CN115939422A - Preparation method of cerium-aluminum organic framework modified biomass carbon composite material for fuel cell cathode - Google Patents

Preparation method of cerium-aluminum organic framework modified biomass carbon composite material for fuel cell cathode Download PDF

Info

Publication number
CN115939422A
CN115939422A CN202211232269.3A CN202211232269A CN115939422A CN 115939422 A CN115939422 A CN 115939422A CN 202211232269 A CN202211232269 A CN 202211232269A CN 115939422 A CN115939422 A CN 115939422A
Authority
CN
China
Prior art keywords
fuel cell
cerium
organic framework
carbon composite
biomass carbon
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211232269.3A
Other languages
Chinese (zh)
Inventor
肖高
胡钰花
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuzhou University
Original Assignee
Fuzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuzhou University filed Critical Fuzhou University
Priority to CN202211232269.3A priority Critical patent/CN115939422A/en
Publication of CN115939422A publication Critical patent/CN115939422A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Catalysts (AREA)

Abstract

The invention discloses a cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for a fuel cell cathode and a preparation method thereof, wherein an active substance of a nano material is Ce-Al @ C PH‑BT . The problems of single precursor and high synthesis cost of the fuel cell catalyst are generally faced at present, while the commercial platinum carbon catalyst has high cost and poor stability. In order to overcome the problems, the invention develops a rare earth metal organic framework nanometer anode material used for a proton fuel cell catalyst based on the unique structure of CeAl-MOF. The material exhibits a uniform laminated sheet-like structure with a high potential and good limiting currentAnd has excellent stability. The adopted synthetic method has the advantages of simple and convenient operation, low cost and short preparation time, and is beneficial to realizing large-scale commercial production.

Description

Preparation method of cerium-aluminum organic framework modified biomass carbon composite material for fuel cell cathode
Technical Field
The invention belongs to the technical field of fuel cell catalysts, and particularly relates to a rare earth-based organic framework nano electro-catalytic material prepared by taking peanut shells as a carrier, and a preparation method and application thereof.
Background
In the rapid development of economic globalization and the modern day of increasingly updated innovative high-tech products, the consumption of fossil energy is gradually increased, a great deal of pollution is generated, and the environment is extremely unfavorable. Based on these problems, it has become indispensable work to create and develop new types of green renewable energy and efficient energy conversion and storage devices. Fuel Cells (FCs) are a new type of power generation device, and have the advantages of Fuel diversity, high Fuel energy density, cleanliness, environmental protection, and low noise. Biomass is an energy source, generally refers to various plants and animal and plant derivatives, and biomass contacted in daily life of people mainly comes from forestry, agriculture and industrial wastes. Biomass contains a large amount of energy and has huge yield, and biomass can be produced by 1.0 x 1011 tons per year in the world, which indicates that the biomass is an ideal renewable energy source. However, the utilization efficiency of the biomass is not high at the present stage, a large amount of agricultural and forestry waste is directly burned or discarded, and the problems of resource waste, environmental pollution and the like are caused. The biomass activated carbon is low in price and wide in source, and comprises peanut shells, coconut shells, rice husks, corn straws, bamboos, pine trees and the like.
Rare earth ions ionize into a positive trivalent ion state, losing first 6s electrons and then 4f and 5d electrons. The 4f, 5d, 6s level electrons have close energies, so that the energy level relation of the rare earth ions is particularly complicated. Rare earth ions have variable coordination numbers, show very rich properties of light, electricity, magnetism and the like, and are important elements in a plurality of novel materials. With the development of chemical research in recent years, rare earth metal organic framework Ce-MOF has been widely applied as a porous material with novel structure and excellent performance in the fields of gas adsorption, storage, separation, heterogeneous catalysis, electrochemistry, biomedicine, magnetism and fluorescence sensing, and more scientists are actively exploring and researching new rare earth complex materials and their uses.
According to the invention, a series of rare earth-based organic frame supported negative catalysts with different CeAl loading amounts and prepared by high-temperature heat treatment are designed and synthesized by taking peanut shells as carbon sources. Electrochemical test research shows that when CeAl-MOFs @ BT/PH catalyst is in 0.1M KOH and the potential is equal to 0.1V, the limiting current density is close to that of a commercial Pt/C catalyst, meanwhile, the reaction process of ORR in an alkaline medium is 4 electrons, and the catalyst has better stability than the commercial Pt/C catalyst.
Disclosure of Invention
The invention aims to solve the problems of the existing fuel cell catalyst, overcome the defects of the prior art, solve the problems of single precursor obstacle and synthesis cost of the existing fuel cell catalyst, and overcome the defects of high cost, toxicity and the like of a platinum-based catalytic material; the biomass carbon composite electrocatalyst material modified by the cerium-aluminum organic framework for the cathode of the fuel cell has high potential, good limiting current and excellent stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for a fuel cell cathode comprises the following steps:
(1) Firstly, preparing a CeAl-MOF polymer substrate, weighing 1.6810g of trimesic acid, dissolving the trimesic acid in 30mL of absolute ethyl alcohol, dissolving 2.3158g of cerous nitrate hexahydrate and 1.0003g of aluminum nitrate nonahydrate in 30mL of deionized water, mixing, carrying out ultrasound treatment at room temperature, pouring the solution of trimesic acid after ultrasound treatment into the mixed solution of cerous nitrate hexahydrate and aluminum nitrate nonahydrate, stirring, then placing the solution into a constant-temperature oscillator for oscillation, finally washing the obtained product with deionized water and ethyl alcohol for several times respectively, and drying to obtain CeAl-MOF;
(2) Washing the peanut shells for several times by using deionized water to remove ash attached to the surfaces of the peanut shells, drying the peanut shells in an oven at 80 ℃ after the peanut shells are washed, crushing the peanut shells into powder and sieving the powder. Soaking the treated peanut shells in distilled water for 12h, performing suction filtration, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 80 ℃;
(3) Dispersing the CeAl-MOF prepared in the step (1) and plant polyphenol in deionized water, and performing ultrasonic treatment at room temperature; multiple ortho phenols in plant polyphenolsHydroxyl can be used as a polybase ligand to carry out complexation reaction with metal ions to form a stable five-membered ring chelate. The complex has many polyphenol coordination groups, strong complexing ability and stable complex, and most metal ions form precipitates after being complexed with polyphenol. Under alkaline conditions, polyphenols and metal ions are prone to form a multi-complex. Polyphenols and certain high valence metal ions such as Cr 6+ 、Fe 3+ And the like, and the metal ions are reduced from a high valence state to a low valence state while complexing. Different plant polyphenols have different grabbing abilities for different metal ions; the plant polyphenol used in the invention is myricetin, including but not limited to (such as tannic acid, valonea, larch and the like);
(4) Dispersing 1.0g of the treated peanut shells in the step (2) in the solution in the step (3);
(5) Washing the product obtained in the step (4) with deionized water and ethanol solution for 3 times respectively, centrifuging, and drying the product in an oven to obtain a precursor of CeAl-MOFs @ BT/PH;
(6) Uniformly dispersing a proper amount of dried precursor at the bottom of a porcelain ark, putting the porcelain ark in a tube furnace for high-temperature pyrolysis in the atmosphere of argon or nitrogen, and naturally cooling to room temperature to obtain a cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material Ce-Al @ C for a fuel cell cathode PH-BT 。
The ultrasonic time of the trimesic acid, the absolute ethyl alcohol, the cerous nitrate hexahydrate, the aluminum nitrate nonahydrate and the deionized water in the step (1) is 5-10 minutes, the stirring time on a magnetic stirrer is 30min, the mixture is shaken at 60 ℃ for 1h, and the mixture is dried at 60-80 ℃ for 15-20h.
The soaking time of the peanut shells in the step (2) is 12h, and the peanut shells are dried at 80 ℃ for 12h.
The mass ratio of the plant polyphenol to the CeAl-MOF in the step (3) is 1;
the addition amount of the plant polyphenol in the step (3) is the same as that in the step (2), and the ultrasonic time is 30-40min;
stirring on a magnetic stirrer at normal temperature for 90min in the step (4);
the drying temperature in the step (5) is 60-80 ℃, and the drying time is 48h;
and (6) carrying out high-temperature pyrolysis, namely directly heating to 500 ℃ at the heating rate of 5 ℃/min in the atmosphere of pure argon or nitrogen, keeping the temperature for 30min, heating to 800 ℃ at the same heating rate, keeping the temperature for 2h, and naturally cooling to room temperature.
The invention has the technical advantages and beneficial effects that:
(1) The invention adopts a simple and convenient synthesis method, and has the characteristics of economy, high efficiency, environmental protection. The synthesis steps are simple and convenient to operate, the reaction conditions are mild and easy to control, and the preparation cost is low. The prepared oxygen reduction catalyst not only shows high potential and good limiting current, but also has excellent stability.
(2) The initial potential of the prepared rare earth-based organic frame cathode material catalyst taking peanut shells as a carbon source is 1.0V, the half-wave potential is 0.67V, and the limiting current density reaches 7.83mA cm -2 Slightly above commercial platinum carbon catalyst and better electrocatalytic stability than commercial Pt/C catalyst, the catalyst is better than commercial platinum carbon catalyst as a whole.
Drawings
FIG. 1 is Ce-Al @ C PH-BT Scanning electron microscopy of the nanocomposite;
FIG. 2 is Ce-Al @ C PH-BT A specific surface area map of (a);
FIG. 3 is Ce-Al @ C PH-BT The aperture distribution map of (a);
FIG. 4 is Ce-Al @ C PH-BT The cyclic voltammetry characteristic curve chart of the catalyst (test voltage sweep range: 0.9-0.1V, sweep rate: 50 mV/s);
FIG. 5 is a graph of the difference between the additives in 2 Linear cyclic voltammograms in saturated 0.1M KOH (scan range-0.9-0.1V, scan rate 10 mv/s);
FIG. 6 shows the different Ce/Al ratios in O in the organic framework 2 Linear cyclic voltammograms in saturated 0.1M KOH (scan range-0.9-0.1V, scan rate 10 mv/s).
FIG. 7 shows the mass ratio of Ce/Al in CeAl-MOF at 1.0g of peanut shell at 2 2 Linear cyclic voltammogram in saturated 0.1M KOH (scanning range)The periphery is-0.9-0.1V, and the scanning speed is 10 mv/s);
FIG. 8 is a graph of Ce-Al @ C at different speeds (400, 625, 900, 1225, 1600, 2025 rmp) PH-BT Linear cyclic voltammograms of the catalyst (scan rate: 10 mV/s);
FIG. 9 is Ce-Al @ C measured by constant-voltage chronoamperometry PH-BT Methanol tolerance test plots for the catalyst and a commercial Pt/C (20wt% Pt) catalyst;
FIG. 10 is Ce-Al @ C measured by constant-voltage chronoamperometry PH-BT Stability test plots for catalyst and commercial Pt/C (20wt% Pt) catalyst.
Detailed Description
The invention provides a method for preparing Ce-Al @ C PH-BT The method of the catalyst comprises the following steps:
(1) Firstly, preparing a CeAl organic framework, weighing 1.6810g of trimesic acid, dissolving the trimesic acid in 30mL of absolute ethyl alcohol, dissolving 2.3158g of cerium nitrate hexahydrate and 1.0003g of aluminum nitrate nonahydrate in 30mL of deionized water, mixing, carrying out ultrasound treatment at room temperature, pouring the solution of trimesic acid after ultrasound treatment into the mixed solution of cerium nitrate hexahydrate and aluminum nitrate nonahydrate, stirring, placing the solution into a constant-temperature oscillator for oscillation, finally washing the obtained product with deionized water and ethyl alcohol for several times respectively, and drying to obtain CeAl-MOF;
(2) Preparing a peanut shell precursor, namely washing the peanut shell for a plurality of times by using deionized water to remove ash attached to the surface of the peanut shell, putting the peanut shell into an oven at 80 ℃ after washing, and crushing the peanut shell into powder after drying for 72 hours. And then, grinding the peanut shell powder, sieving the ground peanut shell powder by using a sieve of 200 meshes, taking the peanut shell powder with the particle size of less than 200 meshes, drying the peanut shell powder at 80 ℃ for 24 hours, and cooling the peanut shell powder to room temperature after the drying is finished to obtain the peanut shell powder. Soaking in distilled water for 12 hr, vacuum filtering, washing with deionized water and anhydrous ethanol for 3 times, and drying in 80 deg.C oven for 12 hr.
(3) Respectively dispersing 0.5g of CeAl-MOF prepared in the step (1) and 0.5g of plant polyphenol in 50ml of deionized water, and after carrying out ultrasonic treatment at room temperature for 5 minutes, pouring the plant polyphenol solution into the CeAl-MOF again for ultrasonic treatment for 30 minutes;
(4) Adding 1.0g of peanut shells into the solution in the step (2), and stirring for 90min at room temperature;
(5) Washing the product obtained in the step (3) with deionized water and ethanol solution, centrifuging, and drying the product in an oven at 80 ℃ for 48 hours to obtain a CeAl-MOFs @ BT/PH precursor;
(6) Uniformly dispersing a proper amount of dried precursor at the bottom of a porcelain ark, putting the porcelain ark into a tube furnace for high-temperature pyrolysis in an argon or nitrogen atmosphere, directly heating to 500 ℃ at a heating rate of 5 ℃/min in a pure nitrogen atmosphere, keeping the temperature for 30 minutes, heating to 800 ℃ at the same heating rate for 2 hours, and naturally cooling to room temperature to obtain Ce-Al @ C PH-BT 。
The invention provides a preparation method of a cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for a fuel cell cathode and application of the material as an oxygen reduction catalyst.
The active substance is abbreviated as Ce-Al @ C PH-BT It exhibits a long strip-like sheet structure.
The invention uses a carbon rod as a counter electrode, a saturated silver chloride electrode (Ag/AgCl) as a reference electrode and a glassy carbon electrode as a working electrode.
The concentration of Nafion added in the preparation process of the catalyst is 5 percent, and the dosage is 15ul.
The catalyst preparation described in the present invention was carried out by dispersing 4mg of the ink in 1mL of a mixed solution (235 uL deionized water, 735uL isopropanol, and 5wt% Nafion solution 15 uL) by balance to prepare a catalyst ink (ink). Then gradually dropping 28uL ink on the surface of the glassy carbon electrode (catalyst loading amount is 0.25mg cm) -2 ) And carrying out an electrocatalysis performance test after naturally drying.
All electrocatalytic performance tests described in the present invention were performed in 0.1M KOH (pH = 13.62) electrolyte, and the experimentally measured potential was converted to a potential relative to a Reversible Hydrogen Electrode (RHE) by the following formula:
E(RHE)＝E(Ag/AgCl)+0.059*pH+0.2224
the potential values referred to in the present invention are all potentials relative to the reversible hydrogen electrode.
The catalyst of the invention requires CV activation for 3 cycles before electrochemical testing.
The catalyst is tested at normal temperature, and the influence of large temperature change difference on the performance of the catalyst is prevented.
The invention will be further illustrated with reference to the following specific examples. For a further understanding of the present invention, preferred embodiments of the present invention are described in conjunction with the examples, but it is to be understood that these descriptions are intended to further illustrate features and advantages of the present invention, and are not intended to limit the claims of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and these equivalents also fall within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1:
this example demonstrates the rare earth-based organic framework cathode electrocatalyst material Ce-Al @ C with peanut shells as carbon source PH-BT The preparation method of (1).
(1) Firstly, preparing a CeAl organic framework, weighing 1.6810g of trimesic acid, dissolving the trimesic acid in 30mL of absolute ethyl alcohol, dissolving 2.3158g of cerium nitrate hexahydrate and 1.0003g of aluminum nitrate nonahydrate in 30mL of deionized water, mixing, carrying out ultrasound treatment at room temperature, pouring the solution of trimesic acid after ultrasound treatment into the mixed solution of cerium nitrate hexahydrate and aluminum nitrate nonahydrate, stirring, placing the solution into a constant-temperature oscillator for oscillation, finally washing the obtained product with deionized water and ethyl alcohol for several times respectively, and drying to obtain CeAl-MOF;
(2) Preparing a peanut shell precursor, namely washing the peanut shell for a plurality of times by using deionized water to remove ash attached to the surface of the peanut shell, putting the peanut shell into an oven at 80 ℃ after the peanut shell is washed, and crushing the peanut shell into powder after the peanut shell is dried for 72 hours. And then, grinding the peanut shell powder, sieving the ground peanut shell powder by using a sieve of 200 meshes, taking the peanut shell powder with the particle size of less than 200 meshes, drying the peanut shell powder at 80 ℃ for 24 hours, and cooling the peanut shell powder to room temperature after the drying is finished to obtain the peanut shell powder. Soaking in distilled water for 12 hr, vacuum filtering, washing with deionized water and anhydrous ethanol for 3 times, and drying in 80 deg.C oven for 12 hr.
(3) Respectively dispersing 0.5g of CeAl-MOF prepared in the step (1) and 0.5g of plant polyphenol in 50ml of deionized water, and after carrying out ultrasonic treatment at room temperature for 5 minutes, pouring the plant polyphenol solution into the CeAl-MOF again for ultrasonic treatment for 30 minutes;
(4) Adding 1.0g of peanut shells into the solution in the step (2), and stirring for 90min at room temperature;
(5) Washing the product obtained in the step (3) with deionized water and ethanol solution, centrifuging, and drying the product in an oven at 80 ℃ for 48h to obtain a CeAl-MOFs @ BT/PH precursor;
(6) Uniformly dispersing a proper amount of dried precursor at the bottom of a porcelain ark, putting the porcelain ark into a tube furnace for high-temperature pyrolysis in an argon or nitrogen atmosphere, directly heating to 500 ℃ at a heating rate of 5 ℃/min in a pure nitrogen atmosphere, keeping the temperature for 30min, heating to 800 ℃ at the same heating rate for 2h, and naturally cooling to room temperature to obtain Ce-Al @ C PH-BT 。
Ce-Al @ C obtained in this example PH-BT Phase identification and microstructure and structure characterization of the material are carried out by using a Raman spectrometer, a Fourier transform infrared spectrometer, a powder X-ray diffractometer and an X-ray photoelectron spectrometer to carry out phase identification on the prepared material and using a scanning electron microscope to carry out microstructure and structure characterization on the obtained material.
FIG. 1 is Ce-Al @ C PH-BT Scanning electron microscopy of the nanocomposite. As can be seen from the figure, the material exhibits a long strip-like sheet structure.
FIG. 2 is Ce-Al @ C PH-BT Specific surface area of the nanocomposite. As can be seen from the figure, the specific surface area of this MOF material is 244.88m 2 g -1 Presents larger specific surface area, accords with the characteristics of MOF materials, and a typical hysteresis loop in a curve indicates that a sample is a mesoporous carbon material and is represented as IIA type isotherm.
FIG. 3 is Ce-Al @ C PH-BT Pore size distribution profile of the nanocomposite. As can be seen from the figure, the catalyst has a pore size structure with a large amount of mesopores and a small amount of micropores, and the average pore diameter is 2.71nm
Example 2:
this example demonstrates the rare earth-based organic framework cathode electrocatalyst material Ce-Al @ C with peanut shells as carbon source PH-BT Is the electrochemical performance research of the catalyst.
The invention uses a carbon rod as a counter electrode, a saturated silver chloride electrode (Ag/AgCl) as a reference electrode and a glassy carbon electrode as a working electrode.
The concentration of Nafion added in the preparation process of the catalyst is 5wt%, and the dosage is 15ul.
The electrode pretreatment in the test process of the invention is to add alpha-Al on a nylon polishing cloth base 2 O 3 Polishing the rotating disc electrode by 8-shaped polishing powder and a small amount of deionized water for 10 minutes, cleaning the residual powder on the electrode by using the deionized water, and finally naturally drying to finish the treatment.
The catalyst is prepared by dispersing 4mg of the catalyst in a 1mL centrifuge tube by using a balance, adding 235uL of deionized water, 735uL of isopropanol and 5wt% of Nafion solution by 15uL, and then performing ultrasonic treatment at room temperature for 50 minutes to obtain the catalyst ink (ink). Then gradually dropping 28uL ink on the surface of the glassy carbon electrode (catalyst loading amount is 0.25mg cm) -2 ) And carrying out an electrocatalysis performance test after naturally drying.
All electrocatalytic performance tests described in the present invention were performed in 0.1M KOH (pH = 13.62) electrolyte, and the experimentally measured potential was converted to a potential relative to a Reversible Hydrogen Electrode (RHE) by the following formula:
E(RHE)＝E(Ag/AgCl)+0.059*pH+0.2224
the potential values referred to in the present invention are all potentials relative to the reversible hydrogen electrode.
The catalyst of the present invention requires CV activation for 3 cycles before electrochemical testing.
The catalyst is tested at normal temperature, and the influence of large temperature change difference on the performance of the catalyst is prevented.
Nafion added in the preparation process of the catalyst is produced by Aldrich sigma company, and the concentration is 5%.
The catalyst is absorbed by a pipette with 7ul and dripped on the working electrode, the step is repeated for 3 times after the catalyst is naturally aired, the working electrode is slowly immersed into 0.1M KOH electrolyte saturated by oxygen, bubbles are prevented from being generated on the working electrode in the step, and the electrolyte is continuously introduced with oxygen in the whole test process to ensure oxygen saturation.
Cyclic voltammetry and linear cyclic voltammetry tests were carried out on the catalyst obtained in this example, cyclic voltammetry experiments were carried out using an electrochemical workstation manufactured by Pine, usa, with a test voltage sweep range of-0.9 to 0.1V and a sweep rate of 50mV/s, and during the tests, cyclic voltammetry tests were carried out after activating it for 3 cycles with a current density of 50mV/s. Linear cyclic voltammetry was also performed using a Pine electrochemical workstation with a test voltage sweep range of-0.9-0.1V and a sweep rate of 50mV/s. The current density of the catalyst material under different rotating speeds can be obtained by rotating speed test, the number of transferred electrons can be obtained by utilizing a K-L equation, the test current density is 10mV/s, and the rotating speeds are 400, 625, 900, 1225, 1600 and 2025rmp. The stability and the methanol tolerance are also important indexes of the catalyst performance, the test is also completed on an electrochemical workstation, the stability test voltage is-0.189V, and the test time is 20 000s; the methanol tolerance test voltage was-0.189V, the test duration was 1 000s, and a 2M methanol solution was dropped at 300 s.
FIG. 4 is Ce-Al @ C PH-BT The cyclic voltammetry characteristic curve of the catalyst (test voltage sweep range: -0.9-0.1V, sweep rate: 50 mV/s) is in O 2 In the saturated electrolyte, a remarkable cathodic oxygen reduction peak exists at 0.66V, which indicates that the catalytic oxygen reduction reaction occurs, and the response to oxygen shows that Ce-Al @ C PH-BT Has obvious oxygen reduction catalytic activity in alkaline solution.
FIG. 5 shows blank and Ce-Al@C PH-BT Linear cyclic voltammogram of the catalyst (test voltage range: -0.9-0.1V, scanning speed: 10 mV/s).
FIG. 6 shows the different Ce/Al ratios in O in the organic framework 2 The linear cyclic voltammogram in saturated 0.1M KOH (scan range-0.9-0.1V, scan rate 10 mv/s) shows that the limiting current density is increased from 4.9mA cm to 800 deg.C when Ce/Al is added at different ratios at the heat treatment temperature from 500 deg.C 2 Increased to 7.83mA cm 2 The ORR performance of the material is optimized when the added Ce/Al is 2.
FIG. 7 shows a blank and Ce-Al @ C PH-BT Linear cyclic voltammogram of catalyst (test voltage range-0.9-0.1V, scanning speed: 10 mV/s), when calcination temperature is 500 ℃ to 800 ℃, ce-Al @ C PH-BT The catalyst performance is optimal.
FIG. 8 is a graph of Ce-Al @ C at different speeds (400, 625, 900, 1225, 1600, 2025 rmp) PH-BT The linear cyclic voltammogram (scanning speed: 10 mV/s) of the catalyst shows that the limiting diffusion current density of the catalyst is gradually increased along with the increase of the rotating speed, because the faster the rotating speed, the faster the diffusion rate of oxygen is, the oxygen reduction catalysis process is controlled by mass transfer and conforms to the first-order kinetic reaction.
FIG. 9 is a graph of the optimum sample Ce-Al @ C determined using the i-t technique by adding 2mL of methanol to 0.1M KOH electrolyte at 1600rmp for 300s PH-BT And commercial 20% methanol tolerance of the pt/C catalyst. From the figure, ce-Al @ C can be observed PH-BT The limiting current density of (2) was only slightly changed, while the Pt/C catalyst showed significant change in current density due to methanol oxidation, and after running for 700s, ce-Al @ C PH-BT The current density still keeps a stable trend, and the Pt/C retention rate decays to below 50%. Description of Ce-Al @C PH-BT Is superior to Pt/C in methanol tolerance.
FIG. 10 is a test of Ce-Al @ C by chronoamperometry PH-BT And Pt/C, the initial current density of the Pt/C catalyst is significantly lost 23% after testing for 20000s, while Ce-Al @ C PH-BT The catalyst was reduced by 13%, indicating that the catalyst has a quotient ofThe Pt/C catalyst was somewhat more stable.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. A preparation method of a cerium-aluminum organic framework modified biomass carbon composite material for a fuel cell cathode is characterized by comprising the following steps:
(1) The preparation of the CeAl-MOF polymer substrate comprises weighing a certain amount of trimesic acid white powder and dissolving the white powder in a certain amount of absolute ethyl alcohol, wherein the dissolved liquid is colorless transparent solution. Weighing a certain amount of colorless transparent crystals of cerium nitrate hexahydrate and aluminum nitrate nonahydrate, and dissolving the crystals in a certain amount of deionized water, wherein the dissolved liquid is also colorless transparent liquid. And then slowly dripping the trimesic acid solution into the mixed solution of cerium nitrate and aluminum nitrate, and stirring on a magnetic stirrer to obtain a white mixture. Transferring the mixture into a water bath kettle, and oscillating the mixture at a certain temperature. Washing the sample obtained after the reaction with deionized water and ethanol for several times, and drying at a certain temperature to obtain white powder CeAl-MOF;
(2) And (2) preparing a peanut shell precursor, namely washing the peanut shell for a plurality of times by using deionized water to remove ash attached to the surface of the peanut shell, drying the peanut shell in an oven after the peanut shell is washed clean, crushing the peanut shell into powder, sieving the powder, drying the sieved peanut shell in the oven, and cooling the dried peanut shell to room temperature. Soaking the treated peanut shells in distilled water for 12 hours, then carrying out suction filtration, washing the peanut shells with deionized water and absolute ethyl alcohol for a plurality of times, and then putting the washed peanut shells into an oven for drying.
(3) Dispersing the CeAl-MOF prepared in the step (1) and plant polyphenol in deionized water, and performing ultrasonic treatment at room temperature;
(4) Pouring the treated peanut shells in the step (2) into the solution subjected to ultrasonic treatment in the step (3), and stirring at room temperature;
(5) Washing the product obtained in the step (4) by using deionized water and ethanol solution, centrifuging, and drying the product in an oven to obtain CeAl-MOFs @ BT/PH;
(6) And uniformly dispersing a proper amount of dried precursor at the bottom of the porcelain ark, putting the porcelain ark in a tube furnace for high-temperature pyrolysis in the atmosphere of argon or nitrogen, and naturally cooling to room temperature to obtain the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the cathode of the fuel cell.
2. The preparation method of the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the negative electrode of the fuel cell according to claim 1 is characterized in that in the step (1), the ultrasonic time is 5-10 minutes, the stirring time on a magnetic stirrer is 30 minutes, the shaking is carried out for 1 hour at 60 ℃, and the drying is carried out for 15-20 hours at 60-80 ℃.
3. The preparation method of the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the negative electrode of the fuel cell according to claim 1 is characterized in that the peanut shell in the step (2) is soaked for 12 hours and dried for 12 hours at 80 ℃.
4. The preparation method of the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the anode of the fuel cell according to claim 1 is characterized in that the mass ratio of the plant polyphenol to the CeAl-MOF in the step (3) is 1.
5. The preparation method of the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the anode of the fuel cell according to claim 1, is characterized in that the stirring time in the step (4) is 90 minutes at normal temperature on a magnetic stirrer.
6. The preparation method of the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the negative electrode of the fuel cell according to claim 1, is characterized in that the drying temperature in the step (5) is 60-80 ℃, and the drying time is 48 hours.
7. The preparation method of the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the negative electrode of the fuel cell according to claim 1, wherein the high-temperature pyrolysis in the step (5) is to directly heat to 500 ℃ at a heating rate of 5 ℃/min in a pure argon or nitrogen atmosphere, keep at the temperature for 30 minutes, heat to 800 ℃ at the same heating rate for 2 hours, and naturally cool to room temperature.
8. A cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for a fuel cell anode prepared by the preparation method according to any one of claims 1 to 7.
9. The application of the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the negative electrode of the fuel cell in the fuel cell as claimed in claim 8 is characterized in that the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the negative electrode of the fuel cell is used as a part of a cathode material of the fuel cell, and the cathode material is prepared by uniformly mixing the cerium-aluminum organic framework modified biomass carbon composite electrocatalyst material for the negative electrode of the fuel cell with isopropanol, deionized water and a Nifion solution.
CN202211232269.3A 2022-10-10 2022-10-10 Preparation method of cerium-aluminum organic framework modified biomass carbon composite material for fuel cell cathode Pending CN115939422A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211232269.3A CN115939422A (en) 2022-10-10 2022-10-10 Preparation method of cerium-aluminum organic framework modified biomass carbon composite material for fuel cell cathode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211232269.3A CN115939422A (en) 2022-10-10 2022-10-10 Preparation method of cerium-aluminum organic framework modified biomass carbon composite material for fuel cell cathode

Publications (1)

Publication Number Publication Date
CN115939422A true CN115939422A (en) 2023-04-07

Family

ID=86549552

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211232269.3A Pending CN115939422A (en) 2022-10-10 2022-10-10 Preparation method of cerium-aluminum organic framework modified biomass carbon composite material for fuel cell cathode

Country Status (1)

Country Link
CN (1) CN115939422A (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004087264A (en) * 2002-08-26 2004-03-18 Mitsui Mining & Smelting Co Ltd Negative electrode material for non-water electrolysis liquid secondary battery, and its manufacturing method
KR101341550B1 (en) * 2012-06-20 2013-12-13 한국에너지기술연구원 Preparation method of catalyst for fuel cell electrode using covaporization and preparation method of fuel cell electrode including catalyst prepared by and fuel cell including the same
CN105895884A (en) * 2016-06-13 2016-08-24 吉林大学 Method for surface modification on hydrogen storage alloy by molybdenum disulfide, and application thereof
CN108428904A (en) * 2018-04-04 2018-08-21 北京航空航天大学 One kind hydrotalcite oxygen reduction catalyst of silver-based containing cerium and the preparation method and application thereof
WO2019031766A2 (en) * 2017-08-10 2019-02-14 주식회사 엘지화학 Method for forming lithium metal and inorganic material composite thin film and method for pre-lithiation of negative electrode for lithium secondary battery by using same
CN109494381A (en) * 2017-09-12 2019-03-19 中国科学院大连化学物理研究所 The monatomic iron-based carbon material of one kind and preparation method and electro-catalysis application
WO2022134932A1 (en) * 2020-12-22 2022-06-30 华南理工大学 High-pt-content and high-performance catalyst having high stability and anti-polarity reversal performance and preparation method therefor
CN114784303A (en) * 2022-04-19 2022-07-22 福州大学 Preparation and application of copper polyphenol supramolecular network interface modified rare earth-based organic frame cathode material
CN115084558A (en) * 2022-07-21 2022-09-20 福州大学 Preparation of lanthanum-based organic framework composite modified waste chromium chip derived porous carbon nano anode material

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004087264A (en) * 2002-08-26 2004-03-18 Mitsui Mining & Smelting Co Ltd Negative electrode material for non-water electrolysis liquid secondary battery, and its manufacturing method
KR101341550B1 (en) * 2012-06-20 2013-12-13 한국에너지기술연구원 Preparation method of catalyst for fuel cell electrode using covaporization and preparation method of fuel cell electrode including catalyst prepared by and fuel cell including the same
CN105895884A (en) * 2016-06-13 2016-08-24 吉林大学 Method for surface modification on hydrogen storage alloy by molybdenum disulfide, and application thereof
WO2019031766A2 (en) * 2017-08-10 2019-02-14 주식회사 엘지화학 Method for forming lithium metal and inorganic material composite thin film and method for pre-lithiation of negative electrode for lithium secondary battery by using same
CN109494381A (en) * 2017-09-12 2019-03-19 中国科学院大连化学物理研究所 The monatomic iron-based carbon material of one kind and preparation method and electro-catalysis application
CN108428904A (en) * 2018-04-04 2018-08-21 北京航空航天大学 One kind hydrotalcite oxygen reduction catalyst of silver-based containing cerium and the preparation method and application thereof
WO2022134932A1 (en) * 2020-12-22 2022-06-30 华南理工大学 High-pt-content and high-performance catalyst having high stability and anti-polarity reversal performance and preparation method therefor
CN114784303A (en) * 2022-04-19 2022-07-22 福州大学 Preparation and application of copper polyphenol supramolecular network interface modified rare earth-based organic frame cathode material
CN115084558A (en) * 2022-07-21 2022-09-20 福州大学 Preparation of lanthanum-based organic framework composite modified waste chromium chip derived porous carbon nano anode material

Similar Documents

Publication Publication Date Title
CN103143378B (en) Preparation method of non-noble metal oxygen reduction electrocatalyst for cathode of fuel cell
CN108923051A (en) A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application
CN111389442A (en) P-N heterojunction composite material loaded on surface of foamed nickel and preparation method and application thereof
CN113437314B (en) Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof
CN111348728B (en) MOF and HrGO co-modified bismuth vanadate electrode and preparation method and application thereof
CN107394217A (en) A kind of nitrating, p-doped biomass carbon material synthetic method and its application in terms of microorganism fuel cell cathode
WO2012071709A1 (en) Ag/mnyox/c catalyst, preparation and application thereof
CN106865506A (en) It is a kind of to constitute controllable nickel cobalt compound nano line and preparation method and application
CN112958116B (en) Bi2O2.33-CdS composite photocatalyst and preparation process thereof
CN109950566A (en) A kind of high-performance oxygen reduction catalyst and its preparation method based on function of surface enhancing
CN110048134A (en) A kind of universality method preparing porous nitrogen fluorine codope carbon oxygen reduction catalyst
CN110400939A (en) A kind of preparation method of biomass nitrating porous carbon oxygen reduction catalyst
CN111437838B (en) Biomass carbon oxygen evolution electrocatalyst and preparation method thereof
CN114784303B (en) Preparation and application of rare earth-based organic framework anode material modified by copper polyphenol supermolecular network interface
CN113497237B (en) Synthesis method and application of copper polyphenol-triazine supermolecular network structure nano composite material
CN113410480B (en) Nickel polyphenol network modified composite triazine-based copolymer carbon nano electro-catalyst material and preparation method and application thereof
CN113174053A (en) Mn-MOF based on urotropine and preparation method and application thereof
CN111193039B (en) Method for preparing oxygen reduction catalyst from biomass and product
CN115084558B (en) Preparation of lanthanum-based organic framework composite modified waste chromium scrap-derived porous carbon nano negative electrode material
Li et al. Chemical etching and phase transformation of Nickel-Cobalt Prussian blue analogs for improved solar-driven water-splitting applications
CN111354951A (en) Synthetic method and application of metal sulfide material based on encapsulated porphyrin
CN115939422A (en) Preparation method of cerium-aluminum organic framework modified biomass carbon composite material for fuel cell cathode
CN113403642B (en) BiVO 4 /Co 1-X Preparation method and application of S composite photoelectrode
CN112760674B (en) System and method for synthesizing ammonia and acetone in one step by electrochemical reduction at normal temperature and normal pressure
CN114243031A (en) Simple MOF-derived Fe single-site oxygen reduction electrocatalyst and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination