CN113832574B - Coordinated atom doped porous carbon fiber domain-limited transition metal monoatomic material and preparation method thereof - Google Patents
Coordinated atom doped porous carbon fiber domain-limited transition metal monoatomic material and preparation method thereof Download PDFInfo
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 46
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 39
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 38
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000835 fiber Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000009987 spinning Methods 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005457 optimization Methods 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 230000001808 coupling effect Effects 0.000 abstract description 2
- 238000001291 vacuum drying Methods 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 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 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
- D01F11/121—Halogen, halogenic acids or their salts
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
Abstract
The application discloses a coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, dissolving a transition metal source in an N, N-dimethylformamide solvent, then adding tetraethoxysilane, a high molecular polymer and a coordination atom source, and stirring in a water bath; s2, carrying out electrostatic spinning on the prepared precursor spinning solution to prepare a precursor fiber membrane, and carrying out vacuum drying; s3, pre-oxidizing the precursor fiber membrane in an air atmosphere; then heating up and carbonizing under the protection of inert gas, preserving heat, and finally cooling to room temperature under the protection of inert gas; s4, etching the carbonized fiber by hydrofluoric acid to remove SiO 2 And (5) soaking the hard template in acid, and centrifuging to obtain the product. The transition metal monoatoms and the coordination atoms in the material have stronger electron coupling effect, and the optimization of the performance of the transition metal monoatoms can be realized by adjusting the coordination environment.
Description
Technical Field
The application relates to the technical field of new energy materials, in particular to a coordination atom doped porous carbon fiber confinement transition metal monoatomic material and a preparation method thereof.
Background
The single atom has the highest atom utilization rate and unsaturated coordination active center, so that the active sites can be fully exposed, and the number of the active sites is increased; furthermore, the monoatomic material has a uniform structure, the active site is highly dispersed at the atomic level, and the enhanced interaction and charge transfer equivalent between the monoatomic material and the carrier can obviously improve the intrinsic activity of the active site. However, the monatomic has very high surface energy and migration capability, so that nanoparticles with larger and more stable sizes are easy to agglomerate to form, the performance of the nanoparticles is reduced, the prevention of agglomeration of metal monatoms is still an important challenge for preparing monatomic metals, and searching a suitable carrier for supporting the monatomic materials is an effective means for solving the problem. The stable presence of a single atom is premised on the existence of a strong interaction with the support, which generally causes the single atom to exist in ionic form rather than in an atomic state, i.e., generally the single atom will have a certain oxidation state.
The microstructure and coordination environment of the metal monoatoms on the electronic and atomic scale are critical. The activity of the monoatomic active site is closely related to the coordination environment, and the coordination site or the coordination group is designed on the surface of the carrier, so that the transition metal monoatomic is captured and limited by utilizing the strong interaction between the coordination site or the coordination group and the transition metal monoatomic, the migration and agglomeration of the monoatomic are prevented, and the synthesis of the monoatomic can be realized. The coordinating atoms used to anchor the monoatoms can affect the local electronic structure of the active center and thus affect the properties of the monoatomic material. The transition metal monoatoms and atoms with different peripheries can establish various coupling structures to form a specific integral coordination configuration, and the clear coordination structure is important for further understanding the action mechanism of the monoatoms. In conclusion, the method has important research value for regulating the coordination environment of the transition metal monoatoms and carrier hetero atoms and elucidating the action mechanism of the coordination atoms, coordinating the stability of the monoatoms and enhancing the performance of the monoatoms.
The inventors have found that carbon fibers with a large surface area, high conductivity and stable chemical properties are common substrates supporting a single metal atom. Another advantage of carbon fibers is that the electron interactions can be modulated by incorporating precise heteroatoms (e.g., boron, nitrogen, sulfur, phosphorus) on the support. The single-atom material with high load and high stability is designed by taking the single-atom and the chemical environment around the single-atom as a whole. The design can improve the conductivity to the greatest extent by constructing porous carbon fiber confined transition metal single atoms based on different coordination environments, and can improve the long-term durability by preventing the single atoms from moving and gathering. Compared with strategies such as a hydrothermal method, an in-situ growth method, nucleation crystallization and the like, the electrostatic spinning can directly construct a porous carbon fiber structure with a porous structure, has the advantages of simple process and good operability, utilizes an electrostatic spinning technology to construct porous carbon fiber confined transition metal monoatoms based on different coordination environments, and can realize high-efficiency load and performance optimization of the transition metal monoatoms.
It should be noted that the above information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
In addition, only one Chinese patent document is found to have certain relevance through searching. The application discloses an electrolytic water catalyst for loading transition metal monoatoms and a preparation method thereof, wherein the electrolytic water catalyst utilizes electrostatic spinning fibers and phthalocyanine to jointly limit and synthesize the high-dispersion transition metal monoatoms, the electrolytic water catalyst is composed of a carrier and a catalytic active component, the carrier is ultrafine carbon nano fibers, and the catalytic active component is the transition metal monoatoms. The fiber-supported transition metal monoatomic electrolyzed water catalyst prepared by the method has the characteristics of high active site performance and good dispersibility, has good alkaline electrolyzed water hydrogen-separating activity, and can be directly used as a self-supporting electrode material for electrocatalytic hydrogen production.
However, the electrolytic water catalyst loaded with transition metal monoatoms does not incorporate accurate heteroatoms (such as boron, nitrogen, sulfur and phosphorus) on a carrier to regulate electronic interaction, and does not construct porous carbon fiber confined transition metal monoatoms based on different coordination environments. But also the raw materials used are different. The raw material phthalocyanine complex and ligand used in the application are obviously different from the application.
Disclosure of Invention
In view of the above, the present application provides a coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material and a preparation method thereof, wherein the coordination atoms in the carbon fiber, such as carbon, nitrogen, sulfur, phosphorus, boron and other atom domain-limited transition metal monoatoms, are utilized to disperse the atoms into the porous carbon fiber in an atomic scale, so as to improve the loading capacity of the monoatoms and regulate the performance of the monoatoms.
The adopted technical scheme is as follows:
the application discloses a preparation method of a coordination atom doped porous carbon fiber confined transition metal monoatomic material, which comprises the following steps:
s1, dissolving a transition metal source in an N, N-dimethylformamide solvent, then adding tetraethoxysilane, a high molecular polymer and a coordination atom source, and stirring in a water bath to prepare a precursor spinning solution;
s2, carrying out electrostatic spinning on the precursor spinning solution prepared in the step S1 to prepare a precursor fiber membrane, and drying the precursor fiber membrane under vacuum;
s3, pre-oxidizing the precursor fiber film dried in the S2 in an air atmosphere; then heating and carbonizing under the protection of inert gas, preserving heat, and finally cooling to room temperature under the protection of inert gas to obtain carbonized fibers;
s4, etching the carbonized fiber in the S3 by hydrofluoric acid to remove SiO 2 And (3) soaking the hard template with acid, and centrifugally separating to obtain the coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material.
Further, in S1, the metal source is any one of a Ni source, a Co source, a Fe source, a Cu source, a Mo source, a W source, and a Mn source.
In S1, the polymer is one or a combination of more than two of polyvinylpyrrolidone, polyacrylonitrile, polyvinyl alcohol and polytetrafluoroethylene.
In the step S1, the coordination atom source is any one of urea, thiourea, thioacetamide, phosphoric acid and boric acid.
Further, in S1, the amount of the transition metal source is 0.1-2mmol, the amount of the tetraethoxysilane is 1-4mL, the amount of the high polymer is 1.5-3g, the amount of the coordination atom source is 0.1-1g, and the amount of the solvent is 10-20mL.
Further, in S1, stirring is carried out in a water bath at 40-70 ℃ for 4-10h.
Further, in S2, the spinning voltage is controlled to be 15-20kV during electrostatic spinning, the vertical distance between the injector and the receiving plate is 10-24cm, and the pushing rate of the injector is 0.5-1.5mL/h.
Further, in S3, placing the precursor fiber membrane in a porcelain boat, placing the porcelain boat in the middle of a tube furnace, introducing air for pre-oxidation, heating the tube furnace to 250-300 ℃, heating at a speed of 2-2.5 ℃/min, and preserving the heat for 1-4 hours; and then heating to 600-1200 ℃ under the protection of inert gas, keeping the heating rate at 4-5 ℃/min for 2-5h, and finally cooling to room temperature under the protection of inert gas to obtain carbonized fibers.
Further, in S4, the carbonized fiber in S3 is etched for 4 to 15 hours by hydrofluoric acid with the concentration of 10 to 20 weight percent to remove SiO 2 And (3) soaking the hard template in sulfuric acid, hydrochloric acid or nitric acid with the concentration of 3-6 mol/L.
The application discloses a coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material, which is prepared by the preparation method according to any scheme.
The beneficial technical effects obtained by the application are as follows:
the application provides a prepared coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material, and develops a heteroatom doped porous carbon fiber domain-limited transition metal monoatomic method, a porous carbon fiber carrier has high specific surface area and porosity, and the provided porous structure can realize high-efficiency load of transition metal monoatoms and avoid aggregation of the transition metal monoatoms in the high-temperature carbonization process; the transition metal monoatomic and the coordination atom have stronger electron coupling effect, and the optimization of the performance of the transition metal monoatomic can be realized by adjusting the coordination environment.
The application provides a preparation method of a coordination atom doped porous carbon fiber confined transition metal monoatomic material and a universality strategy of performance optimization of the coordination atom doped porous carbon fiber confined transition metal monoatomic material, which are suitable for popularization and application.
Drawings
FIG. 1 is a transmission electron micrograph of the sulfur-doped porous carbon fiber confinement Ni monoatomic material prepared in example 1;
FIG. 2 is a spherical aberration electron micrograph of the nitrogen-doped porous carbon fiber domain-limited Ni monoatomic material obtained in example 2;
fig. 3 is a transmission electron micrograph of the boron doped porous carbon fiber confinement Fe monoatomic material prepared in example 3.
Detailed Description
The technical scheme of the present application is further described below by means of specific embodiments and with reference to the accompanying drawings, but the scope of the present application is not limited thereto.
In the present application, the materials and equipment used are commercially available or commonly used in the art, unless otherwise specified.
Example 1
A preparation method of a sulfur-doped porous carbon fiber limited Ni monoatomic material comprises the following steps:
(1) 1.2mmol of nickel nitrate is dissolved in 20mL of N, N-dimethylformamide, then 2mL of tetraethoxysilane, 1.5g of polyvinylpyrrolidone and 0.2g of thiourea are slowly added for multiple times respectively, and the mixture is magnetically stirred for 8 hours under the water bath at 60 ℃ to obtain sol-like solution, namely precursor spinning solution. Then preparing a precursor fiber film by adopting an electrostatic spinning method, controlling the spinning voltage to be 18kV during electrostatic spinning, enabling the distance from a receiving device to a spinning needle to be 20cm, enabling the feeding rate to be 0.8mL/h, and receiving aluminum foils. Specifically, the spinning voltage is controlled to be 18kV, the vertical distance between the injector and the receiving plate is 20cm, and the pushing rate of the injector is 0.8mL/h.
(2) Placing the fiber membrane in a ceramic boat, placing the ceramic boat in the middle of a tube furnace, introducing air for pre-oxidation, heating the tube furnace to 250 ℃, heating the tube furnace at a heating rate of 2.5 ℃/min, and preserving the heat for 1h; then heating to 800 ℃ under the protection of nitrogen, keeping the temperature at a heating rate of 5 ℃/min for 2 hours, and finally cooling to room temperature under the protection of inert gas.
(3) Etching the fiber after high-temperature carbonization with 20wt% hydrofluoric acid for 12 hours to remove SiO 2 And (3) treating the hard template with 4mol/L sulfuric acid for 6 hours, and centrifugally separating to obtain the sulfur-doped porous carbon fiber finite field Ni monoatomic material, which is shown in the figure 1.
As can be seen from fig. 1, the prepared material exhibits a porous fibrous morphology, and no significant agglomeration or larger nanoclusters are found.
Example 2
A preparation method of a nitrogen-doped porous carbon fiber domain-limited Ni monoatomic material comprises the following steps:
(1) 1mmol of nickel nitrate is dissolved in 18mL of N, N-dimethylformamide, then 2.35mL of tetraethoxysilane, 1.8g of polyvinylpyrrolidone and 0.3g of urea are slowly added for multiple times respectively, and the mixture is magnetically stirred for 8 hours under the water bath at 50 ℃ to obtain sol-like solution, namely precursor spinning solution. And preparing a precursor fiber film by adopting an electrostatic spinning method, controlling the spinning voltage to be 20kV during electrostatic spinning, enabling the distance from a receiving device to a spinning needle to be 20cm, enabling the feeding rate to be 0.8mL/h, and receiving aluminum foils. Specifically, the spinning voltage is controlled to be 18kV, the vertical distance between the injector and the receiving plate is 20cm, and the pushing rate of the injector is 0.8mL/h.
(2) Placing the fiber membrane in a ceramic boat, placing the ceramic boat in the middle of a tube furnace, introducing air for pre-oxidation, heating the tube furnace to 250 ℃, heating the tube furnace at a heating rate of 2.5 ℃/min, and preserving the heat for 1h; then heating to 800 ℃ under the protection of nitrogen, keeping the temperature at a heating rate of 5 ℃/min for 2 hours, and finally cooling to room temperature under the protection of inert gas.
(3) The fiber after high temperature carbonization is etched for 12 hours by 20wt percent HF to remove SiO 2 And (3) treating the hard template with 4mol/L sulfuric acid for 6 hours, and centrifugally separating to obtain the nitrogen-doped porous carbon fiber finite field Ni monoatomic material, which is shown in the figure 2.
As can be seen from fig. 2, the white bright spots circled in the high-resolution spherical aberration microscope are nickel monoatoms dispersed in atomic scale.
Example 3
A preparation method of a boron-doped porous carbon fiber domain-limited Fe monoatomic material comprises the following steps:
(1) 1mmol of iron acetylacetonate was dissolved in 20mL of N, N-dimethylformamide, followed by 2.5mL of ethyl orthosilicate, 1.6g of polyacrylonitrile, 0.5mL of boric acid (boric acid density 1.435 g/cm) 3 ) Slowly adding the mixture for multiple times, and magnetically stirring the mixture for 6 hours at the water bath of 65 ℃ to obtain sol-like solution, namely precursor spinning solution. Preparing a precursor fiber film by adopting an electrostatic spinning method, controlling the spinning voltage to be 18kV during electrostatic spinning, enabling the distance from a receiving device to a spinning needle to be 20cm, enabling the feeding rate to be 0.8mL/h, and receiving aluminum foils. Specifically, the spinning voltage is controlled to be 18kV, the vertical distance between the injector and the receiving plate is 20cm, and the pushing rate of the injector is 0.8mL/h.
(2) Placing the fiber membrane in a porcelain boat, placing the porcelain boat in the middle of a tube furnace, introducing air for pre-oxidation, heating the tube furnace to 250 ℃, heating the tube furnace at a heating rate of 2.5 ℃/min, preserving the heat for 1h, heating to 1000 ℃ under the protection of argon, heating at a heating rate of 5 ℃/min, preserving the heat for 2h, and finally cooling to room temperature under the protection of inert gas.
(3) The fibers after high temperature carbonization were etched with 15wt% HF for 10 hours to remove SiO 2 And (3) treating the hard template with 4mol/L nitric acid for 6 hours to remove Fe nano particles, and centrifugally separating to obtain the boron doped porous carbon fiber domain-limited Fe monoatomic material, which is shown in figure 3.
As can be seen from fig. 3, the prepared material exhibits a porous fibrous morphology, has distinct hierarchical pore structure characteristics, and no distinct agglomeration or larger nanoclusters are found.
The detailed description set forth below is merely for the purposes of illustrating the presently contemplated embodiments of the application and is not intended to limit the scope of the application, but is to be accorded the full breadth and scope of the appended claims.
Claims (8)
1. The preparation method of the coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material is characterized by comprising the following steps of:
s1, dissolving a transition metal source in an N, N-dimethylformamide solvent, then adding tetraethoxysilane, a high molecular polymer and a coordination atom source, and stirring in a water bath to prepare a precursor spinning solution; the coordination atom source is any one of thiourea, thioacetamide, phosphoric acid and boric acid;
s2, carrying out electrostatic spinning on the precursor spinning solution prepared in the step S1 to prepare a precursor fiber membrane, and drying the precursor fiber membrane under vacuum;
s3, pre-oxidizing the precursor fiber film dried in the S2 in an air atmosphere; then heating and carbonizing under the protection of inert gas, preserving heat, and finally cooling to room temperature under the protection of inert gas to obtain carbonized fibers;
s4, etching the carbonized fiber in the S3 with 10-20wt% hydrofluoric acid for 4-15h to remove SiO 2 And (3) soaking the hard template in sulfuric acid, hydrochloric acid or nitric acid with the concentration of 3-6mol/L, and centrifugally separating to obtain the coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material.
2. The method for preparing the coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material according to claim 1, wherein in S1, the metal source is any one of a Ni source, a Co source, a Fe source, a Cu source, a Mo source, a W source and a Mn source.
3. The method for preparing the coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material according to claim 1, wherein in S1, the high molecular polymer is any one or more than two of polyvinylpyrrolidone, polyacrylonitrile, polyvinyl alcohol and polytetrafluoroethylene.
4. The method for preparing the coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material according to claim 1, wherein in S1, the amount of the transition metal source is 0.1-2mmol, the amount of the tetraethoxysilane is 1-4mL, the amount of the high polymer is 1.5-3g, the amount of the coordination atom source is 0.1-1g, and the amount of the solvent is 10-20mL.
5. The method for preparing the coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material according to claim 1, wherein in S1, stirring is carried out in a water bath at 40-70 ℃ for 4-10h.
6. The preparation method of the coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material, which is characterized in that in S2, the spinning voltage is controlled to be 15-20kV during electrostatic spinning, the vertical distance between an injector and a receiving plate is 10-24cm, and the pushing rate of the injector is 0.5-1.5mL/h.
7. The preparation method of the coordination atom doped porous carbon fiber domain-limited transition metal monoatomic material, which is characterized in that in S3, a precursor fiber membrane is placed in a porcelain boat, the porcelain boat is placed in the middle of a tube furnace, air is introduced for pre-oxidation, the temperature of the tube furnace is raised to 250-300 ℃, the heating rate is 2-2.5 ℃/min, and the temperature is kept for 1-4 hours; and then heating to 600-1200 ℃ under the protection of inert gas, keeping the heating rate at 4-5 ℃/min for 2-5h, and finally cooling to room temperature under the protection of inert gas to obtain carbonized fibers.
8. A coordinated atom doped porous carbon fiber domain-limited transition metal monoatomic material, characterized in that it is prepared by the preparation method of any one of claims 1 to 7.
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