CN111215108A - Supported transition metal monatomic catalyst and universal preparation method and application thereof - Google Patents
Supported transition metal monatomic catalyst and universal preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 38
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- -1 transition metal cation Chemical class 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 238000004873 anchoring Methods 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000197 pyrolysis Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229920001661 Chitosan Polymers 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 229910021397 glassy carbon Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000001075 voltammogram Methods 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WYAHMVILRVZCLR-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Mn+2].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Mn+2].[N+](=O)([O-])[O-] WYAHMVILRVZCLR-UHFFFAOYSA-N 0.000 description 1
- DTWCOCYXNRTSIA-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Zn+2].[N+](=O)([O-])[O-] DTWCOCYXNRTSIA-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- AHBDJJPEQJQYMC-UHFFFAOYSA-N ethanol nickel(2+) dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] AHBDJJPEQJQYMC-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/391—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- C25B1/28—Per-compounds
- C25B1/30—Peroxides
-
- 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
Abstract
Provides a method for universally preparing a supported transition metal monatomic catalyst. The transition metal comprises non-noble metals of Co, Mn, Fe, Ni, Cu, Zn, V, Ti and Mo, and the noble metals of Ru, Pt, Pd, Au, Rh, Ag and Nb, and the carrier is a carbon carrier with nitrogen anchoring sites. The content of transition metal in the catalyst can be controlled and adjusted to be 0.01-4.0 wt%. The preparation process is universal and simple: preparing a high polymer precursor containing nitrogen and carbon components, and then thermally decomposing at high temperature to obtain the carbon carrier with the nitrogen anchoring site. Adding a certain amount of metal salt, and stirring the liquid phase to prepare the transition metal monatomic catalyst with stable nitrogen coordination. The preparation method has good universality, is suitable for any transition metal cation, and has controllable transition metal monatomic loading. The catalyst has excellent catalytic performance in electrocatalytic oxygen reduction.
Description
Technical Field
The invention relates to a universal preparation strategy of a supported transition metal monatomic catalyst and application of the supported transition metal monatomic catalyst in an electrocatalysis system.
Background
Homogeneous single-site catalysts have high activity and high selectivity in a specific catalytic system, but have poor stability, so that the development of heterogeneous catalysts capable of comparing the activity of homogeneous single-site catalysts is an important direction in catalytic research. Compared with a homogeneous single-site catalyst, the heterogeneous transition metal single-site catalyst not only has similar single-site structure, but also has excellent catalytic activity in a specific reaction system because the heterogeneous transition metal single-site catalyst is different from multiple active sites such as steps, corners and the like of a nano-catalyst: high selectivity, high conversion and high stability. To this end, transition metal monatomic catalysts have become the leading science of the catalytic field. On the basis of continuously and deeply researching the structural characteristics and the catalytic mechanism of the monatomic catalyst, researchers have prepared monatomic catalysts with various structures and compositions by utilizing a coprecipitation method, an impregnation method, an atomic layer deposition method, a reverse Ostwald aging method, a gradual reduction method, a solid-phase melting method and the like. The elements in these monatomic catalysts include: noble metals such as Pt, Ir and Rh and non-noble metals such as Fe, Co, Ni and Zn. Although the research on the monatomic catalyst has been advanced for a long time in the past, the mature and efficient preparation method, the systematic and reliable characterization method and the establishment of the catalytic reaction mechanism are required to be further perfected and studied. Therefore, the research on the preparation method of the novel non-noble metal catalyst and the development of the catalytic potential of the novel non-noble metal catalyst are of great significance to the green, high-efficiency and energy-saving development of the catalytic process.
Disclosure of Invention
The invention aims to provide a novel universal strategy for preparing a transition metal monatomic catalyst, the preparation method is suitable for any cationic transition metal, and the loading capacity of the transition metal can be controllably adjusted; the reaction in an electrocatalysis system has good activity, selectivity and stability.
In order to achieve the purpose, the carrier in the universal preparation strategy of the novel transition metal monatomic catalyst provided by the invention is carbon with a large number of nitrogen anchoring sites, and the nitrogen content is 0.1-15 wt%; the transition metal center comprises non-transition metals of Co, Mn, Fe, Ni, Cu, Zn, V, Ti, Mo, and noble metals of Ru, Pt, Pd, Au, Rh and Ag.
The invention provides
A preparation strategy of a supported transition metal monatomic catalyst comprises the following steps:
1) preparing a carrier high polymer: preparing a carrier high polymer: dispersing a monomer containing a nitrogen-carbon component in a solvent, and adding a certain content (0-50 wt%) of hard template silicon dioxide; finally, an initiator is added to initiate polymerization to form the polymer.
2) High-temperature pyrolysis of high polymer: the high polymer is roasted for 0.5 to 6 hours at the temperature of 500 to 1000 ℃.
3) Etching the silicon dioxide template: and etching with hydrofluoric acid or sodium hydroxide to obtain the porous nitrogen-doped carbon carrier.
4) Preparation of a monatomic catalyst: weighing a certain amount of metal salt precursor, uniformly dissolving in a solvent, adding a certain proportion of carrier, and heating and stirring at 25-100 ℃ for 0.5-20 h.
5) Solvent washing: washing with solvent, filtering, and oven drying at 50-120 deg.C for 4-16 h.
The monomer containing the nitrogen-carbon component is one of pyrrole, aniline, phthalocyanine, 2, 6-diaminopyridine and chitosan. The transition metal salt is one of acetate, nitrate, chloride and acetylacetone compound.
The solvent is one of water, ethanol, methanol, acetone, toluene, tert-butyl alcohol and N, N-dimethylformamide.
Step 2) roasting in an atmosphere of N2Or Ar or NH3One or more of (a).
And 2) adopting programmed heating to reach the required temperature from room temperature or drying temperature, wherein the heating rate is 0.5-10 ℃/min, and the preferred roasting temperature is 500-900 ℃.
The mixing in the step 4) adopts an ultrasonic method, so that the active components and the carrier are fully mixed and contacted, and the ultrasonic time is 10-120 min.
The activity test method of the catalyst provided by the invention comprises the following steps:
electrocatalytic oxygen reduction: reacting the reactant O2Introducing an electrolyte solution into a three-electrode system with the pH value of 0-14, and applying a potential at normal temperature and normal pressure to reduce the electrolyte solution into H2O2/H2And O. The electrolyte solution is one of potassium hydroxide, sulfuric acid and perchloric acid; the three electrodes are reference electrode Ag/AgCl (saturated potassium chloride), the counter electrode is graphite rod, and the working electrode is transition metal single-atom catalyst. Linear sweep voltammograms were recorded. The transition metal monatomic catalyst obtained by the preparation strategy has high activity and high stability for oxygen reduction.
The catalyst is used for selective hydrogenation reduction of nitro compounds, and has excellent catalytic performance. The catalyst is simple to prepare and has high catalytic activity and stability.
The invention has the following effects:
1. the high polymer is polymerized by the nitrogen-carbon monomer, thereby effectively preventing the volatilization of nitrogen components, and obtaining a large amount of carbon substrates with nitrogen anchoring sites through high-temperature pyrolysis.
2. Transition metal cations interact with nitrogen at the anchoring site, and the monatomic dispersed supported catalyst can be universally prepared.
3. The prepared non-noble metal catalyst does not need reduction treatment before use and can be directly used. And the catalyst can be directly stored in an air atmosphere for a long time without deactivation.
Drawings
FIG. 1: Co-N-C monatomic catalyst.
FIG. 2: Cu-N-C monatomic catalyst.
FIG. 3: Ni-N-C monatomic catalyst.
FIG. 4: Zn-N-C monatomic catalyst.
FIG. 5: Mn-N-C monatomic catalyst.
FIG. 6: oxygen reduction performance of M-N-C monatomic catalysts.
Detailed Description
Taking 6.0g of LUDOX @ HS-40collidal silica, H2O400 ml is stirred and mixed evenly, and then 5.5g of 2, 6-diamino are addedAnd stirring the pyridine uniformly. 1.0g NaOH was added to the above mixed solution, and the mixture was ice-cooled and stirred. Adding H into 17.13g of APS2O100 ml, dissolved by stirring. Under the ice-bath condition, APS is added into 2, 6-diaminopyridine at one time, rapidly stirred for 5min and slowly stirred overnight. Filtering and washing with ultrapure water, and drying at 120 ℃ for 12 h. 10% NH3Carrying out high-temperature heat treatment on the mixed gas/He at 800 ℃ for 2 h. Grinding uniformly. And etching by 5 wt% hydrofluoric acid to remove silicon dioxide to obtain the carbon-nitrogen carrier with the nitrogen content of 15 wt%.
Example 1: 5.0mg of cobalt nitrate and 50mL of absolute ethanol were weighed into a round-bottomed flask and stirred at 60 ℃ until completely dissolved. Then weighing 50mg of carrier containing nitrogen and carbon components, adding the carrier into the solution, carrying out ultrasonic treatment for 30min, and then refluxing for 12 hours. Washing the refluxed catalyst solution with absolute ethyl alcohol at 40-50 ℃ and carrying out suction filtration to obtain a solid, and putting the solid into an oven at 80 ℃ for drying overnight. Co-N-C monatomic catalyst, labeled catalyst # 1, with a loading of 2.0 wt%.
The analysis by electron microscope shows that Co is in monoatomic dispersion. FIG. 1: Co-N-C monatomic catalyst.
Example 2: 3.5mg of copper nitrate and 50mL of absolute ethanol were weighed into a round-bottomed flask and stirred at 60 ℃ until completely dissolved. Then weighing 50mg of carrier containing nitrogen and carbon components, adding the carrier into the solution, carrying out ultrasonic treatment for 30min, and then refluxing for 12 hours. Washing the refluxed catalyst solution with absolute ethyl alcohol at 40-50 ℃ and carrying out suction filtration to obtain a solid, and putting the solid into an oven at 80 ℃ for drying overnight. Cu-N-C monatomic catalyst with a loading of 2.0 wt%, designated catalyst # 2.
The electron microscope analysis shows that Cu is in monoatomic dispersion. FIG. 2: Cu-N-C monatomic catalyst.
Example 3: 2.5mL of 6.93mM nickel nitrate ethanol solution was measured, 50mL of absolute ethanol was added to the round-bottomed flask, and stirred at 60 ℃ until completely dissolved. Then weighing 50mg of carrier containing nitrogen and carbon components, adding the carrier into the solution, carrying out ultrasonic treatment for 30min, and then refluxing for 12 hours. Washing the refluxed catalyst solution with absolute ethyl alcohol at 40-50 ℃ and carrying out suction filtration to obtain a solid, and putting the solid into an oven at 80 ℃ for drying overnight. The Ni-N-C monatomic catalyst, labeled as catalyst # 3, was supported at 2.0 wt%. FIG. 3: Ni-N-C monatomic catalyst.
Example 4: 2.6mL of 5.985mM zinc nitrate ethanol solution was measured, 50mL of absolute ethanol was added to the round-bottomed flask, and stirred at 60 ℃ until complete dissolution. Then weighing 50mg of carrier containing nitrogen and carbon components, adding the carrier into the solution, carrying out ultrasonic treatment for 30min, and then refluxing for 12 hours. Washing the refluxed catalyst solution with absolute ethyl alcohol at 40-50 ℃ and carrying out suction filtration to obtain a solid, and putting the solid into an oven at 80 ℃ for drying overnight. Zn-N-C monatomic catalyst with a loading of 2.0 wt%, designated catalyst # 4.
The analysis by electron microscope shows that Zn is in monoatomic dispersion. FIG. 4: Zn-N-C monatomic catalyst.
Example 5: 0.107mL of 0.174M manganese nitrate ethanol solution was measured, 50mL of absolute ethanol was added to the round bottom flask, and stirred at 60 ℃ until completely dissolved. Then weighing 50mg of carrier containing nitrogen and carbon components, adding the carrier into the solution, carrying out ultrasonic treatment for 30min, and then refluxing for 12 hours. Washing the refluxed catalyst solution with absolute ethyl alcohol at 40-50 ℃ and carrying out suction filtration to obtain a solid, and putting the solid into an oven at 80 ℃ for drying overnight. Mn-N-C monatomic catalyst with a loading of 2.0 wt%, designated catalyst # 5.
The analysis by electron microscope revealed that Mn was monoatomic. FIG. 5: Mn-N-C monatomic catalyst.
Application example 1: taking 2.9mg of No. 1 catalyst, 20uL of 5 wt% nafion, 200uL of water, 300uL of isopropanol and carrying out ultrasonic treatment for 60 min; 10uL of the mixed solution is taken by a liquid-transfering gun and dripped on a surface area of 0.246cm2And (5) naturally drying on the glassy carbon electrode surface. In a three-electrode system saturated by oxygen, 0.1M KOH is used as an electrolyte solution, Ag/AgCl (saturated potassium chloride) is used as a reference electrode, a graphite rod is used as a counter electrode, a glassy carbon electrode dropwise added with a No. 1 catalyst is used as a working electrode, and an overpotential of 0-1.0V vs. Linear Sweep Voltammograms (LSVs) were tested and recorded.
Application example 2: taking 2.9mg of 2# catalyst, 20uL of 5 wt% nafion, 200uL of water, 300uL of isopropanol and carrying out ultrasonic treatment for 60 min; 10uL of the mixed solution is taken by a liquid-transfering gun and dripped on a surface area of 0.246cm2And (5) naturally drying on the glassy carbon electrode surface. In a three-electrode system saturated by oxygen, 0.1M KOH is used as electrolyte solution,Ag/AgCl (saturated potassium chloride) is used as a reference electrode, a graphite rod is used as a counter electrode, a glassy carbon electrode added with a No. 1 catalyst in a dripping mode is used as a working electrode, and overpotential of 0-1.0V vs. Linear Sweep Voltammograms (LSVs) were tested and recorded.
Application example 3: taking 2.9mg of 3# catalyst, 20uL of 5 wt% nafion, 200uL of water, 300uL of isopropanol and carrying out ultrasonic treatment for 60 min; 10uL of the mixed solution is taken by a liquid-transfering gun and dripped on a surface area of 0.246cm2And (5) naturally drying on the glassy carbon electrode surface. In a three-electrode system saturated by oxygen, 0.1M KOH is used as an electrolyte solution, Ag/AgCl (saturated potassium chloride) is used as a reference electrode, a graphite rod is used as a counter electrode, a glassy carbon electrode dropwise added with a No. 1 catalyst is used as a working electrode, and an overpotential of 0-1.0V vs. Linear Sweep Voltammograms (LSVs) were tested and recorded.
Application example 4: taking 2.9mg of 4# catalyst, 20uL of 5 wt% nafion, 200uL of water, 300uL of isopropanol and carrying out ultrasonic treatment for 60 min; 10uL of the mixed solution is taken by a liquid-transfering gun and dripped on a surface area of 0.246cm2And (5) naturally drying on the glassy carbon electrode surface. In a three-electrode system saturated by oxygen, 0.1M KOH is used as an electrolyte solution, Ag/AgCl (saturated potassium chloride) is used as a reference electrode, a graphite rod is used as a counter electrode, a glassy carbon electrode dropwise added with a No. 1 catalyst is used as a working electrode, and an overpotential of 0-1.0V vs. Linear Sweep Voltammograms (LSVs) were tested and recorded.
Application example 5: taking 2.9mg of 5# catalyst, 20uL of 5 wt% nafion, 200uL of water, 300uL of isopropanol and carrying out ultrasonic treatment for 60 min; 10uL of the mixed solution is taken by a liquid-transfering gun and dripped on a surface area of 0.246cm2And (5) naturally drying on the glassy carbon electrode surface. In a three-electrode system saturated by oxygen, 0.1M KOH is used as an electrolyte solution, Ag/AgCl (saturated potassium chloride) is used as a reference electrode, a graphite rod is used as a counter electrode, a glassy carbon electrode dropwise added with a No. 1 catalyst is used as a working electrode, and an overpotential of 0-1.0V vs. Linear Sweep Voltammograms (LSVs) were tested and recorded. FIG. 6: oxygen reduction performance of M-N-C monatomic catalysts.
Claims (9)
1. The universal preparation method of the supported transition metal monatomic catalyst is characterized by comprising the following steps: firstly, preparing a carbon carrier with a large number of nitrogen anchoring sites, and then impregnating and adsorbing transition metal cations to universally obtain a monoatomic dispersed transition metal catalyst;
the preparation process comprises the following steps:
1) preparing a carrier high polymer: dispersing a monomer containing a nitrogen-carbon component in a solvent, and adding or adding a certain content (0-50 wt%) of hard template silicon dioxide; finally, adding an initiator to initiate polymerization to form a polymer;
2) high-temperature pyrolysis of high polymer: roasting the high polymer at 500-1000 deg.c for 0.5-6 hr;
3) etching the silicon dioxide template: etching with hydrofluoric acid or sodium hydroxide to obtain porous nitrogen-doped carbon carrier;
4) preparation of a monatomic catalyst: weighing a certain amount of transition metal salt precursor, uniformly dissolving in a solvent, adding the carrier in a required proportion, and heating and stirring at 25-100 ℃ for 0.5-20 h;
5) solvent washing: washing with solvent, filtering, and oven drying at 50-120 deg.C for 4-16 h.
2. The method of claim 1, wherein:
the monomer containing the nitrogen-carbon component is one or more than two of pyrrole, aniline, phthalocyanine, 2, 6-diaminopyridine and chitosan; the transition metal salt is one or more of acetate, nitrate, chloride and acetylacetone compound.
3. The method of claim 1, wherein:
the solvent is one of water, ethanol, methanol, acetone, toluene, tert-butyl alcohol and N, N-dimethylformamide.
4. The method of claim 1, wherein:
step 2) roasting in an atmosphere of N2Or Ar or NH3One or more than two of (a);
step 2) adopting a temperature programming to raise the temperature from room temperature or drying temperature to the required temperature, wherein the temperature raising rate is 0.5-10 ℃/min, and the preferred roasting temperature is 500-900 ℃;
the mixing in the step 4) adopts an ultrasonic method, so that the active components and the carrier are fully mixed and contacted, and the ultrasonic time is 10-120 min.
5. A transition metal monoatomic catalyst produced by the production method according to any one of claims 1 to 4.
6. The catalyst of claim 5, wherein: the carrier has nitrogen anchoring sites, the nitrogen content is 0.1-15 wt%, the active component is one or more than two transition metal cations, the active component is a transition metal monoatomic atom with scattered monoatomic atoms, and the load of the transition metal monoatomic atom is controllable and adjustable.
7. The catalyst of claim 5 or 6, wherein:
the transition metal comprises one or more of Co, Mn, Fe, Ni, Cu, Zn, V, Ti, Mo in non-noble metals, and Ru, Pt, Pd, Au, Rh, Ag and Nb in noble metals; the support is a carbon support having nitrogen anchoring sites; the content of transition metal in the catalyst can be controlled and adjusted to be 0.01-4.0 wt%.
8. Use of a supported transition metal monatomic catalyst according to claim 5, 6 or 7, wherein:
the catalyst is used in an electrocatalytic system, such as an electrocatalytic oxygen reduction reaction.
9. Use according to claim 8, characterized in that:
electrocatalytic oxygen reduction: reacting the reactant O2Introducing an electrolyte solution into a three-electrode system with the pH value of 0-14, and applying a potential at normal temperature and normal pressure to reduce the electrolyte solution into H2O2/H2O; the electrolyte solution is one of potassium hydroxide, sulfuric acid and perchloric acid; the three electrodes are reference electrodes Ag/AgCl (saturated potassium chloride), the counter electrode is a graphite rod, and the working electrode is a transition metal monatomic catalyst; the transition metal monatomic catalyst obtained by the preparation strategy has oxygen pairThe reduction has excellent catalytic activity.
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