CN107331877A - A kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst - Google Patents
A kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst Download PDFInfo
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- CN107331877A CN107331877A CN201710655646.7A CN201710655646A CN107331877A CN 107331877 A CN107331877 A CN 107331877A CN 201710655646 A CN201710655646 A CN 201710655646A CN 107331877 A CN107331877 A CN 107331877A
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Abstract
There is provided a kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy for the problem of present invention is directed to low existing Pt bases catalyst activity, poor stability and low Pt utilization rates；The present invention utilizes zeolite imidazole ester frame structure material (ZIF) growth nucleation process, by surfactant modified Pt nano particles, uniformly it is wrapped in ZIF structures, pass through accuracy controlling high temperature reduction process, ZIF carbonizations, metal reduction and alloying process are controlled, the catalyst structure of three-dimensional carbon skeleton embedding nano platinum alloy is constructed；The present invention dexterously utilizes the structure both shrinks effect in carbonisation, by the carbon skeleton pore passage structure that ZIF thaumatropies are three-dimensional insertion, dexterously utilize the confinement effect of ZIF skeletons under high temperature, by the metal ion home position alloying in platinum grain and ZIF structures, and be embedded in skeleton structure, the three-dimensional catalyst with duct insertion skeleton and nanoscale platinum alloy particles mosaic texture is formed, the utilization rate of the activity, stability and Pt of catalyst greatly improved.
Description
Technical field
The invention belongs to energy conversion and storing technology field, more particularly to a kind of salt recrystallization solid prepares Functional carbon
The method of material.The invention belongs to fuel cell field, more particularly to a kind of system of three-dimensional carbon skeleton embedding nano platinum base alloy
Preparation Method.
Background technology
Fuel cell is a kind of device that chemical energy is directly converted into electric energy, with energy conversion efficiency height, environment friend
The outstanding feature such as good, specific power and specific energy height, it is considered to be following electric automobile and other civilian occasion most promisingization
Learn power supply.In the process of commercializing fuel cells, its Cost Problems and life problems are always that the core for perplexing its development is asked
Topic.The Pt/C catalyst used at present, be in the form of nanoscale Pt particles high dispersive on the carbon carrier, due to Pt and carbon carrier
Between electronic structure otherness it is larger, rely only on weak interaction and stick together, Pt nano-particles are easy in carrier table
Face migration, reunion are grown up, and cause catalyst surface area to reduce, activity reduction.In addition, Pt/C catalyst in fuel cell catalyst layer
Stacked to be unordered, Pt nano particles can not be fully exposed on catalysis three phase boundary, cause Pt consumptions height, utilization rate low.Therefore,
Fuel-cell catalyst of the exploitation with high activity, high stability and high Pt utilization rates is significant.
In recent years, the problem of active relatively low and less stable of fuel-cell catalyst is directed to both at home and abroad achieves
Progress.Chinese patent 200910054736.6 discloses a kind of " low platinum carbon supported nanometer Pd-Pt alloy catalyst preparation method
And its application ", this method is first by Na2PdCl4、K2PtCl4, dispersant, complexing agent and carbon carrier be sufficiently mixed, ultrasonic agitation system
Carbon slurry is obtained, then carbon load PdPt alloy catalysts are acquired by adding the reduction of the step of the reducing agents such as sodium borohydride one Pd, Pt.This method
The catalyst of preparation has a higher Formic Acid Catalytic Oxidation activity, but in the catalyst nano particle with carrier still by weak
Interaction is sticked, it is difficult to suppress migration, reunion of the nano particle in catalytic process.Chinese patent 201610903245.4 is public
Cloth " a kind of preparation method of PtCu alloy nano-spheres ", it is molten that CuCl saturation KCl solution is added to potassium chloroplatinate by this method
In liquid, reduction is stood, PtCu alloy nano-spheres are obtained after centrifugation freeze-drying.PtCu alloys prepared by this method, which have, to be compared
The higher anti methanol toxication ability of Pt/C catalyst is commercialized, but the catalyst carrier-free is scattered, in catalytic process easily
Reunite, less stable, catalytic oxidation-reduction activity is relatively low.Chinese patent 201610850509.4 discloses a kind of " platinum-nickel alloy
Platinum and nickel are deposited to catalyst by the preparation method and product of supported catalyst ", this method simultaneously by atomic vapor deposition method
On carrier, platinum-nickel alloy supported catalyst is obtained.This method preparation technology is simple, and catalyst granules is well dispersed, but the party
Catalyst particle size prepared by method is larger, and easily forms the wrapped structure of noble metal, and noble metal utilisation is relatively low.
The content of the invention
The purpose of the present invention is asked for existing Pt bases catalyst activity is low, stability is poor and Pt utilization rates are relatively low
There is provided a kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy for topic.The present invention utilizes zeolite imidazole ester skeleton structure
Material (ZIF) grows nucleation process, and surfactant modified Pt nano particles are uniformly wrapped in ZIF crystal structures,
By accuracy controlling high temperature reduction process, control ZIF carbonizations, the reduction of alloying metal and alloying process construct three-dimensional carbon
The catalyst structure of skeleton embedding nano platinum alloy.The present invention dexterously utilizes the structure both shrinks effect in carbonisation, by ZIF
Thaumatropy is the carbon skeleton pore passage structure of three-dimensional insertion, dexterously using the confinement effect of ZIF skeleton structures under high temperature, by platinum
Particle and the metal ion home position alloying in ZIF structures, and be embedded in skeleton structure, being formed has duct insertion skeleton
With the three-dimensional catalyst of nanoscale platinum alloy particles mosaic texture, greatly improved the catalytic activity of catalyst, stability and
Pt utilization rate.
The object of the present invention is achieved like this：A kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy, its
Specific method step includes：
(1) preparation of surfactant modified Pt nanoparticulate dispersions
It is the ︰ 0.10~0.30 of 1 ︰ 10~30 by the mass ratio of platinum Qian Qu Ti ︰ organic reducing Ji ︰ surfactants, weighs platinum
Presoma, organic reducing agent and surfactant；Platinum presoma is first dissolved in concentration in 6~12mol/L hydrochloric acid solutions, so
After add organic reducing agent, formed platinum mass concentration be 7.54~18.84mg/mL platinum precursor solution；Again to before above-mentioned platinum
Drive in liquid solution and add surfactant, ultrasonic agitation has after 10~30 minutes with concentration for 1.25~4.75mol/L NaOH
Machine reductant solution is adjusted after pH to 9~10, condensing reflux 2~5 hours, obtains Pt nano particle particle dispersion；By above-mentioned Pt nano particle
Particle dispersion vacuum distillation at 30~76 DEG C is removed after solvent, obtains surfactant modified Pt nano particle solids；
Again by above-mentioned surfactant modified Pt nano particles solid acetone centrifuge washing 3~4 times, after 30~76 DEG C of drying, then
It is secondary to be distributed in organic reducing agent, obtain the surfactant modified Pt nanometers that platinum mass concentration is 0.13~0.78mg/mL
Particle dispersion；Described platinum presoma is chloroplatinic acid, the ammino platinum of tetrachloro two, sub- potassium chloroplatinate, four ammino bicarbonate platinum, six hydroxyls
Base closes one of platinic acid diethanol ammonium；Described organic reducing agent is one of methanol and ethanol；Live on the surface
Property agent be one of polyvinylpyrrolidone, DTAB and sodium citrate.
(2) prepared by the Pt nano particles of ZIF claddings
Metal salt and organic ligand are weighed for 1 ︰ 4~8 by the mol ratio of metal salt ︰ organic ligands, is matched somebody with somebody by metal platinum ︰ is organic
Body mass ratio is 1：623~1515 measure above-mentioned surfactant modified Pt nanoparticulate dispersions；Metal salt is matched somebody with somebody first
Be set to ethanol or methanol or the aqueous solution that concentration is 0.05~0.79mol/L, by organic ligand be configured to concentration for 0.04~
0.48mol/L ethanol or methanol or the aqueous solution；Then organic ligand solution is poured into metal salt solution, stirs 5~60 points
Zhong Hou, adds surfactant modified Pt nanoparticulate dispersions, continues to stir 30~120 minutes, stands reaction 24~72
Hour, centrifuge, ethanol washing after 40~80 DEG C of drying, obtains the Pt nano particles of ZIF claddings；Described metal salt is
One of cabaltous nitrate hexahydrate, four hydration cobalt acetates, cobalt chloride, zinc nitrate hexahydrate, zinc chloride, four hydration zinc acetates；
The organic ligand is one of 2-methylimidazole, DMIZ 1,2 dimethylimidazole and 4-methylimidazole.
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
The Pt nano particles that above-mentioned ZIF is coated are placed in tube furnace first, with air in vacuum pumped tube furnace, then
It is 5~50 ml/mins using hydrogen flowing quantity and nitrogen flow is that 50~200 ml/mins are filled with nitrogen and hydrogen mixed gas,
Under nitrogen and hydrogen mixed gas atmosphere with 0.5~10 DEG C/min be warming up to 300~500 DEG C kept for 0~3 hour after, then with 5~
10 DEG C/min are warming up to 750~900 DEG C and are kept for 0.5~3 hour, finally, room are cooled under nitrogen and hydrogen mixed gas atmosphere
Temperature, obtains catalyst solid powder；Above-mentioned catalyst solid powder is dispersed in 0.1~2.0mol/L protonic acid solution,
60~80 DEG C are stirred 8~24 hours, ion water washing 3 times, and absolute ethyl alcohol is washed 3 times, and 40~60 DEG C are dried in vacuo 24 hours, obtain
Three-dimensional carbon skeleton embedding nano platinum base alloy is obtained, the protonic acid solution is its of hydrochloric acid solution, sulfuric acid solution and salpeter solution
One of.
The present invention is after adopting the above technical scheme, mainly have the following effects：
(1) the three-dimensional carbon skeleton embedding nano platinum base alloy catalyst prepared by the present invention, with three-dimensional porous catalyst
Structure, greatly improves effective utilization rate constructed, improve precious metals pt of three phase boundary in fuel cell catalyst layer；High temperature alloy
The latent active of Pt nano particles is substantially improved in effect, while the pyrolytic conversion of ZIF skeleton structures is nitrogen-doped carbon material, is not only
Nano particle, which is provided, inlays position, suppresses particle migration and reunites, also provides catalytic oxidation-reduction catalytic reaction the second activated centre, catalysis
The catalytic activity and stability of agent are substantially improved.
(2) present invention limits platinum particles using the high temperature migration effect of metal ion in ZIF structures using mosaic texture
Reunion sintering during high temperature pyrolysis a, step builds Pt alloy structures, and operation is simple, efficiency high, is adapted to extensive business
Industry metaplasia is produced.
(3) catalyst prepared by the present invention, which compares existing commercialization Pt/C catalyst, has higher catalytic activity, steady
Qualitative and noble metal utilisation, can be greatly reduced fuel-cell catalyst cost.
The inventive method is simple and easy to apply, safe operation, low production cost.The three-dimensional carbon skeleton edge prepared using the present invention
Embedding Platinum Nanoparticles based alloy catalyst has excellent stability and quality specific activity, and alternative existing Pt/C catalyst is applied to combustion
Expect battery.Fuel cell produced by the present invention is used, electric automobile is can be widely applied to, various spacecrafts, portable electronic is set
It is standby, such as video camera, notebook computer, electronic toy etc..
Brief description of the drawings
Fig. 1 is the high power transmission electron microscope for implementing the three-dimensional carbon skeleton embedding nano platinum cobalt alloy-catalyst in 1 obtained by (3)
(TEM) photo.
Fig. 2 for implement 1 gained different acid reaction variables three-dimensional carbon skeleton embedding nano platinum base alloy catalyst and
Britain Jonhson-Matthey company trades Pt/C (platinum mass percent 40%) catalyst is in rotating disk electrode (r.d.e)
Hydrogen reduction linear scan curve.
In Fig. 2：Curve 1 and curve 2 be with (3) of embodiment 1 and (3) of embodiment 2, different acid reaction variables
Three-dimensional carbon skeleton embedding nano platinum base alloy catalyst is working electrode, and silver/silver chloride electrode is reference electrode, and platinum loop is to electricity
Pole, the high chloro acid solution of the mol/L of oxygen saturation 0.1 is electrolyte, and sweep speed is the hydrogen reduction under the conditions of 10 mv s
Linear scan curve.
During curve 3 is (3) with embodiment 3, the three-dimensional carbon skeleton embedding nano platinum base alloy catalyst of acid treatment is work
Make electrode, silver/silver chloride electrode is reference electrode, and platinum loop is to electrode, the high chloro acid solution of the mol/L of oxygen saturation 0.1
For electrolyte, sweep speed is the hydrogen reduction linear scan curve under the conditions of 10 mv s.
Curve 4 is that Britain Jonhson-Matthey company trades Pt/C (platinum mass percent 40%) catalyst is work
Make electrode, the carrying capacity of platinum is 5ug, and silver/silver chloride electrode is reference electrode, and platinum loop is to electrode, the mol/L of oxygen saturation 0.1
High chloro acid solution be electrolyte, sweep speed be 10 mv s under the conditions of hydrogen reduction linear scan curve.
Curve 5 is that (2) prepare three-dimensional carbon skeleton catalyst for working electrode in contrast experiment 2, and silver/silver chloride electrode is ginseng
Than electrode, platinum loop is that the high chloro acid solution of the mol/L of oxygen saturation 0.1 is electrolyte, and sweep speed is 10 millis to electrode
Hydrogen reduction linear scan curve under the conditions of volt/second.
Fig. 3 is the high power transmission electron microscope (TEM) of the three-dimensional carbon skeleton embedding nano platinum kirsite catalyst of the gained of embodiment 3
Photo.
Fig. 4 is the three-dimensional carbon skeleton embedding nano platinum kirsite catalyst and Britain Jonhson-Matthey obtained by implementation 4
Hydrogen reduction linear scan curve of company trade Pt/C (the platinum mass percent 40%) catalyst in rotating disk electrode (r.d.e).
In Fig. 4：Curve 1 be using in embodiment 4 (3) prepare three-dimensional carbon skeleton embedding nano platinum kirsite catalyst as
Working electrode, silver/silver chloride electrode is reference electrode, and platinum loop is that the perchloric acid of the mol/L of oxygen saturation 0.1 is water-soluble to electrode
Liquid is electrolyte, and sweep speed is the hydrogen reduction linear scan curve under the conditions of 10 mv s.
Curve 2 is that Britain Jonhson-Matthey company trades Pt/C (platinum mass percent 40%) catalyst is work
Make electrode, the carrying capacity of platinum is 5ug, and silver/silver chloride electrode is reference electrode, and platinum loop is to electrode, the mol/L of oxygen saturation 0.1
High chloro acid solution be electrolyte, sweep speed be 10 mv s under the conditions of hydrogen reduction linear scan curve.
Curve 3 is that the three-dimensional carbon skeleton catalyst of (2) preparation in contrast experiment 3 is working electrode, and silver/silver chloride electrode is
Reference electrode, platinum loop is that the high chloro acid solution of the mol/L of oxygen saturation 0.1 is electrolyte, and sweep speed is 10 millis to electrode
Hydrogen reduction linear scan curve under the conditions of volt/second.
Fig. 5 is revolving to implement the stability test of the three-dimensional carbon skeleton embedding nano platinum cobalt alloy-catalyst in 1 obtained by (3)
Turn the hydrogen reduction linear scan curve on disk electrode.
In Fig. 5：In curve 1 and (3) that curve 2 is embodiment 1, prepared three-dimensional carbon skeleton embedding nano platinum cobalt alloy
Catalyst is working electrode, and silver/silver chloride electrode is reference electrode, and platinum loop is that the mol/L of oxygen saturation 0.1 is high to electrode
Chloric acid aqueous solution is electrolyte, and sweep speed is the hydrogen reduction before aging under conditions of 10 mv s, after the circle of aging 8000
Linear scan curve.
Fig. 6 urges for Britain Jonhson-Matthey company trades Pt/C (platinum mass percent 40%) in contrast experiment 1
Hydrogen reduction linear scan curve in the stability test of agent in rotating disk electrode (r.d.e).
In Fig. 6:Curve 1 and curve 2 are with Britain Jonhson-Matthey company trades Pt/C (platinum mass percents
40%) catalyst is working electrode, and silver/silver chloride electrode is reference electrode, platinum loop be to electrode, 0.1 mole of oxygen saturation/
The high chloro acid solution risen is electrolyte, and sweep speed is before aging under conditions of 10 mv s, after the circle of aging 8000
Hydrogen reduction linear scan curve.
Embodiment
With reference to embodiment, the present invention is further illustrated.
Embodiment 1
A kind of preparation method of hydrogen reduction three-dimensional carbon skeleton embedding nano platinum cobalt alloy-catalyst, its specific method step bag
Include：
(1) preparation of surfactant modified Pt nanoparticulate dispersions
Mass ratio by the Jia Chun Rong Ye ︰ Reduction of methanol Ji ︰ polyvinylpyrrolidones of chloroplatinic acid is the ︰ 0.20 of 1 ︰ 18, is weighed
Methanol solution, Reduction of methanol agent and the polyvinylpyrrolidone of chloroplatinic acid；The methanol solution of chloroplatinic acid first is dissolved in into concentration is
In 9mol/L hydrochloric acid solutions, Reduction of methanol agent is then added, the platinum precursor solution that platinum mass concentration is 9.42mg/mL is formed；
Polyvinylpyrrolidone is added into the methanol solution of above-mentioned chloroplatinic acid again, ultrasonic agitation is with concentration after 20 minutes
2.92mol/L NaOH organic reducings agent solution is adjusted after pH to 9~10, condensing reflux 3 hours, is obtained Pt nano particle particle and is disperseed
Liquid；By above-mentioned Pt nano particle particle dispersion, vacuum distillation is removed after solvent at 76 DEG C, is obtained surfactant modified Pt and is received
Rice grain solid；Again by above-mentioned surfactant modified Pt nano particles solid acetone centrifuge washing 3 times, 76 DEG C of drying
Afterwards, it is dispersed back into Reduction of methanol agent, obtains the surfactant modified Pt nanometers that platinum mass concentration is 0.26mg/mL
Grain dispersion liquid.
(2) prepared by the Pt nano particles of ZIF-67 claddings
Metal salt and organic ligand are weighed for 1 ︰ 8 by the mol ratio of acetic acid cobalt ︰ 2-methylimidazoles, by metal platinum ︰ 2- methyl
Imidazoles mass ratio is that 1 ︰ 1248 measures above-mentioned surfactant modified Pt nanoparticulate dispersions；First by cobalt acetate and 2- first
Base imidazoles is each configured to the ethanol solution that concentration is 0.050 and 0.40mol/L；Then 2-methylimidazole solution is poured into acetic acid
In cobalt liquor, after stirring 30 minutes, surfactant modified Pt nanoparticulate dispersions are added, continue to stir 30 minutes, it is quiet
Reaction 24 hours is put, is centrifuged, ethanol washing after 80 DEG C of drying, obtains the Pt nano particles of ZIF-67 claddings.
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
The Pt nano particles that above-mentioned ZIF-67 is coated are placed in tube furnace first, it is hollow with vacuum pumped tube furnace
Gas, then it is 5 ml/mins using hydrogen flowing quantity and nitrogen flow is that 50 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen
With under hydrogen mixed gas atmosphere with 1 DEG C/min be warming up to 300~400 DEG C kept for 2 hours after, then with 5 DEG C/min be warming up to 750
DEG C kept for 1 hour, finally, be cooled to room temperature under nitrogen and hydrogen mixed gas atmosphere, obtain catalyst solid powder；Will be upper
State catalyst solid powder to be dispersed in 1.0mol/L protonic acid solution, 80 DEG C are stirred 24 hours, ion water washing 3 times, nothing
Water-ethanol is washed 3 times, and 60 DEG C are dried in vacuo 24 hours, obtain three-dimensional carbon skeleton embedding nano platinum base alloy.
(4) the transmission electron microscope test of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst
The three-dimensional carbon skeleton embedding nano platinum cobalt alloy-catalyst prepared obtains the high score in Fig. 1 with transmissioning electric mirror test
Distinguish transmission electron microscope (HRTEM) photo.
(5) electrochemical property test of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst
2 milligrams of solid catalyst powder before and after the pickling of (3) step is weighed respectively, is added in 400 microlitres of absolute ethyl alcohols,
After sonic oscillation is uniformly dispersed for 10 minutes, microsyringe is drawn 25 microlitres and is evenly applied in vitreous carbon rotating disk electrode (r.d.e),
Kept for 2 hours at 60 DEG C.As working electrode, silver/silver chloride electrode is reference electrode, and platinum filament is auxiliary electrode, with nitrogen
The high chloro acid solution of 0.1 mol/L of saturation is electrolyte solution, and record current density is with voltage on electrochemical workstation
Situation of change, cyclic voltammetry scan 60 encloses with activated catalyst and the electrochemical active surface of catalyst evaluated.
Catalyst is carried out after surface active, linear scan volt-ampere is tested in the perchloric acid solution of 0.1 mol/L of oxygen saturation bent
Line, the rotating speed of rotation electrode is 1600 revs/min, 0~1.2V of scanning range (relative to standard hydrogen electrode), and sweep speed is 10
Curve 1 in mv s, difference corresponding diagram 2.
Embodiment 2
A kind of preparation method of hydrogen reduction three-dimensional carbon skeleton embedding nano platinum cobalt alloy-catalyst, its specific method step bag
Include：
(1) preparation of surfactant modified Pt nanoparticulate dispersions
Mass ratio by the Jia Chun Rong Ye ︰ Reduction of methanol Ji ︰ polyvinylpyrrolidones of chloroplatinic acid is the ︰ 0.10 of 1 ︰ 10, is weighed
Methanol solution, Reduction of methanol agent and the polyvinylpyrrolidone of chloroplatinic acid；The methanol solution of chloroplatinic acid first is dissolved in into concentration is
In 6mol/L hydrochloric acid solutions, Reduction of methanol agent is then added, the platinum precursor solution that platinum mass concentration is 7.54mg/mL is formed；
Polyvinylpyrrolidone is added into the methanol solution of above-mentioned chloroplatinic acid again, ultrasonic agitation is with concentration after 10 minutes
1.25mol/L NaOH organic reducings agent solution is adjusted after pH to 9~10, condensing reflux 3 hours, is obtained Pt nano particle particle and is disperseed
Liquid；By above-mentioned Pt nano particle particle dispersion, vacuum distillation is removed after solvent at 76 DEG C, is obtained surfactant modified Pt and is received
Rice grain solid；Again by above-mentioned surfactant modified Pt nano particles solid acetone centrifuge washing 4 times, 76 DEG C of drying
Afterwards, it is dispersed back into Reduction of methanol agent, obtains the surfactant modified Pt nanometers that platinum mass concentration is 0.13mg/mL
Grain dispersion liquid.
(2) prepared by the Pt nano particles of ZIF-67 claddings
Metal salt and organic ligand are weighed for 1 ︰ 8 by the mol ratio of acetic acid cobalt ︰ 2-methylimidazoles, by metal platinum ︰ 2- methyl
Imidazoles mass ratio is that 1 ︰ 1248 measures above-mentioned surfactant modified Pt nanoparticulate dispersions；First by cobalt acetate and 2- first
Base imidazoles is each configured to the ethanol solution that concentration is 0.050 and 0.40mol/L；Then 2-methylimidazole solution is poured into acetic acid
In cobalt liquor, after stirring 30 minutes, surfactant modified Pt nanoparticulate dispersions are added, continue to stir 30 minutes, it is quiet
Reaction 24 hours is put, is centrifuged, ethanol washing after 80 DEG C of drying, obtains the Pt nano particles of ZIF-67 claddings.
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
The Pt nano particles that above-mentioned ZIF-67 is coated are placed in tube furnace first, it is hollow with vacuum pumped tube furnace
Gas, then it is 5 ml/mins using hydrogen flowing quantity and nitrogen flow is that 50 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen
With under hydrogen mixed gas atmosphere with 1 DEG C/min be warming up to 300~400 DEG C kept for 2 hours after, then with 5 DEG C/min be warming up to 750
DEG C kept for 1 hour, finally, be cooled to room temperature under nitrogen and hydrogen mixed gas atmosphere, obtain catalyst solid powder；Will be upper
State catalyst solid powder to be dispersed in 1.0mol/L protonic acid solution, 60 DEG C are stirred 16 hours, ion water washing 3 times, nothing
Water-ethanol is washed 3 times, and 60 DEG C are dried in vacuo 24 hours, obtain three-dimensional carbon skeleton embedding nano platinum base alloy.
(4) electrochemical property test of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst
2 milligrams of solid catalyst powder before and after the pickling of (3) step is weighed respectively, is added in 400 microlitres of absolute ethyl alcohols,
After sonic oscillation is uniformly dispersed for 10 minutes, microsyringe is drawn 25 microlitres and is evenly applied in vitreous carbon rotating disk electrode (r.d.e),
Kept for 2 hours at 60 DEG C.As working electrode, silver/silver chloride electrode is reference electrode, and platinum filament is auxiliary electrode, with nitrogen
The high chloro acid solution of 0.1 mol/L of saturation is electrolyte solution, and record current density is with voltage on electrochemical workstation
Situation of change, cyclic voltammetry scan 60 encloses with activated catalyst and the electrochemical active surface of catalyst evaluated.
Catalyst is carried out after surface active, linear scan volt-ampere is tested in the perchloric acid solution of 0.1 mol/L of oxygen saturation bent
Line, the rotating speed of rotation electrode is 1600 revs/min, 0~1.2V of scanning range (relative to standard hydrogen electrode), and sweep speed is 10
Curve 2 in mv s, difference corresponding diagram 2.
Embodiment 3
A kind of preparation method of hydrogen reduction three-dimensional carbon skeleton embedding nano platinum cobalt alloy-catalyst, its specific method step bag
Include：
(1) preparation of surfactant modified Pt nanoparticulate dispersions
Mass ratio by the Jia Chun Rong Ye ︰ Reduction of methanol Ji ︰ polyvinylpyrrolidones of sub- potassium chloroplatinate is the ︰ 0.30 of 1 ︰ 30,
Weigh methanol solution, Reduction of methanol agent and the polyvinylpyrrolidone of sub- potassium chloroplatinate；First by the methanol solution of sub- potassium chloroplatinate
It is dissolved in concentration in 12mol/L hydrochloric acid solutions, then to add Reduction of methanol agent, it is 18.84mg/mL's to form platinum mass concentration
Platinum precursor solution；Polyvinylpyrrolidone, ultrasonic agitation 30 minutes are added into the methanol solution of above-mentioned sub- potassium chloroplatinate again
Afterwards, the NaOH organic reducings agent solution for being 4.75mol/L with concentration is adjusted after pH to 9~10, and condensing reflux 5 hours obtains nanometer
Pt particle dispersions；By above-mentioned Pt nano particle particle dispersion, vacuum distillation is removed after solvent at 76 DEG C, obtains surfactant
The Pt nano particle solids of modification；Again by above-mentioned surfactant modified Pt nano particles solid acetone centrifuge washing 3 times,
After 76 DEG C of drying, it is dispersed back into Reduction of methanol agent, it is the surfactant modified of 0.78mg/mL to obtain platinum mass concentration
Pt nanoparticulate dispersions.
(2) prepared by the Pt nano particles of ZIF claddings
Cabaltous nitrate hexahydrate and 2-methylimidazole are weighed for 1 ︰ 4 by the mol ratio of acetic acid cobalt ︰ 2-methylimidazoles, by metal
Bo ︰ 2- methylimidazoles mass ratio is 1：623 measure above-mentioned surfactant modified Pt nanoparticulate dispersions；First by vinegar
Sour cobalt and 2-methylimidazole are each configured to the ethanol solution that concentration is 0.05mol/L and 0.79mol/L；Then by 2- methyl
Imidazole solution is poured into cabaltous nitrate hexahydrate solution, after stirring 60 minutes, adds surfactant modified Pt nano particles point
Dispersion liquid, continues to stir 120 minutes, stands reaction 48 hours, centrifuge, and ethanol washing after 80 DEG C of drying, obtains ZIF-67 bags
The Pt nano particles covered.
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
The Pt nano particles that above-mentioned ZIF is coated are placed in tube furnace first, with air in vacuum pumped tube furnace, then
Be 20 ml/mins using hydrogen flowing quantity and nitrogen flow be that 200 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen and
Under hydrogen mixed gas atmosphere with 1 DEG C/min be warming up to 300~400 DEG C kept for 2 hours after, then with 5 DEG C/min be warming up to 750 DEG C
Kept for 1 hour, finally, room temperature is cooled under nitrogen and hydrogen mixed gas atmosphere, obtains catalyst solid powder, will be above-mentioned
Catalyst solid powder is dispersed in 1.0mol/L protonic acid solution, and 70 DEG C are stirred 8 hours, ion water washing 3 times, anhydrous second
Alcohol is washed 3 times, and 60 DEG C are dried in vacuo 24 hours, obtain three-dimensional carbon skeleton embedding nano platinum base alloy.
(4) electrochemical property test of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst
2 milligrams of solid catalyst powder before and after the pickling of (3) step is weighed respectively, is added in 400 microlitres of absolute ethyl alcohols,
After sonic oscillation is uniformly dispersed for 10 minutes, microsyringe is drawn 25 microlitres and is evenly applied in vitreous carbon rotating disk electrode (r.d.e),
Kept for 2 hours at 60 DEG C.As working electrode, silver/silver chloride electrode is reference electrode, and platinum filament is auxiliary electrode, with nitrogen
The high chloro acid solution of 0.1 mol/L of saturation is electrolyte solution, and record current density is with voltage on electrochemical workstation
Situation of change, cyclic voltammetry scan 60 encloses with activated catalyst and the electrochemical active surface of catalyst evaluated.
Catalyst is carried out after surface active, linear scan volt-ampere is tested in the perchloric acid solution of 0.1 mol/L of oxygen saturation bent
Line, the rotating speed of rotation electrode is 1600 revs/min, 0~1.2V of scanning range (relative to standard hydrogen electrode), and sweep speed is 10
Curve 3 in mv s, difference corresponding diagram 2.
Embodiment 4
A kind of preparation method of hydrogen reduction three-dimensional carbon skeleton embedding nano platinum kirsite catalyst, its specific method step bag
Include：
(1) preparation of surfactant modified Pt nanoparticulate dispersions
Mass ratio by the Jia Chun Rong Ye ︰ Reduction of methanol Ji ︰ polyvinylpyrrolidones of chloroplatinic acid is the ︰ 0.20 of 1 ︰ 18, is weighed
Methanol solution, Reduction of methanol agent and the polyvinylpyrrolidone of chloroplatinic acid；The methanol solution of chloroplatinic acid first is dissolved in into concentration is
In 9mol/L hydrochloric acid solutions, Reduction of methanol agent is then added, the platinum precursor solution that platinum mass concentration is 9.42mg/mL is formed；
Polyvinylpyrrolidone is added into the methanol solution of above-mentioned chloroplatinic acid again, ultrasonic agitation is with concentration after 20 minutes
2.92mol/L NaOH organic reducings agent solution is adjusted after pH to 9~10, condensing reflux 3 hours, is obtained Pt nano particle particle and is disperseed
Liquid；By above-mentioned Pt nano particle particle dispersion, vacuum distillation is removed after solvent at 76 DEG C, is obtained surfactant modified Pt and is received
Rice grain solid；Again by above-mentioned surfactant modified Pt nano particles solid acetone centrifuge washing 3 times, 76 DEG C of drying
Afterwards, it is dispersed back into Reduction of methanol agent, obtains the surfactant modified Pt nanometers that platinum mass concentration is 0.26mg/mL
Grain dispersion liquid.
(2) prepared by the Pt nano particles of ZIF-8 claddings
Zinc acetate and 2-methylimidazole are weighed for 1 ︰ 8 by the mol ratio of the sour zinc ︰ 2-methylimidazoles of vinegar, by metal platinum ︰ 2- first
Base imidazoles mass ratio is that 1 ︰ 1515 measures above-mentioned surfactant modified Pt nanoparticulate dispersions；First by zinc acetate and 2-
Methylimidazole is each configured to the ethanol solution that concentration is 0.06 and 0.48mol/L；Then 2-methylimidazole solution is poured into vinegar
In sour zinc solution, after stirring 30 minutes, surfactant modified Pt nanoparticulate dispersions are added, continue to stir 30 minutes,
Reaction 24 hours are stood, are centrifuged, ethanol washing after 80 DEG C of drying, obtains the Pt nano particles of ZIF-8 claddings.
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
The Pt nano particles that above-mentioned ZIF-8 is coated are placed in tube furnace first, with air in vacuum pumped tube furnace,
Be 5 ml/mins using hydrogen flowing quantity again and nitrogen flow be that 50 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen and
Under hydrogen mixed gas atmosphere with 5 DEG C/min be warming up to 900 DEG C keep 1 hour after, finally, in nitrogen and hydrogen mixed gas atmosphere
Under be cooled to room temperature, obtain catalyst solid powder.
(4) the transmission electron microscope test of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst
The three-dimensional carbon skeleton embedding nano platinum kirsite catalyst prepared obtains the high score in Fig. 3 with transmissioning electric mirror test
Distinguish transmission electron microscope (HRTEM) photo.
(5) platinum kirsite is embedded in the electrochemical property test of zeolite imidazole ester skeleton catalyst
2 milligrams of (3) step solid catalyst powder is weighed respectively, is added in 400 microlitres of absolute ethyl alcohols, sonic oscillation 10
After minute is uniformly dispersed, microsyringe is drawn 25 microlitres and is evenly applied in vitreous carbon rotating disk electrode (r.d.e), and 2 are kept at 60 DEG C
Hour.As working electrode, silver/silver chloride electrode is reference electrode, and platinum filament is auxiliary electrode, is rubbed with the 0.1 of nitrogen saturation
You/liter high chloro acid solution be electrolyte solution, on electrochemical workstation record current density with voltage situation of change,
Cyclic voltammetry scan 60 encloses with activated catalyst and the electrochemical active surface of catalyst is evaluated.Catalyst is carried out
After surface active, linear scan volt-ampere curve, rotation electrode are tested in the perchloric acid solution of 0.1 mol/L of oxygen saturation
Rotating speed be 1600 revs/min, 0~1.2V of scanning range (relative to standard hydrogen electrode), sweep speed be 10 mv s, it is right
Answer the curve 1 in Fig. 4.
Contrast experiment
Contrast experiment 1
(1) preparation of business platinum carbon catalysis electrode
2 milligrams of Britain Jonhson-Matthey company trades Pt/C (platinum mass percent 40%) catalyst are weighed to add
Enter into 800 microlitres of absolute ethyl alcohols, after sonic oscillation is uniformly dispersed for 10 minutes, 20 microlitres of uniform paintings are drawn with microsyringe
It is overlying in vitreous carbon rotating disk electrode (r.d.e), is kept for 2 hours at 60 DEG C, it is 5ug to control platinum carrying capacity, and is uniformly coated on several times
Business Pt/C catalysis electrodes are obtained on electrode.
(2) redox active with tradition Pt/C (Jonhson-Matthey, mass percent 40%) compares
Using three-electrode system, the glass-carbon electrode for being loaded with Pt/C catalyst is working electrode, and silver/silver chloride electrode is ginseng
Than electrode, platinum filament is that 0.1 mole every liter of the high chloro acid solution using oxygen saturation is electrolyte solution, in electrification to electrode
Learn and hydrogen reduction curve is recorded on work station, hydrogen reduction linear scan scope is 0~1.2V (relative to standard hydrogen electrode), scanning speed
Spend for 10 mv s, rotating speed is the curve 4 in 1600 revs/min, corresponding diagram 2, the curve 2 in Fig. 4.
Contrast experiment 2
(1) preparation of ZIF-67 catalyst
Metal salt and organic ligand are weighed for 1 ︰ 8 by the mol ratio of acetic acid Gu ︰ 2-methylimidazoles, first by cobalt acetate and 2-
Methylimidazole is each configured to the ethanol solution that concentration is 0.050 and 0.40mol/L；Then 2-methylimidazole solution is poured into vinegar
In acidic cobalt solution, after stirring 30 minutes, reaction 24 hours are stood, are centrifuged, ethanol washing after 80 DEG C dry, obtains ZIF-
The Pt nano particles of 67 claddings.
(2) preparation of three-dimensional carbon skeleton catalyst
The Pt nano particles that above-mentioned ZIF-67 is coated are placed in tube furnace first, it is hollow with vacuum pumped tube furnace
Gas, then it is 5 ml/mins using hydrogen flowing quantity and nitrogen flow is that 50 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen
With under hydrogen mixed gas atmosphere with 1 DEG C/min be warming up to 300~400 DEG C kept for 2 hours after, then with 5 DEG C/min be warming up to 750
DEG C kept for 1 hour, finally, be cooled to room temperature under nitrogen and hydrogen mixed gas atmosphere, obtain catalyst solid powder.
(3) electrochemical property test of three-dimensional carbon skeleton catalyst
Weigh obtained carbonization zeolite imidazole ester skeleton (ZIF-67) catalyst of 2 milligrams of (2) steps and be added to 400 microlitres of nothings
In water-ethanol, after sonic oscillation is uniformly dispersed for 10 minutes, microsyringe draws 25 microlitres and is evenly applied to vitreous carbon rotational circle
On disc electrode, kept for 2 hours at 60 DEG C.As working electrode, silver/silver chloride electrode is reference electrode, and platinum filament is auxiliary electricity
Pole, the high chloro acid solution using 0.1 mol/L of nitrogen saturation is electrolyte solution, the record current on electrochemical workstation
Density is with the situation of change of voltage, and cyclic voltammetry scan 60 enclosed with activated catalyst and to the electrochemical active surface of catalyst
Evaluated.Catalyst is carried out after surface active, tests linear in the perchloric acid solution of 0.1 mol/L of oxygen saturation
Volt-ampere curve is scanned, the rotating speed of rotation electrode is 1600 revs/min, and 0~1.2V of scanning range (relative to standard hydrogen electrode) is swept
Speed is retouched for 10 mv s, the curve 5 in corresponding diagram 2.
Contrast experiment 3
(1) preparation of ZIF-8 catalyst
Weigh zinc acetate and 2-methylimidazole by the mol ratio of Cu Suan Xin ︰ 2-methylimidazoles for 1 ︰ 8, first by zinc acetate and
2- methylimidazoles are each configured to the ethanol solution that concentration is 0.06 and 0.48mol/L；Then 2-methylimidazole solution is poured into
In zinc acetate solution, after stirring 30 minutes, surfactant modified Pt nanoparticulate dispersions are added, continue to stir 30 points
Clock, stands reaction 24 hours, centrifuges, ethanol washing, after 80 DEG C of drying, obtains ZIF-8 catalyst.
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
Above-mentioned ZIF-8 catalyst is placed in tube furnace first, with air in vacuum pumped tube furnace, then with hydrogen stream
Amount is 5 ml/mins and nitrogen flow is that 50 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen and hydrogen mixed gas
Under atmosphere with 5 DEG C/min be warming up to 900 DEG C keep 1 hour after, finally, room is cooled under nitrogen and hydrogen mixed gas atmosphere
Temperature, obtains catalyst solid powder.
(3) electrochemical property test of three-dimensional carbon skeleton catalyst
Weigh 2 milligrams of three-dimensional carbon skeleton catalyst obtained by (2) step to be added in 400 microlitres of absolute ethyl alcohols, ultrasound is shaken
Swing after being uniformly dispersed within 30 minutes, microsyringe is drawn 15 microlitres and is evenly applied in vitreous carbon rotating disk electrode (r.d.e), at 60 DEG C
Kept for 2 hours.As working electrode, silver/silver chloride electrode is reference electrode, and platinum filament is auxiliary electrode, with nitrogen saturation
The high chloro acid solution of 0.1 mol/L be electrolyte solution, on electrochemical workstation record current density with voltage change
Change situation, cyclic voltammetry scan 60 encloses with activated catalyst and the electrochemical active surface of catalyst is evaluated.To urging
Agent is carried out after surface active, and linear scan volt-ampere curve is tested in the perchloric acid solution of 0.1 mol/L of oxygen saturation,
The rotating speed of rotation electrode is 1600 revs/min, 0~1.2V of scanning range (relative to standard hydrogen electrode), and sweep speed is 10 millis
Curve 3 in volt/second, corresponding diagram 4.
The result of the test of the present invention：
Three-dimensional carbon skeleton embedding nano platinum base alloy catalyst prepared by the present invention, with three-dimensional porous catalyst knot
Structure, shows from the TEM (Fig. 2,3) of three-dimensional carbon skeleton embedding nano platinum cobalt alloy-catalyst：This method shape of invention
Into catalyst particle size be uniformly dispersed, the particle diameter of platinum grain is evenly distributed probably in 4~5nm or so；High temperature alloy is imitated
The latent active of Pt nano particles should be substantially improved, while the pyrolytic conversion of ZIF skeleton structures is nitrogen-doped carbon material, it is not only to receive
Rice grain, which is provided, inlays position, suppresses particle migration and reunites, also provides catalytic oxidation-reduction catalytic reaction the second activated centre, catalyst
Catalytic activity and stability be substantially improved；It can be seen that the three-dimensional carbon skeleton of preparation is inlayed from Fig. 4 redox curve maps to receive
Miboplatin kirsite catalyst half wave potential is improved compared with 5ug commercialization Pt/C (platinum mass percent 40%) catalyst
18mV or so, jk1.2528 can be reached under the conditions of 0.9V, nearly 1.25 are improved compared to traditional Pt/C (0.674) catalyst
Times；Three-dimensional carbon skeleton embedding nano platinum cobalt alloy-catalyst half wave potential and 5ug are can be seen that from Fig. 2 redox curve maps
Commercialization Pt/C (platinum mass percent 40%) catalyst is compared, and improves 53mV, jkIt can be reached under the conditions of 0.9V
6.41mA, is improved more than 6 times compared to traditional Pt/C (1.02mA) catalyst；Jm is 0.990A.mg-1, compared to traditional Pt/C
(0.204A.mg-1) catalyst improved more than 4 times；The catalyst that i.e. we make has very high oxygen reduction activity.
And can be seen that the catalyst according to the method for invention compared to traditional Pt/C from Fig. 5 and Fig. 6
Catalyst is greatly improved in stability.Fig. 6 shows that traditional Pt/C catalyst is enclosing cyclic voltammetric survey by 8000
After examination, 1 curve is compared with curve 2, it can be seen that activity decrease is a lot, and half wave potential has been decayed nearly 40mV.Fig. 6 shows to prepare
Three-dimensional carbon skeleton embedding nano platinum cobalt alloy catalysis by 8000 enclose cyclic voltammetries after, activity, which is substantially all, not to be had
Change, half wave potential has only been decayed 6mV, illustrate that we have very high stability by obtained catalyst.
Claims (5)
1. a kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy, its specific method step includes
It is characterized in that：
(1) preparation of surfactant modified Pt nanoparticulate dispersions
It is the ︰ 0.10~0.30 of 1 ︰ 10~30 by the mass ratio of platinum Qian Qu Ti ︰ organic reducing Ji ︰ surfactants, weighs platinum forerunner
Body, organic reducing agent and surfactant；Platinum presoma is first dissolved in concentration in 6~12mol/L hydrochloric acid solutions, Ran Houjia
Enter organic reducing agent, form the platinum precursor solution that platinum mass concentration is 7.54~18.84mg/mL；Again to above-mentioned platinum presoma
Surfactant is added in solution, ultrasonic agitation is organic also for 1.25~4.75mol/L NaOH with concentration after 10~30 minutes
Former agent solution is adjusted after pH to 9~10, condensing reflux 2~5 hours, obtains Pt nano particle particle dispersion；By above-mentioned Pt nano particle particle
Dispersion liquid vacuum distillation at 30~76 DEG C is removed after solvent, obtains surfactant modified Pt nano particle solids；Again will
Above-mentioned surfactant modified Pt nano particles solid acetone centrifuge washing 3~4 times, after 30~76 DEG C of drying, divides again
It is scattered in organic reducing agent, obtains the surfactant modified Pt nano particles that platinum mass concentration is 0.13~0.78mg/mL
Dispersion liquid；
(2) prepared by the Pt nano particles of ZIF claddings
Metal salt and organic ligand are weighed for 1 ︰ 4~8 by the mol ratio of metal salt ︰ organic ligands, by metal platinum ︰ organic ligand matter
Amount is than being 1：623~1515 measure above-mentioned surfactant modified Pt nanoparticulate dispersions；Metal salt is configured to first
Concentration is 0.05~0.79mol/L ethanol or methanol or the aqueous solution, by organic ligand be configured to concentration for 0.04~
0.48mol/L ethanol or methanol or the aqueous solution；Then above-mentioned organic ligand solution is poured into above-mentioned metal salt solution, stirred
After 5~60 minutes, surfactant modified Pt nanoparticulate dispersions are added, continues to stir 30~120 minutes, stands reaction
24~72 hours, centrifuge, ethanol washing after 40~80 DEG C of drying, obtains the Pt nano particles of ZIF claddings；
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
The Pt nano particles that above-mentioned ZIF is coated are placed in tube furnace first, with air in vacuum pumped tube furnace, then with hydrogen
Throughput is 5~50 ml/mins and nitrogen flow is that 50~200 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen
With under hydrogen mixed gas atmosphere with 0.5~10 DEG C/min be warming up to 300~500 DEG C keep 0~3 hour after, then with 5~10 DEG C/
Minute is warming up to 750~900 DEG C and kept for 0.5~3 hour, finally, is cooled to room temperature under nitrogen and hydrogen mixed gas atmosphere, obtains
Obtain catalyst solid powder；Above-mentioned catalyst solid powder is dispersed in 0.1~2.0mol/L protonic acid solution, 60~80
DEG C stirring 8~24 hours, ion water washing 3 times, absolute ethyl alcohol is washed 3 times, and 40~60 DEG C are dried in vacuo 24 hours, obtain three-dimensional
Carbon skeleton embedding nano platinum base alloy；
Described platinum presoma is chloroplatinic acid, the ammino platinum of tetrachloro two, sub- potassium chloroplatinate, four ammino bicarbonate platinum, hexahydroxy conjunction platinum
One of sour diethanol ammonium；Described organic reducing agent is one of methanol and ethanol；The surfactant is
One of polyvinylpyrrolidone, DTAB and sodium citrate；Described metal salt is six hydrations
One of cobalt nitrate, four hydration cobalt acetates, zinc nitrate hexahydrate, four hydration zinc acetates；The organic ligand is 2- methyl
One of imidazoles, DMIZ 1,2 dimethylimidazole and 4-methylimidazole；The protonic acid solution be hydrochloric acid solution, sulfuric acid solution and
One of salpeter solution.
2. according to a kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy described in claim 1, it is characterised in that
The step of specific preparation method (1)~(3)：
(1) preparation of surfactant modified Pt nanoparticulate dispersions
Mass ratio by the Jia Chun Rong Ye ︰ Reduction of methanol Ji ︰ polyvinylpyrrolidones of chloroplatinic acid is the ︰ 0.20 of 1 ︰ 18, weighs chlorine platinum
Methanol solution, Reduction of methanol agent and the polyvinylpyrrolidone of acid；The methanol solution of chloroplatinic acid is first dissolved in concentration for 9mol/
In L hydrochloric acid solutions, Reduction of methanol agent is then added, the platinum precursor solution that platinum mass concentration is 9.42mg/mL is formed；It is upward again
Polyvinylpyrrolidone is added in the methanol solution for stating chloroplatinic acid, ultrasonic agitation was 2.92mol/L's with concentration after 20 minutes
NaOH organic reducings agent solution is adjusted after pH to 9~10, condensing reflux 3 hours, obtains Pt nano particle particle dispersion；By above-mentioned nanometer
The vacuum distillation at 76 DEG C of Pt particle dispersions is removed after solvent, obtains surfactant modified Pt nano particle solids；Again
By above-mentioned surfactant modified Pt nano particles solid acetone centrifuge washing 3 times, after 76 DEG C of drying, first is dispersed back into
In alcohol reducing agent, the surfactant modified Pt nanoparticulate dispersions that platinum mass concentration is 0.26mg/mL are obtained；
(2) prepared by the Pt nano particles of ZIF-67 claddings
Metal salt and organic ligand are weighed for 1 ︰ 8 by the mol ratio of acetic acid cobalt ︰ 2-methylimidazoles, by metal platinum ︰ 2-methylimidazoles
Mass ratio is that 1 ︰ 1248 measures above-mentioned surfactant modified Pt nanoparticulate dispersions；First by cobalt acetate and 2- methyl miaows
Azoles is each configured to the ethanol solution that concentration is 0.050 and 0.40mol/L；Then 2-methylimidazole solution is poured into cobalt acetate molten
In liquid, after stirring 30 minutes, surfactant modified Pt nanoparticulate dispersions are added, continues to stir 30 minutes, stands instead
Answer 24 hours, centrifuge, ethanol washing after 80 DEG C of drying, obtains the Pt nano particles of ZIF-67 claddings；
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
The Pt nano particles that above-mentioned ZIF-67 is coated are placed in tube furnace first, with air in vacuum pumped tube furnace, then
It is 5 ml/mins using hydrogen flowing quantity and nitrogen flow is that 50 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen and hydrogen
Under gas gaseous mixture atmosphere with 1 DEG C/min be warming up to 300~400 DEG C kept for 2 hours after, then with 5 DEG C/min be warming up to 750 DEG C of guarantors
Hold 1 hour, finally, room temperature is cooled under nitrogen and hydrogen mixed gas atmosphere, obtains catalyst solid powder；By above-mentioned catalysis
Agent solid powder is dispersed in 1.0mol/L protonic acid solution, and 80 DEG C are stirred 24 hours, ion water washing 3 times, absolute ethyl alcohol
Washing 3 times, 60 DEG C are dried in vacuo 24 hours, obtain three-dimensional carbon skeleton embedding nano platinum base alloy.
3. according to a kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy described in claim 1, it is characterised in that
The step of specific preparation method (1)~(3)：
(1) preparation of surfactant modified Pt nanoparticulate dispersions
Mass ratio by the Jia Chun Rong Ye ︰ Reduction of methanol Ji ︰ polyvinylpyrrolidones of chloroplatinic acid is the ︰ 0.10 of 1 ︰ 10, weighs chlorine platinum
Methanol solution, Reduction of methanol agent and the polyvinylpyrrolidone of acid；The methanol solution of chloroplatinic acid is first dissolved in concentration for 6mol/
In L hydrochloric acid solutions, Reduction of methanol agent is then added, the platinum precursor solution that platinum mass concentration is 7.54mg/mL is formed；It is upward again
Polyvinylpyrrolidone is added in the methanol solution for stating chloroplatinic acid, ultrasonic agitation was 1.25mol/L's with concentration after 10 minutes
NaOH organic reducings agent solution is adjusted after pH to 9~10, condensing reflux 3 hours, obtains Pt nano particle particle dispersion；By above-mentioned nanometer
The vacuum distillation at 76 DEG C of Pt particle dispersions is removed after solvent, obtains surfactant modified Pt nano particle solids；Again
By above-mentioned surfactant modified Pt nano particles solid acetone centrifuge washing 4 times, after 76 DEG C of drying, first is dispersed back into
In alcohol reducing agent, the surfactant modified Pt nanoparticulate dispersions that platinum mass concentration is 0.13mg/mL are obtained；
(2) prepared by the Pt nano particles of ZIF-67 claddings
Metal salt and organic ligand are weighed for 1 ︰ 8 by the mol ratio of acetic acid cobalt ︰ 2-methylimidazoles, by metal platinum ︰ 2-methylimidazoles
Mass ratio is that 1 ︰ 1248 measures above-mentioned surfactant modified Pt nanoparticulate dispersions；First by cobalt acetate and 2- methyl miaows
Azoles is each configured to the ethanol solution that concentration is 0.050 and 0.40mol/L；Then 2-methylimidazole solution is poured into cobalt acetate molten
In liquid, after stirring 30 minutes, surfactant modified Pt nanoparticulate dispersions are added, continues to stir 30 minutes, stands instead
Answer 24 hours, centrifuge, ethanol washing after 80 DEG C of drying, obtains the Pt nano particles of ZIF-67 claddings；
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
The Pt nano particles that above-mentioned ZIF-67 is coated are placed in tube furnace first, with air in vacuum pumped tube furnace, then
It is 5 ml/mins using hydrogen flowing quantity and nitrogen flow is that 50 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen and hydrogen
Under gas gaseous mixture atmosphere with 1 DEG C/min be warming up to 300~400 DEG C kept for 2 hours after, then with 5 DEG C/min be warming up to 750 DEG C of guarantors
Hold 1 hour, finally, room temperature is cooled under nitrogen and hydrogen mixed gas atmosphere, obtains catalyst solid powder；By above-mentioned catalysis
Agent solid powder is dispersed in 1.0mol/L protonic acid solution, and 60 DEG C are stirred 16 hours, ion water washing 3 times, absolute ethyl alcohol
Washing 3 times, 60 DEG C are dried in vacuo 24 hours, obtain three-dimensional carbon skeleton embedding nano platinum base alloy.
4. according to a kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy described in claim 1, it is characterised in that
The step of specific preparation method (1)~(3)：
(1) preparation of surfactant modified Pt nanoparticulate dispersions
Mass ratio by the Jia Chun Rong Ye ︰ Reduction of methanol Ji ︰ polyvinylpyrrolidones of sub- potassium chloroplatinate is the ︰ 0.30 of 1 ︰ 30, is weighed
Methanol solution, Reduction of methanol agent and the polyvinylpyrrolidone of sub- potassium chloroplatinate；First the methanol solution of sub- potassium chloroplatinate is dissolved
In concentration is 12mol/L hydrochloric acid solutions, Reduction of methanol agent is then added, is formed before the platinum that platinum mass concentration is 18.84mg/mL
Drive liquid solution；Polyvinylpyrrolidone is added into the methanol solution of above-mentioned sub- chloroplatinic acid again, ultrasonic agitation is after 30 minutes, with dense
Spend and adjusted for 4.75mol/L NaOH organic reducings agent solution after pH to 9~10, condensing reflux 5 hours obtains Pt nano particle particle point
Dispersion liquid；By above-mentioned Pt nano particle particle dispersion, vacuum distillation is removed after solvent at 76 DEG C, obtains surfactant modified Pt
Nano particle solid；Again by above-mentioned surfactant modified Pt nano particles solid acetone centrifuge washing 3 times, 76 DEG C of drying
Afterwards, it is dispersed back into Reduction of methanol agent, obtains the surfactant modified Pt nanometers that platinum mass concentration is 0.78mg/mL
Grain dispersion liquid；
(2) prepared by the Pt nano particles of ZIF claddings
Cabaltous nitrate hexahydrate and 2-methylimidazole are weighed for 1 ︰ 4 by the mol ratio of acetic acid cobalt ︰ 2-methylimidazoles, by metal platinum ︰ 2-
Methylimidazole mass ratio is that 1 ︰ 623 measures above-mentioned surfactant modified Pt nanoparticulate dispersions；First nitre is hydrated by six
Sour cobalt and 2-methylimidazole are each configured to the ethanol solution that concentration is 0.05mol/L and 0.79mol/L；Then by 2- methyl miaows
Azoles solution is poured into cabaltous nitrate hexahydrate solution, after stirring 60 minutes, is added surfactant modified Pt nano particles and is disperseed
Liquid, continues to stir 120 minutes, stands reaction 48 hours, centrifuge, ethanol washing, after 80 DEG C of drying, obtains ZIF-67 claddings
Pt nano particles；
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
The Pt nano particles that above-mentioned ZIF-67 is coated are placed in tube furnace first, with air in vacuum pumped tube furnace, then
It is 5 ml/mins using hydrogen flowing quantity and nitrogen flow is that 50 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen and hydrogen
Under gas gaseous mixture atmosphere with 1 DEG C/min be warming up to 300~400 DEG C kept for 2 hours after, then with 5 DEG C/min be warming up to 750 DEG C of guarantors
Hold 1 hour, finally, room temperature is cooled under nitrogen and hydrogen mixed gas atmosphere, obtains catalyst solid powder；By above-mentioned catalysis
Agent solid powder is dispersed in 1.0mol/L protonic acid solution, and 70 DEG C are stirred 8 hours, ion water washing 3 times, and absolute ethyl alcohol is washed
Wash 3 times, 60 DEG C are dried in vacuo 24 hours, obtain three-dimensional carbon skeleton embedding nano platinum base alloy.
5. according to a kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy described in claim 1, it is characterised in that
The step of specific preparation method (1)~(3)：
(1) preparation of surfactant modified Pt nanoparticulate dispersions
Mass ratio by the Jia Chun Rong Ye ︰ Reduction of methanol Ji ︰ polyvinylpyrrolidones of chloroplatinic acid is the ︰ 0.20 of 1 ︰ 18, weighs chlorine platinum
Methanol solution, Reduction of methanol agent and the polyvinylpyrrolidone of acid；The methanol solution of chloroplatinic acid is first dissolved in concentration for 9mol/
In L hydrochloric acid solutions, Reduction of methanol agent is then added, the platinum precursor solution that platinum mass concentration is 9.42mg/mL is formed；It is upward again
Polyvinylpyrrolidone is added in the methanol solution for stating chloroplatinic acid, ultrasonic agitation was 2.92mol/L's with concentration after 20 minutes
NaOH organic reducings agent solution is adjusted after pH to 9~10, condensing reflux 3 hours, obtains Pt nano particle particle dispersion；By above-mentioned nanometer
The vacuum distillation at 76 DEG C of Pt particle dispersions is removed after solvent, obtains surfactant modified Pt nano particle solids；Again
By above-mentioned surfactant modified Pt nano particles solid acetone centrifuge washing 3 times, after 76 DEG C of drying, first is dispersed back into
In alcohol reducing agent, the surfactant modified Pt nanoparticulate dispersions that platinum mass concentration is 0.26mg/mL are obtained；
(2) prepared by the Pt nano particles of ZIF-8 claddings
Zinc acetate and 2-methylimidazole are weighed for 1 ︰ 8 by the mol ratio of the sour zinc ︰ 2-methylimidazoles of vinegar, by metal platinum ︰ 2- methyl miaows
Azoles mass ratio is that 1 ︰ 1515 measures above-mentioned surfactant modified Pt nanoparticulate dispersions；First by zinc acetate and 2- methyl
Imidazoles is each configured to the ethanol solution that concentration is 0.06 and 0.48mol/L；Then 2-methylimidazole solution is poured into zinc acetate
In solution, after stirring 30 minutes, surfactant modified Pt nanoparticulate dispersions are added, continues to stir 30 minutes, stands
Reaction 24 hours, is centrifuged, ethanol washing, after 80 DEG C of drying, obtains the Pt nano particles of ZIF-8 claddings；
(3) preparation of three-dimensional carbon skeleton embedding nano platinum base alloy
The Pt nano particles that above-mentioned ZIF-8 is coated are placed in tube furnace first, with air in vacuum pumped tube furnace, then with
Hydrogen flowing quantity is 5 ml/mins and nitrogen flow is that 50 ml/mins are filled with nitrogen and hydrogen mixed gas, in nitrogen and hydrogen
Under gaseous mixture atmosphere with 5 DEG C/min be warming up to 900 DEG C keep 1 hour after, it is finally, cold under nitrogen and hydrogen mixed gas atmosphere
But to room temperature, catalyst solid powder is obtained.
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