CN114210345B - Homologous heterogeneous interface structure composite material and preparation method thereof - Google Patents
Homologous heterogeneous interface structure composite material and preparation method thereof Download PDFInfo
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
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- 241001579016 Nanoa Species 0.000 description 1
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- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
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- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/342—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electric, magnetic or electromagnetic fields, e.g. for magnetic separation
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Abstract
The invention discloses a composite material with a homologous heterogeneous interface structure and a preparation method thereof, wherein the composite material is an interface structure M/M consisting of transition metal or alloy and corresponding sulfide x S y Composite nanoparticles; wherein M is a metal simple substance or an alloy, M x S y Is sulfide corresponding to metal simple substance or alloy; the M/M x S y In the composite material, the heterogeneous interface structure of the metal simple substance or the alloy and the corresponding sulfide is an AB left-right type interface structure. The invention quickly grows M/M on the surface of the carbon fiber by applying instantaneous voltage x S y The heterostructure is compounded with the nano particles, and the heterostructure is highly dispersed, and the generated heterogeneous interface of the metal simple substance/alloy and the metal sulfide is an AB left-right type interface, so that the active sites can be well exposed, and the electrocatalytic activity of the composite material is obviously improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical catalysis, particularly relates to a composite material with a homologous heterogeneous interface structure and a preparation method thereof, and particularly relates to a composite material with a homologous heterogeneous interface structure of a metal/metal sulfide interface or an alloy/alloy sulfide, which is formed by transition metal or alloy and sulfide thereof, and a preparation method thereof.
Background
With the development of science and technology, it is of great significance to develop and design a catalytic material with high efficiency, low cost, high stability and excellent performance, which is applied to the fields of environment and energy. Research shows that the size and structure of the nano material can strongly influence the physical and electrochemical properties of the nano material. The single-component catalytic material can not meet the requirements of energy and material technology due to single physical and chemical properties, and compared with a single material, the two-phase composite material system not only can keep the advantages and properties of the original component materials, but also can play a synergistic role among the component materials. A heterogeneous interface constructed by combining two or more components can bring about changes of physicochemical properties (such as special atomic structures, electronic effects, carrier charge transmission characteristics and the like), and has important influences on optimizing absorption and desorption energy barriers of active material intermediates, enhancing charge transmission, improving electrochemical activity and stability and the like. Therefore, the method becomes an important way for developing the high-efficiency multifunctional electrocatalyst material by constructing a heterogeneous interface and regulating and controlling the microstructure characteristics of the interface. At present, typical heterogeneous interface systems include four major categories, namely metal/metal (alloy), metal/substrate (carbon, silicon and other substrates), metal/compound and compound/compound, wherein the metal/compound system has both the metal characteristic of good conductivity and the compound property of significant catalytic effect, and shows stronger electronic interaction and stronger chemical bond interaction, thereby providing more active sites for catalytic reaction.
At least one noble metal or inert metal is often present in the metal/compound interface structure, and a heterogeneous interface can be formed only by making full use of the great difference of chemical reaction activities between two metal elements, so that the component range of the composite structure is strictly limited, and the noble metal or the inert metal often has the characteristics of high price, rare resources, single catalytic performance and the like, and the development of the noble metal or the inert metal in the field of electrocatalysis is severely limited. Therefore, non-noble metals with rich resources and low price are used for replacing noble metals or inert metals, the strong electron coupling effect between interfaces is fully utilized, and a synergistic catalysis mechanism is exerted, so that the method is the key for developing a novel high-efficiency multifunctional metal/compound heterogeneous interface electrocatalyst.
In addition to the optimization of the composition of the metal elements, the preparation technology should be further improved. The methods for preparing the composite material containing the nano particles are still few at present, and the synthesis method of an interface system is complex and inefficient, so that a plurality of reactions are often required, most of the reactions are firstly synthesizing a compound and then performing subsequent synthesis on the basis of the compound, and the obtained compound is not very tightly combined. Meanwhile, the synthesis process has the disadvantages of complex equipment, high temperature and high pressure, environmental pollution, time consumption and the like. Therefore, the novel rapid preparation process has important significance for synthesizing the heterogeneous interface composite material.
In the prior report, it is described that a catalyst having a core-shell Structure is prepared by a heat treatment method (see "Structure-reactivity relationships of Ni-NiO core-shell co-catalysts on Ta published on pages 58-64 in the journal" Applied catalysts B: environmental "volume 172-173 of 8 months 2015) 2 O 5 for solar hydrogen production "), since the method involves multiple steps of reaction, a reduction-oxidation process is required, and the core-shell co-catalyst structure is easily deactivated during the reaction.
The metal/compound interface system composed of the same transition metal and its compound is referred to as homogeneous heterogeneous interface (M/MxNy). Through research and development, research reports on a homologous heterogeneous interface are few at present, most of the homologous heterogeneous interfaces are obtained by carrying out incomplete oxidation or vulcanization on transition metals, the structures of the homologous heterogeneous interfaces are mostly core-shell structures, and the core-shell structures cannot fully play a role in an electrocatalysis process due to the fact that interface structures and internal substances of the core-shell structures cannot be well exposed and cannot fully reflect the essential characteristics of the homologous heterogeneous interfaces.
Patent document CN107460725A describes a sulfur-doped cobalt phosphide-carbon nanofiber composite material and a preparation method thereof, which comprises the steps of dispersing a cobalt salt and thiourea in an organic solvent in proportion, then carrying out solvothermal reaction on the dispersion liquid and a carbon nanofiber pretreatment film to obtain a cobalt monosulfide/carbon nanofiber composite material, and carrying out a phosphating reaction on the cobalt monosulfide/carbon nanofiber composite material and sodium hypophosphite to obtain the sulfur-doped cobalt phosphide/carbon nanofiber composite material. The prepared composite material is a sulfur-doped cobalt phosphide single-phase material, is compounded with carbon fibers, and is a common interface formed between cobalt sulfide and the carbon fibers. And the composite material can be applied to hydrogen evolution reaction.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to develop a novel interface structure through a rapid high-temperature flash combustion technology, thereby providing a homologous heterogeneous interface structure composite material and a preparation method thereof, and typical particles with AB left and right type homologous heterogeneous interface structures of metal/metal sulfides and alloy/alloy sulfides are prepared on the surface of electrostatic spinning carbon nanofibers by regulating and controlling process parameters. The structure not only has the characteristics of a 'homologous' structure different from other heterogeneous interfaces, but also can well expose the active sites of the structure, and is beneficial to improving the electrocatalytic activity.
In order to solve the technical problems, the invention is realized by adopting the following technical scheme:
the invention provides a composite material with a homologous heterogeneous interface structure, which is a composite material with a heterogeneous structure consisting of transition metal or alloy and sulfide thereof, and has a general formula of M/M x S y (ii) a Wherein M is a metal simple substance or an alloy, M x S y Is a metal sulfide corresponding to a metal simple substance or an alloy; the M/M x S y In the composite material, the heterogeneous interface structure of the metal simple substance or the alloy and the corresponding sulfide is an AB left-right type interface structure, but not a core-shell structure or an atom doping structure.
Preferably, the M is selected from one simple metal or an alloy consisting of two or more metals of Co, ni and Fe.
Preferably, the M/M x S y Selected from Fe/Fe x S y ,Co/Co x S y ，Ni/Ni x S y ，FeNi/(FeNi) x S y , FeCo/(FeCo) x S y ，NiCo/(NiCo) x S y ，FeNiCo/(FeNiCo) x S y Any one of them.
The invention also provides a preparation method of the composite material with the homologous heterogeneous interface structure, which comprises the following steps:
A. preparing a carbon fiber substrate loaded metal salt and a thiourea precursor: soaking the carbon fiber substrate in a mixed aqueous solution of metal salt and thiourea to obtain metal salt and thiourea-loaded carbon fibers;
B. preparing a homologous heterogeneous interface composite material: and connecting the metal salt and the thiourea-loaded carbon fiber with an external circuit, and instantaneously electrifying to obtain the homologous heterogeneous interface composite material.
Preferably, in the step A, the concentration of the mixed aqueous solution of the metal salt and the thiourea is 100-300mM; in the mixed aqueous solution of the metal salt and the thiourea, the molar concentration ratio of the metal salt to the thiourea is 1.
Preferably, in the step A, the soaking time is 2-4h.
Preferably, in step a, the metal in the metal salt is selected from one or more of cobalt, nickel and iron, and the salt is selected from at least one of acetate, nitrate and acetylacetonate.
Preferably, in the step A, the diameter size of the carbon fiber substrate is 200-500nm, and the carbon fiber is carbon nanofiber.
Preferably, the specific steps of step B are:
connecting metal salt and thiourea-loaded carbon fiber at two ends of a power line in a glove box in argon environment, flatly laying on an insulating glass plate, and electrifying for 0.5-1s to obtain M x S y The homogeneous heterogeneous interface structure composite material of the system.
Preferably, in the step B, the electrified applied voltage is 15-25V and the current is 2-10A.
Preferably, the carbon fiber substrate is prepared by electrospinning.
Preferably, the specific preparation method of the carbon fiber substrate comprises the following steps:
and (2) dissolving polyacrylonitrile in an organic solvent to obtain a homogeneous solution, performing electrostatic spinning to obtain electrostatic spinning nanofibers, and performing pre-oxidation and carbonization treatment on the electrostatic spinning nanofibers to obtain the electrostatic spinning carbon nanofibers.
Preferably, the organic solvent is N, N-dimethylformamide; the mass ratio of the polyacrylonitrile to the organic solvent is 1;
the electrostatic spinning adopts the following working parameter conditions: working voltage is 20-26kV, and between the needle point and the collectorThe distance of (2) is 12-16cm, the flow rate of the homogeneous solution is 0.5-2.5mL h -1 。
Preferably, the specific conditions of the pre-oxidation are: heating the electrostatic spinning nano-fiber to 250-270 ℃ and keeping for 0.5-2h;
the specific conditions of the carbonization treatment are as follows: heating the pre-oxidized electrostatic spinning nanofiber to 900-1200 ℃ in an inert atmosphere, and keeping the temperature for 0.5-1h;
the pre-oxidation process comprises controlling the heating rate to be 0.5-2 ℃ for min -1 ；
In the carbonization process, the heating rate is controlled to be 4-10 ℃ for min -1 。
The invention also provides a carbon fiber material loaded with the homologous heterogeneous interface structure, which comprises a carbon material substrate and a composite material loaded with the homologous heterogeneous interface structure on the carbon material substrate;
the composite material with the homologous heterogeneous interface structure is a composite material with a heterogeneous structure, which is composed of transition metal or alloy and sulfide thereof, and has a general formula of M/M x S y (ii) a Wherein M is a metal simple substance or an alloy, M x S y Is a metal sulfide corresponding to a metal simple substance or an alloy; the M/M x S y In the composite material, the heterogeneous interface structure of the metal simple substance or alloy and the corresponding sulfide is an AB left-right type interface structure, but not a core-shell structure or an atom-doped structure.
Preferably, the M is selected from one simple metal or an alloy consisting of two or more metals of Co, ni and Fe.
Preferably, said M/M x S y Selected from Fe/Fe x S y ,Co/Co x S y ，Ni/Ni x S y ，FeNi/(FeNi) x S y , FeCo/(FeCo) x S y ，NiCo/(NiCo) x S y ，FeNiCo/(FeNiCo) x S y Any one of them.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention regulates and controls working voltage, synthesis temperature and the like through a systemTechnological parameters, the M/M can be rapidly grown on the surface of the carbon nano fiber x S y The nano particles are highly dispersed, and the homologous heterogeneous interface of the generated metal/alloy and the sulfide thereof is an AB left-right type interface structure, but not a core-shell structure or other structures such as atom doping and the like.
(2) Compared with a single-phase catalyst, the M/M synthesized by the invention x S y The system shows stronger electronic interaction, has obvious interface effect, generates stronger chemical bond effect at the interface, increases the exposure of the catalytic active sites of the material, and has excellent OER electro-catalytic activity and stability.
(3) The composite material prepared by the invention has simple process and low cost, can generate a high-temperature environment instantly, and realizes the rapid heating and cooling of the material; and the synthesis method can realize the formation of the interface structure within 0.5-1 second.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 shows Co/Co prepared in example 1 of the present invention 9 S 8 Carbon nanofiber-loaded composite (Co/Co) 9 S 8 -characterization results of CNF); wherein, FIG. 1 (a) is an SEM image; FIGS. 1 (b) and 1 (c) are HRTEM images; FIG. 1 (d) is an XRD pattern; FIG. 1 (e) is a HAADF diagram; FIG. 1 (f) is a linear scan;
FIG. 2 shows Co/Co prepared in example 1 of the present invention 9 S 8 -CNF and Co-CNF, co prepared in comparative example 9 S 8 CNF and commercial IrO 2 OER-LSV curve of (1);
FIG. 3 shows Ni/Ni prepared in example 2 3 S 2 OER-LSV curves for CNF and Fe/FeS-CNF prepared in example 3;
FIG. 4 shows FeCo/(FeCo) S-CNF prepared in example 4 and FeNi/(FeNi) prepared in example 5 9 S 8 CNF, niCo/(NiCo) prepared in example 6 9 S 8 -OER-LSV curve of CNF;
FIG. 5 is FeCoNi/(FeCo) prepared in example 7Ni) 9 S 8 -characterization of CNF; wherein, FIG. 5 (a) is an SEM image; FIG. 5 (b) is a TEM image; FIG. 5 (c) is a HRTEM image; FIG. 5 (d) is an XRD pattern; FIG. 5 (e) is a HAADF diagram; FIG. 5 (f) is a linear scan;
FIG. 6 shows FeCoNi/(FeCoNi) prepared in example 7 9 S 8 -OER-LSV curve of CNF;
and, FIG. 7 shows Co/Co prepared in examples 8 and 9 9 S 8 -CNF-100mM、Co/Co 9 S 8 CNF-OER-LSV curve at 300 mM.
Detailed Description
Unless otherwise defined, technical or scientific terms used in the present specification and claims should have the ordinary meaning as understood by one of ordinary skill in the art to which this application belongs. All numerical values recited herein as between the lowest value and the highest value are intended to mean all values obtained in increments of one unit between the lowest value and the highest value when there is a difference of more than two units between the lowest value and the highest value.
In the following detailed description of the present application, it is noted that in order to provide a concise description of these embodiments, all features of an actual implementation may not be described in detail. Modifications and substitutions can be made to the embodiments of the present application by those skilled in the art without departing from the spirit and scope of the present application, and the resulting embodiments are also within the scope of the present application.
The invention provides a composite material with a homologous heterogeneous interface, which is a composite material with a heterogeneous structure and composed of transition metal or alloy and sulfide thereof, and the general formula is M/M x S y (ii) a Wherein M is a metal simple substance or an alloy, M x S y Is a metal sulfide corresponding to a metal simple substance or an alloy; the M/M x S y In the composite material, the heterogeneous interface structure of the metal simple substance or the alloy and the corresponding sulfide is an AB left-right type interface structure, but not a core-shell structure or an atom doping structure.
In a specific embodiment, the M is selected from one simple metal or an alloy consisting of two or more metals of Co, ni and Fe.
In one embodiment, the M/M x S y Selected from Fe/Fe x S y ,Co/Co x S y ，Ni/Ni x S y ， FeNi/(FeNi) x S y ,FeCo/(FeCo) x S y ，NiCo/(NiCo) x S y ，FeNiCo/(FeNiCo) x S y Any one of them. According to a large amount of previous experimental exploration, when other metals are doped, namely M is other metals, uniform composite materials are difficult to prepare.
The composite material prepared by the invention is an interface structure formed by metal or alloy and corresponding sulfide thereof, is a novel interface structure, and is defined as a homologous heterogeneous interface structure in the patent.
The composite material with the homologous heterogeneous interface structure can be applied to oxygen evolution reaction.
In a specific embodiment, a method for preparing a homoeogous heterointerface composite material is also provided, which comprises the following steps:
A. preparing a carbon fiber substrate loaded metal salt and a thiourea precursor: soaking the carbon fiber substrate in a mixed aqueous solution of metal salt and thiourea to obtain metal salt and thiourea-loaded carbon fibers;
B. preparing a homologous heterogeneous interface composite material: and connecting the metal salt and the thiourea-loaded carbon fiber with an external circuit, and instantaneously electrifying to obtain the homologous heterogeneous interface composite material.
The method comprises the steps of soaking carbon fibers in a mixed solution of metal salt and thiourea, and then carrying out instantaneous energization, so that metal/alloy sulfides are firstly generated on the surfaces of the carbon fibers in the process, and the sulfides are reduced into metal/alloy under the carbothermic reduction action, and finally a homologous heterogeneous interface is generated. The formation mechanism is that sulfide is generated from the precursor in the middle temperature section, while in the high temperature section, the sulfide facing the high temperature section is reduced into metal, while the sulfide facing away from the high temperature section is kept stable, and the interface structure is stably maintained due to the characteristic of rapid temperature reduction.
In one embodiment, in the step A, the concentration of the mixed aqueous solution of the metal salt and the thiourea is 100-300mM; in the mixed aqueous solution of the metal salt and the thiourea, the molar concentration ratio of the metal salt to the thiourea is 1.
In a specific embodiment, in step a, the soaking time is 2 to 4 hours.
In a specific embodiment, the metal in the metal salt is selected from one or more of cobalt, nickel and iron, and the salt is selected from at least one of acetate, nitrate and acetylacetone salt. For example, the metal salt is cobalt acetate, nickel acetate, ferrous acetate, cobalt nitrate, nickel nitrate, ferrous nitrate, cobalt acetylacetonate, nickel acetylacetonate, or ferrous acetylacetonate.
In a specific embodiment, in step a, the diameter size of the carbon fiber substrate is 200-500nm, and the carbon fiber is carbon nanofiber.
In a specific embodiment, the specific steps of step B are:
connecting metal salt and thiourea-loaded carbon fiber at two ends of a power line in a glove box in argon environment, flatly laying on an insulating glass plate, and electrifying for 0.5-1s to obtain M x S y The homogeneous heterogeneous interface structure composite material of the system. If the electrifying time exceeds 1s, the reaction time is too long, so that the nano particles are aggregated and grown, and the metal/alloy sulfide is completely reduced into metal/alloy, so that a homologous heterogeneous interface cannot be generated.
In a specific embodiment, in the step B, the voltage applied by the electrification is 15-25V, and the current is 2-10A. If the applied voltage is too large, such as 30V, metal or alloy is generated on the surface of the carbon fiber; if the applied voltage is too low, all of the metal sulfides or alloy sulfides are formed on the surface of the carbon nanofibers at an applied voltage of 10V, and a homoheterogeneous interface cannot be formed.
In a specific embodiment, the carbon fiber substrate is a carbon nanofiber prepared by electrospinning, but is not limited thereto.
In one embodiment, the specific preparation method of the carbon nanofiber comprises the following steps:
and (2) dissolving polyacrylonitrile in an organic solvent to obtain a homogeneous solution, performing electrostatic spinning to obtain electrostatic spinning nanofibers, and performing pre-oxidation and carbonization treatment on the electrostatic spinning nanofibers to obtain the electrostatic spinning carbon nanofibers.
In one embodiment, the organic solvent is N, N-dimethylformamide; the mass ratio of the polyacrylonitrile to the organic solvent is 1;
the electrostatic spinning adopts the following working parameter conditions: working voltage is 20-26kV, the distance between the needle point and the collector (receiving distance) is 12-16cm, and the flow rate of the homogeneous solution is 0.5-2.5mL h -1 。
In one embodiment, the pre-oxidation is performed under the following conditions: heating the electrostatic spinning nanofiber to 250-270 ℃ and keeping for 1-2h;
the specific conditions of the carbonization treatment are as follows: heating the pre-oxidized electrostatic spinning nano-fiber to 900-1200 ℃ in an inert atmosphere, and keeping the temperature for 0.5-2h;
the pre-oxidation process comprises controlling the heating rate at 0.5-2 deg.C for min -1 ；
In the carbonization process, the heating rate is controlled to be 4-10 ℃ for min -1 。
In a specific embodiment, the invention also provides a carbon fiber material loaded on the homologous heterogeneous interface structure, which comprises a carbon material substrate and a composite material loaded on the carbon material substrate and having the homologous heterogeneous interface structure;
the composite material with the homologous heterogeneous interface structure is a composite material with a heterogeneous structure, which is composed of transition metal or alloy and sulfide thereof, and has a general formula of M/M x S y (ii) a Wherein M is a metal simple substance or an alloy, M x S y Is a metal sulfide corresponding to a metal simple substance or an alloy; the M/M x S y In the composite material, the heterogeneous interface structure of the metal simple substance or alloy and the corresponding sulfide is an AB left-right type interface structure, but not a core-shell structure or an atom-doped structure.
Examples
The following examples will be described in detail, which are carried out on the premise of the technical solution of the present application, and detailed embodiments and specific operation procedures are given, but the scope of the present application is not limited to the following examples.
Example 1
This example provides a homogeneous heterointerface Co/Co 9 S 8 The preparation method of the loaded carbon nanofiber composite material comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of the Polyacrylonitrile (PAN) to the N, N-Dimethylformamide (DMF) is 1:9;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 25kV, the distance between the needle tip and the collector is 15cm, and the solution flow rate is 1mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrospun nanofibers in a tube furnace at room temperature for 1 min -1 Is heated to 270 ℃ for 2h for pre-oxidation and then, is kept at 5 ℃ for min in an inert atmosphere -1 Heating to 1000 ℃, keeping for 1h for carbonization, naturally cooling to room temperature to obtain electrostatic spinning carbon nanofiber, and cutting into 1 x 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in a mixed water solution of cobalt acetate tetrahydrate and thiourea with the concentration of 200mM (the concentration ratio of the cobalt acetate tetrahydrate to the thiourea is 1), taking out after 3h soaking, and drying in vacuum at 60 ℃ to obtain a cobalt salt and thiourea-loaded electrostatic spinning carbon nanofiber membrane;
(5) Connecting metal cobalt salt and thiourea-loaded electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and sticking the carbon nanofiber membranes on a glass slide by conductive silver adhesive, electrifying the glass slide in a glove box for 1s (the voltage applied by electrifying is 20V, and the current is about 7.5A) to obtain Co/Co 9 S 8 Supported carbonNanofiber composites (Co/Co) 9 S 8 -CNF)。
Co/Co prepared in this example 9 S 8 Carbon nanofiber-loaded composite (Co/Co) 9 S 8 CNF) is shown in FIG. 1 (a), and it can be seen that Co/Co with heterogeneous interface is uniformly distributed on the surface of the carbon nanofiber 9 S 8 And (3) nanoparticles.
Co/Co 9 S 8 HRTEM images of the carbon nanofiber-loaded composite are shown in FIGS. 1 (b) and 1 (c), from which a single Co/Co can be seen 9 S 8 The presence of a heterogeneous interface in the nanoparticle; the lattice spacing at the upper left corner in FIG. 1 (c) is 0.57nm, corresponding to Co 9 S 8 The lattice spacing in the lower right corner of the (111) plane of (C) is 0.20nm, which corresponds to the (111) plane of Co.
Co/Co 9 S 8 The XRD pattern of the carbon nanofiber-loaded composite material is shown in figure 1 (d), wherein two peaks in a dotted line part correspond to the (111) crystal face and the (200) crystal face of Co at 44.216 degrees and 51.522 degrees respectively, and the rest peaks correspond to the Co at 15.447 degrees, 29.825 degrees, 31.184 degrees, 39.536 degrees, 47.554 degrees and 52.071 degrees respectively 9 S 8 The (111), (311), (222), (331), (511), (440) crystal planes of (A), and the results of HRTEM images are consistent.
Co/Co 9 S 8 Co/Co in loaded carbon nano-fiber composite material 9 S 8 The HAADF of the nanoparticles is shown in FIG. 1 (e), which shows two areas of different contrast, the black oval area having a high position contrast, corresponding to Co, and the remainder being Co 9 S 8 。
To Co/Co 9 S 8 EDS linear scanning (in the direction of white straight line in FIG. 1 (e)) is carried out on the nano-particles to obtain a linear scanning image in FIG. 1 (f), and the peak positions of Co element and S element can be seen from the linear scanning image, thereby further proving that Co/Co in the particles is different from that of the S element 9 S 8 The presence of a heterogeneous interface.
Co/Co prepared in this example 9 S 8 OER electrocatalytic activity tests carried out on-CNF gave the OER-LSV curve shown in FIG. 2, from which it can be seen that at a current density of 10mA cm -2 Co/Co 9 S 8 the-CNF showed an overpotential of 290mV, which is superior to that of Co-CNF (361 mV) prepared in comparative example 1 and Co prepared in comparative example 2 9 S 8 CNF (308 mV) and commercial IrO 2 (377 mV). It can be seen that the Co/Co with homogeneous heterogeneous interface prepared in this example 9 S 8 the-CNF catalyst has more excellent OER electrocatalytic activity.
Example 2
This example provides a homogeneous-heterogeneous interface Ni/Ni 3 S 2 The preparation method of the loaded carbon nanofiber composite material comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of Polyacrylonitrile (PAN) to N, N-Dimethylformamide (DMF) is 1:9;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 25kV, the distance between the needle tip and the collector is 15cm, and the solution flow rate is 1mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrospun nanofibers in a tube furnace at room temperature for 1 min -1 Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere -1 Heating to 1000 ℃, keeping for 1h for carbonization, naturally cooling to room temperature to finally obtain electrostatic spinning carbon nanofibers, and cutting into 1 x 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in a mixed aqueous solution of nickel acetate tetrahydrate and thiourea with the concentration of 200mM (the concentration ratio of the nickel acetate tetrahydrate to the thiourea is 1), taking out the carbon nanofiber after soaking for 3h, and drying the carbon nanofiber at the temperature of 60 ℃ in vacuum to obtain a nickel salt and thiourea-loaded electrostatic spinning carbon nanofiber membrane;
(5) Connecting metal nickel salt and thiourea-loaded electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and sticking the carbon nanofiber membranes on a glass slide by conductive silver adhesive, electrifying the glass slide in a glove box for 1s (the voltage applied by electrifying is 20V, and the current is about 7.5A) to obtain Ni/Ni 3 S 2 Supported carbon nanoA rice fiber composite material.
Ni/Ni prepared in this example 3 S 2 The characterization result of the carbon nanofiber-loaded composite shows that: the surface of the carbon nano fiber is uniformly distributed with Ni/Ni with a heterogeneous interface structure with an AB left-right type interface 3 S 2 And (3) nanoparticles. The OER electrocatalytic activity results are shown in FIG. 3: at a current density of 10mA cm -2 Ni/Ni 3 S 2 CNF exhibits an overpotential of 232 mV.
Example 3
The embodiment provides a preparation method of a homologous heterogeneous interface Fe/FeS loaded carbon nanofiber composite material, which comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of Polyacrylonitrile (PAN) to N, N-Dimethylformamide (DMF) is 1:9;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 25kV, the distance between the needle tip and the collector is 15cm, and the solution flow rate is 1mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrospun nanofibers in a tube furnace at room temperature for 1 min -1 Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere -1 Heating to 1000 ℃, keeping for 1h for carbonization, naturally cooling to room temperature to obtain electrostatic spinning carbon nanofiber, and cutting into 1 x 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in a mixed aqueous solution of anhydrous ferrous acetate and thiourea (the concentration ratio of the anhydrous ferrous acetate to the thiourea is 1) with the concentration of 200mM for 3h, taking out the carbon nanofiber and drying the carbon nanofiber at the temperature of 60 ℃ in vacuum to obtain a ferrite and thiourea loaded electrostatic spinning carbon nanofiber membrane;
(5) And connecting the metal iron salt and the thiourea-loaded electrostatic spinning carbon nanofiber membrane at two ends of a power line, tiling and pasting the membrane on a glass slide by conductive silver adhesive, and electrifying the membrane in a glove box for 1s (the voltage applied by electrifying is 20V, and the current is about 7.5A), thereby obtaining the Fe/FeS-loaded carbon nanofiber composite material.
The characterization result of the Fe/FeS loaded carbon nanofiber composite material prepared in this example shows that: fe/FeS nano particles with a heterogeneous interface structure of an AB left-right type interface are uniformly distributed on the surface of the carbon nano fiber. The OER electrocatalytic activity results are shown in FIG. 3: at a current density of 10mA cm -2 Fe/FeS-CNF showed 359mV overpotential.
Example 4
The embodiment provides a preparation method of a homogeneous heterogeneous interface FeCo/(FeCo) S loaded carbon nanofiber composite material, which comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of Polyacrylonitrile (PAN) to N, N-Dimethylformamide (DMF) is 1:9;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 25kV, the distance between the needle point and the collector is 15cm, and the solution flow rate is 1mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrospun nanofibers in a tube furnace at room temperature for 1 min -1 Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere -1 Heating to 1000 ℃, keeping for 1h for carbonization, naturally cooling to room temperature to finally obtain electrostatic spinning carbon nanofibers, and cutting into 1 x 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in a mixed aqueous solution of 100mM cobalt acetate tetrahydrate, 100mM ferrous acetate tetrahydrate and 200mM thiourea, taking out after soaking for 3h, and drying at 60 ℃ in vacuum to obtain a metal salt and thiourea-loaded electrostatic spinning carbon nanofiber membrane;
(5) Connecting metal salt and thiourea-loaded electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and pasting the metal salt and thiourea-loaded electrostatic spinning carbon nanofiber membranes on a glass slide by conductive silver adhesive, and electrifying the glass slide in a glove box for 1S (the voltage applied by electrifying is 20V, and the current is about 7.5A), thereby obtaining the FeCo/(FeCo) S-loaded carbon nanofiber composite material.
The characterization result of the FeCo/(FeCo) S-supported carbon nanofiber composite (FeCo/(FeCo) S-CNF) prepared in this example shows: feCo/(FeCo) S nanoparticles having a heterogeneous interface structure of an AB left-right type structure are uniformly distributed on the surface of the carbon nanofiber. The OER electrocatalytic activity results are shown in FIG. 4: at a current density of 10mA cm -2 FeCo/(FeCo) S-CNF showed an overpotential of 287 mV.
Example 5
This example provides a homogeneous heterogeneous interface FeNi/(FeNi) 9 S 8 The preparation method of the loaded carbon nanofiber composite material comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of Polyacrylonitrile (PAN) to N, N-Dimethylformamide (DMF) is 1:9;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 25kV, the distance between the needle point and the collector is 15cm, and the solution flow rate is 1mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrospun nanofibers in a tube furnace at room temperature for 1 min -1 Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere -1 Heating to 1000 ℃, keeping for 1h for carbonization, naturally cooling to room temperature to obtain electrostatic spinning carbon nanofiber, and cutting into 1 x 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in 100mM nickel acetate tetrahydrate, 100mM ferrous acetate tetrahydrate and 200mM thiourea mixed aqueous solution for 3h, taking out, and drying at 60 ℃ in vacuum to obtain a metal salt and thiourea-loaded electrostatic spinning carbon nanofiber membrane;
(5) Connecting metal salt and thiourea-loaded electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and sticking the metal salt and thiourea-loaded electrostatic spinning carbon nanofiber membranes on a glass slide by conductive silver adhesiveThe glove box was energized for 1s (the applied voltage was 20V, and the current was about 7.5A) to obtain FeNi/(FeNi) 9 S 8 A carbon nanofiber-loaded composite.
FeNi/(FeNi) prepared in this example 9 S 8 Carbon nanofiber composite material (FeNi/(FeNi) 9 S 8 CNF) characterization results show: the surface of the carbon nano fiber is uniformly distributed with FeNi/(FeNi) with a heterogeneous interface structure with an AB left and right structure 9 S 8 And (3) nanoparticles. The OER electrocatalytic activity results are shown in FIG. 4: at a current density of 10mA cm -2 Times FeNi/(FeNi) 9 S 8 CNF showed an overpotential of 269 mV.
Example 6
This example provides a homogeneous heterogeneous interface CoNi/(CoNi) 9 S 8 The preparation method of the loaded carbon nanofiber composite material comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of Polyacrylonitrile (PAN) to N, N-Dimethylformamide (DMF) is 1:9;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 25kV, the distance between the needle point and the collector is 15cm, and the solution flow rate is 1mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrostatic spinning nanofiber in a tube furnace, and heating the electrostatic spinning nanofiber at room temperature for 1 ℃ min -1 Is heated to 270 ℃ for 2h for pre-oxidation and then, is kept at 5 ℃ for min in an inert atmosphere -1 Heating to 1000 ℃, keeping for 1h for carbonization, naturally cooling to room temperature to obtain electrostatic spinning carbon nanofiber, and cutting into 1 x 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in a mixed aqueous solution of 100mM cobalt acetate tetrahydrate, 100mM nickel acetate tetrahydrate and 200mM thiourea, taking out after soaking for 3h, and drying at 60 ℃ in vacuum to obtain a metal salt and thiourea-loaded electrostatic spinning carbon nanofiber membrane;
(5) Connecting metal salt and thiourea-loaded electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and sticking the carbon nanofiber membranes on a glass slide by conductive silver adhesive, electrifying the glass slide in a glove box for 1s (the voltage applied by electrifying is 20V, and the current is about 7.5A), and obtaining CoNi/(CoNi) 9 S 8 A carbon nanofiber-loaded composite.
CoNi/(CoNi) prepared in this example 9 S 8 Carbon nanofiber composite material (CoNi/(CoNi) 9 S 8 CNF) characterization results show: the surface of the carbon nano fiber is uniformly distributed with CoNi/(CoNi) with a heterogeneous interface structure with an AB left and right structure 9 S 8 And (3) nanoparticles. The OER electrocatalytic activity results are shown in FIG. 4: at a current density of 10mA cm -2 Time CoNi/(CoNi) 9 S 8 the-CNF showed an overpotential of 333 mV.
Example 7
This example provides a homogeneous heterogeneous interface FeCoNi/(FeCoNi) 9 S 8 The preparation method of the loaded carbon nanofiber composite material comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of the Polyacrylonitrile (PAN) to the N, N-Dimethylformamide (DMF) is 1:9;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 25kV, the distance between the needle tip and the collector is 15cm, and the solution flow rate is 1mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrostatic spinning nanofiber in a tube furnace, and heating the electrostatic spinning nanofiber at room temperature for 1 ℃ min -1 Is heated to 270 ℃ for 2h for pre-oxidation and then, is kept at 5 ℃ for min in an inert atmosphere -1 Heating to 1000 ℃, keeping for 1h for carbonization, naturally cooling to room temperature to obtain electrostatic spinning carbon nanofiber, and cutting into 1 x 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in 66.7mM cobalt acetate tetrahydrate, 66.7mM nickel acetate tetrahydrate and 66.7mM ferrous acetate tetrahydrate and 200mM thiourea mixed aqueous solution for 3h, taking out the mixture, and drying the mixture in vacuum at 60 ℃ to obtain a metal salt and thiourea-loaded electrostatic spinning carbon nanofiber membrane;
(5) Connecting metal salt and thiourea-loaded electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and pasting the carbon nanofiber membranes on a glass slide by conductive silver adhesive, electrifying the glass slide in a glove box for 1s (the voltage applied by electrification is 20V, and the current is about 7.5A), and obtaining FeCoNi/(FeCoNi) 9 S 8 A carbon nanofiber-loaded composite.
FeCoNi/(FeCoNi) prepared by this example 9 S 8 Carbon nanofiber composite material (FeCoNi/(FeCoNi) 9 S 8 -CNF) is shown in FIG. 5 (a) and a TEM is shown in FIG. 5 (b), from which it can be seen that FeCoNi/(FeCoNi) having a heterogeneous interface is uniformly distributed on the surface of the carbon nanofibers 9 S 8 And (3) nanoparticles.
FeCoNi/(FeCoNi) 9 S 8 An HRTEM image of the carbon nanofiber-loaded composite material is shown in FIG. 5 (c), from which it can be seen that a single FeCoNi/(FeCoNi) 9 S 8 The presence of a heterogeneous interface in the nanoparticle; the lattice spacing on the left side in FIG. 5 (c) is 0.57nm, corresponding to (FeCoNi) 9 S 8 The lattice spacing of the upper right corner of the (111) crystal plane of FeCoNi is 0.20nm corresponding to the (111) crystal plane of FeCoNi.
FeCoNi/(FeCoNi) 9 S 8 The XRD pattern of the carbon nanofiber-loaded composite material is shown in FIG. 5 (d), in which the peak marked by the dotted line corresponds to the (111) crystal plane of CoFeNi at 44.216 deg., and the other peaks correspond to (Co, fe, ni) at 15.397 deg., 29.675 deg., 31.048 deg., 39.347 deg., 47.357 deg. and 51.814 deg., respectively 9 S 8 The (111), (311), (222), (331), (511), (440) crystal planes of (A) are in agreement with the results of HRTEM images.
FeCoNi/(FeCoNi) 9 S 8 The HAADF image of the loaded carbon nanofiber composite is shown in FIG. 5 (e), which shows two areas with different contrast, the black oval area has high contrast, corresponding to CoFeNi, and the rest is (Co, fe, ni) 9 S 8 。
For FeCoNi/(FeCoNi) 9 S 8 The particles were subjected to EDS linear scanning (in the direction of the white straight line in FIG. 5 (e)) to obtain a linear scanning pattern in FIG. 5 (f), from which the peak positions of Fe, co, ni elements and S elements were different, further confirming FeCoNi/(FeCoNi) in the particles 9 S 8 The presence of a heterogeneous interface.
FeCoNi/(FeCoNi) prepared in this example 9 S 8 CNF was subjected to OER electrocatalytic activity test, whose OER electrocatalytic activity results are shown in fig. 6: at a current density of 10mA cm -2 Hour FeCoNi/(FeCoNi) 9 S 8 The CNF showed an overpotential of 236 mV.
Example 8
This example provides a homogeneous heterointerface Co/Co 9 S 8 The preparation method of the loaded carbon nanofiber composite material comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of Polyacrylonitrile (PAN) to N, N-Dimethylformamide (DMF) is 1:10;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 26kV, the distance between the needle point and the collector is 16cm, and the solution flow rate is 0.5mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrospun nanofibers in a tube furnace at 0.5 deg.C for min from room temperature -1 Is heated to 260 ℃ for 0.5h for pre-oxidation and then is kept at 4 ℃ for min in an inert atmosphere -1 Heating to 900 ℃, keeping for 1h for carbonization, naturally cooling to room temperature to obtain electrostatic spinning carbon nanofiber, and cutting into 1 x 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in a mixed aqueous solution of cobalt acetate tetrahydrate and thiourea with the concentration of 100mM (the concentration ratio of the cobalt acetate tetrahydrate to the thiourea is 1), taking out the carbon nanofiber membrane after soaking for 4h, and drying the carbon nanofiber membrane at the temperature of 60 ℃ in vacuum to obtain a cobalt salt and thiourea-loaded electrostatic spinning carbon nanofiber membrane;
(5) Connecting metal cobalt salt and thiourea-loaded electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and pasting the carbon nanofiber membranes on a glass slide by conductive silver adhesive, electrifying the glass slide in a glove box for 0.5s (the voltage applied by electrifying is 25V, and the current is about 10A), and obtaining Co/Co 9 S 8 Carbon nanofiber loaded composite (Co/Co) 9 S 8 -CNF)。
Co/Co prepared in this example 9 S 8 Carbon nanofiber-loaded composite (Co/Co) 9 S 8 -CNF-300 mM) with Co/Co prepared in example 1 9 S 8 The loaded carbon nanofiber composites were substantially uniform. The OER electrocatalytic activity test is shown in FIG. 7, at a current density of 10mA cm -2 Co/Co prepared in this example 9 S 8 The overpotential of-CNF-300 mM is 329mV.
Example 9
This example provides a Co/Co homogeneous heterointerface 9 S 8 The preparation method of the loaded carbon nanofiber composite material comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of Polyacrylonitrile (PAN) to N, N-Dimethylformamide (DMF) is 1:10;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 20kV, the distance between the needle tip and the collector is 12cm, and the solution flow rate is 2.5mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrostatic spinning nanofiber in a tube furnace at room temperature for 2 min -1 Is heated to 250 ℃ and kept for 1h for pre-oxidation, and then is heated for 10 min in an inert atmosphere -1 Heating to 1200 ℃, keeping for 0.5h for carbonization, naturally cooling to room temperature to obtain electrostatic spinning carbon nanofiber, and cutting into 1 x 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in a mixed aqueous solution of 300mM cobalt acetate tetrahydrate and thiourea (the concentration ratio of the cobalt acetate tetrahydrate to the thiourea is 1), taking out the carbon nanofiber membrane after soaking for 2h, and drying the carbon nanofiber membrane at 60 ℃ in vacuum to obtain a cobalt salt and thiourea-loaded electrostatic spinning carbon nanofiber membrane;
(5) Connecting metal cobalt salt and thiourea-loaded electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and sticking the carbon nanofiber membranes on a glass slide by conductive silver adhesive, electrifying the glass slide in a glove box for 1s (the voltage applied by electrifying is 15V, and the current is about 3A) to obtain Co/Co 9 S 8 Carbon nanofiber-loaded composite (Co/Co) 9 S 8 -CNF)。
Co/Co prepared in this example 9 S 8 Carbon nanofiber loaded composite (Co/Co) 9 S 8 -CNF-100 mM) with Co/Co prepared in example 1 9 S 8 The loaded carbon nanofiber composites were substantially uniform. The OER electrocatalytic activity is shown in FIG. 7, at a current density of 10mA cm -2 Co/Co prepared in this example 9 S 8 The overpotential of-CNF-100 mM is 303mV.
Comparative example 1
The comparative example provides a preparation method of a Co particle-loaded carbon nanofiber composite material, which comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of Polyacrylonitrile (PAN) to N, N-Dimethylformamide (DMF) is 1:9;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 25kV, the distance between the needle tip and the collector is 15cm, and the solution flow rate is 1mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrostatic spinning nanofiber in a tube furnace, and heating the electrostatic spinning nanofiber at room temperature for 1 ℃ min -1 Is heated to 270 ℃ for 2h for pre-oxidation and then, is kept at 5 ℃ for min in an inert atmosphere -1 Heating to 1000 deg.C, maintaining for 1h, carbonizing, naturally cooling to room temperature to obtain electrostatic spinning carbon nanofiber, and shearingForming into 1 × 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in 200mM cobalt acetate tetrahydrate aqueous solution, taking out after soaking for 3 hours, and drying at 60 ℃ in vacuum to obtain a cobalt salt supported electrostatic spinning carbon nanofiber membrane;
(5) And connecting the metal cobalt salt loaded electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and pasting the metal cobalt salt loaded electrostatic spinning carbon nanofiber membranes on a glass slide by conductive silver adhesive, and electrifying the glass slide in a glove box for 1s (the voltage applied by electrifying is 20V, and the current is about 7.5A) to obtain the Co particle loaded carbon nanofiber composite material (Co-CNF). The results of the OER-LSV curve of the obtained Co-CNF are shown in FIG. 2.
Comparative example 2
This comparative example provides a Co 9 S 8 The preparation method of the particle-loaded carbon nanofiber composite material comprises the following steps:
(1) Preparing an electrostatic spinning solution: dissolving Polyacrylonitrile (PAN) in N, N-Dimethylformamide (DMF), and stirring to obtain a homogeneous solution, wherein the mass ratio of Polyacrylonitrile (PAN) to N, N-Dimethylformamide (DMF) is 1:9;
(2) Transferring the homogeneous solution into an injector, and carrying out electrostatic spinning by using an electrostatic spinning machine, wherein the working parameters of the electrostatic spinning are as follows: the working voltage is 25kV, the distance between the needle tip and the collector is 15cm, and the solution flow rate is 1mL h -1 Obtaining white felty electrostatic spinning nano-fiber;
(3) Placing the electrostatic spinning nanofiber in a tube furnace, and heating the electrostatic spinning nanofiber at room temperature for 1 ℃ min -1 Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere -1 Heating to 1000 ℃, keeping for 1h for carbonization, naturally cooling to room temperature to obtain electrostatic spinning carbon nanofiber, and cutting into 1 x 2cm for later use;
(4) Soaking 1 x 2cm carbon nanofiber in a mixed aqueous solution of 200mM cobalt acetate tetrahydrate and 400mM thiourea, taking out the mixture after soaking for 3 hours, and drying the mixture in vacuum at 60 ℃ to obtain a metal cobalt salt and thiourea-loaded electrostatic spinning carbon nanofiber membrane;
(5) Loading metal cobalt salt and thiourea on electrostatic spinning carbon nanoThe rice fiber membrane is connected at two ends of the power line, is tiled and stuck on the glass slide by conductive silver adhesive, and is electrified for 1s in the glove box (the electrified applied voltage is 10V, the current is about 2A), so as to obtain the Co particle loaded carbon nanofiber composite material (Co particle loaded carbon nanofiber composite material) 9 S 8 -CNF). Obtained Co 9 S 8 The results of OER-LSV curve of-CNF are shown in FIG. 2.
The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.
Claims (7)
1. A carbon fiber material loaded with a homologous heterogeneous interface structure is characterized by comprising a carbon material substrate and a composite material loaded with the homologous heterogeneous interface structure on the carbon material substrate;
the composite material with the homologous heterogeneous interface structure is a composite material with a heterogeneous structure, which is composed of transition metal or alloy and sulfide thereof, and has a general formula of M/M x S y (ii) a Wherein M is a simple metal or an alloy, M x S y Is sulfide corresponding to metal simple substance or alloy; the M/M x S y In the composite material, the heterogeneous interface structure of the metal simple substance or alloy and the corresponding sulfide is an AB left-right type interface structure, but not a core-shell structure or an atom doped structure;
wherein the homoeogous heterointerface structure composite is prepared by a process comprising the steps of:
A. preparing a carbon fiber substrate loaded metal salt and a thiourea precursor: soaking the carbon fiber substrate in a mixed aqueous solution of metal salt and thiourea to obtain metal salt and thiourea-loaded carbon fibers;
B. preparing a homologous heterogeneous interface composite material: connecting metal salt and thiourea-loaded carbon fibers with an external circuit, and instantly electrifying to obtain the homologous heterogeneous interface composite material;
the specific method of the step B comprises the following steps:
connecting metal salt and thiourea-loaded carbon fiber at two ends of a power line in a glove box in argon environment, flatly spreading on an insulating glass plate, and electrifying for 0.5-1s to obtain M x S y A homogeneous heterogeneous interface structure composite material of the system;
in the step B, the voltage applied by electrifying is 15-25V, and the current is 2-10A.
2. The carbon fiber material loaded on the homologous heterogeneous interface structure according to claim 1, wherein M is selected from one simple metal or an alloy consisting of two or more metals selected from Co, ni and Fe.
3. The homoeogenic heterointerface structure-supported carbon fiber material according to claim 1 or 2, wherein said M/M is selected from the group consisting of x S y Selected from Fe/Fe x S y , Co/Co x S y ，Ni/Ni x S y ，FeNi/(FeNi) x S y , FeCo/(FeCo) x S y ，NiCo/(NiCo) x S y ，FeNiCo/(FeNiCo) x S y Any one of them.
4. A method for preparing a carbon fiber material loaded with a homologous heterogeneous interface structure according to claim 1, comprising the following steps:
A. preparing a carbon fiber substrate loaded metal salt and a thiourea precursor: soaking the carbon fiber substrate in a mixed aqueous solution of metal salt and thiourea to obtain metal salt and thiourea-loaded carbon fibers;
B. preparing a homologous heterogeneous interface composite material: connecting metal salt and thiourea-loaded carbon fibers with an external circuit, and instantaneously electrifying to obtain the homologous heterogeneous interface composite material;
the specific method of the step B comprises the following steps:
connecting metal salt and thiourea-loaded carbon fiber to a power supply in a glove box in an argon environmentTwo ends of the wire are flatly laid on the insulating glass plate and electrified for 0.5-1s to obtain M x S y A homogeneous heterogeneous interface structure composite of the system;
in the step B, the voltage applied by electrifying is 15-25V, and the current is 2-10A.
5. The method according to claim 4, wherein the concentration of the mixed aqueous solution of the metal salt and thiourea in step A is 100 to 300mM; in the mixed aqueous solution of the metal salt and the thiourea, the molar concentration ratio of the metal salt to the thiourea is 1.
6. The method according to claim 4, wherein in step A, the metal in the metal salt is selected from one or more of cobalt, nickel and iron, and the salt is selected from at least one of acetate, nitrate and acetylacetonate.
7. The method according to claim 4, wherein in the step A, the diameter of the carbon fiber substrate is 200-500nm, and the carbon fiber is carbon nanofiber.
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