CN108892773A - A kind of porphyrin polymer nano material, preparation method and application - Google Patents
A kind of porphyrin polymer nano material, preparation method and application Download PDFInfo
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Abstract
A kind of porphyrin polymer nano material, preparation method and application, belong to materials chemistry and electrochemical technology field, include the following steps：（1）By the acetonitrile dispersion liquid of PMAA or PEGDMA, centrifugation takes precipitating to be added in the ethanol solution of inorganic salts, stirs at least 10 ~ 15h, and centrifugation takes precipitating to obtain template, and the inorganic salts are sodium acetate, ferric nitrate or copper nitrate；（2）Porphyrin presoma is dissolved in polar solvent, porphyrin precursor solution is obtained；（3）Step（1）Template be dispersed in water, obtain template solution；（4）By step（2）Solution be added step（3）Solution in, stir evenly, 50 ~ 180 DEG C reaction 2 ~ for 24 hours, centrifugation, take precipitating, obtain porphyrin polymer nano material.
Description
Technical field
The invention belongs to materials chemistry and electrochemical field more particularly to a kind of porphyrin polymer nano materials, its preparation
Method and application.
Background technique
The problem of resource exhaustion environmental pollution, has just caused the extensive concern of people, many cleaning nothings before very early
Energy of pollution such as Hydrogen Energy, solar energy, tide energy etc. is just gradually by human use.People are opened again while using clean energy resource
Many novel technologies are sent out, such as in order to which the discharge for reducing vehicle exhaust uses the instead preceding traditional gasoline car of electric car.
Wherein fuel-cell vehicle directly becomes electric energy by hydrogen-oxygen chemical reaction, in the mistake of reaction using hydrogen or methane gas as fuel
Hazardous substances will not be generated in journey, be a kind of trip walking-replacing tool of cleanliness without any pollution.
Oxygen reduction reaction（ORR）The reaction that fuel battery negative pole occurs, be by catalyst, to be related to polyelectron more
The slow process of dynamics for walking elementary reaction is that the rate controlling of fuel cell walks and determines the efficiency of fuel cell.So wanting
Think the performance of raising fuel cell, most importantly improves the catalytic performance of cathod catalyst.But presently, there are cathode oxygen
Reducing catalyst there are at high cost, the service life is short, not acid corrosion-resistant the problems such as, therefore find Cheap highly effective oxygen reduction catalyst be
Improve the key of hydrogen reduction performance.
Pt series catalysts are the cathod catalysts that fuel cell is common on the market now and performance is best, but its price is high
It is expensive.1964, Nature reported that cobalt phthalocyanine there is catalytic performance to cause the extensive concern of brainstrust ORR for the first time, through it is too long when
Between the study found that have transition metal macrocyclic compound that can show good ORR catalytic performance, wherein metalloporphyrin
H can be promoted in acidic electrolysis bath by closing object2O2Decomposition, can overcome the problems, such as click corrosion oxidation, it is considered to be most have latent
The base metal ORR catalyst of power.In general, porphyrin polymer has higher conjugated structure, can show than monomer more
Excellent hydrogen reduction performance.Therefore, it is necessary to make further inquire into porphyrin polymer nano material property and preparation process
And research.
Summary of the invention
The purpose of the present invention is to provide a kind of porphyrin polymer nano material, preparation method and applications.The present invention obtains
The porphyrin polymer appearance of nano material arrived is uniform, is solid or hollow microballoon, and preparation method is simple, it is easy to accomplish.
Based on above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of preparation method of porphyrin polymer nano material, includes the following steps：
The first step：The preparation of template：
(1) sodium acetate is dissolved in ethanol solution, prepares the ethanol solution of 0.00328 ~ 0.01g/mL；Prepare PMAA or
The acetonitrile solution of PEGDMA polymer microballoon, concentration are 40 ~ 50 mg/mL；
(2) by the acetonitrile solution of PMAA or PEGDMA, centrifugation takes precipitating to be scattered in the ethanol solution of sodium acetate, ion exchange
After reacting at least 12 h, centrifugation removes supernatant collection precipitating, obtains PMAA-Na or PEGDMA-Na；Wherein, sodium acetate with
The mass ratio of PMAA or PEGDMA（0.68~6.5）:1；
(3) 1200mg PMAA-Na or PEGDMA-Na are dispersed in the ethanol solution of 1200mL ferric nitrate（0.01212 ~0.05
g/mL）Or the ethanol solution of 1200mL copper nitrate（0.0725~0.1g/mL）In, i.e. PMAA-Na or PEGDMA-Na and ferric nitrate
Mass ratio be 1:（0.01212 ~0.05）, the mass ratio of PMAA-Na or PEGDMA-Na and copper nitrate is 1:（0.0725~
0.1）, after being stirred to react at least 12 h, centrifugation, remove supernatant collection precipitating, respectively obtain PMAA-Fe, PEGDMA-Fe,
PMAA-Cu, PEGDMA-Cu template；
Second step：Porphyrin presoma is dissolved in polar solvent, obtaining concentration is that 0.01-0.015 mol/L porphyrin presoma is molten
Liquid；The polar solvent is N,N-dimethylformamide（DMF）Or dimethyl sulfoxide（DMSO）；
Third step：It takes the template of the 5mg first step to be scattered in the water of 9 ~ 9.8mL, obtains template solution；
4th step：Porphyrin precursor solution is added in template solution, the volume ratio of template solution and porphyrin precursor solution is
1 ︰（9~49）, it stirs evenly, 50 ~ 180 DEG C of reactions 2 ~ for 24 hours, centrifugation takes precipitating, obtains porphyrin polymer porphyrin polymer nano material.
The porphyrin presoma is 5,10,15,20- tetra- (4- aminobenzene) -21H, 23H- porphyrin (i.e. TAPP) or Ni (II) -
5,10,15,20- tetra- (4- aminophenyl) porphyrin（That is Ni-TAPP）.
Porphyrin polymer nano material made from the above method, the pattern of the porphyrin polymer nano material be it is solid or
Tiny balloon.
Above-mentioned porphyrin polymer nano material can be used as ORR catalyst.
In the present invention, PMAA-Fe, PMAA-Cu, PEGDMA-Fe, PEGDMA-Cu are PMAA-Na and PEGDMA-Na
It is obtained by exchange reaction.The present invention is polymerize using hydro-thermal method by template surface metal ion catalysis porphyrin, the porphyrin of preparation
Polymer nano material size uniformity, can be prepared on a large scale.
The present invention does not have special restriction to the mixed mode, using hybrid mode well known to those skilled in the art
, specifically, such as stirring.
The present invention mixes porphyrin presoma with polar solvent, obtains porphyrin precursor solution.The porphyrin presoma is excellent
It is selected as 5,10,15,20- tetra- (4- aminobenzene) -21H, 23H- porphyrin（TAPP, phenylamino porphyrin）Or Ni (II) -5,10,15,20-
Four (4- aminophenyl) porphyrins（Ni-TAPP）, the polar solvent is preferably n,N-Dimethylformamide（DMF）Or dimethyl is sub-
Sulfone（DMSO）.In the present invention, the polar solvent is the bad of porphyrin presoma to porphyrin presoma good dissolubility energy, water
Solvent, while being sunk to the polymerization catalyzed effect of porphyrin presoma by injecting porphyrin precursor solution in water using metal ion
For template surface, and then template surface metal ion catalysis is promoted to polymerize, realizes the preparation of porphyrin polymer nano material.By
It is largely dissolved in polar solvent in porphyrin presoma, solves production problems.
The present invention does not have special restriction to the addition sequence of the template, water and porphyrin precursor solution, using ability
Addition sequence known to field technique personnel, specifically, such as first mixing template with water, then mixed with porphyrin precursor solution
It closes.
The present invention does not have special restriction to the mixed mode, using hybrid mode well known to those skilled in the art
, specifically, such as kettle heat.
In the present invention, the concentration of the porphyrin precursor solution is preferably 0.01 ~ 0.015 mol/L, more preferably
0.01 mol/L。
Hydro-thermal after porphyrin precursor solution is mixed with template aqueous solution occurs catalytic polymerization, obtains porphyrin polymer
Nano material.In the present invention, the volume ratio of the porphyrin precursor solution and template aqueous solution is 1:49 ~ 9, with volume ratio
Increase, the shell progressive additive of obtained material.
PMAA and PEGDMA is prepared porphyrin polymer nano material by the present invention, using two kinds of metals of Fe and Cu
The catalyst that ion polymerize as anilino- porphyrin.In the present invention, template selects that be preferably PMAA-Cu react as catalysis
Template, the hydro-thermal reaction preferably carries out at high temperature, more preferable 160 ~ 180 DEG C, most preferably 180 DEG C；The reaction
Time is preferably 2 ~ 24 h, more preferably 12 ~ 24 h.
After the completion of polymerization reaction, preferably reaction product is centrifuged by the present invention, obtains porphyrin polymer nanometer material
Material.The present invention does not have special restriction to the time of the centrifuge separation, revolving speed, can be realized separation of solid and liquid, specifically
15 min are such as centrifuged at 8000 rpm.
The size of porphyrin polymer nano material of the present invention is 300 ~ 400 nm, the porphyrin polymer nano material
Pattern include solid or hollow ball.
The present invention provides a kind of preparation method of porphyrin polymer nano material, by the rich carboxylic PEGDMA in surface or
PMAA is scattered in the ethanol solution of metal salt, passes through cation and H+Exchange between ion obtains surface with different metal
The polymer template PEGDMA or PMAA of ion；High-temperature kettle heat, hair after porphyrin precursor solution and the aqueous solution of template are mixed
The polymerization of raw porphyrin and the depolymerization reaction of template, obtain porphyrin polymer nano material.The present invention use PEGDMA or PMAA for
Template preparation porphyrin polymer Microsphere Size is uniform, rough surface, there is big specific surface area, high thermal stability and adjustable
Metal active site.Present invention incorporates polar solvents to anilino- porphyrin good dissolubility energy, passes through template PEGDMA
Or metal ion acts on the catalytic polymerization of anilino- porphyrin in PMAA, makes porphyrin polymerization in template surface, is reacted by adjusting
Temperature and time can not only accelerate the progress of reaction, can also make polymer depolymerization during the reaction, obtain hollow porphin
Quinoline polymer nanocomposite ball, and since solid porphyrin polymer nanosphere also can be obtained in the difference of crosslinked polymer degree.The present invention
In using PEGDMA or PMAA as template, by the available PEGDMA or PMAA metallo-chelate of base exchange method, and with this
For template, the catalytic action induced polymerization being polymerize using metal ion Cu, Fe to anilino- regulates and controls reaction temperature and reaction time
And the uniform porphyrin polymer nano material of pattern is finally obtained, the ball shaped nano material after this polymerization is in a fuel cell
Oxygen reduction reaction in have well application.
Preparation method synthesis technology provided by the invention is simple, low for equipment requirements, and the nano material is in acidic electrolysis
It can be stabilized in matter, in oxygen reduction reaction with good application prospect.
Further, in the present invention, by the metal ion and reaction temperature of regulation template surface and time to reality
The depolymerization degree of existing polymer porphyrin nano material internal template, so as to obtain hollow and solid porphyrin polymer nanometer
Ball.
Detailed description of the invention
Fig. 1 is the PEGDMA-Fe that embodiment 1 obtains（1A）,PMAA-Fe（1B）,PMAA-Cu（1C）The SEM of template schemes；
Fig. 2 is the SEM figure and TEM figure that PEGDMA-Fe is porphyrin polymer nano material prepared by template in embodiment 1；
Fig. 3 is the SEM figure that PMAA-Fe is porphyrin polymer nano material prepared by template in embodiment 2；
Fig. 4 is the TEM figure of the porphyrin polymer nano material prepared under 3 different temperatures of embodiment by template of PMAA-Cu；
Fig. 5 is the TEM figure of the porphyrin polymer nano material prepared under 4 different time of embodiment by template of PMAA-Cu；
Fig. 6 is the TEM figure for the porphyrin polymer nano material that the additional amount of the different porphyrin presomas of embodiment 5 obtains；
Fig. 7 is the SEM figure that the porphyrin polymer nano material that variety classes porphyrin presoma obtains is added in embodiment 6；
Fig. 8 be embodiment 7 in PMAA-Fe-TAPP, PTAPP 0.1M HClO4CV test curve in electrolyte solution；
Fig. 9 is PTAPP in embodiment 7（A figure）,PNiTAPP（B figure）LSV in 0.1 M KOH electrolyte solution tests bent
Line is successively 200 r, 500 r, 1000 r, 1500 r, 2000 r, 2500 r, 3000 r, 3600 r from top to bottom in figure；
Figure 10 is PTAPP in embodiment 7（A figure）,PNiTAPP（B figure）In 0.5 M H2SO4LSV test in electrolyte solution
Curve is successively 200 r, 500 r, 1000 r, 1500 r, 2000 r, 2500 r, 3000 r, 3600 r from top to bottom in figure.
Specific embodiment
It is urged below with reference to embodiment to porphyrin polymer nano material provided by the invention and preparation method thereof and as ORR
The application of agent is described in detail, but they cannot be interpreted as limiting the scope of the present invention.Configure PMAA
Or the preparation of PEGDMA polymer microballoon is using the distillation precipitation method：α-methacrylic acid (MAA) (10.0mL), azodiisobutyronitrile
（AIBN）Acetonitrile 400mL is added in 0.2067g, is then refluxed for 3h, and reaction stops, and solution is white from the colourless milk that becomes, centrifugation
After being washed twice with acetonitrile, as PMAA microballoon is dispersed in acetonitrile and is saved；Bibliography：（Bai, F.;
Huang, B.; Yang, X.; Huang, W., Synthesis of monodisperse poly (methacrylic
acid) microspheres by distillation-precipitation polymerization. European
Polymer Journal, 2007, 43 (9), 3923-3932。
By α-methacrylic acid (MAA) (8.0mL), ethylene glycol dimethacrylate（EGDMA）2.0mL, azo two are different
Butyronitrile（AIBN）Acetonitrile 400mL is added in 0.2067g, is then refluxed for 3h, and reaction stops, and solution is white from the colourless milk that becomes, centrifugation
After precipitating is washed twice with acetonitrile, as PEGDMA microballoon is dispersed in acetonitrile and is saved；Bibliography： Bai, F.,
X. Yang, and W. Huang, Preparation of narrow or monodisperse poly
(ethyleneglycol dimethacrylate) microspheres by distillation–precipitation
polymerization. European Polymer Journal, 2006. 42(9): 2088-2097.
Embodiment 1
A kind of preparation method of porphyrin polymer nano material, including：
（1）The preparation of template：
A. sodium acetate is dissolved in ethanol solution, prepares the ethanol solution of 0.00328 g/mL；Prepare PMAA or PEGDMA polymerization
The acetonitrile solution of object microballoon, concentration are 40 mg/mL；
B. the acetonitrile solution of 30 mLPMAA or PEGDMA is centrifuged, precipitating is taken to be scattered in the ethanol solution of 1200 mL sodium acetates
In, after ion-exchange reactions 12h, 8000 rpm be centrifuged 15 min, remove supernatant collection precipitating, obtain PMAA-Na or
PEGDMA-Na；
C. the PMAA-Na of 1200mg or PEGDMA-Na are dispersed in the ethanol solution of 1200mL ferric nitrate（0.01212g/mL）
Or the ethanol solution of copper nitrate（0.0725g/mL）In, after being stirred to react 12 h, 8000 rpm are centrifuged 15 min, remove supernatant
Precipitating is collected, PMAA-Fe, PEGDMA-Fe, PMAA-Cu, PEGDMA-Cu template is respectively obtained, is scattered in standby in ethanol solution
With.
Template surface connects the color that different metal ions makes template that different metal ions be presented, PEGDMA-Fe with
PMAA-Fe is brick-red in ferric ion, and blue is presented in PMAA-Cu, as can be seen from Figure 1 template connection different metal from
Surface after son is opposed flattened, and for partial size in 300 nm or so, size is uniform.
（2）It disperses the PEGDMA-Fe template of 5 mg in 9.5 mL water, ultrasound mixes；
（3）By 5,10,15,20- tetra- (4- aminobenzene) -21H, 23H- porphyrin (i.e. TAPP) is dissolved in DMF, and 0.01 M aniline is made
The DMF solution of base porphyrin；
（4）By 0.5 mL step（3）The solution of preparation is injected into 9.5 mL steps（2）Solution in, ultrasonic agitation uniformly, 140
DEG C reaction 6 h after be cooled to room temperature, 8000 rpm be centrifuged 15 min after, remove supernatant collection precipitating to get arrive polymer porphin
Quinoline nano material.
It is main in 300 nm's shown in the pattern of polymer porphyrin nano material such as Fig. 2 A (SEM), Fig. 2 B (TEM)
Solid spherical, surface are uniformly distributed porphyrin polymer, can be seen that the PEGDMA-Fe template at center fails in conjunction with two figures
It removes.
Embodiment 2
Change the template in embodiment 1, includes the following steps：
(1) it disperses the PMAA-Fe template of 5 mg in 9.5 mL water, ultrasound mixes；
(2) anilino- porphyrin is dissolved in DMF, the DMF solution of 0.01 M anilino- porphyrin is made；
(3) by 0.5 mL step（2）The solution of preparation is injected into 9.5 mL steps（1）Solution in, ultrasonic agitation uniformly, 140
DEG C reaction 8 h after be cooled to room temperature, 8000 rpm be centrifuged 15 min after, remove supernatant, collect precipitating to get arrive polymer porphin
Quinoline nano material.
PMAA-Fe is as shown in Figure 3 as the porphyrin polymer appearance of nano material that template obtains, it can be seen that porphyrin polymer
It being wrapped in outside template in the sheet of fold, this is different from the porphyrin polymer nano material that PEGDMA-Fe is template preparation, this
It may be as caused by template difference, as seen from the figure, also there is no remove for the template for the nano material that this method obtains.
Embodiment 3
Change the temperature of the metal ion of template surface load and hydro-thermal reaction in embodiment 2, includes the following steps：
(1) it disperses the PMAA-Cu template of 5 mg in 9.8 mL water, ultrasound mixes, and prepares four parts of template solutions；
(2) anilino- porphyrin is dissolved in DMF, the DMF solution of 0.01 M anilino- porphyrin is made；
(3) respectively by 0.2 mL step（2）The solution of preparation is injected into four parts of steps（1）In the solution of 9.8 obtained mL, surpass
Sound stirs evenly, and four parts of reaction solutions are cooled to room temperature after 50 DEG C, 100 DEG C, 150 DEG C, 180 DEG C of 24 h of reaction respectively, and 8000
After rpm is centrifuged 15 min, supernatant is removed, collects precipitating to get polymer porphyrin nano material is arrived.
The pattern of the porphyrin polymer nano material obtained under different temperatures is as shown in figure 4, A, B, C, D in Fig. 4 distinguish
The TEM figure for representing the nano material prepared at 50 DEG C, 100 DEG C, 150 DEG C, 180 DEG C, as reaction temperature is gradually increasing, PMAA-
The surface Cu porphyrin polymer gradually increases, and is mainly shown as that surface roughness gradually increases.And as the temperature rises, as
The PMAA-Cu of template gradually depolymerization obtains hollow porphyrin polymer nano material.
Embodiment 4
Change the hydro-thermal reaction time in embodiment 3, includes the following steps：
(1) it disperses the PMAA-Cu template of 5 mg in 9.8 mL water, ultrasound mixes, and prepares four parts of template solutions；
(2) anilino- porphyrin is dissolved in DMF, the DMF solution of 0.01 M anilino- porphyrin is made；
(3) respectively by 0.2 mL step（2）The solution of preparation is injected into four parts of steps（1）In the solution of 9.8 obtained mL, surpass
Sound stirs evenly, and after four parts of reaction solutions react 2 h, 6 h, 12 h, 24 h at 180 DEG C respectively, is cooled to room temperature, 8000 rpm from
After 15 min of the heart, supernatant is removed, collects precipitating to get polymer porphyrin nano material is arrived.
The pattern for the porphyrin polymer nano material that different polymerization times obtain is as shown in figure 5, A, B, C, D in Fig. 5 divide
Biao Shi not be at 180 DEG C, 2 h, 6 h, 12 h, the TEM of the nano material of preparation schemes in 24 h times, under 180 DEG C of different times
Obtained porphyrin polymer nano material is apparently completely the same, but gradually increasing with the reaction time, porphyrin polymer
Nano material gradually appears hollow phenomenon.
Embodiment 5
The additional amount for changing 4 mesoporphyrin presoma of embodiment, includes the following steps：
(1) it disperses the PMAA-Cu template of 5 mg in 9.8 mL or 9 mL water, ultrasound mixes；
(2) anilino- porphyrin is dissolved in DMF, the DMF solution of 0.01 M anilino- porphyrin is made；
(3) by 0.2 mL or 1 mL step（2）The solution of preparation is injected separately into 9.8 mL or 9 mL steps（1）Solution in,
Ultrasonic agitation uniformly, is cooled to room temperature after 180 DEG C of 24 h of reaction, after 8000 rpm are centrifuged 15 min, removes supernatant, and it is heavy to collect
It forms sediment to get polymer porphyrin nano material is arrived.
Under 180 DEG C of 24 h conditions of reaction, different amounts of porphyrin precursor solution is added（6A represents 0.2 mL, and 6B represents 1
mL）The pattern of obtained porphyrin polymer nano material as shown in fig. 6, with additional amount increase, shell thickness gradually increases,
Specifically, from 75 ± 5 nm progressive additives be 127 ± 5 nm.
In conjunction with above embodiments it is found that hydrothermal temperature changes the extent of polymerization of anilino-, it is mainly shown as：With anti-
Temperature is answered to gradually rise, the amount of polymerization gradually increases, so optimal that show as 160 DEG C ~ 180 DEG C；Change under optimal polymerization temperature
The time of hydro-thermal reaction, template gradually depolymerization obtain hollow porphyrin polymer nano material；Change porphyrin precursor solution
Additional amount can change the thickness of hollow shell layer.
Embodiment 6
Change porphyrin presoma type, includes the following steps：
(1) it disperses the PMAA-Cu template of 5 mg in 9.8 mL water, ultrasound mixes, and prepares two parts of template solutions；
(2) TAPP, NiTAPP are dissolved in DMF respectively, 0.01 M porphyrin precursor solution is made；
(3) respectively by 0.2 mL step（2）The solution of preparation is injected separately into 9.8 mL steps（1）Solution in, ultrasonic agitation
Uniformly, be cooled to room temperature after 180 DEG C of 24 h of reaction, 8000 rpm be centrifuged 15 min after, remove supernatant, collect precipitating to get
To polymer porphyrin nano material（It is denoted as PTAPP, PNiTAPP respectively）.
Using optimal conditions in above-described embodiment, i.e., at 180 DEG C, reacts under 24 h, select TAPP respectively（Center is without gold
Belong to）And NiTAPP（Center band W metal）It is polymerize, the SEM figure and Fig. 7 B if Fig. 7 A is products therefrom PTAPP are
The SEM of PNiTAPP schemes, and obtains hollow porphyrin polymer nano material.
Embodiment 7
The LSV of porphyrin polymer nano material is tested, and is included the following steps：
(1) PTAPP, PNiTAPP obtained in PMAA-Fe-TAPP made from embodiment 2, embodiment 6 are taken 0.135 mg points
It is dissipated in 50 μ L water, the Nafion dispersion liquid of 12.5 μ L is added in ultrasound after mixing（5% w/w water and 1- propanol solution, exchange
Capacity>0.92 meq/g）, wherein water and Nifion dispersion liquid volume ratio are 4:1.
(2) material in step (1) is dripped dropwise in the platinum carbon electrode surface that diameter is 3mm（Electrode surface area is
7.07*10-2cm2）, the amount of dropwise addition is about 0.5 mg/cm2, naturally dry, obtain porphyrin polymer material modification after platinum carbon
Electrode；
(3) use three-electrode system using the platinum carbon electrode after the modification of porphyrin polymer material as working electrode, Pt are pair
Electrode, CV of the Ag/AgCl electrode as reference electrode test material（Cyclic voltammetry curve method）, LSV（Linear sweep voltammetry）
To characterize its electrocatalytic oxidation reducing property.CV（Cyclic voltammetry curve method）The electrolyte solution of test is the HClO of 0.1M4（Scanning
Current potential is：- 0.2 ~ 0.8 V, scanning speed 10mV/s）, lead to test after oxygen 30min, test results are shown in figure 8, PMAA-
Cu-TAPP（That is PTAPP）Porphyrin polymer does not have apparent peak, and PMAA-Fe-TAPP porphyrin polymer is in the oxygen gas of saturation
There is a redox peak in atmosphere at 0.21V, and the peak ORR for the Pt/C that we survey is at 0.65V.And LSV（Linear scan volt
An Fa）Electrolyte solution use 0.1 M KOH respectively（Scanning current potential is：-0.05 V~-0.8 V）Shown in Fig. 9 or 0.5 M
H2SO4（Scanning current potential is：0.8 V~0.05 V）In solution shown in Figure 10.After logical 30 min of oxygen, respectively revolving speed be 200 r,
LSV curve is tested under 500 r, 1000 r, 1500 r, 2000 r, 2500 r, 3000 r, 3600 r.It tests under different rotating speeds
Shown in LSV curve graph 9,10（A figure is PTAPP, and B figure is PNiTAPP）.The results show that with the increase of revolving speed, polarization current by
It is cumulative big, and PTAPP, PNiTAPP show stable electrocatalytic oxidation reducing property under alkaline condition, under different rotating speeds；
And in acid condition, PTAPP is more stable, and metal nickel-porphyrin PNiTAPP is unstable, this may have with falling off for metallic nickel
It closes.The porphyrin polymer microballoon done when the result shows that prepared porphyrin polymer microsphere nano material is using PMAA-Fe as template
Show certain ORR performance, but compared with commercial catalysts Pt/C or difference farther out, this may in its electro-chemical activity
The heart is less related, subsequent that Ar/H can be used2Calcining is improved under atmosphere.But the application is to prepare electrocatalytic oxidation reduction
（ORR）Catalyst provides a kind of new preparation method.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of porphyrin polymer nano material, characterized in that include the following steps：
（1）By the acetonitrile dispersion liquid of PMAA or PEGDMA, centrifugation takes precipitating to be added in the ethanol solution of sodium acetate, and stirring is extremely
Few 10 ~ 15h, centrifugation take precipitating to obtain PMAA-Na or PEGDMA-Na, disperse ferric nitrate for PMAA-Na or PEGDMA-Na
It in the ethanol solution of ethanol solution or copper nitrate, stirs, centrifugation takes precipitating, respectively obtains PMAA-Fe, PEGDMA-Fe, PMAA-
Cu, PEGDMA-Cu template；
（2）Porphyrin presoma is dissolved in polar solvent, porphyrin precursor solution is obtained；
（3）Step（1）Template be dispersed in water, obtain template solution；
（4）By step（2）Solution be added step（3）Solution in, stir evenly, 50 ~ 180 DEG C reaction 2 ~ for 24 hours, centrifugation, take precipitating,
Obtain porphyrin polymer nano material.
2. the preparation method of porphyrin polymer nano material as described in claim 1, characterized in that the ethyl alcohol of the sodium acetate is molten
Liquid concentration is 0.00328 ~ 0.010g/mL；The mass ratio of the sodium acetate and PMAA or PEGDMA is（0.68~6.5）:1.
3. the preparation method of porphyrin polymer nano material as described in claim 1, characterized in that the ethyl alcohol of the ferric nitrate is molten
Liquid concentration is 0.01212 ~ 0.05 g/mL；The ethanol solution concentration of the copper nitrate be 0.0725 ~ 0.1g/mL, PMAA-Na or
The mass ratio of PEGDMA-Na and ferric nitrate is 1:（0.01212~0.05）, the quality of PMAA-Na or PEGDMA-Na and copper nitrate
Than being 1:（0.0725~0.1）.
4. the preparation method of porphyrin polymer nano material as described in claim 1, characterized in that the porphyrin presoma is 5,
10,15,20- tetra- (4- aminobenzene) -21H, 23H- porphyrin or Ni (II) -5,10,15,20- four (4- aminophenyl) porphyrin.
5. the preparation method of porphyrin polymer nano material as claimed in claim 4, characterized in that the polar solvent is DMF
Or DMSO.
6. the preparation method of porphyrin polymer nano material as claimed in claim 5, characterized in that the porphyrin precursor solution
Concentration be 0.01-0.015 mol/L.
7. the preparation method of porphyrin polymer nano material as claimed in claim 6, characterized in that the step（3）In take 5mg
Template is scattered in the water of 9 ~ 9.8mL, and template solution and the volume ratio of porphyrin precursor solution are 1 ︰（9~49）.
8. the preparation method of porphyrin polymer nano material as claimed in claim 6, characterized in that the step（4）In 160
~ 180 DEG C of reactions 12 ~ for 24 hours.
9. porphyrin polymer nano material made from any method of claim 1 to 8.
10. application of the porphyrin polymer nano material as ORR catalyst described in claim 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113933363A (en) * | 2021-08-06 | 2022-01-14 | 济南大学 | Gas sensor for detecting acetone and application thereof |
| CN114477097A (en) * | 2022-01-12 | 2022-05-13 | 江南大学 | Method for producing hydrogen peroxide based on porphyrin-based supramolecules through photo-thermal catalysis without sacrificial agent |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020183470A1 (en) * | 2000-11-27 | 2002-12-05 | Sukant Tripathy | Polymerization of aromatic monomers using derivatives of hematin |
| US7374599B1 (en) * | 2004-07-08 | 2008-05-20 | Sandia Corporation | Dendritic metal nanostructures |
| CN102603972A (en) * | 2012-03-13 | 2012-07-25 | 重庆大学 | Preparation method of dimethyl methylphosphonate (DMMP) molecular imprinting polymer microspheres |
| CN104557948A (en) * | 2013-10-09 | 2015-04-29 | 中国科学院化学研究所 | Method for preparing monodispersed porphyrin molecule particles by water droplet templating method |
| CN106220636A (en) * | 2016-07-26 | 2016-12-14 | 河南大学 | A kind of method using cosolvent method to prepare phenylamino porphyrin self-assembled nanometer material |
-
2018
- 2018-05-07 CN CN201810425211.8A patent/CN108892773B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020183470A1 (en) * | 2000-11-27 | 2002-12-05 | Sukant Tripathy | Polymerization of aromatic monomers using derivatives of hematin |
| US7374599B1 (en) * | 2004-07-08 | 2008-05-20 | Sandia Corporation | Dendritic metal nanostructures |
| CN102603972A (en) * | 2012-03-13 | 2012-07-25 | 重庆大学 | Preparation method of dimethyl methylphosphonate (DMMP) molecular imprinting polymer microspheres |
| CN104557948A (en) * | 2013-10-09 | 2015-04-29 | 中国科学院化学研究所 | Method for preparing monodispersed porphyrin molecule particles by water droplet templating method |
| CN106220636A (en) * | 2016-07-26 | 2016-12-14 | 河南大学 | A kind of method using cosolvent method to prepare phenylamino porphyrin self-assembled nanometer material |
Non-Patent Citations (1)
| Title |
|---|
| HADI NUR ET AL.: ""Iron-porphyrin encapsulated in poly(methacrylic acid) and mesoporous Al-MCM-41 as catalysts in the oxidation of benzene to phenol"", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113933363A (en) * | 2021-08-06 | 2022-01-14 | 济南大学 | Gas sensor for detecting acetone and application thereof |
| CN114477097A (en) * | 2022-01-12 | 2022-05-13 | 江南大学 | Method for producing hydrogen peroxide based on porphyrin-based supramolecules through photo-thermal catalysis without sacrificial agent |
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