CN114210345A - Homologous heterogeneous interface structure composite material and preparation method thereof - Google Patents
Homologous heterogeneous interface structure composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114210345A CN114210345A CN202111400507.2A CN202111400507A CN114210345A CN 114210345 A CN114210345 A CN 114210345A CN 202111400507 A CN202111400507 A CN 202111400507A CN 114210345 A CN114210345 A CN 114210345A
- Authority
- CN
- China
- Prior art keywords
- composite material
- metal
- alloy
- thiourea
- loaded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title abstract description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 140
- 229910052751 metal Inorganic materials 0.000 claims abstract description 109
- 239000002184 metal Substances 0.000 claims abstract description 107
- 239000000956 alloy Substances 0.000 claims abstract description 48
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 46
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 33
- 239000004917 carbon fiber Substances 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 27
- 229910016323 MxSy Inorganic materials 0.000 claims abstract description 26
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 239000002134 carbon nanofiber Substances 0.000 claims description 154
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 130
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 65
- 150000003839 salts Chemical class 0.000 claims description 43
- 238000002791 soaking Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 239000011521 glass Substances 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 229910002546 FeCo Inorganic materials 0.000 claims description 22
- 229910002555 FeNi Inorganic materials 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 20
- 239000011258 core-shell material Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 229910003266 NiCo Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000003575 carbonaceous material Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910002463 CoxSy Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 19
- 239000002105 nanoparticle Substances 0.000 abstract description 16
- 229910052976 metal sulfide Inorganic materials 0.000 abstract description 9
- 238000010041 electrostatic spinning Methods 0.000 description 108
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 94
- 229920002239 polyacrylonitrile Polymers 0.000 description 48
- 239000012528 membrane Substances 0.000 description 34
- 229910002545 FeCoNi Inorganic materials 0.000 description 33
- 239000002121 nanofiber Substances 0.000 description 30
- 239000012456 homogeneous solution Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 21
- 238000007254 oxidation reaction Methods 0.000 description 21
- 230000003647 oxidation Effects 0.000 description 20
- 238000003763 carbonization Methods 0.000 description 17
- 229910002441 CoNi Inorganic materials 0.000 description 12
- 150000001868 cobalt Chemical class 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000001035 drying Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 5
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- WXEICPMZIKLINJ-UHFFFAOYSA-L iron(2+) diacetate tetrahydrate Chemical compound O.O.O.O.[Fe+2].CC([O-])=O.CC([O-])=O WXEICPMZIKLINJ-UHFFFAOYSA-L 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019233 CoFeNi Inorganic materials 0.000 description 2
- 102000020897 Formins Human genes 0.000 description 2
- 108091022623 Formins Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910016285 MxNy Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 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
- 239000012300 argon atmosphere 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
- 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
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 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
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
-
- 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
- B01J35/58—Fabrics or filaments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
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 sulfidexSyComposite nanoparticles; wherein M is a metal simple substance or an alloy, MxSyIs sulfide corresponding to metal simple substance or alloy; the M/MxSyIn 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 voltagexSyHeterostructured composite nanoparticles, and highly dispersed, resulting metalsThe heterogeneous interface of the simple substance/alloy and the metal sulfide is an AB left-right type interface, so that the active sites of the simple substance/alloy and the metal sulfide 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 can not only keep the advantages and properties of the original component materials, but also play a synergistic role among the component materials. A heterogeneous interface formed by combining two or more components brings 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 multi-step reactions are often required, most of the reactions are firstly synthesizing a compound and then carrying out subsequent synthesis on the basis of the compound, and the obtained compound is not 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 the publication "Applied catalysts B: Environmental" Vol. 172-173, pp. 58-64 of "Structure-reactivity relationships of Ni-NiO core-shell co-catalysts on Ta 2015 8/8)2O5for 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 cobalt salt and thiourea in an organic solvent in proportion, then carrying out solvothermal reaction on the dispersion 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/MxSy(ii) a Wherein M is a metal simple substance or an alloy, MxSyIs a metal sulfide corresponding to a metal simple substance or an alloy; the M-MxSyIn 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, said M/MxSySelected from Fe/FexSy,Co/CoxSy,Ni/NixSy,FeNi/(FeNi)xSy, FeCo/(FeCo)xSy,NiCo/(NiCo)xSy,FeNiCo/(FeNiCo)xSyAny 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 100-300 mM; 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: 1.
Preferably, in the step A, the soaking time is 2-4 h.
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:
in a glove box under argon atmosphere, adding goldConnecting the metal salt and thiourea-loaded carbon fiber at two ends of power line, spreading on insulating glass plate, and electrifying for 0.5-1s to obtain MxSyThe 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: 9-10;
the electrostatic spinning adopts the following working parameter conditions: working voltage is 20-26kV, distance between needle point and collector is 12-16cm, flow rate of 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 the temperature for 0.5-2 h;
the specific conditions of the carbonization treatment are as follows: heating the electrostatic spinning nano-fiber subjected to pre-oxidation treatment to 900-1200 ℃ in an inert atmosphere, and keeping the temperature for 0.5-1 h;
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 consisting of transition metal or alloy and sulfide thereofMaterial of the general formula M/MxSy(ii) a Wherein M is a metal simple substance or an alloy, MxSyIs a metal sulfide corresponding to a metal simple substance or an alloy; the M/MxSyIn 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/MxSySelected from Fe/FexSy,Co/CoxSy,Ni/NixSy,FeNi/(FeNi)xSy, FeCo/(FeCo)xSy,NiCo/(NiCo)xSy,FeNiCo/(FeNiCo)xSyAny one of them.
Compared with the prior art, the invention has the following beneficial effects:
1) the invention quickly grows M/M on the surface of the carbon nanofiber by regulating and controlling the process parameters such as working voltage, synthesis temperature and the like by a systemxSyThe 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 inventionxSyThe 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 the non-limiting embodiments with reference to the following drawings:
FIG. 1 shows Co/Co prepared in example 1 of the present invention9S8Carbon nanofiber-loaded composite (Co/Co)9S8-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 invention9S8-CNF and Co-CNF, Co prepared in comparative example9S8CNF and commercial IrO2OER-LSV curve of (1);
FIG. 3 shows Ni/Ni prepared in example 23S2OER-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 59S8CNF, NiCo/(NiCo) prepared in example 69S8-OER-LSV curve of CNF;
FIG. 5 shows FeCoNi/(FeCoNi) prepared in example 79S8-characterization results 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 79S8-OER-LSV curve of CNF;
and, FIG. 7 shows Co/Co prepared in examples 8 and 99S8-CNF-100mM、Co/Co9S8CNF-OER-LSV curve at 300 mM.
Detailed Description
Unless otherwise defined, technical or scientific terms used in the specification and claims should have the ordinary meaning as understood by those 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 between the lowest value and the highest value in increments of one unit when there is more than two units difference 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 may be made to the embodiments by those skilled in the art without departing from the spirit and scope of the present application, and the resulting embodiments are 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/MxSy(ii) a Wherein M is a metal simple substance or an alloy, MxSyIs a metal sulfide corresponding to a metal simple substance or an alloy; the M/MxSyIn 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/MxSySelected from Fe/FexSy,Co/CoxSy,Ni/NixSy, FeNi/(FeNi)xSy,FeCo/(FeCo)xSy,NiCo/(NiCo)xSy,FeNiCo/(FeNiCo)xSyAny 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, there is also provided a method for preparing a homoeogous heterointerface composite material, 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: 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 carbon fiber is soaked in the mixed solution of metal salt and thiourea and then is electrified instantaneously, so that metal/alloy sulfide is firstly generated on the surface of the carbon fiber in the process, and the sulfide is reduced into metal/alloy under the action of carbothermic reduction, and finally a homologous heterogeneous interface is generated. The formation mechanism is that sulfide is generated in the precursor at the middle temperature section, the sulfide facing the high temperature section is reduced into metal at the high temperature section, the sulfide facing the high temperature section is kept stable, and the interface structure is stably kept due to the characteristic of rapid temperature reduction.
In one embodiment, in step A, the concentration of the mixed aqueous solution of the metal salt and the thiourea is 100-300 mM; 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: 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 one embodiment, in step a, the diameter of the carbon fiber substrate is 200-500nm, and the carbon fiber is a carbon nanofiber.
In one 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 spreading on an insulating glass plate, and electrifying for 0.5-1s to obtain MxSyThe 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 small, all metal sulfides or alloy sulfides are formed on the surface of the carbon nanofibers at an applied voltage of 10V, and a homogeneous heterogeneous 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: 9-10;
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 nano-fiber to 250-270 ℃ and keeping the temperature for 1-2 h;
the specific conditions of the carbonization treatment are as follows: heating the electrostatic spinning nano-fiber subjected to pre-oxidation treatment to 900-1200 ℃ in an inert atmosphere, and keeping the temperature for 0.5-2 h;
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。
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/MxSy(ii) a Wherein M is a metal simple substance or an alloy, MxSyIs a metal sulfide corresponding to a metal simple substance or an alloy; the M/MxSyIn 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/Co9S8The 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: working voltage 25kV, distance between needle point and collectorThe separation is 15cm, and the solution flow rate is 1mL h-1Obtaining white felty electrostatic spinning nano-fiber;
(3) placing the electrospun nanofibers in a tube furnace at room temperature for 1 min-1Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere-1Heating 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 of carbon nanofiber in a mixed aqueous solution of cobalt acetate tetrahydrate and thiourea with the concentration of 200mM (the concentration ratio of the cobalt acetate tetrahydrate to the thiourea is 1:1), taking out the carbon nanofiber after soaking for 3 hours, and drying the carbon nanofiber 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 1s (the voltage applied by electrifying is 20V, and the current is about 7.5A), and obtaining Co/Co9S8Carbon nanofiber-loaded composite (Co/Co)9S8-CNF)。
Co/Co prepared in this example9S8Carbon nanofiber-loaded composite (Co/Co)9S8CNF) 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 nanofiber9S8And (3) nanoparticles.
Co/Co9S8HRTEM images of the carbon nanofiber-loaded composite are shown in FIGS. 1(b) and 1(c), from which a single Co/Co can be seen9S8The 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 Co9S8The 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/Co9S8The 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 plane and the (200) crystal plane of Co at 44.216 degrees and 51.522 degrees respectively, and the rest arePeaks 15.447 °, 29.825 °, 31.184 °, 39.536 °, 47.554 ° and 52.071 ° correspond to Co, respectively9S8The (111), (311), (222), (331), (511), (440) crystal planes of (A) and (B) are consistent with the results of HRTEM images.
Co/Co9S8Co/Co in loaded carbon nanofiber composite material9S8The 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 Co9S8。
To Co/Co9S8EDS 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 particles9S8The presence of a heterogeneous interface.
Co/Co prepared in this example9S8OER 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-2Co/Co9S8the-CNF showed an overpotential of 290mV, which is superior to that of Co-CNF (361mV) prepared in comparative example 1 and Co prepared in comparative example 29S8CNF (308mV) and commercial IrO2(377 mV). It can be seen that the Co/Co with homogeneous heterointerface prepared in this example9S8the-CNF catalyst has more excellent OER electrocatalytic activity.
Example 2
This example provides a homogeneous heterointerface Ni/Ni3S2The 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: working voltage is 25kV, and the distance between the needle point and the collector is15cm, solution flow rate 1mL h-1Obtaining white felty electrostatic spinning nano-fiber;
(3) placing the electrospun nanofibers in a tube furnace at room temperature for 1 min-1Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere-1Heating 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 of 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 1:1), taking out the carbon nanofiber after soaking for 3 hours, 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 pasting the metal nickel salt and thiourea-loaded electrostatic spinning 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 Ni/Ni3S2A carbon nanofiber-loaded composite.
Ni/Ni prepared in this example3S2The 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 interface3S2And (3) nanoparticles. The OER electrocatalytic activity results are shown in FIG. 3: at a current density of 10mA cm-2Ni/Ni3S2The CNF showed 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, performing electrostatic spinning by using an electrostatic spinning machine,the working parameters of 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-1Obtaining white felty electrostatic spinning nano-fiber;
(3) placing the electrospun nanofibers in a tube furnace at room temperature for 1 min-1Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere-1Heating 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 of 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 1:1) with the concentration of 200mM, taking out the carbon nanofiber after soaking for 3 hours, 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-2Fe/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 performing electrostatic spinning by using an electrostatic spinning machineThe working parameters of 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-1Obtaining white felty electrostatic spinning nano-fiber;
(3) placing the electrospun nanofibers in a tube furnace at room temperature for 1 min-1Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere-1Heating 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 of 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-2FeCo/(FeCo) S-CNF showed an overpotential of 287 mV.
Example 5
This example provides a homogeneous heterogeneous interface FeNi/(FeNi)9S8The 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 solutionAnd (3) carrying out electrostatic spinning in an injector 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-1Obtaining white felty electrostatic spinning nano-fiber;
(3) placing the electrospun nanofibers in a tube furnace at room temperature for 1 min-1Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere-1Heating 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 of carbon nanofiber in a mixed aqueous solution of 100mM nickel acetate tetrahydrate, 100mM ferrous acetate tetrahydrate and 200mM thiourea, taking out the mixture after soaking for 3 hours, 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 load electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and pasting the metal salt and thiourea load electrostatic spinning 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 FeNi/(FeNi)9S8A carbon nanofiber-loaded composite.
FeNi/(FeNi) prepared in this example9S8Load carbon nanofiber composite material (FeNi/(FeNi)9S8CNF) 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 structure9S8And (3) nanoparticles. The OER electrocatalytic activity results are shown in FIG. 4: at a current density of 10mA cm-2Times FeNi/(FeNi)9S8CNF showed an overpotential of 269 mV.
Example 6
This example provides a homogeneous heterogeneous interface CoNi/(CoNi)9S8The 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-1Obtaining white felty electrostatic spinning nano-fiber;
(3) placing the electrospun nanofibers in a tube furnace at room temperature for 1 min-1Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere-1Heating 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 of carbon nanofiber in a mixed aqueous solution of 100mM cobalt acetate tetrahydrate, 100mM nickel acetate tetrahydrate and 200mM thiourea, taking out the mixture after soaking for 3 hours, 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 load electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and pasting the metal salt and thiourea load electrostatic spinning 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)9S8A carbon nanofiber-loaded composite.
CoNi/(CoNi) prepared by this example9S8Carbon nanofiber composite material (CoNi/(CoNi)9S8CNF) characterization results show: CoNi/(CoNi) with a heterogeneous interface structure with an AB left-right type structure is uniformly distributed on the surface of the carbon nanofiber9S8And (3) nanoparticles. The OER electrocatalytic activity results are shown in FIG. 4: at a current density of 10mA cm-2Time CoNi/(CoNi)9S8the-CNF showed an overpotential of 333 mV.
Example 7
This example provides a homogeneous heterogeneous interface FeCoNi/(FeCoNi)9S8Supported carbon nanoThe preparation method of the rice fiber 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-1Obtaining white felty electrostatic spinning nano-fiber;
(3) placing the electrospun nanofibers in a tube furnace at room temperature for 1 min-1Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere-1Heating 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 of carbon nanofiber in a mixed aqueous solution of 66.7mM of cobalt acetate tetrahydrate, 66.7mM of nickel acetate tetrahydrate, 66.7mM of ferrous acetate tetrahydrate and 200mM of thiourea, taking out the mixture after soaking for 3 hours, 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 load 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 electrifying is 20V, the current is about 7.5A), and obtaining FeCoNi/(FeCoNi)9S8A carbon nanofiber-loaded composite.
FeCoNi/(FeCoNi) prepared by this example9S8Carbon nanofiber composite material (FeCoNi/(FeCoNi)9S8-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 nanofibers9S8And (3) nanoparticles.
FeCoNi/(FeCoNi)9S8Load(s)An HRTEM image of the carbon nanofiber composite is shown in FIG. 5(c), from which it can be seen that FeCoNi/(FeCoNi)9S8The 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)9S8The 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)9S8The XRD pattern of the carbon nanofiber-loaded composite material is shown in FIG. 5(d), wherein the peak marked by the dotted line corresponds to the (111) crystal face of CoFeNi at 44.216 degrees, and the other peaks correspond to (Co, Fe, Ni) at 15.397 degrees, 29.675 degrees, 31.048 degrees, 39.347 degrees, 47.357 degrees and 51.814 degrees respectively9S8The (111), (311), (222), (331), (511), (440) crystal planes of (A) are in agreement with the results of HRTEM images.
FeCoNi/(FeCoNi)9S8The HAADF image of the carbon nanofiber-loaded composite is shown in FIG. 5(e), which shows two regions with different contrast, the black oval region has high position contrast, corresponding to CoFeNi, and the rest is (Co, Fe, Ni)9S8。
For FeCoNi/(FeCoNi)9S8The 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 particles9S8The presence of a heterogeneous interface.
FeCoNi/(FeCoNi) prepared in this example9S8CNF was subjected to OER electrocatalytic activity test, whose OER electrocatalytic activity results are shown in fig. 6: at a current density of 10mA cm-2Hour FeCoNi/(FeCoNi)9S8The CNF showed an overpotential of 236 mV.
Example 8
This example provides a homogeneous heterointerface Co/Co9S8The 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 tip and the collector is 16cm, and the solution flow rate is 0.5mL h-1Obtaining 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-1Is heated to 260 ℃ and kept for 0.5h for pre-oxidation, and then is heated for 4 ℃ min in an inert atmosphere-1Heating 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 of 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 1:1), taking out the carbon nanofiber after soaking for 4 hours, and drying the carbon nanofiber 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/Co9S8Carbon nanofiber-loaded composite (Co/Co)9S8-CNF)。
Co/Co prepared in this example9S8Carbon nanofiber-loaded composite (Co/Co)9S8CNF-300mM) with Co/Co prepared in example 19S8The loaded carbon nanofiber composites were substantially uniform. The OER electrocatalytic activity test is shown in FIG. 7, at a current density of 10mA cm-2Co/Co prepared in this example9S8The overpotential of-CNF-300 mM is 329 mV.
Example 9
This example provides a homogeneous heterointerface Co/Co9S8Preparation of carbon nanofiber-loaded composite materialThe method 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-1Obtaining white felty electrostatic spinning nano-fiber;
(3) placing the electrospun nanofibers in a tube furnace at 2 deg.C for min from room temperature-1Is heated to 250 ℃ and kept for 1h for pre-oxidation, and then is heated for 10 min in an inert atmosphere-1Heating to 1200 ℃, keeping for 0.5h for carbonization, naturally cooling to room temperature to finally obtain the 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 1:1), taking out the carbon nanofiber after soaking for 2 hours, and drying the carbon nanofiber 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 pasting the carbon nanofiber membranes on a glass slide by conductive silver adhesive, electrifying the glass slide in a glove box for 1s (the electrified applied voltage is 15V, and the current is about 3A), and obtaining Co/Co9S8Carbon nanofiber-loaded composite (Co/Co)9S8-CNF)。
Co/Co prepared in this example9S8Carbon nanofiber-loaded composite (Co/Co)9S8CNF-100mM) with Co/Co prepared in example 19S8The loaded carbon nanofiber composites were substantially uniform. The OER electrocatalytic activity is shown in FIG. 7, at a current density of 10mA cm-2Co/Co prepared in this example9S8The overpotential of-CNF-100 mM is 303 mV.
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-1Obtaining white felty electrostatic spinning nano-fiber;
(3) placing the electrospun nanofibers in a tube furnace at room temperature for 1 min-1Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere-1Heating 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 of carbon nanofiber in 200mM aqueous solution of cobalt acetate tetrahydrate, taking out after soaking for 3h, and vacuum drying at 60 ℃ to obtain a cobalt salt loaded 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 Co9S8The 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-1Obtaining white felty electrostatic spinning nano-fiber;
(3) placing the electrospun nanofibers in a tube furnace at room temperature for 1 min-1Is heated to 270 ℃ and kept for 2h for pre-oxidation, and then is heated for 5 ℃ min in an inert atmosphere-1Heating 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 of carbon nanofiber in a mixed aqueous solution of 200mM of cobalt acetate tetrahydrate and 400mM of 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) connecting the metal cobalt salt and thiourea loaded electrostatic spinning carbon nanofiber membranes at two ends of a power line, tiling and pasting the 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 10V, and the current is about 2A), and obtaining the Co particle loaded carbon nanofiber composite material (Co particle loaded carbon nanofiber composite material)9S8-CNF). Obtained Co9S8The results of the OER-LSV curve for-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 (10)
1. The composite material with the same source and heterogeneous interface structure is characterized by being 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/MxSy(ii) a Wherein M is a metal simple substance or an alloy, MxSyIs sulfide corresponding to metal simple substance or alloy; the M/MxSyIn 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.
2. The homoeogenic heterointerface structure composite material according to claim 1, wherein said M is selected from the group consisting of Co, Ni, Fe, a single metal or an alloy of two or more metals.
3. The homoeographic heterointerface structure composite material according to claim 1 or 2, wherein said M/M isxSySelected from Fe/FexSy,Co/CoxSy,Ni/NixSy,FeNi/(FeNi)xSy,FeCo/(FeCo)xSy,NiCo/(NiCo)xSy,FeNiCo/(FeNiCo)xSyAny one of them.
4. A method for preparing a homoeogenic heterointerface structure composite according to claim 1, characterized in that it 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.
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 100-300 mM; 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: 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 as claimed in claim 4, wherein in step A, the diameter of the carbon fiber substrate is 200-500nm, and the carbon fiber is carbon nanofiber.
8. The method for preparing a homoeogenic heterointerface composite material according to claim 4, wherein the specific method of step B is as follows:
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 MxSyThe homogeneous heterogeneous interface structure composite material of the system.
9. The method according to claim 4 or 8, wherein in step B, the applied voltage is 15-25V and the current is 2-10A.
10. 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/MxSy(ii) a Wherein M is a metal simple substance or an alloy, MxSyIs sulfide corresponding to metal simple substance or alloy; the M/MxSyIn the composite material, the metal simple substance or alloy and the corresponding sulfide are in a heterojunction interfaceThe structure is an AB left-right type interface structure, but not a core-shell structure or an atom doping structure.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111400507.2A CN114210345B (en) | 2021-11-19 | 2021-11-19 | Homologous heterogeneous interface structure composite material and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202111400507.2A CN114210345B (en) | 2021-11-19 | 2021-11-19 | Homologous heterogeneous interface structure composite material and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114210345A true CN114210345A (en) | 2022-03-22 |
CN114210345B CN114210345B (en) | 2022-12-13 |
Family
ID=80698071
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202111400507.2A Active CN114210345B (en) | 2021-11-19 | 2021-11-19 | Homologous heterogeneous interface structure composite material and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114210345B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114717600A (en) * | 2022-05-17 | 2022-07-08 | 中国科学院兰州化学物理研究所 | Preparation of carbon-supported small-particle nano metal rhenium catalyst and application of catalyst in hydrogen production by water electrolysis |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016190818A1 (en) * | 2015-05-26 | 2016-12-01 | Nanyang Technological University | Synthesis and application of tungsten chalcogenide hetero-structured nanomaterials |
CN107447200A (en) * | 2016-10-28 | 2017-12-08 | 北京大学 | A kind of method for preparing transient metal chalcogenide compound/two-dimensional layer material interlayer heterojunction structure using two step chemical vapour deposition techniques |
CN109235024A (en) * | 2018-09-04 | 2019-01-18 | 北京邮电大学 | A kind of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide and preparation method thereof of carbon cloth load |
CN110314690A (en) * | 2019-07-16 | 2019-10-11 | 广州大学 | Bimetallic sulfide Ni with heterogeneous interface coupling3S2/ FeS composite material and preparation method and application |
CN111554514A (en) * | 2020-05-11 | 2020-08-18 | 东北大学秦皇岛分校 | Flexible heterogeneous nanosheet pseudocapacitance positive electrode material and preparation method thereof |
CN112023944A (en) * | 2020-07-27 | 2020-12-04 | 天津大学 | Preparation method for in-situ synthesis of rhenium and rhenium disulfide heterostructure composite material |
CN112760715A (en) * | 2020-12-04 | 2021-05-07 | 北京交通大学 | Method for preparing two-dimensional transition metal chalcogenide in-plane heterojunction |
CN113638005A (en) * | 2021-08-20 | 2021-11-12 | 中国科学院过程工程研究所 | Preparation method and application of efficient and bifunctional heterostructure full-electrolysis water-electricity catalyst |
-
2021
- 2021-11-19 CN CN202111400507.2A patent/CN114210345B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016190818A1 (en) * | 2015-05-26 | 2016-12-01 | Nanyang Technological University | Synthesis and application of tungsten chalcogenide hetero-structured nanomaterials |
CN107447200A (en) * | 2016-10-28 | 2017-12-08 | 北京大学 | A kind of method for preparing transient metal chalcogenide compound/two-dimensional layer material interlayer heterojunction structure using two step chemical vapour deposition techniques |
CN109235024A (en) * | 2018-09-04 | 2019-01-18 | 北京邮电大学 | A kind of heterogeneous nano-chip arrays structure of nickel sulfide-molybdenum sulfide and preparation method thereof of carbon cloth load |
CN110314690A (en) * | 2019-07-16 | 2019-10-11 | 广州大学 | Bimetallic sulfide Ni with heterogeneous interface coupling3S2/ FeS composite material and preparation method and application |
CN111554514A (en) * | 2020-05-11 | 2020-08-18 | 东北大学秦皇岛分校 | Flexible heterogeneous nanosheet pseudocapacitance positive electrode material and preparation method thereof |
CN112023944A (en) * | 2020-07-27 | 2020-12-04 | 天津大学 | Preparation method for in-situ synthesis of rhenium and rhenium disulfide heterostructure composite material |
CN112760715A (en) * | 2020-12-04 | 2021-05-07 | 北京交通大学 | Method for preparing two-dimensional transition metal chalcogenide in-plane heterojunction |
CN113638005A (en) * | 2021-08-20 | 2021-11-12 | 中国科学院过程工程研究所 | Preparation method and application of efficient and bifunctional heterostructure full-electrolysis water-electricity catalyst |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114717600A (en) * | 2022-05-17 | 2022-07-08 | 中国科学院兰州化学物理研究所 | Preparation of carbon-supported small-particle nano metal rhenium catalyst and application of catalyst in hydrogen production by water electrolysis |
CN114717600B (en) * | 2022-05-17 | 2023-09-26 | 中国科学院兰州化学物理研究所 | Preparation of carbon-supported small-particle nano metal rhenium catalyst and application of catalyst in hydrogen production by water electrolysis |
Also Published As
Publication number | Publication date |
---|---|
CN114210345B (en) | 2022-12-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108543545B (en) | A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications | |
CN107649160B (en) | Graphene-loaded transition group metal monodisperse atomic catalyst and preparation method and application thereof | |
CN109678146A (en) | A kind of porous class graphitic carbon nano piece of N doping and its preparation and electro-catalysis application | |
CN111346640B (en) | Transition metal monoatomic-supported electrolyzed water catalyst and preparation method thereof | |
Yang et al. | Core-shell trimetallic NiFeV disulfides and amorphous high-valance NiFe hydroxide nanosheets enhancing oxygen evolution reaction | |
KR102011066B1 (en) | MANUFACTURING METHOD OF FeP NANOPARTICLES FOR FUEL CELL CATALYST AND FeP NANOPARTICLES MANUFACTURED THEREBY | |
CN113061937B (en) | FeCoNiIrRu high-entropy nanoparticle catalytic material applied to acidic oxygen evolution reaction and preparation method thereof | |
CN109701545A (en) | A kind of electrocatalysis material and preparation method thereof loading vanadium cobalt alloy nanoparticles | |
CN113161561B (en) | Carbon cloth modified with MOFs-derived Fe2O3 and preparation method and application thereof | |
CN109621969B (en) | Self-supporting bimetal nickel-tungsten carbide fully-hydrolyzed material and preparation method thereof | |
KR20130139577A (en) | Process for preparing highly efficient carbon supported platinum-metal catalyst and carbon supported platinum-metal catalyst thereof | |
KR102201082B1 (en) | The method of generating oxygen vacancies in nickel-cobalt oxide for oxygen reduction reaction and nickel-cobalt oxide thereby | |
Shi et al. | Ce-substituted spinel CuCo2O4 quantum dots with high oxygen vacancies and greatly improved electrocatalytic activity for oxygen evolution reaction | |
CN114452982B (en) | W (W) 18 O 49 /CoO/CoWO 4 Self-supporting electro-catalytic material of/NF and preparation method thereof | |
CN111068734A (en) | Bamboo-like nitrogen-doped carbon nanofiber-coated transition metal alloy nanoparticle catalytic material for efficient bifunctional electrocatalysis | |
CN114210345B (en) | Homologous heterogeneous interface structure composite material and preparation method thereof | |
CN109898097A (en) | Monatomic iron-the carbon-coating of immersion-type modifies Ni-based or cobalt-based composite electrode preparation method and applications | |
CN113215611A (en) | Transition metal phosphide catalyst nanoparticle, preparation method thereof and electrode | |
Xiao et al. | Microwave‐Positioning Assembly: Structure and Surface Optimizations for Catalysts | |
KR20150119697A (en) | Nano fiber composite supported catalyst and method comprising the same | |
Tong et al. | Spontaneous synthesis of Ag nanoparticles on ultrathin Co (OH) 2 nanosheets@ nitrogen-doped carbon nanoflake arrays for high-efficient water oxidation | |
CN110237847A (en) | Elctro-catalyst, electrode and its preparation method and application | |
Wu et al. | Formation of feathery-shaped dual-function S-doped FeNi-MOFs to achieve advanced electrocatalytic activity for OER and HER | |
CN109585860A (en) | A kind of preparation method of sulfur doping cobalt oxide and sulphur, nitrogen, oxygen doping carbon In-situ reaction electrode | |
Rowell et al. | General route to colloidally stable, low-dispersity manganese-based ternary spinel oxide nanocrystals |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |