CN115347199A - Nitrogen-doped carbon composite material with high load of transition metal single atom, preparation method and application thereof - Google Patents
Nitrogen-doped carbon composite material with high load of transition metal single atom, preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 109
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 57
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 125000004429 atom Chemical group 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 27
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- 239000000463 material Substances 0.000 claims abstract description 19
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 6
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 11
- -1 nitrogen-containing small molecule Chemical class 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical group C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 7
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- 239000007789 gas Substances 0.000 claims description 6
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- 230000001681 protective effect Effects 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
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- 238000012360 testing method Methods 0.000 description 22
- 230000000694 effects Effects 0.000 description 14
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 10
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- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
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- 229910002804 graphite Inorganic materials 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 238000011160 research Methods 0.000 description 2
- 229910020676 Co—N Inorganic materials 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
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- 239000004743 Polypropylene Substances 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 description 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The invention relates to a nitrogen-doped carbon composite material with high load of transition metal single atoms, a preparation method and application thereof, belonging to the technical field of photocatalysts. The composite material takes a nitrogen-doped carbon material as a carrier, transition metal single atoms are loaded on the carrier, and one transition metal single atom is coordinated with four nitrogen atoms to form M-N 4 The transition metal M is Fe, co, ni, cu or Mn. The method comprises the steps of mixing a surfactant, a first nitrogen-containing micromolecule and a second nitrogen-containing micromolecule, adding a soluble transition metal M salt solution and a soluble zinc salt solution, stirring and drying to obtain a powder material, and pyrolyzing to obtain the composite material. The composite material is used as an ORR electrocatalyst and has high catalytic activity.
Description
Technical Field
The invention relates to a nitrogen-doped carbon composite material with high load of transition metal single atoms, a preparation method and application thereof, belonging to the technical field of electrocatalysts.
Background
Oxygen Reduction Reaction (ORR) in metal-air batteries, fuel cells, and the likeThe field is an important half-reaction. Currently common ORR electrocatalysts include noble Pt-based catalysts, heteroatom-doped carbon, nitrogen-doped carbon, and carbon-coated Fe 3 C complexes, monatomic catalysts, and the like. Due to the scarcity, high cost, poor stability and other problems of noble metals, the development of cheap and efficient non-noble metal catalysts (such as Fe, co and the like or non-metal catalyst carbon) capable of replacing noble metal catalysts is an important research direction in the field of energy technology research, and plays an important role in solving some key technical problems and cost problems in the field of energy storage and conversion.
Monatomic catalysts have received much attention because of their high atom utilization, high selectivity, adjustable coordination environment, and excellent catalytic activity. Generally, the metal-nitrogen-carbon (M-N-C, M is Fe, co, ni, cu, zn or Mn) catalyst has definite M-N metal active centers at atomic level 4 The coordination configuration provides convenient conditions for the exertion of electrocatalysis performance and the regulation and control of coordination structure and the like. Of the plurality of M-N-C catalysts, having Fe-N 4 The configured Fe-N-C catalyst has more proper binding energy to oxygen-containing intermediates in an ORR process, so that the Fe-N-C catalyst shows very excellent ORR catalytic activity and stability and is considered as a material which has potential to replace noble metal platinum catalysts [ Angew. Chem.2017,129,13988-13992; adv.mater.2018,30,1803220; adv. Mater.2020,32,2004900]. Increasing the intrinsic activity of the catalyst and the number of active sites are two major ways to increase the activity of the catalyst [ Science,2017,355, eaad4998]. The design of the carrier material plays an important role in regulating and controlling the loading capacity and intrinsic activity of the catalyst. Heteroatom doped carbon materials, particularly nitrogen doped carbon, are commonly used support materials for single atom catalysts, and by selecting appropriate materials containing precursors of carbon and nitrogen elements, favorable conditions can be provided for the loading and dispersion of metal active centers. In the high-temperature pyrolysis treatment process, the precursor compound can be converted into nitrogen-doped carbon under the high-temperature condition, the relatively strong electronegativity of nitrogen element can enable metal atoms to be anchored on a nitrogen-doped carbon carrier, the graphitization degree of a carbon material formed in the pyrolysis process can be improved due to the existence of the metal element, and the catalysis is further improvedThe conductivity of the agent. Bamboo-like carbon nanotube/Fe prepared by adopting surfactant P123, melamine and ferric nitrate 3 In the C nanoparticle composite catalyst, metal in the precursor composite can agglomerate and form particles in the high-temperature pyrolysis process, and it is difficult to obtain a uniformly dispersed monatomic catalyst [ J.Am.chem.Soc.2015,137,1436-1439 [ ]]. When a metal organic framework structure-NH is adopted 2 -MIL (Fe) -as a precursor material, when phytic acid and melamine are used for regulating and preparing a metal monatomic catalyst, the obtained composite structure of the Fe-N-C catalyst and iron phosphide FeP [ J.colloid Interface Sci.,583 (2021) 371-375]. The above examples demonstrate that the selection of the precursors of the synthesis catalyst and the proportion of the amounts of the precursors have a very significant influence on the morphology of the final catalyst, the form in which the metallic elements are present. The loading of metal atoms in most of the catalysts is generally low, the loading of most of Ni monatomic catalysts is only 1wt%, and the Fe is mostly less than 2 wt%; nat. Nanotechnol.2022,17,174-181]. The low loading capacity is not beneficial to the application of the catalyst in the actual industrial production, so the development of the monatomic catalyst with high loading capacity and high stability is also a great key problem in the field of catalysis.
Disclosure of Invention
In view of the above, the present invention provides a nitrogen-doped carbon composite material with a high loading of transition metal single atom, a preparation method and an application thereof. In the invention, in an aqueous solution of a surfactant, hydrogen bond interaction is generated between a first nitrogen-containing micromolecule and a second nitrogen-containing micromolecule to form a nanosheet structure, abundant nitrogen-containing sites can be subjected to coordination bonding with a transition metal M ion to form a coordination complex, and Zn ions exist to perform competitive coordination with the transition metal M ion, so that the M ion is dispersed more uniformly in the coordination complex, aggregation of target metal ions in the pyrolysis process is avoided, and then the target metal ions are pyrolyzed to form M-N 4 And meanwhile, zn is removed, and the nitrogen-doped carbon composite material with high transition metal loading and single atomic molecule is prepared.
In order to realize the purpose, the technical scheme of the invention is as follows:
a method for preparing a nitrogen-doped carbon composite material with high load of transition metal single atoms, comprising the following steps:
(1) Dispersing a surfactant in water with the purity higher than that of deionized water, adding a first nitrogen-containing micromolecule and a second nitrogen-containing micromolecule, and stirring and dispersing uniformly to obtain a premix; wherein the first nitrogen-containing small molecule is melamine or dicyandiamide; the second nitrogen-containing small molecule is cyanuric acid;
(2) Dropwise adding a soluble transition metal M salt solution and a soluble zinc salt solution into the premix under stirring, continuously stirring for 5-10 h to obtain a mixture, and drying to obtain a powder material; wherein the transition metal is more than one of Fe, co, ni, cu and Mn; the molar ratio of the transition metal M salt to the zinc salt to the first nitrogen-containing micromolecule is 0.025-0.25;
(3) And under the protection of protective gas, preserving the temperature of the powder material at 240-300 ℃ for 1-2 h, then heating to 900-1100 ℃ and preserving the temperature for 2-5 h, and obtaining the nitrogen-doped carbon composite material with high load of transition metal monoatomic atoms after the heat preservation is finished.
Preferably, in step (1), the surfactant is poloxamer F127, polyvinylpyrrolidone or a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123).
Preferably, in step (1), the mass ratio of the surfactant to the first nitrogen-containing small molecule to the second nitrogen-containing small molecule is 0.3 to 1.0.
Preferably, in the step (2), the soluble transition metal M salt solution is firstly dripped, and then the soluble zinc salt solution is dripped.
Preferably, in the step (2), the soluble transition metal M salt is more than one of ferric nitrate, copper sulfate, copper nitrate, nickel sulfate, nickel nitrate, manganese nitrate and cobalt nitrate; the soluble zinc salt is zinc nitrate.
Preferably, in the step (2), during drying, the mixture is firstly cooled in liquid nitrogen and then freeze-dried or dried at 110-120 ℃ for 6-10 h.
Preferably, the heating rate in the step (3) is 2 ℃/min to 5 ℃/min.
The composite material takes the nitrogen-doped carbon material as a carrier, the carrier is loaded with the transition metal monoatomic, and one transition metal monoatomic coordinates with four nitrogen atoms to form M-N 4 The transition metal M is Fe, co, ni, cu or Mn.
Preferably, the loading amount of the transition metal single atom is 4-10.5% based on 100% of the total mass of the composite material.
The invention relates to application of a nitrogen-doped carbon composite material with high load of transition metal single atoms, which is used as an ORR electrocatalyst.
Advantageous effects
The invention provides a preparation method of a nitrogen-doped carbon composite material with high load of transition metal single atoms, which is characterized in that the uniform dispersion of metal ions in transition metal M salt and zinc salt is realized based on the uniform dispersion and coordination of a surfactant, a first nitrogen-containing small molecule and a second nitrogen-containing small molecule to a metal precursor, the coordination of the transition metal M atoms is more uniform through the bonding effect of organic molecules and the competitive coordination effect of zinc ions, and Zn atoms are removed due to volatilization in the high-temperature pyrolysis process, so that the single atom dispersion load of the transition metal M atoms to the maximum extent is realized, and the load capacity of the transition metal M atoms can be effectively improved.
In the method, the surfactant adopts poloxamer F127, polyvinylpyrrolidone or P123; the first nitrogen-containing micromolecules are melamine or dicyandiamide; the second nitrogen-containing micromolecules are cyanuric acid, under the action of the surfactant, a compound is formed between the first nitrogen-containing micromolecules and the second nitrogen-containing micromolecules through polymerization, and the compound contains abundant nitrogen-containing sites and can perform coordination on transition metal M atoms, so that uniform coordination on metal elements is realized.
In the method, the metal precursor can be rapidly and uniformly dispersed in a short time by controlling the dripping sequence of the soluble transition metal M salt solution and the soluble zinc salt solution. The competitive coordination effect between the zinc ions and the target metal atoms on the compound precursor is utilized to enable the target metal element M to be dispersed on the carrier more uniformly, and the aggregation and particle formation of the metal atoms in the subsequent pyrolysis process are avoided as far as possible.
In the method, the pyrolysis process adopts two-step segmented heating, firstly, a small amount of unstable components can be removed by pretreatment in the first stage, the subsequent high-temperature pyrolysis process is convenient, and the high-temperature pyrolysis in the second stage can convert precursor materials into nitrogen-doped carbon and simultaneously obtain M-N 4 The monoatomic catalyst with the configuration can also ensure the volatilization removal of metal Zn under the high-temperature condition.
The invention provides a nitrogen-doped carbon composite material with high load of transition metal single atoms, wherein the composite material takes a nitrogen-doped carbon material as a carrier, the carrier is loaded with the transition metal single atoms, and one transition metal single atom is coordinated with four nitrogen atoms to form M-N 4 The transition metal M is Fe, co, ni, cu or Mn; and the loading amount of the transition metal M atom is more than 4 percent.
The invention provides an application of a nitrogen-doped carbon composite material with high load of transition metal single atoms, wherein the composite material is used as an ORR electrocatalyst and has higher catalytic activity.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
FIG. 2 is an X-ray diffraction (XRD) pattern of the composites of examples 1-3.
FIG. 3 is a Transmission Electron Microscope (TEM) image of the composite material described in example 1.
FIG. 4 is a TEM image of the composite material described in example 2.
FIG. 5 is a TEM image of the composite material described in example 3.
FIG. 6 is the results of synchrotron radiation fitting of the composite material described in example 3.
FIG. 7 is a transmission electron micrograph of spherical aberration corrected composite material of example 3.
FIG. 8 is a graph of ORR activity of the alkaline medium for composites described in examples 1-3.
Fig. 9 is a TEM image of the composite material described in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
In the following examples or comparative examples:
(1) XRD test: japanese science Rigaku desktop X-ray diffractometer MiniFlex 600.
(2) TEM test: HITACHI H-7700 Transmission Electron microscope.
(3) High Resolution Transmission Electron Microscopy (HRTEM) test: JEOL JEM-2100F high resolution transmission electron microscope.
(4) Inductively coupled plasma emission spectroscopy: shimadzu ICPE-9800 (OES) Japan
(5) And (3) synchronous radiation fitting: beijing synchrotron radiation center 1W1B workstation
(6) Transmission electron microscope for spherical aberration correction: titan 80-300 scanning/projection electron microscope
(7) Alkaline medium ORR activity test: test on Shanghai Chenhua electrochemical workstation CHI 760E.
Example 1
(1) Weighing 0.6g of poloxamer F127, dispersing in 30mL of ultrapure water, and stirring for 30min until the dispersion is uniform; adding 1.0g of melamine, and stirring for 30min until the melamine is uniformly dispersed; adding 1.0g of cyanuric acid, and stirring for 30min until the cyanuric acid is uniformly dispersed to obtain a premix;
(2) Under stirring, sequentially dropwise adding 0.25mL of 200mg/mL ferric nitrate solution and 0.25mL of 200mg/mL zinc nitrate solution into the premix, continuously stirring for 10h to obtain a mixture, rapidly cooling the mixture in liquid nitrogen, and then freeze-drying in a freeze dryer to obtain a powder material;
(3) And under the protection of protective gas, putting the powder material into a tube furnace, firstly heating to 240 ℃, preserving heat for 1h, then heating to 900 ℃, preserving heat for 2h, wherein the heating rate is 5 ℃/min in the heating process, and obtaining the high-load iron metal monatomic nitrogen-doped carbon composite material after heat preservation.
The XRD test result of the composite material is shown in fig. 2, in which a peak of graphitic carbon is found only at about 26 °, and no peak of impurity phase such as other metal phase or metal carbide is found, which preliminarily proves that no aggregation of metal atoms occurs in the composite material.
The TEM test result of the composite material is shown in fig. 3, and the HRTEM result shows that no metal particles or metal phases exist in the composite material, which further proves that the composite material prepared in this example does not have metal agglomeration.
The synchrotron radiation characterization result of the composite material proves that the configuration of the composite material is Fe-N dispersed at atomic level 4 And (5) structure.
The result of inductively coupled plasma emission spectroscopy shows that the content of Fe in the composite material is 5.01wt%.
The basic oxygen reduction activity polarization curve of the composite material is shown in figure 8, and the result shows that the half-wave potential of the composite material is 0.878V vs.RHE, and the composite material has higher potential of catalyzing oxygen reduction.
Example 2
(1) Weighing 0.6g of poloxamer F127, dispersing in 30mL of ultrapure water, and stirring for 30min until the dispersion is uniform; adding 1.0g of melamine, and stirring for 30min until the melamine is uniformly dispersed; adding 1.0g of cyanuric acid, and stirring for 30min until the cyanuric acid is uniformly dispersed to obtain a premix;
(2) Dropwise adding 0.35mL of 200mg/mL ferric nitrate solution and 0.35mL of 200mg/mL zinc nitrate solution into the premix in sequence under stirring, continuously stirring for 10 hours to obtain a mixture, rapidly cooling the mixture in liquid nitrogen, and then freeze-drying in a freeze-dryer to obtain a powder material;
(3) And under the protection of protective gas, putting the powder material into a tubular furnace, firstly heating to 300 ℃, preserving heat for 1h, then heating to 950 ℃, preserving heat for 2h, wherein the heating rate is 5 ℃/min in the heating process, and obtaining the nitrogen-doped carbon composite material with high load of iron metal single atoms after heat preservation.
The XRD test result of the composite material is shown in fig. 2, in which only the graphite carbon peak is found at about 26 °, and no other metal phase or impurity phase such as metal carbide is found, which preliminarily proves that no aggregation of metal atoms occurs in the composite material.
The TEM test result of the composite material is shown in fig. 4, and the HRTEM result shows that no metal particles or metal phases exist in the composite material, which further proves that the composite material prepared in this embodiment does not have metal agglomeration.
The synchrotron radiation characterization result of the composite material proves that the configuration of the composite material is Fe-N dispersed at atomic level 4 And (5) structure.
The result of inductively coupled plasma emission spectroscopy shows that the content of Fe in the composite material is 6.9wt%.
The alkaline oxygen reduction activity polarization curve of the composite material is shown in fig. 8, and the result shows that the half-wave potential of the composite material is 0.870 v/s.rhe, and the composite material has higher potential of catalyzing oxygen reduction.
Example 3
(1) Weighing 0.6g of poloxamer F127, dispersing in 30mL of ultrapure water, and stirring for 30min until the dispersion is uniform; adding 1.0g of melamine, and stirring for 30min until the melamine is uniformly dispersed; adding 1.0g of cyanuric acid, and stirring for 30min until the cyanuric acid is uniformly dispersed to obtain a premix;
(2) Under stirring, sequentially dropwise adding 0.5mL of 200mg/mL ferric nitrate solution and 0.5mL of 200mg/mL zinc nitrate solution into the premix, continuously stirring for 10h to obtain a mixture, rapidly cooling the mixture in liquid nitrogen, and then freeze-drying in a freeze dryer to obtain a powder material;
(3) And under the protection of protective gas, putting the powder material into a tubular furnace, firstly heating to 300 ℃, preserving heat for 1h, then heating to 900 ℃, preserving heat for 2h, wherein the heating rate is 5 ℃/min in the heating process, and obtaining the nitrogen-doped carbon composite material with high load of iron metal single atoms after heat preservation.
The XRD test result of the composite material is shown in fig. 2, in which only the graphite carbon peak is found at about 26 °, and no other metal phase or impurity phase such as metal carbide is found, which preliminarily proves that no aggregation of metal atoms occurs in the composite material.
The TEM test result of the composite material is shown in fig. 5, and the HRTEM result shows that no metal particles or metal phases exist in the composite material, which further proves that the composite material prepared in this example does not have metal agglomeration.
FIG. 6 is a Fourier transform and fit plot of the EXAFS of the synchrotron radiation characterized Fe K-edge of the composite material, where
The typical atomic level of Fe-N appears nearby 4 The peaks of correlation, and no peaks of metallic phase were found; thus proving that the configuration of the composite material is Fe-N dispersed at atomic level 4 And (5) structure. The spherical aberration electron microscope image shown in fig. 7 more intuitively proves the atomic-level dispersion of Fe atoms in the composite material.
The result of inductively coupled plasma emission spectroscopy shows that the content of Fe in the composite material is 10.1wt%.
The alkaline oxygen reduction activity polarization curve of the composite material is shown in figure 8, and the result shows that the half-wave potential of the composite material is 0.886V vs. RHE, and the composite material has higher potential of catalyzing oxygen reduction.
Example 4
In this example, copper nitrate was used in place of the iron nitrate in example 3, and the rest was the same as in example 3.
XRD and TEM test results of the composite material show that no agglomeration of metal atoms occurs.
The synchrotron radiation characterization result of the composite material proves that the configuration of the composite material is atomically dispersed Cu-N 4 And (5) structure.
The alkaline medium ORR activity test result of the composite material shows that the composite material has higher catalytic oxygen reduction capability.
Example 5
In this example, nickel nitrate was used in place of the iron nitrate in example 3, and the rest was the same as in example 3.
XRD and TEM test results of the composite material show that no agglomeration of metal atoms occurs.
The synchrotron radiation characterization result of the composite material proves that the configuration of the composite material is the Ni-N dispersed at atomic level 4 And (5) structure.
The alkaline medium ORR activity test result of the composite material shows that the composite material has higher catalytic oxygen reduction capability.
Example 6
In this example, cobalt nitrate was used in place of the iron nitrate in example 3, and the rest was the same as in example 3.
XRD and TEM test results of the composite material show that no agglomeration of metal atoms occurs.
The synchrotron radiation characterization result of the composite material proves that the configuration of the composite material is atomically dispersed Co-N 4 And (5) structure.
The alkaline medium ORR activity test result of the composite material shows that the composite material has higher catalytic oxygen reduction capability.
Example 7
In this example, P123 was used as a surfactant in place of F127 in example 3, and the remainder was the same as in example 3.
XRD and TEM test results of the composite material show that no agglomeration of metal atoms occurs.
The synchrotron radiation characterization result of the composite material proves that the configuration of the composite material is Fe-N dispersed at atomic level 4 And (5) structure.
The alkaline medium ORR activity test result of the composite material shows that the composite material has higher catalytic oxygen reduction capability.
Example 8
In this example, dicyandiamide was used in place of the melamine in example 3, and the rest is the same as example 3.
XRD and TEM test results of the composite material show that no agglomeration of metal atoms occurs.
The synchrotron radiation characterization result of the composite material proves that the configuration of the composite material isAtomically dispersed Fe-N 4 And (5) structure.
The alkaline medium ORR activity test result of the composite material shows that the composite material has higher catalytic oxygen reduction capability.
Comparative example 1
(1) Weighing 0.6g of poloxamer F127, dispersing in 30mL of ultrapure water, and stirring for 30min until the uniform dispersion is achieved; adding 1.0g of melamine, and stirring for 30min until the melamine is uniformly dispersed; adding 1.0g of cyanuric acid, and stirring for 30min until the cyanuric acid is uniformly dispersed to obtain a premix;
(2) Under stirring, sequentially dropwise adding 0.6mL of 200mg/mL ferric nitrate solution and 0.6mL of 200mg/mL zinc nitrate solution into the premix, continuously stirring for 10h to obtain a mixture, rapidly cooling the mixture in liquid nitrogen, and then freeze-drying in a freeze dryer to obtain a powder material;
(3) And under the protection of protective gas, putting the powder material into a tubular furnace, firstly heating to 300 ℃, preserving heat for 1h, then heating to 900 ℃, preserving heat for 2h, wherein the heating rate is 5 ℃/min in the heating process, and obtaining the iron-loaded nitrogen-doped carbon composite material after the heat preservation is finished.
The TEM test result of the composite material is shown in FIG. 9, and the result shows that the metal atoms are aggregated and form particles due to the existence of the particles in the material, and the metal atoms are no longer in a single atom distribution structure.
In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.
Claims (10)
1. A preparation method of a nitrogen-doped carbon composite material with high load of transition metal single atoms is characterized by comprising the following steps: the method comprises the following steps:
(1) Dispersing a surfactant in water with the purity higher than that of deionized water, adding a first nitrogen-containing micromolecule and a second nitrogen-containing micromolecule, and stirring and dispersing uniformly to obtain a premix; wherein the first nitrogen-containing small molecule is melamine or dicyandiamide; the second nitrogen-containing small molecule is cyanuric acid;
(2) Dropwise adding a soluble transition metal M salt solution and a soluble zinc salt solution into the premix under stirring, continuously stirring for 5-10 h to obtain a mixture, and drying to obtain a powder material; wherein the transition metal is more than one of Fe, co, ni, cu and Mn; the molar ratio of the transition metal M salt to the zinc salt to the first nitrogen-containing micromolecule is 0.025-0.25;
(3) And under the protection of protective gas, preserving the heat of the powder material for 1 to 2 hours at the temperature of between 240 and 300 ℃, then heating to between 900 and 1100 ℃ and preserving the heat for 2 to 5 hours, and obtaining the nitrogen-doped carbon composite material with high load of transition metal monoatomic.
2. The method for preparing the nitrogen-doped carbon composite material with high load of transition metal single atoms according to claim 1, wherein the method comprises the following steps: in the step (1), the surfactant is poloxamer F127, polyvinylpyrrolidone or P123.
3. The method for preparing the nitrogen-doped carbon composite material with high load of transition metal single atoms as claimed in claim 2, wherein the method comprises the following steps: in the step (1), the mass ratio of the surfactant to the first nitrogen-containing small molecule to the second nitrogen-containing small molecule is 0.3-1.0.
4. The method for preparing the nitrogen-doped carbon composite material with high load of transition metal single atoms according to claim 1, wherein the method comprises the following steps: in the step (2), a soluble transition metal M salt solution is firstly dripped, and then a soluble zinc salt solution is dripped.
5. The method for preparing a nitrogen-doped carbon composite material with high transition metal single atom loading according to claim 1 or 4, wherein the method comprises the following steps: in the step (2), the soluble transition metal M salt is more than one of ferric nitrate, copper sulfate, cupric nitrate, nickel sulfate, nickel nitrate, manganese nitrate and cobalt nitrate; the soluble zinc salt is zinc nitrate.
6. The method for preparing the nitrogen-doped carbon composite material with high load of transition metal single atoms according to claim 1, wherein the method comprises the following steps: when drying, firstly, the mixture is cooled in liquid nitrogen, and then freeze-dried or dried for 6 to 10 hours at the temperature of 110 to 120 ℃.
7. The method for preparing the nitrogen-doped carbon composite material with high load of the transition metal single atom according to claim 1, wherein the method comprises the following steps: in the step (3), the heating rate is 2-5 ℃/min.
8. A nitrogen-doped carbon composite material with high load of transition metal single atoms is characterized in that: the composite material is prepared by the preparation method of any one of claims 1 to 7, the composite material takes a nitrogen-doped carbon material as a carrier, transition metal single atoms are loaded on the carrier, and one transition metal single atom is coordinated with four nitrogen atoms to form M-N 4 The transition metal M is Fe, co, ni, cu or Mn.
9. The highly transition metal monatomic nitrogen-doped carbon composite of claim 8, wherein: the total mass of the composite material is 100%, and the load capacity of the transition metal single atom is 4% -10.5%.
10. Use of a highly transition metal single atom loaded nitrogen doped carbon composite as claimed in claim 8 or 9 wherein: the composite material is used as an ORR electrocatalyst.
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| CN107930672A (en) * | 2017-12-04 | 2018-04-20 | 北京化工大学 | A kind of metal is in metal nitrogen carbon material, the preparation method and use that atom level is disperseed |
| CN111939961A (en) * | 2020-08-24 | 2020-11-17 | 南昌航空大学 | Controllable synthesis method of low-cost and high-load monatomic catalyst |
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| CN107930672A (en) * | 2017-12-04 | 2018-04-20 | 北京化工大学 | A kind of metal is in metal nitrogen carbon material, the preparation method and use that atom level is disperseed |
| CN111939961A (en) * | 2020-08-24 | 2020-11-17 | 南昌航空大学 | Controllable synthesis method of low-cost and high-load monatomic catalyst |
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