CN114695904A - Preparation and application of self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster - Google Patents
Preparation and application of self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster Download PDFInfo
- Publication number
- CN114695904A CN114695904A CN202210424468.8A CN202210424468A CN114695904A CN 114695904 A CN114695904 A CN 114695904A CN 202210424468 A CN202210424468 A CN 202210424468A CN 114695904 A CN114695904 A CN 114695904A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- doped carbon
- self
- carbon nanotube
- carbon cloth
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 142
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 74
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 73
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 68
- 239000004744 fabric Substances 0.000 claims abstract description 64
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002070 nanowire Substances 0.000 claims abstract description 20
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000446 fuel Substances 0.000 claims abstract description 17
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- -1 cobalt iron nitrate hexahydrate Chemical compound 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 14
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 238000002294 plasma sputter deposition Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- 238000011144 upstream manufacturing Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 229910003321 CoFe Inorganic materials 0.000 description 22
- 230000000694 effects Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 238000004502 linear sweep voltammetry Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 6
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
Abstract
The invention discloses preparation and application of a self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster. The preparation method comprises the following steps: the carbon cloth is used as a precursor, and cobalt iron nitrate hexahydrate, ferric nitrate nonahydrate, ammonium fluoride and urea are used for preparing the cobalt iron nanowire. And then preparing the nitrogen-doped carbon nano tube by using the carbon cloth for growing the cobalt-iron nano wire and dicyandiamide. The application of the three-functional catalyst of the direct methanol fuel cell in catalyzing ORR and MOR reactions of the direct methanol fuel cell and the electrocatalysis performance in HER reactions can obviously enhance the adsorption efficiency of adsorbed gas and improve the stability and the conductivity, has lower overpotential and cost in the ORR, MOR and HER reactions, and can meet the requirements of commercial application.
Description
Technical Field
The invention belongs to the technical field of direct methanol fuel cell catalysts, and particularly relates to a self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster, a preparation method thereof and application thereof in a direct methanol fuel cell.
Background
At present, the world energy is limited, and unreasonable exploitation and waste of human beings cause energy crisis, environmental pollution and other problems, and in order to meet the needs of the modern society and relieve the ecological health problem, the research focus in the world energy field is to find an efficient, clean and sustainable energy technology.
The Oxygen Reduction Reaction (ORR) and the Methanol Oxidation Reaction (MOR) are the core reaction processes of important renewable energy technology, and the application relates to the fields of fuel cells, metal-air batteries and the like. Among fuel cells, Proton Exchange Membrane Fuel Cells (PEMFCs) employ perfluorosulfonic acid membranes as electrolytes, and have the advantages of no corrosion of the electrolytes, low required working temperature, large working current, high power density, light weight, quick start, environmental friendliness, long service life and the like, and thus, they have become important in research. Direct Methanol Fuel Cells (DMFCs) are the most energy intensive fuel cells, except for hydrogen fuel. DMFCs, as power generation devices that directly convert chemical energy into electrical energy, have the advantages of high energy conversion efficiency, simple operation, fast start-up, greenness, no pollution, and the like. However, its performance is also affected by several factors. First, methanol can permeate from the anode to the cathode catalyst layer through the electrolyte membrane, which can severely coat the Pt surface, reducing the ORR active sites. And creates a "mixed potential" at the cathode, reducing the fuel conversion efficiency and the output power of the cell. Second, the slow kinetics of the electrochemical reaction lead to a loss of active polarization that reduces the cell voltage. At the same time, methanol and its oxygenated intermediates (CO) also poison commercial platinum carbon catalysts (Pt/C), affecting the catalytic activity of Pt on ORR. Finally, the rare and limited platinum content on earth, the high cost of commercial Pt/C catalysts, and the like are all factors that contribute to the commercial development of DMFCs. Therefore, finding and designing efficient, inexpensive, novel catalysts with high platinum utilization, high catalytic activity, stability, and strong CO poisoning resistance is a primary task for commercial development of DMFCs.
In order to find alternatives to Pt-based catalysts, 3D Transition Metals (TMs) are also widely used in the field of DMFCs catalysts, such as Fe, Co, Ni, and the like. When the metal and alloy nanoparticles are used as a catalyst, the catalyst not only has non-noble metal active sites, but also enriches the functions of single metal by alloying, and creates a new possibility for improving the electrocatalytic activity. However, agglomeration of the nanoparticles reduces the active sites, reducing the activity and stability of the catalyst. Therefore, it is important to confine the alloy nanoparticles in a limited space and maintain their excellent electrochemical activity. For example, nitrogen-doped carbon nanotubes have the advantages of unique hollow structure, excellent electronic conductivity, high mechanical strength, high specific surface area, good chemical stability and the like, and are considered to be an ideal electrocatalyst support material. In previous studies, the catalyst was usually present in powder form and the electrodes were made using a polymer binder, such as Nafion. The use of binders can result in increased charge transfer resistance and can result in a decrease in the active surface area of the catalyst, which in turn affects the performance and future development of DMFCs. Therefore, the active material growing on the carbon cloth can effectively prevent the agglomeration of the active material, fully utilize the active sites and improve the stability of the catalyst. Magnetron sputtering (PVD) is a plasma-based high-speed physical vapor deposition technique that bombards a target with ionized particles to cause atoms on the surface of the target to break off and then deposit on a substrate to form a thin film. PVD is a green and low-cost nano material preparation technology. Therefore, the key point of using the platinum nano cluster loaded on the nitrogen-doped carbon nano tube as the high-efficiency ORR/MOR bifunctional catalyst of the direct methanol fuel cell is that platinum is uniformly loaded on the surface of the nitrogen-doped carbon nano tube by utilizing plasma sputtering deposition, and the structure of the nitrogen-doped carbon nano tube is not damaged, so that the electrocatalytic performance and the Pt utilization rate are improved.
Disclosure of Invention
In order to solve the technical problems, the invention realizes the uniform loading of the platinum nano cluster by loading the platinum nano cluster on the self-supporting nitrogen-doped carbon nano tube, has the advantages of high platinum utilization rate, strong electron conductivity, high catalytic activity and the like, and can be applied to direct methanol fuel cell electrode materials.
In order to achieve the purpose, the invention adopts the technical scheme that:
a platinum nano cluster loaded on a self-supporting nitrogen-doped carbon nanotube is characterized in that a structural unit of the carbon nanotube is carbon cloth, the nitrogen-doped carbon nanotube (NCNTs) is a conductive network, the platinum nano cluster is a load, and the platinum nano cluster is loaded on the nitrogen-doped carbon nanotube by means of plasma sputtering deposition.
A preparation method of the self-supporting nitrogen-doped carbon nanotube-loaded platinum nanocluster specifically comprises the following steps:
firstly, preparing cobalt-iron nanowires: and (3) carrying out ultrasonic treatment on the carbon cloth in a 10 wt.% potassium permanganate solution for 10-30min, and continuing to carry out ultrasonic treatment in deionized water and ethanol until the solution is completely clear. And taking out the carbon cloth, and drying in a vacuum oven at 40-60 ℃ for 6-24 h. Sequentially adding cobalt, iron transition metal salt, ammonium fluoride and urea into deionized water while stirring, and continuously stirring for 10-30min at room temperature to form a uniform mixed solution. Quickly transferring the mixture to a hydrothermal reaction kettle, soaking the cleaned carbon cloth in the hydrothermal reaction kettle, and reacting for 6-12h at the temperature of 100-140 ℃. Taking out the carbon cloth, washing the carbon cloth with deionized water and ethanol, and drying the carbon cloth in a vacuum oven at 40-60 ℃ for 6-24h to obtain the cobalt-iron nanowire;
secondly, preparing the nitrogen-doped carbon nano tube: placing carbon cloth for growing the cobalt-iron nanowire and dicyandiamide in two different porcelain boats of a tube furnace, wherein dicyandiamide is positioned at the upstream of the tube furnace, heating to 400-ion-doped carbon nanotubes for annealing for 2-4h at a certain heating rate in an inert gas atmosphere, and then heating to 800-ion-doped carbon nanotubes for further annealing for 2-4h to obtain nitrogen-doped carbon nanotubes;
thirdly, preparing the self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster: and arranging carbon for growing the nitrogen-doped carbon nano tube on a substrate of a magnetron sputtering instrument, and loading the platinum nano cluster on the surface of the self-supporting nitrogen-doped carbon nano tube by plasma sputtering deposition under proper working parameters to prepare the platinum nano cluster loaded by the self-supporting nitrogen-doped carbon nano tube.
Preferably, in the first step, the mass ratio of the cobalt transition metal salt, the iron transition metal salt, the ammonium fluoride and the urea is 200-: 150-350: 100-250: 500-700, the size of the carbon cloth is: 2-4cm multiplied by 3-5cm, the volume of deionized water is as follows: 30-50 mL.
Preferably, in the first step, Co (NO) is used as the cobalt transition metal salt3)2·6H2O、CoCl2·6H2O、Co(CH3COO)2、CoCl2、CoSO4·7H2O、CoSO4·H2One of O; the iron transition metal salt is Fe (NO)3)3·9H2O、FeCl3·6H2O、Fe(OH)(CH3COO)2、FeSO4One kind of (1).
Preferably, in the second step, the mass of dicyandiamide is 1000-3000 mg.
Preferably, in the second step, the inert gas atmosphere is N2Ar or He.
Preferably, in the second step, the temperature rise rate is 3-5 ℃/min.
Preferably, in the third step, the sputtering pressure, power and duration of the plasma sputtering deposition are respectively: 2-8Pa, 70-150W, 1-10 min.
The application of the self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster as an electrode material of a direct methanol fuel cell is characterized in that the self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster is used as a catalyst of the direct methanol fuel cell, so that the adsorption efficiency of adsorbed gas can be obviously enhanced, the stability and the electric conductivity are improved, and the catalyst has higher catalytic activity in ORR and MOR reactions.
Compared with the prior art, the preparation and application of the self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster have the following beneficial effects:
(1) the transition metal is encapsulated in the carbon material (graphene, carbon nano tube and the like), the outer-layer carbon material not only effectively prevents the dissolution and agglomeration of the metal in an acidic medium, but also keeps the initial structure and activity of the metal, and the obtained catalyst has good electrocatalytic activity and long-term stability. Among them, Carbon Nanotubes (CNTs) have an extremely high specific surface area and volume ratio, excellent stability, and a regular pore structure and a conductive path. And, at high temperature, the carbon material has high solubility in transition metals, has a high diffusion rate, and has strong adhesion with the prepared carbon nanotubes. Heteroatom-doped carbon-coated transition metal compound catalysts have achieved high catalytic activity and stability and have been widely used in DMFCs.
(2) The self-supporting nitrogen-doped carbon nano tubes can be connected with each other to form an excellent electric conduction network, the defect of insufficient conductivity of metal oxides is improved, more electrochemical active substances are favorably exposed on the surfaces of the carbon nano tubes, the platinum nano cluster loaded on the self-supporting nitrogen-doped carbon nano tubes has a high specific surface area and a stable three-dimensional network structure, and the special three-dimensional structure provides a good template for efficient deposition of the platinum nano cluster, so that the application of the material is greatly expanded. The platinum nano cluster is uniformly loaded on the surface of the self-supporting nitrogen-doped carbon nanotube, so that the problem of serious agglomeration of platinum metal structural units in the traditional preparation technical process can be effectively solved, and the electrochemical performance of the platinum nano cluster is improved.
(3) Because the carbon cloth has larger specific surface area, excellent flexibility, abundant active sites and good synergistic effect between the electrocatalyst and the conductive substrate, the CNTs are orderly arranged on the carbon cloth, and the performance of the catalyst can be maximized.
(4) The electrode material prepared by the plasma sputtering deposition technology is controllable to construct the nano structure on the substrate. Compared with the traditional electrocatalyst prepared by a chemical method, PVD is a green and low-cost nano material preparation technology. The sputtering device has the unique advantages of simple structure, quick preparation process, no by-product in the sputtering process, uniform distribution of the sputtered metal, high purity and density, strong adhesive force between the metal and the substrate, accurate control of the metal loading capacity, high loading of the active components of the sputtered metal, good corrosion resistance and the like. The method has the advantages that the Pt utilization rate is improved to the maximum extent while the load of noble metal Pt is reduced to the maximum extent.
Drawings
FIG. 1 is a microscopic morphology of the platinum nanoclusters loaded on the self-supporting N-doped carbon nanotubes prepared in example 1 under a Scanning Electron Microscope (SEM);
fig. 2 is a linear sweep voltammetry test chart (LSV) of Oxygen Reduction Reaction (ORR) under alkaline conditions for self-supporting nitrogen doped carbon nanotube supported platinum nanoclusters prepared in example 1, comparative example 1, and a commercial 20 wt.% Pt/C catalyst;
fig. 3 is a linear sweep voltammetry test chart (LSV) of Oxygen Reduction Reaction (ORR) under acidic conditions for self-supporting nitrogen doped carbon nanotube supported platinum nanoclusters prepared in example 1, comparative example 1, and a commercial 20 wt.% Pt/C catalyst;
fig. 4 is a linear sweep voltammetry test chart (LSV) of Oxygen Reduction Reaction (ORR) of the self-supporting nitrogen-doped carbon nanotube-supported platinum nanoclusters prepared in example 1, example 2, example 3, example 4 and example 5 under alkaline conditions;
fig. 5 is a linear sweep voltammetry test chart (LSV) of Oxygen Reduction Reaction (ORR) of the self-supporting nitrogen-doped carbon nanotube-supported platinum nanoclusters prepared in example 1, example 2, example 3, example 4 and example 5 under acidic conditions;
fig. 6 is a linear sweep voltammetry test plot (LSV) of Methanol Oxidation Reaction (MOR) of self-supporting nitrogen doped carbon nanotubes supporting platinum nanoclusters and a commercial 20 wt.% Pt/C catalyst prepared in example 1;
Detailed Description
In order to make the purpose, technical scheme and beneficial technical effects of the present invention clearer, the following describes in detail the preparation and application of the self-supporting nitrogen-doped carbon nanotube-loaded platinum nanocluster of the present invention with reference to the accompanying drawings and specific embodiments. It should be understood that the embodiments described in this specification are only for the purpose of illustrating the invention and are not to be construed as limiting the invention, and the parameters, proportions and the like of the embodiments may be suitably selected without materially affecting the results.
Example 1: a preparation method of a self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster specifically comprises the following steps:
(1) and (3) synthesis of the cobalt-iron nanowire:
and (3) carrying out ultrasonic treatment on a carbon cloth with the size of 3cm multiplied by 4cm in a potassium permanganate solution of 10 wt% for 10min, continuing the ultrasonic treatment in deionized water and ethanol until the solution is completely clear, and then placing the carbon cloth in a vacuum oven at 60 ℃ for drying for 12 h. 388mg of cobalt nitrate hexahydrate, 270mg of iron nitrate nonahydrate, 186mg of ammonium fluoride and 600mg of urea were added to 40ml of deionized water with stirring, and stirring was continued at room temperature for 10min to form a uniformly mixed solution. Transferring the mixture to a hydrothermal reaction kettle, immersing the carbon cloth in the hydrothermal reaction kettle, and standing the mixture for 6 hours at 120 ℃. Then, the carbon cloth was taken out, washed with deionized water and ethanol in sequence, and finally dried in a vacuum oven at 40 ℃ for 12 hours. The resulting sample was designated CoFe NWs/CFC.
(2) And (3) synthesis of nitrogen-doped carbon nanotubes:
placing carbon cloth for growing the cobalt-iron nanowire and 1.5g of dicyandiamide in two different porcelain boats of a tube furnace, annealing dicyandiamide at 400 ℃ for 2h in Ar gas atmosphere at the upstream of the tube furnace, heating to 800 ℃, and continuing to anneal for 2h at the heating rate of 5 ℃/min. The resulting sample was designated CoFe @ NCNT/CFC.
(3) Synthesizing a nitrogen-doped carbon nanotube-loaded platinum nano cluster:
fixing the carbon cloth for growing the nitrogen-doped carbon nanotube on a substrate of a magnetron sputtering instrument, and carrying out plasma sputtering deposition for 7min under 5Pa and 110W to load the platinum nano cluster on the surface of the carbon cloth. The resulting sample was designated Pt-CoFe @ NCNT/CFC-7 min.
The morphology of the Pt-CoFe @ NCNT/CFC-7min material obtained in example 1 was analyzed by a Scanning Electron Microscope (SEM), and the result is shown in FIG. 1, wherein the NCNTs surface is rough and opaque, and the Pt nanoclusters are uniformly loaded on the CoFe @ NCNT/CFC surface.
ORR and MOR catalytic performance evaluation:
all electrochemical tests were performed using an electrochemical workstation model CHI 760E equipped with a PINE rotating disk electrode test system and were performed at room temperature.
Preparation of a working electrode: before using a Rotating Disk Electrode (RDE), i.e. a glassy carbon electrode (GCE, d ═ 0.4cm), Al was first used2O3Grinding the surface of the electrode on polishing cloth to a mirror surface by using powder, then washing the electrode with distilled water for several times, ultrasonically oscillating for 10s, and drying the electrode at room temperature for later use. A sample having a diameter of 4mm was cut out from the prepared sample by a punch, and 5 to 10 μ L of Nafion solution (5 wt.%) was attached to the surface of GCE and naturally dried to obtain a working electrode for test use. Comparative sampleThe same electrode preparation method was used for preparation and testing. The platinum loading in the electrode surface catalyst was about 0.7mg cm-2As a control experiment, 14mg of commercial 20 wt.% Pt/C, 261 μ L isopropanol, 652 μ L deionized water, 87 μ L nafion (5 wt.%) were weighed and mixed, and the mixture was sonicated for 1h to give a homogeneous slurry. And finally, dripping the prepared slurry on the surface of a carbon cloth with the thickness of 1cm multiplied by 4cm, and naturally drying to obtain the working electrode used for testing.
And (3) electrochemical performance testing: in the testing process, a standard three-electrode electrochemical testing system is adopted, wherein the counter electrode is a Pt sheet, the reference electrode is a Saturated Calomel Electrode (SCE) and the prepared working electrode is adopted.
The sample of example 1 and a commercial 20 wt.% Pt/C catalyst were separately tested on O using a Rotating Disk Electrode (RDE)2Saturated 0.1M KOH and 0.5M H2SO4ORR catalytic activity in electrolytes. FIGS. 2 and 3 are LSV curves for ORR catalytic performance of the samples of example 1, respectively. As shown in fig. 2, the ORR electrocatalytic activity onset potential and half-wave potential of the sample of example 1 were 0.97 and 0.807V vs. rhe, respectively, in 0.1M KOH; as shown in fig. 3, at 0.5M H2SO4Of (1), the samples of example 1 had an onset potential and a half-wave potential of 0.852 and 0.723V vs. RHE, respectively, and the ORR electrocatalytic activity was very close to that of a commercial 20 wt.% Pt/C catalyst tested under the same conditions (onset potential and half-wave potential of 1.01 and 0.743V vs. RHE, respectively, in 0.1M KOH; at 0.5M H2SO4In, the initial potential and half-wave potential are 0.837 and 0.69V vs. rhe), respectively). In alkaline electrolyte, the half-wave potential of the example 1 sample is more positive than Pt/C. In the acid electrolyte, not only the half-wave potential of the sample of example 1 was more positive than Pt/C, but the onset potential was also higher than Pt/C. The self-supporting Pt-CoFe @ NCNT/CFC-7min electrode has faster reaction kinetics and excellent activity in the ORR electrocatalysis process.
The sample of example 1 and a commercial 20 wt.% Pt/C catalyst were tested in N using a Rotating Disk Electrode (RDE)2Saturated 0.5M H2SO4And 0.5M CH3MOR catalytic activity in OH mixed electrolytes. FIG. 6 is a graph showing the MOR catalytic performance of the samples of example 1LSV curve of (d). The maximum current density value of the sample of example 1 was 15.5mA mg when scanned in the forward direction-1 PtWhile the maximum current density value of the commercial 20 wt.% Pt/C catalyst was 4.338mA mg-1 Pt. The maximum current density values for the example 1 sample and the commercial 20 wt.% Pt/C catalyst, respectively, were 7.774mA mg on the reverse scan-1 PtAnd 3.768mA mg-1 Pt. The peak current density of the sample of example 1 was the greatest under the same test conditions, indicating that the self-supporting Pt-CoFe @ NCNT/CFC-7min electrode had excellent MOR electrocatalytic activity.
Comparative example 1: the preparation method of the self-supporting nitrogen-doped carbon nanotube specifically comprises the following steps:
(1) and (3) synthesis of the cobalt-iron nanowire:
and (3) carrying out ultrasonic treatment on a carbon cloth with the size of 3cm multiplied by 4cm in a potassium permanganate solution of 10 wt% for 10min, continuing the ultrasonic treatment in deionized water and ethanol until the solution is completely clear, and then placing the carbon cloth in a vacuum oven at 60 ℃ for drying for 12 h. 388mg of cobalt nitrate hexahydrate, 270mg of iron nitrate nonahydrate, 186mg of ammonium fluoride and 600mg of urea were added to 40ml of deionized water with stirring, and stirring was continued at room temperature for 10min to form a uniformly mixed solution. Transferring the mixture to a hydrothermal reaction kettle, immersing the carbon cloth in the hydrothermal reaction kettle, and standing the mixture for 6 hours at 120 ℃. Then, the carbon cloth was taken out, washed with deionized water and ethanol in sequence, and finally dried in a vacuum oven at 40 ℃ for 12 hours. The resulting sample was designated CoFe NWs/CFC.
(2) And (3) synthesis of nitrogen-doped carbon nanotubes:
placing carbon cloth for growing the cobalt-iron nanowire and 1.5g of dicyandiamide in two different porcelain boats of a tube furnace, annealing dicyandiamide at 400 ℃ for 2h in Ar gas atmosphere at the upstream of the tube furnace, heating to 800 ℃, and continuing to anneal for 2h at the heating rate of 5 ℃/min. The resulting sample was designated CoFe @ NCNT/CFC.
Comparative example 1 sample was tested using a Rotating Disk Electrode (RDE) at O2Saturated 0.1M KOH and 0.5M H2SO4ORR catalytic activity in electrolytes. As shown in fig. 2, the initial potential and half-wave potential of the comparative example 1 sample were 0.92 and 0.783V vs. rhe, respectively, in 0.1M KOH; as shown in fig. 3, at 0.5M H2SO4In comparative example 1, the initial potential and half-wave potential of the sample were 0.791 and 0.682V vs. RHE, respectively, and the electrocatalytic activity of the ORR was much worse than that of the Pt-CoFe @ NCNT/CFC-7min sample tested under the same conditions.
Example 2: a preparation method of a self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster specifically comprises the following steps:
(1) and (3) synthesis of the cobalt-iron nanowire:
and (3) carrying out ultrasonic treatment on a carbon cloth with the size of 3cm multiplied by 4cm in a potassium permanganate solution of 10 wt% for 10min, continuing the ultrasonic treatment in deionized water and ethanol until the solution is completely clear, and then placing the carbon cloth in a vacuum oven at 60 ℃ for drying for 12 h. 388mg of cobalt nitrate hexahydrate, 270mg of iron nitrate nonahydrate, 186mg of ammonium fluoride and 600mg of urea were added to 40ml of deionized water with stirring, and stirring was continued at room temperature for 10min to form a uniformly mixed solution. Transferring the mixture to a hydrothermal reaction kettle, immersing the carbon cloth in the hydrothermal reaction kettle, and standing the mixture for 6 hours at 120 ℃. Then, the carbon cloth was taken out, washed with deionized water and ethanol in sequence, and finally dried in a vacuum oven at 40 ℃ for 12 hours. The resulting sample was designated CoFe NWs/CFC.
(2) And (3) synthesis of nitrogen-doped carbon nanotubes:
placing carbon cloth for growing the cobalt-iron nanowire and 1.5g of dicyandiamide in two different porcelain boats of a tube furnace, annealing dicyandiamide at 400 ℃ for 2h in Ar gas atmosphere at the upstream of the tube furnace, heating to 800 ℃, and continuing to anneal for 2h at the heating rate of 5 ℃/min. The resulting sample was designated CoFe @ NCNT/CFC.
(3) Synthesizing a nitrogen-doped carbon nanotube-loaded platinum nano cluster:
fixing the carbon cloth for growing the nitrogen-doped carbon nanotube on a substrate of a magnetron sputtering instrument, and carrying out plasma sputtering deposition for 1min under 5Pa and 110W to load the platinum nano cluster on the surface of the carbon cloth. The resulting sample was designated Pt-CoFe @ NCNT/CFC-1 min.
The sample of example 2 was tested using a Rotating Disk Electrode (RDE) at O2Saturated 0.1M KOH and 0.5M H2SO4ORR catalytic activity in the electrolyte. As shown in fig. 4, the initial potential and half-wave potential of the sample of example 2 were 0.922 and 0, respectively, in 0.1M KOH.782V vs. rhe; as shown in fig. 5, at 0.5M H2SO4In example 2, the initial potential and half-wave potential of the sample were 0.787 and 0.615V vs. rhe, respectively. The ORR is much less electrocatalytic than the sample of example 1 tested under the same conditions.
Example 3: a preparation method of a self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster specifically comprises the following steps:
(1) and (3) synthesis of the cobalt-iron nanowire:
and (3) carrying out ultrasonic treatment on a carbon cloth with the size of 3cm multiplied by 4cm in a 10 wt.% potassium permanganate solution for 10min, continuing the ultrasonic treatment in deionized water and ethanol until the solution is completely clear, and then placing the solution in a vacuum oven at 60 ℃ for drying for 12 h. 388mg of cobalt nitrate hexahydrate, 270mg of iron nitrate nonahydrate, 186mg of ammonium fluoride and 600mg of urea were added to 40ml of deionized water with stirring, and stirring was continued at room temperature for 10min to form a uniformly mixed solution. Transferring the mixture to a hydrothermal reaction kettle, immersing the carbon cloth in the hydrothermal reaction kettle, and standing the mixture for 6 hours at 120 ℃. Then, the carbon cloth was taken out, washed with deionized water and ethanol in sequence, and finally dried in a vacuum oven at 40 ℃ for 12 hours. The resulting sample was designated CoFe NWs/CFC.
(2) And (3) synthesis of nitrogen-doped carbon nanotubes:
placing carbon cloth for growing the cobalt-iron nanowire and 1.5g of dicyandiamide in two different porcelain boats of a tube furnace, annealing dicyandiamide at 400 ℃ for 2h in Ar gas atmosphere at the upstream of the tube furnace, heating to 800 ℃, and continuing to anneal for 2h at the heating rate of 5 ℃/min. The resulting sample was designated CoFe @ NCNT/CFC.
(3) Synthesizing a nitrogen-doped carbon nanotube-loaded platinum nano cluster:
fixing the carbon cloth for growing the nitrogen-doped carbon nanotube on a substrate of a magnetron sputtering instrument, and carrying out plasma sputtering deposition for 3min under 5Pa and 110W to load the platinum nano cluster on the surface of the carbon cloth. The resulting sample was designated Pt-CoFe @ NCNT/CFC-3 min.
The sample of example 3 was tested using a Rotating Disk Electrode (RDE) at O2Saturated 0.1M KOH and 0.5M H2SO4ORR catalytic activity in electrolytes. As shown in FIG. 4, the initial potential and half-wave voltage of the sample of example 3 in 0.1M KOHBits 0.913 and 0.773V vs. rhe, respectively; as shown in fig. 5, at 0.5M H2SO4In example 3, the initial potential and half-wave potential of the sample were 0.79 and 0.636V vs. rhe, respectively, and the electrocatalytic activity of the ORR was much worse than that of the sample of example 1 tested under the same conditions.
Example 4: a preparation method of a self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster specifically comprises the following steps:
(1) and (3) synthesis of the cobalt-iron nanowire:
and (3) carrying out ultrasonic treatment on a carbon cloth with the size of 3cm multiplied by 4cm in a potassium permanganate solution of 10 wt% for 10min, continuing the ultrasonic treatment in deionized water and ethanol until the solution is completely clear, and then placing the carbon cloth in a vacuum oven at 60 ℃ for drying for 12 h. 388mg of cobalt nitrate hexahydrate, 270mg of iron nitrate nonahydrate, 186mg of ammonium fluoride and 600mg of urea were added to 40ml of deionized water with stirring, and stirring was continued at room temperature for 10min to form a uniformly mixed solution. Transferring the mixture to a hydrothermal reaction kettle, immersing the carbon cloth in the hydrothermal reaction kettle, and standing the mixture for 6 hours at 120 ℃. Then, the carbon cloth was taken out, washed with deionized water and ethanol in sequence, and finally dried in a vacuum oven at 40 ℃ for 12 hours. The resulting sample was designated CoFe NWs/CFC.
(2) And (3) synthesis of nitrogen-doped carbon nanotubes:
placing carbon cloth for growing the cobalt-iron nanowire and 1.5g of dicyandiamide in two different porcelain boats of a tube furnace, annealing dicyandiamide at 400 ℃ for 2h in Ar gas atmosphere at the upstream of the tube furnace, heating to 800 ℃, and continuing to anneal for 2h at the heating rate of 5 ℃/min. The resulting sample was designated CoFe @ NCNT/CFC.
(3) Synthesizing a nitrogen-doped carbon nanotube-loaded platinum nano cluster:
fixing the carbon cloth for growing the nitrogen-doped carbon nanotube on a substrate of a magnetron sputtering instrument, and carrying out plasma sputtering deposition for 5min under 5Pa and 110W to load the platinum nano cluster on the surface of the carbon cloth. The resulting sample was designated Pt-CoFe @ NCNT/CFC-5 min.
The sample of example 4 was tested using a Rotating Disk Electrode (RDE) at O2Saturated 0.1M KOH and 0.5M H2SO4ORR catalytic activity in electrolytes. As shown in FIG. 4, the samples of example 4 were taken in 0.1M KOHThe initial potential and the half-wave potential are respectively 0.932 and 0.771V vs. RHE; as shown in fig. 5, at 0.5M H2SO4In example 4, the initial potential and half-wave potential of the sample are 0.816 and 0.634V vs. rhe, respectively, and the electrocatalytic activity of the ORR is much worse than that of the sample of example 1 tested under the same conditions.
Example 5: a preparation method of a self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster specifically comprises the following steps:
(1) and (3) synthesis of the cobalt-iron nanowire:
and (3) carrying out ultrasonic treatment on a carbon cloth with the size of 3cm multiplied by 4cm in a potassium permanganate solution of 10 wt% for 10min, continuing the ultrasonic treatment in deionized water and ethanol until the solution is completely clear, and then placing the carbon cloth in a vacuum oven at 60 ℃ for drying for 12 h. 388mg of cobalt nitrate hexahydrate, 270mg of iron nitrate nonahydrate, 186mg of ammonium fluoride and 600mg of urea were added to 40ml of deionized water with stirring, and stirring was continued at room temperature for 10min to form a uniformly mixed solution. Transferring the mixture to a hydrothermal reaction kettle, immersing the carbon cloth in the hydrothermal reaction kettle, and standing the mixture for 6 hours at 120 ℃. Then, the carbon cloth was taken out, washed with deionized water and ethanol in sequence, and finally dried in a vacuum oven at 40 ℃ for 12 hours. The resulting sample was designated CoFe NWs/CFC.
(2) And (3) synthesis of nitrogen-doped carbon nanotubes:
placing carbon cloth for growing the cobalt-iron nanowire and 1.5g of dicyandiamide in two different porcelain boats of a tube furnace, annealing dicyandiamide at 400 ℃ for 2h in Ar gas atmosphere at the upstream of the tube furnace, heating to 800 ℃, and continuing to anneal for 2h at the heating rate of 5 ℃/min. The resulting sample was designated CoFe @ NCNT/CFC.
(3) Synthesizing a nitrogen-doped carbon nanotube-loaded platinum nano cluster:
fixing the carbon cloth for growing the nitrogen-doped carbon nanotube on a substrate of a magnetron sputtering instrument, and carrying out plasma sputtering deposition for 10min under 5Pa and 110W to load the platinum nano cluster on the surface of the carbon cloth. The resulting sample was designated Pt-CoFe @ NCNT/CFC-10 min.
The sample of example 5 was tested using a Rotating Disk Electrode (RDE) at O2Saturated 0.1M KOH and 0.5M H2SO4ORR catalytic activity in electrolytes. As shown in fig. 4, in 0.1M KOHThe initial potential and half-wave potential of the sample of example 5 were 0.975 and 0.843V vs. rhe, respectively; as shown in fig. 5, at 0.5M H2SO4In example 5, the initial potential and half-wave potential of the sample were 0.827 and 0.742V vs. rhe, respectively, and the electrocatalytic activity of ORR was much worse than that of the sample of example 1 tested under the same conditions.
Finally, it should also be mentioned that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A preparation method of a self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster is characterized in that a structural unit of a carbon nanotube is carbon cloth, nitrogen-doped carbon nanotubes (NCNTs) are used as an electric conduction network, the platinum nano cluster is used as a load, and the platinum nano cluster is loaded on the nitrogen-doped carbon nanotube by means of plasma sputtering deposition.
2. The method of claim 1, wherein the method comprises the steps of:
firstly, preparing cobalt-iron nanowires: and (3) carrying out ultrasonic treatment on the carbon cloth in a 10 wt.% potassium permanganate solution for 10-30min, and continuing to carry out ultrasonic treatment in deionized water and ethanol until the solution is completely clear. And taking out the carbon cloth, and drying in a vacuum oven at 40-60 ℃ for 6-24 h. Sequentially adding cobalt, iron transition metal salt, ammonium fluoride and urea into deionized water while stirring, and continuously stirring for 10-30min at room temperature to form a uniform mixed solution. Quickly transferring the mixture to a hydrothermal reaction kettle, soaking the cleaned carbon cloth in the hydrothermal reaction kettle, and reacting for 6-12h at the temperature of 100-140 ℃. Taking out the carbon cloth, washing the carbon cloth with deionized water and ethanol, and drying the carbon cloth in a vacuum oven at 40-60 ℃ for 6-24h to obtain the cobalt-iron nanowire;
secondly, preparing the nitrogen-doped carbon nano tube: placing carbon cloth for growing the cobalt-iron nanowire and dicyandiamide in two different porcelain boats of a tube furnace, wherein dicyandiamide is positioned at the upstream of the tube furnace, heating to 400-ion at a certain heating rate in an inert gas atmosphere for annealing for 2-4h, and then heating to 800-ion at 950 ℃ for continuing annealing for 2-4h to obtain a nitrogen-doped carbon nanotube;
thirdly, preparing the self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster: and arranging carbon for growing the nitrogen-doped carbon nano tube on a substrate of a magnetron sputtering instrument, and loading platinum metal on the surface of the self-supporting nitrogen-doped carbon nano tube by plasma sputtering deposition under proper working parameters to prepare a platinum nano cluster loaded by the self-supporting nitrogen-doped carbon nano tube.
3. The method for preparing the platinum nanocluster loaded on the self-supporting nitrogen-doped carbon nanotube as claimed in claim 2, wherein the mass ratio of the cobalt transition metal salt, the iron transition metal salt, the ammonium fluoride and the urea in the step one is 200-400: 150-350: 100-250: 500-700, the size of the carbon cloth is as follows: 2-4cm multiplied by 3-5cm, the volume of deionized water is as follows: 30-50 ml.
4. The method of claim 2, wherein in the step one, Co (NO) is used as the cobalt transition metal salt3)2·6H2O、CoCl2·6H2O、Co(CH3COO)2、CoCl2、CoSO4·7H2O、CoSO4·H2One of O; the iron transition metal salt is Fe (NO)3)3·9H2O、FeCl3·6H2O、Fe(OH)(CH3COO)2、FeSO4One kind of (1).
5. The method as claimed in claim 2, wherein the mass of dicyandiamide in step two is 1000-3000 mg.
6. The method of claim 2, wherein the inert gas atmosphere in step two is N2Ar or He.
7. The method of claim 2, wherein the temperature increase rate in the second step is 3-5 ℃/min.
8. The method of claim 2, wherein the pressure, power and duration of the plasma sputtering deposition in the third step are respectively: 2-8Pa, 70-150W, 1-10 min.
9. The application of the self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster as the electrode material of the direct methanol fuel cell is characterized in that the self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster is used as a catalyst of the direct methanol fuel cell, can obviously enhance the adsorption efficiency of adsorbed gas, improves the stability and the electrical conductivity, and has higher catalytic activity in ORR and MOR reactions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210424468.8A CN114695904A (en) | 2022-04-21 | 2022-04-21 | Preparation and application of self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210424468.8A CN114695904A (en) | 2022-04-21 | 2022-04-21 | Preparation and application of self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114695904A true CN114695904A (en) | 2022-07-01 |
Family
ID=82144962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210424468.8A Pending CN114695904A (en) | 2022-04-21 | 2022-04-21 | Preparation and application of self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114695904A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115424871A (en) * | 2022-07-28 | 2022-12-02 | 西北工业大学宁波研究院 | Three-dimensional nitrogen-doped carbon nanotube fiber electrode and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101120468A (en) * | 2005-02-14 | 2008-02-06 | 堀胜 | Method and apparatus for producing catalyst layer for fuel cell |
| US20090004552A1 (en) * | 2006-12-01 | 2009-01-01 | Gm Global Technology Operations, Inc. | Nanowire supported catalysts for fuel cell electrodes |
| US20100041544A1 (en) * | 2007-05-10 | 2010-02-18 | Nanjing University | Electrode Catalyst of Carbon Nitride Nanotubes Supported by Platinum and Ruthenium Nanoparticles and Preparation Method Thereof |
| CN102157741A (en) * | 2011-03-07 | 2011-08-17 | 中国科学院等离子体物理研究所 | Manufacturing method of membrane electrode of novel ultrathin proton exchange membrane fuel cell |
| CN103259023A (en) * | 2012-11-13 | 2013-08-21 | 山东省科学院新材料研究所 | Preparation method of hydrogen cell electrode material |
| KR20190022161A (en) * | 2017-08-25 | 2019-03-06 | 한국과학기술원 | Catalyst for oxygen reduction reaction comprising porous carbon nanofiber co-doped with transition metal and nitrogen and preparation method thereof |
| CN112838225A (en) * | 2021-01-06 | 2021-05-25 | 中国地质大学（武汉） | Fuel cell catalyst and preparation method and application thereof |
-
2022
- 2022-04-21 CN CN202210424468.8A patent/CN114695904A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101120468A (en) * | 2005-02-14 | 2008-02-06 | 堀胜 | Method and apparatus for producing catalyst layer for fuel cell |
| US20090004552A1 (en) * | 2006-12-01 | 2009-01-01 | Gm Global Technology Operations, Inc. | Nanowire supported catalysts for fuel cell electrodes |
| US20100041544A1 (en) * | 2007-05-10 | 2010-02-18 | Nanjing University | Electrode Catalyst of Carbon Nitride Nanotubes Supported by Platinum and Ruthenium Nanoparticles and Preparation Method Thereof |
| CN102157741A (en) * | 2011-03-07 | 2011-08-17 | 中国科学院等离子体物理研究所 | Manufacturing method of membrane electrode of novel ultrathin proton exchange membrane fuel cell |
| CN103259023A (en) * | 2012-11-13 | 2013-08-21 | 山东省科学院新材料研究所 | Preparation method of hydrogen cell electrode material |
| KR20190022161A (en) * | 2017-08-25 | 2019-03-06 | 한국과학기술원 | Catalyst for oxygen reduction reaction comprising porous carbon nanofiber co-doped with transition metal and nitrogen and preparation method thereof |
| CN112838225A (en) * | 2021-01-06 | 2021-05-25 | 中国地质大学（武汉） | Fuel cell catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| LINA LIU ETAL: "Self-supported N-doped CNT arrays for flexible Zn–air batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》, pages 18162 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115424871A (en) * | 2022-07-28 | 2022-12-02 | 西北工业大学宁波研究院 | Three-dimensional nitrogen-doped carbon nanotube fiber electrode and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Nanoflower-branch LDHs and CoNi alloy derived from electrospun carbon nanofibers for efficient oxygen electrocatalysis in microbial fuel cells | |
| CN106602092B (en) | Preparation method and application of single-walled carbon nanotube hollow sphere oxygen reduction catalyst | |
| Hsieh et al. | Microwave-assisted polyol synthesis of Pt–Zn electrocatalysts on carbon nanotube electrodes for methanol oxidation | |
| CN109103474B (en) | Preparation method of high-performance nitrogen-doped porous carbon-loaded PtNi alloy particle methanol fuel cell catalyst | |
| CN106571474B (en) | Preparation method of platinum-nickel alloy nanocluster and fuel cell adopting platinum-nickel alloy nanocluster | |
| CN103413951A (en) | Nitrogen-doped graphene-loaded Pt-based alloy nanometre electrocatalyst and preparation method thereof | |
| Li et al. | Graphitized carbon nanocages/palladium nanoparticles: Sustainable preparation and electrocatalytic performances towards ethanol oxidation reaction | |
| CN101339999B (en) | Direct sodium borohydride fuel cell using ferrocene as cathode catalyst | |
| CN101728545A (en) | Anode nanometer alloy catalyst of direct methanol fuel cell and preparation method thereof | |
| CN112968184B (en) | Electrocatalyst with sandwich structure and preparation method and application thereof | |
| CN112142037A (en) | Cobalt and nitrogen doped carbon nano tube and preparation method and application thereof | |
| CN110890559B (en) | Preparation method of carbonized wood loaded PdCo alloy composite electrocatalyst | |
| CN113036160A (en) | Preparation method of nanocellulose-derived carbon-supported cobalt electrocatalyst | |
| CN109546166B (en) | Pt/metallic carbide/carbon nano material catalyst and preparation method thereof | |
| CN114695904A (en) | Preparation and application of self-supporting nitrogen-doped carbon nanotube-loaded platinum nano cluster | |
| CN110350204B (en) | Fuel cell catalyst with gold nanocluster as core and platinum as shell layer and preparation method and application thereof | |
| CN109802143B (en) | Preparation method and application of PdRh alloy electrocatalyst with 3D mesh structure of fuel cell | |
| CN114744224B (en) | Preparation and application of nitrogen-doped carbon nanotube-loaded nickel-cobalt composite nanowire | |
| Xu et al. | Electrosynthesis of dendritic palladium supported on Ti/TiO2NTs/Ni/CeO2 as high-performing and stable anode electrocatalyst for methanol electrooxidation | |
| Tan et al. | Nanostructured RuO 2–Co 3 O 4@ RuCo-EO with low Ru loading as a high-efficiency electrochemical oxygen evolution catalyst | |
| Hameed | Tin oxide species as promotive additives to Ni-P/C electrocatalysts for ethanol electro-oxidation in NaOH solution | |
| CN114725405A (en) | Preparation and application of composite carbon nanoparticles loaded with cobalt-iron core-shell structure | |
| CN112701309A (en) | Platinum-carbon catalyst for fuel cell stability and preparation method thereof | |
| KR20090104210A (en) | Development of advanced performance in fuel cell with mixture of metal/CNF/ACF and metal/carbon composites | |
| CN112877663B (en) | Flexible anode material applied to fuel cell and preparation method thereof |
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 |