CN105609793A - Iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and preparation method and application therefor - Google Patents
Iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and preparation method and application therefor Download PDFInfo
- Publication number
- CN105609793A CN105609793A CN201511015619.0A CN201511015619A CN105609793A CN 105609793 A CN105609793 A CN 105609793A CN 201511015619 A CN201511015619 A CN 201511015619A CN 105609793 A CN105609793 A CN 105609793A
- Authority
- CN
- China
- Prior art keywords
- graphene
- iron
- porous material
- nitrogen
- ferric
- 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
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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- 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
-
- 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
-
- 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 invention belongs to the technical field of a nanomaterial, and specifically relates to an iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and a preparation method and an application therefor. The porous material is formed by embedding graphite-carbon-coated iron carbide into a nitrogen-doped porous graphene band network structure; the preparation method for the iron-nitrogen-doped graphene porous material comprises the steps of preparing a graphene oxide solution; adding a proper amount of conductive macromolecular pyrrole to the graphene oxide solution; obtaining uniform hydrogel through a hydrothermal process; performing oxidative polymerization on the hydrogel by ferric iron; then dispersing the hydrogel into a fresh ferric iron solution to complete adsorption; then performing drying and high-temperature carbonization thermal processing; and finally removing non-active and free iron phase from the reaction system by dilute acid so as to obtain the iron-nitrogen-doped graphene porous material. The porous material can be used as the negative electrode catalyst for a fuel cell, and shows quite high catalytic oxygen reduction activity, so that the porous material has quite important research meaning and bright application prospects.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to iron nitrogen-doped graphene porous material of a kind of dual site catalytic oxidation-reduction and its preparation method and application.
Background technology
Along with the develop rapidly of modern industry, people are also increasing to the demand of the energy. Fuel cell becomes a kind of novel clean type, alternative energy storage mode gradually with its high energy density and power density. In the building block of fuel cell, the cathod catalyst of its electrode is one of them epochmaking center element and is often determining the performance that fuel cell is final. Although for a long time, noble metal platinum and compound thereof are regarded as excellent catalyst material with its high catalytic activity, and the production cost that it is high and lower chemical stability have greatly limited it and promoted the use of. Therefore, people are in the urgent need to finding better negative electrode alternative catalysts of a kind of efficient, cheap, environmental friendliness, selective and stability. Based on this target, many scientists both domestic and external have carried out many trials, and the macrocyclic polymer of some non-noble metal oxide/carbide, transition-metal coordination, transition metal/carbon-nitrogen compound (Fe/Co-N-C) and the doping carbon material without metal are considered to desirable alternative catalyst material at present. Among this, the high catalytic activity that transition metal/carbon-nitrogen compound is given with its low production cost and unique metal-nitrogen coordinate bond (being proved to be the catalytic site of effective hydrogen reduction) is considered to have researching value. Although at present a lot of bibliographical informations relevant similar material, these materials are limited to low specific area and limited effective active site mostly. Therefore metal/carbon-nitrogen the compound that, how to obtain high-specific surface area and enrich avtive spot remains a huge challenge.
Porous graphene or graphene nano sieve, a kind of novel porous nano Graphene, due to the open bandgap structure of its uniqueness, large specific area and high optical transparence, is one of research field of the focuses such as current physics, chemistry, materialogy. Compare the graphene nanometer sheet that conventional plane is complete, on porous graphene two dimensional surface, be rich in abundant nano level pore space structure, these pore space structures not only can significantly improve the specific area (being conducive to the transmission of electronics and material) of material, but also provide abundant avtive spot (giving its high electro-chemical activity) for material. Therefore, compare graphene nanometer sheet, porous graphene is more suitable for promoting the use of as a kind of Graphene of functional form. The preparation of porous graphene is at present confined to some preparation means high-accuracy and consuming time, lithography, plasma etching method, photocatalytic oxidation and chemical vapour deposition technique of for example block copolymer etc. mostly. Therefore, obtain porous graphene in enormous quantities by simple scheme the functionalization of development Graphene is seemed to particularly important. On the other hand, before us, prove to be assembled into three-dimensional pillared network structure by easily there is heavy stacking grapheme material, not only can suppress the gathering between Graphene, but also can pass through pore structure and the specific area of assembly and regulation material, thereby optimize its application at aspects such as the energy, catalysis and absorption.
Summary of the invention
The object of this invention is to provide a kind of Graphene porous material, preparation method and application thereof of iron nitrogen doping. Described porous material is that the cementite that is coated by graphitic carbon embeds in the porous graphene network structure of nitrogen doping and forms. Owing to can generate a large amount of accessory substance iron oxide in the process that forms cementite, the defect carbon generation high temperature carbonization reaction under high temperature in iron oxide meeting and Graphene, thus etching Graphene forms porous graphene. Therefore the material of gained has large specific area and abundant avtive spot, thereby guarantees that this material has material and electronics transmission efficiency faster. In the time being applied to the cathod catalyst of fuel cell, this material list reveals the ability of very high hydrogen reduction catalysis, far above current other Graphene base material class catalyst.
For achieving the above object, technical scheme of the present invention is as follows:
A Graphene porous material for iron nitrogen doping, described porous material is that cementite coated graphitic carbon is embedded in porous graphene network structure and formed. Then react Graphene is carried out to heteroatomic doping by high temperature carbonization, improve the electro-chemical activity of material.
The Graphene porous material of described iron nitrogen doping, after Graphene and conducting polymer pyrroles assemble altogether, by using ferric iron in-situ polymerization pyrroles to form polypyrrole, then by the N coordination Fe that is rich in electronics in polypyrrole, adsorb ferric iron, finally by a step high temperature carbonization reaction, obtain in porous graphene network structure that the coated cementite of graphitic carbon is embedded in nitrogen doping. Wherein being used for the graphitic carbon of coated cementite mainly comes from polypyrrole. The nitrogenous source of the nitrogen doping of porous graphene also mainly comes from polypyrrole. The porous feature of porous graphene is mainly because the accessory substance iron oxide generation high temperature etching reaction generating in the defect carbon in Graphene under high temperature and carbonization reaction forms. The abundant pore structure generating in Graphene plane, is conducive to shorten the distance of material substance and electric transmission, thereby promotes greatly its transmission efficiency. Because the porous graphene of cementite and doping has the ability of catalytic oxidation-reduction simultaneously, therefore after organically combining, both can show concerted catalysis effect, and cause prepared material to there is very high hydrogen reduction catalytic capability.
The aperture of the Graphene porous material of preferred described iron nitrogen doping is 1nm～50 μ m, and porosity is 80～99%, and density is 0.05～2.0g/cm3, specific area is 10～2000m2/g。
A preparation method for the Graphene porous material of iron nitrogen doping, described method step is as follows:
(1) preparation of graphene oxide material:
The preparation of graphene oxide: the preparation of graphene oxide is to make according to Hummer ' the s method of improvement version. Specific embodiments is as follows: 1. measure the 25mL concentrated sulfuric acid and add in 100mL flask, be heated to 90 DEG C, then slowly add successively 5g potassium peroxydisulfate and 5g phosphorus pentoxide. In the time that temperature is down to 80 DEG C, add 5g graphite powder, react 4.5 hours. Then add the distilled water diluting of 1L and the placement of spending the night. 2. with 2L distilled water, pre-oxidation graphite is above filtered to washing, remove most of acid, then the powdered graphite obtaining is placed in to 50 DEG C of dried overnight. 3. get the flask that the 230mL concentrated sulfuric acid is placed in 1L, with the cooling 20min of ice bath, then slowly add successively pre-oxidation graphite and the 30g potassium permanganate processed above, and stir energetically 20min, then reaction system being placed in to 35 DEG C of water-baths reacts 2 hours, then in reaction system, slowly add 460mL distilled water, add fashionable until work as last distilled water, no longer cause obvious variations in temperature, and then add the distilled water diluting of 1.4L, after stirring reaction 2 hours, add the hydrogen peroxide of 25mL30%, now solution colour becomes khaki. Finally use the dilute hydrochloric acid precipitated 3 times of 5wt%, 2L distilled water diluting 2 times, centrifugally obtains denseer graphene oxide solution. 4. the graphene oxide obtaining with distilled water diluting, then ultrasonic peeling off, until become transparent brown suspension.
Described graphite powder is preferentially selected from: crystalline flake graphite, all kinds of graphite materials such as expanded graphite.
The synthetic of stannic oxide/graphene nano band obtains in water system environment by CNT is longitudinally separated to slide fastener, specific embodiment is as follows: ultrasonic 1g CNT or stirring 1～12h are dispersed in to (volume of the concentrated sulfuric acid is 20-500 times of carbon pipe quality) in 20～500mL concentrated sulfuric acid, then disperse to add in the phosphoric acid of 10～250mL (volume of phosphoric acid is the half of concentrated sulfuric acid volume), under room temperature, continue to stir 1-2h; 2. in reaction system, slowly add 5～10g potassium permanganate (speed that adds of potassium permanganate is 2g/h) oxidation cutting carbon nanotubes (addition of potassium permanganate is the quality of 5～10 times of CNTs); 3. after stirring at normal temperature 1～24h, be placed on (20～200 DEG C, heat up naturally) reaction 10min～24h in oil bath; After 4 cooling reactant liquors, add 20～2000mL frozen water and 10～100mL hydrogen peroxide, hold over night, then use the pickling twice of 5wt%, get lower sediment dialyse (being placed in ultra-pure water with the bag filter that molecular cut off is 3500Da dialyses 1～30 day) after centrifugal; 5. after dialysis, taking out add water ultrasonic 1～24h of reactant becomes brown liquid to be the stannic oxide/graphene nano band aqueous solution.
Described CNT is preferentially selected from: SWCN, double-walled carbon nano-tube, three wall carbon nano tubes, multi-walled carbon nano-tubes, many walls array carbon nano tube etc. Carbon nanotube production process is not limit, and can be that chemical vapour deposition (CVD) can be also that arc discharge method is produced.
(2) preparation and the adsorb ferric iron of graphene oxide material/polypyrrole composite aquogel
The graphene oxide material water solution (0.1～50mg/mL) of getting variable concentrations adds the pyrroles of 1～100vol% (volume that pyrroles adds is 1～100vol% of graphene oxide material volume), then be placed in 20mL hydrothermal reaction kettle, 30～200 DEG C of hydro-thermal 1～48h, obtain graphene oxide material/pyrroles composite aquogel that uniform mechanical property is good. Then the hydrogel obtaining is scattered in and in the ferric iron aqueous solution of 10～500mL0.24M, stirs 1～24h and complete pyrroles's in-situ polymerization. After polymerization completes, wash accessory substance and the unpolymerized pyrrole monomer of polymerisation (remove) with distilled water and ethanol. After having washed, the hydrogel solid obtaining is scattered in the ferric iron aqueous solution that 20～1000mL0.24M is fresh again, stirs 1～48h and complete adsorption process, finally filter and obtain graphene oxide material/polypyrrole (containing ferric iron) composite aquogel.
Described ferric iron can be selected from the ferric inorganic salts of some routines: the soluble ferric iron salt such as such as ferric nitrate, iron chloride, ferric sulfate, ironic citrate.
(3) pretreatment (dry run) of graphene oxide material/polypyrrole composite aquogel:
In preferred steps (3), described dry run is freeze drying, concrete grammar for to add water in wet gel, after soaking 5～10h, water is poured out, repeat after 2～4 times, by freezing at-5～50 DEG C wet gel >=60min, then at-50～100 DEG C of dry 30min～48h, obtain the block porous material of structural integrity; Freezing and dry run is all carried out under the vacuum of 1～1000Pa.
Described freeze drying process is not subject to the restriction of freeze drying equipment, can in freeze drying equipment any business or non-commercial, complete. Wet gel also can first adopt liquid nitrogen frozen, then proceeds to vacuum drying in freeze-dryer; Also can directly freeze drying in freeze-dryer. Freezing mode can adopt directed freezing (controlling freezing direction), also can adopt non-directional freezing.
In preferred steps (3), described dry run is that supercritical fluid mode is dry, be specially in wet gel and add ethanol or acetone, after soaking 2～10h, pour out, repeat 6～8 times, obtain alcogel or ketone gel, then with Supercritical Ethanol or be dried >=12h of supercritical carbon dioxide, obtain the block porous material of structural integrity.
Described supercritical drying drying process is not subject to the restriction of supercritical drying equipment, can in supercritical drying equipment any business or non-commercial, complete the supercritical drying of alcohol (or ketone) gel, to obtain corresponding block porous material.
In preferred steps (3), described dry run is that normal heating is dry, is specially: the wet gel obtaining is in advance put into preheated in advance baking oven (temperature control is 30～200 DEG C), and heat drying 1～24h, obtains corresponding xerogel material.
Described heat drying technique is not subject to the restriction of firing equipment, can in the baking oven of any business or non-commercial, complete dry run.
(4) one step high temperature cabonization reactions:
The drying sample obtaining is put into high temperature process furnances and carry out high temperature carbonization heat treatment, described carbonization temperature is 200～1500 DEG C, and inert gas is argon gas or nitrogen, and heating rate is 1～50 DEG C/min, carbonization time is 1～48h, and rate of temperature fall is 1～50 DEG C/min. In the high-temperature tubular retort that described carbonization process can be bought in any business, carry out.
(5) post processing of porous material:
By the sample dispersion after charing in 100～1000mL1～12M hydrochloric acid or sulfuric acid, 30～100 DEG C of stirring reaction 1～24h, then filter, and wash with distilled water and absolute ethyl alcohol, again carry out dry run (step as above), obtain the Graphene porous material of final iron nitrogen doping.
An application for the Graphene porous material of iron nitrogen doping, described application is that this porous material is made to electrode, the process of catalytic oxidation-reduction. As an example, we select the Graphene porous material of 800 DEG C of iron nitrogen doping under charing as prototype. Prove through electro-chemical test: the take-off potential of its catalytic oxidation-reduction and business Pt/C electrode be (being 0.02V) quite, its half wave potential is-0.148V(Pt/C electrode is-0.130V), the Tafel slope of catalytic process is that 61mV/decade(Pt/C electrode is 56mV/decade), and metastatic electron number within the scope of whole test voltage is all close to 4 electronics. This catalyst material is not subject to the interference of fuel molecule methyl alcohol, and has stronger chemical stability, and after scan round 20000s, its effective catalytic efficiency still can reach more than 90%.
Useful invention effect:
(1) the invention provides the Graphene porous material of a kind of iron nitrogen doping, described porous material is that the cementite that is coated by a large amount of graphitic carbons embeds in the porous graphene network structure of nitrogen doping and forms. This material combines the characteristic of many excellences such as Graphene, cementite, has utilized in addition the advantage such as specific area and abundant avtive spot that porous graphene is large.
(2) the invention provides the preparation method of the Graphene porous material of a kind of iron nitrogen doping. Wherein a large amount of pyrrole monomers in-situ polymerization under ferric effect forms polypyrrole, then forms the coated cementite nucleocapsid structure of graphitic carbon with polypyrrole original position under high temperature carbonization condition of ferric iron coordination. Meanwhile, the accessory substance iron oxide forming in carbonization reaction again can with Graphene in the anti-raw high temperature carbonization reactive ion etching Graphene of defect carbon, form porous graphene structure, now the polypyrrole of part also can mix in the lattice of porous graphene as nitrogenous source original position. The final coated cementite of graphitic carbon that forms embeds nitrogen-doped graphene porous material.
(3) the Graphene porous material of iron nitrogen doping provided by the invention has larger specific area and abundant active site. In this material, Graphene can original position form three-dimensional pillared network structure under pyrroles's effect, by forming porous graphene three-dimensional net structure after iron oxide high temperature etching. This structure not only has larger specific area, and the mesoporous active site that can be used as forming after etching, thereby promotes greatly its electro-chemical activity. Therefore in this material, its material and electronics transmission efficiency are very high. And in this material, cementite is being coated formation nucleocapsid structure by graphitic carbon, in this nucleocapsid structure, cementite can effectively activate outer field graphite linings, becomes the avtive spot of catalytic oxidation-reduction, thereby has further promoted its catalytic performance. And the cementite being coated by graphite linings is due to the barrier effect of outer graphite linings, can avoid the corrosion impact of soda acid, improve the chemical stability of material.
(4) the Graphene porous material structural model of iron nitrogen doping provided by the invention can not only effectively suppress the reunion collection of Graphene, but also can promote its specific area and chemism in its surperficial pore-creating. Be embodied in: the Graphene of easily piling up is assembled into three-dimensional pillared network structure and can prevents that its gathering from forming the laminated structure of " class graphite ". And after high temperature carbonization etching processing, the meso-hole structure that Graphene Surface Creation is a large amount of, is conducive to promote specific area and the electro-chemical activity of material.
(5) the Graphene porous material set of iron nitrogen provided by the invention doping the characteristic of many excellences such as cementite and nitrogen-doped graphene. Because cementite and nitrogen-doped graphene are all the active material of catalytic oxidation-reduction, both in conjunction with after can bring into play concerted catalysis effect, its electro-chemical activity is obviously strengthened. In the time that the cathod catalyst as fuel cell uses, show as very high catalytic activity (its catalytic activity is quite in business Pt/C catalyst), far above current other Graphene base material class catalyst.
(6) the Graphene porous material of iron nitrogen provided by the invention doping be also expected to be applied in bio-sensing, super capacitor and, the field such as lithium ion battery, catalyst carrier and life science.
Brief description of the drawings
Fig. 1 is the scanning electron microscope image of the Graphene porous material of the iron nitrogen doping that obtains in embodiment 1.
Fig. 2 is the images of transmissive electron microscope of the Graphene porous material of the iron nitrogen doping that obtains in embodiment 2.
Fig. 3 is nitrogen adsorption-desorption curve of the Graphene porous material of the iron nitrogen doping that obtains in embodiment 3.
Fig. 4 is the X-ray diffraction pattern of the Graphene porous material of the iron nitrogen doping that obtains in embodiment 4.
Fig. 5 is that the Graphene porous material electrode of iron nitrogen doping is at O2And N2Under cyclic voltammetry curve.
Fig. 6 is that the Graphene porous material electrode of iron nitrogen doping is at O2Linescan under atmosphere.
Fig. 7 is the Graphene porous material of the iron nitrogen doping metastatic electron number under different catalysis current potentials.
Fig. 8 is the Graphene porous material electrode of the iron nitrogen doping Tafel curve in catalytic process.
Fig. 9 is the Graphene porous material of iron nitrogen doping and the methyl alcohol cross response curve of business Pt/C catalyst.
Figure 10 is the Graphene porous material of iron nitrogen doping and the stability curve of business Pt/C catalyst.
Detailed description of the invention
Below by embodiment, the invention will be further described:
Wherein the stannic oxide/graphene nano band aqueous solution in embodiment 1-3 obtains by the following method:
(1) accurately take 1g CNT with high-accuracy electronic pallet balance, be scattered in the concentrated sulfuric acid of 150mL, under room temperature, stir 1-24h, add subsequently the phosphoric acid of 20mL, under room temperature, continue to stir 2h.
(2) take 5g potassium permanganate, join slowly in above-mentioned reaction system, adding speed is 2g/h, under room temperature, stirs energetically.
(3) under room temperature, stir after 5h, 1-24h is reacted in the oil bath that reaction system is placed in to 20-200 DEG C, after reaction finishes, takes out reactant liquor, is placed under room temperature standing cooling.
(4), toward the hydrogen peroxide of pouring the 30wt% of 500mL frozen water and 20mL in reactant liquor into, stir after half an hour hold over night. Then use the watery hydrochloric acid pickling twice of 5wt%, last centrifugal taking-up sediment carries out dialysis treatment.
(5) dialysis, after 7-30 days, is taken out sediment, and the ultrasonic 1-24h that adds water, finally becomes 0.1-50mg/mL stand-by solution preparation.
Graphite oxide aqueous solution in embodiment 4-6 makes by following scheme:
(1) sulfuric acid that is 98wt% by 25mL concentration adds in 100mL flask, is heated to 90 DEG C, slowly adds successively 5g potassium peroxydisulfate and 5g phosphorus pentoxide under stirring condition. Then be cooled to 80 DEG C, add 5g graphite powder, stirring reaction 4.5 hours, adds the distilled water of 1L to leave standstill 12h, obtains pre-oxidation graphite.
(2) with 2L distilled water, the pre-oxidation graphite obtaining is carried out after filtering and washing, by pre-oxidation graphite 50℃Dry 12h down.
(3) getting 230mL concentration is the flask that the sulfuric acid of 98wt% is placed in 1L, with the cooling 20min of ice bath, then slowly adds successively dried pre-oxidation graphite and 30g potassium permanganate, magnetic agitation 20min; Flask is reacted after 2h in 35 DEG C of water-baths, slowly add 460mL distilled water, then add the distilled water diluting of 1.4L, after stirring reaction 2h, add the hydrogen peroxide of 25mL30wt%, now the color of reactant liquor becomes khaki;
(4) to the hydrochloric acid that adds 5wt% in reactant liquor, after standing sedimentation, supernatant is poured out, repeated 3 times; Add again 2L distilled water, after standing sedimentation, supernatant is poured out, centrifugal after repeating 2 times, obtain graphene oxide, described graphene oxide is made into and needs the graphene oxide of concentration aaerosol solution.
Embodiment 1
(1) get the stannic oxide/graphene nano band aqueous solution of 10mL1mg/mL, add the pyrroles of 4vol%, ultrasonic dispersion is until form uniform suspension 1.
(2) suspension 1 is sealed in the autoclave of 20mL, the baking oven that is placed in 80 DEG C reacts 12h, obtains the good stannic oxide/graphene nano band/pyrroles of mechanical property composite aquogel.
(3) hydrogel obtaining is scattered in the ferric chloride solution of 25mL0.24M, stirring reaction 1-12h, completes polymerisation, then uses the sample (removing accessory substance and the unreacted pyrrole monomer of polymerisation) of distilled water and absolute ethanol washing gained. Subsequently the sample after cleaning is scattered in 50mL0.24M ferric chloride solution again, stirring reaction 1-12h, completes ferric absorption. Finally filter and obtain wet hydrogel.
(4) in wet hydrogel, add the tert-butyl alcohol, after immersion 5h, the tert-butyl alcohol is poured out, repeat, after 3 times, alcogel, at freezing at-25 DEG C >=30min, then, at 70 DEG C of dry 30min, to be obtained to dry solid sample; Freezing and dry run is all carried out under the vacuum of 10Pa.
(5) high temperature process furnances (production of Tianjin Zhong Huan experimental electric furnace company) that the drying sample obtaining is in advance placed in to argon shield carries out charing heat treatment, and carbonization temperature is 700 DEG C, and carbonization time is 1h, and the speed of intensification and cooling is 10 DEG C/min.
(6) by the sample dispersion after charing in the watery hydrochloric acid of 1M, remove reaction in inactive, free Fe phase. Reaction temperature is 80 DEG C, and the reaction time is 8h. Filter subsequently, washing, dry (step is as above) again, obtains the Graphene porous material that final iron nitrogen adulterates.
Embodiment 2
(1) get the stannic oxide/graphene nano band aqueous solution of 10mL5mg/mL, add the pyrroles of 8vol%, ultrasonic dispersion is until form uniform suspension 2.
(2) suspension 2 is sealed in the autoclave of 20mL, as for reacting 6h in the baking oven of 100 DEG C, obtains the good stannic oxide/graphene nano band/pyrroles of mechanical property composite aquogel.
(3) hydrogel obtaining is scattered in the iron nitrate solution of 50mL0.24M, stirring reaction 1-12h, completes polymerisation, then uses the sample (removing accessory substance and the unreacted pyrrole monomer of polymerisation) of distilled water and absolute ethanol washing gained. Subsequently the sample after cleaning is scattered in 100mL0.24M iron nitrate solution again, stirring reaction 1-12h, completes ferric absorption. Finally filter and obtain wet hydrogel.
(4) in wet hydrogel, add ethanol, after immersion 5h, ethanol is poured out, repeat, after 5 times, to obtain alcogel. The supercritical CO of producing with SFT company of the U.S.2Drying instrument is dried 48h, supercritical CO2Dry critical-temperature is 40 DEG C, and critical pressure is 7.5Pa.
(5) high temperature process furnances that the sample obtaining is in advance placed in to nitrogen protection carries out charing heat treatment, and carbonization temperature is 800 DEG C, and carbonization time is 2h, and the speed of intensification and cooling is 20 DEG C/min.
(6) by the sample dispersion after charing in the dilute sulfuric acid of 2M, remove reaction in inactive, free Fe phase. Reaction temperature is 100 DEG C, and the reaction time is 10h. Filter subsequently, washing, dry (step is as above) again, obtains the Graphene porous material that final iron nitrogen adulterates.
Embodiment 3
(1) get the stannic oxide/graphene nano band aqueous solution of 10mL10mg/mL, add the pyrroles of 12vol%, ultrasonic dispersion is until form uniform suspension 3.
(2) suspension 3 is sealed in the autoclave of 20mL, as for reacting 6h in the baking oven of 120 DEG C, obtains the good stannic oxide/graphene nano band/pyrroles of mechanical property composite aquogel.
(3) hydrogel obtaining is scattered in the ferrum sulfuricum oxydatum solutum of 100mL0.24M, stirring reaction 2-10h, completes polymerisation, then uses the sample (removing accessory substance and the unreacted pyrrole monomer of polymerisation) of distilled water and absolute ethanol washing gained. Subsequently the sample after cleaning is scattered in 200mL0.24M ferrum sulfuricum oxydatum solutum again, stirring reaction 2-10h, completes ferric absorption. Finally filter and obtain wet hydrogel.
(4) in wet hydrogel, add the tert-butyl alcohol, after immersion 10h, the tert-butyl alcohol is poured out, repeat, after 3 times, alcogel, at freezing at-80 DEG C >=30min, then, at 70 DEG C of dry 10h, to be obtained to dry sample; Freezing and dry run is all carried out under the vacuum of 10Pa.
(5) high temperature process furnances (production of Tianjin Zhong Huan experimental electric furnace company) that the sample obtaining is in advance placed in to argon shield carries out charing heat treatment, and carbonization temperature is 900 DEG C, and carbonization time is 3h, and the speed of intensification and cooling is 20 DEG C/min.
(6) by the sample dispersion after charing in the watery hydrochloric acid of 6M, remove reaction in inactive, free Fe phase. Reaction temperature is 120 DEG C, and the reaction time is 5h. Filter subsequently, washing, dry (step is as above) again, obtains the Graphene porous material that final iron nitrogen adulterates.
Embodiment 4
(1) get the graphite oxide aqueous solution of 30mL6mg/mL, add the pyrroles of 10vol%, ultrasonic dispersion is until form uniform suspension 4.
(2) suspension 4 is sealed in the autoclave of 50mL, as for reacting 10h in the baking oven of 140 DEG C, obtains the good graphene oxide/pyrroles of mechanical property composite aquogel.
(3) hydrogel obtaining is scattered in the ironic citrate solution of 150mL0.24M, stirring reaction 2-10h, complete polymerisation, then use the sample (removing accessory substance and the unreacted pyrrole monomer of polymerisation) of distilled water and absolute ethanol washing gained. Subsequently the sample after cleaning is scattered in 250mL0.24M ironic citrate solution again, stirring reaction 2-10h, completes ferric absorption. Finally filter and obtain wet hydrogel.
(4) wet hydrogel is put into the preheated baking oven of 80 DEG C in advance, dry 12h, completes dry run.
(5) high temperature process furnances (production of Tianjin Zhong Huan experimental electric furnace company) that the dry sample obtaining is in advance placed in to argon shield carries out charing heat treatment, and carbonization temperature is 1000 DEG C, and carbonization time is 2.5h, and the speed of intensification and cooling is 30 DEG C/min.
(6) by the sample dispersion after charing in the dilute sulfuric acid of 8M, remove reaction in inactive, free Fe phase. Reaction temperature is 140 DEG C, and the reaction time is 10h. Filter subsequently, washing, dry (step is as above) again, obtains the Graphene porous material that final iron nitrogen adulterates.
Embodiment 5
(1) get the graphite oxide aqueous solution of 30mL15mg/mL, add the pyrroles of 20vol%, ultrasonic dispersion is until form uniform suspension 5.
(2) suspension 5 is sealed in the autoclave of 50mL, as for reacting 18h in the baking oven of 150 DEG C, obtains the good graphene oxide/pyrroles of mechanical property composite aquogel.
(3) hydrogel obtaining is scattered in the iron nitrate solution of 150mL0.24M, stirring reaction 5-24h, completes polymerisation, then uses the sample (removing accessory substance and the unreacted pyrrole monomer of polymerisation) of distilled water and absolute ethanol washing gained. Subsequently the sample after cleaning is scattered in 250mL0.24M iron nitrate solution again, stirring reaction 5-24h, completes ferric absorption. Finally filter and obtain wet hydrogel.
(4) wet hydrogel is put into the preheated baking oven of 100 DEG C in advance, dry 10h, completes dry run.
(5) high temperature process furnances (production of Tianjin Zhong Huan experimental electric furnace company) that the dry sample obtaining is in advance placed in to argon shield carries out charing heat treatment, and carbonization temperature is 850 DEG C, and carbonization time is 2h, and the speed of intensification and cooling is 40℃/min。
(6) by the sample dispersion after charing in the watery hydrochloric acid of 6M, remove reaction in inactive, free Fe phase. Reaction temperature is 150 DEG C, and the reaction time is 10h. Filter subsequently, washing, dry (step is as above) again, obtains the Graphene porous material that final iron nitrogen adulterates.
Embodiment 6
(1) get the graphite oxide aqueous solution of 80mL10mg/mL, add the pyrroles of 8vol%, ultrasonic dispersion is until form uniform suspension 6.
(2) suspension 6 is sealed in the autoclave of 100mL, as for reacting 16h in the baking oven of 70 DEG C, obtains the good graphene oxide/pyrroles of mechanical property composite aquogel.
(3) hydrogel obtaining is scattered in the ferrum sulfuricum oxydatum solutum of 200mL0.24M, stirring reaction 2-10h, completes polymerisation, then uses the sample (removing accessory substance and the unreacted pyrrole monomer of polymerisation) of distilled water and absolute ethanol washing gained. Subsequently the sample after cleaning is scattered in 400mL0.24M ferrum sulfuricum oxydatum solutum again, stirring reaction 2-10h, completes ferric absorption. Finally filter and obtain wet hydrogel.
(4) in wet hydrogel, add the tert-butyl alcohol, after immersion 10h, the tert-butyl alcohol is poured out, repeat, after 3 times, alcogel, at freezing at-80 DEG C >=30min, then, at 70 DEG C of dry 10h, to be obtained to dry sample; Freezing and dry run is all carried out under the vacuum of 10Pa.
(5) high temperature process furnances (production of Tianjin Zhong Huan experimental electric furnace company) that the sample obtaining is in advance placed in to argon shield carries out charing heat treatment, and carbonization temperature is 1100 DEG C, and carbonization time is 3h, and the speed of intensification and cooling is 50 DEG C/min.
(6) by the sample dispersion after charing in the watery hydrochloric acid of 12M, remove reaction in inactive, free Fe phase. Reaction temperature is 70 DEG C, and the reaction time is 12h. Filter subsequently, washing, dry (step is as above) again, obtains the Graphene porous material that final iron nitrogen adulterates.
Graphene porous material to the iron nitrogen doping obtaining in embodiment 1-6 is tested, and result is as follows:
Fig. 1 is the scanning electron microscope image of the Graphene porous material of the iron nitrogen doping that obtains in embodiment 1; Fig. 2 is the images of transmissive electron microscope of the Graphene porous material of the iron nitrogen doping that obtains in embodiment 2. As can be seen from Figure 1, the Graphene porous material of described iron nitrogen doping has three-dimensional hierarchical loose structure, and in figure, the sparklet of white is the coated cementite nano particle of graphite linings. As seen from the figure, cementite nano particle is evenly embedded in the network structure of Graphene. As can be seen from Figure 2, in the Graphene porous material of described iron nitrogen doping, be rich in the coated cementite nano particle of many graphite linings that are evenly distributed, the size of cementite particle is about 20-100nm, and the thickness of graphite linings is about 2-15nm. The coated cementite of graphite linings evenly drops on formation structure comparatively closely on porous graphene skeleton.
Fig. 3 is nitrogen adsorption-desorption curve of the Graphene porous material of the iron nitrogen doping that obtains in embodiment 3. The wherein pressure of abscissa representative test, ordinate is adsorbance. Be a kind of typical mesoporous material by known this material of adsorption-desorption curve shape, its specific area is 542m2/ g, aperture is 2-80nm. Learn that by mass/volume the density of this porous material is 150g/cm3. The specific surface area data of the porous material that embodiment 4 ~ 6 obtains is 20-2000m2/ g, aperture is 1nm ~ 50 μ m, density is 0.05 ~ 2gcm-3, specific area is 20 ~ 2000m2g-1。
Fig. 4 is the X-ray diffraction pattern of the Graphene porous material of the iron nitrogen doping that obtains in embodiment 4. As can be seen from the figure, 25oThe strong diffraction maximum of the left and right characteristic diffraction peak that is Graphene, shows to contain in material a large amount of Graphenes. Other characteristic diffraction peaks are all corresponding to the standard diffraction maximum of cementite, show that the iron that obtains in material is mutually for cementite but not other iron phases.
Graphene porous material to the iron nitrogen doping obtaining in embodiment 1-6 carries out electrochemical catalysis hydrogen reduction test, and method of testing and result are as follows:
The Graphene porous material of the iron nitrogen doping of gained in embodiment 2 is ground with mortar, take the sample of 5mg after grinding, be scattered in the absolute ethyl alcohol of 1mL, then add the Nafion solution (5wt%) of 50 μ L, ultrasonic 6h is to being uniformly dispersed. Measure subsequently even the dripping in upper rotating disk electrode (r.d.e) (diameter 5mm) of dispersion liquid of 5 μ L with liquid-transfering gun, after oven dry, test as working electrode. Before test, first logical halfhour oxygen reaches capacity by oxygen in electrolyte, and Ag/AgCl is as reference electrode, and Pt silk is as to electrode, 0.1KOH or 0.5MH2SO4Solution is as electrolyte. Rotating disk electrode (r.d.e) equipment is to buy from Pine company of the U.S., and all electro-chemical tests tests such as () cyclic voltammetric and line sweeps are all produced in CHI760D(Shanghai Chen Hua company) carry out in electrochemical workstation. Fig. 5 is that the Graphene porous material electrode of iron nitrogen doping is at O2And N2Cyclic voltammetry curve under atmosphere. Find after tested, this electrode is at N2In without any ampere response, but at O2In atmosphere, there is obvious redox peak in-0.1V left and right, show now to have occurred oxygen reduction reaction, thereby prove that this material can catalytic oxygen be reduced into the reaction of water. Fig. 6 is that the Graphene porous material electrode of iron nitrogen doping is at O2Under atmosphere, the linescan under rotating speed 1600rpm. In order to contrast with it, the Pt/C catalyst of business also carries out same test, and data as shown in the figure. The catalysis take-off potential of the Graphene porous material electrode of iron nitrogen doping is suitable with Pt/C catalyst, be 0.02V, and the half wave potential of the Graphene porous material of iron nitrogen doping is-0.148V, business Pt/C catalyst is-0.130V, both only differ 18mV, show that the Graphene porous material of iron nitrogen doping has excellent catalytic oxidation-reduction activity. Fig. 7 is the Graphene porous material electrode of the iron nitrogen doping metastatic electron number under different test voltages, as can be seen from the figure, the Graphene porous material electrode of this iron nitrogen doping is similar to business Pt/C electrode, within the scope of whole measuring voltage, is step 4 electron reactions. Fig. 8 is Graphene porous material electrode and the Tafel slope curve of Pt/C electrode in catalytic reaction process of iron nitrogen doping, as can be seen from the figure, the slope of the Tafel of business Pt/C catalyst is 56mV/decade, the Graphene porous material electrode of iron nitrogen doping is 61mV/decade, both gaps are very little, the Graphene porous material that shows the doping of iron nitrogen has good electronics transmission efficiency, and in its catalytic reaction process, electrode impedance is less. Fig. 9 is the cross response curve of two kinds of catalyst, as can be seen from the figure, when adding in reaction system after a certain amount of fuel molecule (methyl alcohol), there is at once catalyst poisoning reaction (showing as obvious electrical current fluctuations) in Pt/C catalyst, the impact that the Graphene porous material electrode of iron nitrogen doping is not added by methyl alcohol, its catalytic current value stabilization is a constant level, shows that this electrode material has good selective. Figure 10 is the Graphene porous material electrode of iron nitrogen doping and the stability curve of business Pt/C catalyst, and as seen from the figure, the Graphene porous material electrode of iron nitrogen doping is compared Pt/C and had better stability. Circulate under the same conditions after 20000s, the Graphene porous material electrode of iron nitrogen doping still can maintain original 90% activity, and business Pt/C catalyst has lost nearly 40% catalytic activity. All experimental phenomenas show, this material is the extremely promising functional material of one, has very important Research Significance.
In sum, these are only preferred embodiment of the present invention, be not intended to limit protection scope of the present invention. Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (6)
1. an iron nitrogen-doped graphene porous material for dual site catalytic oxidation-reduction, is characterized in that described porous material is that the cementite that is coated by graphitic carbon embeds in the porous graphene network structure of nitrogen doping and forms; Utilize polypyrrole and ferric coordination, by a step charing heat treatment, be the coated cementite of graphitic carbon by polypyrrole situ converting, and can generate a large amount of accessory substance iron oxide in the process that forms cementite, defect carbon generation high temperature carbonization reaction under high temperature in iron oxide and Graphene, thereby etching Graphene, forms porous graphene; Because the porous graphene of cementite and doping has the ability of catalytic oxidation-reduction simultaneously, therefore after organically combining, both can show concerted catalysis effect, and cause prepared material to there is very high hydrogen reduction catalytic capability.
2. the iron nitrogen-doped graphene porous material of a kind of dual site according to claim 1 catalytic oxidation-reduction, is characterized in that: described iron nitrogen-doped graphene aperture of porous material is 1nm ~ 50 μ m, and porosity is 80 ~ 99%, and density is 0.05 ~ 2g/cm3, specific area is 10 ~ 2000m2/g。
3. a preparation method for the iron nitrogen-doped graphene porous material of dual site catalytic oxidation-reduction as claimed in claim 1, is characterized in that described method step is as follows:
(1) preparation of graphene oxide material:
Utilize Hummer ' the s method of improvement version to prepare graphene oxide or CNT is longitudinally separated to slide fastener and in water system environment, obtain stannic oxide/graphene nano band;
(2) preparation and the adsorb ferric iron of graphene oxide material/polypyrrole composite aquogel:
Get 0.1～50mg/mL graphene oxide material water solution and add the pyrroles of 1～100vol%, the volume that pyrroles adds is 1～100vol% of graphene oxide material volume, then be placed in 20mL hydrothermal reaction kettle, 30～200 DEG C of hydro-thermal 1～48h, obtain graphene oxide material/pyrroles composite aquogel that uniform mechanical property is good;
Then the hydrogel obtaining is scattered in and in the ferric iron aqueous solution of 10～500mL0.24M, stirs 1～24h and complete pyrroles's in-situ polymerization;
After polymerization completes, wash accessory substance and the unpolymerized pyrrole monomer of removing polymerisation with distilled water and ethanol;
After having washed, the hydrogel solid obtaining is scattered in the ferric iron aqueous solution that 20～1000mL0.24M is fresh again, stirs 1～48h and complete adsorption process, finally filter and obtain containing ferric graphene oxide material/polypyrrole composite aquogel;
(3) dry run of graphene oxide material/polypyrrole composite aquogel:
Be dried or the dry xerogel material that obtains of normal heating by freeze drying, supercritical fluid mode;
(4) one step high temperature cabonization reactions:
The drying sample obtaining is put into high temperature process furnances and carry out high temperature carbonization heat treatment, described carbonization temperature is 200～1500 DEG C, and inert gas is argon gas or nitrogen, and heating rate is 1～50 DEG C/min, carbonization time is 1～48h, and rate of temperature fall is 1～50 DEG C/min;
(5) post processing of porous material:
By the sample dispersion after charing in 100～1000mL1～12M hydrochloric acid or sulfuric acid, 30～100 DEG C of stirring reaction 1～24h, then filter, and wash with distilled water and absolute ethyl alcohol, again carry out dry run (step as above), obtain the Graphene porous material of final iron nitrogen doping.
4. the preparation method of the iron nitrogen-doped graphene porous material of dual site according to claim 3 catalytic oxidation-reduction, is characterized in that: described CNT is single-walled nanotube, multi-walled carbon nano-tubes, double-walled carbon nano-tube, three wall carbon nano tubes or many walls array carbon nano tube.
5. the preparation method of the iron nitrogen-doped graphene porous material of dual site according to claim 3 catalytic oxidation-reduction, is characterized in that: described ferric iron is selected from conventional ferric soluble inorganic salt and comprises: ferric nitrate, iron chloride, ferric sulfate, ironic citrate.
6. the application of the iron nitrogen-doped graphene porous material of the dual site catalytic oxidation-reduction as described in claim 1 or 3, it is characterized in that described iron nitrogen-doped graphene porous material can be used as electrode material, the reduction of the negative electrode oxygen of catalytic fuel battery, shows as very high catalytic activity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511015619.0A CN105609793A (en) | 2015-12-31 | 2015-12-31 | Iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and preparation method and application therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511015619.0A CN105609793A (en) | 2015-12-31 | 2015-12-31 | Iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and preparation method and application therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105609793A true CN105609793A (en) | 2016-05-25 |
Family
ID=55989518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511015619.0A Pending CN105609793A (en) | 2015-12-31 | 2015-12-31 | Iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and preparation method and application therefor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105609793A (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106067546A (en) * | 2016-08-10 | 2016-11-02 | 上海交通大学 | Carbon/nano silicon carbide two iron composite material, combination electrode and preparation method and application |
| CN106532071A (en) * | 2016-12-01 | 2017-03-22 | 浙江师范大学 | Method for preparing N-doped graphene-coated ferroelectric carbide catalyst |
| CN107739074A (en) * | 2017-09-08 | 2018-02-27 | 南开大学 | A kind of high catalytic activity nitrogen-doped graphene composite cathode preparation method and degradable organic pollutant technology |
| CN108010748A (en) * | 2017-12-18 | 2018-05-08 | 上海交通大学 | The preparation method of the mesoporous polypyrrole/graphene composite material of two dimensional oxidation Fe2O3 doping |
| CN108264037A (en) * | 2018-02-06 | 2018-07-10 | 北京科技大学 | Three-dimensional porous nitrogen-doped graphene answers the preparation method of material and nitrogen-doped graphene |
| CN108428905A (en) * | 2018-04-04 | 2018-08-21 | 江苏新亿源环保科技有限公司 | A kind of preparation method of fuel cell electrode catalyst material |
| CN108767278A (en) * | 2018-06-11 | 2018-11-06 | 佛山腾鲤新能源科技有限公司 | A kind of fuel-cell catalyst |
| CN109728260A (en) * | 2018-11-28 | 2019-05-07 | 广西大学 | The preparation method of the carbon-coated cementite combination electrode material of nitrogen sulfur doping |
| CN110155998A (en) * | 2019-05-13 | 2019-08-23 | 东南大学 | A kind of ribbon nitrogen-doped graphene and its preparation method and application |
| CN110273162A (en) * | 2018-03-15 | 2019-09-24 | 浙江大学 | A kind of iron/cobalt/nickel nitrogen coupling C-base composte material and its application |
| CN110380067A (en) * | 2019-08-15 | 2019-10-25 | 中国科学技术大学 | A kind of fuel cell membrane electrode catalyst, preparation method and application |
| CN110606480A (en) * | 2018-06-16 | 2019-12-24 | 浙江晨阳新材料有限公司 | Nitrogen-doped porous graphene and preparation method thereof |
| CN110950325A (en) * | 2019-11-19 | 2020-04-03 | 珠海复旦创新研究院 | Porous multi-element doped graphene prepared by chemical method and preparation method thereof |
| CN111704123A (en) * | 2020-06-28 | 2020-09-25 | 河南大学 | Metal nitrogen-doped carbon material, and preparation method and application thereof |
| CN112827504A (en) * | 2020-12-30 | 2021-05-25 | 中国科学技术大学 | Method for preparing pyridine or pyrrole iron-nitrogen site catalyst, product and application thereof |
| CN113980427A (en) * | 2021-11-01 | 2022-01-28 | 陕西工业职业技术学院 | Epoxy resin-based biomass charcoal electromagnetic shielding composite material and preparation method thereof |
| CN115246641A (en) * | 2021-03-02 | 2022-10-28 | 青岛大学 | Self-luminous fluorescent material in visible light region and preparation method thereof |
| US20220376230A1 (en) * | 2021-05-10 | 2022-11-24 | Guangdong University Of Technology | Fe3C-DOPED GRADED POROUS CARBON POLYMER POTASSIUM ION ANODE MATERIAL, PREPARATION METHOD AND APPLICATION THEREOF |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014202749A1 (en) * | 2013-06-21 | 2014-12-24 | Technical University Of Denmark | Novel non-platinum metal catalyst material |
| CN104437278A (en) * | 2014-11-18 | 2015-03-25 | 复旦大学 | Heteroatom doped leaf-shaped carbon nanometer aerogel material and preparation method and application thereof |
| CN105107539A (en) * | 2015-08-26 | 2015-12-02 | 华南理工大学 | Graphene-iron-nitrogen codoped porous carbon composite catalyst for fuel cell and preparation method for graphene-iron-nitrogen codoped porous carbon composite catalyst |
-
2015
- 2015-12-31 CN CN201511015619.0A patent/CN105609793A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014202749A1 (en) * | 2013-06-21 | 2014-12-24 | Technical University Of Denmark | Novel non-platinum metal catalyst material |
| CN104437278A (en) * | 2014-11-18 | 2015-03-25 | 复旦大学 | Heteroatom doped leaf-shaped carbon nanometer aerogel material and preparation method and application thereof |
| CN105107539A (en) * | 2015-08-26 | 2015-12-02 | 华南理工大学 | Graphene-iron-nitrogen codoped porous carbon composite catalyst for fuel cell and preparation method for graphene-iron-nitrogen codoped porous carbon composite catalyst |
Non-Patent Citations (3)
| Title |
|---|
| LIANG CHEN等: "Three-dimensional nitrogen-doped graphene nanoribbons aerogel as a highly efficient catalyst for the oxygen reduction reaction", 《SMALL》 * |
| THANGAVELU PALANISELVAM等: "An efficient oxygen reduction electrocatalyst from graphene by simultaneously generating pores and nitrogen doped active sites", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| ZHEN-YU WU等: "Iron carbide nanoparticles encapsulated in mesoporous Fe-N-doped carbon nanofibers for efficient electrocatalysis", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106067546A (en) * | 2016-08-10 | 2016-11-02 | 上海交通大学 | Carbon/nano silicon carbide two iron composite material, combination electrode and preparation method and application |
| CN106532071B (en) * | 2016-12-01 | 2019-05-31 | 浙江师范大学 | A method of preparing N doped graphene package cementite elctro-catalyst |
| CN106532071A (en) * | 2016-12-01 | 2017-03-22 | 浙江师范大学 | Method for preparing N-doped graphene-coated ferroelectric carbide catalyst |
| CN107739074A (en) * | 2017-09-08 | 2018-02-27 | 南开大学 | A kind of high catalytic activity nitrogen-doped graphene composite cathode preparation method and degradable organic pollutant technology |
| CN107739074B (en) * | 2017-09-08 | 2021-07-09 | 南开大学 | Preparation method of nitrogen-doped graphene composite cathode with high catalytic activity and technology for degrading organic pollutants |
| CN108010748A (en) * | 2017-12-18 | 2018-05-08 | 上海交通大学 | The preparation method of the mesoporous polypyrrole/graphene composite material of two dimensional oxidation Fe2O3 doping |
| CN108264037A (en) * | 2018-02-06 | 2018-07-10 | 北京科技大学 | Three-dimensional porous nitrogen-doped graphene answers the preparation method of material and nitrogen-doped graphene |
| CN110273162B (en) * | 2018-03-15 | 2020-11-03 | 浙江大学 | Iron/cobalt/nickel-nitrogen coupled carbon-based composite material and application thereof |
| CN110273162A (en) * | 2018-03-15 | 2019-09-24 | 浙江大学 | A kind of iron/cobalt/nickel nitrogen coupling C-base composte material and its application |
| CN108428905A (en) * | 2018-04-04 | 2018-08-21 | 江苏新亿源环保科技有限公司 | A kind of preparation method of fuel cell electrode catalyst material |
| CN108767278A (en) * | 2018-06-11 | 2018-11-06 | 佛山腾鲤新能源科技有限公司 | A kind of fuel-cell catalyst |
| CN110606480A (en) * | 2018-06-16 | 2019-12-24 | 浙江晨阳新材料有限公司 | Nitrogen-doped porous graphene and preparation method thereof |
| CN109728260A (en) * | 2018-11-28 | 2019-05-07 | 广西大学 | The preparation method of the carbon-coated cementite combination electrode material of nitrogen sulfur doping |
| CN110155998A (en) * | 2019-05-13 | 2019-08-23 | 东南大学 | A kind of ribbon nitrogen-doped graphene and its preparation method and application |
| CN110155998B (en) * | 2019-05-13 | 2023-02-21 | 东南大学 | Strip-shaped nitrogen-doped graphene and preparation method and application thereof |
| CN110380067A (en) * | 2019-08-15 | 2019-10-25 | 中国科学技术大学 | A kind of fuel cell membrane electrode catalyst, preparation method and application |
| CN110950325A (en) * | 2019-11-19 | 2020-04-03 | 珠海复旦创新研究院 | Porous multi-element doped graphene prepared by chemical method and preparation method thereof |
| CN111704123A (en) * | 2020-06-28 | 2020-09-25 | 河南大学 | Metal nitrogen-doped carbon material, and preparation method and application thereof |
| CN111704123B (en) * | 2020-06-28 | 2021-12-14 | 河南大学 | Metal nitrogen-doped carbon material, and preparation method and application thereof |
| CN112827504A (en) * | 2020-12-30 | 2021-05-25 | 中国科学技术大学 | Method for preparing pyridine or pyrrole iron-nitrogen site catalyst, product and application thereof |
| CN115246641A (en) * | 2021-03-02 | 2022-10-28 | 青岛大学 | Self-luminous fluorescent material in visible light region and preparation method thereof |
| US20220376230A1 (en) * | 2021-05-10 | 2022-11-24 | Guangdong University Of Technology | Fe3C-DOPED GRADED POROUS CARBON POLYMER POTASSIUM ION ANODE MATERIAL, PREPARATION METHOD AND APPLICATION THEREOF |
| CN113980427A (en) * | 2021-11-01 | 2022-01-28 | 陕西工业职业技术学院 | Epoxy resin-based biomass charcoal electromagnetic shielding composite material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105609793A (en) | Iron-nitrogen-doped graphene porous material with dual-site catalytic oxygen reduction activity, and preparation method and application therefor | |
| Lyu et al. | Ultra-high surface area graphitic Fe-NC nanospheres with single-atom iron sites as highly efficient non-precious metal bifunctional catalysts towards oxygen redox reactions | |
| Li et al. | Synergistic effects between doped nitrogen and phosphorus in metal-free cathode for zinc-air battery from covalent organic frameworks coated CNT | |
| Shah et al. | Direct addition of sulfur and nitrogen functional groups to graphite felt electrodes for improving all-vanadium redox flow battery performance | |
| Wang et al. | Capacitive deionization using carbon derived from an array of zeolitic-imidazolate frameworks | |
| Zhang et al. | Rational surface tailoring oxygen functional groups on carbon spheres for capacitive mechanistic study | |
| Ni et al. | O-doping boosts the electrochemical oxygen reduction activity of a single Fe site in hydrophilic carbon with deep mesopores | |
| Wu et al. | Mesoporous carbon derived from pomelo peel as a high-performance electrode material for zinc-bromine flow batteries | |
| Yang et al. | Electrocatalytic activity of nitrogen-doped CNT graphite felt hybrid for all-vanadium redox flow batteries | |
| Wei et al. | Chemical crosslinking engineered nitrogen-doped carbon aerogels from polyaniline-boric acid-polyvinyl alcohol gels for high-performance electrochemical capacitors | |
| Ramírez-Pérez et al. | Effect of nitrogen-functional groups on the ORR activity of activated carbon fiber-polypyrrole-based electrodes | |
| El-Khodary et al. | Sonochemical assisted fabrication of 3D hierarchical porous carbon for high-performance symmetric supercapacitor | |
| Wang et al. | Plant polyphenols induced the synthesis of rich oxygen vacancies Co3O4/Co@ N-doped carbon hollow nanomaterials for electrochemical energy storage and conversion | |
| Zhang et al. | A pioneering melamine foam-based electrode via facile synthesis as prospective direction for vanadium redox flow batteries | |
| He et al. | Design and synthesis of N-doped carbon skeleton assembled by carbon nanotubes and graphene as a high-performance electrode material for supercapacitors | |
| Lobato-Peralta et al. | Polymer superabsorbent from disposable diaper as a sustainable precursor for the development of stable supercapacitor electrode | |
| Ye et al. | Co-loaded N-doped biochar as a high-performance oxygen reduction reaction electrocatalyst by combined pyrolysis of biomass | |
| Gang et al. | Surface redox pseudocapacitance boosting Fe/Fe3C nanoparticles-encapsulated N-doped graphene-like carbon for high-performance capacitive deionization | |
| Cheng et al. | Plasma-Assisted Synthesis of Defect-Rich O and N Codoped Carbon Nanofibers Loaded with Manganese Oxides as an Efficient Oxygen Reduction Electrocatalyst for Aluminum–Air Batteries | |
| CN105489397A (en) | Preparation method and application of chemically-modified carbon material/graphene/RuO2 ternary composite material | |
| Xu et al. | Trace iron-decorated nitrogen/sulfur co-doped hierarchically porous carbon for oxygen reduction and lithium–sulfur batteries | |
| Shao et al. | A N-doped Cobalt@ graphitized carbon material derived from ZIF-67 assisted polyvinylidene fluoride hollow fiber membrane for supercapacitors | |
| He et al. | Performance of nitrogen-containing macroporous carbon supported cobalt catalyst synthesized through in-situ construction of catalytic sites for oxygen reduction reaction | |
| Tiwari et al. | Synergistic combination of N/P dual-doped activated carbon with redox-active electrolyte for high performance supercapacitors | |
| Li et al. | Bimetallic salts template-assisted strategy towards the preparation of hierarchical porous polyimide-derived carbon electrode for supercapacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160525 |
|
| WD01 | Invention patent application deemed withdrawn after publication |