CN114804090B - Three-dimensional carrier, catalyst and preparation method thereof - Google Patents
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Abstract
The application particularly relates to a three-dimensional carrier, a catalyst and a preparation method thereof, which belong to the technical field of fuel cells, and the interaction between a carbon nano tube and graphene oxide is enhanced by carrying out functionalization treatment on the carbon nano tube, and the construction of the three-dimensional composite carrier of the carbon nano tube and graphene is further promoted by hydrothermal reaction, so that a rapid mass transfer channel is formed, and the catalytic reaction rate is improved; by introducing the carbon nanotubes, stacking among graphene sheets is effectively avoided, the advantages of large specific surface area, high stability and strong metal-carrier interaction of graphene and the carbon nanotubes are cooperatively exerted, the dispersing sites of metal particles are increased, and the stability of the metal particles is improved; the introduction of the cationic functional groups uniformly disperses the supported metal on the surface of the carrier in situ, reduces the particle size of the metal and improves the effective reaction activity area.
Description
Technical Field
The application belongs to the technical field of fuel cells, and particularly relates to a three-dimensional carrier, a catalyst and a preparation method thereof.
Background
The Proton Exchange Membrane Fuel Cell (PEMFC) has the advantages of high power density, high energy efficiency, high starting speed, small environmental pollution and the like, is an ideal clean energy source, and has wide application prospect in the fields of fixed power stations, transportation and the like. However, since the kinetics of the cathodic oxygen reduction reaction of the fuel cell is slow, a large amount of Pt catalyst is required, and the popularization and application of the fuel cell are severely restricted by the high price and resource scarcity, so that development of an efficient electrochemical catalyst to reduce the amount of Pt is urgently required.
The Pt and the non-noble metal form an alloy catalyst, and the electron, the geometric configuration and the d-band center position of the Pt are regulated and controlled by the non-noble metal element, so that the bonding energy of oxygen-containing species on the surface of the catalyst is reduced, and the ORR catalytic activity of the Pt can be effectively improved. As one of non-noble metals, cu has great advantages in price and reserve, and can meet the market demand. In addition, because the electronegativity difference between Cu and Pt is smaller, a simple and controllable liquid phase reduction method can be adopted to prepare the Pt-Cu alloy catalyst. Studies show that the bonding effect of Cu and Pt can greatly improve the ORR performance of Pt, for example, the ORR activity of PtCu/C catalysts prepared by Coleman and the like is improved by 2-3 times compared with that of commercial Pt/C catalysts (Johnson Matthey), and the improvement of the catalytic activity is mainly caused by the reduction of the adsorption energy of oxygen-containing species OHID on the catalytic surface.
Besides improving the catalytic activity of Pt by modulating components, the controllable design of the structure and the morphology of the catalyst is also an effective path. It was found that the (111) crystal plane of the Pt alloy catalyst has excellent ORR catalytic activity and is much higher than the (110) and (100) crystal planes. Therefore, great research interest is drawn in designing and synthesizing (111) crystal face coated Pt alloy octahedra.
In the prior art, chinese patent application No. CN108258258A is a method for synthesizing a Cu-rich octahedral PtCu nano catalyst, which obtains unsupported Cu-rich octahedral PtCu nano crystals by a solvothermal method. The Chinese patent application CN111293322B discloses a carbon-supported octahedral shape platinum-copper-molybdenum ternary alloy catalyst for a fuel cell and a preparation method thereof, wherein platinum-copper-molybdenum metal particles are obtained through a solvothermal method, and carbon powder is added into ethanol slurry of the platinum-copper-molybdenum metal particles to obtain the carbon-supported octahedral shape platinum-copper-molybdenum ternary alloy catalyst. In the prior art, no anchor site is formed by crystal nucleus in PtCu/PtCuMo octahedron synthesis process or no carrier is added, the alloy particle size is larger, and the number of reactive sites is reduced; or the added carbon carrier is XC-72 carbon black, which is easy to corrode in the working environment of the fuel cell, thereby causing agglomeration of metal particles and reduction of the activity of the catalyst; and no transition metal etching treatment is adopted, and the dissolution of transition metal in the catalyst can cause the attenuation of the catalyst activity and the degradation of the membrane, so that the durability of the proton exchange membrane fuel cell is affected.
Disclosure of Invention
The application aims to at least solve the problem of low activity caused by the adoption of a carbon black carrier at present to a certain extent, and therefore, the application provides a three-dimensional carrier, a catalyst and a preparation method thereof.
Applicants found during the course of the application that: according to the synthesis method of the Cu-rich octahedral PtCu nano catalyst in the prior art, no carrier is added in a reaction system, so that no anchor site is formed by crystal nucleus, the alloy particle size is large, the number of reactive sites is reduced, and metal particles are easy to stack in the preparation process of a fuel cell electrode, so that the activity of the catalyst is reduced; without the transition metal etching treatment, the dissolution of the transition metal in the catalyst can cause the attenuation of the catalyst activity and the degradation of the membrane, and the durability of the proton exchange membrane fuel cell is affected. In the platinum copper molybdenum ternary alloy catalyst with the carbon-supported octahedron morphology for the fuel cell and the preparation method thereof, the carrier supporting the PtCuMo octahedron is XC-72 carbon black, and corrosion is easy to occur in the working environment of the fuel cell, so that agglomeration of metal particles and activity reduction of the catalyst are caused; without the transition metal etching treatment, the dissolution of the transition metal in the catalyst can cause the attenuation of the catalyst activity and the degradation of the membrane, and the durability of the proton exchange membrane fuel cell is affected.
Aiming at the problems that a carbon carrier is easy to corrode, the alloy particle size is large, transition element Cu is easy to run away in the operation process and the like in the traditional PtCu alloy octahedral catalyst, the stability of the carrier is enhanced, the interaction between the carrier and an active component is enhanced, unstable transition metals are reduced and the like, and the performance and the stability of the PtCu alloy octahedral catalyst are improved.
According to a first aspect of an embodiment of the present application, there is provided a three-dimensional carrier, the raw materials of the three-dimensional carrier including:
oxidized graphene; and
a functionalized carbon nanotube, the functionalized carbon nanotube comprising: the preparation method comprises the steps of pretreating a carbon nano tube and polydiallyl dimethyl ammonium chloride solution, wherein the pretreated carbon nano tube is prepared by mixing and pretreating the carbon nano tube and an acid solution.
By carrying out functionalization treatment on the carbon nano tube, the interaction between the carbon nano tube and graphene oxide is enhanced, the construction of a three-dimensional composite carrier of the carbon nano tube and the graphene is promoted, a rapid mass transfer channel is formed, and the catalytic reaction rate is improved; by introducing the carbon nano tube, stacking among graphene sheets is effectively avoided, the advantages of large specific surface area, high stability and strong metal-carrier interaction of graphene and the carbon nano tube are cooperatively exerted, the dispersing sites of the subsequent carried metal particles can be increased, and the stability of the metal particles is improved; the introduction of the cationic functional groups can uniformly disperse the subsequent carried metal on the surface of the carrier in situ, reduce the particle size of the metal and improve the effective reaction activity area.
In addition, the three-dimensional carrier according to the above embodiment of the present application may further have the following additional technical features:
in some embodiments, the acid solution is HNO 3 And H 2 SO 4 Is used as a mixed acid solution of the above-mentioned components.
In some embodiments, the mixed acid solution comprises HNO 3 And H 2 SO 4 The molar ratio of (2) is 1:2-2:1, wherein HNO 3 The molar concentration of (C) is 5mol/L to 10mol/L.
In some embodiments, the relationship between the carbon nanotubes and the amount of acid solution used satisfies: 1mg to 3mg of the carbon nanotubes are mixed per 1mL of the acid solution.
The effects of controlling the parameters and removing impurities and increasing oxygen-containing functional groups are obvious, and the structure of the carbon nano tube is not damaged.
In some embodiments, the polydiallyl dimethyl ammonium chloride solution has a mass concentration of 3mg/mL to 10mg/mL.
In some embodiments, the relation between the amount of pretreated carbon nanotubes and the polydiallyl dimethyl ammonium chloride solution used satisfies: 1mg to 3mg of the pretreated carbon nanotubes are mixed per 1mL of the polydiallyl dimethyl ammonium chloride solution.
In some embodiments, the mass ratio of the functionalized carbon nanotubes to the graphene oxide is 1:1-5:1, wherein the mass concentration of the graphene oxide is 0.5mg/mL-3mg/mL.
The mass ratio of the FCNT to the GO of the graphene oxide is too small, and the effect of supporting the GO sheets is not obvious; the mass ratio is too large, and redundant FCNT cannot form a three-dimensional composite structure with GO;
the graphene oxide GO is too small in concentration, a graphene three-dimensional hydrogel structure is difficult to form under general operation, the graphene oxide GO is too large in concentration, and the graphene oxide GO is difficult to completely disperse in water under general operation.
A second aspect of an embodiment of the present application provides a method for preparing a three-dimensional carrier, the method including:
mixing and pre-treating the carbon nano tube and the acid solution to remove impurities of the carbon nano tube and increase the concentration of oxygen-containing functional groups on the surface of the carbon nano tube so as to obtain a pre-treated carbon nano tube;
mixing the pretreated carbon nanotube with polydiallyl dimethyl ammonium chloride solution to obtain a functionalized carbon nanotube;
and carrying out hydrothermal reaction on the functionalized carbon nano tube and graphene oxide to obtain the three-dimensional carrier.
According to the method, through functionalization treatment of the carbon nano tube, the interaction between the carbon nano tube and graphene oxide is enhanced, and further through hydrothermal reaction, the construction of a three-dimensional composite carrier of the carbon nano tube and graphene is promoted, a rapid mass transfer channel is formed, and the catalytic reaction rate is improved; by introducing the carbon nano tube, stacking among graphene sheets is effectively avoided, the advantages of large specific surface area, high stability and strong metal-carrier interaction of graphene and the carbon nano tube are cooperatively exerted, the dispersing sites of the subsequent carried metal particles can be increased, and the stability of the metal particles is improved; the introduction of the cationic functional groups can uniformly disperse the subsequent carried metal on the surface of the carrier in situ, reduce the particle size of the metal and improve the effective reaction activity area.
In addition, the preparation method of the three-dimensional carrier according to the embodiment of the application may further have the following additional technical features:
in some embodiments, the acid solution is HNO 3 And H 2 SO 4 Is used as a mixed acid solution of the above-mentioned components.
In some embodiments, the mixed acid solution comprises HNO 3 And H 2 SO 4 Is 1:2-2:1, HNO 3 The molar concentration of (C) is 5mol/L to 10mol/L.
In some embodiments, 1mg to 3mg of the carbon nanotubes are mixed per 1mL of the acid solution in the mixing pretreatment for a period of 2h to 6h.
The effects of controlling the parameters and removing impurities and increasing oxygen-containing functional groups are obvious, and the structure of the carbon nano tube is not damaged.
In some embodiments, the polydiallyl dimethyl ammonium chloride solution has a mass concentration of 3mg/mL to 10mg/mL.
In some embodiments, 1mg to 3mg of the pretreated carbon nanotubes are mixed per 1mL of the polydiallyl dimethyl ammonium chloride solution in the mixing reaction.
In some embodiments, the mixing reaction is for a period of time ranging from 2 hours to 12 hours, and the temperature of the mixing reaction is from 20 ℃ to 50 ℃.
In some embodiments, the mass ratio of the functionalized carbon nanotubes to the graphene oxide is 1:1-5:1, and the mass concentration of the graphene oxide is 0.5mg/mL-3mg/mL.
In some embodiments, the temperature of the hydrothermal reaction is 120 ℃ to 160 ℃ and the time of the hydrothermal reaction is 3h to 12h.
The hydrothermal reaction temperature is too low, and a certain reaction pressure is difficult to form under common operation, so that a three-dimensional structure is difficult to form; the reaction temperature is too high, so that the air pressure in the reaction kettle is too high, a certain safety risk exists, and the energy consumption is correspondingly increased.
The reaction time is too short, the reaction is difficult to fully react under the general operation, the reaction time is too long, the waste of time is caused, and the efficiency is reduced.
A third aspect of embodiments of the present application provides a catalyst whose feedstock comprises the three-dimensional support provided in the first aspect.
By adding the three-dimensional carrier, the cationic functional groups of the three-dimensional carrier are introduced, pt crystal nuclei are uniformly dispersed on the surface of the carrier in situ, the metal particle size is reduced, and the effective reaction activity area is improved.
A fourth aspect of an embodiment of the present application provides a method for preparing a catalyst, the method comprising:
mixing N, N-dimethylformamide, chloroplatinic acid, cupric chloride, ascorbic acid and cetyltrimethylammonium bromide to obtain a transparent solution;
mixing the transparent solution and the three-dimensional carrier according to the first aspect, and then performing solvothermal reaction to obtain a catalyst primary product;
and removing the Cu simple substance from the catalyst primary product to obtain the catalyst.
By adding the three-dimensional carrier in the preparation process and introducing the cationic functional groups of the three-dimensional carrier, pt crystal nuclei are uniformly and in-situ dispersed on the surface of the carrier, so that the metal particle size is reduced, and the effective reaction activity area is improved; and through acid etching treatment, cu elements on the surfaces of the alloy particles and a Cu simple substance which is not alloyed with Pt are removed, so that the stability of the alloy is further improved. The prepared catalyst has good catalytic activity and stability for cathode oxygen reduction reaction of proton exchange membrane fuel cells.
In addition, the preparation method of the three-dimensional carrier according to the embodiment of the application may further have the following additional technical features:
in some embodiments, the molar concentration of the chloroplatinic acid in the transparent solution is 1mmol/L to 5mmol/L, the molar ratio of the chloroplatinic acid to the copper chloride is 1:1 to 1:3, the molar ratio of the ascorbic acid to the chloroplatinic acid is 10:1 to 20:1, and the molar ratio of the cetyltrimethylammonium bromide to the chloroplatinic acid is 3:1 to 5:1.
In some embodiments, the mass ratio of Pt in the chloroplatinic acid to the three-dimensional support is 1:10 to 3:1.
Too small a chloroplatinic acid concentration results in reduced yields; the concentration of chloroplatinic acid increases, so that the larger the particles produced, the lower the catalytic activity.
The molar ratio of chloroplatinic acid to cupric chloride is too small, and too much unalloyed copper is unstable; the molar ratio of chloroplatinic acid to cupric chloride is too large to be alloyed sufficiently under ordinary operation.
The ratio of the reducing agent ascorbic acid to the surfactant cetyl trimethyl ammonium bromide to the platinum is too small, so that the metal precursor is difficult to completely reduce or plays a role in structure guiding under the general operation; the ratio of the reducing agent ascorbic acid and the surfactant cetyltrimethylammonium bromide to platinum is too large, which results in a certain degree of material waste.
The mass ratio of chloroplatinic acid to the composite carrier is determined by the loading of the catalyst commonly used in general. Too small a catalyst is not suitable for practical use, and too large a carrier has limited loading capacity.
In some embodiments, the solvothermal reaction is at a temperature of 130-180 ℃ and the solvothermal reaction is for a time of 6-18 hours.
In some embodiments, the removing Cu element from the catalyst primary product to obtain a catalyst specifically includes:
mixing the catalyst primary product with sulfuric acid solution, and centrifuging, washing and drying to obtain a catalyst;
wherein the concentration of the sulfuric acid solution is 0.1-10mol/L, and 1-10 mL of the sulfuric acid solution is mixed with every 2mg of the catalyst initial product.
The foregoing description is only an overview of the present application, and is intended to be implemented in accordance with the teachings of the present application in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present application more readily apparent.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart of a method provided by an embodiment of the present application.
Detailed Description
The advantages and various effects of embodiments of the present application will be more clearly apparent from the following description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the application, not to limit the application.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
The technical scheme of the embodiment of the application aims to solve the technical problems, and the overall thought is as follows:
the embodiment provides a three-dimensional carrier, the raw materials of the three-dimensional carrier include:
oxidized graphene; and
a functionalized carbon nanotube, the functionalized carbon nanotube comprising: the preparation method comprises the steps of pretreating a carbon nano tube and polydiallyl dimethyl ammonium chloride solution, wherein the pretreated carbon nano tube is prepared by mixing and pretreating the carbon nano tube and an acid solution.
The embodiment also provides a preparation method of the three-dimensional carrier, which comprises the following steps:
s1, mixing and preprocessing a carbon nano tube and an acid solution to remove impurities of the carbon nano tube and increase the concentration of oxygen-containing functional groups on the surface of the carbon nano tube, so as to obtain a preprocessed carbon nano tube;
specifically, HNO is added to the carbon nanotubes 3 And H 2 SO 4 After being stirred uniformly, the mixed acid solution is subjected to ultrasonic reaction at normal temperature to remove impurities such as amorphous carbon, metal nano particles and the like in the carbon nano tube, and the concentration of oxygen-containing functional groups is increased on the surface of the carbon nano tube, so that the further dispersion and assembly are facilitated; and after the reaction is finished, centrifuging, washing and freeze-drying to obtain the pretreated carbon nanotube after the treatment. Wherein, HNO in the mixed acid solution 3 And H 2 SO 4 Is 1:2-2:1, HNO 3 And H 2 SO 4 The molar concentration in the mixed acid solution is 5-10mol/L, the molar concentration includes but is not limited to 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L and 10mol/L, the volume ratio of the mass of the carbon nano tube to the mixed acid solution is 1-3mg/ml, the volume ratio includes but is not limited to 1mg/ml, 1.5mg/ml, 2mg/ml, 2.5mg/ml and 3mg/ml, the ultrasonic reaction time is 2-6h, and the ultrasonic reaction time includes but is not limited to 2h, 3h, 4h, 5h and 6h.
S2, carrying out a mixing reaction on the pretreated carbon nanotube and polydiallyl dimethyl ammonium chloride solution to obtain a functionalized carbon nanotube;
specifically, the obtained pretreated carbon nanotubes and an aqueous solution of polydiallyldimethyl ammonium chloride (PDDA) are mixed, and after being uniformly dispersed by ultrasound, the mixture is stirred for reaction. And after the reaction is finished, performing suction filtration and washing to remove redundant PDDA, and performing freeze drying to obtain the PDDA Functionalized Carbon Nano Tube (FCNT). Wherein the mass concentration of the PDDA aqueous solution is 3-10mg/ml, the mass concentration comprises but not limited to 3mg/ml, 4mg/ml, 5mg/ml, 6mg/ml, 7mg/ml, 8mg/ml, 9mg/ml and 10mg/ml, the volume ratio of the mass of the carbon nano tube to the PDDA aqueous solution is 1-3mg/ml, the volume ratio comprises but not limited to 1mg/ml, 1.5mg/ml, 2mg/ml, 2.5mg/ml and 3mg/ml, the stirring reaction time comprises but not limited to 2h, 4h, 6h, 8h, 10h and 12h, the stirring reaction temperature is 20-50 ℃, the stirring reaction temperature comprises but not limited to 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ and 50 ℃.
S3, carrying out hydrothermal reaction on the functionalized carbon nano tube and graphene oxide to obtain the three-dimensional carrier.
Specifically, uniformly mixing FCNT and Graphene Oxide (GO) aqueous dispersion by stirring ultrasonic, transferring the mixture into a reaction kettle, performing hydrothermal reaction, cooling, centrifuging, and washing to obtain the three-dimensional composite carrier (FCNT-rGO, namely the three-dimensional carrier) of the functionalized carbon nanotube and the graphene. Wherein, in the reaction mixture, the mass ratio of FCNT to GO is 1:1-5:1, the mass ratio of FCNT to GO comprises but is not limited to 1:1, 2:1, 3:1, 4:1 and 5:1, the concentration of GO is 0.5-3mg/ml, and the concentration of GO comprises but is not limited to 0.5mg/ml, 1mg/ml, 1.5mg/ml, 2mg/ml, 2.5mg/ml and 3mg/ml; the hydrothermal reaction temperature is 120-160 ℃, the hydrothermal reaction temperature includes but is not limited to 120 ℃, 130 ℃, 140 ℃, 150 ℃ and 160 ℃, the hydrothermal reaction time is 3-12h, and the hydrothermal reaction time includes but is not limited to 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h and 12h.
The embodiment also provides a three-dimensional carrier, which is prepared by adopting the preparation method of the three-dimensional carrier.
The present example also provides a catalyst whose raw materials include the three-dimensional carrier as described above.
The embodiment also provides a preparation method of the catalyst, which comprises the following steps:
s1, mixing and preprocessing a carbon nano tube and an acid solution to remove impurities of the carbon nano tube and increase the concentration of oxygen-containing functional groups on the surface of the carbon nano tube, so as to obtain a preprocessed carbon nano tube;
s2, carrying out a mixing reaction on the pretreated carbon nanotube and polydiallyl dimethyl ammonium chloride solution to obtain a functionalized carbon nanotube;
s3, carrying out hydrothermal reaction on the functionalized carbon nano tube and graphene oxide to obtain a three-dimensional carrier;
s4, mixing N, N-dimethylformamide, chloroplatinic acid, copper chloride, ascorbic acid and cetyltrimethylammonium bromide to obtain a transparent solution;
specifically, chloroplatinic acid, cupric chloride, ascorbic acid and cetyltrimethylammonium bromide were added to N, N-dimethylformamide, and the solution was stirred at room temperature until the solution became clear. Wherein the concentration of chloroplatinic acid in the reaction mixed solution is 1-5mmol/L, the concentration of chloroplatinic acid in the reaction mixed solution comprises but is not limited to 1mmol/L, 2mmol/L, 3mmol/L, 4mmol/L and 5mmol/L, the molar ratio of chloroplatinic acid to cupric chloride is 1:1-1:3, the molar ratio of chloroplatinic acid to cupric chloride comprises but is not limited to 1:1, 1:2 and 1:3, the molar ratio of ascorbic acid to chloroplatinic acid is 10:1-20:1, the molar ratio of ascorbic acid to chloroplatinic acid comprises but is not limited to 10:1, 12:1, 14:1, 16:1, 18:1 and 20:1, the molar ratio of cetyltrimethylammonium bromide to chloroplatinic acid is 3:1-5:1, the molar ratio of cetyltrimethylammonium bromide to chloroplatinic acid comprises but is not limited to 3:1, 3.5:1, 4.5:1 and 5:1, the molar ratio of the mass in the chloroplatinic acid to the three-dimensional carrier comprises but is not limited to 1:1, the three-dimensional carrier comprises but is 10:1:1, the molar ratio of cetyltrimethylammonium bromide to chloroplatinic acid to 1:2:1, the three-dimensional carrier comprises but is not limited to 1:1:1:1.
S5, mixing the transparent solution and the three-dimensional carrier, and performing solvothermal reaction to obtain a catalyst primary product;
specifically, adding a three-dimensional carrier into a transparent solution, uniformly dispersing, transferring to a reaction kettle, cooling, centrifuging, washing, and freeze-drying after the solvothermal reaction is finished, thereby obtaining the octahedral PtCu nano particles (namely a catalyst primary product) supported by the FCNT-rGO three-dimensional composite carrier. Wherein the solvothermal reaction temperature is 130-180 ℃, the solvothermal reaction temperature comprises but is not limited to 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃ and 180 ℃, the solvothermal reaction time is 6-18h, and the solvothermal reaction time comprises but is not limited to 6h, 8h, 10h, 12h, 14h, 16h and 18h.
S6, removing the Cu simple substance from the catalyst primary product to obtain the catalyst.
Specifically, ptCu nano particles carried by the FCNT-rGO three-dimensional composite carrier are taken and added into sulfuric acid solution for stirring reaction, cu elements on the surfaces of the PtCu particles and Cu simple substances which are not alloyed with Pt are removed, and the octahedral PtCu catalyst carried by the FCNT-rGO three-dimensional composite carrier is obtained after centrifugation, washing and drying. Wherein the concentration of the sulfuric acid solution is 0.1-10mol/L, the concentration of the sulfuric acid solution comprises but is not limited to 0.1mol/L, 2mol/L, 4mol/L, 6mol/L, 8mol/L and 10mol/L, the volume ratio of the mass of PtCu nano particles supported by the FCNT-rGO three-dimensional composite carrier to sulfuric acid is 2:1-1:5mg/ml, the volume ratio of the mass of PtCu nano particles supported by the FCNT-rGO three-dimensional composite carrier to sulfuric acid comprises but is not limited to 2:1, 2:3, 2:5, 1:1, 1:3 and 1:5, the stirring reaction temperature is 30-80 ℃, the stirring reaction temperature is 30 ℃, 40 ℃, 50 ℃, 60 ℃,70 ℃ and 80 ℃, the stirring reaction time is 3-24h, and the stirring reaction time comprises but is not limited to 3h, 5h, 8h, 10h, 13h, 15h, 18h, 20h and 24h.
The three-dimensional support, catalyst and method for preparing the same according to the present application will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
A method of preparing a catalyst, the method comprising:
(1) Pretreatment of carbon nanotubes:
100ml HNO was added to 100mg of carbon nanotubes 3 And H 2 SO 4 After the mixed acid solutions with the concentration of 8mol/L are uniformly stirred, carrying out ultrasonic reaction for 3 hours at normal temperature, removing impurities such as amorphous carbon, metal nano particles and the like in the carbon nano tube, and increasing the concentration of oxygen-containing functional groups on the surface of the carbon nano tube so as to facilitate further dispersion and assembly; and after the reaction is finished, centrifuging, washing and freeze-drying to obtain the treated carbon nano tube.
(2) Preparation of functionalized carbon nanotubes:
mixing the carbon nano tube obtained in the step (1) with 100ml of aqueous solution of polydiallyl dimethyl ammonium chloride (PDDA) with the concentration of 4mg/ml, and stirring and reacting for 3 hours at 25 ℃ after ultrasonic dispersion is uniform. And after the reaction is finished, performing suction filtration and washing to remove redundant PDDA, and performing freeze drying to obtain the PDDA functionalized carbon nano tube FCNT.
(3) Preparation of a three-dimensional graphene-functionalized carbon nano tube composite carrier:
by stirring ultrasoundUniformly mixing 75mgFCNT and 25ml of Graphene Oxide (GO) aqueous dispersion with the concentration of 1mg/ml, transferring the mixture into a reaction kettle, performing hydrothermal reaction at 130 ℃ for 12 hours, cooling, centrifuging, and washing to obtain a three-dimensional composite carrier (FCNT) of graphene and functionalized carbon nanotubes 3 -rGO 1 )。
(4) Support of octahedral PtCu particles on three-dimensional composite support:
104mg of H are added to 100ml of N, N-dimethylformamide 2 PtCl 6 ·6H 2 O，68mgCuCl 2 ·2H 2 O,704mg of ascorbic acid and 219mg of cetyltrimethylammonium bromide, stirring at room temperature until the solution is transparent, adding the three-dimensional composite carrier prepared in the step (3), uniformly dispersing, transferring into a reaction kettle, cooling, centrifuging, washing, and freeze-drying after the solvothermal reaction is finished to obtain FCNT 3 -rGO 1 Octahedral Pt supported by three-dimensional composite carrier 1 Cu 2 And (3) nanoparticles. .
(5) Removing unstable Cu elements in PtCu alloy:
taking 100mg of FCNT prepared in step (3) 3 -rGO 1 Pt supported by three-dimensional composite carrier 1 Cu 2 Adding the nano particles into 100ml of sulfuric acid solution with the concentration of 1mol/L, stirring at 80 ℃ for reaction for 24 hours, and removing P 1 tCu 2 Cu element on the particle surface and Cu simple substance which is not alloyed with Pt are centrifugated, washed and dried to obtain the three-dimensional FCNT 3 -rGO 1 Supported octahedral Pt 1 Cu 1 Catalyst (Pt) 1 Cu 1 /FCNT 3 -rGO 1 )。
Example 2
A method of preparing a catalyst, the method comprising:
(1) Pretreatment of carbon nanotubes:
100ml HNO was added to 100mg of carbon nanotubes 3 And H 2 SO 4 After the mixed acid solutions with the concentration of 8mol/L are uniformly stirred, carrying out ultrasonic reaction for 3 hours at normal temperature, removing impurities such as amorphous carbon, metal nano particles and the like in the carbon nano tube, and increasing the concentration of oxygen-containing functional groups on the surface of the carbon nano tubeThe further dispersion and the assembly are convenient; and after the reaction is finished, centrifuging, washing and freeze-drying to obtain the treated carbon nano tube.
(2) Preparation of functionalized carbon nanotubes:
mixing the carbon nano tube obtained in the step (1) with 100ml of aqueous solution of polydiallyl dimethyl ammonium chloride (PDDA) with the concentration of 3mg/ml, and stirring and reacting for 6 hours at 25 ℃ after ultrasonic dispersion is uniform. And after the reaction is finished, performing suction filtration and washing to remove redundant PDDA, and performing freeze drying to obtain the PDDA functionalized carbon nano tube FCNT.
(3) Preparation of a three-dimensional graphene-functionalized carbon nano tube composite carrier:
uniformly mixing 66mgFCNT and 33ml Graphene Oxide (GO) aqueous dispersion with concentration of 1mg/ml by stirring and ultrasonic treatment, transferring the mixture into a reaction kettle, performing hydrothermal reaction at 160 ℃ for 12h, cooling, centrifuging, and washing to obtain the three-dimensional composite carrier (FCNT) of graphene and functionalized carbon nanotubes 2 -rGO 1 )。
(4) Support of octahedral PtCu particles on three-dimensional composite support:
104mg of H are added to 100ml of N, N-dimethylformamide 2 PtCl 6 ·6H 2 O，34mgCuCl 2 ·2H 2 O,704mg of ascorbic acid and 219mg of cetyltrimethylammonium bromide, stirring at room temperature until the solution is transparent, adding the three-dimensional composite carrier prepared in the step (3), uniformly dispersing, transferring into a reaction kettle, cooling, centrifuging, washing, and freeze-drying after the solvothermal reaction is finished to obtain FCNT 2 -rGO 1 Octahedral Pt supported by three-dimensional composite carrier 1 Cu 1 And (3) nanoparticles.
(5) Removing unstable Cu elements in PtCu alloy:
taking 100mg of FCNT prepared in step (3) 2 -rGO 1 Pt supported by three-dimensional composite carrier 1 Cu 1 Adding the nano particles into 100ml of sulfuric acid solution with the concentration of 2mol/L, stirring at 80 ℃ for reaction for 24 hours, and removing Pt 1 Cu 1 Cu element on the particle surface and Cu simple substance which is not alloyed with Pt are centrifugated, washed and dried to obtain the three-dimensional FCNT 2 -rGO 1 Supported octahedral Pt 2 Cu 1 Catalyst (Pt) 2 Cu 1 /FCNT 2 -rGO 1 )。
Example 3
A method of preparing a catalyst, the method comprising:
(1) Pretreatment of carbon nanotubes:
100ml HNO was added to 100mg of carbon nanotubes 3 And H 2 SO 4 After the mixed acid solutions with the concentration of 8mol/L are uniformly stirred, carrying out ultrasonic reaction for 3 hours at normal temperature, removing impurities such as amorphous carbon, metal nano particles and the like in the carbon nano tube, and increasing the concentration of oxygen-containing functional groups on the surface of the carbon nano tube so as to facilitate further dispersion and assembly; and after the reaction is finished, centrifuging, washing and freeze-drying to obtain the treated carbon nano tube.
(2) Preparation of functionalized carbon nanotubes:
mixing the carbon nano tube obtained in the step (1) with 100ml of an aqueous solution of polydiallyl dimethyl ammonium chloride (PDDA) with the concentration of 5mg/ml, and stirring and reacting for 10 hours at 25 ℃ after ultrasonic dispersion is uniform. And after the reaction is finished, performing suction filtration and washing to remove redundant PDDA, and performing freeze drying to obtain the PDDA functionalized carbon nano tube FCNT.
(3) Preparation of a three-dimensional graphene-functionalized carbon nano tube composite carrier:
uniformly mixing 50mgFCNT and 50ml of Graphene Oxide (GO) aqueous dispersion with the concentration of 1mg/ml by stirring and ultrasonic treatment, transferring the mixture into a reaction kettle, performing hydrothermal reaction at 180 ℃ for 3 hours, cooling, centrifuging and washing to obtain the three-dimensional composite carrier (FCNT) of graphene and functionalized carbon nano tubes 1 -rGO 1 )。
(4) Support of octahedral PtCu particles on three-dimensional composite support:
104mg of H are added to 100ml of N, N-dimethylformamide 2 PtCl 6 ·6H 2 O，17mgCuCl 2 ·2H 2 O,704mg of ascorbic acid and 219mg of cetyltrimethylammonium bromide, stirring at room temperature until the solution is transparent, adding the three-dimensional composite carrier prepared in the step (3), uniformly dispersing, transferring into a reaction kettle, and waiting for reactionAfter the solvothermal reaction is finished, cooling, centrifuging, washing, and freeze-drying to obtain FCNT 1 -rGO 1 Octahedral Pt supported by three-dimensional composite carrier 2 Cu 1 And (3) nanoparticles. .
(5) Removing unstable Cu elements in PtCu alloy:
taking 100mg of FCNT prepared in step (3) 1 -rGO 1 Pt supported by three-dimensional composite carrier 2 Cu 1 Adding the nano particles into 100ml of sulfuric acid solution with the concentration of 2mol/L, stirring at 80 ℃ for reaction for 24 hours, and removing Pt 2 Cu 1 Cu element on the particle surface and Cu simple substance which is not alloyed with Pt are centrifugated, washed and dried to obtain the three-dimensional FCNT 1 -rGO 1 Supported octahedral Pt 3 Cu 1 Catalyst (Pt) 3 Cu 1 /FCNT 1 -rGO 1 )。
Comparative example 1
This comparative example differs from example 1 in that carbon black XC-72 was used instead of carbon nanotubes in the preparation of the three-dimensional support, and the catalyst obtained was designated Pt 1 Cu 1 /FCB 3 -rGO 1 . The rest of the contents are the same as those described in example 1.
Comparative example 2
This comparative example is different from example 1 in that the carbon nanotubes were not functionalized during the preparation of the three-dimensional support, and the resulting catalyst was designated Pt 1 Cu 1 /CNT 3 -rGO. The rest of the contents are the same as those described in example 1.
Comparative example 3
This comparative example differs from example 1 in that no functionalized carbon nanotubes were added during the preparation of the three-dimensional support, and the resulting catalyst was designated Pt 1 Cu 1 /rGO. The rest of the contents are the same as those described in example 1.
Comparative example 4
This comparative example differs from example 1 in that the support added during the loading of the octahedral PtCu particles is carbon black XC-72. The catalyst obtained is denoted Pt 1 Cu 1 XC-72. The rest of the contents are the same as those described in example 1.
Experimental example
The catalysts provided in examples 1-3 and comparative examples 1-4 were tested and the results are shown in the following table.
The specific conditions for half-cell testing of the catalyst were as follows: the catalysts were electrochemically tested at room temperature using a standard three electrode system, wherein the working electrode, counter electrode and reference electrode were a glassy carbon electrode, pt sheet electrode and saturated calomel electrode, respectively. The test instrument is an electrochemical workstation and a rotary disk electrode system. Test electrolyte was 0.1M HClO 4 An aqueous solution. The preparation steps of the working electrode are as follows: 5mg of catalyst was weighed, 2.5mL of isopropanol and 20. Mu.L of 5wt.% Nafion solution were added, and the mixture was dispersed ultrasonically. Taking 6uL of dispersion liquid by a microsyringe, dripping the dispersion liquid onto the surface of the glassy carbon electrode for a plurality of times, and naturally airing at room temperature; ORR polarization curve test: firstly, introducing high-purity O into electrolyte 2 And last for at least 30min to form O 2 Saturated, then immersing the working electrode in the electrolyte solution at a potential of 10mV s in the range of 0.2 to 1.0V at an RDE rotation speed of 1600rpm -1 Is scanned, tested and the ORR polarization curve is recorded. The whole process always keeps O 2 Introducing; half-cell accelerated decay test: adopts electrokinetic potential cyclic scanning method, and at room temperature, under N 2 Saturated 0.1M HClO 4 Immersing the working electrode in the aqueous solution, and then immersing the working electrode in the aqueous solution at 50mV s -1 The scanning speed of the test tube is circularly scanned for 1500 circles between 0.6 and 1.2V, and CV curves before and after the dynamic potential scanning are tested and recorded; transfer of working electrode to O 2 Saturated 0.1M HClO 4 ORR polarization curves before and after potentiodynamic scanning were tested and recorded in aqueous solution.
As can be seen from the table, the metal particle size, the mass specific activity after the half-cell accelerated decay test and other performances of the catalyst prepared by the method are obviously improved compared with the comparative example.
One or more technical solutions in the embodiments of the present application at least have the following technical effects or advantages:
(1) According to the method provided by the embodiment of the application, the interaction between the carbon nano tube and graphene oxide is enhanced by performing functionalization treatment on the carbon nano tube, and the construction of a three-dimensional composite carrier of the carbon nano tube and graphene is further promoted by hydrothermal reaction, so that a rapid mass transfer channel is formed, and the catalytic reaction rate is improved; by introducing the carbon nanotubes, stacking among graphene sheets is effectively avoided, the advantages of large specific surface area, high stability and strong metal-carrier interaction of graphene and the carbon nanotubes are cooperatively exerted, the dispersing sites of metal particles are increased, and the stability of the metal particles is improved; the introduction of the cationic functional groups uniformly disperses Pt crystal nuclei on the surface of the carrier in situ, so that the size of the metal particle diameter is reduced, and the effective reaction activity area is increased;
(2) According to the method provided by the embodiment of the application, through acid etching treatment, cu elements on the surfaces of alloy particles and Cu simple substances which are not alloyed with Pt are removed, so that the stability of the alloy is further improved;
(3) The catalyst provided by the embodiment of the application has good catalytic activity and stability for the cathode oxygen reduction reaction of the proton exchange membrane fuel cell.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the embodiments of the application. Thus, if such modifications and variations of the embodiments of the present application fall within the scope of the claims and the equivalents thereof, the present application is also intended to include such modifications and variations.
Claims (7)
1. A method of preparing a catalyst, the method comprising:
mixing N, N-dimethylformamide, chloroplatinic acid, cupric chloride, ascorbic acid and cetyltrimethylammonium bromide to obtain a transparent solution;
mixing the transparent solution with a three-dimensional carrier, and performing solvothermal reaction to obtain a catalyst primary product;
removing Cu simple substance from the catalyst primary product to obtain a catalyst;
the molar concentration of the chloroplatinic acid in the transparent solution is 1mmol/L-5mmol/L, the molar ratio of the chloroplatinic acid to the cupric chloride is 1:1-1:3, the molar ratio of the ascorbic acid to the chloroplatinic acid is 10:1-20:1, and the molar ratio of the cetyl trimethylammonium bromide to the chloroplatinic acid is 3:1-5:1;
the mass ratio of Pt in the chloroplatinic acid to the three-dimensional carrier is 1:10-3:1;
the preparation method of the three-dimensional carrier comprises the following steps:
mixing and pre-treating the carbon nano tube and the acid solution to remove impurities of the carbon nano tube and increase the concentration of oxygen-containing functional groups on the surface of the carbon nano tube so as to obtain a pre-treated carbon nano tube;
mixing the pretreated carbon nanotube with polydiallyl dimethyl ammonium chloride solution to obtain a functionalized carbon nanotube;
carrying out hydrothermal reaction on the functionalized carbon nano tube and graphene oxide to obtain a three-dimensional carrier;
the relation between the use amounts of the pretreated carbon nano tube and the polydiallyl dimethyl ammonium chloride solution is as follows: mixing 1mg-3mg of the pretreated carbon nanotubes per 1mL of the polydiallyl dimethyl ammonium chloride solution; the mass concentration of the polydiallyl dimethyl ammonium chloride solution is 3mg/mL-10mg/mL, and the mass ratio of the functionalized carbon nano tube to the graphene oxide is 1:1-5:1.
2. The method for preparing a catalyst according to claim 1, wherein the acid solution is HNO 3 And H 2 SO 4 In the mixed acid solution, HNO 3 And H 2 SO 4 The molar ratio of (2) is 1:2-2:1, wherein HNO 3 The molar concentration of (C) is 5mol/L to 10mol/L.
3. The method for preparing a catalyst according to claim 1, wherein the relation between the amounts of the carbon nanotubes and the acid solution satisfies: 1mg to 3mg of the carbon nanotubes are mixed per 1mL of the acid solution.
4. The method for preparing the catalyst according to claim 1, wherein the solvothermal reaction is carried out at a temperature of 130-180 ℃ for a time of 6-18 h.
5. The method for preparing the catalyst according to claim 1, wherein the method for removing the Cu element from the catalyst primary product comprises the following steps:
mixing the catalyst primary product with sulfuric acid solution, and centrifuging, washing and drying to obtain a catalyst;
wherein the concentration of the sulfuric acid solution is 0.1-10mol/L, and 1-10 mL of the sulfuric acid solution is mixed with every 2mg of the catalyst initial product.
6. The method for preparing the catalyst according to claim 1, wherein the mass concentration of the graphene oxide is 0.5mg/mL to 3mg/mL.
7. The method for preparing a catalyst according to claim 1, wherein the time of the mixing pretreatment is 2h to 6h;
the time of the mixing reaction is 2-12h, and the temperature of the mixing reaction is 20-50 ℃;
the temperature of the hydrothermal reaction is 120-160 ℃, and the time of the hydrothermal reaction is 3-12 h.
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