CN108298518B - Preparation method of monoatomic dispersed carbon material - Google Patents
Preparation method of monoatomic dispersed carbon material Download PDFInfo
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- CN108298518B CN108298518B CN201810146697.1A CN201810146697A CN108298518B CN 108298518 B CN108298518 B CN 108298518B CN 201810146697 A CN201810146697 A CN 201810146697A CN 108298518 B CN108298518 B CN 108298518B
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 89
- 239000013384 organic framework Substances 0.000 claims abstract description 79
- 150000003624 transition metals Chemical class 0.000 claims abstract description 44
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 150000004033 porphyrin derivatives Chemical class 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 125000004429 atom Chemical group 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- -1 polyethylene Polymers 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 8
- 229910052734 helium Inorganic materials 0.000 claims description 8
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920000767 polyaniline Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 21
- 238000001308 synthesis method Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 238000001035 drying Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 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 1
- 239000011148 porous material Substances 0.000 description 1
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
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Abstract
The invention discloses a preparation method of a monoatomic dispersed carbon material, and belongs to the technical field of new material preparation. The preparation method of the material is that a hybrid precursor formed by a porphyrin organic framework coordinated with transition metal in a porphyrin ring and a carbon material or a porphyrin organic framework coordinated with transition metal in the porphyrin ring and a polymer is calcined under certain temperature and atmosphere conditions. Wherein the porphyrin organic framework is formed by connecting porphyrin and porphyrin derivative structural units through covalent bonds; forming a hybrid by the porphyrin organic framework and the carbon material or the porphyrin organic framework and the polymer through intermolecular force; the obtained material is prepared by dispersing transition metal single atoms in a carbon material framework. The preparation method adopts a porphyrin organic framework precursor suitable for forming a monoatomic site, and the obtained material has high monoatomic density and stability, is simple in synthesis method, high in yield, suitable for various transition metals, and capable of preparing a large amount of monoatomic dispersed carbon materials.
Description
Technical Field
The invention belongs to the technical field of new material preparation, and particularly relates to a preparation method of a monoatomic dispersed carbon material.
Background
The precise regulation and control of materials on the atomic scale is one of the key problems of material science. The material with dispersed single atom has definite chemical structure, ultrahigh-density atomic sites and fully exposed active sites, and thus has wide application prospect in the fields of catalysis, energy, electronics, sensing, biology and the like. In particular, the monodisperse transition metal atom supported on the carbon skeleton material not only has the advantages of high density and high exposure of the monatomic active sites of the monatomic material, but also shows the advantages of high conductivity, high specific surface area, rich pore structure and the like of the carbon material, and has higher diversity in chemical composition and morphological characteristics, thereby receiving wide attention.
However, effective synthesis means for monatomic materials have not been sufficiently developed and studied at present. For a system in which a single-dispersed transition metal atom is supported on a carbon skeleton material, a main synthesis strategy at present is to pyrolyze a precursor containing a transition metal and a carbon skeleton to prepare a single-atom-dispersed carbon material. Yuanjun Chen et al report that a material prepared by pyrolyzing a metal-organic framework material to load monatomic iron on graphene exhibits high electrochemical activity for oxygen reduction (Yuanjun Chen et al, angelwalde Chemie International Edition,2017,56, 1). Ruiguo Cao et al reported that a monatomic iron-supported carbon nanotube material prepared based on pyrolytic phthalocyanine iron exhibited high energy storage activity and stability (Ruiguo Cao et al, Nature Communications,2013,4, 2076).
Although single transition metal atom dispersed carbon materials have been prepared in some studies, it is still very difficult to synthesize carbon materials having a higher density of single transition metal atom sites simply, efficiently and on a large scale. During pyrolysis at high temperatures, the transition metal atoms tend to spontaneously aggregate or form carbides with the carbon skeleton, greatly reducing the transition metal sites in a monoatomic dispersion state. Meanwhile, due to the instability of the carbon precursor at high temperature, the chemical composition and structure around the transition metal monoatomic atom are not controllable. These factors greatly restrict the effective construction and application of monatomic materials. Aiming at a high-temperature pyrolysis system, the regulation and control of a precursor of the high-temperature pyrolysis system are key factors for directionally constructing a product after pyrolysis. Therefore, selecting a monatomic material precursor with a proper structure and constructing monatomic and surrounding chemical structure sites in advance is an effective means for efficiently preparing the high-density monatomic site material.
Disclosure of Invention
The invention aims to provide a preparation method of a monoatomic dispersed carbon material, which adopts the following technical scheme:
a method for producing a monoatomic dispersion carbon material, comprising the steps of:
1) placing a hybrid formed by a porphyrin organic framework coordinated with transition metal in a porphyrin ring and a carbon material or a porphyrin organic framework coordinated with transition metal in the porphyrin ring and a polymer as a precursor in a reactor, and heating to 400-1100 ℃ under the atmosphere of carrier gas of inert gas; wherein the transition metal is coordinated in the porphyrin organic framework hybrid in a monoatomic dispersion form to be used as a precursor;
2) keeping the temperature of the reactor constant for 1-48 hours after the temperature of the reactor is reached, calcining at the constant temperature, stopping heating, and cooling to room temperature under the protection of inert gas;
3) and taking out the calcined product, adding an acid solution to remove impurities, fully reacting, and filtering and washing the product to obtain the carbon material with the monoatomic dispersion of the transition metal.
The monoatomic dispersed carbon material is one or more of transition metals of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag and Au which are dispersed in a carbon material framework in the form of monoatomic existence.
The hybrid formed by the porphyrin organic framework and the carbon material or the porphyrin organic framework and the polymer is formed by the porphyrin organic framework and the carbon material or the porphyrin organic framework and the polymer through intermolecular force; wherein the porphyrin organic framework is an organic framework formed by connecting porphyrin and porphyrin derivatives through covalent bonds; the mass ratio of the carbon material to the porphyrin organic framework is 1:0.1-1: 10; the mass ratio of the polymer to the porphyrin organic framework is 1:0.1-1: 10.
The inner ring heteroatom of the porphyrin and the porphyrin derivative is one or more than one of N, O and S; the coordination atoms of the inner ring are one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag and Au, and the coordination atoms are dispersedly coordinated in the porphyrin inner ring; the porphyrin organic framework is of a two-dimensional or three-dimensional structure.
Preferably, the carbon material is graphite, graphene, carbon nanotubes, carbon fibers or carbon black; the polymer is polyethylene, polypropylene, polystyrene, polyaniline, polyvinylidene fluoride or polytetrafluoroethylene.
The transition metal monoatomic atom in the monoatomic dispersed carbon material is the same as the kind of the coordination transition metal atom in the porphyrin organic framework precursor.
Preferably, the inert gas is one of nitrogen, argon or helium, and the flow rate of the inert gas is 100--1. The acid is aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, acetic acid or hydrofluoric acid, and the concentration of the acid is 1-10mol L-1。
The temperature of the acid treatment process is 25-100 ℃, and the reaction time is 1-24 hours.
The invention has the following advantages and prominent technical effects: the monoatomic dispersion carbon material effectively constructs a monoatomic site structure due to a monoatomic dispersion complex formed by porphyrin and transition metal in a porphyrin organic framework precursor, so that the derived monoatomic carbon material has higher monoatomic site density and stability. The synthesis method of the material is simple, convenient and effective, is suitable for various transition metals, can prepare a material system with single transition metal atoms dispersed in a carbon skeleton in a large scale, and provides a high application prospect for the material system in the fields of catalysis, energy, sensing, biology, electronics and the like.
Detailed Description
The invention provides a preparation method of a monoatomic dispersed carbon material, which specifically comprises the following steps:
1) placing a hybrid formed by a porphyrin organic framework coordinated with transition metal in a porphyrin ring and a carbon material or a porphyrin organic framework coordinated with transition metal in the porphyrin ring and a polymer as a precursor in a reactor, and heating to 400-1100 ℃ under the atmosphere of carrier gas of inert gas; wherein the transition metal is coordinated in the porphyrin organic framework hybrid in a monoatomic dispersion form to be used as a precursor; the monoatomic dispersed carbon material is in transitionOne or more of metals Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag and Au are dispersed in the carbon material skeleton in the form of single atoms; the hybrid formed by the porphyrin organic framework and the carbon material or the porphyrin organic framework and the polymer is formed by the porphyrin organic framework and the carbon material or the porphyrin organic framework and the polymer through intermolecular force; wherein the porphyrin organic framework is an organic framework formed by connecting porphyrin and porphyrin derivatives through covalent bonds; the mass ratio of the carbon material to the porphyrin organic framework is 1:0.1-1: 10; the mass ratio of the polymer to the porphyrin organic framework is 1:0.1-1: 10; the inner ring heteroatom of the porphyrin and the porphyrin derivative is one or more than one of N, O and S; the coordination atoms of the inner ring are one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag and Au, and the coordination atoms are dispersedly coordinated in the porphyrin inner ring; the porphyrin organic framework is of a two-dimensional or three-dimensional structure; the carbon material is graphite, graphene, carbon nanotubes, carbon fibers or carbon black; the polymer is polyethylene, polypropylene, polystyrene, polyaniline, polyvinylidene fluoride or polytetrafluoroethylene; the transition metal single atom in the monoatomic dispersed carbon material is the same as the coordination transition metal atom in the porphyrin organic framework precursor; the inert gas is one of nitrogen, argon or helium, and the flow rate of the inert gas is 100--1；
2) Keeping the temperature of the reactor constant for 1-48 hours after the temperature of the reactor is reached, calcining at the constant temperature, stopping heating, and cooling to room temperature under the protection of inert gas;
3) taking out the calcined product, adding an acid solution to remove impurities, and filtering and washing the product after full reaction to obtain a carbon material with the single-atom dispersed transition metal; the acid is one of aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and hydrofluoric acid, and the concentration of the acid is 1-10mol L-1(ii) a The temperature of the acid treatment process is 25-100 ℃, and the reaction time is 1-24 hours.
The present invention is further described below with reference to examples to further understand the present invention by those of ordinary skill in the art.
Example 1
10.0g of Co-coordinated N-porphyrin organic framework and graphene hybrid is placed in a reactor for 100mL min-1Heating to 800 deg.C under nitrogen atmosphere with flow rate, and heating rate of 10 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 12 hours. After the constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of nitrogen. The calcined product was subsequently removed and 150mL of 1mol L were added-1The hydrochloric acid solution was transferred to a 500mL flask and reacted at 50 ℃ for 12 hours to remove impurities. After full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 60 ℃ for 24 hours to obtain the carbon material with the dispersed monatomic Co derived from the N porphyrin organic framework with Co coordination. The test showed a 3.1% content of monatomic Co.
Example 2
Placing 15.0g of Pd-coordinated O-porphyrin organic framework and polyvinylidene fluoride hybrid in a reactor for 200mL min-1Heating to 650 deg.C under argon atmosphere at a flow rate of 10 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 48 hours. After constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of argon. The calcined product was subsequently removed and 250mL of 5mol L were added-1Was transferred to a 500mL flask and reacted at 25 ℃ for 24 hours to remove impurities. After full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 80 ℃ for 24 hours to obtain the carbon material with the single atom Pd dispersed, wherein the single atom Pd is derived from the O porphyrin organic framework coordinated by Pd. The test showed a content of monatomic Pd of 4.2%.
Example 3
15.0g of Cu-coordinated organic framework of S-porphyrin and hybrid carbon fiber was placed in a reactor for 500mL min-1Heating to 1100 deg.C under nitrogen atmosphere with flow rate, and heating rate of 20 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 6 hours. After the constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of nitrogen. The calcined product was subsequently removed and 250mL of 3mol L were added-1Was transferred to a 500mL flask and reacted at 65 ℃ for 1 hour to remove impurities. After sufficient reaction, the product was filtered and washed with ethanolAnd then, drying for 24 hours at 60 ℃ to obtain the monoatomic Cu dispersed carbon material derived from the Cu coordinated S porphyrin organic framework. The test showed a monoatomic Cu content of 2.9%.
Example 4
20.0g of Mn coordinated N-porphyrin organic framework and polyaniline hybrid is placed in a reactor for 250mL min-1Heating to 400 deg.C under helium atmosphere at flow rate, and heating rate of 10 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 1 hour. And (5) stopping heating after constant temperature treatment, and cooling to room temperature under the protection of helium. The calcined product was subsequently removed and 150mL of 10mol L were added-1Was transferred to a 500mL flask and reacted at 100 ℃ for 2 hours to remove impurities. And after full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 60 ℃ for 24 hours to obtain the carbon material with dispersed monatomic Mn derived from the Mn-coordinated N porphyrin organic framework. The test showed a content of 4.3% of monoatomic Mn.
Example 5
10.0g of Cr-coordinated S-porphyrin organic framework and graphite hybrid are placed in a reactor for 500mL min-1Heating to 600 deg.C under nitrogen atmosphere with flow rate, and heating rate of 10 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 20 hours. After the constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of nitrogen. The calcined product was subsequently removed and 250mL of 6mol L were added-1The solution was transferred to a 500mL flask and reacted at 30 ℃ for 12 hours to remove impurities. After full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 60 ℃ for 24 hours to obtain the carbon material with dispersed monoatomic Cr derived from the S porphyrin organic framework with Cr coordination. The test shows that the content of the monoatomic Cr is 3.2 percent.
Example 6
15.0g of Ti coordinated N porphyrin organic framework and carbon nanotube hybrid is placed in a reactor for 300mL min-1Heating to 800 deg.C under argon atmosphere at flow rate, and heating rate of 25 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 3 hours. After constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of argon. Then will beThe calcined product was taken out and 150mL of 2mol L was added-1The hydrochloric acid solution was transferred to a 500mL flask and reacted at 75 ℃ for 6 hours to remove impurities. After full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 60 ℃ for 24 hours to obtain the Ti-coordinated carbon material with monoatomic Ti dispersion derived from the N porphyrin organic framework. The test showed a content of 2.9% of monoatomic Ti.
Example 7
10.0g of Ag coordinated O porphyrin organic framework and polypropylene hybrid is placed in a reactor for 100mL min-1Heating to 550 deg.C under nitrogen atmosphere with flow rate, and heating rate of 15 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 8 hours. After the constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of nitrogen. The calcined product was subsequently removed and 150mL of 9mol L were added-1Was transferred to a 500mL flask and reacted at 95 ℃ for 12 hours to remove impurities. After full reaction, filtering the product, washing the product with ethanol for three times, and drying the product for 24 hours at the temperature of 60 ℃ to obtain the monoatomic Ag dispersed carbon material derived from the Ag coordinated O porphyrin organic framework. The test shows that the content of the monoatomic Ag is 3.8%.
Example 8
25.0g of Zn-coordinated N-porphyrin organic framework and polyethylene hybrid was placed in a reactor for 250mL min-1Heating to 1000 deg.C under nitrogen atmosphere with flow rate, and heating rate of 20 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 12 hours. After the constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of nitrogen. The calcined product was subsequently removed and 120mL of 1mol L were added-1Was transferred to a 500mL flask and reacted at 25 ℃ for 24 hours to remove impurities. And after full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 70 ℃ for 24 hours to obtain the monoatomic Zn-dispersed carbon material derived from the Zn-coordinated N porphyrin organic framework. The test showed a content of 4.6% of monoatomic Zn.
Example 9
12.0g of Fe-coordinated N-porphyrin organic framework and polystyrene hybrid is placed in a reactor for 500mL min-1Flow rate of heliumHeating to 750 deg.C in gas atmosphere at a heating rate of 10 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 18 hours. And (5) stopping heating after constant temperature treatment, and cooling to room temperature under the protection of helium. The calcined product was subsequently removed and 100mL of 1mol L were added-1The solution was transferred to a 500mL flask and reacted at 40 ℃ for 1 hour to remove impurities. And after full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 60 ℃ for 24 hours to obtain the Fe-coordinated carbon material with the dispersed monatomic Fe derived from the N porphyrin organic framework. The test shows that the content of the monoatomic Fe is 2.6 percent.
Example 10
Placing 5.0g of Pt coordinated O porphyrin organic framework and graphene hybrid in a reactor for 150mL min-1Heating to 1100 deg.C under nitrogen atmosphere with flow rate, and heating rate of 20 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 12 hours. After the constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of nitrogen. The calcined product was subsequently removed and 500mL of 3mol L were added-1Was transferred to a 1L flask and reacted at 40 ℃ for 3 hours to remove impurities. And after full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 60 ℃ for 24 hours to obtain the Pt-coordinated O porphyrin organic framework derived monoatomic Pt dispersed carbon material. The test showed a content of 4.5% of monoatomic Pt.
Example 11
Placing the 10.0g V coordinated N porphyrin organic framework and carbon black hybrid in a reactor at 150mL min-1Heating to 400 ℃ under argon atmosphere with flow, wherein the heating rate is 5 ℃ for min-1. After the reactor reached the above temperature, the temperature was maintained for 24 hours. After constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of argon. The calcined product was subsequently removed and 250mL of 5mol L were added-1The hydrochloric acid solution was transferred to a 500mL flask and reacted at 70 ℃ for 4 hours to remove impurities. After full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 60 ℃ for 24 hours to obtain the monoatomic V-dispersed carbon material derived from the V-coordinated N-porphyrin organic framework. The test showed a content of monoatomic V of 2.9%.
Example 12
Placing 15.0g of Co and Ni double-coordinated N porphyrin organic framework and carbon nanotube hybrid in a reactor for 200mL min-1Heating to 950 deg.C under nitrogen atmosphere with flow rate, and heating rate of 10 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 24 hours. After the constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of nitrogen. The calcined product was subsequently removed and 200mL of 5mol L were added-1The sulfuric acid solution was transferred to a 500mL flask and reacted at 80 ℃ for 12 hours to remove impurities. After full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 60 ℃ for 24 hours to obtain the carbon material with dispersed single atoms of Co and Ni derived from the Co and Ni double-coordinated N porphyrin organic framework. The test shows that the content of the monoatomic Co is 2.6 percent; the content of monoatomic Ni was 2.6%.
Example 13
Placing 5.0g of Cu-coordinated S-porphyrin organic framework and graphene hybrid in a reactor for 500mL min-1Heating to 550 deg.C under helium atmosphere at flow rate, and heating rate of 10 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 1 hour. And (5) stopping heating after constant temperature treatment, and cooling to room temperature under the protection of helium. The calcined product was subsequently removed and 150mL of 9mol L were added-1Was transferred to a 500mL flask and reacted at 100 ℃ for 6 hours to remove impurities. And after full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 60 ℃ for 24 hours to obtain the monoatomic Cu-dispersed carbon material derived from the Cu-coordinated S-porphyrin organic framework. The test showed a 3.3% content of monoatomic Cu.
Example 14
25.0g of Pt and Pd double-coordinated O porphyrin organic framework and graphene hybrid are placed in a reactor for 200mL min-1Heating to 1000 deg.C under nitrogen atmosphere with flow rate, and heating rate of 10 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 12 hours. After the constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of nitrogen. The calcined product was subsequently removed and 500mL of 2mol L were added-1The hydrofluoric acid solution is transferred into a 1L flask and is subjected to 60 DEG CThe reaction was continued for 12 hours to remove impurities. After full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 60 ℃ for 24 hours to obtain the carbon material with dispersed monoatomic Pt and Pd derived from the Pt and Pd double-coordinated O-porphyrin organic framework. The test shows that the content of the monoatomic Pt is 2.9 percent; the content of monatomic Pd was 2.1%.
Example 15
Placing 8.0g Ni-coordinated N porphyrin organic framework and polytetrafluoroethylene hybrid in a reactor for 200mL min-1Heating to 600 deg.C under nitrogen atmosphere with flow rate, and heating rate of 10 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 3 hours. After the constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of nitrogen. The calcined product was subsequently removed and 100mL of 2mol L were added-1Was transferred to a 500mL flask and reacted at 40 ℃ for 4 hours to remove impurities. After full reaction, filtering the product, washing the product with ethanol for three times, and drying the product for 24 hours at the temperature of 60 ℃ to obtain the carbon material with the dispersed monatomic Ni derived from the N porphyrin organic framework with Ni coordination. The test showed a 3.4% content of monoatomic Ni.
Example 16
15.0g of Au-coordinated organic framework of S-porphyrin and polystyrene hybrid was placed in a reactor for 400mL min-1Heating to 1100 deg.C under argon atmosphere at a flow rate of 20 deg.C for min-1. After the reactor reached the above temperature, the temperature was maintained for 8 hours. After constant temperature treatment, the heating is stopped, and the mixture is cooled to room temperature under the protection of argon. The calcined product was subsequently removed and 250mL of 1mol L were added-1The solution was transferred to a 500mL flask and reacted at 25 ℃ for 6 hours to remove impurities. And after full reaction, filtering the product, washing the product with ethanol for three times, and drying the product at 70 ℃ for 24 hours to obtain the Au-coordinated S porphyrin organic framework-derived monoatomic Au-dispersed carbon material. The test showed a content of 4.0% of monoatomic Au.
Claims (7)
1. A method for producing a monoatomic dispersion carbon material, comprising the steps of:
1) placing a hybrid formed by a porphyrin organic framework coordinated with transition metal in a porphyrin ring and a carbon material or a polymer as a precursor in a reactor, and heating to 400-1100 ℃ under the atmosphere of carrier gas of inert gas; the hybrid formed by the porphyrin organic framework coordinated with the transition metal in the porphyrin ring and the carbon material or the porphyrin organic framework coordinated with the transition metal in the porphyrin ring and the polymer is formed by the porphyrin organic framework coordinated with the transition metal in the porphyrin ring and the carbon material or the porphyrin organic framework coordinated with the transition metal in the porphyrin ring and the polymer through intermolecular force; wherein the porphyrin organic framework coordinated with the transition metal is an organic framework formed by connecting porphyrin coordinated with the transition metal and porphyrin derivatives through covalent bonds; the mass ratio of the carbon material to the porphyrin organic framework coordinated with the transition metal is 1:0.1-1: 10; the mass ratio of the polymer to the porphyrin organic framework coordinated with the transition metal is 1:0.1-1: 10; wherein the inner ring coordination atoms of the porphyrin coordinated with the transition metal and the porphyrin derivative are one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag and Au; wherein the transition metal is coordinated in the porphyrin organic framework hybrid in a monoatomic dispersion form to be used as a precursor;
2) keeping the temperature of the reactor constant for 1-48 hours after the temperature of the reactor is reached, calcining at the constant temperature, stopping heating, and cooling to room temperature under the protection of inert gas;
3) taking out the calcined product, performing acid treatment to remove impurities, and filtering and washing the product after full reaction to obtain a carbon material with single-atom dispersed transition metal; wherein the transition metal is one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pd, Pt, Ag and Au; the transition metal is dispersed in the carbon material in the form of a single atom.
2. The method for producing a monoatomic dispersed carbon material according to claim 1, wherein in a hybrid formed by a porphyrin organic skeleton and a carbon material or a porphyrin organic skeleton and a polymer, the inner ring heteroatom of the porphyrin or the porphyrin derivative is one or more of N, O and S; the coordination atoms are dispersedly coordinated in the porphyrin inner ring in a monoatomic manner; the porphyrin organic framework is of a two-dimensional or three-dimensional structure.
3. The method according to claim 2, wherein the carbon material is graphite, graphene, carbon nanotubes, carbon fibers or carbon black in the hybrid of the porphyrin organic framework and the carbon material or the hybrid of the porphyrin organic framework and the polymer; the polymer is polyethylene, polypropylene, polystyrene, polyaniline, polyvinylidene fluoride or polytetrafluoroethylene.
4. The method according to claim 1, wherein the transition metal monoatomic atom in the monoatomic dispersed carbon material is the same as the coordinated transition metal atom in the porphyrin organic framework precursor.
5. The method for preparing a monoatomic dispersion carbon material according to claim 1, wherein the inert gas is one of nitrogen, argon or helium, and the flow rate of the inert gas is 100--1。
6. The method for producing a monoatomic dispersion carbon material according to claim 1, wherein the acid is an aqueous solution of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, or hydrofluoric acid, and has a molar concentration of 1 to 10mol L-1。
7. The method for producing a monoatomic dispersion carbon material according to claim 1, wherein the temperature of the acid treatment is 25 to 100 ℃, and the reaction time is 1 to 24 hours.
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| CN110124714B (en) * | 2019-05-08 | 2022-08-30 | 南京邮电大学 | Cu-N-C-based carbon nanosheet and preparation method and application thereof |
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| CN111604093B (en) * | 2020-06-16 | 2023-01-24 | 中国民航大学 | Preparation method and application of aluminum monatomic catalyst |
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| CN112973750B (en) * | 2021-01-29 | 2023-09-26 | 南京工业大学 | Carbon quantum dot coated metal monoatomic-carbon nitride composite material and preparation method thereof |
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