by stirring 2-methylimidazole and cobalt salt in absolute ethanol, and the molar ratio of the 2-methylimidazole to the cobalt salt is 8:1.
4. The method according to claim 2, wherein the in-situ polymerization of melamine resin MF on the surface of ZIF-67 to obtain the ZIF-67/MF composite material comprises: stirring and dissolving cyanamide oligomer and glyoxylate in ZIF-67 ethanol solution to obtain the catalyst;
the addition sequence of the cyanuric acid, the glyoxylic acid and the melamine is as follows: dissolving cyanuric acid and glyoxylic acid in ZIF-67 ethanol solution under stirring, and adding melamine and stirring.
5. The method according to claim 4, wherein the melamine oligomer is melamine and cyanuric acid, and the molar ratio of melamine, cyanuric acid and glyoxylic acid is (0.5-1.5): 1.
6. The method according to claim 2, wherein the calcination method is to obtain the C-ZIF-67/MF nanocomposite by centrifugation, washing, drying, and calcination, and the calcination is to keep the temperature at 650-700 ℃ for 2-5 hours under nitrogen atmosphere, and the temperature rising rate is controlled at about 2-10 ℃/min.
7. Use of a N, S doped porous carbon loaded Co composite material according to claim 1 or prepared according to any of the methods of claims 2-6 for electrocatalytic oxygen evolution reactions.
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| CN109704305A (en) * | 2019-01-22 | 2019-05-03 | 齐鲁工业大学 | It is a kind of using ZIF-67 as the preparation method and application of templated synthesis melamine resin base Carbon Materials |
| CN111908451A (en) * | 2020-06-19 | 2020-11-10 | 齐鲁工业大学 | Preparation method of hollow vermicular carbon nano tube |
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