CN106887608A - The preparation method and application of inexpensive hollow carbon sphere base oxygen reduction catalyst - Google Patents
The preparation method and application of inexpensive hollow carbon sphere base oxygen reduction catalyst Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention provides a kind of inexpensive hollow carbon sphere catalyst and the preparation method of the hollow carbon sphere of the scattered transition metal oxide nano-particles catalyst of Load Balanced.The preparation method of the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide, comprises the following steps：1. appropriate template and transition-metal cation salt is weighed, the hollow polymer ball presoma of carrying transition metal oxide is synthesized using hydro-thermal reaction；2. the hollow polymer ball presoma for 1. step being obtained is placed in calciner plant, high-temperature calcination is for a period of time under an inert atmosphere, then room temperature is naturally cooled to, and is stored at room temperature appropriate time, that is, obtain the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide nano-particles.Preparation method of the present invention is simple, easily operated, and the prices of raw materials are cheap, help to realize its industrialized application.
Description
Technical field
The invention belongs to field of environment engineering, and in particular to the preparation of hollow carbon sphere base oxygen reduction catalyst, more particularly to a kind of use
In the preparation and its application of the hollow carbon sphere catalyst of the carrying transition metal oxide of catalytic oxygen reduction.
Background technology
At present, with the continuous deterioration of global environment, it is new that people begin to focus on fuel cell, solar cell and lithium battery etc.
Clean energy resource, to realize the sustainable development of the mankind.In recent years, Chinese haze weather is frequently occurred, and causes each bound pair
Automotive emission and the common concern of combustion of fossil fuel, allow FC-EV to turn into international new-energy automobile once again
The research and development focus in field.In all kinds of fuel cell, Proton Exchange Membrane Fuel Cells have high power density,
High-energy conversion efficiency, cold-starting and advantages of environment protection, most promise to be the dynamic of various portable power sources and electric automobile
Power source.Although Proton Exchange Membrane Fuel Cells has many advantages and great potential, electricity in terms of chemical energy is converted into electric energy
Pond cost and durability constrain the process of its commercialization.
Proton Exchange Membrane Fuel Cells includes two important fundamental reactions, i.e. cathodic oxygen reduction and anode hydroxide.Wherein, fire
Redox reactions mechanism on material cell cathode is extremely complex, and overpotential is high, and reaction speed is slow, in the feelings without catalyst
It is difficult to occur under condition；This is also the principal element of fuel cell power.Therefore, the quality of oxygen reduction reaction catalyst is determined
The quality of battery performance, so as to determining the height of energy conversion efficiency and battery cost.The alloy of Pt or Pt is wide at present
The oxygen reduction electro-catalyst of general application, but Pt is expensive and reserves are limited.For example, commercialized carbon carries Pt nanoparticles
Muonic catalysis agent occupies a cost for fuel cell pack 55% (R.Bashyam et al., Nature, 2006,443,63-66), and this is big
The big commercial applications for constraining fuel cell.Therefore, the oxygen reduction catalyst of exploitation high-performance, low cost is for developing and promoting
The commercial Application for entering fuel cell is significant.
In recent years, researcher starts to design and develop the new non-Pt for having suitable catalytic oxidation-reduction activity with Pt catalyst and is catalyzed
Agent, to solve the problems, such as precious metals pt catalyst high cost.Recently, the composite of various metal oxide/carbon is good due to its
Electrocatalytic oxidation reducing activity receive the concern of people.Such as Dai Hongjie professors seminar devises cobalt oxide/Graphene and oxidation
The composites such as cobalt/CNT ((1) Y.Y.Liang, Y.G.Li, H.L.Wang, J.G.Zhou, J.Wang, T.Regier, H.
J.Dai,Nat.Mater.,2011,10,781-786.(2)Y.Y.Liang,H.L.Wang,et.al.H.J.Dai,J.Am.Chem.
Soc.2012,134,15849-15857), find due to the couple between carbon material and metal oxide, it has enhanced
Electrocatalytic oxidation reducing property.But there is problems with the preparation of above-mentioned catalyst：(1) carbon material used by such as Graphene and carbon are received
Mitron needs are previously prepared, and its synthesis program is more complicated；(2), it is necessary to use oxygen when anchor closes metal oxide on the carbon material
Change method pre-processes various carbon material such as Graphenes and CNT, and position is closed as metal oxide anchor to generate various oxy radicals
Point, so as to improve the active force between metal oxide and Graphene or CNT；So make the preparation process of composite compared with
Cumbersome, time-consuming, high cost, it is difficult to industrialized production.
Recently, researcher employs the precious metals pt and its alloy PtCo that hydro-thermal one kettle way has prepared load particle diameter 3nm or so
The hollow carbon sphere of nano-particle, the hydrolysis for being catalyzed 5- hydroxymethylfurans is this heavy to generate 2,5- dimethyl furans
The liquid fuel (G.H.Wang et al., Nat.Mater., 2014,13,293-300) wanted.The hydro-thermal one pot reaction condition
Gently, it is simple to operate, and the preparation of carbon ball presoma and the load of precious metal ion precursor salt, reduction etc. are merged into one
Step is carried out, and greatlys save the reaction time, and reduce cost.However, its problem for existing is：Using electronegative PtCl4 2-
Used as noble metal precursor body ion, there are electrostatic repulsion forces, cause in this and the carbon ball presoma of electronegative carboxyl-functional between
There is certain agglomeration in the noble metal catalyst particles loaded in ghost carbon ball prepared by the method, so as to drop to a certain extent
Low its catalysis activity.And for electro-catalysis, dispersed particle is beneficial to the raising of catalysis activity.If however, only
It is the transition M for electronegative coordination salt being changed into positively chargedn+Metal ion, the transition metal of electronegative carboxyl and positively charged from
The electrostatic attraction effect of son can weaken the trend of prepared particle aggregation to a certain extent, but still cannot fundamentally prevent
The generation of reunion.
The content of the invention
Regarding to the issue above, the technical problem to be solved in the present invention is to provide a kind of hollow carbon sphere catalyst of low cost and loads equal
The preparation method of the hollow carbon sphere of even scattered transition metal oxide nano-particles catalyst.The method preparation method is simple, easy
In operation, and the prices of raw materials are cheap, help to realize its industrialized application.
The technical scheme is that：
The preparation method of the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide, comprises the following steps：1. weigh appropriate
Template and transition-metal cation salt, the hollow polymer ball presoma of carrying transition metal oxide is synthesized using hydro-thermal reaction；
2. the hollow polymer ball presoma for 1. step being obtained is placed in calciner plant, under an inert atmosphere high-temperature calcination for a period of time,
Then room temperature is naturally cooled to, and is stored at room temperature appropriate time, that is, obtain the hollow of carrying transition metal oxide nano-particles
Carbon ball oxygen reduction catalyst.
Wherein, the template that 1. step uses is triblock copolymer Pluronic P123 and enuatrol, described transition gold
Category cation is Fe3+, Co2+And Ni2+Deng the Pluronic P123：Enuatrol：The mol ratio of transition-metal cation salt
It is 1:16:8-1:64:24, the temperature of the hydro-thermal reaction is 80-240 DEG C；Step calcining heat 2. is 500-1000 DEG C,
Calcination time is 0.5 to 6h.
Preferably, the preparation method of the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide, comprises the following steps：
1. weigh appropriate template and transition-metal cation salt is configured to water solution A；Then appropriate phenol compound is weighed
(such as 2,4- dihydroxy-benzoic acids, para hydroxybenzene propionic acid and PCA etc.) is configured to the aqueous solution, then takes appropriate first
Aldehyde or hexamethylenetetramine are dissolved in phenol compound solution, obtain solution B；Solution B is added into solution under agitation
In A, solution C is obtained；Solution C is carried out into hydro-thermal reaction under the pressure condition of 1-3atm, reacted product is cooled to
Room temperature is simultaneously washed, dried, that is, obtain the hollow polymer ball presoma of carrying transition metal oxide；
2. the hollow polymer ball presoma for 1. step being obtained is placed in calciner plant, under an inert atmosphere during one section of high-temperature calcination
Between, room temperature is then naturally cooled to, and be stored at room temperature appropriate time, that is, obtain carrying transition metal oxide nano-particles
Hollow carbon sphere oxygen reduction catalyst.
Wherein, the step 1. middle Pluronic P123：Enuatrol：The mol ratio of transition-metal cation salt is 1:16:8-1:64:24.
Wherein, the concentration of the formaldehyde is 37.5-75mmol/L, and the concentration of the hexamethylenetetramine is 6.25-12.5mmol/L；Institute
The concentration for stating phenol compound is 15-25mmol/L；The formaldehyde is 15 with the mol ratio of phenol compound:4-6, it is described
Hexamethylenetetramine is 1 with the mol ratio of phenol compound:1.6-2.4.The pressure of the hydro-thermal reaction is 2atm, the hydro-thermal
The temperature of reaction is 80-240 DEG C, and the time of the hydro-thermal reaction is 0.5-6h.Step washing methods 1. is using ultrapure
Water is centrifuged 5-30min under the rotating speed of 7000-13000rpm, in triplicate；Step furnace drying method 1. is at 40-80 DEG C
8-16h is dried in vacuum drying oven.The step 2. in inert atmosphere using the inert atmosphere, the calcining temperature such as nitrogen, argon gas
It is 500-1000 DEG C to spend, and calcination time is 0.5-6h.
The application of the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide, uses it for catalytic oxygen reduction reaction.
The preparation method of hollow carbon sphere oxygen reduction catalyst, comprises the following steps：
1. weigh appropriate template and be configured to water solution A；Then weigh appropriate phenol compound and be configured to the aqueous solution, then take
Appropriate formaldehyde or hexamethylenetetramine are dissolved in the phenol compound aqueous solution, obtain solution B；By solution B in stirring bar
Added under part in solution A, obtain solution C；Solution C is carried out into hydro-thermal reaction under the pressure condition of 1-3atm, after reaction
Product be cooled to room temperature and wash, dry, that is, obtain hollow polymer ball presoma；
2. the hollow polymer ball presoma for 1. step being obtained is placed in calciner plant, under an inert atmosphere during one section of high-temperature calcination
Between, then naturally cool to room temperature, that is, obtain hollow carbon sphere oxygen reduction catalyst.
Wherein, the concentration of the formaldehyde is 37.5-75mmol/L, and the concentration of the hexamethylenetetramine is 6.25-12.5mmol/L；
The concentration of the phenol compound is 15-25mmol/L；The formaldehyde is 15 with the mol ratio of phenol compound:4-6, institute
It is 1 that hexamethylenetetramine is stated with the mol ratio of phenol compound:1.6-2.4.The pressure of the hydro-thermal reaction is 2atm, the water
The temperature of thermal response is 80-240 DEG C, and the time of the hydro-thermal reaction is 0.5-6h；Step washing methods 1. is using super
Pure water is centrifuged 5-30min under the rotating speed of 7000-13000rpm, in triplicate；Step furnace drying method 1. is at 40-80 DEG C
8-16h is dried in vacuum drying oven；The step 2. in inert atmosphere use nitrogen or argon atmosphere, the calcining heat is
500-1000 DEG C, calcination time is 0.5-6h.
The application of hollow carbon sphere oxygen reduction catalyst, uses it for catalytic oxygen reduction reaction.
The present invention is by the selection to slaine species, the control of slaine amount, the selection of various functions carbon matrix precursor, raw material
The control of heating mode and soaking time when the regulation and control and calcining of addition sequence, is successfully prepared the hollow carbon sphere catalysis of low cost
Agent and the hollow carbon sphere catalyst of the scattered transition metal oxide of Load Balanced.
Catalytic oxidation-reduction performance test is carried out to hollow carbon sphere base oxygen reduction catalyst：
(1) modified electrode is prepared：Solid substrate electrode used such as glass-carbon electrode (a diameter of 3mm) are placed on polishing cloth,
With 1 μm and 0.05 μm of alumina powder foot couple, it is processed by shot blasting respectively, then respectively acetone, absolute ethyl alcohol and go from
It is cleaned by ultrasonic 3min in sub- water, nitrogen stream drying is stand-by.The appropriate catalyst prepared according to the above method is weighed, ultrasonic disperse exists
Nafion solution (water:Isopropanol:Nafion volume ratios are 4:1:0.1 mixed liquor) in obtain concentration be 6-18mg/mL dispersion
Liquid.Appropriate dispersant liquid drop is added to the glassy carbon electrode surface handled well, is dried under infrared lamp, that is, obtain hollow carbon sphere base catalyst
The electrode of modification.
(2) electrochemical measurement：It is the hollow of 6-18mg/mL with concentration with 0.1M potassium hydroxide solutions as electrolyte solution
The glass-carbon electrode of the hollow carbon sphere modification of the glass-carbon electrode or carrying transition metal oxide nano-particles catalyst of carbon ball modification is work
Make electrode, Pt rods are that, to electrode, saturation Ag/AgCl electrodes are reference electrode, and catalytic oxidation-reduction active testing is in CHI 842D
Carried out on electrochemical workstation and Japan's ALS RRDE-3A devices.
Concrete operations are as follows：Under the conditions of 25 DEG C of constant temperature, in advance prior to being passed through oxygen about 30min in electrolyte, make the oxygen in solution
Saturation is reached, then polarization curves of oxygen reduction is scanned by high potential 0V with 10mV/s sweep speeds to low potential -0.5V.
By the hollow carbon sphere catalyst modification of the electrode or carrying transition metal oxide nano-particles of present invention gained hollow carbon sphere modification
Glass-carbon electrode is placed in the 0.1M potassium hydroxide solutions of oxygen saturation the Cathodic oxygen reduction for being capable of achieving fuel cell.Characterize the oxygen
The reactivity parameter of reduction reaction includes take-off potential, half wave potential and the limiting current density of oxygen reduction reaction.
Beneficial effects of the present invention：
(1) present invention uses the transition metal ions such as Fe of positively charged3+, Co2+And Ni2+Deng, due to transition-metal cation and
There is interaction force between the carbon ball presoma of electronegative carboxyl-functional, therefore, improve metal in carbon ball presoma
The decentralization of oxide nano-particles, so as to solve the agglomeration traits of loading particle, improves its utilization rate and catalysis activity.
(2) preparation method of the present invention is simple, easily operated, it is not necessary to expensive instrument and equipment, modifies mild condition, and normal temperature is normal
Pressure is carried out in aqueous, is a kind of environment-friendly preparation method thereof of low cost.
(3) the various raw materials that the present invention is used are commercially available, and raw material is easy to get, the prospect for possessing commercial Application.
(4) compared with Pt/C catalyst is commercialized, although the catalyst prepared by the present invention fails to surmount commercialization Pt/C catalysis
Agent, but substantially suitable catalytic performance is presented, and cost is greatly reduced, will greatly promote no-Pt catalyst commercially
The process of application.
Brief description of the drawings：
Fig. 1 is the transmission electron microscope photo of hollow carbon sphere prepared in the embodiment of the present invention 1；
Fig. 2 is the transmission electron microscope photo of the hollow carbon sphere of the load Fe oxide nano-particles of preparation in the embodiment of the present invention 4；
Fig. 3 is the transmission electron microscope photo of the hollow carbon sphere of the load C o oxide nano-particles of preparation in the embodiment of the present invention 5；
Fig. 4 is the hollow carbon sphere of the load C o oxide nano-particles prepared in the embodiment of the present invention 1 and embodiment 7
XRD diffraction spectrograms and standard Co3O4Spectrogram (dotted line) is contrasted.
Specific embodiment
With reference to embodiment, the present invention is described further.
Embodiment 1：The preparation method for preparing hollow carbon sphere oxygen reduction catalyst of hollow carbon sphere oxygen reduction catalyst, including it is following
Step：
1. 66mg template Pluronic P123 and 110mg enuatrols are weighed and is configured to water solution A.Then appropriate 277 are weighed
Mg 2,4- dihydroxy-benzoic acid are configured to concentration and are the aqueous solution of 15mmol/L, then take 105mg hexamethylenetetramines and be dissolved in 2,4-
In dihydroxy-benzoic acid solution, solution B is obtained, the wherein concentration of hexamethylenetetramine is 6.25mmol/L；Solution B is being stirred
Added under the conditions of mixing in solution A, continue to stir 10min, obtain solution C.By solution C it is closed after be placed in baking oven, in 2atm
Pressure condition under, hydro-thermal reaction is carried out under 160 DEG C of temperature conditionss, the reaction time is 2h.Reacted product is cooled to
Room temperature, 10min is centrifuged using ultra-pure water under the rotating speed of 9000rpm, in triplicate, residual impurity after washing reaction；Then
8h is dried in 50 DEG C of vacuum drying oven, that is, obtains hollow polymer ball presoma.
2. the hollow polymer ball presoma for 1. step being obtained is placed in calciner plant, under the inert atmosphere of nitrogen or argon gas,
High-temperature calcination 3h under 600 DEG C of temperature conditionss, then naturally cools to room temperature, that is, obtain hollow carbon sphere catalyst.
Catalytic oxidation-reduction performance test is carried out to hollow carbon sphere oxygen reduction catalyst：
(1) modified electrode is prepared：Basal electrode used such as glass-carbon electrode (a diameter of 3mm) are placed on polishing cloth, respectively
With 1 μm and 0.05 μm of alumina powder foot couple, it is processed by shot blasting, then respectively in acetone, absolute ethyl alcohol and deionization
It is cleaned by ultrasonic 3min in water, nitrogen stream drying is stand-by.The appropriate catalyst prepared according to the above method is weighed, ultrasonic disperse exists
Nafion solution (water:Isopropanol:Nafion volume ratios are 4:1:0.1 mixed liquor) in obtain the dispersion liquid of 6-18mg/mL.Will
Appropriate dispersant liquid drop is added to the glassy carbon electrode surface handled well, is dried under infrared lamp, that is, obtain the electrode of hollow carbon sphere modification.
(2) electrochemical measurement：With 0.1M potassium hydroxide solutions as electrolyte solution, repaiied with the hollow carbon sphere of 6-18mg/mL
The glass-carbon electrode of decorations is working electrode, and Pt rods are that, to electrode, saturation Ag/AgCl electrodes are reference electrode, catalytic oxidation-reduction activity
Test is carried out on CHI 842D electrochemical workstations and Japan's ALS RRDE-3A devices.
Concrete operations are as follows：Under the conditions of 25 DEG C of constant temperature, in advance prior to being passed through oxygen about 30min in electrolyte, make the oxygen in solution
Saturation is reached, then polarization curves of oxygen reduction is scanned by high potential 0V with 10mV/s sweep speeds to low potential -0.5V.
The glass-carbon electrode of present invention gained hollow carbon sphere catalyst modification is placed in the 0.1M potassium hydroxide solutions of oxygen saturation and is capable of achieving
The Cathodic oxygen reduction of fuel cell.
Embodiment 2：The preparation of hollow carbon sphere oxygen reduction catalyst
As different from Example 1,2. middle calcining heat is 900 DEG C to step.
Embodiment 3：The preparation of the hollow carbon sphere of carrying transition metal Fe oxides
As different from Example 1, the preparation method of the hollow carbon sphere of carrying transition metal Fe oxides, comprises the following steps：
1. 66mg templates Pluronic P123,110mg enuatrols are weighed and the water ferric nitrates of 72.72mg nine is configured to the aqueous solution
A.Then appropriate 277mg2 is weighed, 4- dihydroxy-benzoic acids are configured to concentration and are the aqueous solution of 15mmol/L, then take 105mg
Hexamethylenetetramine is dissolved in 2,4- dihydroxy-benzoic acid solution, obtains solution B, and the concentration of wherein hexamethylenetetramine is
6.25mmol/L；Solution B is added under agitation in solution A, continue to stir 10min, obtain solution C.By solution
It is placed in baking oven after C is closed, hydro-thermal reaction, reaction time is carried out under the pressure condition of 2atm, under 160 DEG C of temperature conditionss
It is 2h.Reacted product is cooled to room temperature, 10min is centrifuged under the rotating speed of 9000rpm using ultra-pure water, repeat three
It is secondary, residual impurity after washing reaction；Then 8h is dried in 50 DEG C of vacuum drying oven, that is, obtains hollow polymer ball presoma.
2. the hollow polymer ball presoma for 1. step being obtained is placed in calciner plant, in nitrogen or the inert atmosphere inertia of argon gas
High-temperature calcination 3h under atmosphere, under 600 DEG C of temperature conditionss, then naturally cools to room temperature, and is stored at room temperature appropriate time,
Obtain the hollow carbon sphere oxygen reduction catalyst of carrying transition metal Fe oxide nano-particles.
Embodiment 4：The preparation of the hollow poly- carbon ball of carrying transition metal Fe oxides
As different from Example 3, step 1. in the amount of nine water ferric nitrates that is added be 36.36mg.
Embodiment 5：The preparation of the hollow polymer ball of carrying transition metal Co oxides
As different from Example 1, the preparation method of the hollow carbon sphere of carrying transition metal Co oxides, comprises the following steps：
1. 66mg templates Pluronic P123,110mg enuatrols are weighed and 26.26mg cobalt nitrate hexahydrates is configured to the aqueous solution
A.Then appropriate 277mg 2 is weighed, 4- dihydroxy-benzoic acids are configured to concentration and are the aqueous solution of 15mmol/L, then take 105mg
Hexamethylenetetramine is dissolved in 2,4- dihydroxy-benzoic acid solution, obtains solution B, and the concentration of wherein hexamethylenetetramine is
6.25mmol/L；Solution B is added under agitation in solution A, continue to stir 10min, obtain solution C.By solution
It is placed in baking oven after C is closed, hydro-thermal reaction, reaction time is carried out under the pressure condition of 2atm, under 160 DEG C of temperature conditionss
It is 2h.Reacted product is cooled to room temperature, 10min is centrifuged under the rotating speed of 9000rpm using ultra-pure water, repeat three
It is secondary, residual impurity after washing reaction；Then 8h is dried in 50 DEG C of vacuum drying oven, that is, obtains hollow polymer ball presoma.
2. the hollow polymer ball presoma for 1. step being obtained is placed in calciner plant, under the inert atmosphere of nitrogen or argon gas,
High-temperature calcination 3h under 600 DEG C of temperature conditionss, then naturally cools to room temperature, and is stored at room temperature appropriate time, that is, born
The hollow carbon sphere oxygen reduction catalyst of carried transition metal Co oxide nano-particles.
Embodiment 6：The preparation of the hollow polymer ball of carrying transition metal Co oxides
As different from Example 5,2. middle calcining heat is 800 DEG C to step.
Embodiment 7：The preparation of the hollow polymer ball of carrying transition metal Co oxides
As different from Example 5,2. middle calcining heat is 900 DEG C to step.
Embodiment 8：The preparation of the hollow polymer ball of carrying transition metal Co oxides
As different from Example 7,1. one of middle reactant is 365mg formaldehyde to step.
The performance characterization of hollow carbon sphere base oxygen reduction catalyst prepared by the embodiment 1-8 of table 1.
(electrolyte solution：0.1M potassium hydroxide solutions)
It can be seen from table 1, the catalyst prepared in implementation 2 and 7 presents the initial overpotential and half wave potential of calibration,
And larger limit catalytic current density, therefore these catalyst catalytic performances are optimal.
The hollow carbon sphere base catalyst of the preparation of 2 embodiment of the present invention of table 2 and 7 and the performance comparison of similar catalyst in document
(electrolyte solution：0.1M potassium hydroxide solutions)
It can be seen from table 2, compared with similar catalyst reported in the literature, hollow carbon sphere catalyst and loaded prepared by the present invention
The hollow carbon sphere catalyst of metallic cobalt oxide nano-particles, take-off potential and half wave potential calibration are crossed, limiting current density is maximum,
With optimal catalysis activity.Be commercialized Pt/C catalyst compared with, for example embodiment 2 prepare catalyst take-off potential and
Half wave potential is born moved 50mV and 20mV respectively, but limit catalytic current density is larger.Although the catalysis prepared by the present invention
Agent fails to surmount commercialization Pt/C catalyst, but presents substantially suitable catalytic performance；Above all greatly reduce into
This, this is beneficial for the design of actual catalyst.
Claims (10)
1. the preparation method of the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide nano-particles, it is characterised in that：Including with
Lower step：1. appropriate template and transition-metal cation salt is weighed, is aoxidized using hydro-thermal reaction synthesis carrying transition metal
The hollow polymer ball presoma of thing；2. the hollow polymer ball presoma for 1. step being obtained is placed in calciner plant, lazy
High-temperature calcination naturally cools to room temperature for a period of time, then under property atmosphere, and is stored at room temperature appropriate time, that is, loaded
The hollow carbon sphere oxygen reduction catalyst of transition metal oxide nano-particles.
2. the preparation side of the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide nano-particles according to claim 1
Method, it is characterised in that：The template that 1. step uses is triblock copolymer Pluronic P123 and enuatrol, institute
Transition-metal cation is stated for Fe3+, Co2+And Ni2+, the Pluronic P123：Enuatrol：Transition-metal cation salt
Mol ratio be 1:16:8-1:64:24, the temperature of the hydro-thermal reaction is 80-240 DEG C；Step calcining heat 2. is
500-1000 DEG C, calcination time is 0.5-6h.
3. the preparation side of the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide nano-particles according to claim 1
Method, it is characterised in that：Comprise the following steps：1. weigh appropriate template and transition-metal cation salt be configured to it is water-soluble
Liquid A；Then weigh appropriate phenol compound and be configured to the aqueous solution, then take appropriate formaldehyde or hexamethylenetetramine be dissolved in it is described
In the phenol compound aqueous solution, solution B is obtained；Solution B is added under agitation in solution A, obtain solution C；
Solution C is carried out into hydro-thermal reaction under the pressure condition of 1-3atm, reacted product is cooled to room temperature and is washed, is dried
It is dry, that is, obtain the hollow polymer ball presoma of carrying transition metal oxide nano-particles；
2. the hollow polymer ball presoma for 1. step being obtained is placed in calciner plant, under an inert atmosphere during one section of high-temperature calcination
Between, room temperature is then naturally cooled to, and be stored at room temperature appropriate time, that is, obtain carrying transition metal oxide nano-particles
Hollow carbon sphere oxygen reduction catalyst.
4. the preparation side of the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide nano-particles according to claim 3
Method, it is characterised in that：The step 1. middle Pluronic P123：Enuatrol：The mol ratio of transition-metal cation salt is
1:16:8-1:64:24；The phenol compound is 2,4- dihydroxy-benzoic acids, para hydroxybenzene propionic acid or 3,4- dihydroxy benzenes first
Acid.
5. the preparation side of the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide nano-particles according to claim 4
Method, it is characterised in that：The concentration of the formaldehyde is 37.5-75mmol/L, and the concentration of the hexamethylenetetramine is 6.25-12.5
mmol/L；The concentration of the phenol compound is 15-25mmol/L；The formaldehyde is with the mol ratio of phenol compound
15:4-6, the hexamethylenetetramine is 1 with the mol ratio of phenol compound:1.6-2.4；The pressure of the hydro-thermal reaction is
2atm, the temperature of the hydro-thermal reaction is 80-240 DEG C, and the time of the hydro-thermal reaction is 0.5-6h.
6. the preparation side of the hollow carbon sphere oxygen reduction catalyst of carrying transition metal oxide nano-particles according to claim 3
Method, it is characterised in that：Step washing methods 1. is to be centrifuged under the rotating speed of 7000-13000rpm using ultra-pure water
5-30min, in triplicate；Step furnace drying method 1. is to dry 8-16h in 40-80 DEG C of vacuum drying oven；The step
2. the inert atmosphere in uses nitrogen or argon gas atmosphere, and the calcining heat is 500-1000 DEG C, and calcination time is 0.5-6h.
7. the preparation method of hollow carbon sphere oxygen reduction catalyst, it is characterised in that：Comprise the following steps：1. appropriate template is weighed,
Hollow polymer ball presoma is synthesized using hydro-thermal reaction；2. the hollow polymer ball presoma for 1. step being obtained is placed in calcining
In device, high-temperature calcination under an inert atmosphere for a period of time, then naturally cools to room temperature, that is, obtain hollow carbon sphere hydrogen reduction
Catalyst.
8. the preparation method of hollow carbon sphere oxygen reduction catalyst according to claim 7, it is characterised in that：1. the step uses
Template be triblock copolymer Pluronic P123 and enuatrol, the Pluronic P123：The mol ratio of enuatrol is
1:16-1:64, the temperature of the hydro-thermal reaction is 80-240 DEG C；Step calcining heat 2. is 500-1000 DEG C, calcining
Time is 0.5-6h.
9. the preparation method of hollow carbon sphere oxygen reduction catalyst according to claim 7, it is characterised in that：Comprise the following steps：
1. weigh appropriate template and be configured to water solution A；Then weigh appropriate phenol compound and be configured to the aqueous solution, then take
Appropriate formaldehyde or hexamethylenetetramine are dissolved in the phenol compound aqueous solution, obtain solution B；By solution B in stirring
Under the conditions of add solution A in, obtain solution C；Solution C is carried out into hydro-thermal reaction under the pressure condition of 1-3atm, will
Reacted product is cooled to room temperature and washs, dries, that is, obtain hollow polymer ball presoma；2. 1. step is obtained
Hollow polymer ball presoma is placed in calciner plant, and high-temperature calcination under an inert atmosphere for a period of time, is then naturally cooled to
Room temperature, that is, obtain hollow carbon sphere oxygen reduction catalyst.
10. the preparation method of hollow carbon sphere oxygen reduction catalyst according to claim 9, it is characterised in that：Comprise the following steps：
The concentration of the formaldehyde is 37.5-75mmol/L, and the concentration of the hexamethylenetetramine is 6.25-12.5mmol/L；It is described
The concentration of phenol compound is 15-25mmol/L；The formaldehyde is 15 with the mol ratio of phenol compound:4-6, it is described
Hexamethylenetetramine is 1 with the mol ratio of phenol compound:1.6-2.4；The pressure of the hydro-thermal reaction is 2atm, described
The temperature of hydro-thermal reaction is 80-240 DEG C, and the time of the hydro-thermal reaction is 0.5-6h；Step washing methods 1. is to adopt
5-30min is centrifuged under the rotating speed of 7000-13000rpm with ultra-pure water, in triplicate；Step furnace drying method 1. be
8-16h is dried in 40-80 DEG C of vacuum drying oven；The step 2. in inert atmosphere use nitrogen or argon atmosphere, it is described to forge
It is 500-1000 DEG C to burn temperature, and calcination time is 0.5-6h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109632763A (en) * | 2018-12-24 | 2019-04-16 | 中国计量大学 | A kind of Chemical enhancement SERS substrate preparation method of regulation defect oxide |
| CN109718852A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院大连化学物理研究所 | The preparation method of one pot process spherical shell type stable metal nanocatalyst |
| CN110773141A (en) * | 2019-09-18 | 2020-02-11 | 北京化工大学 | Magnesium oxide/hollow carbon sphere composite material, preparation and application |
| CN112779550A (en) * | 2021-01-11 | 2021-05-11 | 中山大学 | Three-dimensional micron tubular hydrogen evolution reaction electrocatalyst and preparation method thereof |
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| CN115838184A (en) * | 2022-12-09 | 2023-03-24 | 铜仁学院 | Self-assembled porous Al of hollow mesoporous carbon spheres 2 O 3 Preparation method and application of microspheres |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110180513A1 (en) * | 2009-02-24 | 2011-07-28 | Toyota Motor Engineering & Manufacturing North America, Inc. | Hallow carbon spheres |
| CN102198406A (en) * | 2010-03-26 | 2011-09-28 | 北京化工大学 | Method for preparing high-content double-transition metal composite molecular sieve |
| CN102637533A (en) * | 2012-04-27 | 2012-08-15 | 黑龙江大学 | Method for preparing nitrogenous graphitized hollow carbon microspheres |
| CN103193223A (en) * | 2013-04-02 | 2013-07-10 | 中国矿业大学 | Controllable synthetic method of graphitized carbon spheres with hollow structure |
| CN104399508A (en) * | 2014-11-20 | 2015-03-11 | 华南理工大学 | Nitrogen-sulfur co-doped carbon material with electro-catalytic oxygen reduction activity and preparation method of carbon material |
| CN104475074A (en) * | 2014-10-29 | 2015-04-01 | 东南大学 | Preparation method of boron-doped hollow carbon ball and use of boron-doped hollow carbon ball in direct methanol fuel cell cathode |
| CN104891468A (en) * | 2015-03-26 | 2015-09-09 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanospheres, and preparation and application thereof |
-
2015
- 2015-12-16 CN CN201510944701.5A patent/CN106887608B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110180513A1 (en) * | 2009-02-24 | 2011-07-28 | Toyota Motor Engineering & Manufacturing North America, Inc. | Hallow carbon spheres |
| CN102198406A (en) * | 2010-03-26 | 2011-09-28 | 北京化工大学 | Method for preparing high-content double-transition metal composite molecular sieve |
| CN102637533A (en) * | 2012-04-27 | 2012-08-15 | 黑龙江大学 | Method for preparing nitrogenous graphitized hollow carbon microspheres |
| CN103193223A (en) * | 2013-04-02 | 2013-07-10 | 中国矿业大学 | Controllable synthetic method of graphitized carbon spheres with hollow structure |
| CN104475074A (en) * | 2014-10-29 | 2015-04-01 | 东南大学 | Preparation method of boron-doped hollow carbon ball and use of boron-doped hollow carbon ball in direct methanol fuel cell cathode |
| CN104399508A (en) * | 2014-11-20 | 2015-03-11 | 华南理工大学 | Nitrogen-sulfur co-doped carbon material with electro-catalytic oxygen reduction activity and preparation method of carbon material |
| CN104891468A (en) * | 2015-03-26 | 2015-09-09 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanospheres, and preparation and application thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718852A (en) * | 2017-10-31 | 2019-05-07 | 中国科学院大连化学物理研究所 | The preparation method of one pot process spherical shell type stable metal nanocatalyst |
| CN109632763A (en) * | 2018-12-24 | 2019-04-16 | 中国计量大学 | A kind of Chemical enhancement SERS substrate preparation method of regulation defect oxide |
| CN110773141A (en) * | 2019-09-18 | 2020-02-11 | 北京化工大学 | Magnesium oxide/hollow carbon sphere composite material, preparation and application |
| CN112779550A (en) * | 2021-01-11 | 2021-05-11 | 中山大学 | Three-dimensional micron tubular hydrogen evolution reaction electrocatalyst and preparation method thereof |
| CN112779550B (en) * | 2021-01-11 | 2022-05-17 | 中山大学 | Three-dimensional micron tubular hydrogen evolution reaction electrocatalyst and preparation method thereof |
| CN113235113A (en) * | 2021-04-20 | 2021-08-10 | 深圳大学 | Hollow carbon-coated copper oxide nanoparticle catalyst and preparation method and application thereof |
| CN113235113B (en) * | 2021-04-20 | 2022-06-24 | 深圳大学 | Hollow carbon-coated copper oxide nanoparticle catalyst and preparation method and application thereof |
| CN114188557A (en) * | 2021-10-29 | 2022-03-15 | 陕西师范大学 | Preparation method and application of multi-mesoporous transition metal-nitrogen-carbon catalyst |
| CN114188557B (en) * | 2021-10-29 | 2023-03-31 | 陕西师范大学 | Preparation method and application of multi-mesoporous transition metal-nitrogen-carbon catalyst |
| CN115838184A (en) * | 2022-12-09 | 2023-03-24 | 铜仁学院 | Self-assembled porous Al of hollow mesoporous carbon spheres 2 O 3 Preparation method and application of microspheres |
| CN115838184B (en) * | 2022-12-09 | 2023-09-29 | 铜仁学院 | Self-assembled porous Al of hollow mesoporous carbon sphere 2 O 3 Preparation method and application of microsphere |
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