CN109994745A - A kind of fullerene grafting grapheme material loaded palladium catalyst and its preparation and application - Google Patents

A kind of fullerene grafting grapheme material loaded palladium catalyst and its preparation and application Download PDF

Info

Publication number
CN109994745A
CN109994745A CN201910265553.2A CN201910265553A CN109994745A CN 109994745 A CN109994745 A CN 109994745A CN 201910265553 A CN201910265553 A CN 201910265553A CN 109994745 A CN109994745 A CN 109994745A
Authority
CN
China
Prior art keywords
fullerene
solvent
grafting
grapheme material
catalyst
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.)
Granted
Application number
CN201910265553.2A
Other languages
Chinese (zh)
Other versions
CN109994745B (en
Inventor
张煊
张佳伟
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.)
Donghua University
National Dong Hwa University
Original Assignee
Donghua 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 Donghua University filed Critical Donghua University
Priority to CN201910265553.2A priority Critical patent/CN109994745B/en
Publication of CN109994745A publication Critical patent/CN109994745A/en
Application granted granted Critical
Publication of CN109994745B publication Critical patent/CN109994745B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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

Abstract

The present invention relates to a kind of fullerene grafting grapheme material loaded palladium catalyst and its preparations and application.The catalyst is using the fulleropyrrolidine derivative of amino functional and graphene composite material as carrier.The preparation method includes: the fulleropyrrolidine derivative preparation of nitro functionalization, the fulleropyrrolidine derivative preparation of amino functional, fullerene grafting grapheme material preparation, fullerene grafting grapheme material loaded palladium catalyst preparation.The catalytic activity and stability that the catalyst has had have potential application foreground in a fuel cell.

Description

A kind of fullerene grafting grapheme material loaded palladium catalyst and its preparation and application
Technical field
The invention belongs to fuel-cell catalyst and its preparation and application field, in particular to a kind of fullerene grafts graphite Alkene material load palladium catalyst and its preparation method and application.
Background technique
Fuel cell is one of the clean energy resource quickly grown in recent years.Due to being related to precious metal catalyst in fuel cell Agent, therefore at high cost is always to restrict its a wide range of commercialized main bottleneck.In order to reduce cost and improve precious metal catalyst The effective use of agent, currently used method are that noble metal catalyst is loaded to carbon material surface.In many carbon materials, Emerging nano-carbon material such as carbon nanotube, graphene and fullerene-based material are in fuel-cell catalyst carrier application aspect Huge potentiality are shown.Typically by single nano-carbon material be used as carrier come improve catalyst performance and reduce at This, it is still less as the research of carrier using composite Nano carbon material.It discloses and passes through application No. is 201710409807.4 patents Fullerene-graphene three-dimensional composite material loaded palladium catalyst that non-covalent bond self assembly obtains, shows than single carrier The more superior catalytic performance of catalyst.It can be seen that developing composite Nano carbon carrier is one of the effective way for improving catalytic performance. But the carrier material stability combined between fullerene and graphene by weak non-covalent bond effect is poor, it is difficult to effectively overcome The stronger accumulation trend of graphene, therefore further exploring undoubtedly will be advantageous in graphene surface by covalent bond grafting fullerene In the dispersion of graphene, and the catalytic performance of catalyst is improved in turn.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of fullerene grafting grapheme material loaded palladium catalyst and Preparation method and application, to overcome the defect that palladium catalyst catalysis methanol oxidation activity is inadequate in the prior art.
The present invention provides a kind of fullerene grafting grapheme material loaded palladium catalyst, with the fullerene pyrrole of amino functional It coughs up alkane derivatives and graphene composite material is carrier, the structural formula of the fulleropyrrolidine derivative of the amino functional Are as follows:N=1~5 in formula.
The carrier is heated in a solvent instead by the fulleropyrrolidine derivative and graphene oxide of amino functional Should after restore to obtain.
The present invention also provides a kind of preparation methods of fullerene grafting grapheme material loaded palladium catalyst, comprising:
(1) by fullerene C under condition of nitrogen gas60, paranitrobenzaldehyde and sarcosine with mass ratio be 0.8-1.2:1.8- 2.2:1.8-2.2 reacts in a solvent, cooling, and separating-purifying obtains the fulleropyrrolidine derivative of nitro functionalization, wherein Fullerene C60Ratio with solvent is 60-80mg:40-50mL；
(2) fulleropyrrolidine derivative of nitro functionalization in step (1) is dissolved in solvent, it is anti-that reducing agent is added It answers, lower layer's solution that liquid separation obtains adjusts pH to neutrality, filters, washs, drying obtains the fullerene chemistry of amino functional Derivative, wherein the ratio of the fulleropyrrolidine derivative, reducing agent and solvent of nitro functionalization is 95-105mg:250- 300mg:95-105mL；
(3) by the fulleropyrrolidine derivative of amino functional in step (2) and graphene oxide with mass ratio for 1: 6-10 disperses in a solvent, and 80-100 DEG C of reaction 36-48h under condition of nitrogen gas is cooling, centrifuge separation, obtains fullerene grafting stone Black alkene material, wherein the ratio of graphene oxide and solvent is 15-25mg:15-25mL；
(4) fullerene grafting grapheme material in step (3) is dispersed in water, palladium chloride aqueous solution, ultrasound vibration is added It swings, reducing agent solution is added, is stirred to react, be centrifugated, washing obtains fullerene grafting grapheme material load palladium catalysis Agent, wherein the mass ratio of carrier and palladium is 4-6:1 in catalyst, and it is 15- that fullerene, which grafts grapheme material and the ratio of water, 25mg:30mL。
Solvent is toluene in the step (1).
Reaction temperature is 100-120 DEG C in the step (1), reaction time 12-16h.
The fulleropyrrolidine derivative structural formula of nitro functionalization in the step (1) are as follows:
N is 1~5 in formula.
Separating-purifying uses silica gel column chromatography in the step (1), and wherein eluant, eluent is toluene/ethanol (5:1).
Solvent is the toluene and alcohol mixed solvent of volume ratio 1.8-2.2:1 in the step (2).
Reducing agent is stannous chloride in the step (2).
Reaction temperature is room temperature, reaction time 10-15h in the step (2).
Solvent is dimethyl sulfoxide in the step (3)；Graphene oxide is prepared using Hummers method.
Reducing agent is sodium borohydride, while redox graphene and palladium ion in the step (4).
The sonic oscillation time is 25-35min in the step (4).
It is room temperature that temperature is stirred to react in the step (4), and being stirred to react the time is 10-15h.
The present invention also provides a kind of fullerenes to graft grapheme material loaded palladium catalyst answering in methanol fuel cell With.
The electrochemical workstation that electrocatalysis characteristic test utilizes in the application is CHI 660D, and potential scanning speed is 50mV/s, electric potential scanning range are -1~0.2V；Working electrode is glass-carbon electrode, is platinum electrode to electrode, and reference electrode is Saturated calomel electrode (SCE), electrolyte are 1.0M CH3OH+1.0M NaOH solution.
Beneficial effect
(1) compared with the patent application No. is 201710409807.4, the present invention is grafted rich by strong covalent bond effect Alkene is strangled in graphene surface overcomes the poor dispersion of graphene in the former the shortcomings that, and is conducive to improve the catalysis of catalyst in turn Performance；
(2) preparation method of the present invention is easy, and it is negative to be prepared for fullerene grafting grapheme material by room temperature chemical reduction method Carry the new fuel cell catalyst of palladium；
(3) fullerene grafting grapheme material prepared by the present invention has compared with by the palladium catalyst of carrier of simple graphene More superior catalytic performance has potential application foreground in a fuel cell.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of fullerene grafting grapheme material loaded palladium catalyst in embodiment 4.
Fig. 2 is the palladium catalyst (Pd/RGO-NH that fullerene grafting grapheme material is carrier in embodiment 52-C60) and it is single Pure graphene is the palladium catalyst (Pd/RGO) of carrier to anodic oxidation of methanol cyclic voltammetry curve.
Fig. 3 is chronoa mperometric plot of the palladium catalyst in embodiment 5 on different carriers to anodic oxidation of methanol.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
The synthesis of nitro Functional Fullerene pyrrolidin derivatives.
Under a nitrogen atmosphere, the C of 70mg is added into 100ml round-bottomed flask60, 140mg paranitrobenzaldehyde, 140mg Sarcosine and 45ml toluene, 115 DEG C of back flow reaction 12h, cold filtration is pure through silica gel column chromatography after filtrate is concentrated Change, eluant, eluent is toluene/ethanol (5:1).Products therefrom by MALDI-TOF-MS characterize, molecular weight be 897,1077, 1255, serial mass spectra peak is observed at 1431 and 1610, correspond respectively to the nitro Functional Fullerene pyrroles of 1-5 substituent group Alkane derivatives.
Embodiment 2
The synthesis of amino functional fulleropyrrolidine derivative.
Under nitrogen protection, the fulleropyrrolidine derivative (100mg) of above-mentioned nitro functionalization is dissolved in 100ml first 280mg stannous chloride is added in benzene-ethyl alcohol (2:1) in the mixed solvent, reacts 15h, stratification at room temperature, and lower layer's solution leads to It crosses liquid separation to obtain and be separated by filtration the solid being precipitated to neutrality through sodium hydroxide adjusting pH, and is washed with deionized, 40 DEG C drying 24 hours to get arrive amino functional fulleropyrrolidine derivative；Products therefrom passes through MALDI-TOF-MS table Sign is to observe serial mass spectra peak at 867,1015,1164,1312 and 1461 in molecular weight, corresponds respectively to 1-5 substituent group Amino functional fulleropyrrolidine derivative.
Embodiment 3
The preparation of fullerene grafting grapheme material.
By the fulleropyrrolidine derivative (2.5mg) of above-mentioned amino functional and graphene oxide (20mg) ultrasonic disperse In dimethyl sulfoxide (20ml), under nitrogen protection, temperature is heating reaction 48h at 90 DEG C, is cooled to room temperature, is centrifugated, Ethanol washing, 40 DEG C are grafted grapheme material to get to fullerene in drying 24 hours.
Embodiment 4
The preparation of fullerene grafting grapheme material loaded palladium catalyst.
By the above-mentioned fullerene grafting grapheme material ultrasonic disperse of 20mg in 30ml deionized water, 2ml palladium chloride is added Aqueous solution (2mg/ml), then ultrasound 30 minutes, the sodium borohydride aqueous solution (10mg/ml) that 10ml is newly configured is slowly added dropwise, in room It is stirred to react under temperature 12 hours.After centrifuge separation, precipitating deionized water and dehydrated alcohol respectively wash three times, it is placed in vacuum drying Grapheme material loaded palladium catalyst (Pd/RGO-NH is grafted to get fullerene within dry 24 hours at 40 DEG C in case2-C60).Pass through TEM is characterized, it is seen that catalyst nano-particles are dispersed in fullerene grafting grapheme material material surface (Fig. 1).With Simple grapheme material is that the palladium catalyst (Pd/RGO) of carrier is prepared using the above identical process, just with graphite oxide Alkene replaces fullerene to graft grapheme material.
Embodiment 5
Electro-catalysis methanol oxidation performance test.
The made fullerene of embodiment 4 is grafted into grapheme material loaded palladium catalyst (Pd/RGO-NH2-C60) sonic oscillation Dispersion in ethanol (2mg/ml), pipettes 5 μ l and is transferred to glassy carbon electrode surface, after infrared lamp drying, then 5 μ l Nafion are added dropwise Working electrode is made in solution (0.5%).Working electrode obtained is put into 1.0M CH3In OH+1.0M NaOH mixed solution, It is that with saturated calomel electrode (SCE) for reference electrode, the cyclic voltammetric of anodic oxidation of methanol is tested to electrode with platinum electrode Curve and chronoa mperometric plot.It is carried out pair to using simple grapheme material as the test of the palladium catalyst (Pd/RGO) of carrier simultaneously According to.It can be seen that grafting grapheme material loaded palladium catalyst (Pd/RGO-NH with fullerene2-C60) compared with simple graphene material Material is that the palladium catalyst (Pd/RGO) of carrier has higher catalytic activity (Fig. 2) and stability (Fig. 3), and wherein the former electric current is strong Degree improves about 2 times compared with the latter, and still keeps higher current strength after continuous discharge 2500 seconds.It can be seen that the present invention in Fullerene grafting grapheme material is that the palladium catalyst of carrier can significantly improve the performance of catalysis methanol oxidation reaction, in fuel electricity There is potential application foreground in pond.
By the catalyst performance of catalyst in the present invention in application No. is 201710409807.4 patents compared with catalyst, It can be seen that the current density of catalyst methanol oxidation enhances more than 2 times in the present invention, the former has reached 730mA/mgPd(such as Fig. 2 It is shown), and the latter is only 350mA/mgPd, show to urge in the present invention with fullerene-graphene carrier material that covalent bond is grafted Agent has the catalytic performance significantly improved.

Claims (9)

1. a kind of fullerene grafts grapheme material loaded palladium catalyst, which is characterized in that with the fullerene pyrrole of amino functional It coughs up alkane derivatives and graphene composite material is carrier, the structural formula of the fulleropyrrolidine derivative of the amino functional Are as follows:N=1~5 in formula.
2. a kind of preparation method of fullerene grafting grapheme material loaded palladium catalyst, comprising:
(1) by fullerene C under condition of nitrogen gas60, paranitrobenzaldehyde and sarcosine with mass ratio be 0.8-1.2:1.8-2.2: 1.8-2.2 reacts in a solvent, cooling, and separating-purifying obtains the fulleropyrrolidine derivative of nitro functionalization, wherein fowler Alkene C60Ratio with solvent is 60-80mg:40-50mL；
(2) fulleropyrrolidine derivative of nitro functionalization in step (1) is dissolved in solvent, reducing agent reaction is added, Lower layer's solution that liquid separation obtains adjusts pH to neutrality, filters, washs, drying, the fullerene chemistry for obtaining amino functional spreads out Biology, wherein the ratio of the fulleropyrrolidine derivative, reducing agent and solvent of nitro functionalization is 95-105mg:250- 300mg:95-105mL；
It (3) is 1:6-10 with mass ratio by the fulleropyrrolidine derivative of amino functional in step (2) and graphene oxide In a solvent, 80-100 DEG C of reaction 36-48h under condition of nitrogen gas is cooling, centrifuge separation for dispersion, obtains fullerene grafting graphene Material, wherein the ratio of graphene oxide and solvent is 15-25mg:15-25mL；
(4) fullerene grafting grapheme material in step (3) is dispersed in water, palladium chloride aqueous solution is added, sonic oscillation adds Entering reducing agent solution, be stirred to react, is centrifugated, washing obtains fullerene grafting grapheme material loaded palladium catalyst, wherein The mass ratio of carrier and palladium is 4-6:1 in catalyst, and it is 15-25mg:30mL that fullerene, which grafts grapheme material and the ratio of water,.
3. method according to claim 2, which is characterized in that solvent is toluene in the step (1)；Reaction temperature is 100- 120 DEG C, reaction time 12-16h.
4. method according to claim 2, which is characterized in that the fullerene chemistry of nitro functionalization in the step (1) Derivant structure formula are as follows:N is 1~5 in formula.
5. method according to claim 2, which is characterized in that solvent is the first of volume ratio 1.8-2.2:1 in the step (2) Benzene and alcohol mixed solvent；Reducing agent is stannous chloride.
6. method according to claim 2, which is characterized in that reaction temperature is room temperature in the step (2), and the reaction time is 10-15h。
7. method according to claim 2, which is characterized in that solvent is dimethyl sulfoxide in the step (3)；Graphene oxide It is to be prepared using Hummers method.
8. method according to claim 2, which is characterized in that reducing agent is sodium borohydride in the step (4)；Sonic oscillation Time is 25-35min；Being stirred to react temperature is room temperature, and being stirred to react the time is 10-15h.
9. a kind of application of catalyst as described in claim 1 in methanol fuel cell.
CN201910265553.2A 2019-04-03 2019-04-03 Fullerene grafted graphene material supported palladium catalyst and preparation and application thereof Active CN109994745B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910265553.2A CN109994745B (en) 2019-04-03 2019-04-03 Fullerene grafted graphene material supported palladium catalyst and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910265553.2A CN109994745B (en) 2019-04-03 2019-04-03 Fullerene grafted graphene material supported palladium catalyst and preparation and application thereof

Publications (2)

Publication Number Publication Date
CN109994745A true CN109994745A (en) 2019-07-09
CN109994745B CN109994745B (en) 2022-03-04

Family

ID=67132231

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910265553.2A Active CN109994745B (en) 2019-04-03 2019-04-03 Fullerene grafted graphene material supported palladium catalyst and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN109994745B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112656409A (en) * 2021-01-08 2021-04-16 嘉兴学院 Textile ion sensor and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060115712A1 (en) * 2004-11-26 2006-06-01 Hee-Tak Kim Electrode for fuel cell, fuel cell system comprising the same, and method for preparing the same.
CN103242217A (en) * 2013-05-10 2013-08-14 黄山学院 Fullerene derivative micron sheet and preparation method thereof
CN103951606A (en) * 2014-05-07 2014-07-30 黄山学院 Preparation method and application of N-methyl-2-phenyl-3,4-fulleropyrrolidine of micron leaf structure
CN105860957A (en) * 2014-09-26 2016-08-17 重庆文理学院 Preparation method of oxidized graphene composite for drug carrier
CN107195918A (en) * 2017-06-02 2017-09-22 东华大学 A kind of fuel-cell catalyst and its preparation and application using graphene fullerene three-dimensional composite material as carrier

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060115712A1 (en) * 2004-11-26 2006-06-01 Hee-Tak Kim Electrode for fuel cell, fuel cell system comprising the same, and method for preparing the same.
CN103242217A (en) * 2013-05-10 2013-08-14 黄山学院 Fullerene derivative micron sheet and preparation method thereof
CN103951606A (en) * 2014-05-07 2014-07-30 黄山学院 Preparation method and application of N-methyl-2-phenyl-3,4-fulleropyrrolidine of micron leaf structure
CN105860957A (en) * 2014-09-26 2016-08-17 重庆文理学院 Preparation method of oxidized graphene composite for drug carrier
CN107195918A (en) * 2017-06-02 2017-09-22 东华大学 A kind of fuel-cell catalyst and its preparation and application using graphene fullerene three-dimensional composite material as carrier

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112656409A (en) * 2021-01-08 2021-04-16 嘉兴学院 Textile ion sensor and preparation method and application thereof
CN112656409B (en) * 2021-01-08 2022-03-01 嘉兴学院 Textile ion sensor and preparation method and application thereof

Also Published As

Publication number Publication date
CN109994745B (en) 2022-03-04

Similar Documents

Publication Publication Date Title
Xu et al. Methanol electrocatalytic oxidation on Pt nanoparticles on nitrogen doped graphene prepared by the hydrothermal reaction of graphene oxide with urea
KR101287891B1 (en) Method for manufacturing catalyst for fuel cell
KR101641145B1 (en) A method for preparation of catalyst using poly-dopamine, catalyst fabricated by the same and the fuel cell using the catalyst
CN107195918B (en) It is a kind of using graphene-fullerene three-dimensional composite material as the fuel-cell catalyst of carrier and its preparation and application
CN108754523B (en) A method of carbon dioxide is restored based on the synergistic effect electro-catalysis of COF- metal interface
CN108682875B (en) Platinum-nano hollow carbon sphere catalyst based on controllable platinum loading capacity and preparation method thereof
CN101515648A (en) Novel membrane electrode component available for fuel cell, preparation method and application thereof
CN110224149A (en) A kind of nano carbon composite material is palladium catalyst and its preparation and the application of carrier
CN111477891B (en) Preparation method of nitrogen-doped porous hollow carbon sphere compound with low platinum loading capacity, product and application thereof
CN105789639A (en) Method for preparing Au-cluster/carbon nano tube composite catalyst
CN100484631C (en) Preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls
CN108831759A (en) One kind is based on graphene/chitosan multi-porous carbon composite and its preparation method and application
Yang et al. Alkyl group-decorated gC 3 N 4 for enhanced gas-phase CO 2 photoreduction
Tipplook et al. Facile in situ synthesis of amphiphilic carbon-supported Pt: innovative catalyst preparation for proton exchange membrane fuel cells
CN109994745A (en) A kind of fullerene grafting grapheme material loaded palladium catalyst and its preparation and application
CN101562250A (en) Method for preparing cathode catalyst of proton exchange membrane fuel cell
CN103041857A (en) Preparation method of graphite nano-plate-loaded nano-noble metal catalyst
WO2023116939A1 (en) High-output-power fuel cell and preparation method therefor
CN100467125C (en) Carbon supported nanometer WC reinforced oxidation-reduction electrocatalyst and its prepn process
CN111715256B (en) Preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles
CN105680062B (en) One kind improves fuel battery anode catalyst and resists toxic complex carrier
CN110629245B (en) Nitrogen-doped carbon-coated copper cadmium sulfide catalyst for photoelectric reduction of CO2Method of producing a composite material
CN108539216B (en) A kind of porous graphene/nickel tellurium composite catalyst and its preparation method and application
CN112981456A (en) Preparation method of Cu @ MIL-101-Cr electrocatalyst for efficiently preparing acetone
CN113745542A (en) High platinum loading platinum/carbon catalyst for fuel cell and preparation method 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
GR01 Patent grant
GR01 Patent grant