CN105449230A - LaCoO3/N-rGO compound and preparation method and application method therefor - Google Patents
LaCoO3/N-rGO compound and preparation method and application method therefor Download PDFInfo
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- CN105449230A CN105449230A CN201510760611.0A CN201510760611A CN105449230A CN 105449230 A CN105449230 A CN 105449230A CN 201510760611 A CN201510760611 A CN 201510760611A CN 105449230 A CN105449230 A CN 105449230A
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- 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
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- 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
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- 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 discloses an LaCoO3/N-reduced graphene oxide (rGO) compound and a preparation method and an application method therefor. The preparation method comprises the following steps: firstly preparing the LaCoO3 by a sol-gel method and preparing the graphene oxide (GO) by an improved Hummers method; and prepparing and obtaining the LaCoO3/N-rGO compound by a wet chemical method in the presence of ammonia water. The preparation method is simple and low in cost, and the industrial production can be achieved easily; the prepared LaCoO3/N-rGO compound is used as a dual-functional catalyst of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) for a rechargeable metal fuel cell; the prepared LaCoO3/N-rGO compound is high in activity and stability; and compared with commercial 20wt% of Pt/C, LaCoO3/rGO and LaCoO3, the LaCoO3/N-rGO compound provided by the invention is better in comprehensive performance and wide in the application prospects.
Description
Technical field
The present invention relates to the LaCoO of a kind of hydrogen reduction (ORR) and oxygen precipitation (OER) double-function catalyzing
3/ N-redox graphene (rGO) compound and methods for making and using same thereof, belong to electro-catalysis technical field.
Background technology
Along with human kind sustainable development is to continuous growth that is green, regenerative resource demand, countries in the world are found just urgently and are developed efficient and economic stored energy and conversion equipment.The features such as high theoretical energy density, environmental friendliness, safety can be possessed due to it by charge and discharge metal fuel battery, be described as " green energy resource geared to the 21st century ".
But, although can charge and discharge metal fuel battery technology receive much attention in recent years, but its practical application is except except the aeronautical field disregarding cost, can't reach the requirement of business promotion, its main cause will use the precious metals pt base of high cost and Ir sill respectively as itself ORR and OER catalyst.Therefore, the non-precious metal catalyst that exploitation is cheap becomes can the top priority of charge and discharge metal fuel battery widespread commercial.Realization can the integration of ORR and OER catalyst in charge and discharge metal fuel battery, and can greatly simplify can the preparation process of charge and discharge metal fuel battery, and its prospect is very tempting.In more than ten years in the past, some scientists are all over the world devoted to ORR and the OER bifunctional catalyst of developing low-cost, efficient and long stability.Regrettably, also there is no so far suitable can the bifunctional catalyst of practical application.Precious metals pt sill is still considered to the best bifunctional catalyst of current combination property.
Perovskite composite oxide biomolecule expressions is AMO
3(A represents rare earth atom, and M represents transition metal atoms), but generally all there is the oxygen lattice defect of room form in this based composite oxide, its accurate expression formula should be AMO
3-x(﹣ 0.5 ﹤ x ﹤ 0.2).The oxygen lattice defect formed usually can change kind and the quantity of Lattice Oxygen, contributes to accelerating oxygen migration, thus has higher ORR and OER catalytic activity.At present, for perovskite composite oxide, main research still concentrates in the exploitation to its ORR catalytic performance, rarely has report to the exploitation of its OER catalytic performance.As can charge and discharge metal fuel battery ORR and OER catalyst, perovskite composite oxide at present topmost two defects be low mass activity and conductivity.Reduce its physical size and be the effective way solving these two defects and improve its combination property with the material compound of bigger serface high conductivity.
In recent years, rGO, with its excellent conductivity, stability and thermal conductivity and high theoretical specific surface area, becomes a dazzling nova in field of new, carries out N doping vario-property can improve its Electronic Performance further to it.
Summary of the invention
The present invention is directed to single LaCoO in prior art
3low as ORR and OER catalyst activity, conductance is low and the defect of less stable, one of object is to provide the comprehensive catalytic performance of a kind of ORR and OER far above LaCoO
3/ rGO, LaCoO
3and close to the novel LaCoO of 20wt%Pt/C commercial catalyst
3/ N-rGO compound.
Second object of the present invention is to provide the comprehensive catalytic performance of a kind of ORR and OER far above LaCoO
3/ rGO, LaCoO
3and close to the novel LaCoO of 20wt%Pt/C commercial catalyst
3the low cost of/N-rGO compound, easy-operating preparation method.
3rd object of the present invention is to provide a kind of as can the novel LaCoO of charge and discharge metal fuel battery ORR and OER bifunctional catalyst
3the application of/N-rGO compound, in alkaline medium, comprehensive catalytic performance is far above LaCoO
3/ rGO, LaCoO
3and close to 20wt%Pt/C commercial catalyst.
A kind of LaCoO
3/ N-rGO compound, described compound is by Emission in Cubic LaCoO
3load is formed on the N of two dimension adulterates rGO; LaCoO in described compound
3, N and rGO the scope of mass percent be respectively 65% – 95%, 0.5% – 5% and 3% – 30%.
LaCoO in described compound
3, N and rGO mass percent scope be respectively preferably 80% – 90%, 1% – 3% and 8% – 18%.
A kind of LaCoO
3the preparation method of/N-rGO compound, described LaCoO
3/ N-rGO compound is with LaCoO
3be presoma with GO, in process prepared by solvent heat, under solvent heat condition, form nitrating type Graphene by adding ammoniacal liquor, and form LaCoO
3/ N-rGO compound.
LaCoO in described compound
3, N and rGO the scope of mass percent be respectively 65% – 95%, 0.5% – 5% and 3% – 30%.
LaCoO in described compound
3, N and rGO mass percent scope be respectively preferably 80% – 90%, 1% – 3% and 8% – 18%.
Specifically with LaCoO
3be presoma with GO suspension, ultrasonic disperse 10 – 60min, adds the ammoniacal liquor of 0.5 – 5mL, at 140 –, 220 DEG C of solvent thermal reaction 5 – 15h, through centrifugation, deionized water washing and freeze drying, obtains described LaCoO
3/ N-rGO compound.
Above-mentioned preparation method is preferably as follows mode:
Take 24.3mgLaCoO
3particle joins in 2mLGO alcohol suspension, add 60mL absolute ethyl alcohol simultaneously, at 80 DEG C, thermal agitation 5h is added after ultrasonic 30min under room temperature, be transferred in 80mL autoclave after being cooled to room temperature, and drip 2mL ammoniacal liquor, under 180 DEG C of conditions, solvent thermal reaction 10h, is cooled to room temperature, obtains LaCoO finally by centrifugal, deionized water washing, freeze drying
3/ N-rGO compound.
Above-mentioned LaCoO
3laCoO is prepared by sol-gel process in the preparation method of/N-rGO compound
3:
Take 0.01molLa (NO
3)
36H
2o, 0.01molCo (NO
3)
36H
2o and 0.02molEDTA is dissolved in 100mL deionized water, and adds 0.03mol citric acid, then by dripping NH
3h
2o solution modulation solution ph is 8, is constantly stirred until obtain ruddy gel by this solution in 80 DEG C of water-baths; This gel is calcined 1h in 280 DEG C of Muffle furnaces, at 800 DEG C, calcines 2h again after grinding, obtain LaCoO
3particle.
Above-mentioned LaCoO
3the Hummers method of improvement is adopted to prepare GO in the preparation method of/N-rGO compound:
Take 1g crystalline flake graphite and 20gNaCl mixes and grinds 15min, adopt deionized water to wash away NaCl by vacuum filtration mode; Wet graphite powder goes to after in 250mL round-bottomed flask after 60 DEG C of vacuumize 30min, adds 23mL98wt% concentrated sulfuric acid magnetic agitation 24h, then is heated to 35 DEG C and under agitation adds 0.5gNaNO
3, after 5min, suspension is transferred in ice bath, under agitation adds 3gKMnO very lentamente
4and hierarchy of control temperature is lower than 20 DEG C, then heat 120min under 35 DEG C with the condition stirred, be heated to 98 DEG C after slowly adding 46mL deionized water and stir 30min; Continue to stir 30min when this mixture is cooled to room temperature, then add 140mL deionized water and 10mL30wt%H
2o
2; Precipitate through centrifugal, wash 2 to 3 times with 5wt%HCl solution and deionized water respectively after be redispersed in ultrasonic 60min in 1500mL absolute ethyl alcohol, obtain brownish black GO suspension.
Above-mentioned LaCoO
3the application process of/N-rGO compound, described LaCoO
3/ N-rGO compound is as the hydrogen reduction of charge and discharge metal fuel battery and oxygen separating out bifunctional catalyst.
Preparation method of the present invention is simple, cost is low, is conducive to suitability for industrialized production; Prepared LaCoO
3/ N-rGO compound is as can charge and discharge metal fuel battery ORR and OER bifunctional catalyst, and active high, good stability, relative to commercial 20wt%Pt/C, LaCoO
3/ rGO and LaCoO
3, there is better combination property, show good application prospect.
Accompanying drawing explanation
Fig. 1 is LaCoO in embodiment 1, comparative example 2 and comparative example 3
3/ N-rGO, LaCoO
3/ rGO and LaCoO
3xRD figure, show the LaCoO all containing well-crystallized in three kinds of materials
3, do not detect that the characteristic peak of rGO is because its peak intensity is little and content is lower;
Fig. 2 is LaCoO in embodiment 1
3the TEM figure of/N-rGO, shows the LaCoO of about 20nm
3be dispersed in uniform particles on the rGO lamella of two dimension;
Fig. 3 (a) is LaCoO in embodiment 1
3in/N-rGO, the XPS figure of C element, shows LaCoO
3in/N-rGO, C element exists with C=C, C-O and O=C-O form; Fig. 3 (b) is LaCoO in embodiment 1
3in/N-rGO, the XPS figure of N element, shows that N is successfully doped in rGO, and exists with pyrroles type N and pyridine type N form;
Fig. 4 (a) is embodiment 1, LaCoO in comparative example 1, comparative example 2 and comparative example 3
3/ N-rGO, 20wt%Pt/C, LaCoO
3/ rGO and LaCoO
3linear sweep voltammetry figure, rotating speed is 1600rpm, and sweep speed is 10mV/s, and scanning voltage scope is 0.2V Zhi – 0.8V (vs.Hg/HgO); Fig. 4 (b) is LaCoO in embodiment 1 and comparative example 1
3the chronoamperogram of/N-rGO and 20wt%Pt/C, rotating speed is 400rpm;
Fig. 5 (a) is embodiment 1, LaCoO in comparative example 1, comparative example 2 and comparative example 3
3/ N-rGO, 20wt%Pt/C, LaCoO
3/ rGO and LaCoO
3linear sweep voltammetry figure, rotating speed is 400rpm, and sweep speed is 100mV/s, and scanning voltage scope is 0.2V to 1.0V (vs.Hg/HgO); Fig. 5 (b) is embodiment 1, LaCoO in comparative example 1 and comparative example 2
3/ N-rGO, 20wt%Pt/C and LaCoO
3the linear sweep voltammetry figure of the 1st time of/rGO and the 500th time, rotating speed is 400rpm.
Embodiment
Describe the present invention in more detail by embodiment below, but do not limit the scope of the invention.
Embodiment 1
LaCoO
3the preparation of/N-rGO:
First LaCoO is prepared by sol-gel process
3.Take 0.01molLa (NO
3)
36H
2o, 0.01molCo (NO
3)
36H
2o and 0.02molEDTA is dissolved in 100mL deionized water, and adds 0.03mol citric acid.Then by dripping NH
3h
2o solution modulation solution ph is 8, is constantly stirred until obtain ruddy gel by this solution in 80 DEG C of water-baths.This gel is calcined 1h in 280 DEG C of Muffle furnaces, at 800 DEG C, calcines 2h again after grinding, obtain LaCoO
3particle.
The Hummers method of modification is adopted to prepare GO.Take 1g crystalline flake graphite and 20gNaCl mixes and grinds 15min, adopt deionized water to wash away NaCl by vacuum filtration mode.Wet graphite powder goes to after in 250mL round-bottomed flask after 60 DEG C of vacuumize 30min, adds 23mL98wt% concentrated sulfuric acid magnetic agitation 24h, then is heated to 35 DEG C and under agitation adds 0.5gNaNO
3.After 5min, suspension is transferred in ice bath, under agitation adds 3gKMnO very lentamente
4and hierarchy of control temperature is lower than 20 DEG C, then heat 120min under 35 DEG C with the condition stirred, be heated to 98 DEG C after slowly adding 46mL deionized water and stir 30min.Continue to stir 30min when this mixture is cooled to room temperature, then add 140mL deionized water and 10mL30wt%H
2o
2.Precipitate through centrifugal, wash 2 to 3 times with 5wt%HCl solution and deionized water respectively after be redispersed in ultrasonic 60min in 1500mL absolute ethyl alcohol, obtain brownish black GO suspension.
Take 24.3mgLaCoO
3particle joins in 2mLGO alcohol suspension, adds 60mL absolute ethyl alcohol simultaneously.At 80 DEG C, add thermal agitation 5h after ultrasonic 30min under room temperature, be transferred to after being cooled to room temperature in 80mL autoclave, and drip 2mL ammoniacal liquor, solvent thermal reaction 10h under 180 DEG C of conditions.Be cooled to room temperature, obtain LaCoO finally by centrifugal, deionized water washing, freeze drying
3/ N-rGO compound.
Employing X-ray diffractometer (XRD, Rigaku-D/Max2550, Cu-K α, λ=
, 40kV, 300mA) and material phase analysis is carried out to product; Pattern is observed by transmission electron microscope (TEM, JEOL-2010,200kV); Adopt x-ray photoelectron spectroscopy (XPS, ESCALAB250Xi, Al-K α) to determine the element composition of sample and the chemical energy state of element, use XPSPeak4.1 software to carry out swarming and data processing.
Stand in three-electrode system the limiting current density of testing sample by rotating disk electrode (r.d.e) (RDE) through CHI760D electrochemical operation and evaluate itself ORR and OER activity.The preparation of work electrode: take 4mg sample dispersion in the mixed liquor of 1.92mL deionized water/ethanol (2:1V/V) and 0.08mLNafion solution (5wt%), ultrasonic 30min, liquid-transfering gun draws 5 μ L hanging drops and is added on the glass-carbon electrode of diameter 5mm, to be measured after 60 DEG C of dryings.In test process, be platinum electrode to electrode, reference electrode is Hg/HgO electrode.When the ORR of assess sample is active, electrolyte is the 0.1MKOH solution that oxygen is saturated, and rotating speed is 1600rpm, and sweep speed is 10mV/s, and scanning voltage scope is 0.2V Zhi – 0.8V (vs.Hg/HgO); When the OER of assess sample is active, electrolyte is 1MKOH solution, and rotating speed is 400rpm, and sweep speed is 100mV/s, and scanning voltage scope is 0.2V to 1.0V (vs.Hg/HgO).By the stability of chronoamperometry comparative sample ORR catalysis, test voltage Wei – 0.2V (vs.Hg/HgO), rotating speed is 400rpm, and electrolyte is the 6MKOH solution that oxygen is saturated, the test that other conditions are evaluated with above ORR current density.By test limits current density after continuous sweep, the stability of comparative sample OER catalysis.
LaCoO
3/ N-rGO compound is-3.76mA/cm as the limiting current density of ORR catalyst
2, the limiting current density as OER catalyst is 73.9mA/cm
2.In evaluating when galvanometer, after 6000s operates continuously, electric current conservation rate is 82.4%.In the evaluation of OER catalytic stability, through 500 continuous sweep, limiting current density conservation rate is 83.3%.
Comparative example 1
With commercial 20wt%Pt/C for ORR and OER bifunctional catalyst.
The evaluation method of catalytic performance is with embodiment 1.
20wt%Pt/C is-3.88mA/cm as the limiting current density of ORR catalyst
2, the limiting current density as OER catalyst is 14.3mA/cm
2.In chrono-amperometric is evaluated, after 6000s operates continuously, electric current conservation rate is 60.1%.In the evaluation of OER catalytic stability, through 500 continuous sweep, limiting current density conservation rate is 10.5%.
Comparative example 2
By the method for embodiment 1, before solvent heat, do not add 2mL ammoniacal liquor, preparation LaCoO
3/ rGO compound.
The evaluation method of catalytic performance is with embodiment 1.
LaCoO
3/ rGO is-2.01mA/cm as the limiting current density of ORR catalyst
2, the limiting current density as OER catalyst is 31.8mA/cm
2.In the evaluation of OER catalytic stability, through 500 continuous sweep, limiting current density conservation rate is 58.5%.
Comparative example 3
LaCoO is prepared by embodiment 1
3method prepare LaCoO
3.
The evaluation method of catalytic performance is with embodiment 1.
LaCoO
3limiting current density as ORR catalyst is about-1.52mA/cm
2, the limiting current density as OER catalyst is 4.1mA/cm.
Claims (10)
1. a LaCoO
3/ N-rGO compound, is characterized in that, described compound is by Emission in Cubic LaCoO
3load is formed on the N of two dimension adulterates rGO; LaCoO in described compound
3, N and rGO the scope of mass percent be respectively 65% – 95%, 0.5% – 5% and 3% – 30%.
2. LaCoO according to claim 1
3/ N-rGO compound, is characterized in that, LaCoO in described compound
3, N and rGO the scope of mass percent be respectively 80% – 90%, 1% – 3% and 8% – 18%.
3. a LaCoO
3the preparation method of/N-rGO compound, is characterized in that, described LaCoO
3/ N-rGO compound is with LaCoO
3be presoma with GO, in process prepared by solvent heat, under solvent heat condition, form nitrating type Graphene by adding ammoniacal liquor, and form LaCoO
3/ N-rGO compound.
4. LaCoO according to claim 3
3the preparation method of/N-rGO compound, is characterized in that, LaCoO in described compound
3, N and rGO the scope of mass percent be respectively 65% – 95%, 0.5% – 5% and 3% – 30%.
5. LaCoO according to claim 4
3the preparation method of/N-rGO compound, is characterized in that, LaCoO in described compound
3, N and rGO the scope of mass percent be respectively 80% – 90%, 1% – 3% and 8% – 18%.
6. the LaCoO according to any one of claim 3-5
3the preparation method of/N-rGO compound, is characterized in that, with LaCoO
3be presoma with GO suspension, ultrasonic disperse 10 – 60min, adds the ammoniacal liquor of 0.5 – 5mL, at 140 –, 220 DEG C of solvent thermal reaction 5 – 15h, through centrifugation, deionized water washing and freeze drying, obtains described LaCoO
3/ N-rGO compound.
7. LaCoO according to claim 6
3the preparation method of/N-rGO compound, is characterized in that,
Take 24.3mgLaCoO
3particle joins in 2mLGO alcohol suspension, add 60mL absolute ethyl alcohol simultaneously, at 80 DEG C, thermal agitation 5h is added after ultrasonic 30min under room temperature, be transferred in 80mL autoclave after being cooled to room temperature, and drip 2mL ammoniacal liquor, under 180 DEG C of conditions, solvent thermal reaction 10h, is cooled to room temperature, obtains LaCoO finally by centrifugal, deionized water washing, freeze drying
3/ N-rGO compound.
8. the LaCoO according to any one of claim 3-5
3the preparation method of/N-rGO compound, is characterized in that,
LaCoO is prepared by sol-gel process
3:
Take 0.01molLa (NO
3)
36H
2o, 0.01molCo (NO
3)
36H
2o and 0.02molEDTA is dissolved in 100mL deionized water, and adds 0.03mol citric acid, then by dripping NH
3h
2o solution modulation solution ph is 8, is constantly stirred until obtain ruddy gel by this solution in 80 DEG C of water-baths; This gel is calcined 1h in 280 DEG C of Muffle furnaces, at 800 DEG C, calcines 2h again after grinding, obtain LaCoO
3particle.
9. the LaCoO according to any one of claim 3-5
3the preparation method of/N-rGO compound, is characterized in that,
The Hummers method improved is adopted to prepare GO:
Take 1g crystalline flake graphite and 20gNaCl mixes and grinds 15min, adopt deionized water to wash away NaCl by vacuum filtration mode; Wet graphite powder goes to after in 250mL round-bottomed flask after 60 DEG C of vacuumize 30min, adds 23mL98wt% concentrated sulfuric acid magnetic agitation 24h, then is heated to 35 DEG C and under agitation adds 0.5gNaNO
3, after 5min, suspension is transferred in ice bath, under agitation adds 3gKMnO very lentamente
4and hierarchy of control temperature is lower than 20 DEG C, then heat 120min under 35 DEG C with the condition stirred, be heated to 98 DEG C after slowly adding 46mL deionized water and stir 30min; Continue to stir 30min when this mixture is cooled to room temperature, then add 140mL deionized water and 10mL30wt%H
2o
2; Precipitate through centrifugal, wash 2 to 3 times with 5wt%HCl solution and deionized water respectively after be redispersed in ultrasonic 60min in 1500mL absolute ethyl alcohol, obtain brownish black GO suspension.
10. the LaCoO described in a claim 1 or 2
3the application process of/N-rGO compound, is characterized in that, described LaCoO
3/ N-rGO compound is as the hydrogen reduction of charge and discharge metal fuel battery and oxygen separating out bifunctional catalyst.
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| CN105692720A (en) * | 2016-04-20 | 2016-06-22 | 西安建筑科技大学 | Preparation method of spinous yttrium cobaltate microballs |
| CN105870467A (en) * | 2016-05-17 | 2016-08-17 | 中南大学 | Oxygen reduction La(OH)3/reduced graphene oxide composite catalyst as well as preparation method and application thereof |
| CN107086130A (en) * | 2017-04-21 | 2017-08-22 | 南京信息工程大学 | A kind of graphene/DyCoO3Composite and preparation method and application |
| CN107376928A (en) * | 2017-08-04 | 2017-11-24 | 南京邮电大学 | A kind of one-step synthesis method α Fe2O3The method of/Bi compounds |
| CN109126804A (en) * | 2018-08-24 | 2019-01-04 | 广东工业大学 | A kind of boron doping LaCoO3Bifunctional catalyst and its preparation method and application |
| CN109351357A (en) * | 2018-10-16 | 2019-02-19 | 华中科技大学 | A kind of effective universal method for promoting perovskite catalyst catalytic performance |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105692720A (en) * | 2016-04-20 | 2016-06-22 | 西安建筑科技大学 | Preparation method of spinous yttrium cobaltate microballs |
| CN105870467A (en) * | 2016-05-17 | 2016-08-17 | 中南大学 | Oxygen reduction La(OH)3/reduced graphene oxide composite catalyst as well as preparation method and application thereof |
| CN105870467B (en) * | 2016-05-17 | 2019-01-29 | 中南大学 | A kind of hydrogen reduction La (OH)3/ redox graphene composite catalyst and its preparation method and application |
| CN107086130A (en) * | 2017-04-21 | 2017-08-22 | 南京信息工程大学 | A kind of graphene/DyCoO3Composite and preparation method and application |
| CN107376928A (en) * | 2017-08-04 | 2017-11-24 | 南京邮电大学 | A kind of one-step synthesis method α Fe2O3The method of/Bi compounds |
| CN109126804A (en) * | 2018-08-24 | 2019-01-04 | 广东工业大学 | A kind of boron doping LaCoO3Bifunctional catalyst and its preparation method and application |
| CN109351357A (en) * | 2018-10-16 | 2019-02-19 | 华中科技大学 | A kind of effective universal method for promoting perovskite catalyst catalytic performance |
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|---|---|
| CN105449230B (en) | 2018-07-17 |
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