CN108767280B - Pt nanoparticle/hydroxyl cerite nanocluster/graphene composite material and preparation method thereof - Google Patents
Pt nanoparticle/hydroxyl cerite nanocluster/graphene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Pt nanoparticle/hydroxyl cerite nanocluster/graphene composite material and a preparation method thereof. On the basis of preparing the hydroxyl carbon cerium ore nano cluster/graphene composite material, chloroplatinic acid is used as a precursor of platinum by a solvent thermal method, the pH value of a reaction solution is adjusted, and then the platinum is reduced from the solution by an oil bath, so that the platinum is uniformly dispersed on the surface of the hydroxyl carbon cerium ore nano cluster/graphene composite material and is in close contact with the hydroxyl carbon cerium ore nano particles. The preparation method is simple and clear in thought, the prepared product keeps the structural integrity of platinum, hydroxyl cerite and graphene, the hydroxyl ceric carbonate is attached to the surface of the graphene, the alcohol fuel cell is improved, meanwhile, the conductivity is improved by means of the extremely large specific surface area of the graphene, the close contact among the components is realized, the activity and the durability of platinum for catalyzing methanol oxidation can be effectively promoted through the synergistic effect among the components, and the application prospect is wide.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of direct alcohol fuel cells, and relates to a Pt nanoparticle/hydroxyl cerite nanocluster/graphene composite material and a preparation method thereof.
[ background of the invention ]
The rapid development of portable electronic devices such as cell phones and computers has led to a rapid increase in energy demand over the last several decades, as well as new challenges to existing battery technology. The short standby time of the battery of the portable electronic device is a prominent problem in the related art. In the research of many new battery technologies, the direct alcohol fuel cell has the advantages of high energy density, high energy conversion efficiency, easy storage and transportation of fuel, environmental friendliness and the like, is an ideal energy supply technology for portable electronic equipment, and receives more and more attention.
Compared with the prior battery technology, the direct alcohol fuel battery has great advantages, but the commercial application of the direct alcohol fuel battery is limited. Among them, low activity and poor stability of the noble metal catalyst are major factors that restrict commercial application thereof. Taking methanol as an example, methanol is oxidized and decomposed under the catalytic action of platinum, and carbon-oxygen intermediates are generated and exist in the form of carbon monoxide in an adsorption state, so that a large number of platinum active sites are occupied by carbon monoxide along with the continuation of the reaction, and the adsorption and catalysis of new methanol molecules on the platinum active sites, namely the poisoning of a platinum catalyst, are prevented, and the activity and stability of the platinum catalyst are greatly lost.
In recent years, the design of platinum-based multi-component catalysts has been considered to be the most effective measure to address platinum catalyst poisoning. By adding other components, the platinum and the platinum form a synergistic interaction or influence on the electronic structure of the platinum, and the oxidation performance of the platinum for catalyzing methanol is improved. Wherein, the addition of the metal hydroxide or the metal hydroxycarbonate can obviously improve the stability of the platinum catalyst. The metal hydroxide generally has a proliferative defect, and contributes to dissociation of water molecules to form adsorbed hydroxyl, and the adsorbed hydroxyl reacts with carbon monoxide occupying platinum active sites to generate carbon dioxide based on a Langmuir-Hinshelwood mechanism, so that the platinum active sites are promoted to be exposed again, and the stability of methanol catalytic reaction is improved. The metal hydroxycarbonate also has the ability to cleave water to produce adsorbed hydroxyl groups, and therefore, the improvement in the stability of methanol fuel cells is very significant.
As one of the metal hydroxycarbonates, hydroxycarbonatite (formula: Ce (CO))3) OH) also has the ability to crack water to form adsorbed hydroxyl radicals. If the method is applied to the field of electrocatalytic oxidation of methanol, the following points need to be considered: 1. the preparation technology of the nano-level hydroxyl cerous carbonate ore ensures that more surfaces are exposed and the cracking capacity to water is improved; 2. the cerite nanoparticles and the platinum nanoparticles are in close contact to ensure the smooth progress of Langmuir-Hinshelwood reaction; 3. since the ceriumhydrocarb has poor conductivity and requires high dispersion of ceriumhydrocarb nanoparticles and platinum nanoparticles, a support having excellent conductivity and a large specific surface area is required.
Graphene has excellent electrical characteristics (carrier mobility of about 15000 cm)2V.s, extremely large specific surface area (up to 2630 m)2In terms of/g) are desirable support materials. If the hydroxyl carbon cerium ore nano-particles and the platinum nano-particles are loaded on the surface of the graphene, the problem of insufficient conductivity can be solved, and the high dispersibility of the nano-particles can be ensured。
[ summary of the invention ]
The invention aims to provide a preparation method of a Pt nanoparticle/hydroxyl cerite nanocluster/graphene composite material. The process can effectively control the close contact between the hydroxyl carbon cerium ore nano-particles and the Pt nano-particles, and the hydroxyl carbon cerium ore nano-particles are uniformly dispersed on the surface of the graphene. The components of the composite material have good synergistic effect, the activity and durability of Pt for catalyzing alcohol oxidation can be greatly improved, and the application prospect is wide.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a hydroxyl carbon cerium ore nano-cluster/graphene composite material comprises the following steps:
1-1) mixing a graphene oxide solution with an ethylene glycol solution, and performing ultrasonic treatment to obtain a uniform mixed solution; stirring the obtained mixed solution, adding cerium nitrate hexahydrate, and continuously stirring to obtain a uniform suspension mixed solution;
1-2) adding urea into the suspension mixed solution obtained in the step 1-1), adjusting the pH value to 11-13 to obtain a mixed system, placing the mixed system in a high-pressure reaction kettle for hydrothermal reaction, and quickly cooling after the reaction is finished to obtain a mixed solution;
1-3) centrifugally treating the mixed solution obtained in the step 1-2), and collecting precipitates; washing the precipitate for a plurality of times by using a mixed solution of ethanol and deionized water, and drying the washed precipitate to obtain the hydroxyl carbon cerium ore nano-cluster/graphene composite material.
The invention is further improved in that:
preferably, the mass concentration of the graphene oxide solution in the step 1-1) is 1-10 mg/ml, and the volume ratio of the graphene oxide solution to the ethylene glycol solution is 1 (1-3); the ultrasonic treatment time is 50-70 min; the ratio of the added cerous nitrate hexahydrate to the graphene oxide solution is as follows: (1-8) mg: 2 ml.
Preferably, the mass ratio of the urea added in the step 1-2) to the cerium nitrate hexahydrate added in the step 1-1) is (10-20): (1-8); the temperature of the hydrothermal reaction is 200 ℃, and the reaction time is more than or equal to 180 min; and after the hydrothermal reaction, putting the reaction kettle into water, and quickly cooling the mixed solution to room temperature.
Preferably, the volume ratio of the step 1 to the step 3) is 1: (2-5) washing the precipitate for 4-6 times by using a mixed solution of ethanol and deionized water; the drying environment of the precipitate is vacuum or inert atmosphere, the drying temperature is 60-80 ℃, and the drying time is 12-24 hours.
The hydroxyl carbon cerium ore nano-cluster/graphene composite material prepared by the preparation method.
A preparation method of the Pt nano-particles/hydroxyl cerous carbonate nano-cluster/graphene composite material based on the hydroxyl cerous carbonate nano-cluster/graphene composite material comprises the following steps:
2-1) grinding the cerite hydroxyl nanocluster/graphene composite material to obtain powder, putting the powder into an ethylene glycol solution, carrying out ultrasonic treatment on the obtained suspension mixed solution, and adding a mixed solution of chloroplatinic acid and ethylene glycol in the process of magnetically stirring the solution to obtain a mixed solution;
2-2) adjusting the pH value of the mixed solution obtained in the step 2-1) to 12-13, and performing oil bath reflux treatment on the obtained solution; stirring the solution, cooling to room temperature, adjusting the pH value to 2-3, and continuously stirring to obtain a mixed solution;
2-3) centrifugally treating the mixed solution obtained in the step 2-2), and collecting precipitates; and repeatedly washing the composite material for a plurality of times by using a mixed solution of ethanol and deionized water, and drying the washed precipitate to obtain the Pt nano-particles/hydroxyl cerite nano-cluster/graphene composite material.
Preferably, agate is used for grinding the cerite hydroxycarburite nanocluster/graphene composite material in the step 2-1), and the ratio of the added powder to the ethylene glycol solution is (3-10) mg: 4 ml; the mass concentration of platinum in the mixed solution of chloroplatinic acid and ethylene glycol is 5mg/ml, and the ratio of the added mixed solution of chloroplatinic acid and ethylene glycol to the composite material powder is (1-5) ml: (30-100) mg.
Preferably, in the step 2-2), the pH value of the mixed solution is adjusted to 12-13 by using saturated NaOH; the oil bath reflux temperature was: the oil bath reflux time is 2-4 h at 100-200 ℃; and (3) adjusting the solution at room temperature to pH value of 2-3 by using hydrochloric acid, and stirring for 5-30 min to obtain a mixed solution.
Preferably, in the step 2-3), the precipitate is washed for 4-6 times by using a mixed solution of ethanol and deionized water, and the volume ratio of the ethanol to the deionized water is 1: (2-5); the drying environment of the precipitate is vacuum or inert atmosphere, the drying temperature is 60-80 ℃, and the drying time is 12-24 hours.
The Pt nano-particle/hydroxyl carbon cerium ore nano-cluster/graphene composite material prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a hydroxyl carbon cerium ore nano-cluster/graphene composite material. Taking a graphene oxide solution as a precursor of graphene, taking cerous nitrate hexahydrate as a precursor of cerous hydroxycarbonate, adding urea to provide carbonate, and using NaOH to provide OH-CO-production of Ce (CO) with cerium nitrate hexahydrate3) OH; according to the method, the hydroxyl carbon cerium ore nano particles are prepared by a hydrothermal method and uniformly dispersed on the surface of graphene, so that the hydroxyl carbon cerium ore nano cluster/graphene composite material is prepared. The prepared hydroxyl carbon cerium ore nano-cluster can improve the water cracking capability in an alcohol fuel cell, and the adsorption hydroxyl formed by water molecules can react with CO occupying noble metal active sites to generate CO2The active sites of the noble metals are exposed again, so that the catalytic efficiency of the alcohol fuel cell is improved, the stability of the alcohol fuel cell is improved, and the cerium hydroxycarbonate is attached to the surface of the graphene, so that the alcohol fuel cell is improved, and meanwhile, the conductivity is improved by virtue of the extremely large specific surface area of the graphene. The composite material is prepared by a simple hydrothermal method, the used raw materials are easy to obtain, the production efficiency is high, and the method is suitable for industrial production.
The invention also discloses a hydroxyl carbon cerium ore nano-cluster/graphene composite material; in a microscopic state of the composite material, the hydroxyl carbon cerium ore is a nanocluster and is uniformly distributed on the surface of the graphene; the composite material has the excellent performances of both hydroxyl cerium carbonate and graphene, the stability of the noble metal catalyst can be remarkably improved by adding the hydroxyl cerium carbonate, and the graphene has high conductivity.
The invention also discloses a preparation method of the Pt nano-particle/hydroxyl cerite nano-cluster/graphene composite material. On the basis of preparing the hydroxyl carbon cerium ore nano cluster/graphene composite material, taking chloroplatinic acid as a precursor of platinum by a solvothermal method, adjusting the pH value of a reaction solution, and reducing the platinum from the solution by an oil bath to ensure that the platinum is uniformly dispersed on the surface of the hydroxyl carbon cerium ore nano cluster/graphene composite material and is in close contact with hydroxyl carbon cerium ore nano particles; the hardness of the agate mortar is high, so that the fineness of the ground powder can be ensured; the pH value of the hydrochloric acid adjusting solution can ensure that Pt is completely reduced, and Cl of the hydrochloric acid-Cl with chloroplatinic acid-And the prepared composite material comprises three materials, wherein the hydroxyl carbon cerium ore nanocluster can improve the water cracking capability in the alcohol fuel cell, and the adsorption hydroxyl formed by water molecules can react with CO occupying Pt active sites to generate CO2The Pt active sites are exposed again, more surface active sites are provided, the catalytic efficiency is higher, the stability of the alcohol fuel cell taking the Pt base as the catalyst is improved, the cerium hydroxycarbonate is attached to the surface of the graphene, and the conductivity is improved by means of the extremely large specific surface area of the graphene while the alcohol fuel cell is improved. Compared with a Pt nanoparticle/graphene composite material without the added hydroxyl group cerite nanocluster and a Pt nanoparticle/hydroxyl group cerite nanocluster/graphene composite material, the Pt nanoparticle/hydroxyl group cerite nanocluster/graphene composite material shows that the stability of the composite material in the electrocatalytic oxidation of methanol is obviously superior to that of the Pt nanoparticle/graphene composite material, and the CO poisoning resistance of the composite material in the later is also stronger. The preparation method is simple and clear in thought, the prepared product not only keeps the structural integrity of the platinum, the cerite and the graphene, but also realizes the close contact among the components, and the activity and the durability of the platinum for catalyzing the methanol oxidation can be effectively promoted through the synergistic effect among the components, so that the preparation method has a wide application prospect.
The invention also discloses a Pt nano-particle/hydroxyl cerite nano-cluster/graphene composite material. Compared with a Pt nano particle/graphene composite material without adding cerium nitrate hexahydrate, the composite material prepared by the invention can obviously improve the stability of platinum catalytic oxidation methanol, and can more efficiently remove CO adsorbed on the surface of Pt, namely has an excellent CO poisoning resistance effect.
[ description of the drawings ]
FIG. 1 is a TEM image of the morphology of the product of example 1 without addition of cerium nitrate hexahydrate;
FIG. 2 is an XRD pattern of the product of example 2 with cerium nitrate hexahydrate added;
FIG. 3 is a TEM image of the morphology of the product of example 2 with the addition of cerium nitrate hexahydrate;
FIG. 4 is a graph of the mass activity of the products shown in examples 1 and 2 for the electrocatalytic oxidation of methanol;
FIG. 5 is a graph showing the stability of the products shown in examples 1 and 2 in the electrocatalytic oxidation of methanol;
FIG. 6 is a graph showing the results of CO stripping voltammetry experiments for the products of examples 1 and 2.
[ detailed description ] embodiments
The invention is described in further detail below with reference to the accompanying drawings:
the invention discloses a preparation method of a Pt nanoparticle/hydroxyl cerite nanocluster/graphene composite material, which comprises the following steps of:
the first step is as follows: preparation of hydroxyl carbon cerium ore nano-cluster/graphene composite material
1) Mixing a graphene oxide solution with a mass concentration of 1-10 mg/ml and an ethylene glycol solution, wherein the volume ratio of the graphene oxide solution to the ethylene glycol solution is 1 (1-3); carrying out ultrasonic treatment on the obtained solution, wherein the ultrasonic time is 50-70 min, and the ultrasonic power is 150W, so as to obtain a uniform mixed solution;
2) transferring the mixed solution obtained in the step 1) to a magnetic stirrer, adding cerium nitrate hexahydrate in the stirring process, wherein the ratio of the added cerium nitrate hexahydrate to the graphene oxide solution is as follows: (1-8) mg: 2ml, and stirring continuously to obtain a uniform suspension mixed solution;
3) adding urea into the suspension liquid obtained in the step 2), wherein the mass ratio of the added urea to the cerium nitrate hexahydrate is (10-20): (1-8), and then selecting a NaOH solution with the concentration of 1-5 mol/L to adjust the pH value to obtain a mixed system with the pH value of 11-13;
4) putting the mixed system obtained in the step 3) into a stainless steel high-pressure reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and putting the kettle into a constant-temperature oven, and carrying out hydrothermal reaction at 200 ℃ for more than or equal to 180 min; after the reaction is finished, putting the reaction kettle into water, and quickly cooling to room temperature to obtain a mixed solution;
5) centrifuging the mixed solution obtained in the step 4), and collecting precipitates, wherein the centrifugation speed is 8000 r/min; after centrifugation, the volume ratio was 1: (2-5) repeatedly washing the mixed solution for 4-6 times by using the mixed solution of the ethanol and the deionized water;
6) putting the cleaned precipitate into an oven, and drying under vacuum or inert gas at the drying temperature of 60-80 ℃ for 12-24 h to obtain the hydroxyl carbon cerium ore nanocluster/graphene composite material;
the second step is that: preparing the Pt nano-particles/hydroxyl carbon cerium ore nano-cluster/graphene composite material.
7) Slightly grinding the hydroxyl carbon cerium ore nano-cluster/graphene composite material obtained in the step 6) by agate; putting the ground hydroxyl carbon cerium ore nano-cluster/graphene composite material into an ethylene glycol solution, wherein the ratio of the composite material to the ethylene glycol solution is as follows: (3-10) mg: 4ml, carrying out ultrasonic treatment to obtain a uniformly dispersed suspension mixed solution, wherein the ultrasonic power is 150W, and the ultrasonic treatment time is 80-100 min;
8) transferring the suspension mixed solution obtained in the step 7) to a magnetic stirrer, adding a mixed solution of chloroplatinic acid and ethylene glycol, wherein the mass concentration of platinum in the mixed solution of chloroplatinic acid and ethylene glycol is 5mg/ml, and uniformly stirring by magnetic force to obtain a mixed solution; the ratio of the added chloroplatinic acid and glycol mixed solution to the composite material is (1-5) ml: (30-100) mg;
9) adding a saturated NaOH solution into the mixed solution obtained in the step 8) to control the pH value, so as to obtain a mixed solution with the pH value of 12-13.
10) Transferring the mixed solution with the pH value of 12-13 obtained in the step 9) into a flask, preferably a 100ml three-neck flask, performing oil bath heating reflux at 100-200 ℃ for 2-4 h, and continuously stirring until the mixed solution is uniform to obtain the mixed solution.
11) Quickly transferring the mixed solution obtained in the step 10) to a beaker, stirring and cooling to room temperature, adding hydrochloric acid to adjust the pH value to acidity, and uniformly stirring to obtain a solution with the pH value of 2-3; in the invention, the concentration of the hydrochloric acid solution is preferably 1-5 mol/ml.
12) Continuously stirring the solution obtained in the step 11) for 5-30 min, then centrifuging at the speed of 8000r/min, repeatedly washing for 4-6 times by using a mixed solution of ethanol and deionized water to finally obtain a washed precipitate, and collecting the precipitate; the volume ratio of ethanol to deionized water in the mixed solution of ethanol and deionized water is as follows: 1, (2-5).
13) And (3) putting the cleaned precipitate into an oven, and drying in vacuum or inert atmosphere at the drying temperature of 60-80 ℃ for 12-24 h to obtain the Pt nano-particle/hydroxyl cerite nano-cluster/graphene composite material.
The invention will be further elucidated with reference to the following specific embodiments and the accompanying drawings:
example 1: comparative test
Mixing 20ml of graphene oxide solution and 20ml of ethylene glycol solution, performing ultrasonic treatment for 60min under the condition that the ultrasonic power is 150W, transferring the mixed solution to a magnetic stirrer, controlling the pH value of a system to be 12 by using 1mol/ml of sodium hydroxide solution under the stirring action, transferring the mixed solution to a reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and placing the reaction kettle into a constant-temperature oven to keep the temperature at 200 ℃ for 180min, after the reaction is finished, placing the reaction kettle into water to quickly cool to the room temperature, taking out the mixed solution, performing centrifugal collection at 8000r/min, repeatedly performing centrifugal washing for 6 times by using an ethanol/deionized water (1:2) mixed solution, and placing the washed precipitate into a vacuum oven to perform vacuum drying for 12h at 60 ℃ for later use;
weighing 30mg of a sample to be used, slightly grinding the sample, putting the ground sample into 40ml of glycol solution, carrying out ultrasonic treatment for 90min under the condition that the ultrasonic power is 150W, then transferring to a magnetic stirrer, adding 1.5ml of chloroplatinic acid/ethylene glycol solution under the stirring action, continuing stirring for 15min, adding saturated sodium hydroxide solution to control the pH value of the system to be 12, transferring the mixed solution to a 100ml three-neck flask, then placing in an oil bath, heating and refluxing for 2h at 120 ℃, quickly transferring the mixed solution into a beaker after oil bath, stirring and cooling to room temperature, adding 1mol/ml hydrochloric acid to adjust the pH value of the system to 2, continuously stirring for 30min, centrifuging and collecting precipitates, repeatedly centrifuging and washing for 6 times by using an ethanol/deionized water (1:2) mixed solution, and putting the washed precipitates into a vacuum oven for vacuum drying for 12h at 60 ℃ to obtain the platinum nanoparticle/graphene composite material.
Fig. 1 is a TEM photograph of the platinum nanoparticle/graphene composite material prepared in example 1 of the present invention, and it can be seen from fig. 1 that the platinum nanoparticles prepared in example 1 have the same size and are uniformly distributed on the surface of graphene without adding cerous nitrate hexahydrate.
Example 2:
the first step is as follows: preparation of hydroxyl carbon cerium ore nano-cluster/graphene composite material
Mixing 20ml of graphene oxide solution with 20ml of ethylene glycol solution, wherein the mass concentration of the graphene oxide solution is 4 mg/ml; performing ultrasonic treatment for 60min under the condition that the ultrasonic power is 150W; transferring the mixed solution to a magnetic stirrer, adding 40mg of cerous nitrate hexahydrate in the stirring process, adding 150mg of urea after uniformly stirring, adjusting the pH value of a system to be 12 by using 1mol/ml NaOH solution, transferring the mixed solution to a reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and placing the reaction kettle in a constant-temperature oven to keep the temperature at 200 ℃ for 180min, placing the reaction kettle in water to quickly cool to room temperature after the reaction is finished, taking out the mixed solution, centrifuging at 8000r/min, collecting precipitate, repeatedly centrifuging and washing for 6 times by using ethanol/deionized water (1:2) mixed solution, and placing the precipitate in a vacuum oven to carry out vacuum drying at 60 ℃ for 12h for later use;
the second step is that: preparation of Pt nanoparticle/hydroxyl carbon cerium ore nano-cluster/graphene composite material
Weighing 40mg of a sample to be used, slightly grinding the sample, putting the sample into 40ml of glycol solution, carrying out ultrasonic treatment on the solution for 90min under the condition that the ultrasonic power is 150W, transferring the solution to a magnetic stirrer, adding 2ml chloroplatinic acid/ethylene glycol solution under the action of stirring, adding saturated NaOH solution after uniformly stirring to control the pH value of the solution to be 13, transferring the mixed solution into a 100ml three-neck flask, then placing the flask in oil bath, heating and refluxing for 2h at 120 ℃, quickly transferring the mixed solution into a beaker after oil bath, stirring and cooling to room temperature, adding 1mol/ml hydrochloric acid to adjust the pH value of the system to 3, continuously stirring for 30min, centrifugally collecting precipitate, repeatedly centrifugally washing for 6 times by using an ethanol/deionized water (1:2) mixed solution, and placing the washed precipitate into a vacuum oven for vacuum drying for 12h at 60 ℃ to obtain the Pt nano-particles/hydroxyl carbon cerium ore nano-cluster/graphene composite material.
XRD and TEM analyses were performed on the Pt nanoparticle/cerite nanocluster/graphene composite material obtained in example 2, and the results are shown in fig. 2 and 3.
FIG. 2 is an XRD (X-ray diffraction) pattern of a Pt nanoparticle/cerite nanocluster/graphene composite material prepared in example 2 of the invention, and it can be seen that, in addition to a cerite hydroxyl characteristic peak (JCPDS No. 52-0352) and a cerite platinum characteristic peak JCPDS No. 04-0802), the substance prepared in example 2 has no other characteristic peaks of crystal phases, which indicates that the composite material has high purity characteristics, and an amorphous peak at 20-35 degrees is characteristic of graphene;
fig. 3 is a TEM photograph of the Pt nanoparticle/hydroxycarburite nanocluster/graphene composite material prepared in example 2 of the present invention, and it can be seen from fig. 3 that the hydroxycarburite prepared in example 2 is nanocluster and is uniformly distributed on the graphene surface, and the Pt nanoparticles are uniformly dispersed on the entire graphene surface and are in close contact with the hydroxycarbocerite nanoparticles.
Fig. 4 and 5 are experimental results of electrocatalytic oxidation of methanol on the composite materials prepared in examples 1 and 2. Fig. 4 is a comparison of mass activity, and it can be seen that the activity of electrocatalytic oxidation of methanol of the platinum nanoparticle-cerite nanocluster/graphene composite material prepared in example 2 is higher than that of the composite material prepared in example 1; fig. 5 is a stability comparison graph, and it can be seen that the stability of the Pt nanoparticle/cerite nanocluster/graphene composite material prepared in example 2 for the electrocatalytic oxidation of methanol is significantly better than that of the platinum nanoparticle/graphene composite material prepared in example 1. The result shows that the Pt nano-particle/hydroxyl cerite nano-cluster/graphene composite material prepared by the method can obviously improve the stability of methanol catalytic oxidation by platinum.
Fig. 6 is the results of experiments on the CO poisoning resistance of the composite materials prepared in example 2 and example 1. It can be seen that the oxidation peak initiation peak potential of CO of the Pt nanoparticle/cerite nanocluster/graphene composite prepared in example 2 is 0.345V, while the oxidation peak initiation peak potential of CO of the platinum nanoparticle/graphene composite prepared in example 1 is 0.439V. The initial oxidation peak potential of CO of example 2 was about 0.1V earlier than that of example 1, which indicates that example 2 can remove CO adsorbed on the Pt surface more efficiently, i.e., has an excellent CO poisoning resistance.
Example 3:
the first step is as follows: preparation of hydroxyl carbon cerium ore nano-cluster/graphene composite material
Mixing 20ml of graphene oxide solution with 20ml of ethylene glycol solution, wherein the mass concentration of the graphene oxide solution is 4 mg/ml; carrying out ultrasonic treatment for 60min under the condition that the ultrasonic power is 150W, transferring the mixed solution onto a magnetic stirrer, adding 80mg of cerous nitrate hexahydrate during stirring, adding 200mg of urea after uniformly stirring, adjusting the pH value of a system to be 13 by using 1mol/ml NaOH solution, transferring the mixed solution into a reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and placing the reaction kettle into a constant-temperature oven to keep the temperature at 200 ℃ for 180min, after the reaction is finished, placing the reaction kettle into water to quickly cool to the room temperature, taking out the mixed solution, centrifuging at 8000r/min to collect precipitates, repeatedly centrifuging and washing 6 times by using an ethanol/deionized water (1:2) mixed solution, placing the washed precipitates into a vacuum oven to carry out vacuum drying at 60 ℃ for 12h for later use;
the second step is that: preparation of Pt nanoparticle/hydroxyl carbon cerium ore nano-cluster/graphene composite material
Weighing 100mg of a sample to be used, slightly grinding the sample, putting the ground sample into 40ml of glycol solution, carrying out ultrasonic treatment on the solution for 90min under the condition that the ultrasonic power is 150W, then transferring the mixture to a magnetic stirrer, adding 5ml of chloroplatinic acid/ethylene glycol solution under the stirring action, stirring the mixture evenly, adding saturated NaOH solution to control pH value of the solution to be 13, transferring the mixed solution into a 100ml three-neck flask, then placing the flask in oil bath, heating and refluxing for 2h at 120 ℃, quickly transferring the mixed solution into a beaker after the oil bath is finished, stirring and cooling to room temperature, adding 1mol/ml hydrochloric acid to adjust the pH value of the system to 3, continuously stirring for 30min, and centrifuging and collecting the precipitate, repeatedly centrifuging and washing for 6 times by using an ethanol/deionized water (1:2) mixed solution, and putting the washed precipitate into a vacuum oven for vacuum drying for 12 hours at the temperature of 60 ℃ to obtain the platinum nano-particle-hydroxyl cerite nano-cluster/graphene composite material.
Example 4:
the first step is as follows: preparation of hydroxyl carbon cerium ore nano-cluster/graphene composite material
Mixing 20ml of graphene oxide solution with 40ml of ethylene glycol solution, wherein the mass concentration of the graphene oxide solution is 1 mg/ml; performing ultrasonic treatment for 50min under the condition that the ultrasonic power is 150W; transferring the mixed solution to a magnetic stirrer, adding 10mg of cerous nitrate hexahydrate in the stirring process, uniformly stirring, adding 100mg of urea, adjusting the pH value of a system to be 11 by using 2mol/ml NaOH solution, transferring the mixed solution to a reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and placing the reaction kettle in a constant-temperature oven to keep the temperature at 200 ℃ for 220min, placing the reaction kettle in water to quickly cool to room temperature after the reaction is finished, taking out the mixed solution, centrifuging at 8000r/min, collecting precipitate, repeatedly centrifuging and washing for 4 times by using ethanol/deionized water (1:3) mixed solution, and placing the precipitate in a vacuum oven to carry out vacuum drying at 70 ℃ for 15 hours for later use;
the second step is that: preparation of Pt nanoparticle/hydroxyl carbon cerium ore nano-cluster/graphene composite material
Weighing 30mg of a sample to be used, slightly grinding the sample, putting the ground sample into 40ml of glycol solution, carrying out ultrasonic treatment on the solution for 80min under the condition that the ultrasonic power is 150W, then transferring the mixture to a magnetic stirrer, adding 1ml of chloroplatinic acid/ethylene glycol solution under the stirring action, stirring the mixture evenly, adding saturated NaOH solution to control pH value of the solution to be 13, transferring the mixed solution into a 100ml three-neck flask, then placing the flask in oil bath, heating and refluxing for 2h at 100 ℃, quickly transferring the mixed solution into a beaker after the oil bath is finished, stirring and cooling to room temperature, adding 5mol/ml hydrochloric acid to adjust the pH value of the system to 2, continuously stirring for 5min, and centrifuging and collecting the precipitate, repeatedly centrifuging and washing for 6 times by using an ethanol/deionized water (1:3) mixed solution, and putting the washed precipitate into a vacuum oven for vacuum drying for 24 hours at the temperature of 60 ℃ to obtain the platinum nano-particle-hydroxyl cerite nano-cluster/graphene composite material.
Example 5:
the first step is as follows: preparation of hydroxyl carbon cerium ore nano-cluster/graphene composite material
Mixing 20ml of graphene oxide solution with 80ml of ethylene glycol solution, wherein the mass concentration of the graphene oxide solution is 10 mg/ml; performing ultrasonic treatment for 50min under the condition that the ultrasonic power is 150W; transferring the mixed solution to a magnetic stirrer, adding 80mg of cerous nitrate hexahydrate in the stirring process, adding 100mg of urea after uniformly stirring, adjusting the pH value of a system to be 12 by using 5mol/ml NaOH solution, transferring the mixed solution to a reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and placing the reaction kettle in a constant-temperature oven to keep the temperature at 200 ℃ for 200min, placing the reaction kettle into water to quickly cool to room temperature after the reaction is finished, taking out the mixed solution, centrifuging at 8000r/min, collecting precipitate, repeatedly centrifuging and washing for 4 times by using ethanol/deionized water (1:4) mixed solution, and placing the precipitate in the oven under Ar atmosphere to dry for 24 hours at 80 ℃ for later use;
the second step is that: preparation of Pt nanoparticle/hydroxyl carbon cerium ore nano-cluster/graphene composite material
Weighing 100mg of a sample to be used, slightly grinding the sample, putting the ground sample into 40ml of glycol solution, carrying out ultrasonic treatment on the solution for 85min under the condition that the ultrasonic power is 150W, then transferring the mixture to a magnetic stirrer, adding 1ml of chloroplatinic acid/ethylene glycol solution under the stirring action, stirring the mixture evenly, adding saturated NaOH solution to control pH value of the solution to be 12, transferring the mixed solution into a 100ml three-neck flask, then placing the flask in oil bath, heating and refluxing for 3h at 110 ℃, quickly transferring the mixed solution into a beaker after the oil bath is finished, stirring and cooling to room temperature, adding 5mol/ml hydrochloric acid to adjust the pH value of the system to 2, continuously stirring for 10min, and centrifuging and collecting the precipitate, repeatedly centrifuging and washing the precipitate for 6 times by using an ethanol/deionized water (1:4) mixed solution, and drying the washed precipitate in an oven filled with Ar gas at 70 ℃ for 24 hours to obtain the platinum nanoparticle-cerite nanocluster/graphene composite material.
Example 6:
the first step is as follows: preparation of hydroxyl carbon cerium ore nano-cluster/graphene composite material
Mixing 20ml of graphene oxide solution with 60ml of ethylene glycol solution, wherein the mass concentration of the graphene oxide solution is 6 mg/ml; performing ultrasonic treatment for 70min under the condition that the ultrasonic power is 150W; transferring the mixed solution to a magnetic stirrer, adding 60mg of cerous nitrate hexahydrate in the stirring process, uniformly stirring, adding 100mg of urea, adjusting the pH value of a system to be 11 by using 5mol/ml NaOH solution, transferring the mixed solution to a reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and placing the reaction kettle into a constant-temperature oven to keep the temperature at 200 ℃ for 230min, placing the reaction kettle into water to quickly cool to room temperature after the reaction is finished, taking out the mixed solution, centrifuging at 8000r/min, collecting precipitate, repeatedly centrifuging and washing for 5 times by using ethanol/deionized water (1:5) mixed solution, and placing the precipitate into a vacuum oven to carry out vacuum drying at 65 ℃ for 20 hours for later use;
the second step is that: preparation of Pt nanoparticle/hydroxyl carbon cerium ore nano-cluster/graphene composite material
Weighing 60mg of a sample to be used, slightly grinding the sample, putting the ground sample into 40ml of glycol solution, carrying out ultrasonic treatment on the solution for 95min under the condition that the ultrasonic power is 150W, then transferring the mixture to a magnetic stirrer, adding 1ml of chloroplatinic acid/ethylene glycol solution under the stirring action, stirring the mixture evenly, adding saturated NaOH solution to control pH value of the solution to be 12, transferring the mixed solution into a 100ml three-neck flask, then placing the flask in oil bath, heating and refluxing for 3h at 105 ℃, quickly transferring the mixed solution into a beaker after the oil bath is finished, stirring and cooling to room temperature, adding 3mol/ml hydrochloric acid to adjust the pH value of the system to 3, continuously stirring for 15min, and centrifuging and collecting the precipitate, repeatedly centrifuging and washing the precipitate for 4 times by using an ethanol/deionized water (1:3) mixed solution, and drying the washed precipitate in an oven filled with argon at 70 ℃ for 18 hours to obtain the platinum nanoparticle-cerite nanocluster/graphene composite material.
Example 7:
the first step is as follows: preparation of hydroxyl carbon cerium ore nano-cluster/graphene composite material
Mixing 20ml of graphene oxide solution with 100ml of ethylene glycol solution, wherein the mass concentration of the graphene oxide solution is 2 mg/ml; performing ultrasonic treatment for 70min under the condition that the ultrasonic power is 150W; transferring the mixed solution to a magnetic stirrer, adding 10mg of cerous nitrate hexahydrate in the stirring process, uniformly stirring, adding 150mg of urea, adjusting the pH value of a system to be 13 by using 3mol/ml NaOH solution, transferring the mixed solution to a reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and placing the reaction kettle in a constant-temperature oven to keep the temperature at 200 ℃ for 260min, placing the reaction kettle in water to quickly cool to room temperature after the reaction is finished, taking out the mixed solution, centrifuging at 8000r/min, collecting precipitate, repeatedly centrifuging and washing for 5 times by using ethanol/deionized water (1:3) mixed solution, and placing the precipitate in an oven with Ar gas to dry for 18 hours at 75 ℃ for later use;
the second step is that: preparation of Pt nanoparticle/hydroxyl carbon cerium ore nano-cluster/graphene composite material
Weighing 30mg of a sample to be used, slightly grinding the sample, putting the ground sample into 40ml of glycol solution, carrying out ultrasonic treatment on the solution for 80min under the condition that the ultrasonic power is 150W, then transferring the mixture to a magnetic stirrer, adding 5ml of chloroplatinic acid/ethylene glycol solution under the stirring action, stirring the mixture evenly, adding saturated NaOH solution to control pH value of the solution to be 12, transferring the mixed solution into a 100ml three-neck flask, then placing the flask in oil bath, heating and refluxing for 3h at 115 ℃, quickly transferring the mixed solution into a beaker after the oil bath is finished, stirring and cooling to room temperature, adding 3mol/ml hydrochloric acid to adjust the pH value of the system to 3, continuously stirring for 20min, and centrifuging and collecting the precipitate, repeatedly centrifuging and washing the precipitate for 4 times by using an ethanol/deionized water (1:5) mixed solution, and drying the washed precipitate in an oven filled with argon at the temperature of 80 ℃ for 16 hours to obtain the platinum nanoparticle-cerite nanocluster/graphene composite material.
Example 8:
the first step is as follows: preparation of hydroxyl carbon cerium ore nano-cluster/graphene composite material
Mixing 20ml of graphene oxide solution with 40ml of ethylene glycol solution, wherein the mass concentration of the graphene oxide solution is 8 mg/ml; performing ultrasonic treatment for 55min under the condition that the ultrasonic power is 150W; transferring the mixed solution to a magnetic stirrer, adding 80mg of cerous nitrate hexahydrate in the stirring process, adding 150mg of urea after uniformly stirring, adjusting the pH value of a system to be 12 by using 4mol/ml NaOH solution, transferring the mixed solution to a reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and placing the reaction kettle in a constant-temperature oven to keep the temperature at 200 ℃ for 280min, placing the reaction kettle in water to quickly cool to room temperature after the reaction is finished, taking out the mixed solution, centrifuging at 8000r/min, collecting precipitate, repeatedly centrifuging and washing for 6 times by using ethanol/deionized water (1:2) mixed solution, and placing the precipitate in an oven with Ar gas to dry for 22 hours at 80 ℃ for later use;
the second step is that: preparation of Pt nanoparticle/hydroxyl carbon cerium ore nano-cluster/graphene composite material
Weighing 60mg of a sample to be used, slightly grinding the sample, putting the ground sample into 40ml of glycol solution, carrying out ultrasonic treatment on the solution for 100min under the condition that the ultrasonic power is 150W, then transferring the mixture to a magnetic stirrer, adding 5ml of chloroplatinic acid/ethylene glycol solution under the stirring action, stirring the mixture evenly, adding saturated NaOH solution to control pH value of the solution to be 13, transferring the mixed solution into a 100ml three-neck flask, then placing the flask in oil bath, heating and refluxing for 4h at 120 ℃, quickly transferring the mixed solution into a beaker after the oil bath is finished, stirring and cooling to room temperature, adding 2mol/ml hydrochloric acid to adjust the pH value of the system to 2, continuously stirring for 25min, and centrifuging and collecting the precipitate, repeatedly centrifuging and washing the precipitate for 5 times by using an ethanol/deionized water (1:4) mixed solution, and putting the washed precipitate into a vacuum oven for vacuum drying for 20 hours at the temperature of 80 ℃ to obtain the platinum nano-particle-hydroxyl cerite nano-cluster/graphene composite material.
Example 9:
the first step is as follows: preparation of hydroxyl carbon cerium ore nano-cluster/graphene composite material
Mixing 20ml of graphene oxide solution with 20ml of ethylene glycol solution, wherein the mass concentration of the graphene oxide solution is 3 mg/ml; performing ultrasonic treatment for 65min under the condition that the ultrasonic power is 150W; transferring the mixed solution to a magnetic stirrer, adding 10mg of cerous nitrate hexahydrate in the stirring process, adding 200mg of urea after uniformly stirring, adjusting the pH value of a system to be 11 by using 2mol/ml NaOH solution, transferring the mixed solution to a reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and placing the reaction kettle in a constant-temperature oven to keep the temperature at 200 ℃ for 300min, placing the reaction kettle in water to quickly cool to room temperature after the reaction is finished, taking out the mixed solution, centrifuging at 8000r/min, collecting precipitate, repeatedly centrifuging and washing for 5 times by using ethanol/deionized water (1:3) mixed solution, and placing the precipitate in a vacuum oven to carry out vacuum drying at 62 ℃ for 17 hours for later use;
the second step is that: preparation of Pt nanoparticle/hydroxyl carbon cerium ore nano-cluster/graphene composite material
Weighing 30mg of a sample to be used, slightly grinding the sample, putting the ground sample into 40ml of glycol solution, carrying out ultrasonic treatment on the solution for 90min under the condition that the ultrasonic power is 150W, then transferring the mixture to a magnetic stirrer, adding 3ml of chloroplatinic acid/ethylene glycol solution under the stirring action, stirring the mixture evenly, adding saturated NaOH solution to control pH value of the solution to be 13, transferring the mixed solution into a 100ml three-neck flask, then placing the flask in oil bath, heating and refluxing for 4h at 100 ℃, quickly transferring the mixed solution into a beaker after the oil bath is finished, stirring and cooling to room temperature, adding 4mol/ml hydrochloric acid to adjust the pH value of the system to 2, continuously stirring for 5min, and centrifuging and collecting the precipitate, repeatedly centrifuging and washing the precipitate for 5 times by using an ethanol/deionized water (1:3) mixed solution, and putting the washed precipitate into a vacuum oven for vacuum drying for 22 hours at 70 ℃ to obtain the platinum nanoparticle-hydroxycarbocerium ore nanocluster/graphene composite material.
Example 10:
the first step is as follows: preparation of hydroxyl carbon cerium ore nano-cluster/graphene composite material
Mixing 20ml of graphene oxide solution with 100ml of ethylene glycol solution, wherein the mass concentration of the graphene oxide solution is 5 mg/ml; performing ultrasonic treatment for 70min under the condition that the ultrasonic power is 150W; transferring the mixed solution to a magnetic stirrer, adding 30mg of cerous nitrate hexahydrate in the stirring process, adding 200mg of urea after uniformly stirring, adjusting the pH value of a system to be 13 by using 3mol/ml NaOH solution, transferring the mixed solution to a reaction kettle with a lining of 100ml of polytetrafluoroethylene, sealing and placing the reaction kettle in a constant-temperature oven to keep the temperature at 200 ℃ for 320min, placing the reaction kettle in water to quickly cool to room temperature after the reaction is finished, taking out the mixed solution, centrifuging at 8000r/min, collecting precipitate, repeatedly centrifuging and washing for 4 times by using ethanol/deionized water (1:5) mixed solution, and placing the precipitate in a vacuum oven to carry out vacuum drying at 75 ℃ for 23h for later use;
the second step is that: preparation of Pt nanoparticle/hydroxyl carbon cerium ore nano-cluster/graphene composite material
Weighing 100mg of a sample to be used, slightly grinding the sample, putting the ground sample into 40ml of glycol solution, carrying out ultrasonic treatment on the solution for 85min under the condition that the ultrasonic power is 150W, then transferring the mixture to a magnetic stirrer, adding 3ml of chloroplatinic acid/ethylene glycol solution under the stirring action, stirring the mixture evenly, adding saturated NaOH solution to control pH value of the solution to be 12, transferring the mixed solution into a 100ml three-neck flask, then placing the flask in oil bath, heating and refluxing for 4h at 110 ℃, quickly transferring the mixed solution into a beaker after the oil bath is finished, stirring and cooling to room temperature, adding 4mol/ml hydrochloric acid to adjust the pH value of the system to 3, continuously stirring for 20min, and centrifuging and collecting the precipitate, repeatedly centrifuging and washing the precipitate for 4 times by using an ethanol/deionized water (1:5) mixed solution, and drying the washed precipitate in an oven filled with argon at the temperature of 80 ℃ for 14 hours to obtain the platinum nanoparticle-cerite nanocluster/graphene composite material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a hydroxyl carbon cerium ore nano-cluster/graphene composite material is characterized by comprising the following steps: the method comprises the following steps:
1-1) mixing a graphene oxide solution with an ethylene glycol solution, and performing ultrasonic treatment to obtain a uniform mixed solution; stirring the obtained mixed solution, adding cerium nitrate hexahydrate, and continuously stirring to obtain a uniform suspension mixed solution; the mass concentration of the graphene oxide solution is 1-10 mg/ml;
1-2) adding urea into the suspension mixed solution obtained in the step 1-1), adjusting the pH value to 11-13 to obtain a mixed system, placing the mixed system in a high-pressure reaction kettle for hydrothermal reaction, and quickly cooling after the reaction is finished to obtain a mixed solution; the temperature of the hydrothermal reaction is 200 ℃, and the reaction time is more than or equal to 180 min;
1-3) centrifugally treating the mixed solution obtained in the step 1-2), and collecting precipitates; washing the precipitate for a plurality of times by using a mixed solution of ethanol and deionized water, and drying the washed precipitate to obtain the hydroxyl carbon cerium ore nano-cluster/graphene composite material.
2. The method for preparing the cerite hydroxyl nanocluster/graphene composite material according to claim 1, wherein the method comprises the following steps: the volume ratio of the graphene oxide solution to the ethylene glycol solution in the step 1-1) is 1 (1-3); the ultrasonic treatment time is 50-70 min; the ratio of the added cerous nitrate hexahydrate to the graphene oxide solution is as follows: (1-8) mg: 2 ml.
3. The method for preparing the cerite hydroxyl nanocluster/graphene composite material according to claim 1, wherein the method comprises the following steps: the mass ratio of the urea added in the step 1-2) to the cerium nitrate hexahydrate added in the step 1-1) is (10-20): (1-8); and after the hydrothermal reaction, putting the reaction kettle into water, and quickly cooling the mixed solution to room temperature.
4. The method for preparing the cerite hydroxyl nanocluster/graphene composite material according to claim 1, wherein the method comprises the following steps: in the step 1-3), the volume ratio of 1: (2-5) washing the precipitate for 4-6 times by using a mixed solution of ethanol and deionized water; the drying environment of the precipitate is vacuum or inert atmosphere, the drying temperature is 60-80 ℃, and the drying time is 12-24 hours.
5. A hydroxyl carbon cerium ore nano-cluster/graphene composite material prepared by the preparation method of any one of claims 1 to 4.
6. A preparation method of Pt nanoparticles/cerite nanocluster/graphene composite material based on the cerite nanocluster/graphene composite material of claim 5 is characterized by comprising the following steps of:
2-1) grinding the cerite hydroxyl nanocluster/graphene composite material to obtain powder, putting the powder into an ethylene glycol solution, carrying out ultrasonic treatment on the obtained suspension mixed solution, and adding a mixed solution of chloroplatinic acid and ethylene glycol in the process of magnetically stirring the solution to obtain a mixed solution;
2-2) adjusting the pH value of the mixed solution obtained in the step 2-1) to 12-13, and performing oil bath reflux treatment on the obtained solution; stirring the solution, cooling to room temperature, adjusting the pH value to 2-3, and continuously stirring to obtain a mixed solution;
2-3) centrifugally treating the mixed solution obtained in the step 2-2), and collecting precipitates; and repeatedly washing the composite material for a plurality of times by using a mixed solution of ethanol and deionized water, and drying the washed precipitate to obtain the Pt nano-particles/hydroxyl cerite nano-cluster/graphene composite material.
7. The preparation method of the Pt nanoparticles/cerite nanocluster/graphene composite material as claimed in claim 6, wherein in the step 2-1), agate is used for grinding the cerite nanocluster/graphene composite material, and the ratio of the added powder to the glycol solution is (3-10) mg: 4 ml; the mass concentration of platinum in the mixed solution of chloroplatinic acid and ethylene glycol is 5mg/ml, and the ratio of the added mixed solution of chloroplatinic acid and ethylene glycol to the composite material powder is (1-5) ml: (30-100) mg.
8. The preparation method of the Pt nanoparticle/cerite nanocluster/graphene composite material as claimed in claim 6, wherein in the step 2-2), the pH of the mixed solution is adjusted to 12-13 by using saturated NaOH; the oil bath reflux temperature was: the oil bath reflux time is 2-4 h at 100-200 ℃; and (3) adjusting the solution at room temperature to pH value of 2-3 by using hydrochloric acid, and stirring for 5-30 min to obtain a mixed solution.
9. The preparation method of the Pt nanoparticle/cerite nanocluster/graphene composite material as claimed in claim 6, wherein in the step 2-3), the precipitate is washed for 4-6 times with a mixed solution of ethanol and deionized water, and the volume ratio of ethanol to deionized water is 1: (2-5); the drying environment of the precipitate is vacuum or inert atmosphere, the drying temperature is 60-80 ℃, and the drying time is 12-24 hours.
10. A Pt nanoparticle/cerite nanocluster/graphene composite material prepared by the preparation method of any one of claims 6 to 9.
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