CN106848332A - A kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing - Google Patents

A kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing Download PDF

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Publication number
CN106848332A
CN106848332A CN201710087532.7A CN201710087532A CN106848332A CN 106848332 A CN106848332 A CN 106848332A CN 201710087532 A CN201710087532 A CN 201710087532A CN 106848332 A CN106848332 A CN 106848332A
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China
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oxygen reduction
reduction catalyst
cobalt
wing
insect wing
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罗俊
李龙
刘熙俊
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Tianjin University of Technology
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Tianjin University of Technology
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88Processes of manufacture
    • H01M4/8825Methods for deposition of the catalytic active composition
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/86Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90Selection of catalytic material
    • H01M4/9075Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

Abstract

The invention discloses a kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing.First insect wing and carbon black are pre-processed, then being put into the aqueous solution mixed liquor of iron containing compoundses, cobalt compound, nitrogen-containing compound pretreated insect wing and carbon black simultaneously carries out ultrasonic mixing, next in 300 1500 DEG C of temperature ranges, high-temperature heat treatment is carried out in atmosphere of inert gases, efficient oxygen reduction catalyst can be prepared after cooling.The made sample of the present invention possess catalysis activity high, good stability, yield it is high, pollution-free, it is environment-friendly the features such as, be that insect wing class biomaterial provides a thinking for novelty in the preparation of fuel battery cathod catalyst.

Description

A kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing
Technical field
The present invention is that, on carbon material, more particularly to one kind is nitrogen co-doped by iron cobalt with insect wing as substrate, system The method of standby efficient oxygen reduction catalyst.
Background technology
Fuel cell is a kind of by electrochemical reaction, and fuel in fuel cell is directly turned with the chemical energy in oxidant The device of electric energy is turned to, the advantages of possess energy conversion efficiency, high-energy-density, non-pollution discharge.However, fuel cell Development is limited by cathod catalyst cost.At present, platinum based catalyst is still main fuel battery cathod catalyst.But It is platinum scarcity of resources, expensive, seriously constrain the commercialized development of fuel cell.Therefore, cheap, wide material sources are developed Efficient oxygen reduction catalyst, be promote commercializing fuel cells an effective approach.
Carbon-based non noble metal oxygen reduction catalyst has good oxygen reduction catalytic activity, and this kind of catalyst raw material is easy to get, Cheap, preparation method is relatively easy, is that a kind of fuel battery negative pole hydrogen reduction for getting a good chance of substitution platinum based catalyst is urged Agent.Based on this, the present invention, as carbon source, by high-temperature heat treatment in atmosphere of inert gases, and is introduced from insect wing Carbon black, by iron, cobalt and it is nitrogen co-doped prepare new carbon-supported catalysts (Fe/Co/N/C-BW), urged with efficient hydrogen reduction Change activity, its core concept is to prepare efficient oxygen reduction catalyst with raw material cheap and easy to get.
The content of the invention
The purpose of the present invention, is that the preparation cost of existing fuel battery negative pole oxygen reduction catalyst is high, raw material is dilute to overcome It is the shortcomings of scarce, low catalyst activity and poor stability, there is provided a kind of by the use of insect wing as substrate, common by iron cobalt nitrogen Doping, the method for preparing efficient oxygen reduction catalyst.
The present invention is achieved by following technical solution.
The present invention with insect wing as substrate, by infusion process, doping iron content, containing cobalt, containing nitrogen compound, and add charcoal It is black, high-temperature heat treatment is carried out in atmosphere of inert gases, prepare the nitrogen co-doped carbon-based non noble metal oxygen reduction catalysis of the cobalt that taps a blast furnace Agent;The insect wing is the wing of common insect, for example the wing of butterfly, dragonfly and cicada;The iron containing compoundses are to be The formation of oxygen reduction catalyst avtive spot provides the compound of ferro element, such as iron chloride, ferric nitrate etc.;The chemical combination containing cobalt Thing for the formation of oxygen reduction catalyst avtive spot to provide the compound of cobalt element, such as pyridine cobalt, cobalt nitrate etc.;It is described Nitrogen-containing compound for that can provide the compound of nitrogen for the formation of oxygen reduction catalyst avtive spot, such as poly m-phenylene diamine, Melamine etc.;The carbon black is with the carbon black with high conductivity, high-ratio surface, such as BP2000, Vulcan XC-72 Deng.
Specific preparation method is as follows:
A kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing, comprises the following steps that:
(1) insect wing is taken, is put into the container equipped with ultra-pure water, 0.5-48 is heated in 25-100 DEG C of baking oven small When, after being cooled to room temperature, insect wing is taken out, cleaned with ultra-pure water, it is placed again into being dried in baking oven;
(2) carbon black is taken, is put into the container equipped with ultra-pure water, in 25-100 DEG C of temperature range, in ultrasonic washing instrument In it is ultrasonically treated 1-20 hours, after ultrasonically treated end, leach carbon black, be put into baking oven and be dried;
(3) iron containing compoundses, cobalt compound and nitrogen-containing compound are weighed respectively, and mixing is configured to ultra-pure water after mixing Liquid simultaneously stirs;
(4) will the dried insect wing for the treatment of and carbon black in step (1) and step (2), than scope be 1 according to quality: 1-1:5 are added in the mixed liquor that step (3) is prepared, and ultrasonically treated it is fully contacted mixing, ultrasonic time is 10-100 Minute;
(5) after mixture in step (4) is sonicated, it is positioned in the baking oven that temperature is 25-100 DEG C and is done Dry, drying time is 12-72 hours;
(6) mixture obtained after being dried in step (5) is placed in clean porcelain boat, is put into tube type vacuum stove, in In atmosphere of inert gases, high-temperature heat treatment is carried out in 300-1500 DEG C of temperature range, heat treatment time is 0.5-5 hours, so After be cooled to room temperature;
(7) product after high-temperature heat treatment is taken out from tube type vacuum stove, you can obtain efficient oxygen reduction catalyst.
The insect wing of the step (1) is the wing of common butterfly, dragonfly and cicada.
The carbon black of the step (2) is the carbon black with high conductivity, high-ratio surface:BP2000、Vulcan XC-72、 Vulcan P。
The iron containing compoundses of the step (3) for the formation of oxygen reduction catalyst avtive spot to provide containing for ferro element Iron compound:Iron chloride, nitric acid fall, thiocyanation iron, ferric sulfate or ferroheme.
The cobalt compound of the step (3) for the formation of oxygen reduction catalyst avtive spot to provide containing for cobalt element Cobalt compound:Pyridine cobalt, cobalt nitrate, Cobalt Phthalocyanine or cobalt chloride.
The nitrogen-containing compound of the step (3) for the formation of oxygen reduction catalyst avtive spot to provide containing for nitrogen Nitrogen compound:Poly m-phenylene diamine, melamine or hydroxylamine chloride.
The inert atmosphere of the step (5) is nitrogen or argon gas atmosphere.
Beneficial effects of the present invention are as follows:
The preparation method is raw materials used cheap, and wide material sources are simple and easy to get, and preparation technology is easily realized, to environment It is very friendly;Prepared product is the carbon-based oxygen reduction catalyst of base metal doping, stability high with catalysis activity Well, the features such as yield is high.The catalysis activity of oxidant far super business Pt/C, substrate is butterfly's wing, dopant be iron chloride, When pyridine cobalt, m-phenylene diamine (MPD) and carbon BP 2000, take-off potential and half wave potential respectively reach 1.040V and 0.903V, beyond business Industry Pt/C catalyst 56mV and 41mV;Substrate is butterfly's wing, when dopant is iron chloride, hydroxylamine chloride and carbon BP 2000, Take-off potential and half wave potential respectively reach 1.036V and 0.908V, beyond business Pt/C catalyst 52mV and 36mV.Its other party The sample prepared under case equally has excellent hydrogen reduction catalytic effect.The invention is insect wing class biomaterial in fuel A thinking for novelty is provided in the preparation of cell cathode catalyst.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of the original scale structure of the picture and greenbelt Papilio bianor wing of greenbelt Papilio bianor;
Fig. 2 is scanning electron microscope (SEM) photograph (SEM) of the greenbelt Papilio bianor wing by the scale structure after high temperature cabonization.
Fig. 3 is transmission electron microscope picture (TEM) of the greenbelt Papilio bianor wing by the scale structure after high temperature cabonization.
Fig. 4 is greenbelt Papilio bianor wing by the N after high temperature cabonization2Adsorption-desorption isothermal and graph of pore diameter distribution.
Fig. 5 is greenbelt Papilio bianor butterfly's wing and Pt/C hydrogen reduction catalytic performance comparison diagrams after high temperature cabonization.
Fig. 6 is greenbelt Papilio bianor butterfly's wing and Pt/C hydrogen reduction catalytic performance comparison diagrams after mixing iron high temperature cabonization.
Fig. 7 is contrasted with Pt/C hydrogen reduction catalytic performance through mixing greenbelt Papilio bianor butterfly's wing after iron nitrogen carbon high-temp is carbonized Figure.
Fig. 8 is greenbelt Papilio bianor butterfly's wing and Pt/C hydrogen reduction catalytic performance comparison diagrams after mixing iron cobalt high temperature cabonization.
Fig. 9 is greenbelt Papilio bianor butterfly's wing and Pt/C hydrogen reduction catalytic performances pair after the iron carbon co-doped high temperature cabonization of cobalt nitrogen Than figure.
Figure 10 be carbon black after different time is ultrasonically treated, the catalytic performance comparison diagram of product.
Specific embodiment
The present invention is further illustrated below by specific examples below.What embodiment was merely exemplary, rather than limit Property processed.
Embodiment 1
Caste is greenbelt Papilio bianor, and iron containing compoundses are iron chloride, and cobalt compound is pyridine cobalt, nitrogen-containing compound It is melamine, carbon black is BP2000.
Comprise the following steps that:
(1) 10 greenbelt Papilio bianor wings are taken, about 0.1g is put into the reactor equipped with 30ml ultra-pure waters, in an oven Heating 2 hours, temperature is 100 DEG C.After being cooled to room temperature, butterfly's wing is taken out, cleaned with ultra-pure water, being placed again into temperature is Dried 8 hours in 60 DEG C of baking oven;
(2) 0.1g carbon BP 2000s are taken, is put into the beaker equipped with 500ml ultra-pure waters, it is clear in ultrasonic wave at a temperature of 25 DEG C Wash ultrasonically treated 8 hours in instrument.After ultrasonically treated end, with centrifuge, remove supernatant, be centrifuged with ultra-pure water again clear Wash 3 times, after centrifugation terminates, carbon black be put into clean surface plate and be placed in being dried in baking oven, drying temperature is 60 DEG C, Time is 8h.;
(3) melamine for weighing the iron chloride of 0.5mmol, the pyridine cobalt of 0.1mmol and 2.5mmol respectively is poured into totally Beaker, and add the ultra-pure water of 50ml, clean rotor is added in the aqueous solution of mixture, and beaker is placed on temperature control It is stirred on magnetic stirring apparatus, mixing time is 10min;
(4) by the dried butterfly's wing for the treatment of and carbon BP 2000 in step (1) and step (2), it is added to step (3) In the uniform mixed liquor for preparing, ultrasonically treated it is fully contacted mixing, ultrasonic time is 10 minutes, and temperature is 25 DEG C;
(5) after mixture in step (4) is sonicated, it is positioned in the baking oven that temperature is 60 DEG C and is dried, when Between be 24 hours;
(6) mixture obtained after being dried in step (5) is placed in clean porcelain boat, is put into tube type vacuum stove, in N2In atmosphere, high-temperature heat treatment is carried out under 1000 DEG C of temperature conditionss, the time is 2 hours, is subsequently cooled to room temperature;
(7) product after high-temperature heat treatment is taken out from tube type vacuum stove, you can obtain the nitrogen co-doped carbon-based oxygen of iron cobalt Reducing catalyst.
Fig. 1 a are the pictures of greenbelt Papilio bianor, it can be seen that the macrostructure of wing;Fig. 1 b are greenbelt Papilio bianor wings Low power scanning electron microscope (SEM) photograph (SEM), it can be seen that wing is covered by substantial amounts of scale structure;Fig. 1 c-d are scale structures on wing High power scanning electron microscope (SEM) photograph (SEM), it can be seen that the scale has the neat network pore space structure of rule, aperture is 0.5-1 μm.
Fig. 2 a-b are low power scanning electron microscope (SEM) photograph of the greenbelt Papilio bianor wing by the scale structure after high-temperature heat treatment (SEM), it can be seen that still retain by the porous skeleton structure of butterfly's wing scale after high-temperature heat treatment;Fig. 2 c-d are greenbelts Papilio bianor wing by the scale structure after high-temperature heat treatment high power scanning electron microscope (SEM) photograph (SEM), it can also be seen that through high temperature The structure of butterfly's wing scale is not changed significantly after heat treatment.
Fig. 3 is transmission electron microscope picture (TEM) of the greenbelt Papilio bianor wing by the scale structure after high-temperature heat treatment, it can be seen that Transmission electron microscope picture is consistent with scanning electron microscope (SEM) photograph (Fig. 2) pattern result result.
Fig. 4 a are greenbelt Papilio bianor wings by the N after high-temperature heat treatment2Adsorption isotherm, it can be seen that the thermoisopleth is situated between Between first kind thermoisopleth and the 4th class thermoisopleth;Fig. 4 b-c be butterfly's wing by after high-temperature heat treatment with BJH methods and The size distribution figure that DFT method is calculated, it can be seen that the micropore size of material concentrates on 1.5nm or so, mesoporous hole Footpath concentrates on 3.9nm or so.
Fig. 5 is greenbelt Papilio bianor butterfly's wing and Pt/C hydrogen reduction catalytic performance comparison diagrams after high temperature cabonization, it can be seen that Through the butterfly's wing of high-temperature heat treatment undope other elements when, possess certain oxygen reduction catalytic activity, but with business Pt/C Compare, still there is a certain distance.
Fig. 6 greenbelt Papilio bianor butterfly's wing and Pt/C hydrogen reduction catalytic performance comparison diagrams after mixing iron high temperature cabonization, can be with After finding out doping ferro element, product catalysis activity is necessarily lifted, but the poor catalytic activity still than business Pt/C.
Fig. 7 is contrasted with Pt/C hydrogen reduction catalytic performance through mixing greenbelt Papilio bianor butterfly's wing after iron nitrogen carbon high-temp is carbonized Figure, it can be seen that by the codope of iron nitrogen carbon, the catalyst activity of sample is increased dramatically, when the thing of each dopant Matter mass ratio is Fe:N:C=1:20:When 5, catalyst activity is suitable with business Pt/C.
Fig. 8 is greenbelt Papilio bianor butterfly's wing and Pt/C hydrogen reduction catalytic performance comparison diagrams after mixing iron cobalt high temperature cabonization, It can be seen that after through iron cobalt codope, the catalysis activity of product is increased dramatically, the catalytic activity level of business Pt/C is reached. Iron and cobalt different material sample of the amount than under, catalysis activity slightly difference.
Fig. 9 is greenbelt Papilio bianor butterfly's wing and Pt/C hydrogen reduction catalytic performances pair after the iron carbon co-doped high temperature cabonization of cobalt nitrogen Than figure, it can be seen that by after codope, the catalysis activity of oxidant far super business Pt/C, take-off potential and half wave potential divide 1.040V and 0.903V is not reached, beyond business Pt/C catalyst 56mV and 41mV.
Embodiment 2
Caste is greenbelt Papilio bianor, and the iron containing compoundses are ferric nitrate, and cobalt compound is pyridine cobalt, nitrogen Compound is melamine, and carbon black is BP2000.
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is:By the chlorination in step 3 Iron is changed to ferric nitrate.Electrocatalysis material prepared by the program has good hydrogen reduction catalytic performance.
Embodiment 3
Caste is greenbelt Papilio bianor, and the iron containing compoundses are iron chloride, and cobalt compound is pyridine cobalt, nitrogen Compound is melamine, and carbon black is BP2000.
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is:By the pyridine in step 3 Cobalt is changed to cobalt nitrate.Electrocatalysis material prepared by the program has good hydrogen reduction catalytic performance.
Embodiment 4
Caste is greenbelt Papilio bianor, and the iron containing compoundses are iron chloride, and cobalt compound is pyridine cobalt, nitrogen Compound is m-phenylene diamine (MPD), and carbon black is BP2000.
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is:By the trimerization in step 3 Cyanamide is changed to m-phenylene diamine (MPD).Electrocatalysis material prepared by the program has good hydrogen reduction catalytic performance.
Embodiment 5
Caste is greenbelt Papilio bianor, and iron containing compoundses are iron chloride, and cobalt compound is pyridine cobalt, nitrogen-containing compound It is melamine, carbon black is BP2000.
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is:By the carbon black in step 2 The BP2000 ultrasounds different time is doped, and ultrasonic time is respectively 5h, 8h, 11h and 14h, such as Figure 10, it can be seen that By the ultrasonically treated of different time, the catalysis activity of product slightly has difference to carbon black, but can reach goal of the invention.
Embodiment 6
Caste is greenbelt Papilio bianor, and iron containing compoundses are iron chloride, and cobalt compound is pyridine cobalt, nitrogen-containing compound It is melamine, carbon black is BP2000.
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is:By iron content in step 3 Compound, cobalt compound, nitrogen-containing compound configure mixed solution according to the amount ratio of different materials.Electricity prepared by the program is urged Changing material has good hydrogen reduction catalytic performance.
Embodiment 7
Caste is russet grey dragonfly, and iron containing compoundses are iron chloride, and cobalt compound is pyridine cobalt, and nitrogen-containing compound is Melamine, carbon black is BP2000.
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is:By the greenbelt in step 1 Papilio bianor is changed to russet grey dragonfly.The electrocatalysis material prepared with the program has good hydrogen reduction catalytic performance.
Embodiment 8
Caste is black cicada, and iron containing compoundses are iron chloride, and cobalt compound is pyridine cobalt, and nitrogen-containing compound is three Poly cyanamid, carbon black is BP2000.
The preparation method of the electrocatalysis material is substantially the same manner as Example 1, and difference is:By the greenbelt in step 1 Papilio bianor is changed to black cicada.Electrocatalysis material prepared by the program has good hydrogen reduction catalytic performance.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned implementation method Detail, in range of the technology design of the invention, various simple variants can be carried out to technical scheme, this A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can The combination of energy is no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as it is without prejudice to originally The thought of invention, it should equally be considered as content disclosed in this invention.

Claims (7)

1. a kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing, comprises the following steps that:
(1) insect wing is taken, is put into the container equipped with ultra-pure water, heated 0.5-48 hours in 25-100 DEG C of baking oven, treated After being cooled to room temperature, insect wing is taken out, cleaned with ultra-pure water, be placed again into being dried in baking oven;
(2) carbon black is taken, is put into the container equipped with ultra-pure water, in 25-100 DEG C of temperature range, surpassed in ultrasonic washing instrument Sonication 1-20 hours, after ultrasonically treated end, carbon black is leached, be put into baking oven and be dried;
(3) iron containing compoundses, cobalt compound and nitrogen-containing compound are weighed respectively, and mixed liquor is configured to simultaneously with ultra-pure water after mixing Stir;
(4) will the dried insect wing for the treatment of and carbon black in step (1) and step (2), than scope be 1 according to quality:1-1:5 It is added in the mixed liquor that step (3) is prepared, ultrasonically treated it is fully contacted mixing, ultrasonic time is 10-100 minutes;
(5) after mixture in step (4) is sonicated, it is positioned in the baking oven that temperature is 25-100 DEG C and is dried, does The dry time is 12-72 hours;
(6) mixture obtained after being dried in step (5) is placed in clean porcelain boat, is put into tube type vacuum stove, in inertia In atmosphere, high-temperature heat treatment is carried out in 300-1500 DEG C of temperature range, heat treatment time is 0.5-5 hours, Ran Houleng But to room temperature;
(7) product after high-temperature heat treatment is taken out from tube type vacuum stove, you can obtain efficient oxygen reduction catalyst.
2. a kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing according to claim 1, it is special Levy and be, the insect wing of the step (1) is the wing of common butterfly, dragonfly and cicada.
3. a kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing according to claim 1, it is special Levy and be, the carbon black of the step (2) is the carbon black with high conductivity, high-ratio surface:BP2000、Vulcan XC-72、 Vulcan P。
4. a kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing according to claim 1, it is special Levy and be, the iron containing compoundses of the step (3) for the formation of oxygen reduction catalyst avtive spot to provide containing for ferro element Iron compound:Iron chloride, nitric acid fall, thiocyanation iron, ferric sulfate or ferroheme.
5. a kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing according to claim 1, it is special Levy and be, the cobalt compound of the step (3) for the formation of oxygen reduction catalyst avtive spot to provide containing for cobalt element Cobalt compound:Pyridine cobalt, cobalt nitrate, Cobalt Phthalocyanine or cobalt chloride.
6. a kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing according to claim 1, it is special Levy and be, the nitrogen-containing compound of the step (3) for the formation of oxygen reduction catalyst avtive spot to provide containing for nitrogen Nitrogen compound:Poly m-phenylene diamine, melamine or hydroxylamine chloride.
7. a kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing according to claim 1, it is special Levy and be, the inert atmosphere of the step (5) is nitrogen or argon gas atmosphere.
CN201710087532.7A 2017-02-17 2017-02-17 A kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing Pending CN106848332A (en)

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CN112086636A (en) * 2020-08-19 2020-12-15 广东工业大学 Nitrogen-sulfur co-doped three-dimensional honeycomb carbon and preparation method and application thereof

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Application publication date: 20170613