CN109378482B - Non-noble metal catalytic material loaded core-shell catalyst, preparation method and application thereof - Google Patents
Non-noble metal catalytic material loaded core-shell catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a non-noble metal catalytic material loaded core-shell catalyst, a preparation method and application thereof, the catalyst comprises non-noble metal doped carbon nitrogen carrier catalytic material and core-shell particles loaded on the surface of the carbon nitrogen carrier catalytic material, the catalyst is a non-noble metal carbon nitrogen composite material loaded noble metal core-shell catalyst, has a plurality of catalytic activity sites, has better catalytic activity, excellent electron, gas and other substance conduction properties and hydrophobicity, and is low in cost, the preparation method can fully utilize the residual non-noble metal in the preparation process of the non-noble metal catalyst to prepare the core-shell catalytic particles, can save time, simplify electrode manufacturing steps and improve the catalyst activity and the platinum utilization rate, and is characterized in that the catalyst has low platinum content, high platinum utilization rate, low cost, high catalytic activity and a plurality of catalytic activity sites, and the whole composite catalyst has the advantages of porosity, order, better hydrophobic property, good gas and electron conduction property and the like.
Description
Technical Field
The invention relates to the technical field of fuel cell catalytic materials, in particular to a non-noble metal catalytic material loaded core-shell catalyst, a preparation method and application thereof.
Background
The production, supply and consumption modes of energy not only affect the economic development level of an economic body and the living standard of people, but also are particularly related to the environment and climate change of the earth. The contradiction between the limited fossil energy reserves, particularly petroleum, natural gas, coal and the like, and the increasing energy consumption level is more and more prominent. Particularly, with the increasing of the total population of the earth, the current energy consumption mode highly depending on fossil fuels not only seriously increases the burden of the earth and quickly consumes non-renewable resources such as coal, petroleum, natural gas and the like, but also brings extremely obvious irreversible negative effects to the climate and the environment of the earth and aggravates regional friction and even war caused by energy. The rough energy consumption modes of fossil fuel, combustion and the like not only cause huge waste of resources, but also generate a large amount of carbon dioxide, various pollutants containing nitrogen, sulfur and the like, and bring various problems of serious greenhouse effect, acid rain and the like. Obviously, the traditional energy structure and the low-efficiency energy consumption and utilization technology cannot realize the high-efficiency and clean utilization of precious resources, and further cannot meet and maintain the sustainable development of an economic body and even the whole earth. This problem is particularly important in countries or regions where the population is large and the average human resource is relatively scarce. The energy sources and energy technology which are efficient and clean must be developed, popularized and used to realize the fine utilization of various energy sources and the protection of the environment, ensure the energy safety of the country and reduce the dependence on external energy sources.
Fuel cells (fuel cells) are devices that can directly convert chemical energy in fuel and oxidant into electrical energy, can realize the fine and efficient utilization of various chemical fuels, and particularly have the advantages of low environmental pollution, low emission, even zero emission, high energy conversion efficiency, quick start response, extremely wide application range, high system reliability and maintainability, and the like, and are one of the most promising and most promising energy conversion technologies.
Among many types of fuel cells, Proton Exchange Membrane Fuel Cells (PEMFCs), including Direct Alcohol Fuel Cells (DAFCs), have the characteristics of cleanliness, high efficiency, safety, mobility, mild operating conditions and low-temperature starting, and have great industrialization potential, and in recent years, the PEMFCs are valued and popular among countries in the world, especially in developed economy, and are the most rapidly-developed fuel cells with the widest application range. The key factor of the core component and the overall performance of the cell is a membrane electrode assembly which is composed of a solid electrolyte membrane, a catalyst layer, a diffusion electrode and the like, plays roles of catalyzing electrode reactions of a cathode and an anode, conducting protons and electrons and the like in the operation of the fuel cell, and is a decisive component for controlling the performance, the service life and the cost of the proton exchange membrane fuel cell. In a typical pem fuel cell, hydrogen or other fuel such as methanol, ethanol, acetic acid, etc. is oxidized at the anode to form protons, electrons, and/or carbon dioxide, the protons and electrons are conducted to the cathode through the solid electrolyte membrane and an external circuit, respectively, and oxygen reacts with the protons at the cathode to reduce the oxygen to water and heat. Among them, the electrode catalyst is the most important basic material for realizing a rapid and efficient electrode reaction, and is also the material occupying the highest proportion of cost in the fuel cell. The development of low-cost electrode catalysts with high catalytic activity and stability has been one of the most critical factors for promoting and realizing the industrialization of proton exchange membrane fuel cells.
In current Proton Exchange Membrane Fuel Cells (PEMFCs), nanoparticles including a noble metal, particularly platinum, having high catalytic activity and high potential as a main component are widely used as electrode catalysts. On one hand, as a noble metal with high price, platinum is an extremely rare element stored in the earth and has extremely high price, so that the cost of the platinum catalyst is high, and the platinum catalyst is difficult to support the large-scale application of a fuel cell taking platinum as a main catalyst, especially the large-scale application in the traffic field; on the other hand, the catalytic activity and stability of platinum are still insufficient, for example, even when a high-activity catalyst is used, the overpotential for electrochemical reduction of oxygen is still more than 300 mv, and it is difficult to further improve the energy conversion efficiency; in addition, in the long-term use process, the high-dispersion nano platinum particles tend to grow up, the catalytic activity is reduced, and the performance and the stability of the fuel cell are reduced.
In view of the gradual realization of the industrialization of fuel cells, it is necessary to improve the performance of the electrode catalyst and to reduce the cost. For this reason, on the one hand, in order to further improve the activity and stability of the platinum catalyst, many attempts have been made by researchers, such as improving the catalyst preparation method or using new methods to reduce the particle size of platinum particles, to increase the dispersion degree of platinum, or alloying platinum with other cheap transition metals to reduce the amount of platinum used and to improve the performance of the catalyst. In recent years, the development of the platinum-based core-shell catalyst is gradually paid attention, and the development and application of the nano platinum-based catalyst with the core-shell structure can greatly reduce the consumption of platinum in the catalyst and reduce the cost; meanwhile, the catalytic activity of the catalyst can be improved through the interaction between the core metal and the shell metal, so that the application of the catalyst in the fields of catalysis, chemical engineering, electrochemistry and the like is increasingly emphasized.
On the other hand, in recent years, the development of non-noble metal catalysts which have a certain activity and are expected to replace platinum catalysts for oxygen reduction reaction of fuel cells has become another focus in the development of fuel cells, and among them, carbon materials with high nitrogen content and high nitrogen content doped with transition metals are attracting attention because of their advantages such as wide sources of inexpensive materials and abundant and simple preparation structure. The electrochemical reduction reaction of the materials on oxygen shows certain electrocatalytic activity, and recent research results show that some non-platinum catalysts can show catalytic activity equivalent to that of platinum catalysts and better stable life even in an acidic environment (Science,332,2011,443). However, the multi-aspect research results show that the nitrogen-transition metal-carbon system has undeniable catalytic activity on the oxygen reduction reaction, develops ideas for reducing the cost of the proton exchange membrane fuel cell and promoting the industrialized development of the proton exchange membrane fuel cell, and develops new application potential. However, the catalytic mechanism and the active source of the material are not yet determined, and further exploration and cleaning are needed. On the other hand, the overall catalytic performance and stability of various non-noble metal catalysts including transition metal and nitrogen-doped carbon materials are behind the platinum-based catalysts, and the platinum-based catalysts cannot compete with and completely replace the platinum-based catalysts, so that the development of various non-platinum catalysts is mostly limited to laboratory level, and more half-cell tests are reported. Although single cell performance tests are reported, the number of the single cell performance tests is very small, which indicates that the research and the application of the catalyst need a long path and cannot be completely adapted to the rapid development and the application of the current fuel cell, especially a low-temperature proton exchange membrane fuel cell. Further improving the activity of the platinum-based catalyst, or at least maintaining the performance of the current platinum-based catalyst and simultaneously greatly reducing the cost of the catalyst and the usage amount of platinum, not only is beneficial to reducing the cost of the membrane electrode assembly and the fuel cell, but also can promote the rapid development of the proton exchange membrane fuel cell.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a non-noble metal catalytic material-loaded core-shell catalyst, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a core-shell catalyst supported by a non-noble metal catalytic material, including a non-noble metal-doped carbon-nitrogen carrier catalytic material used as a carrier, and core-shell particles supported on the surface of the carbon-nitrogen carrier catalytic material, where an original precursor mixed material of the carbon-nitrogen carrier catalytic material includes a carbon source material, a nitrogen source material, and a non-platinum group transition metal precursor, a core metal material in the core-shell particles is derived from a non-platinum group transition metal precursor for preparing the carbon-nitrogen carrier catalytic material, and an outer thin shell material in the core-shell particles is one or any combination of noble metals, or a metal mixed material or alloy mainly containing noble metals.
The non-noble metal catalytic material loaded core-shell catalyst has at least two catalytic active centers, one is from non-noble metal catalytic active sites on the surface of a non-noble metal-doped carbon nitrogen catalytic carrier material, and the other is from platinum group noble metal catalytic active sites of core-shell particles loaded on the surface of the carbon nitrogen catalytic carrier material. The core metal material in the core-shell particles and the non-noble metal material doped in the carbon-nitrogen catalytic carrier material come from the same source.
Preferably, the non-platinum group transition metal precursor is derived from various inorganic salts or organic compounds of non-platinum group transition metals, including, but not limited to, any one of metal halides, metal acetates, metal nitrates, metal nitrites, metal carbonates, metal cyanides, metal hydroxides, metal phosphates, metal sulfides, metal sulfates, metal sulfites, metal phthalocyanines, metal porphyrins, or combinations thereof.
Preferably, the non-platinum group transition metal includes, but is not limited to, any one of iron, cobalt, molybdenum, nickel, manganese, chromium, copper, zinc, or a combination thereof.
Preferably, the carbon source material includes, but is not limited to, any one of vinylamine (ethylenediamine), phthalocyanine, phenanthroline, melamine, aniline, saccharin, glucose, formaldehyde, phenol, polystyrene, porphyrin, pyrrole, pyridine, carbohydrate, high molecular organic, carbon support material, or a combination thereof.
Preferably, the nitrogen source material includes, but is not limited to, any one or combination of various amine-based compounds such as urea and ammonia, ammonium salt and nitride.
The non-platinum group transition metal precursor, the carbon source material and the nitrogen source material may be the same material or any combination of a plurality of materials.
Preferably, the original precursor mixed material of the carbon-nitrogen carrier catalytic material further comprises a catalyst structure directing agent, and the catalyst structure directing agent comprises a template agent, a chelating agent and a pore-forming agent.
Preferably, the template agent comprises any one or the combination of various molecular sieves, MCM-41, MCM-48, SBA-15 and other ordered mesoporous materials; the chelating agent includes, but is not limited to, any one of complexing agents such as complexone, F127, P123 and the like, surfactants or a combination thereof; the pore-forming agent includes, but is not limited to, any one of or a combination of sodium chloride, zinc chloride, aluminum chloride, magnesium chloride, calcium chloride, various carbonates, various nitrates, various ammonium salts.
Preferably, the original precursor mixed material of the carbon and nitrogen carrier catalytic material further comprises a carbon material for improving the conductivity of the carbon and nitrogen carrier catalytic material, enriching the three-dimensional structure of the carbon and nitrogen carrier catalytic material and dispersing non-noble metal particles, and on the other hand, the carbon material also plays a role of a carbon source, and in the heat treatment or pyrolysis process, the structure of the carbon and nitrogen carrier catalytic material can also have a non-noble metal and nitrogen doping process, and meanwhile, the carbon and nitrogen carrier catalytic material is also beneficial to the dispersion of the non-noble metal particles, so that the core-shell particles can be prepared in the next step. The carbon material includes, but is not limited to, any one or combination of acetylene carbon, carbon spheres, graphitic carbon, carbon nanotubes, carbon fibers, graphene and modifications thereof. The addition of the graphene oxide not only can play a role in dispersion, but also can improve the structure of the generated carbon and nitrogen carrier catalytic material.
Preferably, the noble metal comprises any one of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum and gold or a combination thereof.
The second aspect of the present invention provides a preparation method of the core-shell catalyst supported by the non-noble metal catalytic material in the above technical scheme, including the following steps:
(1) mixing various original precursor mixed materials for preparing the carbon and nitrogen carrier catalytic material with a solvent to prepare a mixed solution;
the raw precursor mixed materials for preparing the carbon and nitrogen carrier catalytic material can be respectively dissolved and then mixed according to the required amount, or can be mixed according to the required amount and then dissolved together.
(2) Evaporating and removing the solvent from the mixed solution obtained in the step (1), drying the solid mixture, roasting or thermally decomposing the obtained solid mixture at high temperature in a specific heat treatment atmosphere, and washing to remove impurities to obtain a non-noble metal-doped carbon nitrogen carrier catalytic material, wherein non-noble metal particles or oxides thereof are carried on the surface of the non-noble metal-doped carbon nitrogen carrier catalytic material;
(3) mixing a precursor solution of noble metal with non-noble metal nano particles or oxides thereof loaded on the surface of a carbon nitrogen carrier catalytic material, loading the noble metal on the surface of the non-noble metal particles by utilizing a replacement reaction between the precursor of the noble metal and the non-noble metal particles, adding a reducing agent to reduce the precursor of the noble metal in the solution together with other non-noble metal ions and depositing and loading the precursor of the noble metal on the surface of the non-noble metal-doped carbon nitrogen carrier catalytic material or the surface of the non-noble metal particles;
or directly dispersing the carbon and nitrogen carrier catalytic material by using an acidic solution to dissolve non-platinum transition metals in the carbon and nitrogen carrier catalytic material, then adding a precursor of noble metal, adding a reducing agent to reduce the precursor of the noble metal in the solution together with other non-noble metal ions and depositing and loading the precursor of the noble metal and the rest non-noble metal ions on the surface of the non-noble metal doped carbon and nitrogen carrier catalytic material or the surface of non-noble metal particles;
(4) carrying out solid-liquid separation on the mixture obtained in the step (3) to remove the solvent, and drying;
(5) placing the carbon and nitrogen carrier catalytic material loaded with the core-shell particles obtained in the step (4) in a reducing atmosphere, performing high-temperature treatment, and then annealing to room temperature;
(6) and (4) washing or boiling the solid obtained in the step (5) by using an acid solution, removing redundant non-noble metal elements on the surface, washing for many times, and drying to obtain a catalyst product.
Preferably, the solvent in step (1) includes, but is not limited to, any one of water, various types of alcohols, various types of ethers, various types of ketones, or a combination thereof; in step (2), the solvent is removed by a method including low-pressure evaporation or heating evaporation.
Preferably, in the step (1), various raw precursor mixed materials for preparing the carbon and nitrogen carrier catalytic material can be fully mixed with the solvent by stirring or ultrasonic vibration dispersion, and the stirring or ultrasonic vibration dispersion time is 0.1-72 hours.
Preferably, in the step (2), the temperature of the high-temperature roasting treatment or the thermal decomposition is 200-1200 ℃; the high-temperature roasting treatment or the thermal decomposition is divided into 1-10 stages, preferably 1-5 stages, and the temperature programming rate of each stage is 0.01-50.0 ℃ per minute, preferably 0.5-10.0 ℃ per minute; the heat treatment atmosphere includes, but is not limited to, an inert atmosphere, a reducing atmosphere, or an atmosphere containing ammonia.
Preferably, in the step (5), the temperature of the high-temperature treatment is 100 to 1200 ℃, the high-temperature treatment is divided into 1 to 10 stages, preferably 1 to 5 stages, the temperature programming rate of each stage is 0.01 to 50.0 ℃ per minute, preferably 0.5 to 10.0 ℃ per minute, and the treatment time of each stage is 0.1 to 36 hours, preferably 0.2 to 12 hours; the reducing atmosphere comprises any one or combination of hydrogen, carbon monoxide, ammonia gas and low-carbon small-molecular hydrocarbon, and the volume content of the reducing gas in the atmosphere is 0.05-100%, preferably 0.1-50%, and further preferably 0.5-30%. The balance gas is an inert gas such as nitrogen, argon, etc.
Preferably, in the step (6), the acid solution includes, but is not limited to, any one or a combination of various inorganic acids and organic acids such as sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, acetic acid, and the like, the required acid washing treatment temperature is-20 to 300 ℃, preferably 20 to 260 ℃, the acid washing treatment time is 0.1 to 80 hours, and the concentration of the acid solution is 0.1 to 5 mol/l, preferably 0.5 to 1.5 mol/l.
Preferably, in step (6), the liquid required for washing includes, but is not limited to, any one of an acidic aqueous solution, a basic aqueous solution, high purity water, various types of alcohols, various types of ketones, or a combination thereof.
Preferably, in the step (2), after the roasting treatment or the thermal decomposition, the carbon nitrogen carrier catalytic material obtained in the step (2) is boiled or washed by a concentrated alkali solution, a catalyst structure directing agent (such as an oxide material containing silicon aluminum such as MCM 41) is removed, the treatment temperature is not higher than 200 ℃, the time is not higher than 3 days, and the carbon nitrogen carrier catalytic material is washed by a solvent for multiple times, wherein the solvent for washing comprises any one or the combination of high-purity water, various alcohols and various ketones.
Preferably, in step (3), the acidic solution for re-dispersing the carbon and nitrogen carrier catalytic material includes, but is not limited to, any one or combination of various inorganic acids and organic acids such as sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, acetic acid, etc., preferably, but not limited to, an acidic solution containing a desired noble metal element, such as chloroplatinic acid, chloroauric acid, chloroiridic acid, etc., and a precursor of the noble metal may be added to the acidic slurry containing the carbon and nitrogen carrier material and thoroughly mixed to prepare a homogeneous slurry.
Preferably, the reducing agent includes, but is not limited to, any one of sodium borohydride, hydrogen, formaldehyde, lower alcohol, and formic acid.
The third aspect of the invention provides an application of a non-noble metal catalytic material supported core-shell catalyst, wherein catalyst slurry or ink prepared by mixing the core-shell catalyst with an ion conduction reagent, an additive and a solvent can be transferred and supported on a solid electrolyte membrane or an electrode diffusion layer, and a membrane electrode assembly is prepared by hot pressing. The ion conducting agent and the main component conducting ions in the solid electrolyte membrane are the same component.
The non-noble metal catalytic material supported core-shell catalyst can be preferentially used for but not limited to fuel cells, particularly preferentially used for but not limited to proton exchange membrane fuel cells, direct alcohol fuel cells, various metal-oxygen (air) cells and the like, and preferentially used for but not limited to the electroreduction reaction of oxygen or air or the electrolysis reaction of water and the like.
Compared with the prior art, the invention has the beneficial effects that:
1. the catalyst of the invention has a plurality of catalytic activity sites, the catalytic activity of the catalyst mainly comes from two parts, one part comes from non-noble metal doped carbon nitrogen carrier catalytic material used as a carrier, the other part comes from core-shell catalytic particles loaded on the carbon nitrogen carrier catalytic material, the core material of the core-shell catalytic particles is non-noble metal used in the preparation of carbon and nitrogen carrier catalytic materials, the outer thin shell is a thin layer of platinum group or is formed by a mixture of rich noble metals, the interaction between the thin shell nano material and the non-noble metal doped carbon nitrogen carrier catalytic material, and the interaction between the shell material and the core material in the thin-shell nano particles improves the catalytic performance and the service life of the catalyst, greatly reduces the use amount of noble metal, reduces the cost of the catalyst and improves the competitiveness of the composite catalyst.
2. The platinum group noble metal in the catalyst has the advantages of low use amount, high utilization rate, low cost, high activity, strong material conductivity and the like, the composite catalyst has the advantages of high activity of a platinum-based catalyst and the like, has the advantages of low cost, strong poisoning resistance and the like of a non-platinum catalyst, and can be used as an electrode catalyst, such as an oxygen reduction electrocatalyst or an electrolytic water catalyst, and can also be used for other chemical reactions. Meanwhile, the composite catalyst has a large specific surface, ordered pore structure distribution and a high hydrophobic property, and is beneficial to the conduction of gas and electrons in the actual electrochemical reaction environment, such as the actual use of a fuel cell, so that the overall performance of the reactor is improved.
3. The preparation method disclosed by the invention can fully utilize the non-noble metal remained in the preparation process of the non-noble metal catalyst to prepare the core-shell catalytic particles, can avoid material consumption and environmental pollution, saves time, simplifies the electrode manufacturing steps and improves the catalyst activity and the platinum utilization rate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a flowchart of a method for preparing a core-shell catalyst supported by a non-noble metal catalytic material according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of cobalt-nitrogen double-doped carbon-nitrogen carrier material (CoO)x/C-N) supported platinum-cobalt core-shell (Co @ Pt) catalyst
In a first step, a cobalt-nitrogen double-doped carbon-nitrogen carrier material (CoO) is preparedx/C-N)：
In a typical example of the preparation of a cobalt nitrogen double doped carbon nitrogen carrier material, Pentaethylenehexamine (Pentaethylenehexamine) is used as carbon and nitrogen source, cobalt nitrate (Co (NO)3)2·6H2O) was used as a cobalt source. Firstly, 6.0 g of pentaethylenehexamine is dissolved in 50 ml of water and stirred for 0.5 hour to be uniformly mixed; then 6.5 g of MCM41 which is ground and dried in advance is added, and the mixture is ultrasonically oscillated and stirred for 2 hours to be uniformly dispersed and kept stirring; thereafter, 2.3 g of polyvinylpyrrolidone (PVP) was dissolved in 50 ml of water, and 1.5 g of cobalt nitrate and 1.6 g of zinc nitrate (Zn (NO)3)2·6H2O), ultrasonically oscillating and stirring for one hour to uniformly mix the three; then, an aqueous solution containing cobalt nitrate, zinc nitrate and PVP was slowly dropped into the slurry containing pentaethylenehexamine, and stirred at room temperature for 12 hours. Mixing thoroughlyAnd removing water from the combined slurry by using a rotary evaporator at 50 ℃, freeze-drying to obtain a black powder sample, and carrying out heat treatment on the black powder sample in a tubular furnace under the protection of high-purity nitrogen. During heat treatment, firstly heating from room temperature to 450 ℃ at a heating rate of 2 ℃ per minute, keeping the temperature for 2 hours, then heating to 1050 ℃ at the same heating rate, keeping the temperature for 3 hours, and finally naturally cooling to room temperature to obtain an initial sample of the cobalt-nitrogen double-doped carbon-nitrogen carrier material. The obtained non-noble metal catalytic carrier material is washed for multiple times by using a sodium hydroxide solution (10.0 mol/L) and an ethanol aqueous solution (1/3V/V) in sequence, finally the washed carbon nitrogen carrier material is subjected to 200-degree hydrothermal activation in a concentrated ammonia aqueous solution (28 percent wt), and after filtration and washing, the carbon nitrogen carrier material is dried for 12 hours at 80 degrees to prepare 0.55 g of cobalt nitrogen double-doped carbon nitrogen carrier material (CoO)x/C-N)。
Secondly, preparing load type core-shell particles on the surface of a carbon and nitrogen carrier:
ultrasonically dispersing the carbon-nitrogen carrier material obtained in the first step into 150 ml of high-purity water again, heating to 60 ℃, stirring, introducing hydrogen for bubbling for 2 hours, treating the carrier, and then introducing nitrogen for bubbling protection. After bubbling nitrogen for 3 hours, 3.5 ml of potassium chloroplatinate solution (0.5 mol/l K) was added2PtCl6) And kept stirring for 6 hours. Then heating to 80 ℃, adding 10 ml of formaldehyde solution (37%), keeping stirring for 1 hour, then cooling to carry out solid-liquid separation, and freeze-drying to obtain a black solid sample. And putting the black sample in a tube furnace, introducing nitrogen-hydrogen mixed gas (hydrogen content is 5%), heating to 120 ℃ at the temperature of 5 ℃/min, keeping for two hours, heating to 650 ℃, treating for 6 hours, cooling to room temperature, and purging with nitrogen for 2 hours to obtain the sample. And dispersing the obtained solid sample in 150 ml of nitric acid solution (1 mol/L), boiling for 24 hours at 60 ℃, removing redundant cobalt, washing the solid-liquid separation by using high-purity water and ethanol for multiple times alternately, and freeze-drying to obtain the final product.
Example 2
Preparation of iron-cobalt-nitrogen doped carbon-nitrogen carrier material (FeCoO)x/C-N) supported platinum iron cobalt core-shell (FeCo @ Pt) catalyst
First, preparing an iron-cobalt-nitrogen doped carbon-nitrogen carrier material (FeCoO)x/C-N)：
In a typical example of the preparation of a ferro-cobalt-nitrogen bi-metal doped carbon-nitrogen carrier material, Pentaethylenehexamine (PEHA) is used as a carbon and nitrogen source, ferric nitrate (Fe (NO)3)3·9H2O) cobalt nitrate (Co (NO)3)2·6H2O) was used as the metal source. Firstly, 8.0 g of pentaethylenehexamine is dissolved in 80 ml of water and stirred for 0.5 hour to be uniformly mixed; then 10.5 grams of previously ground and dried MCM41 was added, ultrasonically oscillated and stirred for 2 hours to be uniformly dispersed and kept stirring; thereafter, 3.3 g of polyvinylpyrrolidone (PVP) was dissolved in 50 ml of water, and 1.5 g of iron nitrate, 1.0 g of cobalt nitrate and 2.0 g of zinc nitrate (Zn (NO)3)2·6H2O), ultrasonically oscillating and stirring for one hour to uniformly mix; then, the mixed aqueous solution containing PVP was slowly dropped into the slurry containing pentaethylenehexamine, and stirred at room temperature for 12 hours. And (3) removing water from the fully mixed and infiltrated mixed slurry by using a rotary evaporator at 50 ℃, freeze-drying to obtain a black powder sample, and carrying out heat treatment on the black powder sample in a tubular furnace under the protection of high-purity nitrogen. During heat treatment, firstly heating from room temperature to 450 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2 hours, then heating to 850 ℃ at the same heating rate, keeping the temperature for 2 hours, and finally naturally cooling to room temperature to obtain an initial sample of the iron-cobalt bimetal doped carbon-nitrogen carrier material. The obtained non-noble metal catalytic carrier is washed for multiple times by using a sodium hydroxide solution (6.0 mol/L) and an ethanol aqueous solution (1/3V/V) in sequence, finally, the washed carbon-nitrogen carrier material is subjected to 200-degree hydrothermal activation in a concentrated ammonia aqueous solution (28 percent wt), and after filtration and washing, the carbon-nitrogen carrier material is dried for 12 hours at 120 degrees to prepare 0.78 g of metal-nitrogen double-doped carbon-nitrogen carrier material (FeCoO) loaded with iron-cobalt metal particlesx/C-N)。
Step two, preparing load type core-shell particles to the surface of a carbon and nitrogen carrier:
ultrasonically dispersing the carbon-nitrogen carrier material obtained in the first step into 150 ml of high-purity water again, heating to 60 ℃, stirring, introducing hydrogen for bubbling for 2 hours, treating the carrier, and then introducing nitrogen for bubbling protection. After bubbling nitrogen for 3 hours, 21 ml of potassium chloroplatinate solution is added(0.05 mol/l K)2PtCl6) And kept stirring for 6 hours. And heating to 80 ℃, adding 10 ml of formaldehyde solution (37%), keeping stirring for 1 hour, cooling, standing, centrifuging to separate out a solid sample, washing with a water-ethanol solution for multiple times, and freeze-drying to obtain a black solid sample. And putting the black sample into a tube furnace, introducing nitrogen-hydrogen mixed gas (hydrogen content is 5%), heating to 120 ℃ at the temperature of 5 ℃/min, keeping for two hours, then heating to 600 ℃, treating for 6 hours, cooling to room temperature, and purging with nitrogen for 2 hours to obtain the sample. And dispersing the obtained solid sample in 150 ml of sulfuric acid solution (1 mol/L), boiling for 18 hours at 65 ℃, removing redundant iron and cobalt, washing the solid-liquid separation with high-purity water for multiple times, and freeze-drying to obtain the final product.
Example 3
Preparation of a cobalt molybdenum nitrogen-doped carbon-nitrogen support material (CoMoO)x/C-N) supported platinum-cobalt-molybdenum core-shell (CoMo @ Pt) catalyst
In a first step, a cobalt molybdenum nitrogen doped carbon nitrogen carrier material (CoMoO) is preparedx/C-N)：
25 g of sodium chloride is dissolved in 100 ml of deionized water, 9.5 g of pentaethylenehexamine (pentaethylenehexamine) is added dropwise, and after stirring for one hour, 15 g of MCM-41 is added and ultrasonic dispersion is carried out for two hours, so as to obtain MCM-41 superfine slurry. 20 ml of ethanol dissolved 1.8 g of cobalt chloride (CoCl)2·6H2O) and 3.1 g ammonium molybdate ((NH)4)6Mo7O24·4H2O), uniformly mixed (the weight ratio of cobalt to molybdenum is 3), added to the MCM-41 slurry and stirred overnight. The viscous paste after removal of most of the solvent by rotary evaporation at 50 ℃ was snap frozen and freeze dried to remove the remaining solvent to give a black sample. Then placing the sample in a tube furnace, introducing high-purity nitrogen, and carrying out temperature programmed heat treatment: increasing from room temperature to 300 degrees at a rate of 1 degree/minute for 2 hours; then raised to 750 degrees at 2 degrees/minute for 3 hours. Cooling to room temperature under the protection of nitrogen, sequentially soaking and washing with aqueous solution of sodium hydroxide (8 mol/L) and aqueous solution of ethanol (1/3V/V) for several times, and drying in an oven at 120 deg.C overnight to obtain non-noble metal carbon nitrogen catalytic carrier (CoMoO) loaded with cobalt molybdenum metal particlesx/C-N)。
Secondly, preparing load type core-shell particles on the surface of a carbon and nitrogen carrier:
ultrasonically dispersing the carbon and nitrogen carrier material obtained in the first step into 250 ml of high-purity water again, introducing nitrogen for bubbling protection, adding an excessive newly-configured sodium borohydride aqueous solution to treat a sample, adjusting the pH value to be alkaline, and bubbling the nitrogen overnight. 1 g of chloroplatinic acid (H)2PtCl6·6H2O) was dissolved in 50 ml of high-purity water and added, and stirring was maintained for 8 hours. Then heating to 80 ℃, adding 10 ml of formaldehyde solution (37%), keeping stirring for 2 hours, then cooling to carry out solid-liquid separation, and freeze-drying to obtain a black solid sample. The black sample is put into a tube furnace and is filled with argon-hydrogen mixed gas (the hydrogen content is 3 percent), the temperature is raised to 120 ℃ at 5 ℃ per minute for two hours, then the temperature is raised to 600 ℃ at 2 ℃ per minute for treatment for 6 hours, the temperature is reduced to room temperature, and the argon is used for blowing for 5 hours to obtain the sample. And dispersing the obtained solid sample in 150 ml of sulfuric acid solution (1 mol/L), boiling for 8 hours at 65 ℃, removing redundant cobalt and molybdenum, washing the solid-liquid separation with high-purity water for multiple times, and freeze-drying to obtain the final product.
Example 4
Preparation of iron-cobalt-nitrogen doped carbon-nitrogen carrier material (FeCoO)x/C-N) supported platinum iron cobalt core-shell (FeCo @ Pt) catalyst
First, preparing an iron-cobalt-nitrogen doped carbon-nitrogen carrier material (FeCoO)x/C-N)：
The previous step was the same as the first step in example 2.
And boiling the obtained non-noble metal catalytic carrier by using a sodium hydroxide solution (6.0 mol/L) in sequence, washing the non-noble metal catalytic carrier by using an ethanol water solution (1/3V/V) for multiple times, and finally ultrasonically oscillating the washed carbon and nitrogen carrier material by using a nitric acid solution (1.5 mol/L) for half an hour for dispersion for later use.
Secondly, preparing load type core-shell particles on the surface of a carbon and nitrogen carrier:
after bubbling nitrogen gas for 2 hours into the nitric acid solution-dispersed carbon nitrogen carrier material slurry obtained in the first step, a chloroplatinic acid solution (0.05 mol/L H) was added2PtCl6) Stirring for 5 hr to mix thoroughly, blendingThe pH value is adjusted to 9. After further warming to 80 ℃, 15 ml of formaldehyde solution (37%) was added and stirring was maintained for 2 hours, and then the solvent was removed by a rotary evaporator, washed with ethanol several times, and freeze-dried to give a black solid sample. The black sample is put into a tube furnace and is filled with nitrogen-hydrogen mixed gas (hydrogen content is 5 percent), the temperature is raised to 120 ℃ at the rate of 5 ℃ per minute and is kept for two hours, then the temperature is raised to 600 ℃ at the rate of 2.5 ℃ per minute for treatment for 6 hours, the temperature is reduced to room temperature, and the nitrogen is used for blowing for 2 hours to obtain the sample. And dispersing the obtained solid sample in 150 ml of nitric acid solution (1.5 mol/L), boiling for 20 hours at 65 ℃, removing redundant iron and cobalt, then carrying out solid-liquid separation, washing with high-purity water for multiple times, and freeze-drying to obtain the final product.
The composite catalyst and the preparation method thereof not only can greatly reduce the usage amount of expensive noble metals, especially platinum, but also can greatly improve the utilization rate of the platinum through a thin shell structure, and improve the overall performance of the catalyst through the interaction of the core shell and the interaction between the core shell particles and the non-noble metal doped carbon nitrogen carrier, so that the cost of the membrane electrode and the overall fuel cell can be greatly reduced by adopting the catalytic electrode disclosed by the invention, and the commercial application of the fuel cell can be greatly promoted. On the other hand, the preparation method disclosed by the invention has simple and direct process, the product has a highly ordered porous structure and better hydrophobic property, is very favorable for gas conduction and water drainage in electrode reaction, avoids the performance attenuation of the fuel cell caused by substance conduction, can obviously prolong the service life of the proton exchange membrane fuel cell, and is also very favorable for industrialization of the fuel cell.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (19)
1. A preparation method of a core-shell catalyst loaded by a non-noble metal catalytic material is characterized by comprising the following steps:
(1) mixing various original precursor mixed materials for preparing the carbon and nitrogen carrier catalytic material with a solvent to prepare a mixed solution;
(2) evaporating and removing the solvent from the mixed solution obtained in the step (1), drying the solid mixture, thermally decomposing the obtained solid mixture at high temperature in a specific heat treatment atmosphere to obtain a primary product, washing the primary product with an alkaline solution and an ethanol aqueous solution for multiple times to remove impurities, and drying the primary product to obtain a secondary product, namely a non-noble metal-doped carbon and nitrogen carrier catalytic material, wherein the surface of the non-noble metal-doped carbon and nitrogen carrier catalytic material is loaded with non-noble metal particles or oxides thereof;
(3) mixing a precursor solution of noble metal and a non-noble metal-doped carbon nitrogen carrier catalytic material, loading noble metal on the surfaces of non-noble metal particles by utilizing a displacement reaction between the precursor of the noble metal and the non-noble metal particles, adding a reducing agent, reducing the precursor of the noble metal in the solution and the displaced non-noble metal ions together, and depositing and loading the precursor of the noble metal on the surfaces of the non-noble metal-doped carbon nitrogen carrier catalytic material or the surfaces of the non-noble metal particles;
or the non-noble metal-doped carbon nitrogen carrier catalytic material is directly dispersed by an acid solution to dissolve non-platinum transition metals, then a precursor of noble metal is added, and a reducing agent is added to reduce the precursor of the noble metal and non-noble metal ions in the solution together and deposit and load the precursor and non-noble metal-doped carbon nitrogen carrier catalytic material on the surface of the non-noble metal-doped carbon nitrogen carrier catalytic material;
(4) carrying out solid-liquid separation on the mixture obtained in the step (3) to remove the solvent, and drying;
(5) placing the carbon and nitrogen carrier catalytic material loaded with the core-shell particles obtained in the step (4) in a reducing atmosphere, performing high-temperature treatment, and then annealing to room temperature;
(6) and (4) washing or boiling the solid obtained in the step (5) by using an acid solution, removing redundant non-noble metal elements on the surface, washing for many times, and drying to obtain a catalyst product.
2. The method for preparing a core-shell catalyst supported by a non-noble metal catalytic material according to claim 1, wherein the solvent in the step (1) comprises any one or combination of water, various alcohols, various ethers, various ketones; in step (2), the solvent is removed by a method including low-pressure evaporation or heating evaporation.
3. The preparation method of the non-noble metal catalytic material supported core-shell catalyst according to claim 1, wherein in the step (1), various original precursor mixed materials for preparing the carbon-nitrogen carrier catalytic material are fully mixed with the solvent by stirring or ultrasonic oscillation dispersion, and the stirring or ultrasonic oscillation dispersion time is 0.1-72 hours.
4. The preparation method of the non-noble metal catalytic material supported core-shell catalyst according to claim 1, wherein in the step (2), the thermal decomposition temperature is 200-1200 ℃; the thermal decomposition is divided into 1-10 stages, and the temperature programming rate of each stage is 0.01-50.0 ℃ per minute; the heat treatment atmosphere comprises inert atmosphere and reducing atmosphere.
5. The preparation method of the non-noble metal catalytic material supported core-shell catalyst according to claim 1, wherein in the step (5), the temperature of the high-temperature treatment is 100-1200 ℃, the high-temperature treatment is divided into 1-10 stages, the temperature programming rate of each stage is 0.01-50.0 ℃ per minute, and the treatment time of each stage is 0.1-36 hours; the reducing atmosphere comprises any one or combination of hydrogen, carbon monoxide, ammonia and low-carbon small-molecule hydrocarbon, and the volume content of the reducing gas in the atmosphere is 0.05-100%.
6. The method for preparing a non-noble metal catalytic material supported core-shell catalyst according to claim 1, wherein in the step (6), the acidic solution comprises any one or a combination of various inorganic acids and organic acids, the required acid washing temperature is-20 to 300 ℃, the acid washing time is 0.1 to 80 hours, and the concentration of the acidic solution is 0.1 to 5 mol/l.
7. The method for preparing a core-shell catalyst supported by a non-noble metal catalytic material according to claim 1, wherein in the step (6), the acidic solution required for washing comprises any one or a combination of sulfuric acid, nitric acid, hydrochloric acid, perchloric acid and acetic acid.
8. The method for preparing a non-noble metal catalytic material supported core-shell catalyst according to claim 1, wherein in the step (2), after thermal decomposition, the carbon nitrogen carrier catalytic material obtained in the step (2) is boiled or washed by a concentrated alkali solution, the catalyst structure directing agent is removed, and the alkali boiling or washing temperature is not more than 200 ℃ and the time is not more than 3 days; washing with solvent for several times, wherein the solvent comprises any one or combination of high purity water, various alcohols, various ketones.
9. The method for preparing a core-shell catalyst supported by a non-noble metal catalytic material as claimed in claim 1, wherein in the step (3), the acidic solution for re-dispersing the carbon nitrogen carrier catalytic material comprises any one or a combination of various inorganic acids and organic acids containing the desired noble metal elements.
10. The method for preparing a core-shell catalyst supported by a non-noble metal catalytic material according to claim 1, wherein the reducing agent comprises any one of sodium borohydride, hydrogen, formaldehyde, lower alcohol and formic acid.
11. The non-noble metal catalytic material supported core-shell catalyst prepared by the preparation method of any one of claims 1 to 10, which comprises a non-noble metal doped carbon-nitrogen carrier catalytic material used as a carrier and core-shell particles supported on the surface of the carbon-nitrogen carrier catalytic material, wherein the raw precursor mixed material of the carbon-nitrogen carrier catalytic material comprises a carbon source material, a nitrogen source material and a non-platinum group transition metal precursor, the core metal material in the core-shell particles is derived from the non-platinum group transition metal precursor for preparing the carbon-nitrogen carrier catalytic material, and the outer layer thin shell material in the core-shell particles is one or more of noble metals or a metal mixed material or alloy mainly containing noble metals.
12. The non-noble metal catalytic material supported core-shell catalyst of claim 11, wherein the non-platinum group transition metal precursor is derived from various inorganic salts or organic compounds of non-platinum group transition metals, including any one or combination of metal halides, metal acetates, metal nitrates, metal nitrites, metal carbonates, metal cyanides, metal hydroxides, metal phosphates, metal sulfides, metal sulfates, metal sulfites, metal phthalocyanines, and metal porphyrins.
13. The non-noble metal catalytic material supported core-shell catalyst of claim 12, wherein the non-platinum group transition metal comprises any one or combination of iron, cobalt, molybdenum, nickel, manganese, chromium, copper, zinc.
14. The core-shell catalyst supported by the non-noble metal catalytic material according to claim 11, wherein the carbon source material comprises any one or a combination of vinylamine, phthalocyanine, phenanthroline, melamine, aniline, saccharin, formaldehyde, phenol, porphyrin, pyrrole, pyridine, carbohydrate, high molecular organic matter, and carbon support material.
15. The non-noble metal catalytic material supported core-shell catalyst of claim 11, wherein the nitrogen source material comprises any one or combination of various types of amine based compounds, nitrides, ammonium salts.
16. The non-noble metal catalytic material supported core-shell catalyst of claim 11, wherein the original precursor mixture of the carbon and nitrogen carrier catalytic material further comprises a catalyst structure directing agent, and the catalyst structure directing agent comprises a template agent, a chelating agent, and a pore-forming agent.
17. The non-noble metal catalytic material supported core-shell catalyst of claim 16, wherein the template comprises any one or combination of various molecular sieves, ordered mesoporous materials; the chelating agent comprises any one or the combination of a complexing agent and a surfactant; the pore-forming agent comprises any one or combination of sodium chloride, zinc chloride, aluminum chloride, magnesium chloride, calcium chloride, various carbonates, various nitrates and various ammonium salts.
18. The non-noble metal catalytic material supported core-shell catalyst of claim 11, wherein the raw precursor mixture of the carbon and nitrogen carrier catalytic material further comprises a carbon material for improving the conductivity of the carbon and nitrogen carrier catalytic material, enriching the three-dimensional structure of the carbon and nitrogen carrier catalytic material, and dispersing non-noble metal particles, and the carbon material comprises any one or a combination of acetylene carbon, carbon spheres, graphitic carbon, carbon nanotubes, carbon fibers, graphene and graphene modifications.
19. The non-noble metal catalytic material supported core-shell catalyst of claim 11, wherein the noble metal comprises any one or combination of ruthenium, rhodium, palladium, silver, osmium, iridium, platinum, gold.
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