CN110676475A - Pt-Ni alloy electrocatalyst with layered framework structure and preparation method thereof - Google Patents
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Abstract
The invention provides a Pt-Ni alloy electrocatalyst with a layered framework structure and a preparation method thereof. The Pt-Ni alloy electrocatalyst provided by the invention has the characteristics of porosity, large specific surface area, high atom utilization rate and strong structure stability, and the dosage of platinum is greatly reduced and the cost is reduced by doping transition metal. The invention has the characteristics of simple process, good repeatability and high yield, and has good development prospect in proton exchange membrane fuel cells and direct methanol fuel cells.
Description
Technical Field
The invention belongs to the technical field of nanotechnology and fuel cells, and relates to a Pt-Ni alloy electrocatalyst with a layered framework structure and a preparation method thereof.
Background
With the development of society, the acquisition of clean energy is more and more concerned by people, and the development of new clean, efficient and sustainable energy has become a problem of important attention all over the world. Hydrogen Proton Exchange Membrane Fuel Cells (PEMFCs) have the characteristics of high energy conversion efficiency, eco-friendliness and the like, and become potential energy sources of automobiles and electronic equipment. In the operation of PEMFCs, the Oxygen Reduction Reaction (ORR) process has a high reduction potential due to cathode oxidation, and the slow cathode oxygen reduction reaction process has become an important obstacle to the development of fuel cells. Platinum (Pt) catalysts have good catalytic performance for ORR and are the most effective oxygen reducing agents in widespread use today. However, the high price of Pt and the scarcity of earth reserves have greatly limited the commercialization of PEMFCs. Therefore, the research on various low-Pt or non-Pt catalysts to obtain high-performance electrocatalysts and the preparation of high-efficiency and low-cost cathode oxygen reduction electrocatalysts are the most critical step for the practical application of fuel cells.
In recent years, in order to change the intrinsic activity of Pt, many researchers have introduced a second element to induce an alloy with a unique morphology, so as to increase the intrinsic activity of Pt, thereby reducing the amount of Pt used. Various novel Pt-based alloy structures such as Pt have been synthesized3Co concave nanocubes, Pt-Cu-Rh heterogeneous nanocrystals, Pt-Ag hollow nanocrystals, octahedral Pt-Ni nanoparticles, porous hollow PtNi/C nanostructures and the like. These catalysts of different geometries and compositions not only change the electronic structure of the noble metal Pt, but also increase the active sites for oxygen adsorption, resulting in a significant improvement in ORR compared to pure Pt. E.g. concave PtCu2The octagonal rhombohedral dodecahedral catalyst has good electrocatalytic performance compared with a Pt/C catalyst. Although the nano-framework structure has the remarkable advantages of large specific surface area, high atom utilization rate and the like, the framework is a hollow structure, so that the interior of the framework is very fragile, and the framework is easy to collapse in electrolyte to cause structural damage. Therefore, how to better utilize the nano-framework structure is a huge challenge.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and aims to provide the Pt-Ni alloy electrocatalyst with the layered framework structure and the preparation method thereof.
The technical scheme is as follows:
(1) mixing and heating sulfuric acid, platinum salt, nickel acetate, hexadecyl trimethyl ammonium chloride and a solvent to prepare a precursor solution;
(2) centrifuging and cleaning the precursor solution to obtain a catalyst, and carrying out acid etching on the catalyst by using an excessive acid solution to obtain an octahedral catalyst with a layered framework structure;
(3) centrifugally collecting the octahedral catalyst with the layered framework structure, drying, dripping chloroform to prepare a chloroform solution of nano particles, and mixing and reacting the chloroform solution with a chloroform solution dispersed with a carbon carrier to obtain a loaded alloy electrocatalyst with the octahedral layered framework structure;
(4) and (3) carrying out heat treatment on the octahedral layered framework structure alloy electrocatalyst in the step (3) in the reducing gas and inert gas atmosphere to obtain the Pt-Ni alloy electrocatalyst.
Wherein, the solvent in the step (1) is oleylamine;
wherein, the platinum salt in the step (1) is one or two of platinum acetylacetonate and chloroplatinic acid;
wherein the dosage of each raw material in the step (1) is as follows: 2ml of a 0.1M sulfuric acid solution, in a molar ratio of 1: 2: 23 parts of platinum salt, nickel acetate and hexadecyl trimethyl ammonium chloride, and 10-15 ml of solvent;
adding sulfuric acid, platinum salt, nickel acetate and hexadecyl trimethyl ammonium chloride into a solvent in the step (1), stirring on a magnetic stirrer at the temperature of 30-60 ℃ until reactants are uniformly mixed, and reacting for 19-30 hours at the temperature of 155-180 ℃ in a sealed reaction container with a polytetrafluoroethylene inner container to obtain a precursor solution; and further stirring the mixture on a magnetic stirrer at the temperature of 50 ℃ until the reactants are uniformly mixed, and reacting the mixture for 20 hours at the temperature of 160 ℃ in a sealed reaction container with a polytetrafluoroethylene inner container to obtain a precursor solution.
Cooling the precursor solution in the step (2) to room temperature, centrifuging to collect the catalyst, cleaning with a mixed solution of absolute ethyl alcohol and acetone, and dispersing the catalyst in n-hexane for storage; further, the operations of centrifugation and washing with a mixture of absolute ethanol and acetone were repeated 5 times.
Adding the cleaned catalyst centrifuged from n-hexane into an excessive acid solution in the step (2), heating to 80-120 ℃ under the condition of magnetic stirring, maintaining for 4-10 hours, and performing centrifugal separation to obtain an octahedral catalyst with a layered framework structure; further, heat to 80 ℃ with magnetic stirring and hold for 4 h.
Wherein, the acid solution in the step (2) is one of acetic acid, sulfuric acid or hydrochloric acid; further, the acid solution is acetic acid.
In the step (3), the carbon carrier is carbon powder or graphene with a three-dimensional structure;
wherein, in the step (3), chloroform is dripped into the dried octahedral catalyst, then ultrasonic treatment is carried out to uniformly disperse the catalyst to obtain a chloroform solution of the nano particles, the chloroform dosage can ensure that all the catalyst is dispersed in the liquid without forming solid sediment to form a similar colloidal solution, and then the chloroform solution of the nano particles is obtained; similarly, chloroform is dripped into the carbon material, and then the carbon material is treated by ultrasonic to obtain a chloroform solution dispersed with the carbon carrier, wherein the amount of the chloroform can ensure that the carbon material particles are not deposited after the ultrasonic treatment, thereby obtaining the chloroform solution dispersed with the carbon carrier;
in the step (3), under the action of ultrasound, dropwise adding the prepared chloroform solution of the nanoparticles into the chloroform solution dispersed with the carbon carriers, continuing to magnetically stir for 24 hours after ultrasound for more than 8 hours, mixing and reacting to obtain a loaded alloy electrocatalyst with an octahedral layered framework structure, and washing with methanol and absolute ethanol for 2 times respectively;
wherein, the reducing gas in the step (4) is one or two of hydrogen and carbon monoxide; further, the reducing gas is hydrogen.
Wherein, the inert gas in the step (4) is argon or nitrogen; further, the inert gas is argon.
Gradually heating the octahedral layered framework structure alloy electrocatalyst in the step (3) to 200-350 ℃ in the atmosphere of reducing gas and inert gas, carrying out heat preservation treatment for 2-8 h, and cooling to obtain the Pt-Ni alloy electrocatalyst; further, carrying out heat preservation treatment for 2 hours at a temperature rise speed of 5-10 ℃ per minute; the preferred rate of temperature rise is 5 c per minute.
The Pt-Ni alloy electrocatalyst prepared by the preparation method is an alloy electrocatalyst with a layered framework structure, the size of the framework is 79nm, and the Pt-Ni alloy electrocatalyst is assembled by a plurality of small particles with the particle size of 3-5 nm and used for catalyzing the oxygen reduction reaction of PEMFCs during working.
Through the technical scheme, the invention has the following beneficial effects:
(1) the Pt-Ni octahedron formed by self-assembled crystal grains is synthesized firstly, and then is converted into the graded Pt-Ni framework nano octahedron (HSN) through acid etching, so that the structure not only exposes a larger surface area, but also can not collapse under a high pressure for a long time, and basically keeps the original shape.
(2) The invention greatly reduces the consumption of platinum and improves the activity by doping transition metal.
(3) The invention has high product conversion rate, high yield and uniform prepared particles.
(4) The invention has the characteristics of simple process, good repeatability and high yield, and has good development prospect in proton exchange membrane fuel cells and direct methanol fuel cells.
Drawings
FIG. 1 shows that the precursor solution obtained in step (1) is centrifuged and washed to obtain a catalyst;
FIG. 2 is an octahedral catalyst with a layered framework structure;
FIG. 3 is an X-ray photoelectron spectrum of an octahedral catalyst having a layered framework structure;
FIG. 4 is a polarization plot of a redox reaction test;
FIG. 5 is a polarization plot of an alcohol oxidation test
Detailed Description
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials and reagents used in the following examples, unless otherwise specified, were all conventional biochemical reagents, available from reagent companies.
Example 1: preparation of Pt-Ni alloy electrocatalyst with layered framework structure
(1) 2ml of a 0.1M sulfuric acid solution and a molar ratio of 1: 2: adding 23 parts of platinum acetylacetonate, nickel acetate and hexadecyl trimethyl ammonium chloride into 10ml of oleylamine, stirring on a magnetic stirrer at 50 ℃ until reactants are uniformly mixed, and reacting for 20 hours at 160 ℃ in a sealed reaction container with a polytetrafluoroethylene inner container to obtain a precursor solution;
(2) after the precursor solution is cooled to room temperature, centrifugally collecting the catalyst, cleaning the catalyst by using a mixed solution of absolute ethyl alcohol and acetone, and dispersing the catalyst in n-hexane for storage; adding excessive sulfuric acid into the cleaned catalyst centrifuged from n-hexane, heating to 100 ℃ under the condition of magnetic stirring and maintaining for 8 hours, and performing centrifugal separation to obtain an octahedral catalyst with a layered framework structure;
(3) centrifugally collecting an octahedral catalyst with a layered framework structure, dripping chloroform into the dried octahedral catalyst, and then performing ultrasonic treatment to uniformly disperse the catalyst to obtain a chloroform solution of nanoparticles, wherein the chloroform is used in an amount which can disperse all the catalyst in a liquid without forming solid sediment to form a similar colloidal solution, so as to obtain a chloroform solution of nanoparticles; the chloroform is also dropped into the carbon powder, and then the carbon carrier-dispersed chloroform solution is obtained by ultrasonic treatment, wherein the amount of the chloroform can ensure that the carbon material particles are not deposited after the ultrasonic treatment, so that the carbon carrier-dispersed chloroform solution is obtained; under the action of ultrasound, dropwise adding a chloroform solution of nanoparticles into a chloroform solution dispersed with a carbon carrier, performing ultrasound for 9 hours, then continuing to perform magnetic stirring for 24 hours, performing mixing reaction to obtain a loaded octahedral layered framework structure alloy electrocatalyst, and respectively cleaning the octahedral layered framework structure alloy electrocatalyst with methanol and absolute ethanol for 2 times;
(4) and (3) in the atmosphere of reducing gas carbon monoxide and inert gas nitrogen, gradually heating the octahedral layered framework structure alloy electrocatalyst in the step (3) to 200 ℃ at the speed of 8 ℃ per minute, carrying out heat preservation treatment for 5 hours, and cooling to obtain the Pt-Ni alloy electrocatalyst.
The Pt-Ni alloy electrocatalyst prepared by the preparation method is an alloy electrocatalyst with a layered framework structure, the size of the framework is 79nm, and the Pt-Ni alloy electrocatalyst is assembled by a plurality of small particles with the particle size of 3-5 nm and used for catalyzing the oxygen reduction reaction of PEMFCs during working.
Example 2: preparation of Pt-Ni alloy electrocatalyst with layered framework structure
(1) 2ml of a 0.1M sulfuric acid solution and a molar ratio of 1: 2: adding 23 parts of chloroplatinic acid, nickel acetate and hexadecyl trimethyl ammonium chloride into 12.5ml of oleylamine, stirring on a magnetic stirrer at 30 ℃ until reactants are uniformly mixed, and reacting for 19 hours at 155 ℃ in a sealed reaction container with a polytetrafluoroethylene inner container to obtain a precursor solution;
(2) after the precursor solution is cooled to room temperature, centrifugally collecting the catalyst, cleaning the catalyst for 5 times by using a mixed solution of absolute ethyl alcohol and acetone, and dispersing the catalyst in n-hexane for storage; adding excessive acetic acid into the cleaned catalyst centrifuged from n-hexane, heating to 80 ℃ under the condition of magnetic stirring and maintaining for 4 hours, and centrifuging to obtain an octahedral catalyst with a layered framework structure;
(3) centrifugally collecting an octahedral catalyst with a layered framework structure, dripping chloroform into the dried octahedral catalyst, and then performing ultrasonic treatment to uniformly disperse the catalyst to obtain a chloroform solution of nanoparticles, wherein the chloroform is used in an amount which can disperse all the catalyst in a liquid without forming solid sediment to form a similar colloidal solution, so as to obtain a chloroform solution of nanoparticles; chloroform is also dripped into the graphene with the three-dimensional structure, then the chloroform solution dispersed with the carbon carrier is obtained by ultrasonic treatment, and the amount of the chloroform can ensure that the carbon material particles are not deposited after the ultrasonic treatment, thereby obtaining the chloroform solution dispersed with the carbon carrier; under the action of ultrasound, dropwise adding a chloroform solution of nanoparticles into a chloroform solution dispersed with a carbon carrier, carrying out ultrasound for 10 hours, then continuing to magnetically stir for 24 hours, carrying out mixing reaction to obtain a loaded octahedral layered framework structure alloy electrocatalyst, and respectively washing the octahedral layered framework structure alloy electrocatalyst with methanol and absolute ethanol for 2 times;
(4) and (3) in the atmosphere of reducing gas hydrogen and inert gas argon, gradually heating the octahedral layered framework structure alloy electrocatalyst in the step (3) to 275 ℃ at the speed of 5 ℃ per minute, carrying out heat preservation treatment for 2 hours, and cooling to obtain the Pt-Ni alloy electrocatalyst.
The Pt-Ni alloy electrocatalyst prepared by the preparation method is an alloy electrocatalyst with a layered framework structure, the size of the framework is 79nm, and the Pt-Ni alloy electrocatalyst is assembled by a plurality of small particles with the particle size of 3-5 nm and used for catalyzing the oxygen reduction reaction of PEMFCs during working.
Example 3: preparation of Pt-Ni alloy electrocatalyst with layered framework structure
(1) 2ml of a 0.1M sulfuric acid solution and a molar ratio of 1: 2: adding 23 parts of chloroplatinic acid, nickel acetate and hexadecyl trimethyl ammonium chloride into 15ml of oleylamine, stirring on a magnetic stirrer at 60 ℃ until reactants are uniformly mixed, and reacting in a sealed reaction container with a polytetrafluoroethylene inner container for 30 hours at 180 ℃ to obtain a precursor solution;
(2) after the precursor solution is cooled to room temperature, centrifugally collecting the catalyst, cleaning the catalyst for 5 times by using a mixed solution of absolute ethyl alcohol and acetone, and dispersing the catalyst in n-hexane for storage; adding excessive hydrochloric acid into the cleaned catalyst centrifuged from n-hexane, heating to 120 ℃ under the condition of magnetic stirring and maintaining for 10 hours, and performing centrifugal separation to obtain an octahedral catalyst with a layered framework structure;
(3) centrifugally collecting an octahedral catalyst with a layered framework structure, dripping chloroform into the dried octahedral catalyst, and then performing ultrasonic treatment to uniformly disperse the catalyst to obtain a chloroform solution of nanoparticles, wherein the chloroform is used in an amount which can disperse all the catalyst in a liquid without forming solid sediment to form a similar colloidal solution, so as to obtain a chloroform solution of nanoparticles; the chloroform is also dropped into the carbon powder, and then the carbon carrier-dispersed chloroform solution is obtained by ultrasonic treatment, wherein the amount of the chloroform can ensure that the carbon material particles are not deposited after the ultrasonic treatment, so that the carbon carrier-dispersed chloroform solution is obtained; under the action of ultrasound, dropwise adding a chloroform solution of nanoparticles into a chloroform solution dispersed with a carbon carrier, carrying out ultrasound for 10 hours, then continuing to magnetically stir for 24 hours, carrying out mixing reaction to obtain a loaded octahedral layered framework structure alloy electrocatalyst, and respectively washing the octahedral layered framework structure alloy electrocatalyst with methanol and absolute ethanol for 2 times;
(4) and (3) in the atmosphere of reducing gases of hydrogen, carbon monoxide and inert gases of argon, gradually heating the octahedral layered framework structure alloy electrocatalyst in the step (3) to 350 ℃ at the speed of 10 ℃ per minute, carrying out heat preservation treatment for 8 hours, and cooling to obtain the Pt-Ni alloy electrocatalyst.
The Pt-Ni alloy electrocatalyst prepared by the preparation method is an alloy electrocatalyst with a layered framework structure, the size of the framework is 79nm, and the Pt-Ni alloy electrocatalyst is assembled by a plurality of small particles with the particle size of 3-5 nm and used for catalyzing the oxygen reduction reaction of PEMFCs during working.
Test example 1: topography observation and analysis
(1) FIG. 1 shows that the precursor solution obtained in step (1) is centrifuged and washed to obtain a catalyst;
as is apparent from FIG. 1, the intermediate product prepared in step (1) of the present invention has uniform size, uniform appearance, and size of about 80nm, and is octahedral layered structure nanoparticles with small particles; through calculation, the produced platinum-nickel alloy accounts for 96% of the theoretical value of the original input metal.
(2) FIG. 2 is an octahedral catalyst with a layered framework structure;
from FIG. 2, it is apparent that the catalyst has a particle diameter of 75-80nm in a layered skeleton structure and 9-12 layers.
(3) FIG. 3 is an X-ray photoelectron spectrum of an octahedral catalyst having a layered framework structure;
it can be seen from FIG. 3 that the bond energy strength is shifted to form a Pt-Ni alloy structure; the atomic ratio of Pt to Ni is 57:43 by ICP test.
Test example 2: redox reaction test
The catalyst prepared in example 2 was subjected to redox reaction test using a 0.1M perchloric acid solution as a solvent, a three-electrode system, reversible hydrogen as a reference electrode, and a commercial platinum carbon available from the company TKK, japan, as a catalyst used in the control group, to obtain a polarization curve shown in fig. 4.
As can be seen from FIG. 4, the Pt-Ni alloy electrocatalyst with a layered framework structure according to the invention has an enhanced mass activity for oxygen reduction reaction at 0.9V (relative to a reversible hydrogen electrode) as
Is a control group business
8.9 times of the catalyst.
Test example 3: alcohol oxidation test
The catalyst prepared in example 2 was subjected to an alcohol oxidation test in a mixed solution of methanol and a sulfuric acid solution, and the catalyst used in the control group was commercial platinum carbon produced by the company of noble metals (TKK) in japan, resulting in a polarization curve shown in fig. 5.
The mass activity of the Pt-Ni alloy electrocatalyst with a layered framework structure at the peak potential is calculated to be
Is a control group business4.2 times of the mass activity of the catalyst; as can be seen from fig. 5, the alcohol oxidation performance of the catalyst of the present invention is significantly increased over commercial platinum carbon.
Claims (10)
1. A preparation method of a Pt-Ni alloy electrocatalyst with a layered framework structure is characterized by comprising the following steps:
(1) mixing and heating sulfuric acid, platinum salt, nickel acetate, hexadecyl trimethyl ammonium chloride and a solvent to prepare a precursor solution;
(2) centrifuging and cleaning the precursor solution to obtain a catalyst, and carrying out acid etching on the catalyst by using an excessive acid solution to obtain an octahedral catalyst with a layered framework structure;
(3) centrifugally collecting the octahedral catalyst with the layered framework structure, drying, dripping chloroform to prepare a chloroform solution of nano particles, and mixing and reacting the chloroform solution with a chloroform solution dispersed with a carbon carrier to obtain a loaded alloy electrocatalyst with the octahedral layered framework structure;
(4) and (3) carrying out heat treatment on the octahedral layered framework structure alloy electrocatalyst obtained in the step (3) in the reducing gas and inert gas atmosphere to obtain the Pt-Ni alloy electrocatalyst.
2. The method of claim 1, wherein: the solvent in the step (1) is oleylamine; the platinum salt is one or two of platinum acetylacetonate and chloroplatinic acid.
3. The method of claim 1, wherein: the dosage of each raw material in the step (1) is as follows: 2ml of a 0.1M sulfuric acid solution, in a molar ratio of 1: 2: 23 parts of platinum salt, nickel acetate and hexadecyl trimethyl ammonium chloride, and 10-15 ml of solvent; adding sulfuric acid, platinum salt, nickel acetate and hexadecyl trimethyl ammonium chloride into a solvent, stirring on a magnetic stirrer at the temperature of 30-60 ℃ until reactants are uniformly mixed, and reacting in a sealed reaction container with a polytetrafluoroethylene inner container at the temperature of 155-180 ℃ for 19-30 h to obtain a precursor solution.
4. The method of claim 3, wherein: adding sulfuric acid, platinum salt, nickel acetate and hexadecyl trimethyl ammonium chloride into a solvent, stirring on a magnetic stirrer at 50 ℃ until reactants are uniformly mixed, and reacting in a sealed reaction container with a polytetrafluoroethylene inner container for 20 hours at 160 ℃ to obtain a precursor solution.
5. The method of claim 1, wherein: cooling the precursor solution in the step (2) to room temperature, centrifuging to collect the catalyst, cleaning with a mixed solution of absolute ethyl alcohol and acetone, and dispersing the catalyst in n-hexane for storage; adding an excessive acid solution into the cleaned catalyst centrifuged from n-hexane, heating to 80-120 ℃ under the condition of magnetic stirring, maintaining for 4-10 hours, and performing centrifugal separation to obtain an octahedral catalyst with a layered framework structure; wherein the acid solution is one of acetic acid, sulfuric acid or hydrochloric acid.
6. The method of claim 5, wherein: the acid solution is acetic acid; heat to 80 ℃ with magnetic stirring and hold for 4 h.
7. The method of claim 1, wherein: in the step (3), chloroform is dripped into the dried octahedral catalyst, and then ultrasonic treatment is carried out to uniformly disperse the catalyst to obtain a chloroform solution of nano particles; dripping chloroform into the carbon material, and then carrying out ultrasonic treatment to obtain a chloroform solution dispersed with the carbon carrier; under the action of ultrasound, dropwise adding a chloroform solution of nanoparticles into a chloroform solution dispersed with a carbon carrier, performing ultrasound for more than 8 hours, then continuing to magnetically stir for 24 hours, performing mixed reaction to obtain a loaded alloy electrocatalyst with an octahedral layered framework structure, and respectively washing the alloy electrocatalyst with methanol and absolute ethanol for 2 times; the carbon carrier is carbon powder or graphene with a three-dimensional structure.
8. The method of claim 1, wherein: in the step (4), in the atmosphere of reducing gas and inert gas, heating the octahedral layered framework structure alloy electrocatalyst obtained in the step (3) to 200-350 ℃ at the speed of 5-10 ℃ per minute, carrying out heat preservation treatment for 2-8 h, and cooling to obtain the Pt-Ni alloy electrocatalyst with a layered framework structure; the reducing gas is one or two of hydrogen and carbon monoxide, and the inert gas is argon or nitrogen.
9. The method of claim 8, wherein: the reducing gas is hydrogen, and the inert gas is argon; and (3) in the atmosphere of reducing gas and inert gas, heating the octahedral layered framework structure alloy electrocatalyst obtained in the step (3) to 200-350 ℃ at the speed of 5 ℃ per minute, carrying out heat preservation treatment for 2 hours, and cooling to obtain the Pt-Ni alloy electrocatalyst.
10. The layered framework structure alloy electrocatalyst obtained by the preparation method according to any one of claims 1 to 9.
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| ZHENG JIANG ET AL: "Facile Method to Synthesie Pt-Ni Octahedral Nanoparticles with Porous and Open Structure Features for Enhanced Oxygen Reduction Catalysis", 《SUSTAINABLE CHEMISTRY & ENGINEERING》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112295571A (en) * | 2020-11-11 | 2021-02-02 | 中国科学院广州能源研究所 | PtNi cage type catalyst and application thereof in preparation of furfuryl alcohol by catalyzing selective hydrogenation of furfural |
| CN112295571B (en) * | 2020-11-11 | 2023-05-02 | 中国科学院广州能源研究所 | PtNi cage catalyst and application thereof in furfuryl alcohol preparation by catalyzing selective hydrogenation of furfural |
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