CN110323452A - A method of oxygen reduction electro-catalyst is prepared by primary raw material of chlorophyll - Google Patents
A method of oxygen reduction electro-catalyst is prepared by primary raw material of chlorophyll Download PDFInfo
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- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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- H—ELECTRICITY
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Abstract
The present invention discloses a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll, raw material used by this method includes chlorophyll solution, source metal, nitrogen source, carbon black, inorganic acid and peroxide, and preparation step is as follows: carbon black is dissolved in water long-time ultrasonic disperse；Wrap up polymer；Washing；Water, chlorophyll solution and source metal are added into the solid after drying, rotates, dry, corase grinding obtains pulverulent solids, and ingredient is the carbon black of the polymer wrapped rich in chlorophyll and doping metals；It is heat-treated for the first time again；Pickling；After secondary heat treatment to obtain the final product.Oxygen reduction electro-catalyst prepared by the present invention is entirely free of noble metal or only containing the noble metal of super low loading, and using cheap nitrogenous compound (based on chlorophyll, cooperate a small amount of phenylenediamine simultaneously) replace the expensive macrocyclic compound such as porphyrin, phthalocyanine, not only prepared oxygen reduction electro-catalyst function admirable, and it is low in cost, it is readily mass-produced.
Description
Technical field
The present invention relates to the preparations of oxygen reduction electro-catalyst, concretely relate to one kind using chlorophyll as primary raw material system
The method of standby oxygen reduction electro-catalyst.
Background technique
Chlorophyll is higher plant and other all a kind of green pigments that can be carried out photosynthetic organism and contain.Leaf
Green element is that plant carries out photosynthetic primary pigments, is a kind of fat-containing pigment family, is located at thylakoid membrane.Chlorophyll absorption
Most feux rouges and purple light but reflection green light, so green is presented in chlorophyll, it plays core in photosynthetic light absorption
Effect.Chlorophyll is magnesium porphyrin compound, including chlorophyll a, b, c, d, f and protochlorophyll and bacteriochlorophyll etc..Ye Lv
Element is not bery stable, and light, acid, alkali, oxygen, oxidant etc. can all make its decomposition.Under acid condition, chlorophyll molecule is easy to lose porphin
Magnesium in quinoline ring becomes de-magnesium pheophytin.Chlorophyll in higher plant chloroplaset mainly has chlorophyll a and two kinds of chlorophyll b.
Chlorophyll a molecular formula: C55H72O5N4Mg；Chlorophyll b molecular formula: C55H70O6N4Mg.In color, chlorophyll a is in blue-green, and
Chlorophyll b is in yellow green.For chemical property, chlorophyll is the ester of chlorophyllin, and saponification can occur.Chlorophyll molecule contains
There are " head " of a porphyrin ring and " tail " of a phytol.Magnesium atom occupy the center of porphyrin ring, is partial to positively charged
Lotus, associated nitrogen-atoms are then partial to negatively charged.The diterpene that leaf-alcohol is made of four isoprene units is one
The aliphatic chain of lipophilic, it determines the fat-soluble of chlorophyll.Chlorophyll is not involved in the transmitting of hydrogen or the redox of hydrogen, and only with
Electron transmission (i.e. redox caused by electron exchange) and the mode of conjugation transmitting (DIRECT ENERGY transmitting) participate in the biography of energy
It passs.
Hydrogen Energy is known as the ultimate clean energy resource of the mankind.Heat after every kilogram of hydrogen burning, about the 3 of gasoline times, burning
Product be water, be the energy most clean in the world.Hydrogen can be produced by water, and water is resource the most abundant on the earth.Greatly
It is the Major Strategic behave for coping with global energy shortage and environmental pollution that power, which develops new-energy automobile,.In numerous new-energy automobiles
In, fuel cell car is considered due to it is with the advantages such as zero-emission, high-efficient, fuel source diversification, the energy is renewable
It is the important directions of future automobile industrial sustainable development, is the ideal scheme for solving the problems, such as global energy and climate change.Beauty
Ministry of Energy, state thinks that there are many obstacles for commercializing fuel cells, and major technical barrier is battery cost and service life first.Fuel electricity
The core of pool technology electricity generation system is based on platinum group metal (PGMs) elctro-catalyst.Platinum is a kind of prohibitively expensive and rare gold
Belong to, be mainly distributed on 5 countries and regions, wherein South Africa, which is occupied, has verified the 75% of platinum reserves, remaining 25% is distributed in saliva bar
Bu Wei, Finland, Russia and North America.Only 200 tons of annual output.Platinum price is generally general chemistry in 300~600 yuan/gram
Tens of thousands of times of product.Currently, the main problem for influencing fuel cell large-scale commercial is must to use a large amount of platinum catalysts, especially
It is Cathodic oxygen reduction, it is very expensive so as to cause fuel cell price.Therefore, it develops non-platinum catalyst and causes very high point
Note.
The type of common conductive black includes: Ketjenblack EC300J, BET surface area 800m2/g；
Ketjenblack EC600JD, BET surface area 1400m2/g；Black Pearls 2000, BET surface area 1450m2/g；
And other conductive blacks.Wherein, conductive black Ketjenblack EC600JD has high BET specific surface area, very small
Resistivity, about 0.3~1 Ω cm.From pattern, the dispersible primary unit of carbon black is known as " aggregation ", it is one
Single, the self-existent and firm colloidal entity of kind, it is functional unit in well dispersed system.To most of charcoals
For black, aggregation is made of the orbicule that many is fused together.Usually these orbicules be called primary " particle " or
" irregular orbicule ".These irregular orbicules are accumulated by many small class graphite linings.These graphite linings structures
At huge multicyclic aromatic ring system, there is inertia.Since carbon black is transformed by hydrocarbons, graphite linings basal plane edge
Upper hanging valence link, it is most of to be saturated by hydrogen.
Summary of the invention
A large amount of platinum catalysts must be used for existing oxygen reduction reaction, there are costs so as to cause products such as fuel cells
Height, expensive problem, the present invention propose a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll, should
Oxygen reduction electro-catalyst function admirable, low in cost prepared by method, and alternative platinum catalyst is used for the production of fuel cell
Equal fields.
The adopted technical solution is that:
A method of oxygen reduction electro-catalyst being prepared by primary raw material of chlorophyll, using the original of following weight
Material is made: 1~50 part of chlorophyll solution, 1~5 part of source metal, 1~5 part of nitrogen source, 5~20 parts of carbon black, 8~15 parts of inorganic acid, mistake
10~60 parts of oxide；
The consumption proportion of each raw material is preferred are as follows: 30~50 parts of chlorophyll solution, 2~5 parts of source metal, 1~3 part of nitrogen source, charcoal
Black 5~20 parts, 10~12 parts of inorganic acid, 10~60 parts of peroxide；
It is more preferred: 30~40 parts of chlorophyll solution, 2~3 parts of source metal, 1~2 part of nitrogen source, 5~10 parts of carbon black, inorganic
10~12 parts, 0~30 part of peroxidase 12 of acid.
Consumption proportion such as selected each raw material is preferred are as follows: 30 parts of chlorophyll solution, 2 parts of source metal, 2 parts of nitrogen source, carbon black 10
Part, 10 parts of inorganic acid, 10 parts of peroxide；Or preferably are as follows: 40 parts of chlorophyll solution, 3 parts of source metal, 1 part of nitrogen source, 7 parts of carbon black,
10 parts of inorganic acid, 5 parts of peroxide；Or preferably are as follows: 35 parts of chlorophyll solution, 3 parts of source metal, 1 part of nitrogen source, 10 parts of carbon black, nothing
10 parts, 5 parts of peroxide of machine acid.
The preparation method comprises the following steps:
(1) it dissolving: highly conductive high-specific surface area carbon black is dissolved in deionized water, ultrasonic disperse obtains carbon black solution,
It saves backup；
(2) it wraps up polymer: nitrogen source and part inorganic acid being added into carbon black solution, mechanical stirring is dispersed at 3~5 DEG C
Uniformly, the cooling peroxide of preparatory ice water is added, is stirred to react at 0~10 DEG C, has been wrapped up the carbon black of polymer
Solution；
(3) it washes: the carbon black solution for having wrapped up polymer is filtered, it is dry after being washed with deionized water, obtain solid；
(4) chlorophyll and source metal are mixed: being added deionized water into the solid after step (3) resulting drying, then plus
Enter high concentration chlorophyll organic solution and source metal, successively rotated, dried, roughly ground, obtain pulverulent solids, ingredient is to mix
Enter carbon blacks metal and containing a large amount of chlorophyll；
(5) first heat treatment: pulverulent solids obtained by step (4) are heat-treated for the first time, natural after constant temperature a few hours
Cooling；
(6) pickling: will be heat-treated gained powder for the first time and mix with remaining inorganic acid, and carry out pickling, then cooling, washing,
It is dried to obtain pulverulent solids；
(7) pulverulent solids obtained by step (6) secondary heat treatment: are subjected to secondary heat treatment, constant temperature a few hours, vacuum shape
Cool down under state, obtains oxygen reduction electro-catalyst.
In the above method, the chlorophyll solution is the organic solution containing chlorophyll, the quality percentage of chlorophyll solution
Specific concentration is 2%~15%, more preferred 5%~10%.Chlorophyll solution can be carried out by chlorophyll finished product and organic solvent
It prepares, acetone, methanol, ethyl alcohol, ethyl acetate etc. can be used in organic solvent.Organic solvent used can be complete in follow-up link
Recycling.
Above-mentioned source metal preferably is selected from source of iron, cobalt source, nickel source, manganese source or platinum source.Source of iron in the source metal preferably is selected from chlorine
Change iron, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous acetate, ferric oxalate, thiocyanation iron, iron to be formed by with nitrogenous organic ligand
At least one of complex such as iron Phen；Cobalt source preferably is selected from cobalt chloride, cobaltous sulfate, cobalt nitrate, cobalt acetate, thiocyanation
Cobalt, cobalt and nitrogenous organic ligand are formed by least one of complex such as cobalt Phen；Nickel source preferably is selected from nickel chloride, sulphur
Sour nickel, sulfuric acid Asia nickel, nickel nitrate, acetic acid Asia nickel, nickel oxalate, thiocyanation nickel, nickel and nitrogenous organic ligand are formed by complex
Such as at least one of nickel Phen；Manganese source preferably is selected from manganese chloride, manganese sulfate, manganese nitrate, manganese acetate, manganese oxalate, thiocyanation
Manganese, manganese and nitrogenous organic ligand are formed by least one of complex such as manganese Phen；Platinum source preferably is selected from chloroplatinic acid, chlorine
At least one of potassium platinate.
Above-mentioned nitrogen source preferably is selected from phenylenediamine or derivatives thereof, and o-phenylenediamine, m-phenylene diamine (MPD) etc. may be selected in phenylenediamine, the nitrogen source
Dosage is less, as supplemental nitrogen source, is fixed on the surface of carbon black-supported, to chlorophyll (main nitrogen) mating reaction.
The carbon black preferably is selected from Ketjenblack EC300J, Ketjenblack EC600JD, Black Pearls
2000, at least one of XC-72 carbon black, acetylene black.
The inorganic acid preferably is selected from least one of hydrochloric acid, sulfuric acid, perchloric acid, nitric acid.
The peroxide preferably is selected from least one of ammonium persulfate, potassium peroxydisulfate.
In step (1): the proportion of the carbon black and deionized water is preferably 2g:300mL, and wherein carbon black is calculated by mass,
Deionized water is in terms of volume；The time of the ultrasound is preferably 1-20h；The storage temperature of the carbon black solution is preferably 0-10
℃。
In step (3): the washing times are preferably 3~5 times, and the drying temperature is preferably 50~120 DEG C.
In step (5): the temperature being heat-treated for the first time is preferably 700 DEG C~1200 DEG C, and constant temperature time is preferably 0.5~
10h uses inert atmosphere protection when the first heat treatment.
In step (6): the pickling temperature is preferably 60~90 DEG C；Washing is using centrifugation or suction filtration side after the cooling
Formula is washed with deionized 4 times；The pickling preferably uses at least one of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid.
In step (7): the temperature of the secondary heat treatment is preferably 700 DEG C~1200 DEG C, and constant temperature time is preferably 0.5~
10h。
Compared with prior art, the invention has the following outstanding advantages:
1, the oxygen reduction electro-catalyst prepared by the present invention is entirely free of noble metal or only containing the noble metal of ultra-low volume,
And the prices such as porphyrin, phthalocyanine are replaced using cheap nitrogenous compound (based on chlorophyll, while cooperating a small amount of phenylenediamine)
Expensive macrocyclic compound, not only prepared oxygen reduction electro-catalyst function admirable, and also it is low in cost, it is readily mass-produced.
2, the present invention not only contributes to active sites uniformly dividing in carbon blacksurface by the way of polymer wrapped carbon black
Cloth increases active site density, and reduces hydrogen reduction by-product H2O2Yield (< 6%), ensure that the stability of catalyst.
3, for the present invention using chlorophyll as main nitrogen, source is extremely abundant.
For correlated performances such as the activity and the stability that promote prepared oxygen reduction electro-catalyst, the present invention is also to preparation
Process has carried out special designing, if chlorophyll and phenylenediamine cooperate jointly, is conducive to being uniformly distributed for active sites.Only nitrogen carbon is made
For catalyst material, in acid system almost without oxygen reduction catalytic activity, when introducing metal such as iron, cobalt, nickel, manganese, high temperature
Metal-nitrogen-carbon fit system, such as FeN is generated when heat treatment4/ C, iron are chelated by four nitrogen-atoms, this is that life system is had
Oxygen reduction activity position when oxygen breathes, it is not only active good, and also stability is high.Pickling after being heat-treated for the first time, is conducive to wash
Fall metal oxide.Known metal oxides are not acidproof, and metal oxide does not have oxygen reduction activity.So pickling is necessary
's.After pickling, second of heat treatment is conducive to further generate more active sites.High-temperature heat treatment is to generate the pass of active sites
Key, so, suitable reaction atmosphere and heat treatment time are controlled, it is especially important.
Detailed description of the invention
The invention will be further described with specific embodiment with reference to the accompanying drawing:
Fig. 1 shows the molecular structure of chlorophyll；
Fig. 2 shows the activity of the oxygen reduction electro-catalyst containing chlorophyll and Pt/C comparable situations；
Fig. 3 shows the hydrogen peroxide yield and Pt/C comparable situation of the oxygen reduction electro-catalyst containing chlorophyll；
Fig. 4 shows the hydrogen reduction stability of manganese nitrogen C catalyst.Curve essentially coincides, and illustrates catalyst in long-term stabilization
Property test in activity do not change.Manganese nitrogen carbon system has evaded destruction of the Fenton effect to catalyst, is conducive to catalyst
The reservation and stabilization of structure.
Specific embodiment
The present invention discloses a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll, uses following heavy
The raw material of amount part proportion is made: 1~50 part of chlorophyll solution, 1~5 part of source metal, 1~5 part of nitrogen source, 5~20 parts of carbon black, inorganic
8~15 parts, 10~60 parts of peroxide of acid.
The preparation method of the oxygen reduction electro-catalyst the following steps are included:
(1) it dissolves: in deionized water by carbon black dissolution, ultrasonic for a long time, cryo-conservation after being dispersed with stirring uniformly.
In step (1), the proportion of the carbon black and deionized water concretely 2g:300mL, wherein carbon black is in mass
It calculates, deionized water is in terms of volume；The time of the ultrasound can be 1~20h；The storage temperature of the carbon black solution can for 0~
10℃。
(2) it wraps up polymer: hydrochloric acid is added into carbon black solution, adds m-phenylene diamine (MPD), sample point is made under cryogenic conditions
It dissipates, adds ammonium persulfate cooling with ice water in advance, obtain KJ600-PmPDA.
In step (2), the hydrochloric acid that is added is specifically 36% concentrated hydrochloric acid that 5~100mL can be added；The addition isophthalic
The amount of diamines can be 1~10g；Temperature under the cryogenic conditions can be 0~10 DEG C；The persulfuric acid cooling with ice water in advance
The ammonium persulfate of 0.1~2M can be used in ammonium.
(3) it washes: directly the carbon black solution (KJ600-PmPDA) for wrapping polymer being filtered, is washed with deionized water
Afterwards, dry.
In step (3), the number of the deionized water washing can be 3~5 times, and the temperature of the drying can be 50~90
℃。
(4) chlorophyll and source metal are mixed: water is added into the solid after step (3) resulting drying, is then added pre-
The first high concentration chlorophyll organic solution of 0~15 DEG C of cryo-conservation, adds FeCl3, rotated, dry, corase grinding obtains powder
Last shape solid, ingredient KJ600-CP-Fe.Recyclable organic solvent when wherein rotating.
In step (4), the solid and FeCl3Proportion can are as follows: 4g:(1~20) mL, wherein solid is in mass
It calculates, FeCl3In terms of volume, the FeCl31M FeCl can be used3。
(5) first heat treatment: pulverulent solids obtained by step (4) are heat-treated for the first time, constant temperature after first heat treatment,
Temperature fall.
In step (5), the temperature being heat-treated for the first time can be 300~1200 DEG C, preferably be respectively adopted 600 DEG C, 900
DEG C, 1200 DEG C, inert atmosphere protection can be used in when first heat treatment；Constant temperature time is 0.5~10h.
(6) pickling: will be heat-treated gained powder and mixed in hydrochloric acid for the first time, carry out pickling, wash after cooling, dry, obtain
Pulverulent solids.
In step (6), the mixed temperature can be 60~90 DEG C；Using centrifugation after washing can cool down after the cooling
Or the mode filtered, it is washed with deionized 4 times.The pickling uses at least one of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid.
(7) secondary heat treatment: after pulverulent solids obtained by step (6) are carried out secondary heat treatment, constant temperature, Temperature fall,
Obtain oxygen reduction electro-catalyst.
In step (7), the temperature of the secondary heat treatment can be 300~1200 DEG C, preferably be respectively adopted 600 DEG C, 900
DEG C, 1200 DEG C, the time of the constant temperature can be 1~3h.
The present invention will be further explained below with reference to the attached drawings and specific examples:
Embodiment 1
A method of oxygen reduction electro-catalyst is prepared by primary raw material of chlorophyll, comprising the following steps:
(1) 2g Ketjenblack EC600JD carbon black (abbreviation KJ600) first carbon black sieving dissolution: is dissolved in 300mL
Deionized water in, ultrasonic 8h obtains carbon black solution so that carbon black is uniformly dispersed in water.It is protected under 0~10 DEG C of cryogenic conditions
It deposits, it is spare.
(2) it wraps up polymer: 36% concentrated hydrochloric acid of 50mL being added into carbon black solution, adds 2g m-phenylene diamine (MPD) (i.e. nitrogen
Source), mechanical stirring 3h keeps sample dispersion uniform under 0~10 DEG C of cryogenic conditions.Ammonium persulfate (APS, 2M) is cold with ice water in advance
But, 6mL is slowly added dropwise.12h is stirred under 0~10 DEG C of cryogenic conditions, obtains the carbon black solution (KJ600- for wrapping polymer
PmPDA)。
(3) it washes: directly the carbon black solution for wrapping polymer being filtered, is washed with deionized water for several times, wash off a large amount of
Inorganic salts and acid, are then dried.
(4) chlorophyll and source metal are mixed: weighing 4g washing obtained solid, appropriate ultrapure water is added, is added preparatory 0~15
Then the 1M of 10mL is added in the 100mL of DEG C cryo-conservation, the chlorophyll solution (main nitrogen) that mass percent concentration is 10%
FeCl3(i.e. source of iron) is rotated, is dried, roughly ground and is sieved with 100 mesh sieve, and pulverulent solids are obtained, and ingredient is incorporation metal and contains
There is the carbon black (KJ600-CP-Fe) of a large amount of chlorophyll.Organic solvent when revolving can complete recycling and reusing.
(5) first heat treatment: pulverulent solids obtained by step (4) are heat-treated for the first time under inert atmosphere protection,
Heat treatment temperature is 900 DEG C, at such a temperature constant temperature 1.5h, subsequent Temperature fall.
(6) pickling: it will be heat-treated gained powder for the first time and mixed with hydrochloric acid (< 6M), 80 DEG C, stir 8h, carry out pickling, wash off
Extra iron ion, while destroying extra unstable structure.After cooling again using centrifugation or filter by the way of, spend from
Sub- water washing four times washes off extra acid and inorganic salts.The substance after washing is dried again, obtains pulverulent solids.
(7) pulverulent solids after pickling secondary heat treatment: are subjected to secondary heat treatment, heat treatment temperature under vacuum conditions
It is 1200 DEG C, constant temperature 3h, Temperature fall obtains oxygen reduction electro-catalyst.
Oxygen reduction electro-catalyst obtained by the embodiment, can reach Fig. 2 and hydrogen reduction performance shown in Fig. 3 (
The quality current density I of 0.75V (vs RHE)K=9.5A/g；In 0.5~0.9V range, hydrogen peroxide (H2O2) yield < 8%.
While Fig. 4 illustrates that the activity of catalyst is good, stability is also fabulous, and after 60,000 circles accelerate decay test, curve is still substantially heavy
It closes.Fig. 2, Fig. 3 and Fig. 4 prove jointly oxygen reduction electro-catalyst obtained by the embodiment it is active it is good, that stability is high etc. is excellent
Benign energy, being can be with the excellent oxygen reduction electro-catalyst of practical application.
Embodiment 2
A method of oxygen reduction electro-catalyst is prepared by primary raw material of chlorophyll, comprising the following steps:
(1) 2g Ketjenblack EC300J carbon black: being first dissolved in the deionized water of 300mL by carbon black sieving dissolution,
Ultrasonic 8h, then mechanical stirring 1h obtain carbon black solution further such that carbon black is uniformly dispersed in water.In 0~10 DEG C of low temperature item
It is saved under part, it is spare.
(2) it wraps up polymer: 36% concentrated hydrochloric acid of 100mL being added into carbon black solution, adds 2g m-phenylene diamine (MPD) (i.e. nitrogen
Source), mechanical stirring 3h keeps sample dispersion uniform under 0~10 DEG C of cryogenic conditions.Ammonium persulfate (APS, 2M) is cold with ice water in advance
But, 6mL is slowly added dropwise.12h is stirred under 0~10 DEG C of cryogenic conditions, obtains the carbon black solution for wrapping polymer.
(3) it washes: directly the carbon black solution for wrapping polymer being filtered, is washed with deionized water for several times, wash off a large amount of
Inorganic salts and acid, are then dried.
(4) chlorophyll and source metal are mixed: weighing 4g washing obtained solid, appropriate ultrapure water is added, is added preparatory 0~5
Then the 1M FeCl of 10mL is added in the 50mL of DEG C cryo-conservation, 15% concentration chlorophyll solution3(i.e. source of iron), rotated,
Drying is roughly ground and is sieved with 100 mesh sieve, and pulverulent solids are obtained, and ingredient is the carbon black for mixing metal and containing a large amount of chlorophyll.
(5) first heat treatment: pulverulent solids obtained by step (4) are heat-treated for the first time under inert atmosphere protection,
Heat treatment temperature is 600 DEG C, at such a temperature constant temperature 3h, subsequent Temperature fall.
(6) pickling: it will be heat-treated gained powder for the first time and mixed with nitric acid, 80 DEG C, stir 8h, carry out pickling, it is extra to wash off
Iron ion, while destroying extra unstable structure.Deionized water is used by the way of centrifugation or filtering again after cooling
Washing four times, washes off extra acid and inorganic salts.The substance after washing is dried again, obtains pulverulent solids.
(7) pulverulent solids after pickling secondary heat treatment: are subjected to secondary heat treatment, heat treatment temperature under vacuum conditions
It is 900 DEG C, constant temperature 3h, Temperature fall obtains oxygen reduction electro-catalyst.
Embodiment 3
A method of oxygen reduction electro-catalyst is prepared by primary raw material of chlorophyll, comprising the following steps:
(1) 2g Ketjenblack EC600JD carbon black (abbreviation KJ600) first carbon black sieving dissolution: is dissolved in 300mL
Deionized water in, ultrasonic 8h obtains carbon black solution so that carbon black is uniformly dispersed in water.It is protected under 0~10 DEG C of cryogenic conditions
It deposits, it is spare.
(2) it wraps up polymer: 36% concentrated hydrochloric acid of 70mL being added into carbon black solution, adds 2g m-phenylene diamine (MPD) (i.e. nitrogen
Source), mechanical stirring 3h keeps sample dispersion uniform under 0~10 DEG C of cryogenic conditions.Ammonium persulfate (APS, 2M) is cold with ice water in advance
But, 6mL is slowly added dropwise.12h is stirred under 0~10 DEG C of cryogenic conditions, obtains the carbon black solution (KJ600- for wrapping polymer
PmPDA)。
(3) it washes: directly the carbon black solution for wrapping polymer being filtered, is washed with deionized water for several times, wash off a large amount of
Inorganic salts and acid, are then dried.
(4) chlorophyll and source metal are mixed: weighing 4g washing obtained solid, appropriate ultrapure water is added, is added preparatory 0~5
Then the 1M FeCl of 15mL is added in the 70mL of DEG C cryo-conservation, 18% concentration chlorophyll solution3(i.e. source of iron), rotated,
Drying is roughly ground and is sieved with 100 mesh sieve, and pulverulent solids are obtained, and ingredient is the carbon black for mixing metal and containing a large amount of chlorophyll
(KJ600-CP-Fe)。
(5) first heat treatment: pulverulent solids obtained by step (4) are heat-treated for the first time under inert atmosphere protection,
Heat treatment temperature is 600 DEG C, at such a temperature constant temperature 4h, subsequent Temperature fall.
(6) pickling: it will be heat-treated gained powder for the first time and mixed with hydrochloric acid (< 6M), 80 DEG C, stir 8h, carry out pickling, wash off
Extra iron ion, while destroying extra unstable structure.After cooling again using centrifugation or filter by the way of, spend from
Sub- water washing four times washes off extra acid and inorganic salts.The substance after washing is dried again, obtains pulverulent solids.
(7) pulverulent solids after pickling secondary heat treatment: are subjected to secondary heat treatment, heat treatment temperature under vacuum conditions
It is 1200 DEG C, constant temperature 3h, Temperature fall obtains oxygen reduction electro-catalyst.
Embodiment 4
Carbon black types are changed, other are the same as embodiment 1, experimental result such as the following table 1.
Table 1
Table 1 the experimental results showed that, the change of carbon black-supported, to activity and hydrogen peroxide yield, have apparent influence.
Embodiment 5
Change source of iron, other are the same as embodiment 1, experimental result such as the following table 2.
Table 2
Table 2 the experimental results showed that, the type of molysite, hence it is evident that influence the activity and hydrogen peroxide yield of catalyst.
Embodiment 6
Change cobalt source, other are the same as embodiment 1, experimental result such as the following table 3.
Table 3
Table 3 the experimental results showed that, change the source of iron in embodiment 1 into cobalt source, be conducive to improve catalyst stability.
Embodiment 7
Change nickel source, other are the same as embodiment 1, experimental result such as the following table 4.
Table 4
Table 4 the experimental results showed that, change the source of iron in embodiment 1 into nickel source, be conducive to improve catalyst stability.
Embodiment 8
Change manganese source, other are the same as embodiment 1, experimental result such as the following table 5.
Table 5
Table 5 the experimental results showed that, change the source of iron in embodiment 1 into manganese source, be conducive to improve catalyst stability.
Embodiment 9
Change source of iron and cobalt source (amount ratio of source of iron and cobalt source is 1: 1), other are the same as embodiment 1, experimental result such as following table
6。
Table 6
Table 6 the experimental results showed that, using the mixture of cobalt salt and molysite, advantageously ensure that the activity and stabilization of catalyst
Property.
Embodiment 10
Only change the time of heat treatment for the first time, other are the same as embodiment 1, experimental result such as the following table 7.
Table 7
Embodiment 11
Only change the time of second of heat treatment, other are the same as embodiment 1, experimental result such as the following table 8.
Table 8
Embodiment 12
Only change the diluted acid of pickling, other are the same as embodiment 1, experimental result such as the following table 9.
Table 9
The catalytic performance available cycles voltammetry of oxygen reduction electro-catalyst prepared by the present invention containing chlorophyll characterizes, electricity
Solving liquid is the 0.1M H that oxygen is saturated or nitrogen is saturated2SO4Solution.Reference electrode is reversible hydrogen electrode (RHE).
Test carries out in traditional three-electrode cell, using platinum loop-glass carbon disk electrode (RRDE), loads on glass carbon disk
Prepared catalyst 0.6mg/cm2, it is 1cm × 8cm × 2mm graphite flake to electrode, reference electrode is reversible hydrogen electrode
(RHE), supporting electrolyte is 0.1M H2SO4.The preparation method of catalyst pulp: 6mg non-platinum catalyst is weighed, 2mL is transferred to
In vial, 0.5mL ethyl alcohol and 0.5mL methanol is added, 50 μ L 5%Nafion solution, ultrasonic disperse 4h is added.Other conditions:
25 DEG C of bath temperature, electrode revolving speed 900rpm, ring electrode current potential is fixed on 1.2V (RHE), and the potential scanning speed of disc electrode is
10mV s-1, sweep interval is 0.2~1.0V (RHE).First in the 0.1M H of oxygen saturation2SO4Solution scan cycle volt-ampere, obtains
To the volt-ampere curve of stable state, then survey the background loop volt-ampere curve of nitrogen saturated solution.Curve and nitrogen when oxygen is saturated
Curve when saturation carries out subtractive to get the hydrogen reduction volt-ampere curve being just inversely overlapped.The quality of manganese nitrogen C catalyst hydrogen reduction
Power current density (in 0.75V, IK=9.44A/g) be mass transfer is corrected by Koutecky-Levich equation, then
It is calculated divided by catalyst loadings.
Koutecky-Levich equation:
The collection efficiency N of ring electrodeOIt is 0.386, and the yield of hydrogen peroxide (in 0.5~0.9V, %H2O2< 4%) under
Formula obtains:
Wherein IRFor circular current, IDFor disk electric current.
Test example 1
Using oxygen reduction electro-catalyst prepared by embodiment 1 as the cathod catalyst of hydrogen-air fuel cell, fuel is carried out
Stability test test, fixed 0.6V electric discharge, electric current maintain 0.2Acm substantially-2, have reached the stability of 600h.
Test example 2
Using oxygen reduction electro-catalyst prepared by embodiment 1 as the cathod catalyst of hydrogen-air fuel cell, fuel is carried out
Stability test test, fixed 0.4V electric discharge, electric current maintain 0.5Acm substantially-2, have reached the stability of 1000h.
Test example 3
Using oxygen reduction electro-catalyst prepared by embodiment 2 as the cathod catalyst of hydrogen-air fuel cell, fuel is carried out
Stability test test, fixed 0.6V electric discharge, electric current maintain 0.10Acm substantially-2, have reached the stability of 600h.
Test example 4
Using oxygen reduction electro-catalyst prepared by embodiment 3 as the cathod catalyst of hydrogen-air fuel cell, fuel is carried out
Stability test test, 0.4V electric discharge, 0.4Acm-2, have reached the stability of 800h.
The present invention be by carrier (such as conductive black), by wrap up a small amount of polymer with nitrogen (such as poly m-phenylene diamine) with
And a large amount of nitrogen source chlorophyll, and molysite or cobalt salt (such as FeCl is added3、CoCl2Deng) high-temperature heat treatment is carried out, elctro-catalyst is made,
It can be used for the electrochemical cathodes oxygen reduction reaction such as fuel cell.
Oxygen reduction electro-catalyst prepared by the present invention in the preparation used by raw material be conductive black, molysite or cobalt salt,
M-phenylene diamine (MPD), ammonium persulfate, inorganic acid etc. are common chemicals, and price is extremely low, and chlorophyll finished product can be used in chlorophyll solution
It carries out the mode such as preparing with organic solvent and prepare, therefore the cost of catalyst can be greatly reduced.Hydrogen-oxygen fuel cell, direct first
The low-temperature protonics exchange film fuel batteries such as alcohol fuel battery, other alcohol fuel batteries, aminic acid fuel battery, biological fuel cell
(< 100 DEG C), cathodic oxygen reduction elctro-catalyst used in high temperature proton exchange film fuel cell (120~180 DEG C), metal-air
The cathod catalyst of battery, can be used this oxygen reduction electro-catalyst.
Claims (8)
1. a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll, it is characterised in that use following parts by weight
The raw material of proportion is made: 1~50 part of chlorophyll solution, 1~5 part of source metal, 1~5 part of nitrogen source, 5~20 parts of carbon black, inorganic acid 8
~15 parts, 10~60 parts of peroxide；
The preparation method comprises the following steps:
(1) it dissolves: first carbon black being ground and sieved, is then dissolved in deionized water, ultrasonic disperse obtains carbon black solution, saves
It is spare；
(2) it wraps up polymer: nitrogen source and part inorganic acid being added into carbon black solution, mechanical stirring dispersion is equal at 3~5 DEG C
It is even, the cooling peroxide of preparatory ice water is added, is stirred to react at 0~10 DEG C, the carbon black for having been wrapped up polymer is molten
Liquid；
(3) it washes: the carbon black solution for having wrapped up polymer is filtered, it is dry after being washed with deionized water, obtain solid；
(4) chlorophyll and source metal are mixed: deionized water is added into the solid after step (3) resulting drying, adds leaf
Green element solution and source metal, is successively rotated, is dried, is roughly ground, and obtains pulverulent solids, ingredient be incorporation metal and contain
The carbon black of a large amount of chlorophyll；
(5) first heat treatment: pulverulent solids obtained by step (4) are heat-treated for the first time, Temperature fall after constant temperature a few hours；
(6) pickling: powder obtained by being heat-treated for the first time is mixed with remaining inorganic acid, carries out pickling, then cooling, washing, drying
Obtain pulverulent solids；
(7) secondary heat treatment: carrying out secondary heat treatment for pulverulent solids obtained by step (6), constant temperature a few hours, under vacuum state
Cooling, obtains oxygen reduction electro-catalyst.
2. a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll according to claim 1, special
Sign is: the chlorophyll solution is the organic solution containing chlorophyll, and mass percent concentration is 2%~15%.
3. a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll according to claim 1, special
Sign is: the source metal is selected from source of iron, cobalt source, nickel source, manganese source or platinum source；
Source of iron in the source metal is selected from iron chloride, ferric sulfate, ferrous sulfate, ferric nitrate, ferrous acetate, ferric oxalate, sulphur cyanogen
Change iron, iron and nitrogenous organic ligand and is formed by least one of complex；Cobalt source be selected from cobalt chloride, cobaltous sulfate, cobalt nitrate,
Cobalt acetate, thiocyanation cobalt, cobalt and nitrogenous organic ligand are formed by least one of complex；Nickel source is selected from nickel chloride, sulphur
Sour nickel, sulfuric acid Asia nickel, nickel nitrate, acetic acid Asia nickel, nickel oxalate, thiocyanation nickel, nickel and nitrogenous organic ligand are formed by complex
At least one of；Manganese source be selected from manganese chloride, manganese sulfate, manganese nitrate, manganese acetate, manganese oxalate, thiocyanation manganese, manganese with it is nitrogenous organic
Ligand is formed by least one of complex；Platinum source is selected from least one of chloroplatinic acid, potassium chloroplatinate；
The nitrogen source is selected from phenylenediamine or derivatives thereof；
The carbon black is selected from Ketjenblack EC300J, Ketjenblack EC600JD, Black Pearls 2000, XC-
At least one of 72 carbon blacks, acetylene black；
The inorganic acid is selected from least one of hydrochloric acid, sulfuric acid, perchloric acid, nitric acid；
The peroxide is selected from least one of ammonium persulfate, potassium peroxydisulfate.
4. a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll according to claim 1, special
Sign is, in step (1): the proportion of the carbon black and deionized water is 2g:300mL, and wherein carbon black is calculated by mass, deionization
Water is in terms of volume；The time of the ultrasound is 1-20h；The storage temperature of the carbon black solution is 0-10 DEG C.
5. a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll according to claim 1, special
Sign is, in step (3): the washing times are 3~5 times, and the drying temperature is 50~120 DEG C.
6. a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll according to claim 1, special
Sign is, in step (5): the temperature being heat-treated for the first time is 700 DEG C~1200 DEG C, and constant temperature time is 0.5~10h, described
Inert atmosphere protection is used when first heat treatment.
7. a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll according to claim 1, special
Sign is, in step (6): the pickling temperature is 60~90 DEG C；Washing is spent using being centrifuged or filtering mode after the cooling
Ion water washing 4 times；The pickling uses at least one of hydrochloric acid, sulfuric acid, nitric acid, perchloric acid.
8. a kind of method for preparing oxygen reduction electro-catalyst as primary raw material using chlorophyll according to claim 1, special
Sign is, in step (7): the temperature of the secondary heat treatment is 700 DEG C~1200 DEG C, and constant temperature time is 0.5~10h.
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| CN101259437A (en) * | 2008-04-10 | 2008-09-10 | 上海交通大学 | Oxygen reduction electrocatalyst and preparation thereof |
| CN103326041A (en) * | 2013-06-19 | 2013-09-25 | 厦门大学 | Oxygen reduction electrocatalyst and preparation method thereof |
| CN104143643A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Supported catalyst for fuel cells and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101259437A (en) * | 2008-04-10 | 2008-09-10 | 上海交通大学 | Oxygen reduction electrocatalyst and preparation thereof |
| CN104143643A (en) * | 2013-05-09 | 2014-11-12 | 中国科学院大连化学物理研究所 | Supported catalyst for fuel cells and application thereof |
| CN103326041A (en) * | 2013-06-19 | 2013-09-25 | 厦门大学 | Oxygen reduction electrocatalyst and preparation method thereof |
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| CN114005684A (en) * | 2021-11-05 | 2022-02-01 | 吉林大学 | Electrochemical polymerization film of unsaturated chlorophyll and application thereof in super capacitor |
| CN114005684B (en) * | 2021-11-05 | 2023-05-05 | 吉林大学 | Electrochemical polymerized film of unsaturated chlorophyll and application thereof in super capacitor |
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Application publication date: 20191011 |