CN108199053A - A kind of preparation method of high efficiency, low cost oxygen reduction catalyst - Google Patents
A kind of preparation method of high efficiency, low cost oxygen reduction catalyst Download PDFInfo
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- CN108199053A CN108199053A CN201810007108.1A CN201810007108A CN108199053A CN 108199053 A CN108199053 A CN 108199053A CN 201810007108 A CN201810007108 A CN 201810007108A CN 108199053 A CN108199053 A CN 108199053A
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- oxygen reduction
- reduction catalyst
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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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- 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
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Abstract
The invention discloses a kind of preparation method of high efficiency, low cost oxygen reduction catalyst, method is:Step 1: the maize straw of clean and reuse and being cut into the fritter of 2cm;Step 2: by the straw powder made in step 1 and activator with 1:3 mass ratio is soluble in water after being mixed to be stirred for 24 hours, after carrying out pickling, mixture is washed till when pH value is 7 using deionized water and obtains the carbon material with spongy high-specific surface area structure;Step 3: by the carbon material handled well in step 2 with 1:2:0.1 mass ratio after being mixed with nitrogen precursor with cobalt precursors soluble in water reach be uniformly mixed, be pyrolyzed;The oxygen reduction catalyst of doping nitrogen and cobalt element is obtained Step 4: being washed till when pH value is 7 using deionized water after the product in step 3 is carried out pickling with the hydrochloric acid solution of 3mol/L.Advantageous effect:Can make maize straw " turning waste into wealth ", solve the problems, such as pollution environment, it is easy to use, without security risk, derive from a wealth of sources, it is cheap the advantages that.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, more particularly to a kind of system of high efficiency, low cost oxygen reduction catalyst
Preparation Method.
Background technology
Since 19th century, human society persistently consumes non-renewable fossil energy, not only causes serious environment
Pollution, an energy crisis will be faced by also resulting in the mankind.In order to solve these problems, it is badly in need of a kind of pollution-free, reproducible
Green novel energy source replaces fossil energy.Air-fuel battery has the characteristics that fuel source is cheap, product is pollution-free, has huge
Potentiality substitute fossil energy become the main energy source of human society.Through studying for many years, the electricity production of air-fuel battery
It can be significantly increased, but still fail to spread to various in electric installation.The reason is that it is widely used in air combustion now
It is platinum carbon to expect the catalyst on cell cathode, and platinum category noble metal, and not only source is rare expensive, and also catalyst is easily poisoned
The defects of, seriously limit the industrialized production of air-fuel battery.Therefore, be badly in need of it is a kind of it is renewable, yield is more, at low cost
Effective catalyst makes air-fuel battery really realize industrial applications to substitute platinum carbon catalyst.
At present, the carbon-based oxygen reduction catalyst of base metal doping become substitute traditional platinum carbon catalyst important materials it
One.In the research for preparing carbon-based oxygen reduction catalyst in the past, researchers are using carbon nanotube, graphene or other synthesis
High molecular material as carbon matrix precursor, and nitrogen doped or transition elements prepare oxygen reduction catalyst.Pass through chemistry
Method prepares the materials process such as carbon nanotube, graphene complexity, has pollution and higher price.Therefore, the selection of carbon-based material
The cost of oxygen reduction catalyst can inherently be reduced, reduced environmental pollution, worked out a kind of green, at low cost, renewable, high
The carbon-based material of efficiency is most important.China's corn yield occupies the second in the world and the consumption of the corn of No. second big country.Every year
A large amount of maize straw cannot be applied reasonably, and peasant has to field burning, not only causes the environmental pollutions such as haze and asks
Topic, wastes this valuable biomass.Based on this, this patent design is a kind of by the use of maize straw as carbon-based material,
And it can realize the method that industrialized production prepares oxygen reduction catalyst.
Invention content
The main object of the present invention is in order to which the platinum carbon catalyst source for solving to use on air-fuel battery cathode is dilute
There is the problem of expensive and easy poisoning;
Another object of the present invention cannot be reasonably applied to solve a large amount of maize straw, causes corn stalk
Stalk burns in field and causes the environmental pollutions such as haze, and the problem of waste this valuable biomass.
The present invention in order to achieve the above object, a kind of high efficiency, low cost oxygen reduction catalyst for solving the above problems and providing
Preparation method.
The preparation method of high efficiency, low cost oxygen reduction catalyst provided by the invention, method are as described below:
Step 1: the maize straw of clean and reuse and being cut into the fritter of 2cm, processing is dried in 80 DEG C of baking oven
For 24 hours, powder is made in stalk by dry straw utilization pulverizer;
Step 2: by the straw powder made in step 1 and activator with 1:3 mass ratio is soluble in water after being mixed
For 24 hours, uniformly mixed mixture is placed in 105 DEG C of baking oven, until fully removing the moisture in mixture, later for stirring
Mixture in inert gas to be protected and is heat-treated at a temperature of 800 DEG C, the rate of heat addition is maintained at 5 DEG C/min, etc.
Furnace temperature is dropped to after 25-50 DEG C after carrying out pickling in the hydrochloric acid solution of mixture merging 3mol/L, will be mixed using deionized water
Object is washed till when pH value is 7 and obtains the carbon material with spongy high-specific surface area structure;
Step 3: by the carbon material handled well in step 2 with 1:2:0.1 mass ratio is carried out with nitrogen precursor and cobalt precursors
It is soluble in water after mixing to reach uniformly mixed, then mixed solution is dried in 80 DEG C of baking ovens, it will be dried
Mixture is pyrolyzed under conditions of 900 DEG C of temperature and inert gas shielding;
Step 4: it is washed after the product in step 3 is carried out pickling with the hydrochloric acid solution of 3mol/L using deionized water
To pH value be 7 when obtain doping nitrogen and cobalt element oxygen reduction catalyst.
Activator in step 2 is potassium hydroxide or zinc chloride or phosphoric acid, preferably potassium hydroxide.
Inert gas in step 2 and step 3 is nitrogen or argon gas, preferably nitrogen.
Nitrogen precursor in step 3 is urea or melamine or ammonia, preferably urea;Cobalt precursors are cobalt nitrate or chlorination
Cobalt, preferably cobalt chloride.
Baking oven and pulverizer in above-mentioned steps are the assembling of existing equipment, and therefore, concrete model and specification do not carry out
It repeats.
Beneficial effects of the present invention:
Maize straw used in the present invention, not only derive from a wealth of sources it is cheap, but also can make maize straw " change give up into
It is precious ", provide a kind of resolving ideas for the problem of crop straw burning pollution environment.The nitrogen presoma urea used in the present invention compared to
Traditional nitrogen presoma ammonia have the advantages that it is easy to use, without security risk, derive from a wealth of sources, cheap.Prepared by the present invention urges
Agent can pass through the step of activation of potassium hydroxide first, make it have honeycomb structure and 1877.28cm2g-1High-ratio surface
Product, so as to increase area and the more nitrogen-doping sites of offer that gas/solid/liquid three phase boundary is formed.The present invention passes through
High temperature pyrolysis means improve the conductive characteristic of carbon-based material.The present invention spreads out under the premise of increasing specific surface area in maize straw
Nitrogen is not only doped in liveliness proof carbon, but also is doped into a series of transition elements, is urged such as ferro element and cobalt element, to give
Agent provides more catalytic sites, can play the effect for improving air-fuel battery potential.The present invention is from can industrialized production
Inexpensive oxygen reduction catalyst is starting point, and the specific surface area of maize straw derived carbon is improved by activation of potassium hydroxide step
Afterwards, a series of transition elements raising catalytic performances are adulterated, high efficiency, low cost oxygen reduction catalyst is made.
Description of the drawings
Attached drawing 1 is maize straw scanning electron microscope schematic diagram.
Attached drawing 2 is the stalk derived carbon scanning electron microscope schematic diagram after activation.
Attached drawing 3 derives catalyst scanning electron microscope schematic diagram for stalk.
Attached drawing 4 derives the transmission electron microscope schematic diagram of catalyst for stalk.
Attached drawing 5 is nitrogen adsorption analysis chart, in figure ★ represent it is a kind of adulterate nitrogen, the maize straw of cobalt element derives hydrogen reduction
The nitrogen adsorption analysis chart of catalyst, ■ represents the nitrogen adsorption analysis chart of maize straw in figure;
Attached drawing 6 be adulterate nitrogen, cobalt element maize straw derive oxygen reduction catalyst polarization curves of oxygen reduction figure.
Attached drawing 7 is linear sweep voltammetry curve graph, in figure ★ represent it is a kind of adulterate nitrogen, the maize straw of cobalt element derives oxygen
The linear sweep voltammetry curve of reducing catalyst, ■ represents the linear sweep voltammetry curve of Pt/C catalyst in figure.
Attached drawing 8 is the maize straw derivative linear volt-ampere curve figure of oxygen reduction catalyst for adulterating nitrogen, cobalt element.
Attached drawing 9 is constant voltage discharge curve graph, in figure ★ represent it is a kind of adulterate nitrogen, the maize straw of cobalt element derives hydrogen reduction
The constant voltage discharge curve of catalyst.■ represents the constant voltage discharge curve of Pt/C catalyst in figure.
Specific embodiment
It please refers to Fig.1 to shown in Fig. 9:
Embodiment 1:
Step 1: as shown in Figure 1, first maize straw is gone after root, peeling, defoliation to be cleaned stalk with deionized water.
The stalk handled well is cut into the fritter of a length of 2cm.The fritter that cuts puts into beaker dries 24 hours under conditions of 80 DEG C, directly
Moisture into stalk fully removes.The equipment of drying is air dry oven.Dry stalk is put into after fully removing moisture removal
Chinese medicine pulverizer obtains uniform stalk powder in 15 minutes.
Step 2: by straw powder obtained in step 1 and potassium hydroxide and water with 1g:3g:The ratio mixing of 200mL is equal
It stirs the mixture for 24 hours, being stirred after even under the rotating speed of 800rpm with magnetic stirring apparatus and is placed in 105 DEG C of baking oven until fully
Remove the moisture in mixture.By the mixture dried using mortar grinder into uniform powder, process of lapping is rapid, avoids
Mixture moisture absorption.Then mixture is embedded in tube furnace, being passed through high pure nitrogen makes the mixture in tube furnace be in inertia
In gaseous environment.Tube furnace heating rate is controlled at 5 DEG C/minute, and 1h is kept the temperature after being warming up to 800 DEG C makes potassium hydroxide abundant with stalk
Reaction.In order to fully remove the substances such as the byproduct metal potassium in activation process, potassium oxide, wait stoves drop to 50 DEG C after by sample
Mixture is fully ground into uniform powder with mortar, then is added in into the hydrochloric acid solution of the 3mol/L of 200mL ground
Using magnetic stirring apparatus pickling 8h under 800rpm rotating speeds after powder, later with deionized water by activated carbon to be washed till pH value be 7 when,
3h is dried after water is filtered out using vacuum filtration machine in 80 DEG C of baking ovens.
Step 3: by the product in step 2 and urea, cobalt chloride with 1g:2g:The ratio of 0.1g is being ground after mixing
It is placed again into tube furnace after alms bowl grinding uniformly.The heating rate of tube furnace is controlled at 5 DEG C/minute, is kept the temperature after being warming up to 900 DEG C
1h。
Turn after sample obtained in 800rpm Step 4: being added in step 3 into the hydrochloric acid solution of the 3mol/L of 200mL
Speed is lower to carry out pickling 8h, product is washed till after pH value is 7 with deionized water later, 80 after using vacuum filtration machine, water is filtered out
Dry 3h in DEG C baking oven, obtains stalk and derives ORR catalyst.
Embodiment 2:
By the product in the step 2 in embodiment 1 and melamine, cobalt nitrate with 1g:2g:The ratio of 0.1g is uniformly mixed
It is placed again into tube furnace after mortar grinder is uniform afterwards.The heating rate of tube furnace is controlled at 5 DEG C/minute, after being warming up to 900 DEG C
Keep the temperature 1h.It is added in into the hydrochloric acid solution of the 3mol/L of 200mL and carries out pickling 8h after sample under 800rpm rotating speeds, spent later
Ionized water by product to be washed till pH value be 7 when, after using vacuum filtration machine, water is filtered out in 80 DEG C of baking ovens dry 3h, obtain stalk
Derivative oxygen reduction catalyst.
Embodiment 3:
By by the product in the step 2 in embodiment 1 and urea, cobalt chloride with 1g:2g:The ratio of 0.1g is after mixing
It is placed again into tube furnace after mortar grinder is uniform.The heating rate of tube furnace is controlled at 5 DEG C/minute, is protected after being warming up to 900 DEG C
Warm 1h is passed through ammonia in pyrolytic process.Into the hydrochloric acid solution of the 3mol/L of 200mL add in sample after under 800rpm rotating speeds into
Row pickling 8h, later with deionized water by product be washed till pH value for 7 when, in 80 DEG C of baking ovens after using vacuum filtration machine, water is filtered out
In dry 3h, obtain stalk and derive oxygen reduction catalyst.
Claims (4)
1. a kind of preparation method of high efficiency, low cost oxygen reduction catalyst, it is characterised in that:Its method is as described below:
Step 1: the maize straw of clean and reuse and being cut into the fritter of 2cm, processing is dried in 80 DEG C of baking oven for 24 hours, it will
Powder is made in stalk by dry straw utilization pulverizer;
Step 2: by the straw powder made in step 1 and activator with 1:The stirring soluble in water after being mixed of 3 mass ratio
For 24 hours, uniformly mixed mixture is placed in 105 DEG C of baking oven, later will be mixed until fully removing the moisture in mixture
Close object protect in inert gas and be heat-treated at a temperature of 800 DEG C, the rate of heat addition is maintained at 5 DEG C/min, etc. furnace temperature
It drops to after 25-50 DEG C after carrying out pickling in the hydrochloric acid solution of mixture merging 3mol/L, is washed mixture using deionized water
To pH value be 7 when obtain the carbon material with spongy high-specific surface area structure;
Step 3: by the carbon material handled well in step 2 with 1:2:0.1 mass ratio is mixed with nitrogen precursor with cobalt precursors
It is soluble in water afterwards to reach uniformly mixed, then mixed solution is dried in 80 DEG C of baking ovens, by dried mixing
Object is pyrolyzed under conditions of 900 DEG C of temperature and inert gas shielding;
Step 4: PH is washed till using deionized water after the product in step 3 is carried out pickling with the hydrochloric acid solution of 3mol/L
It is worth the oxygen reduction catalyst that doping nitrogen and cobalt element are obtained when being 7.
2. a kind of preparation method of high efficiency, low cost oxygen reduction catalyst according to claim 1, it is characterised in that:It is described
The step of two in activator be potassium hydroxide or zinc chloride or phosphoric acid, preferably potassium hydroxide.
3. a kind of preparation method of high efficiency, low cost oxygen reduction catalyst according to claim 1, it is characterised in that:It is described
The step of two and step 3 in inert gas for nitrogen or argon gas, preferred nitrogen.
4. a kind of preparation method of high efficiency, low cost oxygen reduction catalyst according to claim 1, it is characterised in that:It is described
The step of three in nitrogen precursor be urea or melamine or ammonia, preferably urea;Cobalt precursors be cobalt nitrate or cobalt chloride, preferably
Cobalt chloride.
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Cited By (6)
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CN109888311A (en) * | 2019-03-04 | 2019-06-14 | 上海交通大学 | Carbon composite oxygen reduction catalyst based on biomass derived and preparation method thereof |
CN110474057A (en) * | 2019-08-30 | 2019-11-19 | 太原理工大学 | A kind of preparation method and application of the oxygen reduction electro-catalyst based on lignocellulose-like biomass carbon |
CN110474060A (en) * | 2019-07-01 | 2019-11-19 | 吉林大学 | A kind of preparation method and oxygen reduction catalyst application of efficiently three-dimensional netted nitrogen auto-dope carbon aerogels |
CN111129522A (en) * | 2019-12-06 | 2020-05-08 | 同济大学 | Preparation and application of nickel-iron alloy/nitrogen-doped carbon fiber serving as zinc-air battery oxygen electrocatalyst |
CN113388857A (en) * | 2021-06-08 | 2021-09-14 | 河北师范大学 | Method for preparing integral sacrificial anode for hydrogen production by electrolyzing water by utilizing wood fiber biomass |
WO2022052539A1 (en) * | 2020-09-10 | 2022-03-17 | 中国矿业大学 | Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof |
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CN105344369A (en) * | 2015-11-30 | 2016-02-24 | 北京化工大学 | Cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of three-dimensional hierarchical porous structure and preparation and application thereof |
CN105375042A (en) * | 2015-12-01 | 2016-03-02 | 沈阳农业大学 | Biomass carbon catalyst and preparation method and application thereof |
CN106684396A (en) * | 2016-12-21 | 2017-05-17 | 北京化工大学 | Method for preparing bifunctional catalyst from peanut hull |
CN106848332A (en) * | 2017-02-17 | 2017-06-13 | 天津理工大学 | A kind of method for preparing efficient oxygen reduction catalyst as substrate with insect wing |
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CN103332687A (en) * | 2013-07-11 | 2013-10-02 | 黑龙江大学 | Method for preparing boron and nitrogen codoped graphitized nano carbon by taking biomass as carbon source |
CN105344369A (en) * | 2015-11-30 | 2016-02-24 | 北京化工大学 | Cobalt and nitrogen codoped carbon-based oxygen reduction catalyst of three-dimensional hierarchical porous structure and preparation and application thereof |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109888311A (en) * | 2019-03-04 | 2019-06-14 | 上海交通大学 | Carbon composite oxygen reduction catalyst based on biomass derived and preparation method thereof |
CN110474060A (en) * | 2019-07-01 | 2019-11-19 | 吉林大学 | A kind of preparation method and oxygen reduction catalyst application of efficiently three-dimensional netted nitrogen auto-dope carbon aerogels |
CN110474057A (en) * | 2019-08-30 | 2019-11-19 | 太原理工大学 | A kind of preparation method and application of the oxygen reduction electro-catalyst based on lignocellulose-like biomass carbon |
CN111129522A (en) * | 2019-12-06 | 2020-05-08 | 同济大学 | Preparation and application of nickel-iron alloy/nitrogen-doped carbon fiber serving as zinc-air battery oxygen electrocatalyst |
WO2022052539A1 (en) * | 2020-09-10 | 2022-03-17 | 中国矿业大学 | Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof |
GB2603717A (en) * | 2020-09-10 | 2022-08-10 | Univ China Mining | Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof |
GB2603717B (en) * | 2020-09-10 | 2023-03-22 | Univ China Mining | Crop straw-based nitrogen-doped porous carbon material preparation method and application thereof |
CN113388857A (en) * | 2021-06-08 | 2021-09-14 | 河北师范大学 | Method for preparing integral sacrificial anode for hydrogen production by electrolyzing water by utilizing wood fiber biomass |
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