CN110137516A - The sulfur and nitrogen co-doped carbon elctro-catalyst and preparation method of ferro-tin alloy load - Google Patents
The sulfur and nitrogen co-doped carbon elctro-catalyst and preparation method of ferro-tin alloy load Download PDFInfo
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- CN110137516A CN110137516A CN201910411013.0A CN201910411013A CN110137516A CN 110137516 A CN110137516 A CN 110137516A CN 201910411013 A CN201910411013 A CN 201910411013A CN 110137516 A CN110137516 A CN 110137516A
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Abstract
The invention discloses the sulfur and nitrogen co-doped carbon elctro-catalysts and preparation method of a kind of load of ferro-tin alloy, belong to the preparation field of cell cathode oxygen reduction catalyst.The present invention is using doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl porphyrins and 2, for 6- dicarbaldehyde pyridine under 60 DEG C of nitrogen protections, glacial acetic acid (analysis pure) makees catalyst, anhydrous FeCl3As source metal, the covalent organic polymer loaded by Sn-Fe has been synthesized, after high temperature pyrolysis, FeSn is made2The carbon material of alloy load.The ferro-tin alloy of this novel duplex shell structure loads carbon-based elctro-catalyst; with two-dimentional porous structure; the nonmetallic tin catalysis strategy in the area P is promoted using metallic iron; middle metal oxide layer provides good channel for the transmitting and transfer of charge in system; accelerate the progress of mass transport process; to provide new thinking to open up the area P non noble metal oxygen reduction elctro-catalyst, preparation process is simple and easy, it is easy to accomplish large-scale industrial application.
Description
Technical field
The present invention relates to cell cathode oxygen reduction catalyst technical field, derived from specifically covalent porphyryl skeleton
The sulfur and nitrogen co-doped carbon electrocatalysis material of ferro-tin alloy nanometer particle load with duplex shell structure, that is, ferro-tin alloy load sulphur nitrogen
Codope carbon elctro-catalyst and preparation method.
Background technique
In order to efficiently solve the contradiction increasingly sharpened between economic development and energy shortage and environmental pollution, development cleaning,
Efficiently, renewable energy storage and switch technology (such as Proton Exchange Membrane Fuel Cells, zinc and air cell) have become very urgent
Task.Since cell cathode oxygen reduction reaction rate is slow, the power output of fuel cell is limited, this kind of battery is hindered
Large-scale commercial applications application.Therefore, seek the electrocatalyst for cathode of enhancing oxygen reduction reaction rate, improve chemical energy to electric energy
Efficient Conversion has become the focus of research.In general, a large amount of Pt base elctro-catalyst enjoys great popularity because of with lower overpotential,
However Pt Precious Metals Resources are rare, at high price, are easily poisoned, so that commercializing fuel cells are by huge obstruction.Development of Novel
Hydrogen reduction base metal or non-noble metal oxide elctro-catalyst (especially nontoxic, the inexpensive area P metal) to replace completely
Pt base catalysis material becomes research hotspot in recent years.
Currently, tinbase oxygen reduction electro-catalyst is due to very high electron mobility, excellent electric conductivity, long-term chemical
Stability and environmental-friendly characteristic are considered as a kind of very promising electrode material extensively.Such as Pt-Sn, Au-Sn, Pd-Sn
Alloy etc. has been used as hydrogen reduction electrocatalysis material for being catalyzed ORR in alkaline medium.Although having paid huge effort, due to
The limitation of noble metal, reducing bullion content and improving electro catalytic activity is still a major challenge.Seek transition metal-tinbase electricity
Catalyst replaces noble metal-tinbase catalysis material to become the main task of research completely.Covalent organic framework (COF) is due to it
Two dimension or three-D space structure and show one's talent in many materials with bigger serface and abundant pore structure, this avoids
The aggregation of active component simultaneously effectively increases active site density.Its lower skeletal density can be with the work as carbon carrier
Property material generate simultaneously, the Nomenclature Composition and Structure of Complexes of adjustable COFs is generated and function point analysis with promoting the molecule of catalysis material.Cause
This, prepares FeSn as material of main part using two-dimentional covalently organic polymer2Alloy support type oxygen reduction electro-catalyst is used to
It improves oxygen reduction catalytic activity and has become the emphasis of research for fields such as zinc and air cells.
Summary of the invention
The purpose of the present invention is in view of the deficiencies of the prior art and provide a kind of ferro-tin alloy load it is sulfur and nitrogen co-doped
Carbon elctro-catalyst and preparation method, the present invention use Sn (OH)x5,10,15,20- tetra- (amino) the phenyl porphyrins and 2,6- of doping
For dicarbaldehyde pyridine under 60 DEG C of nitrogen protections, glacial acetic acid (analysis is pure) makees catalyst, and anhydrous ferric chloride is added, and passes through schiff bases idol
Connection reaction has synthesized one kind by Fe, and ferro-tin alloy load is made after high temperature pyrolysis in Sn metal-doped covalent organic polymer
The elctro-catalyst of sulfur and nitrogen co-doped carbon.Realize the structure of the molecular structure of efficiently derivative tinbase non noble metal oxygen reduction elctro-catalyst
It builds, breaches dependence of the elctro-catalyst to noble metal or precious metal alloys, by covalent organic framework two-dimensional channel knot abundant
Structure is effectively increased the density of sulphur nitrogen-doped carbon active sites in the porous material, so that the activity of hydrogen reduction is improved, for certainly
The synthesis of the main group base metal of load type efficient stable-sulfur and nitrogen co-doped carbon oxygen reduction electro-catalyst lays the foundation.
Realizing the specific technical solution of the object of the invention is:
A kind of preparation method of the sulfur and nitrogen co-doped carbon elctro-catalyst of ferro-tin alloy load, this method includes walking in detail below
It is rapid:
Step 1: 5,10,15,20- tetra- (nitro) phenyl porphyrins of preparation
Paranitrobenzaldehyde and pyrroles are mixed by 1: 2~4 molar ratios, it is pure that the analysis that 100~150 volume ratios are boiled is added
In propionic acid, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is sufficiently washed with deionized water, and vacuum is dry
It is dry；Later with pyridine flow back wash, cool overnight, filter post analysis pure acetone wash it is colourless to filtrate, after vacuum drying be made
5,10,15,20- tetra- (nitro) phenyl porphyrins；
Step 2: preparation doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl porphyrins
Under nitrogen protection, obtained above 5,10,15,20- tetra- (amino) phenyl porphyrins and SnCl are taken2·2H2O massage
You are dissolved with dense HCl than 1: 8~10 mixing, stir 2.5h under room temperature, are warming up to 70 DEG C, react 30min, and reaction terminates
Ice-water bath is cooling afterwards, pours into the deionized water of 5~10 volume ratios, adjusts pH to 8-9, and suction filtration obtains doping Sn (OH)x5,10,
15,20- tetra- (amino) phenyl porphyrins；Wherein, X=2 or 4；
Step 3: preparing covalent metal organic polymer
Under nitrogen protection, doping Sn (OH) is weighedx5,10,15,20- tetra- (amino) phenyl porphyrins, 2,6- dicarbaldehyde
Pyridine and anhydrous ferric chloride press 1: 4~5: 1~3 molar ratio mixed dissolutions in analytically pure dimethyl sulfoxide, with the pure ice of analysis
Vinegar acid as catalyst, 60 DEG C are heated to reflux 15h, after reaction, the solid filtered out with analyze pure methanol wash it is colourless to filtrate,
Obtain brick-red solid i.e. covalent metal organic polymer；
Step 4: preparing alloy and load covalent organic polymer
Under nitrogen protection, by covalent metal organic polymer obtained above at a temperature of 800~1000 DEG C, heating speed
2~5 DEG C/min of rate, heat preservation 4h carry out pyrolysis processing, the sulfur and nitrogen co-doped carbon elctro-catalyst of ferro-tin alloy load are made.
A kind of sulfur and nitrogen co-doped carbon elctro-catalyst of the load of ferro-tin alloy made from the above method.
The present invention has successfully prepared the ferro-tin alloy load carbon consuming cell electrocatalyst for cathode of low cost, high activity,
There is novel microporous structure biggish pore volume and relatively narrow pore-size distribution, active site to be evenly distributed, and improve the electricity of material
Chemical property makes elctro-catalyst show higher catalytic activity and stability.The bivalve of special carbon-coating and oxide layer package
Layer structure substantially increases the stability of material, and the transfer of electronics is promoted during electro-catalysis.Elctro-catalyst of the invention
Higher open circuit potential and preferable stability are also shown in zinc and air cell.The present invention is to open up the area p base metal electricity
Catalyst provides new thinking.
Detailed description of the invention
Fig. 1 is Sn (OH) in the embodiment of the present invention 1xThe infrared spectrogram of@TAPP and Fe-Sn-CPFs；
Fig. 2 is FeSn in the embodiment of the present invention 12/FeSnOxThe linear scan curve graph of@S-N-C-1000；
Fig. 3 is FeSn in the embodiment of the present invention 22@FeSnOxThe linear scan curve graph of@S-N-C-800；
Fig. 4 is FeSn in the embodiment of the present invention 32@FeSnOxThe big angle X-ray powder diffraction pattern of@S-N-C-800；
Fig. 5 is FeSn in the embodiment of the present invention 42@FeSnOxThe nitrogen adsorption desorption curve graph of@S-N-C-1000 and aperture point
Butut；
Fig. 6 is FeSn in the embodiment of the present invention 52@FeSnOxThe linear scan curve graph of@S-N-C-900；
Fig. 7 is FeSn in the embodiment of the present invention 62@FeSnOxThe transmission electron microscope figure of@S-N-C-900；
Fig. 8 is FeSn in the embodiment of the present invention 72@FeSnOxThe Raman spectrogram of@S-N-C-900；
Fig. 9 is FeSn in the embodiment of the present invention 82@FeSnOxThe nitrogen adsorption desorption curve graph and pore-size distribution of@S-N-C-800
Figure；
Figure 10 is FeSn in the embodiment of the present invention 92@FeSnOxThe zinc and air cell charge-discharge performance curve of@S-N-C-900 and
Stability diagram.
Specific embodiment
The present invention will be described in detail with reference to the accompanying drawings and embodiments.
The synthesis process of elctro-catalyst of the present invention is shown below:
Embodiment 1
A. 5,10,15,20- tetra- (nitro) phenyl porphyrins are prepared
0.1 mole of paranitrobenzaldehyde is added in the propionic acid (analysis is pure) that 100mL boils and stirs 30min, dropwise addition contains
The 10mL propionic acid of 0.2 mole of pyrroles, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is filled with deionized water
Divide washing, and is dried in vacuo.Flowed back and washed with pyridine later, cool overnight, after suction filtration acetone (analysis is pure) washing to filtrate without
Color is 5,10,15,20- tetra- (nitro) phenyl porphyrins (TNPP) after vacuum drying.
B. doping Sn (OH) is preparedx5,10,15,20- tetra- (amino) phenyl porphyrins
Under nitrogen protection, 0.1 mole 5 of above-mentioned synthesis is taken, 10,15,20- tetra- (nitro) phenyl porphyrins are dissolved in
0.8 mole of SnCl in 100mL concentrated hydrochloric acid (analysis is pure)2·2H2O is dissolved in 25mL concentrated hydrochloric acid (analysis is pure) and is added drop-wise to above-mentioned body
In system, 2.5h is stirred under room temperature, is warming up to 70 DEG C, reacts 30min, and ice-water bath is cooling after reaction, pours into and is equipped with
50mL H2In the beaker of O, pH to 8-9 is adjusted, suction filtration obtains 5.5 grams of doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl porphins
Quinoline (Sn (OH)x@TAPP)。
C. covalent metal organic polymer is prepared
Under nitrogen protection, 0.1 mole of doping Sn (OH) is weighedx5,10,15,20- tetra- (amino) phenyl porphyrins, 0.4
Mole 2,6- dicarbaldehyde pyridine and 0.3 mole of anhydrous ferric chloride mixed dissolution in dimethyl sulfoxide (analysis is pure), glacial acetic acid (point
Analyse pure) make catalyst, 60 DEG C are heated to reflux 12 hours, and after reaction, the solid filtered out is washed with methanol (analysis is pure) to filter
Liquid is colourless, obtains brick-red solid covalent metal organic polymer Fe-Sn-CPFs；
D. it prepares alloy and loads covalent organic polymer
Under nitrogen protection, by covalent metal organic polymer obtained above at a temperature of 1000 DEG C, heating rate 3
DEG C/min, 4 hours progress pyrolysis processings are kept the temperature, the sulfur and nitrogen co-doped carbon electro-catalysis FeSn of ferro-tin alloy load is made2@FeSnOx@
S-N-C-1000。
Refering to attached drawing 1,0.1 mole of doping Sn (OH) of above-mentioned preparationx5,10,15,20- tetra- (amino) phenyl porphyrins
(Sn(OH)x@TAPP) raw material and covalent metal organic backbone (Fe-Sn-CPFs) be through infrared detection, it is known that in 3380cm-1Near
Biabsorption peak occur is NH on skeleton2Stretching vibration, 1280cm-1Absorption peak be phenyl ring and amino C-N stretching vibration,
1600cm-1,1500cm-1Locate the synthesis that clearly infrared absorption peak shows phenyl and the main skeleton of pyrroles in TAPP.Simultaneously
Infrared detection is carried out to the covalent organic polymer backbones of above-mentioned preparation, it is known that in 3380cm-1The bimodal disappearance occurred,
1709cm-1And 1400cm-1There is the stretching vibration absworption peak of C=N and C-C=N-C in place, shows 5,10,15,20- tetra- (ammonia
Base) phenyl porphyrin and 2,6- dicarbaldehyde pyridine successful polymerization.
By the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-1000 electrocatalysis material is adopted in CHI760C electrochemical workstation
Electro-chemical activity test is technically carried out with cyclic voltammetry (CV) and rotating disk electrode (r.d.e).The test uses three electrode bodies
System, using the glass-carbon electrode of diameter 3mm as working electrode, Ag/AgCl (3MKCl) is reference electrode, and Pt are used as to electrode,
0.1MKOH solution is electrolyte.Al is used after working electrode is polished with abrasive paper for metallograph2O3Polished, then respectively with ethyl alcohol and
Deionized water is cleaned by ultrasonic electrode, dries under infrared lamp, takes the FeSn of the above-mentioned preparation of 10mg2@FeSnOx@S-N-C-1000 electricity is urged
Agent is added in the mixed liquor of 30uL Nafion and 1.25mL ethyl alcohol and is ultrasonically treated, and will obtain finely dispersed mixing
On the working electrode of solution even spread after a polish, then the evaporation of solvent under infrared lamp, is made glass-carbon electrode surface layer and applies
There is FeSn2@FeSnOxThe working electrode of@S-N-C-1000 elctro-catalyst film.High pure nitrogen or oxygen are each led into before testing
15min is made gas in electrolyte reach saturation state, is scanned at room temperature with the speed of 50mV/s.
Refering to attached drawing 2, to the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-1000 elctro-catalyst and business platinum carbon carry out electricity
Test chemical, FeSn2@FeSnOxThe half wave potential of@S-N-C-1000 is 0.80V, but respectively lower than platinum carbon 60mV.Though illustrating
Right FeSn2@FeSnOxThe catalytic activity of@S-N-C-1000 is not as good as platinum carbon, but FeSn2The doping of alloy substantially increases this and urges
Change the catalytic performance of material.
Embodiment 2
A. 5,10,15,20- tetra- (nitro) phenyl porphyrins are prepared
0.1 mole of paranitrobenzaldehyde is added in the propionic acid that 120mL boils and stirs 30min, is added dropwise and contains 0.3 mole of pyrrole
The 10mL propionic acid coughed up, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is sufficiently washed with deionized water, and
Vacuum drying.It is washed later with pyridine reflux, cool overnight, acetone (analysis is pure) washing is colourless to filtrate after suction filtration, and vacuum is dry
It is 5,10,15,20- tetra- (nitro) phenyl porphyrins (TNPP) after dry.
B. doping Sn (OH) is preparedx5,10,15,20- tetra- (amino) phenyl porphyrins
Under nitrogen protection, 0.1 mole of doping Sn (OH) obtained above is takenx5,10,15,20- tetra- (amino) phenyl
Porphyrin and 0.9 mole of SnCl2·2H2O mixing is stirred 2.5 hours under room temperature, is warming up to concentrated hydrochloric acid (analysis is pure) dissolution
It 70 DEG C, reacts 30 minutes, ice-water bath is cooling after reaction, pours into 100 milliliters of deionized water, adjusts pH to 8-9, and suction filtration obtains
6.7 grams of doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl porphyrins；
C. covalent metal organic polymer is prepared
Under nitrogen protection, 0.1 mole of doping Sn (OH) is weighedx5,10,15,20- tetra- (amino) phenyl porphyrins, 0.4
Mole 2,6- dicarbaldehyde pyridine and 0.2 mole of anhydrous ferric chloride mixed dissolution in dimethyl sulfoxide (analysis is pure), glacial acetic acid (point
Analyse pure) make catalyst, 60 DEG C are heated to reflux 13 hours, and after reaction, the solid filtered out is washed with methanol (analysis is pure) to filter
Liquid is colourless, obtains brick-red solid i.e. covalent metal organic polymer Fe-Sn-CPFs；
D. alloy sulfur loaded nitrogen-doped carbon elctro-catalyst is prepared
Under nitrogen protection, after covalent metal organic polymer obtained above being ground under high pure nitrogen atmosphere, with 2
DEG C/heating rate of min is warming up to 800 DEG C of temperature, 4 hours are kept the temperature, the sulfur and nitrogen co-doped of ferro-tin alloy load is made after cooling
Carbon elctro-catalyst (FeSn2@FeSnOx@S-N-C-800)。
Refering to attached drawing 3, to the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-800 elctro-catalyst carries out electro-chemical test,
FeSn2@FeSnOxThe half wave potential of@S-N-C-800 elctro-catalyst is 0.82V, illustrates that the material is still at 800 DEG C of heat treatment temperature
So there is good catalytic activity.
Embodiment 3
A.5, the preparation of 10,15,20- tetra- (nitro) phenyl porphyrins
0.1 mole of paranitrobenzaldehyde is added in the propionic acid that 150mL boils and stirs 30min, is added dropwise and contains 0.3 mole of pyrrole
The 10mL propionic acid coughed up, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is sufficiently washed with deionized water, and
Vacuum drying.It is washed later with pyridine reflux, cool overnight, acetone (analysis is pure) washing is colourless to filtrate after suction filtration, and vacuum is dry
It is 5,10,15,20- tetra- (nitro) phenyl porphyrins (TNPP) after dry.
B. Sn (OH) is adulteratedx5,10,15,20- tetra- (amino) phenyl porphyrins preparation
Under nitrogen protection, 0.1 mole 5 of above-mentioned synthesis is taken, 10,15,20- tetra- (nitro) phenyl porphyrins are dissolved in
1.0 moles of SnCl in 100mL concentrated hydrochloric acid (analysis is pure)2·2H2O is dissolved in 25mL concentrated hydrochloric acid (analysis is pure) and is added drop-wise to above-mentioned body
In system, 2.5h is stirred under room temperature, is warming up to 70 DEG C, reacts 30min, and ice-water bath is cooling after reaction, pours into and is equipped with
100mL H2In the beaker of O, pH to 8-9 is adjusted, suction filtration obtains 7.0 grams of doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl
Porphyrin (Sn (OH)x@TAPP)。
C. the preparation of covalent organic polymer Fe-Sn-CPFs
Under nitrogen protection, the Sn (OH) of 0.1 mole of above-mentioned preparation is weighedx@TAPP and 0.5 mole of 2,6- dicarbaldehyde pyridine
For mixed dissolution in dimethyl sulfoxide (analysis is pure), glacial acetic acid (analysis is pure) makees catalyst, and the anhydrous FeCl of 0.1mol is added3,60
DEG C it is heated to reflux 14h, after reaction, the solid filtered out wash, obtained Fe-Sn- colourless to filtrate with methanol (analysis is pure)
CPFs。
d.FeSn2@FeSnOxThe preparation of@S-N-C-800 elctro-catalyst.
It is risen respectively under high pure nitrogen atmosphere with 2 DEG C/min after the Fe-Sn-CPFs electrocatalysis material of above-mentioned preparation is ground
Temperature is cooled to room temperature after being heat-treated 4 hours to 800 DEG C, and FeSn is made2@FeSnOx@S-N-C-800 catalysis material.
Refering to attached drawing 4, to the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-800 elctro-catalyst carries out X-ray diffraction test,
By spectrogram it is found that there is the diffraction maximum of graphitic carbon in 2 θ=26.5 °, correspond respectively to (002) crystal face of graphitic carbon, 2 θ=
33 ° (002), 35 ° (211), 39.1 ° (112), 43.8 ° (310), 61.1 ° (411), 67.3 ° (402), 71 ° of and (004) go out
Existing diffraction maximum corresponds to FeSn2(PDF#73-2030) and Fe4C (PDF#65-3286), it was demonstrated that have FeSn in material prepared2With
Fe4C crystal phase exists, this provides active site for the electrocatalysis characteristic of material.
Embodiment 4
A.5, the preparation of 10,15,20- tetra- (nitro) phenyl porphyrins
0.1 mole of paranitrobenzaldehyde is added in the propionic acid that 140mL boils and stirs 30min, is added dropwise and contains 0.4 mole of pyrrole
The 10mL propionic acid coughed up, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is sufficiently washed with deionized water, and
Vacuum drying.It is washed later with pyridine reflux, cool overnight, acetone (analysis is pure) washing is colourless to filtrate after suction filtration, and vacuum is dry
It is 5,10,15,20- tetra- (nitro) phenyl porphyrins (TNPP) after dry.
B. the preparation of 5,10,15,20- tetra- (amino) phenyl porphyrins of Sn (OH) x is adulterated
Under nitrogen protection, 0.1 mole 5 of above-mentioned synthesis is taken, 10,15,20- tetra- (nitro) phenyl porphyrins are dissolved in
1.0 moles of SnCl in 100mL concentrated hydrochloric acid (analysis is pure)2·2H2O is dissolved in 25mL concentrated hydrochloric acid (analysis is pure) and is added drop-wise to above-mentioned body
In system, 2.5h is stirred under room temperature, is warming up to 70 DEG C, reacts 30min, and ice-water bath is cooling after reaction, pours into and is equipped with
100mL H2In the beaker of O, pH to 8-9 is adjusted, suction filtration obtains doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl porphyrins
(Sn(OH)x@TAPP) 6.9 grams.
C. the preparation of covalent organic polymer Fe-Sn-CPFs
Under nitrogen protection, the Sn (OH) of 0.1 mole of above-mentioned preparation is weighedx@TAPP and 0.5 mole of 2,6- dicarbaldehyde pyridine
For mixed dissolution in dimethyl sulfoxide (analysis pure), glacial acetic acid (analysis is pure) makees catalyst, is added 0.2mol anhydrous ferric chloride, and 60
DEG C it is heated to reflux 15h, after reaction, the solid filtered out wash, obtained Fe-Sn- colourless to filtrate with methanol (analysis is pure)
CPFs。
d.FeSn2@FeSnOxThe preparation of@S-N-C-1000 catalysis material
It is risen respectively with 2 DEG C/min under high pure nitrogen atmosphere again after the Fe-Sn-CPFs electrocatalysis material of above-mentioned preparation is ground
Temperature is cooled to room temperature after being heat-treated 4 hours to 1000 DEG C, and it is FeSn that covalent metal organic polymer, which is made,2@FeSnOx@S-N-C-
1000 catalysis materials.
Refering to attached drawing 5, to the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-1000 elctro-catalyst carries out the survey of nitrogen adsorption desorption
Examination, by test spectrogram it is found that FeSn2@FeSnOx@S-N-C-1000 meets typical first kind adsorption isotherm, has typical
Poromerics feature, BET specific surface value are 602m2g-1, micropore size is distributed in 0.45nm or so.
Embodiment 5
A.5, the preparation of 10,15,20- tetra- (nitro) phenyl porphyrins
0.1 mole of paranitrobenzaldehyde is added in the propionic acid that 150mL boils and stirs 30min, is added dropwise and contains 0.2 mole of pyrrole
The 10mL propionic acid coughed up, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is sufficiently washed with deionized water, and
Vacuum drying.It is washed later with pyridine reflux, cool overnight, acetone (analysis is pure) washing is colourless to filtrate after suction filtration, and vacuum is dry
It is 5,10,15,20- tetra- (nitro) phenyl porphyrins (TNPP) after dry.
B. Sn (OH) is adulteratedx5,10,15,20- tetra- (amino) phenyl porphyrins preparation
Under nitrogen protection, 0.1 mole 5 of above-mentioned synthesis is taken, 10,15,20- tetra- (nitro) phenyl porphyrins are dissolved in
1.0 moles of SnCl in 100mL concentrated hydrochloric acid (analysis is pure)2·2H2O is dissolved in 25mL concentrated hydrochloric acid (analysis is pure) and is added drop-wise to above-mentioned body
In system, 2.5h is stirred under room temperature, is warming up to 70 DEG C, reacts 30min, and ice-water bath is cooling after reaction, pours into and is equipped with
100mL H2In the beaker of O, pH to 8-9 is adjusted, suction filtration obtains 8.5 grams of doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl
Porphyrin (Sn (OH)x@TAPP)。
C. the preparation of covalent organic polymer
Under nitrogen protection, the Sn (OH) of 0.1 mole of above-mentioned preparation is weighedx@TAPP and 0.4 mole of 2,6- dicarbaldehyde pyridine
For mixed dissolution in dimethyl sulfoxide (analysis is pure), glacial acetic acid (analysis is pure) makees catalyst, and the anhydrous FeCl of 0.3mol is added3,60
DEG C it is heated to reflux 16h, after reaction, the solid filtered out wash, obtained Fe-Sn- colourless to filtrate with methanol (analysis is pure)
CPFs。
d.FeSn2@FeSnOxThe preparation of@S-N-C-900 catalysis material
It is risen respectively with 2 DEG C/min under high pure nitrogen atmosphere again after the Fe-Sn-CPFs electrocatalysis material of above-mentioned preparation is ground
Temperature is cooled to room temperature after being heat-treated 4 hours to 900 DEG C, and it is FeSn that covalent metal organic polymer, which is made,2@FeSnOx@S-N-C-
900 catalysis materials.
Refering to attached drawing 6, to the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-900 elctro-catalyst carries out electro-chemical test,
FeSn2@FeSnOxThe half wave potential of@S-N-C-900 is 0.88V, is higher than business platinum carbon 20mV, illustrates FeSn2Alloy is as material
Activated centre improve hydrogen reduction electrocatalysis characteristic.
Embodiment 6
A.5, the preparation of 10,15,20- tetra- (nitro) phenyl porphyrins
0.1 mole of paranitrobenzaldehyde is added in the propionic acid that 110mL boils and stirs 30min, is added dropwise and contains 0.2 mole of pyrrole
The 10mL propionic acid coughed up, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is sufficiently washed with deionized water, and
Vacuum drying.It is washed later with pyridine reflux, cool overnight, acetone (analysis is pure) washing is colourless to filtrate after suction filtration, and vacuum is dry
It is 5,10,15,20- tetra- (nitro) phenyl porphyrins (TNPP) after dry.
B. Sn (OH) is adulteratedx5,10,15,20- tetra- (amino) phenyl porphyrins preparation
Under nitrogen protection, 0.1 mole 5 of above-mentioned synthesis is taken, 10,15,20- tetra- (nitro) phenyl porphyrins are dissolved in
In 100mL concentrated hydrochloric acid, 0.9 mole of SnCl2·2H2O is dissolved in 25mL concentrated hydrochloric acid and is added drop-wise in above-mentioned system, under room temperature
2.5h is stirred, is warming up to 70 DEG C, reacts 30min, ice-water bath is cooling after reaction, pours into equipped with 100mL H2In the beaker of O,
PH to 8-9 is adjusted, suction filtration obtains 7.2 grams of doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl porphyrin (Sn (OH)x@TAPP)。
C. the preparation of covalent organic polymer Fe-Sn-CPFs
Under nitrogen protection, the Sn (OH) of 0.1 mole of above-mentioned preparation is weighedx@TAPP, 0.4 mole of 2,6- dicarbaldehyde pyridine,
0.3 mole of anhydrous FeCl3Mixed dissolution is in dimethyl sulfoxide (analysis is pure), and glacial acetic acid (analysis is pure) makees catalyst, and 60 DEG C add
Heat reflux 18h, after reaction, the solid filtered out is washed colourless to filtrate with methanol (analysis pure), and covalent organic polymer is made
Object Fe-Sn-CPFs material.
d.FeSn2@FeSnOxThe preparation of@S-N-C-900 elctro-catalyst.
900 DEG C are warming up to 2 DEG C/min under high pure nitrogen atmosphere again after the Fe-Sn-CPFs material of above-mentioned preparation is ground,
Heat treatment was cooled to room temperature after 4 hours, and it is FeSn that covalent organic metal organic polymer, which is made,2@FeSnOx@S-N-C-900 catalysis
Material.
Refering to attached drawing 7, to the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-900 catalysis material transmission electron microscope into
Row morphology characterization shows being uniformly distributed for active site it can be observed that ferro-tin alloy nanoparticle is evenly distributed on carbon-coating
It is more advantageous to the electrocatalysis characteristic and stability for improving material.
Embodiment 7
A.5, the preparation of 10,15,20- tetra- (nitro) phenyl porphyrins
0.1 mole of paranitrobenzaldehyde is added in the propionic acid that 140mL boils and stirs 30min, is added dropwise and contains 0.1 mole of pyrrole
The 10mL propionic acid coughed up, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is sufficiently washed with deionized water, and
Vacuum drying.It is washed later with pyridine reflux, cool overnight, acetone (analysis is pure) washing is colourless to filtrate after suction filtration, and vacuum is dry
It is 5,10,15,20- tetra- (nitro) phenyl porphyrins (TNPP) after dry.
B. Sn (OH) is adulteratedx5,10,15,20- tetra- (amino) phenyl porphyrins preparation
Under nitrogen protection, 0.1 mole 5 of above-mentioned synthesis is taken, 10,15,20- tetra- (nitro) phenyl porphyrins are dissolved in
In 100mL concentrated hydrochloric acid (analysis is pure), 1 mole of SnCl2·2H2O is dissolved in 25mL concentrated hydrochloric acid (analysis is pure) and is added drop-wise to above-mentioned system
In, 2.5h is stirred under room temperature, is warming up to 70 DEG C, reacts 30min, and ice-water bath is cooling after reaction, pours into equipped with 100mL
H2In the beaker of O, pH to 8-9 is adjusted, suction filtration obtains 8.2 grams of doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl porphyrin (Sn
(OH)x@TAPP)。
C. covalent organic polymer0.3The preparation of Fe-Sn-CPFs
Under nitrogen protection, the Sn (OH) of 0.1 mole of above-mentioned preparation is weighedx@TAPP, 0.5 mole of 2,6- dicarbaldehyde pyridine,
0.2 mole of anhydrous FeCl3Mixed dissolution is in dimethyl sulfoxide (analysis is pure), and glacial acetic acid (analysis is pure) makees catalyst, and 60 DEG C add
Heat reflux 19h, after reaction, the solid filtered out is washed colourless to filtrate with methanol (analysis pure), and covalent organic polymer is made
Object Fe-Sn-CPFs material.
d.FeSn2@FeSnOxThe preparation of@S-N-C-900 catalysis material.
It is warming up to respectively with 2 DEG C/min under high pure nitrogen atmosphere again after the Fe-Sn-CPFs material of above-mentioned preparation is ground
900 DEG C heat treatment 4 hours after be cooled to room temperature, be made covalent organic metal organic polymer be FeSn2@FeSnOx@S-N-C-
900 catalysis materials.
Refering to attached drawing 8, to the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-900 electrocatalysis material carries out Raman test, by
Spectrogram is it is found that in 2800cm-1There is the 2D broad peak of graphitic carbon, and I in placeD/IGValue be 0.94, it is certain to illustrate that material has
Degree of graphitization, this result can be confirmed by XRD result.
Embodiment 8
A.5, the preparation of 10,15,20- tetra- (nitro) phenyl porphyrins
0.1 mole of paranitrobenzaldehyde is added in the propionic acid that 150mL boils and stirs 30min, is added dropwise and contains 0.3 mole of pyrrole
The 10mL propionic acid coughed up, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is sufficiently washed with deionized water, and
Vacuum drying.It is washed later with pyridine reflux, cool overnight, acetone (analysis is pure) washing is colourless to filtrate after suction filtration, and vacuum is dry
It is 5,10,15,20- tetra- (nitro) phenyl porphyrins (TNPP) after dry.
B. Sn (OH) is adulteratedx5,10,15,20- tetra- (amino) phenyl porphyrins preparation
Under nitrogen protection, 0.1 mole 5 of above-mentioned synthesis is taken, 10,15,20- tetra- (nitro) phenyl porphyrins are dissolved in
In 100mL concentrated hydrochloric acid (analysis is pure), 0.8 mole of SnCl2·2H2O is dissolved in 25mL concentrated hydrochloric acid (analysis is pure) and is added drop-wise to above-mentioned body
In system, 2.5h is stirred under room temperature, is warming up to 70 DEG C, reacts 30min, and ice-water bath is cooling after reaction, pours into and is equipped with
100mL H2In the beaker of O, pH to 8-9 is adjusted, suction filtration obtains 6.9 grams of doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl
Porphyrin (Sn (OH)x@TAPP)。
C. the preparation of covalent organic polymer Fe-Sn-CPFs
Under nitrogen protection, the Sn (OH) of 0.1 mole of above-mentioned preparation is weighedx@TAPP, 0.5 mole of 2,6- dicarbaldehyde pyridine,
0.3 mole of anhydrous FeCl3Mixed dissolution is in dimethyl sulfoxide (analysis is pure), and glacial acetic acid (analysis is pure) makees catalyst, and 60 DEG C add
Heat reflux 16h, after reaction, the solid filtered out is washed colourless to filtrate with methanol (analysis pure), and covalent organic polymer is made
Object Fe-Sn-CPFs material.
d.FeSn2@FeSnOxThe preparation of@S-N-C-800 catalysis material.
It is warming up to respectively with 2 DEG C/min under high pure nitrogen atmosphere again after the Fe-Sn-CPFs material of above-mentioned preparation is ground
800 DEG C heat treatment 4 hours after be cooled to room temperature, be made covalent organic metal organic polymer be FeSn2@FeSnOx@S-N-C-
800 catalysis materials.
Refering to attached drawing 9, to the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-800 elctro-catalyst carries out the survey of nitrogen adsorption desorption
Examination, by test spectrogram it is found that FeSn2@FeSnOx@S-N-C-800 meets typical first kind adsorption isotherm, has micropore material
The feature of material, BET specific surface value are 936m2g-1, micropore size is distributed in 0.38nm or so.
Embodiment 9
A.5, the preparation of 10,15,20- tetra- (nitro) phenyl porphyrins
0.1 mole of paranitrobenzaldehyde is added in the propionic acid that 150mL boils and stirs 30min, is added dropwise and contains 0.2 mole of pyrrole
The 10mL propionic acid coughed up, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is sufficiently washed with deionized water, and
Vacuum drying.It is washed later with pyridine reflux, cool overnight, acetone (analysis is pure) washing is colourless to filtrate after suction filtration, and vacuum is dry
It is 5,10,15,20- tetra- (nitro) phenyl porphyrins (TNPP) after dry.
B. Sn (OH) is adulteratedx5,10,15,20- tetra- (amino) phenyl porphyrins preparation
Under nitrogen protection, 0.1 mole 5 of above-mentioned synthesis is taken, 10,15,20- tetra- (nitro) phenyl porphyrins are dissolved in
In 150mL concentrated hydrochloric acid (analysis is pure), 0.8 mole of SnCl2·2H2O is dissolved in 25mL concentrated hydrochloric acid (analysis is pure) and is added drop-wise to above-mentioned body
In system, 2.5h is stirred under room temperature, is warming up to 70 DEG C, reacts 30min, and ice-water bath is cooling after reaction, pours into and is equipped with
100mL H2In the beaker of O, pH to 8-9 is adjusted, suction filtration obtains 7.5 grams of doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl
Porphyrin (Sn (OH)x@TAPP)。
C. the preparation of covalent organic polymer Fe-Sn-CPFs
Under nitrogen protection, the Sn (OH) of 0.1 mole of above-mentioned preparation is weighedx@TAPP, 0.3 mole of 2,6- dicarbaldehyde pyridine,
0.3 mole of anhydrous FeCl3Mixed dissolution is in dimethyl sulfoxide (analysis is pure), and glacial acetic acid (analysis is pure) makees catalyst, and 60 DEG C add
Heat reflux 20h, after reaction, the solid filtered out is washed colourless to filtrate with methanol (analysis pure), and covalent organic polymer is made
Object Fe-Sn-CPFs material.
d.FeSn2@FeSnOxThe preparation of@S-N-C-900
It is warming up to respectively with 2 DEG C/min under high pure nitrogen atmosphere again after the Fe-Sn-CPFs material of above-mentioned preparation is ground
900 DEG C heat treatment 4 hours after be cooled to room temperature, be made covalent organic metal organic polymer be FeSn2@FeSnOx@S-N-C-
900 catalysis materials.
By the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-900 catalysis material is assembled into chargeable electric discharge according to the following steps
Zinc-air battery.By the way that by catalyst, (load capacity is 4mg cm-2) be distributed on carbon cloth to prepare air cathode.Use polishing
Zinc foil as anode, prepare containing 0.2 rub zinc acetate 6 molar potassium hydroxide solution as electrolyte.At room temperature, pass through note
Constant temperature electric discharge-charging cycle curve is recorded, to draw electric discharge polarization and power density diagram.One of circulation includes an electric discharge step
Rapid and current density, a duration identical charge step (20mA cm-2Continue 24 hours, recycle 10 minutes).
Refering to attached drawing 10, to the FeSn of above-mentioned preparation2@FeSnOx@S-N-C-900 catalysis material carries out zinc and air cell test,
As shown, the material shows the open circuit potential of 1.49V and the power density better than platinum carbon.Illustrate that the electrocatalysis material has
Superior practical application performance.
Claims (2)
1. a kind of preparation method of the sulfur and nitrogen co-doped carbon elctro-catalyst of ferro-tin alloy load, which is characterized in that this method includes
Step in detail below:
Step 1: 5,10,15,20- tetra- (nitro) phenyl porphyrins of preparation
Paranitrobenzaldehyde and pyrroles are mixed by 1: 2~4 molar ratios, the analysis pure C acid that 100~150 volume ratios are boiled is added
In, 130 DEG C at a temperature of flow back 1h, the product filtered out after reaction is sufficiently washed with deionized water, and is dried in vacuo；It
Afterwards with pyridine flow back wash, cool overnight, filter post analysis pure acetone wash it is colourless to filtrate, after vacuum drying be made 5,10,
15,20- tetra- (nitro) phenyl porphyrins；
Step 2: preparation doping Sn (OH)x5,10,15,20- tetra- (amino) phenyl porphyrins
Under nitrogen protection, obtained above 5,10,15,20- tetra- (amino) phenyl porphyrins and SnCl are taken2·2H2O is in molar ratio
1: 8~10 mixing, are dissolved with dense HCl, stir 2.5h under room temperature, are warming up to 70 DEG C, react 30min, after reaction ice
Water-bath cooling pours into the deionized water of 5~10 volume ratios, adjusts pH to 8-9, and suction filtration obtains doping Sn (OH)x5,10,15,20-
Four (amino) phenyl porphyrins；Wherein, X=2 or 4；
Step 3: preparing covalent metal organic polymer
Under nitrogen protection, doping Sn (OH) is weighedx5,10,15,20- tetra- (amino) phenyl porphyrins, 2,6- dicarbaldehyde pyridine and
Anhydrous ferric chloride in analytically pure dimethyl sulfoxide, is made by 1: 4~5: 1~3 molar ratio mixed dissolutions with pure glacial acetic acid is analyzed
Catalyst, 60 DEG C are heated to reflux 15h, and after reaction, the solid filtered out washs colourless to filtrate with analyzing pure methanol, obtain
Brick-red solid, that is, covalent metal organic polymer；
Step 4: preparing alloy and load covalent organic polymer
Under nitrogen protection, by covalent metal organic polymer obtained above at a temperature of 800~1000 DEG C, heating rate 2
~5 DEG C/min, heat preservation 4h carries out pyrolysis processing, and the sulfur and nitrogen co-doped carbon elctro-catalyst of ferro-tin alloy load is made.
2. a kind of sulfur and nitrogen co-doped carbon elctro-catalyst of the load of ferro-tin alloy made from claim 1 the method.
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