CN109449451A - One kind is by derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs and preparation method thereof - Google Patents
One kind is by derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs and preparation method thereof Download PDFInfo
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- CN109449451A CN109449451A CN201811434888.4A CN201811434888A CN109449451A CN 109449451 A CN109449451 A CN 109449451A CN 201811434888 A CN201811434888 A CN 201811434888A CN 109449451 A CN109449451 A CN 109449451A
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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
- H01M4/8605—Porous electrodes
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
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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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- 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
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- H—ELECTRICITY
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- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to one kind by derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs and preparation method thereof, comprising the following steps: is template, 2-methylimidazole and Zn (NO using PS bead3)2·6H2O is MOFs ligand, uses cheap Fe (NO3)3·9H2O is source metal, and the Fe/N/C hollow structure catalyst for having higher catalytic activity to oxygen reduction reaction is made using high-temperature calcination.Compared with prior art, the present invention has higher stability and methanol tolerant performance；Moreover, low in raw material price and abundance, preparation process is simple, is conducive to large-scale production, practical value with higher.
Description
Technical field
The present invention relates to a kind of preparation methods of catalyst, more particularly, to one kind by the derivative hollow Fe/N/C fuel of MOFs
Battery oxygen reduction catalyst and preparation method thereof.
Background technique
As human society continues to develop, energy crisis is shown especially gradually, and development cleaning, efficient energy industry are compeled in eyebrow
Eyelash.Low-temperature fuel cell is a kind of energy conversion device that the chemical energy of fuel is converted directly into electric energy, it has fuel
Source is abundant, it is cheap, carry and storage safe ready, the advantages that energy density is high, it is considered to be ideal civil and military
Portable power and traffic equipment power supply.However, fuel cell, which will really move towards market, is still faced with many problems: catalyst at
This height, utilization rate are low, and methanol crossover makes catalyst poisoning, water management difficulty etc..Wherein, catalyst material is the core of fuel cell
The heart, therefore, the elctro-catalyst for researching and developing high efficiency low cost become the key to solve the problem place.
Currently, catalyst used in low-temperature fuel cell, the noble metal catalyst mainly based on platinum.Platinum is proved to
The optimum catalyst active component for low-temperature fuel cell, but use platinum as fuel-cell catalyst there is also following tight
Weight problem: (1) platinum scarcity of resources；(2) expensive；(3) poison resistance is poor.In order to reduce the production cost of fuel cell, increase
By force to the anti-poisoning capability of by-product, main task is to develop the non-precious metal catalyst with greater activity at this stage, should
Type catalyst usually have preferable alcohol resistance and excellent stability and rich reserves, it is cheap and easy to get be that ideal Pt base is urged
The alternative materials of agent.MOFs has very high surface area, nano-porous structure, adjustable aperture and catalyst form, structure
Carbon rich in unit, good transition metal ions center and organic ligand and be listed in most promising one kind ORR
Catalyst.Also, hollow nanostructured material becomes a hot spot of current research as a kind of new structural material, with reality
Heart block materials are compared, and nano hollow structure material has the characteristics such as density is low, permeability is good, while combining nano material
Dimensional effect, quantum effect, skin effect and quantum tunneling effect, impart its more unique performance.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind to be derived by MOFs
Empty Fe/N/C fuel cell oxygen reduction catalyst and preparation method thereof.
The purpose of the invention is to overcome, traditional Pt/C catalyst noble metal dosage is big, catalyst utilization is low, urges
Change the low technical problem of activity, and provides a kind of by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs and its preparation
Method.
The purpose of the present invention can be achieved through the following technical solutions:
The present invention is template, 2-methylimidazole and Zn (NO using PS bead3)2·6H2O is MOFs ligand, low using price
Honest and clean Fe (NO3)3·9H2O is source metal, and the Fe/N/ for having higher catalytic activity to oxygen reduction reaction is made using high-temperature calcination
C hollow structure catalyst.
A kind of preparation method by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs, comprising the following steps:
(1) it prepares PS bead template: taking styrene, acrylic acid, methyl methacrylate, ammonium hydrogen carbonate is added, will mix
Object is dissolved in first time heat temperature raising in ultrapure water, is then added ammonium persulfate, second of heat temperature raising, cooling after reaction,
PS bead is obtained after centrifugation, washing, drying；
(2) it prepares Fe/N/C catalyst precarsor: zinc nitrate, ferric nitrate and methanol solution being mixed into ultrasonic agitation and obtain solution
A PS bead template obtained in 2-methylimidazole, step (1) is added molten with the same amount of methanol of methanol solution of solution A
Liquid, mixing ultrasonic agitation obtain solution B, solution A are slowly at the uniform velocity poured into solution B, is stirred to react, cooling after reaction,
Centrifugation, washing, obtain Fe/N/C catalyst precarsor after dry；
(3) hollow Fe/N/C catalyst is prepared: by the Fe/N/C catalyst precarsor being prepared in step (2) in indifferent gas
Under body protection, high-temperature calcination is carried out, hollow Fe/N/C catalyst (hollow Fe/N/C) is obtained.
Preferably, in step (1): styrene, acrylic acid, methyl methacrylate volume ratio be (20-25): (1-
1.5):(0.9-1)。
Preferably, in step (1): the ratio between additional amount of ammonium hydrogen carbonate and styrene is (0.4-0.5) g:(20-25) ml,
The volume ratio of ultrapure water and styrene is 100:(20-25), the ratio between additional amount of ammonium persulfate and styrene is (0.5-0.6) g:
(20-25)ml。
Preferably, in step (1): the temperature of first time heat temperature raising is 50-70 DEG C, and the temperature of second of heat temperature raising is
80-100 DEG C, reaction time 6-24h.
Preferably, in step (1): the revolving speed of centrifugation is 8000rpm, and washing is multiple using milli-Q water, dry to use
Freeze-drying.
Step (1) is during synthesizing PS bead template, if temperature overruns, the PS bead size synthesized is not
Uniformly.If the additive amount of reactant overruns, PS bead is easy to happen reunion, and subsequent MOFs is caused not coat uniformly,
And influence catalyst performance.
Preferably, in step (2): the ratio between additive amount of zinc nitrate, ferric nitrate, 2-methylimidazole and PS bead is 1mol:
(0.025-0.25)mol:(4-16)mol:(50-500)mg.If Zn is excessive relative to the content of Fe, the Zn in calcination process
Volatilization is gone out, and Fe can not fully take up the vacancy of Zn, causes defect excessive, influences the hydrogen reduction performance of catalyst.If 2- first
The amount of base imidazoles is excessive, and the MOFs of formation is oversized, and negligible amounts are wrapped up outside PS, and active site is few, influences catalyst performance
Energy；The amount of 2-methylimidazole is very few, and the MOFs of formation is undersized, is easy to reunite, active site can not all expose, thus shadow
Ring performance.The additional amount of PS bead template is very few, and more MOFs can not be wrapped on PS bead, and the addition of PS bead template
Amount is excessive, then does not have MOFs on many PS beads.
Preferably, in step (2): it is 100-150ml that the amount of methanol, which is added, in every molar nitric acid zinc in solution A.Methanol is added
Amount it is bigger, the size of MOFs is smaller, when be added it is excessive when, MOFs can reunite.
Preferably, in step (2): ultrasonic 10min stirs 10min, and reaction temperature is 40-60 DEG C, reaction time 12-
48h.MOFs structure can not well, be uniformly wrapped on PS bead when the temperature is low, and the lower package effect of temperature is more
Difference；If temperature is excessively high, more than the boiling point of methanol solution, it is unfavorable for the progress of reaction.
Preferably, in step (2): the revolving speed of centrifugation is 8000rpm, and washing uses a large amount of ethanol washings for several times.
Preferably, in step (2): using vacuum drying, the dry 12h at 60 DEG C.
Preferably, in step (3): calcination temperature is 910-1000 DEG C, maintains 2-6h, heating rate is 1-5 DEG C/min, lazy
Property gas be N2Or Ar.The boiling point of Zn is 907 DEG C, and when being lower than this temperature, Zn can not be evaporated, and Fe cannot occupy Zn's
Site can not generate more FeNx active site, and temperature is lower, and degree of graphitization is bad, and electric conductivity is bad, causes to urge
The limiting current density of agent is smaller；Temperature is higher than this range, and in calcination process, catalyst can collapse, and lead to one
A little FeNx active sites can not be exposed to surface, and influence performance.
The present invention is template, 2-methylimidazole and Zn (NO using PS bead3)2·6H2O is MOFs ligand, low using price
Honest and clean Fe (NO3)3·9H2O is source metal, and the Fe/N/ for having higher catalytic activity to oxygen reduction reaction is made using high-temperature calcination
C hollow structure catalyst.Compared with common Pt base catalyst, ORR performance and business 20wt.%Pt/C in alkaline medium
Catalytic phase is worked as, and has higher stability and methanol tolerant performance；In addition, low in raw material price and abundance, preparation process letter
It is single, be conducive to large-scale production, practical value with higher.
Compared with prior art, beneficial effects of the present invention:
1, the hollow Fe/N/C catalyst that the present invention is prepared, can be used as the Proton Exchange Membrane Fuel Cells haveing excellent performance
Cathod catalyst has higher catalytic activity and good stability；
2, compared with common Pt base catalyst, ORR performance and business 20wt.%Pt/C catalytic phase in alkaline medium
When with higher stability and methanol tolerant performance；
3, preparation method low in raw material price of the invention and abundance, preparation process is simple, is conducive to scale metaplasia
It produces, practical value with higher.
Detailed description of the invention
Fig. 1 is the transmission electron microscope picture of the hollow Fe/N/C catalyst of embodiment 1；
The hollow Fe/N/C catalyst and commercial catalysts JM 20wt.%Pt/C that Fig. 2 is embodiment 1 are in O2Saturation
Linear Circulation volt-ampere test chart when revolving speed is 1600rpm in 0.1mol/L KOH solution；
The hollow Fe/N/C catalyst and commercial catalysts JM 20wt.%Pt/C that Fig. 3 is embodiment 1 are in O2Saturation
The chronoamperogram of 10h in 0.1mol/L KOH solution.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
A kind of preparation method by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs, the specific steps are as follows:
(1) preparation of PS bead template
21ml styrene, 1.1ml acrylic acid, 0.92ml methyl methacrylate are measured, and weighs 0.49g ammonium hydrogen carbonate and adds
Enter wherein, mixture is dissolved in 100ml ultrapure water (H2O in), 70 DEG C are warming up to, 0.53g ammonium persulfate is added, is warming up to 80
DEG C, 12h is stirred, after the liquid in flask is cooling, 8000rpm centrifuge separation, then for several times with a large amount of milli-Q waters, freezing
It is spare after drying process.
(2) preparation of Fe/N/C catalyst precarsor
594.98mg zinc nitrate, 20.20mg ferric nitrate and 691.28mg 2-methylimidazole are weighed, 200mg step is weighed
(1) product in.By zinc nitrate, ferric nitrate is placed in a three neck round bottom flask and (is denoted as bottle 1), 2-methylimidazole and PS small ball mould
Plate is placed in another three neck round bottom flask and (is denoted as bottle 2), and the methanol solution of 100ml is added into two round-bottomed flasks, super
Sound 10min stirs 10min, then slowly at the uniform velocity pours into solution in bottle 1 in bottle 2, is warming up to 60 DEG C, stirs for 24 hours, to flask
In liquid it is cooling after, 8000rpm centrifuge separation, then for several times with a large amount of ethanol washings, in a vacuum drying oven 60 DEG C later
Dry 12h.
(3) preparation (hollow Fe/N/C) of hollow Fe/N/C catalyst
Sample grinding after drying is placed in tube furnace, under inert gas shielding, 950 DEG C of temperature lower calcination steps
(2) gained catalyst precarsor in, keeps 2h, and the heating rate for being warming up to calcination temperature from initial temperature is 2 DEG C/min, described lazy
Property gas be N2。
Fig. 1 is the transmission electron microscope picture for the hollow Fe/N/C catalyst being prepared.In figure, it will be seen that embodiment 1
Sample obtained is uniform hollow spheres, and the thickness of ball about 20nm, this structure specific surface area is larger, can increase
Active site improves catalytic activity.
Fig. 2 is the hollow Fe/N/C catalyst being prepared and commercial catalysts JM 20%Pt/C in O2Saturation
Linear Circulation volt-ampere test chart when revolving speed is 1600rpm in 0.1mol/L KOH solution.In test chart, can significantly it find out,
Between 0.8-0.9V, the scanning curve of hollow Fe/N/C catalyst and business Pt/C catalyst is almost overlapped, half wave potential point
Not Wei 0.844V and 0.842V, illustrate preparation hollow Fe/N/C catalyst towards oxygen reduction reaction have higher catalytic activity, can
To match in excellence or beauty with commercialized.
Fig. 3 is the hollow Fe/N/C catalyst being prepared and commercial catalysts JM 20%Pt/C in O2Saturation
The chronoamperogram of 10h in 0.1mol/L KOH solution.As shown in figure, with the passage of the time of test, hollow Fe/N/C with
The stability of business JM 20wt.%Pt/C catalyst gradually decreases.Generally speaking, the Opposed Current of hollow Fe/N/C catalyst
Fall off rate is slower than business JM 20wt.%Pt/C, and after 10h, hollow Fe/N/C catalyst Opposed Current number is 94.5%,
Business JM 20wt.%Pt/C is 67.4%, therefore the stability of hollow Fe/N/C catalyst under the above conditions is significantly better than quotient
Industry JM 20wt.%Pt/C.
Embodiment 2
A kind of preparation method by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs, the specific steps are as follows:
(1) preparation of PS bead template
20ml styrene, 1ml acrylic acid, 0.9ml methyl methacrylate are measured, and weighs 0.4g ammonium hydrogen carbonate and it is added
In, mixture is dissolved in 100ml ultrapure water (H2O in), 50 DEG C are warming up to, 0.5g ammonium persulfate is added, is warming up to 90 DEG C, stirring
6h, after the liquid in flask is cooling, 8000rpm centrifuge separation, then for several times with a large amount of milli-Q waters, freeze-drying process
It is spare afterwards.
(2) preparation of Fe/N/C catalyst precarsor
297.49mg zinc nitrate, 40.40mg ferric nitrate and 328.4mg 2-methylimidazole are weighed, 50mg step (1) is weighed
Middle product.By zinc nitrate, ferric nitrate is placed in a three neck round bottom flask and (is denoted as bottle 1), 2-methylimidazole and PS bead template
It is placed in another three neck round bottom flask and (is denoted as bottle 2), the methanol solution of 130ml, ultrasound are added into two round-bottomed flasks
10min stirs 10min, then slowly at the uniform velocity pours into bottle 2 solution in bottle 1,12h is stirred to react at 40 DEG C, in flask
After liquid is cooling, 8000rpm centrifuge separation, then for several times with a large amount of ethanol washings, 60 DEG C of dryings in a vacuum drying oven later
12h。
(3) preparation of hollow Fe/N/C catalyst
Sample grinding after drying is placed in tube furnace, under inert gas shielding, 910 DEG C of temperature lower calcination steps
(2) gained catalyst precarsor in, keeps 6h, and the heating rate for being warming up to calcination temperature from initial temperature is 1 DEG C/min, described lazy
Property gas be Ar.
Embodiment 3
A kind of preparation method by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs, the specific steps are as follows:
(1) preparation of PS bead template
25ml styrene, 1.5ml acrylic acid, 1ml methyl methacrylate are measured, and weighs 0.5g ammonium hydrogen carbonate and it is added
In, mixture is dissolved in 100ml ultrapure water (H2O in), 60 DEG C are warming up to, 0.6g ammonium persulfate is added, is warming up to 100 DEG C, stirs
It mixes for 24 hours, after the liquid in flask is cooling, 8000rpm centrifuge separation, then for several times with a large amount of milli-Q waters, freeze-drying
It is spare after processing.
(2) preparation of Fe/N/C catalyst precarsor
297.49mg zinc nitrate, 101.00mg ferric nitrate and 1313.6mg 2-methylimidazole are weighed, 500mg step is weighed
(1) product in.By zinc nitrate, ferric nitrate is placed in a three neck round bottom flask and (is denoted as bottle 1), 2-methylimidazole and PS small ball mould
Plate is placed in another three neck round bottom flask and (is denoted as bottle 2), and the methanol solution of 150ml is added into two round-bottomed flasks, super
Sound 10min stirs 10min, then slowly at the uniform velocity pours into solution in bottle 1 in bottle 2, is warming up to 50 DEG C, 48h is stirred, to flask
In liquid it is cooling after, 8000rpm centrifuge separation, then for several times with a large amount of ethanol washings, in a vacuum drying oven 60 DEG C later
Dry 12h.
(3) preparation of hollow Fe/N/C catalyst
Sample grinding after drying is placed in tube furnace, under inert gas shielding, 1000 DEG C of temperature lower calcination steps
(2) gained catalyst precarsor in, keeps 4h, and the heating rate for being warming up to calcination temperature from initial temperature is 5 DEG C/min, described lazy
Property gas be N2。
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs, which is characterized in that including
Following steps:
(1) it prepares PS bead template: taking styrene, acrylic acid, methyl methacrylate, ammonium hydrogen carbonate is added, mixture is molten
The first time heat temperature raising in ultrapure water, is then added ammonium persulfate, second of heat temperature raising, it is cooling after reaction, be centrifuged,
PS bead is obtained after washing, drying；
(2) it prepares Fe/N/C catalyst precarsor: zinc nitrate, ferric nitrate and methanol solution being mixed into ultrasonic agitation and obtain solution A, it will
The same amount of methanol solution of methanol solution with solution A is added in PS bead template obtained in 2-methylimidazole, step (1), mixes
It closes ultrasonic agitation and obtains solution B, solution A is slowly at the uniform velocity poured into solution B, is stirred to react, cooling after reaction, centrifugation,
Washing obtains Fe/N/C catalyst precarsor after dry；
(3) it prepares hollow Fe/N/C catalyst: the Fe/N/C catalyst precarsor being prepared in step (2) is protected in inert gas
Under shield, high-temperature calcination is carried out, hollow Fe/N/C catalyst is obtained.
2. a kind of preparation side by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs according to claim 1
Method, which is characterized in that in step (1): styrene, acrylic acid, methyl methacrylate volume ratio be (20-25): (1-
1.5):(0.9-1)。
3. a kind of preparation side by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs according to claim 1
Method, which is characterized in that in step (1): the ratio between additional amount of ammonium hydrogen carbonate and styrene is (0.4-0.5) g:(20-25) ml, surpass
The volume ratio of pure water and styrene is 100:(20-25), the ratio between additional amount of ammonium persulfate and styrene is (0.5-0.6) g:
(20-25)ml。
4. a kind of preparation side by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs according to claim 1
Method, which is characterized in that in step (1): the temperature of first time heat temperature raising is 50-70 DEG C, and the temperature of second of heat temperature raising is
80-100 DEG C, reaction time 6-24h.
5. a kind of preparation side by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs according to claim 1
Method, which is characterized in that in step (2): the ratio between additional amount of zinc nitrate, ferric nitrate, 2-methylimidazole and PS bead is 1mol:
(0.025-0.25)mol:(4-16)mol:(50-500)mg。
6. a kind of preparation side by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs according to claim 1
Method, which is characterized in that in step (2): it is 100-150ml that the amount of methanol, which is added, in every molar nitric acid zinc in solution A.
7. a kind of preparation side by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs according to claim 1
Method, which is characterized in that in step (2): ultrasonic 10min, reaction temperature are 40-60 DEG C, reaction time 12-48h.
8. a kind of preparation side by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs according to claim 1
Method, which is characterized in that in step (2): using vacuum drying, the dry 12h at 60 DEG C.
9. a kind of preparation side by the derivative hollow Fe/N/C fuel cell oxygen reduction catalyst of MOFs according to claim 1
Method, which is characterized in that in step (3): calcination temperature is 910-1000 DEG C, maintains 2-6h, and heating rate is 1-5 DEG C/min.
10. being prepared using any one of the claim 1-9 preparation method electric by the derivative hollow Fe/N/C fuel of MOFs
Pond oxygen reduction catalyst.
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| CN110339851A (en) * | 2019-07-15 | 2019-10-18 | 浙江师范大学 | The catalyst and preparation method thereof of preparation 2,3,5-trimethylhydroquinone is hydrogenated for 2,3,5-trimethylbenzoquinoe |
| CN112349916A (en) * | 2020-11-16 | 2021-02-09 | 大连理工大学 | Iron-doped ZIF8 and Ce-based metal organic framework composite electrocatalyst and preparation method and application thereof |
| CN112642457A (en) * | 2020-12-21 | 2021-04-13 | 安徽师范大学 | Hollow iron-based metal organic framework material, iron-doped carbon-nitrogen nano material and preparation method |
| CN113054205A (en) * | 2021-03-31 | 2021-06-29 | 哈尔滨工业大学 | Heat treatment process for improving oxygen reduction catalytic activity of non-noble metal catalyst |
| CN114656337A (en) * | 2022-04-22 | 2022-06-24 | 陕西科技大学 | Method for preparing 2-methoxy-4-methylphenol from biomass-based vanillin |
| CN116328808A (en) * | 2021-12-22 | 2023-06-27 | 南京理工大学 | Three-dimensional ordered porous Fe-NC catalyst and preparation method and application thereof |
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