CN107394222B - Cerium oxide/precious metal/graphene ternary composite material and preparation method and application thereof - Google Patents
Cerium oxide/precious metal/graphene ternary composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cerium oxide/noble metal/graphene ternary composite material which is of a layered structure and consists of nanoscale cerium oxide, noble metal and graphene, wherein the general formula of the ternary composite material is CeO2/M/graphene, wherein M is Pd, Pt or Au. The cerium oxide and the noble metal in the composite material can be uniformly distributed and have small granularity due to the dispersion and bearing effects of the graphene, and form a layered structure, so that the catalytic performance of the ternary composite material can be effectively improved, and the ternary composite material can be used as a lithium-air battery anode material. The invention also discloses a one-step low-temperature preparation method of the composite material, which has the advantages of simple process, low cost, short period, low energy consumption and the like and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the field of composite materials for lithium-air batteries, in particular to a cerium oxide/precious metal/graphene ternary composite material and a preparation method and application thereof.
Background
The lithium-air battery is a novel energy storage device which takes metal lithium as a negative electrode, air (or oxygen) as a positive electrode and a lithium ion conductor as electrolyte. The theoretical energy density of the lithium-air battery is as high as 11680Wh/kg (excluding O)2If it comprises O2And then 5200 Wh/kg). The actual available energy density of a lithium-air battery, considering the weight of the catalyst, electrolyte, battery pack, etc., is about 1700Wh/kg, which is comparable to that of gasoline, much higher than nickel-hydrogen (50Wh/kg), lithium ion (typically), and the like<200Wh/kg), lithium-sulfur (370Wh/kg), zinc-air (350Wh/kg) cells. Due to the high energy density of the lithium-air battery, the lithium-air battery has an important application prospect in the fields of vehicle power batteries, energy storage of power grids and the like. Just as lithium-air batteries have very important application prospects, some famous companies and scientific research institutes in the world have started the research on lithium-air batteries. For example, IBM corporation of america initiated the "Battery 500 Project" research program, the ultimate goal of which was to use lithium-air batteries for automobiles. "500" in this study plan stands for each timeThe charged car travels 500 miles (800 km).
There are many factors that affect the performance of lithium-air batteries, but the composition and structure of the catalyst are critical factors. Recently, various novel catalysts such as noble metal M (M ═ Ru, Au, Pd, Pt), PtAu, MnO2、MnO2/Ti、MnO2[ Pd ], MoN/graphene, MnCo ]2O4Graphene and the like have been developed. For the catalyst component, with respect to the metal oxide (e.g., Fe)2O3、MnO2) The catalyst, noble metal catalyst, has unique performance advantages, and is the most ideal catalyst for lithium-air battery air. However, since the noble metal catalyst is relatively expensive, it is a trend of catalyst development in the future to reduce the amount of noble metal used, and among them, development of a metal oxide/noble metal composite catalyst is one of effective means for solving the problem. In addition, uniform dispersion of the noble metal on the oxide is also one of the methods for reducing the amount thereof used. For catalyst design, the composition and structure of the catalyst support are also important elements, and the preferred matrix material is a carbon material. Among various carbon materials, graphene is a very desirable matrix material because of its high electrical conductivity, high mechanical strength, large specific surface area agent, and porosity.
In the prior art, many reports exist on the preparation of composite materials by taking graphene as a matrix material, but the reports on the preparation of composite materials used as a lithium-air battery catalyst carrier are few, for example, Chinese patent application CN201110405944.3 discloses a graphene-platinum nano composite catalyst for a lithium-air battery and a preparation method thereof, wherein the composite catalyst consists of graphene and platinum nano particles, solid platinum is used as a target material, and a liquid-phase pulse laser ablation technology is adopted to grow nano platinum particles on the graphene. The composite catalytic material has good catalytic performance, reversible capacity of 4000mAh/g under the current of 100mA/g, smaller overvoltage and good circulation stability. Therefore, the development of graphene, namely the composite catalytic material has wide application prospect. However, a ternary composite catalyst using graphene as a carrier is rarely reported at present.
Disclosure of Invention
The invention provides a cerium oxide/precious metal/graphene ternary composite material with a layered structure and good electrochemical properties such as high capacity, low overpotential, high cycling stability and the like, and also provides a preparation method of the cerium oxide/precious metal/graphene ternary composite material with the layered structure.
A cerium oxide/noble metal/graphene ternary composite material is characterized by comprising nano-scale cerium oxide CeO2Noble metal and graphene, wherein CeO2And noble metal is positioned between the graphene sheet layers to form a layered structure, and the general formula of the ternary composite material is CeO2The catalyst is/M/graphene, wherein the noble metal M is Pt, Pd or Au.
Further, the weight percentage content of the graphene in the ternary composite material is 1% -20%, and more preferably 6% -15%.
Further, the weight percentage content of the noble metal in the ternary composite material is 1% -10%, and further preferably 4% -8%.
Excess CeO2Not beneficial to uniform loading on graphene and leaving gaps and too little CeO between layers2The cooperative catalytic performance is weakened. Too much noble metal content can result in particle agglomeration and increased cell cost, and too little noble metal can diminish the concerted catalytic action. Thus, CeO is added2And noble metals at the above levels are suitable.
Furthermore, the particle diameter of the nano-scale cerium oxide is 5-15 nanometers, and the particle diameter of the nano-scale noble metal is 1-5 nanometers.
The smaller the diameter of the cerium oxide particles, the easier the cerium oxide particles are to be loaded on graphene, but the undersize of the particles is not favorable for reserving interlayer gaps and loading noble metals; the smaller the particle diameter of the noble metal, the more easily the noble metal is supported on the surface of the cerium oxide particles, but the particle diameter is too small, and the particles are easily agglomerated, and therefore the particle diameter is selected as described above.
Furthermore, the nano-cerium oxide and the noble metal nano-particles are uniformly dispersed in graphene sheet layers to form a layered structure with the graphene sheet layers, and gaps are formed among the layers, and the number of the layers is less than 5.
Unlike the conventional bulk structure, this structure facilitates the diffusion of oxygen and the transport of lithium ions, as well as the deposition of lithium peroxide, thereby improving the performance of the lithium-air battery. In addition, in the structure, because cerium oxide nanoparticles are uniformly loaded and dispersed, the agglomeration of the noble metal nanoparticles is inhibited, so that the catalytic activity and the durability of the noble metal nanoparticles are improved, the using amount of the noble metal nanoparticles is reduced, and the cost of the battery is reduced.
Furthermore, the noble metal particles are loaded on the surface of the cerium oxide nano particles, and the cerium oxide nano particles are uniformly dispersed.
A method for preparing the cerium oxide/precious metal/graphene ternary composite material, which comprises the following steps:
(1) dissolving trivalent Ce salt in reducing organic solvent to obtain Ce3+Adding graphene oxide GO into the solution with the concentration of 0.01-0.1 mol/L, and performing ultrasonic dispersion to obtain a mixed solution;
the addition of GO is the final product cerium oxide CeO 25 to 50 percent of theoretical weight; further preferably 17% to 47%;
(2) sealing the solution in the step (1), heating to 180-220 ℃, reacting for 12-48 hours, cooling, collecting a solid product, alternately and repeatedly washing with deionized water and absolute ethyl alcohol, and drying to obtain the cerium oxide/graphene composite material with a laminated structure;
(3) dispersing the cerium oxide/graphene composite material obtained in the step (2) in a reducing organic solvent, and then adding a compound containing noble metal, wherein the adding amount of the compound is the final product cerium oxide CeO25-25% of theoretical weight, sealing after ultrasonic dispersion, heating to 100-160 ℃, reacting for 1-6 hours, cooling, collecting solid products, alternately and repeatedly washing with deionized water and absolute ethyl alcohol, and drying to obtain the cerium oxide/M/graphene composite material with a layered structure, wherein M is Pd, Pt or Au.
According to the method, reducing agents such as hydrazine hydrate and sodium borohydride are not needed, graphene oxide can be reduced into graphene through solvothermal reduction in a reducing solvent, and a compound containing precious metal can also be reduced into precious metal.
The method also does not require the use of toxic oxygen-generating agents such as NaBH4Or hydrazine hydrate, in the ultrasonic dispersion process of the step (1), the trivalent Ce is easy to be dissolved in the solution2Oxidized to tetravalent Ce, but the dissolved oxygen does not affect the reduction of graphene.
Further, the trivalent Ce salt is fluoride of trivalent Ce, chloride of trivalent Ce, nitrate of trivalent Ce, sulfate of trivalent Ce, oxalate of trivalent Ce, acetate of trivalent Ce or hydrate of any one of the salts;
the noble metal-containing compound comprises H2PdCl4、Pd(NH3)4Cl2、Pd(NH3)2Cl2、Pd(NH3)4SO4、Pd(NH3)4(NO3)2、H2PtCl6、H2PtCl4、K2PtCl6、(NH4)2PtCl6、K2PtCl4、(NH4)2PtCl4、HAuCl4、NaAuCl4、KAuCl4Or a hydrate of any of the compounds.
Further, the reducing organic solvent is ethanol, glycerol, methanol, ethylene glycol, 1-butanol, N-dimethylformamide, ethylenediamine or oleylamine.
In the step (2), the reaction is further preferably carried out for 20 to 32 hours at 180 to 220 ℃ and then cooled;
in the step (3), the reaction is further preferably carried out for 2 to 4 hours at 110 to 140 ℃ and then cooled;
the reaction temperature is high, the reaction time is long, cerium oxide is easy to form, graphene oxide is easy to reduce into graphene, a compound containing precious metal is easy to reduce into precious metal, and the growth of cerium oxide and precious metal particles and the agglomeration of graphene are easy to cause influence on the catalytic effect of the catalyst at an excessively high temperature and for an excessively long time.
The cooling temperature is not strictly limited, and is mainly suitable for operation, and generally can be cooled to an ambient temperature of 15 ℃ to 30 ℃.
The application of the cerium oxide/precious metal/graphene ternary composite material as a lithium-air battery positive electrode material.
According to the invention, cerium oxide, noble metal and graphene are compounded, and the electrochemical performance of the lithium air battery is improved by utilizing the synergistic catalytic action of the cerium oxide, the noble metal and the graphene, so that the overpotential is particularly reduced. The synergistic catalytic mechanism is that the noble metal is often used as the active center of the oxidation/precipitation reaction due to the high catalytic activity, and the cerium oxide contains Ce3+/Ce4+The redox couple acts as a buffer for oxygen, and graphene is favorable for lithium peroxide Li due to high conductivity and large specific surface area2O2So that the combination of the three is beneficial to improving the performance of the lithium-air battery.
Compared with the prior art, the invention has the following advantages:
1. the method adopts a two-step solvothermal method to prepare the cerium oxide/noble metal/graphene ternary composite material at a low temperature, and has the advantages of simple process, low cost, short period, low energy consumption, suitability for industrial production and the like.
2. Due to the dispersion and bearing effects of the graphene, the cerium oxide in the composite material has small granularity, the diameter of the cerium oxide is about 5-15 nanometers, and the cerium oxide is distributed uniformly; the noble metal particles are small, have the diameter of about 1 to 5 nanometers, and are easy to disperse and fix by cerium oxide.
3. The nano cerium oxide particles and the noble metal particles are positioned in the graphene sheet layers, and the graphene sheet layers form a layered structure which is beneficial to oxygen transmission, lithium ion diffusion and lithium peroxide deposition, so that the electrochemical performance of the lithium-air battery is improved.
Drawings
FIG. 1 shows CeO obtained in example 12The X-ray diffraction pattern of the/Pt/graphene composite material;
FIG. 2 shows CeO obtained in example 12A transmission electron microscope photo of the/Pt/graphene composite material;
FIG. 3 shows CeO obtained in example 12Scanning of/Pt/graphene compositesElectron microscope photographs;
FIG. 4 shows CeO obtained in example 12And the electrochemical performance diagram of the/Pt/graphene composite material.
Detailed Description
Example 1
Reacting CeCl3·6H2Dissolving O in glycol to prepare 80 ml Ce3+Adding 65 mg of GO into a solution with the concentration of 0.01mol/L to prepare a mixed solution, wherein the adding amount of GO is the final product cerium oxide CeO2Carrying out ultrasonic dispersion on 47 percent of theoretical weight to obtain a mixed solution, placing the mixed solution into a high-pressure reaction kettle with the capacity of 100 ml and the filling degree of 80 percent by volume, sealing the reaction kettle, reacting for 20 hours at 180 ℃, and naturally cooling to room temperature; collecting a solid reaction product, alternately and repeatedly washing the product with deionized water and absolute ethyl alcohol, drying to obtain a cerium oxide/graphene composite material, dispersing the composite material in ethylene glycol, and adding 15 mg of H2PtCl4In the amount of the final product cerium oxide CeO211% of theoretical weight, sealing after ultrasonic dispersion, heating to 110 ℃, reacting for 2 hours, cooling, collecting a solid product, alternately and repeatedly washing with deionized water and absolute ethyl alcohol, and drying to obtain 0.16g of cerium oxide/Pt/graphene composite material, wherein the weight percentage of the graphene is 15%, and the weight percentage of the Pt is 5%.
The obtained composite material has X-ray diffraction pattern, transmission electron micrograph and scanning electron micrograph shown in figures 1, 2 and 3 respectively, and the diffraction peak of X-ray in figure 1 can be classified as CeO2And the diffraction peak of the graphene cannot be seen from the X-ray diffraction pattern, which indicates that the graphene is already coated by CeO2The particles are dispersed. In addition, no diffraction peak of platinum was observed from the X-ray diffraction pattern of FIG. 1, because the content of Pt was relatively low, and it is clear from the transmission electron microscope of FIG. 2 that the obtained composite material was CeO2/Pt/graphene composite material, CeO2The particle size is nano-scale, the diameter is 5-15 nm, and the distribution is relatively uniform; the Pt particles are also nano-sized, have the diameter of 1-5 nanometers and are uniformly dispersed in the CeO2GranulesA surface. As can be seen from the scanning electron micrograph of FIG. 3, the ternary composite material has a layered structure, i.e., CeO2And Pt nano particles are uniformly dispersed in the graphene sheet layers of each layer, and the number of the layers is less than 5.
CeO prepared in this example2the/Pt/graphene ternary composite material is used as a lithium-air battery anode, metal lithium is used as a cathode, a polypropylene film (the trademark Celgard C480, Celgard company, USA) is used as a diaphragm, and LiClO4The triethylene glycol dimethyl ether TEGDME solution is used as electrolyte, and a battery is assembled in a glove box filled with argon. After the oxygen gas of 1 atm was introduced, the charge and discharge test was carried out, and the cycle curve thereof is shown in fig. 4.
According to the constant-capacitance charge-discharge test that the capacity is limited to 500mAh/g, the current density is 100mA/g, and the voltage range is 2V-4.5V, wherein the capacity and the current density are both based on the total weight of the composite material, the lithium-oxygen battery can keep stable circulation in the secondary charge-discharge process. After 40 cycles, the charge cut-off potential and the discharge cut-off potential are respectively kept at about 3.95V and 2.28V, and the low polarization and the good cycle stability are shown.
Example 2
Adding Ce (NO)3)3·6H2O is dissolved in ethylenediamine to prepare 80 ml of Ce3+Adding 258 mg of GO into the solution with the total concentration of 0.05mol/L to prepare a mixed solution, wherein the adding amount of GO is the final product cerium oxide CeO2Performing ultrasonic dispersion on 37% of theoretical weight to obtain a mixed solution, placing the mixed solution into a high-pressure reaction kettle with the capacity of 100 ml, sealing the reaction kettle, reacting at 200 ℃ for 24 hours, and naturally cooling to room temperature, wherein the filling degree of the mixed solution is 80% of volume percentage; collecting a solid reaction product, alternately and repeatedly washing the product with deionized water and absolute ethyl alcohol, drying to obtain a cerium oxide/graphene composite material, dispersing the composite material in ethylenediamine, and adding 162 mg of H2PdCl4In the amount of the final product cerium oxide CeO223% of theoretical weight, sealing after ultrasonic dispersion, heating to 120 ℃, reacting for 4 hours, cooling, collecting solid product, alternately and repeatedly washing with deionized water and absolute ethyl alcohol, and drying to obtain the product0.85g of cerium oxide/Pd/graphene composite material, wherein the weight percentage of the graphene is 12%, and the weight percentage of the Pd is 8%.
The obtained composite material is characterized by X-ray diffraction pattern, transmission electron microscope photo and scanning electron microscope photo to determine CeO2a/Pd/graphene ternary composite material, wherein CeO2The particle size is nano-scale, the diameter is 5-15 nm, and the distribution is relatively uniform; the Pd particles are also nano-sized, have the diameter of 1-5 nanometers and are uniformly dispersed in the CeO2The surface of the particles. The ternary composite material being in the form of a layered structure, i.e. CeO2And the Pd nano particles are uniformly dispersed in the graphene sheet layers of each layer, and the number of the layers is less than 5.
CeO prepared in this example2the/Pd/graphene ternary composite material is used as a lithium-air battery anode, metal lithium is used as a cathode, a polypropylene film (the trademark Celgard C480, Celgard company, USA) is used as a diaphragm, and LiClO4The triethylene glycol dimethyl ether TEGDME solution is used as electrolyte, and a battery is assembled in a glove box filled with argon. After the oxygen gas of 1 atmosphere was introduced, a charge and discharge test was performed.
According to the constant-capacitance charge-discharge test that the capacity is limited to 500mAh/g, the current density is 100mA/g, and the voltage range is 2V-4.5V, wherein the capacity and the current density are both based on the total weight of the composite material, the lithium-oxygen battery can keep stable circulation in the secondary charge-discharge process. After 40 cycles, the charge cut-off potential and the discharge cut-off potential are respectively kept at about 3.98V and 2.32V, and lower polarization and better cycle stability are shown.
Example 3
Adding Ce2(SO4)3·8H2O is dissolved in N, N-dimethylformamide to prepare 80 ml of Ce3+Adding 230 mg of GO into a solution with the concentration of 0.1mol/L to prepare a mixed solution, wherein the adding amount of the mixed solution is that of the final product cerium oxide CeO217% of theoretical weight, and obtaining a mixed solution through ultrasonic dispersion; placing the mixed solution into a high-pressure reaction kettle (filling degree is 80%, volume percentage) with the capacity of 100 ml, sealing the reaction kettle, reacting for 32 hours at 220 ℃, and naturally cooling to room temperature; collecting the solid reaction productAlternately and repeatedly washing and drying the product by deionized water and absolute ethyl alcohol to obtain a cerium oxide/graphene composite material, dispersing the composite material in N, N-dimethylformamide, and adding 117 mg of KAuCl4In the amount of the final product cerium oxide CeO28.5% of theoretical weight, sealing after ultrasonic dispersion, heating to 140 ℃, reacting for 3 hours, cooling, collecting a solid product, alternately and repeatedly washing with deionized water and absolute ethyl alcohol, and drying to obtain 1.5g of cerium oxide/Au/graphene composite material, wherein the weight percentage content of graphene is 6%, and the weight percentage content of Au is 4%.
The obtained composite material is characterized by X-ray diffraction pattern, transmission electron microscope photo and scanning electron microscope photo to determine CeO2Au/graphene ternary composite material, wherein CeO2The particle size is nano-scale, the diameter is 5-15 nm, and the distribution is relatively uniform; the Au particles are also nano-sized, have the diameter of 1-5 nanometers and are uniformly dispersed in the CeO2The surface of the particles. The ternary composite material being in the form of a layered structure, i.e. CeO2And the Pd nano particles are uniformly dispersed in the graphene sheet layers of each layer, and the number of the layers is less than 5.
CeO prepared in this example2the/Au/graphene ternary composite material is used as a lithium-air battery anode, metal lithium is used as a cathode, a polypropylene film (the trademark Celgard C480, Celgard company, USA) is used as a diaphragm, and LiClO4The triethylene glycol dimethyl ether TEGDME solution is used as electrolyte, and a battery is assembled in a glove box filled with argon. After the oxygen gas of 1 atmosphere was introduced, a charge and discharge test was performed.
According to the constant-capacitance charge-discharge test that the capacity is limited to 500mAh/g, the current density is 100mA/g, and the voltage range is 2V-4.5V, wherein the capacity and the current density are both based on the total weight of the composite material, the lithium-oxygen battery can keep stable circulation in the secondary charge-discharge process. After 40 cycles, the charge cut-off potential and the discharge cut-off potential are respectively kept at about 4.02V and 2.21V, and the low polarization and the good cycle stability are shown.
Claims (8)
1. Preparation of cerium oxide/precious metal/grapheneThe method of the ternary composite material comprises the following steps of preparing the cerium oxide/precious metal/graphene ternary composite material from nano cerium oxide CeO2Noble metal and graphene, wherein CeO2And noble metal is positioned between the graphene sheet layers to form a layered structure, and the general formula of the ternary composite material is CeO2The preparation method comprises the following steps of/M/graphene, wherein the noble metal M is Pt, Pd or Au; the particle diameter of the nano-scale cerium oxide is 5-15 nanometers, and the particle diameter of the nano-scale noble metal is 1-5 nanometers;
the method comprises the following steps:
(1) dissolving trivalent Ce salt in reducing organic solvent to obtain Ce3+Adding graphene oxide GO into the solution with the concentration of 0.01-0.1 mol/L, and performing ultrasonic dispersion to obtain a mixed solution;
the addition of GO is the final product cerium oxide CeO25% -50% of theoretical weight; further preferably 17% -47%;
(2) sealing the solution obtained in the step (1), heating to 180-220 ℃, reacting for 12-48 hours, cooling, collecting a solid product, alternately and repeatedly washing with deionized water and absolute ethyl alcohol, and drying to obtain a cerium oxide/graphene composite material with a laminated structure;
(3) dispersing the cerium oxide/graphene composite material obtained in the step (2) in a reducing organic solvent, and then adding a compound containing noble metal, wherein the adding amount of the compound is the final product cerium oxide CeO25-25% of theoretical weight, sealing after ultrasonic dispersion, heating to 100-160 ℃, reacting for 1-6 hours, cooling, collecting a solid product, alternately and repeatedly washing with deionized water and absolute ethyl alcohol, and drying to obtain the cerium oxide/M/graphene composite material with a layered structure, wherein M is Pd, Pt or Au.
2. The method for preparing the cerium oxide/noble metal/graphene ternary composite material according to claim 1, wherein the weight percentage of graphene in the ternary composite material is 1% to 20%, and more preferably 6% to 15%.
3. The method for preparing the cerium oxide/precious metal/graphene ternary composite material according to claim 1, wherein the weight percentage of the precious metal in the ternary composite material is 1% to 10%, and more preferably 4% to 8%.
4. The method for preparing the cerium oxide/noble metal/graphene ternary composite according to claim 1, wherein the nano-sized cerium oxide and noble metal nanoparticles are uniformly dispersed in graphene sheets, and the graphene sheets form a layered structure, and gaps are formed between the layers, and the number of the layers is less than 5.
5. The method for preparing the ternary composite material of cerium oxide/noble metal/graphene as claimed in claim 4, wherein the noble metal particles are supported on the surface of the cerium oxide nanoparticles, and the cerium oxide nanoparticles are uniformly dispersed.
6. The method for preparing the cerium oxide/noble metal/graphene ternary composite material according to claim 1, wherein the trivalent Ce salt is a fluoride of trivalent Ce, a chloride of trivalent Ce, a nitrate of trivalent Ce, a sulfate of trivalent Ce, an oxalate of trivalent Ce, an acetate of trivalent Ce or a hydrate of any one of the salts;
the noble metal-containing compound comprises H2PdCl4、Pd(NH3)4Cl2、Pd(NH3)2Cl2、Pd(NH3)4SO4、Pd(NH3)4(NO3)2、H2PtCl6、H2PtCl4、K2PtCl6、(NH4)2PtCl6、K2PtCl4、(NH4)2PtCl4、HAuCl4、NaAuCl4、KAuCl4Or a hydrate of any of the compounds.
7. The method for preparing the cerium oxide/noble metal/graphene ternary composite according to claim 6, wherein the reducing organic solvent is ethanol, glycerol, methanol, ethylene glycol, 1-butanol, N-dimethylformamide, ethylenediamine or oleylamine.
8. Use of the cerium oxide/noble metal/graphene ternary composite material according to any one of claims 1 to 7 as a positive electrode material for a lithium-air battery.
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CN111180745B (en) * | 2019-12-30 | 2021-11-23 | 浙江工业大学 | CeO (CeO)xPreparation method and application of/MC nanosheet material |
WO2021181085A1 (en) * | 2020-03-10 | 2021-09-16 | Amalyst Limited | Catalyst |
CN113231061A (en) * | 2021-03-04 | 2021-08-10 | 广东工业大学 | Cerium dioxide nanorod supported catalyst and preparation method and application thereof |
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CN106457210A (en) * | 2014-03-18 | 2017-02-22 | 巴斯夫欧洲公司 | A process for the production of a carbon supported catalyst |
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