CN105728009B - A kind of classifying porous elctro-catalyst of metal/nitrogen/carbon and its preparation and application - Google Patents
A kind of classifying porous elctro-catalyst of metal/nitrogen/carbon and its preparation and application Download PDFInfo
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Abstract
A kind of classifying porous elctro-catalyst based on metal/nitrogen/carbon, the metallic element being doped in including the N C C frameworks adulterated and in the form of metal carbides in the skeleton；C content is 60 90% in the elctro-catalyst, and N content is 1 15%, and tenor is 0.05 30%；The elctro-catalyst has the micropore that pore diameter range is less than 2nm in the macropore of 1 μm of 50nm, pore diameter range in the mesoporous and pore diameter range of 2 50nm.Metal of the present invention/classifying porous the elctro-catalyst of nitrogen/carbon, macropore and it is mesoporous help to improve mass transfer, micropore contributes to the raising of oxygen reduction reaction activity, and the addition of transition metal contributes to the further raising of oxygen reduction reaction activity.The preparation method of the classifying porous elctro-catalyst of metal/nitrogen/carbon of the present invention is simple, is easily achieved.Wherein, alkali metal is at high temperature to the increase being etched with conducive to specific surface area of conducting polymer, while is also conducive to the raising of oxygen reduction reaction Activity and stabill.
Description
Technical field
The present invention relates to technical field of nano material, more particularly to a kind of classifying porous electro-catalysis of metal/nitrogen/carbon
Agent；Present invention simultaneously relates to the preparation method and application of the elctro-catalyst.
Background technology
At present, commercializing fuel cells process is slow, and one of reason is noble metal used in Cathodic oxygen reduction (ORR)
Catalyst (such as Pt and its alloy) resource is limited, higher price.Design a kind of base metal oxygen with high activity, low cost
Reduction elctro-catalyst has far-reaching significance.Compared to Pt base catalyst, the catalyst activity group of no-Pt catalyst unit volume
It is point less, so the thickness of Catalytic Layer is larger.Therefore, the active component of unit volume is improved, improves mass transfer, needs design more
The no-Pt catalyst of pore structure.
Invention content
In view of the problems of the existing technology the present invention, is prepared for a kind of classifying porous elctro-catalyst of metal/nitrogen/carbon.
To achieve the above object, the present invention is realized using scheme in detail below：
A kind of classifying porous elctro-catalyst based on metal/nitrogen/carbon, the elctro-catalyst include N doping C-C skeletons and
The metallic element being doped in the form of metal carbides in the skeleton, N doping C-C skeletons in N deposited in the form of C-N
.
C content is 60-90%, N content 1-15%, tenor 0.05-30% in the porous elctro-catalyst.
The metal is one or more of Fe, Co, Ni.
The porous elctro-catalyst have pore diameter range 50nm-1 μm macropore, pore diameter range in the mesoporous of 2-50nm and
Pore diameter range is less than the micropore of 2nm；The percentage that the specific surface area that wherein micropore is provided accounts for total specific surface area is 70-93%.
A kind of preparation method of the classifying porous elctro-catalyst based on metal/nitrogen/carbon, includes the following steps,
(1) in elctro-catalyst N adulterate C-C skeletons preparation：
A. in water and/or ethyl alcohol, the conducting polymer containing C-N structures and/or the big cyclisation containing C-N structures are added in
Object is closed, while adds in alkali metal compound, through solvent evaporated and solid is dried to obtain after gained mixed solution is stirred evenly
Substance A；
B. by step a obtained solids substance A, calcination process obtains solid matter B at 500-1000 DEG C；
C. step b obtained solid substance Bs are dispersed in acid solution, gained mixed solution is filtered, washing, does
The dry C-C framework materials for obtaining N doping；
(2) preparation of the classifying porous elctro-catalyst of metal/nitrogen/carbon：
A. in water and/or ethyl alcohol, C-C framework materials, metal precursor salts and the metal ligand of N doping are added in, gained is molten
Liquid be uniformly mixed after through solvent evaporated and drying process, obtain solid matter C；
B. by step a obtained solids substance C roasted at 500-1000 DEG C metal/nitrogen/carbon classifying porous electro-catalysis
Agent.
Alkali metal compound described in step (1) a is K2CO3, KHCO3, NaOH, Na2CO3, NaHCO3, NaCl, EDTA-
2Na、EDTANaFe、Na3C6H5O7And K3C6H5O7One or more of, the alkali metal compound and conducting polymer
And/or the ratio of the gross mass of the macrocyclic compound containing C-N structures is 1：10-5:1.
Conducting polymer described in step (1) a is polypyrrole and/or polyaniline, and the conducting polymer is in water and/or second
A concentration of 10-100g/L in alcohol.
Macrocyclic compound described in step (1) a is one or more of VB12, ferriporphyrin, Cob altporphyrin；It is described to lead
Electric polymer is 0.1 with mass ratio of the macrocyclic compound in water and/or ethyl alcohol:1-10:1.
Metal precursor salts described in step (2) a are precursor salts one or more kinds of in Fe, Co or Ni；The metal
Ligand is Phen, NH3, one or more of melamine.
Acid solution described in step (1) c is one or more of hydrochloric acid, sulfuric acid, nitric acid；The acid solution
Middle H+A concentration of 0.1-3mol/L.
Concentration of the metal salt precursor in water and/or ethyl alcohol described in step (2) a is 0.001-10mol/L, metal ligand
Concentration in water and/or ethyl alcohol is 0.001-30mol/L；Mass concentration of the C-C skeletons of N doping in water and/or ethyl alcohol
It is 0.5-10g/L.
The elctro-catalyst is the oxygen reduction electro-catalyst under alkalinity or acid condition.
Compared with prior art, the invention has the advantages that：
1. the classifying porous elctro-catalyst of metal/nitrogen/carbon of the present invention, oxygen reduction activity are suitable with commodity Pt.
2. macropore and it is mesoporous help to improve mass transfer, alkali metal at high temperature generates the etching of conducting polymer a large amount of micro-
Hole is conducive to increase specific surface area, while is also conducive to the raising of oxygen reduction reaction Activity and stabill.
3. the addition of transition metal contributes to oxygen reduction reaction activity is further to improve.
Description of the drawings
Fig. 1 is a kind of SEM tests of the classifying porous elctro-catalyst (sample two) of metal/nitrogen/carbon prepared in embodiment 1
As a result.As shown in the figure, sample two is porous structure, including pore diameter range in 50nm-1 μm of macropore, pore diameter range is in 2-50nm
It is mesoporous.
Fig. 2 is that figure is swept in classifying porous elctro-catalyst (sample two) the SEM faces of metal/nitrogen/carbon.Wherein, Fe, N element are uniform
Ground is distributed in C element.
Fig. 3 is that a kind of N prepared in embodiment 1 adulterates C-material (sample one), the classifying porous electro-catalysis of metal/nitrogen/carbon
The polypyrrole prepared in agent (sample two) and comparative example 1 roasts the nitrogen Adsorption and desorption isotherms of 1h (sample three) in 800 DEG C.With sample
Product three are compared, and the adsorbance of sample one and sample two significantly increases, this is primarily due in alkali metal compound EDTA-2Na
Na plays corrasion to polypyrrole at high temperature, increases the content of micropore.
A kind of XRD characterization results of the classifying porous elctro-catalyst (sample two) of metal/nitrogen/carbon of Fig. 4.2 θ be located at 44.8 °,
Diffraction maximum near 43.6 ° and 42.7 ° is attributed to Fe respectively3(031), (102) and (211) diffraction maximum [JCPDS 65- of C
0393]。
Fig. 5 is that the N prepared in embodiment 1 adulterates C-material (sample one), a kind of classifying porous electro-catalysis of metal/nitrogen/carbon
The polypyrrole prepared in agent (sample two) comparative example 1 roasts 1h (sample three) and commodity 20wt.%Pt/C catalyst in 800 DEG C
Four sample RDE test results in (sample four).
Test condition is：O2The 0.1mol/L NaOH electrolyte of saturation, electric potential scanning section -0.82V to 0.3V
(vs.MMO), sweep speed 10mV/s.
The carrying current of sample three is -0.80mA, and half wave potential is -0.27V, and the carrying current of sample one is -0.98mA,
Half wave potential is -0.12V.Compared with sample three, the oxygen reduction activity of sample one improves a lot, this is because the alkali added in
Metal has corrasion in high temperature to carbon material, produces more active sites, promotes the raising of oxygen reduction activity.Sample two
Half wave potential is close to commodity 20%Pt/C.This is because add in Fe precursor salts it is fired again after, elctro-catalyst active site density
It further improves so that oxygen reduction activity is further improved.
Specific embodiment
Embodiment 1：
1g EDTA-2Na are dissolved in 20mL deionized waters, add in 500mg polypyrroles, stir 3h.By mixed liquor in 70
DEG C water is evaporated, places into air-blaster drying.After grinding, 1h is roasted in 800 DEG C, 1M HCl ultrasounds 2h is used after taking-up.It will
Mixed liquor filters, and is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral.85 DEG C of dry 8h, grinding is abundant, obtains having and divide
The C-C skeletons of the N doping of grade porous structure, labeled as sample one.
100mL absolute ethyl alcohols are taken, add in the FeCl of 4mL 0.05mmol/mL3/ ethanol solution adds in 2mL ammonium hydroxide
(25%), 100 DEG C of reflux 1h are heated to.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.It will
Solvent revolving is dry, is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 900 DEG C, obtains Fe/N/C classifications
Porous elctro-catalyst, labeled as sample two.
Embodiment 2：
1g EDTA-2Na are dissolved in 20mL deionized waters, add in 500mg polypyrroles, stir 3h.Mixed liquor is in 70 DEG C
Water is evaporated, sample is put into air-blaster drying.After grinding, 1h is roasted in 800 DEG C, 0.5M H are used after taking-up2SO4Ultrasound
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
100mL absolute ethyl alcohols are taken, add in the FeCl of 4mL 0.05mmol/mL3/ ethanol solution adds in 2mL melamines,
It is heated to 100 DEG C of reflux 2h.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.Solvent is rotated
It is dry, it is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 950 DEG C, obtains the classifying porous electricity of Fe/N/C and urge
Agent.
Embodiment 3：
Weigh 0.2g K2CO3, it is dissolved in 20mL deionized waters, adds in 500mg polypyrroles, stirs 3h.Mixed liquor is in 70
DEG C water is evaporated, sample is put into air-blaster drying.After grinding, 1h is roasted in 700 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
100mL absolute ethyl alcohols are taken, add in the Fe of 4mL 0.05mmol/mL2(SO4)3/ aqueous solution adds in 2mL ammonium hydroxide
(25%), 100 DEG C of reflux 2h are heated to.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.It will
Solvent revolving is dry, is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 900 DEG C, obtains Fe/N/C classifications
Porous elctro-catalyst.
Embodiment 4：
Weigh 0.2g KHCO3, it is dissolved in 20mL deionized waters, adds in 500mg polypyrroles, stirs 3h.Mixed liquor is in 70
DEG C water is evaporated, sample is put into air-blaster drying.After grinding, 1h is roasted in 700 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
100mL absolute ethyl alcohols are taken, add in the Fe (NO of 4mL 0.05mmol/mL3)3/ ethanol solution adds in 2mL melamines
Amine is heated to 100 DEG C of reflux 2h.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.By solvent
Revolving is dry, is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 950 DEG C, it is classifying porous to obtain Fe/N/C
Elctro-catalyst.
Embodiment 5：
Weigh 0.5g Na3C6H5O7, it is dissolved in 20mL deionized waters, adds in 500mg polypyrroles, stirs 3h.Mixed liquor
Water is evaporated in 70 DEG C, sample is put into air-blaster drying.After grinding, 1h is roasted in 900 DEG C, is surpassed after taking-up with 1M HCl
Sound 2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, obtains
The C-C skeletons adulterated with classifying porous N.
100mL absolute ethyl alcohols are taken, add in the FeCl of 4mL 0.05mmol/mL2/ ethanol solution adds in 2mL melamines,
It is heated to 100 DEG C of reflux 2h.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.Solvent is rotated
It is dry, it is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 900 DEG C, obtains the classifying porous electricity of Fe/N/C and urge
Agent.
Embodiment 6：
Weigh 1g K3C6H5O7, it is dissolved in 20mL deionized waters, adds in 500mg polypyrroles, stirs 3h.Mixed liquor is in 70
DEG C water is evaporated, sample is put into air-blaster drying.After grinding, 1h is roasted in 900 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
100mL absolute ethyl alcohols are taken, add in the Fe (AC) of 4mL 0.05mmol/mL2/ ethanol solution adds in 2mL melamines
Amine is heated to 100 DEG C of reflux 2h.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.By solvent
Revolving is dry, is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 950 DEG C, it is classifying porous to obtain Fe/N/C
Elctro-catalyst.
Embodiment 7：
0.2g NaOH are weighed, are dissolved in 20mL deionized waters, add in 500mg polypyrroles, stir 3h.Mixed liquor is in 70
DEG C water is evaporated, sample is put into air-blaster drying.After grinding, 1h is roasted in 800 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
100mL absolute ethyl alcohols are taken, add in the FeCl of 1mL 0.05mmol/mL3/ aqueous solution adds in 0.5mL ammonium hydroxide (25%),
It is heated to 100 DEG C of reflux 2h.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.Solvent is rotated
It is dry, it is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 900 DEG C, obtains the classifying porous electricity of Fe/N/C and urge
Agent.
Embodiment 8：
Weigh 0.2g Na2CO3, it is dissolved in 20mL deionized waters, adds in 500mg polypyrroles, stirs 3h.Mixed liquor is in 70
DEG C water is evaporated, sample is put into air-blaster drying.After grinding, 1h is roasted in 800 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
100mL absolute ethyl alcohols are taken, add in the FeCl of 10mL 0.05mmol/mL3/ aqueous solution adds in 5mL ammonium hydroxide (25%),
It is heated to 100 DEG C of reflux 2h.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.Solvent is rotated
It is dry, it is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 900 DEG C, obtains the classifying porous electricity of Fe/N/C and urge
Agent.
Embodiment 9：
Weigh 0.2g NaHCO3, it is dissolved in 20mL deionized waters, adds in 500mg polyanilines, stirs 3h.Mixed liquor in
70 DEG C are evaporated water, and sample is put into air-blaster drying.After grinding, 1h is roasted in 900 DEG C, 1M H are used after taking-up2SO4It is super
Sound 2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, obtains
The C-C skeletons adulterated with classifying porous N.
100mL absolute ethyl alcohols are taken, add in the FeCl of 2mL 0.05mmol/mL3/ ethanol solution adds in 1mL ammonium hydroxide
(25%), 100 DEG C of reflux 2h are heated to.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.It will
Solvent revolving is dry, is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 900 DEG C, obtains Fe/N/C classifications
Porous elctro-catalyst.
Embodiment 10：
1g EDTA-2Na are weighed, are dissolved in 20mL deionized waters, add in 500mg polyanilines, stir 3h.Mixed liquor in
70 DEG C are evaporated water, and sample is put into air-blaster drying.After grinding, 1h is roasted in 800 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
100mL absolute ethyl alcohols are taken, add in the FeCl of 2mL 0.05mmol/mL3/ ethanol solution adds in 1mL ammonium hydroxide
(25%), 100 DEG C of reflux 2h are heated to.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.It will
Solvent revolving is dry, is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 900 DEG C, obtains Fe/N/C classifications
Porous elctro-catalyst.
Embodiment 11：
0.5g NaCl are weighed, are dissolved in 20mL deionized waters, add in 500mg polypyrroles, stir 3h.Mixed liquor is in 70
DEG C water is evaporated, sample is put into air-blaster drying.After grinding, 1h is roasted in 800 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
100mL absolute ethyl alcohols are taken, add in the CoCl of 2mL 0.05mmol/mL2/ ethanol solution adds in 1mL ammonium hydroxide
(25%), 100 DEG C of reflux 2h are heated to.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.It will
Solvent revolving is dry, is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 900 DEG C, obtains sample Co/N/C
Classifying porous elctro-catalyst.
Embodiment 12：
1g EDTA-2Na are weighed, are dissolved in 20mL deionized waters, add in 500mg polypyrroles, stir 3h.Mixed liquor in
70 DEG C are evaporated water, and sample is put into air-blaster drying.After grinding, 1h is roasted in 800 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
100mL absolute ethyl alcohols are taken, add in the Ni (NO of 2mL 0.05mmol/mL3)2/ ethanol solution adds in 1mL ammonium hydroxide
(25%), 100 DEG C of reflux 2h are heated to.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.It will
Solvent revolving is dry, is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 900 DEG C, obtains sample Ni/N/C
Elctro-catalyst.
Embodiment 13：
1g EDTA-2Na are weighed, are dissolved in 20mL deionized waters, add in 500mg polypyrroles, stir 3h.Mixed liquor in
70 DEG C are evaporated water, and sample is put into air-blaster drying.After grinding, 1h is roasted in 800 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
100mL absolute ethyl alcohols are taken, add in the FeCl of 2mL 0.05mmol/mL2/ ethanol solution adds in 0.1mmol melamines
Amine is heated to 100 DEG C of reflux 2h.The C-C skeletons that there is 200mg classifying porous N to adulterate are added in, continue the 4h that flows back.By solvent
Revolving is dry, is put into the dry 8h of 80 DEG C of vacuum drying oven.Sample is fully ground, 1h is roasted at 900 DEG C, it is classifying porous to obtain Fe/N/C
Elctro-catalyst.
Embodiment 14：
1.6g EDTA-2Na are weighed, are dissolved in 20mL deionized waters, add in 200mgVB12, stir 3h.Mixed liquor in
70 DEG C are evaporated water, and sample is put into air-blaster drying.After grinding, 1h is roasted in 800 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
Take the FeCl of 1mL 0.05mmol/mL3/ ethanol solution adds in 3mL ethyl alcohol, 15mL deionized waters.It is adjacent to add in 30mg
Phenanthroline adds in the C-C skeletons that there is 100mg classifying porous N to adulterate, in 70 DEG C of solvent evaporateds, sample is put into sky later
Enraged wind turbine drying.It is fully ground, roasts 1h at 900 DEG C, obtain the classifying porous elctro-catalysts of sample F eCo/N/C.
Embodiment 15：
1.6g EDTA-2Na are weighed, are dissolved in 20mL deionized waters, add in 200mgVB12, stir 3h.Mixed liquor in
70 DEG C are evaporated water, and sample is put into air-blaster drying.After grinding, 1h is roasted in 800 DEG C, with 1M HCl ultrasounds after taking-up
2h.Mixed liquor is filtered, is washed through 60 DEG C of hot water to filtrate pH value and reaches neutral, 85 DEG C of dry 8h, grinding is abundant, is had
There are the C-C skeletons of classifying porous N doping.
Take the Co (NO of 1mL 0.05mmol/mL3)2/ ethanol solution adds in 3mL ethyl alcohol, 15mL deionized waters.Add in 30mg
Phen adds in the C-C skeletons that there is 100mg classifying porous N to adulterate, in 70 DEG C of solvent evaporateds, is later put into sample
Air-blaster is dried.It is fully ground, roasts 1h at 900 DEG C, obtain the classifying porous elctro-catalysts of sample Co/N/C.
Comparative example 1：
Polypyrrole is roasted into 1h in 800 DEG C, labeled as sample three.
Comparative example 2：
By commodity 20wt.%Pt/C catalyst (Johnson Matthey companies), labeled as sample four, as a comparison.
Table 1 is a kind of C-C skeletons (sample one) adulterated with classifying porous N prepared in embodiment 1, metal/nitrogen/
The polypyrrole prepared in the classifying porous elctro-catalyst (sample two) and comparative example 1 of carbon roasts the ratio of 1h (sample three) in 800 DEG C
Surface area.Compared with sample three, the specific surface area of sample one and sample two significantly increases, and based on micropore specific area.
This Na being primarily due in EDTA-2Na plays corrasion to PPy at high temperature, increases the content of micropore.
3 material specific surface area of table, micropore specific area compare
| Sample | Sample one | Sample two | Sample three |
| BET specific surface area (meters squared per gram) | 1002 | 1241 | 53 |
Claims (10)
1. a kind of preparation method of the classifying porous elctro-catalyst based on metal/nitrogen/carbon, it is characterised in that：The elctro-catalyst
The metallic element being doped in including the N C-C skeletons adulterated and in the form of metal carbides in the skeleton, the C-C bones of N doping
N exists in the form of C-N in frame, includes the following steps,
（1）The preparation for the C-C skeletons that N is adulterated in elctro-catalyst：
A. it in water and/or ethyl alcohol, adds in the conducting polymer containing C-N structures and/or the big cyclisation containing C-N structures is closed
Object, while add in alkali metal compound through solvent evaporated and is dried to obtain solids after gained mixed solution is stirred evenly
Matter A；
B. by step a obtained solids substance A, calcination process obtains solid matter B at 500-1000 DEG C；
C. step b obtained solid substance Bs are dispersed in acid solution, gained mixed solution is filtered, washing, dry
The C-C framework materials of N doping；
（2）The preparation of the classifying porous elctro-catalyst of metal/nitrogen/carbon：
A. in water and/or ethyl alcohol, C-C framework materials, metal precursor salts and the metal ligand of N doping are added in, acquired solution is mixed
Through solvent evaporated and drying process after closing uniformly, solid matter C is obtained；The metal ligand is Phen, ammonium hydroxide, melamine
One or more of；
B. by step a obtained solids substance C roasted at 500-1000 DEG C metal/nitrogen/carbon classifying porous elctro-catalyst；
The porous elctro-catalyst have pore diameter range 50nm-1 μm macropore, pore diameter range is in the mesoporous and aperture of 2-50nm
Range is less than the micropore of 2nm；The percentage that the specific surface area that wherein micropore is provided accounts for total specific surface area is 70-93%.
2. the preparation method of the classifying porous elctro-catalyst as described in claim 1 based on metal/nitrogen/carbon, it is characterised in that：Institute
It is 60-90%, N content 1-15%, tenor 0.05-30% to state C content in porous elctro-catalyst.
3. the preparation method of the classifying porous elctro-catalyst based on metal/nitrogen/carbon as described in claim 1-2 is any, feature
It is：The metal is one or more of Fe, Co, Ni.
4. the preparation method of the classifying porous elctro-catalyst as described in claim 1 based on metal/nitrogen/carbon, it is characterised in that：Step
Suddenly（1）Alkali metal compound described in a is K2CO3, KHCO3, NaOH, Na2CO3, NaHCO3, NaCl, EDTA-2Na,
EDTANaFe、Na3C6H5O7And K3C6H5O7One or more of, the alkali metal compound and conducting polymer and/or
The ratio of the gross mass of macrocyclic compound containing C-N structures is 1：10-5:1.
5. the preparation method of the classifying porous elctro-catalyst as described in claim 1 based on metal/nitrogen/carbon, it is characterised in that：Step
Suddenly（1）Conducting polymer described in a be polypyrrole and/or polyaniline, concentration of the conducting polymer in water and/or ethyl alcohol
For 10-100g/L.
6. the preparation method of the classifying porous elctro-catalyst as described in claim 1 based on metal/nitrogen/carbon, it is characterised in that：Step
Suddenly（1）Macrocyclic compound described in a is one or more of VB12, ferriporphyrin, Cob altporphyrin；The conducting polymer with
Mass ratio of the macrocyclic compound in water and/or ethyl alcohol is 0.1:1-10:1.
7. the preparation method of the classifying porous elctro-catalyst as described in claim 1 based on metal/nitrogen/carbon, it is characterised in that：Step
Suddenly（2）Metal precursor salts described in a are precursor salts one or more kinds of in Fe, Co or Ni.
8. the preparation method of the classifying porous elctro-catalyst as described in claim 1 based on metal/nitrogen/carbon, it is characterised in that：Step
Suddenly（1）Acid solution described in c is one or more of hydrochloric acid, sulfuric acid, nitric acid；H in the acid solution+Concentration
For 0.1-3 mol/L.
9. the preparation method of the classifying porous elctro-catalyst based on metal/nitrogen/carbon as described in claim 1 or 7, feature exist
In：Step（2）Concentration of the metal precursor salts described in a in water and/or ethyl alcohol is 0.001-10 mol/L, and metal ligand is in water
And/or the concentration in ethyl alcohol is 0.001-30 mol/L；Mass concentration of the C-C skeletons in water and/or ethyl alcohol of N doping be
0.5-10g/L。
10. a kind of preparation method of classifying porous elctro-catalyst as described in claim 1 based on metal/nitrogen/carbon, feature exist
In：The elctro-catalyst of the preparation of the classifying porous elctro-catalyst based on metal/nitrogen/carbon is the oxygen under alkalinity or acid condition
Restore elctro-catalyst.
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| KR101894920B1 (en) * | 2016-12-21 | 2018-09-04 | 현대자동차주식회사 | Non-noble metal based catalyst and method of manufacturing the same |
| CN107895801A (en) * | 2017-11-01 | 2018-04-10 | 重庆文理学院 | A kind of preparation method of bioprotein synthesis non noble metal oxygen reduction catalyst |
| CN109921040A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | The carbon-based elctro-catalyst of a kind of Ni, Fe doping and its preparation and application |
| CN108232209B (en) * | 2017-12-18 | 2021-06-08 | 北京航空航天大学 | Medium-temperature carbonized metal skeleton compound hole expanding technology for preparing high-activity iron-nitrogen-carbon catalyst |
| CN108321403A (en) * | 2018-01-22 | 2018-07-24 | 厦门大学 | A kind of oxidation reduction catalyst and preparation method thereof |
| CN108336374B (en) * | 2018-01-24 | 2020-09-29 | 桂林电子科技大学 | High-performance ternary Fe-Co-Ni Co-doped nitrogen-containing carbon material and preparation method and application thereof |
| WO2020016898A1 (en) * | 2018-07-18 | 2020-01-23 | Technion Research & Development Foundation Limited | Hydrazine oxidation catalysts |
| CN109546162B (en) * | 2018-10-26 | 2021-06-22 | 江苏大学 | Recyclable preparation method of microporous iron-nitrogen doped carbon catalyst material |
| GB201819118D0 (en) * | 2018-11-23 | 2019-01-09 | Univ Tartu | Carbon nanomaterial for use as a catalyst |
| CN111261884B (en) * | 2018-11-30 | 2021-02-12 | 中国科学院大连化学物理研究所 | Carbon material with yolk shell structure and preparation method and application thereof |
| CN109364978B (en) * | 2018-12-06 | 2021-06-22 | 滨州学院 | Preparation method of Fenton-like catalyst and application of Fenton-like catalyst in organic wastewater treatment |
| CN111313040B (en) * | 2018-12-12 | 2021-07-23 | 中国科学院大连化学物理研究所 | Fe-N-C catalyst and preparation and application thereof |
| CN109599569B (en) * | 2018-12-14 | 2021-12-07 | 北京化工大学 | Metal and nitrogen co-doped ultrathin carbon nanosheet catalyst and preparation method and application thereof |
| CN110302825B (en) * | 2019-08-21 | 2022-06-07 | 河南师范大学 | Preparation method of transition metal-N-C composite electro-catalytic material |
| CN114618554B (en) * | 2022-03-24 | 2023-11-07 | 湖南大学 | Iron porphyrin derived porous iron-nitrogen doped carbon composite electro-Fenton catalytic material, and preparation method and application thereof |
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