CN108232212A - A kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst and preparation method and application - Google Patents
A kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst and preparation method and application Download PDFInfo
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- CN108232212A CN108232212A CN201810249976.0A CN201810249976A CN108232212A CN 108232212 A CN108232212 A CN 108232212A CN 201810249976 A CN201810249976 A CN 201810249976A CN 108232212 A CN108232212 A CN 108232212A
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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
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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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
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 discloses a kind of preparation methods of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst, include the following steps：1) preparation of hollow nano carbon microsphere；2) hollow nano carbon microsphere is distributed in dispersant, by the way that oleic acid is added dropwise, the surface of hollow nano carbon microsphere is made to combine carboxyl-reactive group；3) using above-mentioned hollow nano carbon microsphere as carrier, silver nitrate is added in as silver-colored source, and ethylene glycol is added dropwise, restored using citric acid, obtain hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst.The present invention is using silver nitrate as silver-colored source, using hollow nano carbon microsphere as carrier, by the way that oleic acid carbon ball surface active is added dropwise, silver nitrate is restored using citric acid, and by the way that ethylene glycol is added dropwise, so that the particle of silver more refines, preparation process operation is succinct, and the product particle of preparation is uniform, load capacity is high.
Description
Technical field
The invention belongs to fuel cell electro-catalysis technical field more particularly to a kind of hollow nano carbon microsphere load nanometer Ags
Grain fuel cell oxygen reduction catalyst and preparation method and application.
Background technology
With the increasingly depleted of fossil energy and in use to the pollution of environment, it is desirable that we develop as early as possible
Cleaning, regenerative resource.Fuel cell is a kind of efficient green clean energy resource converting system of current great potential, is after fire
The 4th class generation technology after power, waterpower and nuclear energy power generation is a kind of by fuel (hydrogen, natural gas, alcohols etc.) and oxidation
The chemical energy of agent (oxygen) reaction, by electrochemical reaction without by burning, the electrochemistry for being directly translated into electric energy is anti-
Answer device [Zhou Chonglin, Wei Xianquan, Jiang Ningning, etc..Fuel cells applications and prospect, Lu dayization science and technology, 2009,4：409-412].
Yellow children chrysanthemum et al. also fuel battery cathod catalyst has been done certain further investigation [Huang Youju, yellow lead is green, Huang Hongliang, etc..Combustion
The present Research of material cell catalyst, battery industry, 2007,01:57-60].
Cathodic oxygen reduction (ORR) is limitation Proton Exchange Membrane Fuel Cells (PEMFC) and direct methanol fuel cell
(DMFC) an important factor for performance.At present, it is believed that ORR is mainly occurred by two kinds of approach, i.e., four electronics of tetrahydrochysene is complete
The process of the partial reduction generation hydrogen peroxide of two electronics of process and dihydro of reduction generation water.
Nowadays the wider fuel battery cathod catalyst of application is Pt/C catalyst, but because Pt electrodes are of high cost, resistance to
Long property is low, resource shortage, and easily poisoning serious [Zhang, L.；Zhang,J.；Wilkinson,D.P.；Wang,H.J.Power
Sources 2006,156,171.] constrain fuel cell large-scale application and commercialized development.Therefore it is cheap, resistance to be badly in need of exploitation
With, it is efficient and stablize non-platinum base cathodic oxygen reduction catalyst.
Carbon material is since preparation is simple, be easy to mass produce and has good chemical property, mechanical stability, by people
It is widely used for fuel-cell catalyst carrier.Honda etc. be prepared from pitch for the first time micron-sized carbon ball [H Honda,
H Kimura,Y Sanada,et al.Carbon,1970,8(2):181~183], there is chemical stability and thermal stability
By force, the advantages that low-density, specific surface area are controllable, compression strength is high, chemical inertness is big, thus nano carbon microsphere in fuel cell, urge
Agent carrier, lithium ion battery negative material, electrode material for super capacitor etc. are with a wide range of applications.Du Jianping
Etc. the application of nano carbon particle in the catalyst is reviewed, [Du Jianping, Zhao Ruihua, Yu Feng wait nano carbon particles in catalysis
Application and prospect [J] material Leaders, 2010,24 (17):49-52], Liu Yunfang has in terms of nano carbon microsphere doping into one
The research of step, [Liu Yunfang, Chi Weidong, Liu Bo wait the preparation of the Nano carbon balls of load nano iron particles and magnetic property research
[J] Beijing University of Chemical Technology journal (natural science edition), 2011,38 (2):58-62].Illustrate nano carbon microsphere in fuel cell catalyst
Agent field has been achieved for no small breakthrough.
Invention content
The purpose of the present invention is to provide a kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalysis
Agent and preparation method and application.The present invention makees carrier with hollow nano carbon microsphere, provides higher specific surface area, metallic silver particles
As activated centre site, to reach higher oxygen reduction catalytic activity.The present invention increases hollow receive by a series of processing
The load capacity of Argent grain obtains one kind using hollow nano carbon microsphere as carrier in rice carbon ball, and Argent grain is the fuel cell oxygen of active sites
Reducing catalyst shows the excellent hydrogen reduction performance of the material and its application in a fuel cell.
The present invention is achieved through the following technical solutions, and the present invention provides a kind of hollow nano carbon microsphere load nanometer Ag
The preparation method of grain fuel cell oxygen reduction catalyst, includes the following steps：
S101：The preparation of hollow nano carbon microsphere；
Hollow micron order carbon ball is with chemical stability and thermal stability are strong, low-density, specific surface area are controllable, compression strength
High, the advantages that chemical inertness is big, therefore the oxygen reduction catalyst prepared using hollow nano carbon microsphere as carrier can be applied to fuel
Battery, catalyst carrier, lithium ion battery negative material, electrode material for super capacitor etc..
S102：Hollow nano carbon microsphere is distributed in dispersant, oleic acid, which is added dropwise, makes the surface of hollow nano carbon microsphere combine carboxylic
Base active group；
Contain carboxylic group in oleic acid, reactivity is high, can be by hollow nano carbon microsphere using the method that oleic acid is added dropwise
Functionalization makes the surface of hollow nano carbon microsphere combine carboxyl-reactive group, increases the adsorbance to silver ion；Lead in the prior art
Often carrier is pre-processed using acid or alkali so that preferably combine between active component and carrier, can break in the process
The original structure of bad carrier, this patent are to utilize to add in oleic acid method, increase the activity on hollow nano carbon microsphere surface, directly will be silver-colored
On particle reduction to hollow nano carbon microsphere, load capacity not only ensure that, but also retain carrier original structure and be not destroyed；It is prepared
Material granule is evenly distributed, and load capacity is high, and good activity is shown in terms of fuel cell catalyst hydrogen reduction.
S103：Using hollow nano carbon microsphere as carrier, silver nitrate solution is added in as silver-colored source, ethylene glycol is added dropwise, utilizes lemon
Lemon acid solution restores, and carries out post-processing to obtain final product after reduction reaction.
Silver nitrate is selected as silver-colored source, silver nitrate is readily soluble, it is easy obtain, stability it is strong, the nitrate anion later stage passes through washing
It removes；Citric acid solution is selected as reducing agent, sodium citrate solution reproducibility is not strong so that reduction process is very mildly so that also
The Argent grain grain size smaller of original out；Ethylene glycol is selected as dispersant, ethylene glycol grain refinement effect is good so that Argent grain is more
Bonus point dissipates, uniformly.
It is silver-colored source by silver nitrate, nano-Ag particles can be obtained under the reduction of citric acid solution, by nano carbon microsphere
Nano-Ag particles, then again can successfully be born the method for silver ion reduction by the upper active group for increasing absorption silver ion
It is downloaded on nano carbon microsphere.Silver itself has preferable catalytic oxidation-reduction performance, and nano level Argent grain performance is more excellent, this is
It is more due to nano level silver-colored active sites exposure, enhance catalytic performance.Hollow nano carbon microsphere loads Ag nano particles fuel
Battery oxygen reduction catalyst, since it is with certain stability and flexibility, nanoscale thickness on a macroscopic level
Degree is hopeful to be more widely used in fuel cell.It is used as dispersant by adding in ethylene glycol so that Argent grain more bonus point
It dissipates, uniformly, refines Argent grain.
Preferably, in S101, the preparation of hollow nano carbon microsphere, step is as follows：Glucose solution is prepared, glucose is molten
Liquid is poured into reaction kettle, is put into baking oven and is carried out hydro-thermal reaction, obtains centrifuge washing after rufous product, dry, is obtained hollow
Nano carbon microsphere.
Glucose solution is selected as the raw material for preparing hollow nano carbon microsphere, glucose solution is easy to get and can reach pre-
The hollow spheres porous structure of phase；It is uniformly dispersed using the hollow spheres porous structure grain size that glucose solution is prepared as raw material
Property is good；The hollow spheres porous structure has higher specific surface area, load capacity bigger as carrier, hollow nano carbon microsphere.
Preferably, a concentration of 50~60g/L of the glucose solution；Hydrothermal reaction condition is 160~180 DEG C of conditions
10~12h of lower hydro-thermal.
Both the conjunction of hollow nano carbon microsphere had been can guarantee under the conditions of 160~180 DEG C under the hydrothermal reaction condition of 10~12h of hydro-thermal
Into but be unlikely to agglomeration occurs that the yield of hollow nano carbon microsphere can also be improved.
Preferably, in order to ensure washes clean while it is as much as possible product is made to settle down, product is passed through
8000r/min centrifuge washings 6 times are crossed, every time 5~10min, the dry 12h in 60~80 DEG C of baking oven.
Preferably, in S102, dispersant selection absolute ethyl alcohol, hollow nano carbon microsphere ultrasonic disperse 1h in absolute ethyl alcohol
After oleic acid is added dropwise, then proceed to ultrasonic 30min.
Dispersant selects absolute ethyl alcohol, and absolute ethyl alcohol has the characteristics that good dispersion, volatile, the later stage is tractable；It is hollow
Nano carbon microsphere ultrasonic disperse 1h in absolute ethyl alcohol, first so that carbon ball is fully dispersed, ultrasound 30min can after oleic acid is added dropwise
So that oleic acid adheres on carbon ball surface.
Preferably, in S103, ultrasound after ethylene glycol is added dropwise in hollow nano carbon microsphere and silver nitrate solution mixture
Then citric acid solution is added dropwise in 30min dropwise, continue 5~10min of ultrasound after adding.
Ethylene glycol and citric acid by the way of being separately added dropwise, this be in order to before silver ion reduction so that ethylene glycol fills
Dispersion；Citric acid solution selection is added to prevent from reacting too fast, crystal grain thinning；The advantages of using ultrasonic disperse：
1st, so that all reactants and additive are uniformly dispersed 2, give the formation that one energy of system promotes nucleus.
Preferably, in S103, the silver nitrate solution of addition and the molar ratio of citric acid solution are 1：1.The two 1:1
Reaction makes its reaction fully not waste reagent again.
Preferably, in S103, in order to enable reduction reaction is more abundant, using the time of citric acid solution reduction for for 24 hours,
When for 24 hours, reduction reaction has been completed for reaction.
Preferably, in S103, post processing is by the centrifugation under 8000r/min rotating speeds of reduction reaction product, is continued
Centrifuge washing 5~6 times, by the abundant washes clean of heteroion；Dry 12h obtains final product under the conditions of 60~80 DEG C.
A kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst, using described in any of the above-described
Hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst preparation method be prepared.With hollow nanometer
Carbon ball is carrier, increases its surface active groups by adding in oleic acid, adsorbs more silver ions, then restored with citric acid,
It realizes the loading nano silvery particle on hollow nano carbon microsphere, obtains hollow nano carbon microsphere load Ag nano particles fuel cell oxygen also
Raw catalyst, the catalyst have preferable hydrogen reduction performance, and electro-catalysis is efficient, large specific surface area, have potential industry
Application prospect.
A kind of application of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst hollow is received above-mentioned
Rice carbon ball load Ag nano particles fuel cell oxygen reduction catalyst is used for the oxygen reduction reaction of catalytic fuel cell.Present invention system
Standby hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst, due to having preferable hydrogen reduction performance,
Electro-catalysis is efficient, large specific surface area, is had broad application prospects in terms of fuel cell oxygen reduction.
Beneficial effects of the present invention are：
1) the advantages of preparation method of the present invention：A. raw material sources are wide, and method is simply controllable, easily operated, if
Standby simple, pollution is few；B. obtained hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst, specific surface
Product is big, and electro-catalysis is efficient.
2) present invention is successfully prepared a kind of hollow nano carbon microsphere load Ag nano particles combustion by a kind of easy method
Expect battery oxygen reduction catalyst, this method is by controlling the load capacity of nano-Ag particles to show splendid hydrogen reduction catalytic
Energy.Since this method is raw materials used cheap and easy to get, simple and efficient to handle, energy consumption is small, and to equipment without particular/special requirement, it is dirty to add environment
Dye is few, it is made to have good application prospect in fuel cell field, is a kind of efficient, low price, environmental-friendly green syt
Method.
3) the hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst that prepared by the present invention, is especially used
Oleic acid increases the load capacity of Argent grain by after carbon ball functionalization so that has higher activity in electrochemical reaction.
Description of the drawings
It in order to illustrate the embodiment of the utility model or the technical proposal in the existing technology more clearly, below will be to embodiment
Or attached drawing needed to be used in the description of the prior art is briefly described, it is therefore apparent that the accompanying drawings in the following description is only
Some embodiments of the utility model, for those of ordinary skill in the art, without creative efforts,
It can also be obtained according to these attached drawings other attached drawings.
Fig. 1 is that the hollow nano carbon microsphere (being denoted as CNHS) of preparation and hollow nano carbon microsphere load Ag nano particles (are denoted as Ag@
CNHS) the XRD diagram of fuel cell oxygen reduction catalyst.
Fig. 2 is that the hollow nano carbon microsphere (being denoted as CNHS) of preparation and hollow nano carbon microsphere load Ag nano particles (are denoted as Ag@
CNHS) the SEM figures of fuel cell oxygen reduction catalyst and TEM figures.
Fig. 3 for Ag@CNHS fuel cell oxygen reduction catalysts difference in 0.1M KOH solutions sweep speed (5,10,20,50,
100mV s-1) under cyclic voltammetry curve figure (CV curves).
Fig. 4 for CNHS differences in 0.1MKOH solution sweep speed (5,10,20,50,100mV s-1) under cyclic voltammetry curve
Scheme (CV curves).
Fig. 5 is rotating circular disk of the Ag@CNHS fuel cell oxygen reduction catalysts in the 0.1M KOH solutions of oxygen saturation
Curve.
Fig. 6 is rotating circular disk curves of the CNHS in the 0.1M KOH solutions of oxygen saturation.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.It is unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It is nowadays Pt/C catalysis using wider fuel battery cathod catalyst as background technology part is introduced
Agent, but because Pt electrodes are of high cost, durability is low, resource shortage, and easily poisoning seriously constrains fuel cell large-scale application
And commercialized development.Therefore it is badly in need of the non-platinum base cathodic oxygen reduction catalyst that exploitation is cheap, durable, efficient and stablizes.
Carbon material is since preparation is simple, be easy to mass produce and has good chemical property, mechanical stability, by people
It is widely used for fuel-cell catalyst carrier.Micron-sized carbon ball is prepared in Honda etc. from pitch for the first time, has chemistry
The advantages that stability and thermal stability are strong, low-density, specific surface area is controllable, compression strength is high, chemical inertness is big, therefore nano-sized carbon
Ball has extensive in fuel cell, catalyst carrier, lithium ion battery negative material, electrode material for super capacitor etc.
Application prospect.Du builds equality and reviews the application of nano carbon particle in the catalyst, and Liu Yunfang has in terms of nano carbon microsphere doping
Further research, illustrates that nano carbon microsphere has been achieved for no small breakthrough in fuel-cell catalyst field.
In one embodiment of the present invention, the hollow nano carbon microsphere of the present invention loads Ag nano particles fuel cell oxygen also
The preparation method of raw catalyst, includes the following steps：
S101：The preparation of hollow nano carbon microsphere；
Hollow micron order carbon ball is with chemical stability and thermal stability are strong, low-density, specific surface area are controllable, compression strength
High, the advantages that chemical inertness is big, therefore the oxygen reduction catalyst prepared using hollow nano carbon microsphere as carrier can be applied to fuel
Battery, catalyst carrier, lithium ion battery negative material, electrode material for super capacitor etc..
In S101, the preparation of hollow nano carbon microsphere, step is as follows：Glucose solution is prepared, glucose solution is poured into instead
It answers in kettle, is put into baking oven and carries out hydro-thermal reaction, a concentration of 50~60g/L of the glucose solution；Hydrothermal reaction condition is
10~12h of hydro-thermal under the conditions of 160~180 DEG C；Centrifuge washing after rufous product is obtained, it is dry, obtain hollow nano carbon microsphere；For
Can ensure it is as much as possible while washes clean product is made to settle down, product is passed through into 8000r/min centrifuge washings 6
Secondary, 5~10min, dries 12h in 60~80 DEG C of baking oven every time.
Glucose solution is selected as the raw material for preparing hollow nano carbon microsphere, glucose solution is easy to get and can reach pre-
The hollow spheres porous structure of phase；It is uniformly dispersed using the hollow spheres porous structure grain size that glucose solution is prepared as raw material
Property is good；The hollow spheres porous structure has higher specific surface area, load capacity bigger as carrier, hollow nano carbon microsphere.
Both the conjunction of hollow nano carbon microsphere had been can guarantee under the conditions of 160~180 DEG C under the hydrothermal reaction condition of 10~12h of hydro-thermal
Into but be unlikely to agglomeration occurs that the yield of hollow nano carbon microsphere can also be improved.
S102：Hollow nano carbon microsphere is distributed in dispersant, oleic acid, which is added dropwise, makes the surface of hollow nano carbon microsphere combine carboxylic
Base active group；
Contain carboxylic group in oleic acid, reactivity is high, can be by hollow nano carbon microsphere using the method that oleic acid is added dropwise
Functionalization makes the surface of hollow nano carbon microsphere combine carboxyl-reactive group, increases the adsorbance to silver ion；Lead in the prior art
Often carrier is pre-processed using acid or alkali so that preferably combine between active component and carrier, can break in the process
The original structure of bad carrier, this patent are to utilize to add in oleic acid method, increase the activity on hollow nano carbon microsphere surface, directly will be silver-colored
On particle reduction to hollow nano carbon microsphere, load capacity not only ensure that, but also retain carrier original structure and be not destroyed；It is prepared
Material granule is evenly distributed, and load capacity is high, and good activity is shown in terms of fuel cell catalyst hydrogen reduction.
In S102, since absolute ethyl alcohol has the characteristics that good dispersion, volatile, the later stage is tractable, dispersant selection nothing
Oleic acid is added dropwise after ultrasonic disperse 1h in absolute ethyl alcohol in water-ethanol, hollow nano carbon microsphere, then proceedes to ultrasonic 30min.For the first time
For ultrasound so that carbon ball is fully dispersed, second of ultrasound enables to oleic acid to adhere on carbon ball surface.
S103：Using hollow nano carbon microsphere as carrier, silver nitrate solution is added in as silver-colored source, ethylene glycol is added dropwise, utilizes lemon
Lemon acid solution restores, and carries out post-processing to obtain final product after reduction reaction.
Silver nitrate is selected as silver-colored source, silver nitrate is readily soluble, it is easy obtain, stability it is strong, the nitrate anion later stage passes through washing
It removes；Citric acid solution is selected as reducing agent, sodium citrate solution reproducibility is not strong so that reduction process is very mildly so that also
The Argent grain grain size smaller of original out；Ethylene glycol is selected as dispersant, ethylene glycol grain refinement effect is good so that Argent grain is more
Bonus point dissipates, uniformly.
It is silver-colored source by silver nitrate, nano-Ag particles can be obtained under the reduction of citric acid solution, by nano carbon microsphere
Nano-Ag particles, then again can successfully be born the method for silver ion reduction by the upper active group for increasing absorption silver ion
It is downloaded on nano carbon microsphere.Silver itself has preferable catalytic oxidation-reduction performance, and nano level Argent grain performance is more excellent, this is
It is more due to nano level silver-colored active sites exposure, enhance catalytic performance.Hollow nano carbon microsphere loads Ag nano particles fuel
Battery oxygen reduction catalyst, since it is with certain stability and flexibility, nanoscale thickness on a macroscopic level
Degree is hopeful to be more widely used in fuel cell.It is used as dispersant by adding in ethylene glycol so that Argent grain more bonus point
It dissipates, uniformly, refines Argent grain.
In S103, in order to cause that ethylene glycol is fully dispersed before silver ion reduction；Ethylene glycol and citric acid are using separately
Ultrasound 30min after ethylene glycol is added dropwise in hollow nano carbon microsphere and silver nitrate solution mixture, then drips dropwise for the mode of dropwise addition
Adding citric acid solution continues 5~10min of ultrasound after adding.Citric acid solution selection is added to prevent from reacting
Soon, crystal grain thinning；The advantages of using ultrasonic disperse：1st, so that all reactants and additive are uniformly dispersed 2, give system one
Energy promotes the formation of nucleus.
The silver nitrate solution and the molar ratio of citric acid solution added in is 1：1.The two 1:1 reaction, fills its reaction
Divide and do not waste reagent again.In order to enable reduction reaction is more abundant, using the time of citric acid solution reduction for 24 hours, to react for 24 hours
When, reduction reaction has been completed.In order to which by the abundant washes clean of heteroion, post processing is in 8000r/ by reduction reaction product
Centrifugation under min rotating speeds, continues centrifuge washing 5~6 times；Dry 12h obtains final product under the conditions of 60~80 DEG C.
In order to enable those skilled in the art can clearly understand the technical solution of the application, below with reference to tool
The technical solution of the application is described in detail in the embodiment of body.
Test material used in the embodiment of the present invention is the test material of this field routine, can pass through commercial channel
It is commercially available.
Embodiment 1
Silver ion is restored in carbon ball using citric acid reduction method, is obtained using Argent grain as active site, hollow nano-sized carbon
Ball is the fuel cell oxygen reduction catalyst of carrier.
4.5g glucose is taken, is dissolved into the deionized water of 75mL and stirred evenly, its solution is placed in 100mL reactions
In kettle, baking oven is put into, 160~180 DEG C keep hydro-thermal 10~12 hours.Then, deionized water and absolute ethyl alcohol washing, pass through
8000r/min centrifuge washings 6 times, 5~10min, 12h is dried in 60~80 DEG C of baking oven, obtains hollow nano carbon microsphere every time；
Obtained nano carbon microsphere is weighed into 0.25g, is distributed in 30mL absolute ethyl alcohols, ultrasonic 1h and dropwise addition 1~3 oil dripping acid continue
Ultrasonic 30min；Obtain the hollow nano carbon microsphere of functionalization；It is 1 to weigh molar ratio respectively：1 silver nitrate (0.5g) and citric acid
Solution is configured in (0.6g is slightly excessive), first adds in silver nitrate solution in the hollow nano carbon microsphere of functionalization, and 1~3 drop second two is added dropwise
Alcohol, ultrasonic 30min, is added dropwise citric acid solution, continues 5~10min of ultrasound after adding, by mixing liquid stirring for 24 hours, so
It centrifuges and is precipitated under 8000r/min rotating speeds afterwards, continue centrifuge washing 5~6 times, obtain clean hollow nano carbon microsphere load
Ag nano particles, dry 12h obtains final product under the conditions of 60~80 DEG C.
The X ray diffracting spectrum of Ag CNHS fuel cell oxygen reduction catalysts of the Fig. 1 obtained by the present embodiment, Yi Jizhong
The X ray diffracting spectrum of empty nano carbon microsphere, the substance that can obtain loading on hollow nano carbon microsphere by the analysis of Jade softwares are
Argent grain, and have at 23 ° the diffraction maximum of carbon.
Fig. 2 be the present embodiment obtained by Ag@CNHS fuel cell oxygen reduction catalysts and CNHS scanning electron microscopic picture and
Transmission electron microscope picture, CNHS obtained is spherical structure of uniform particle sizes' diameter in 150~200nm, and Argent grain is attached to carbon
Ball surface forms nucleocapsid, and Argent grain average grain diameter is 5~6nm, is conducive to the progress of oxygen reduction reaction.
Catalyst obtained is tested for the property as follows：
It will be in the modification to electrode of Ag@CNHS fuel cell oxygen reduction catalysts.Glass-carbon electrode (diameter 3mm) is passed through before test
Cross following steps processing：First use the Al of 50nm2O3Powder film is polished, and is then cleaned respectively with ethyl alcohol, ultra-pure water (in ultrasonic instrument
In), it dries in air.Preparing for working electrode is as follows：5mg catalyst is taken to add in 450 μ L ultra-pure waters, adds in 50 μ L mass point
Number is in 5% Nafion solution, ultrasonic disperse 1 hour takes above-mentioned 5 μ L of catalyst solution in glass-carbon electrode with micropipette rifle
On, it dries in air.Rotating disk electrode (r.d.e) (diameter 5mm) passes through same processing method, and 10 μ L is then taken to drop in electrode table
Face is dried in air.
Fig. 3 is the 0.1molL of the Ag@CNHS fuel cell oxygen reduction catalysts in oxygen saturation of the present embodiment-1KOH is molten
In the different cyclic voltammetry curves swept under speed in liquid.During scanning, Ag CNHS start appearance near -0.3V, and peak position is set to -
0.3V to -0.5V, density peak value are -0.5mAcm-2。
Fig. 4 is the 0.1molLs of the CNHS in oxygen saturation of the present embodiment-1In the different cycles swept under speed in KOH solution
Volt-ampere curve.During scanning, CNHS starts appearance near -0.3V, and peak position is set to -0.3V to -0.45V, density peak value for -
0.25mAcm-2。
Fig. 5 is the 0.1molL of the Ag@CNHS fuel cell oxygen reduction catalysts in oxygen saturation of the present embodiment-1KOH is molten
Rotating circular disk curve in liquid increases with the increase current density of rotating speed, it is seen that and its hydrogen reduction process is controlled by diffusion,
Be calculated for catalyst Ag@CNHS shifted at -0.45, -0.5, -0.55, -0.6V electron number n be respectively 3.71,
3.73、3.74、3.77。
Fig. 6 is the 0.1molLs of the CNHS in oxygen saturation of the present embodiment-1Rotating circular disk curve in KOH solution calculates
Show that it is respectively 2.29,2.32,2.32,2.35 that electron number n is shifted at -0.45, -0.5, -0.55, -0.6V for CNHS.
Actual conditions are as follows：Electrochemistry is carried out with CHI 760d types electrochemical workstation (Shanghai Chen Hua Instrument Ltd.)
Property is tested, and prepared catalyst is coated on glass-carbon electrode as working electrode, Hg/Hg2Cl2Electrode and Pt electrodes are used as
Reference electrode and auxiliary electrode are tested in 0.1M potassium hydroxide solutions and obtain cyclic voltammogram (CV figures).
Certainly, above description is also not limited to the example above, the technical characteristic of the invention without description can by or
It is realized using the prior art, details are not described herein；Above example and attached drawing are merely to illustrate technical scheme of the present invention
It is limitation of the present invention, the present invention is described in detail with reference to preferred embodiment, the ordinary skill people of this field
Member is it should be appreciated that variation, remodeling, the addition that those skilled in the art are made in the essential scope of the present invention
Or replace the claims that without departure from spirit of the invention, should also belong to the present invention.
Claims (9)
1. a kind of preparation method of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst, feature exist
In：Include the following steps：
S101：The preparation of hollow nano carbon microsphere；
S102：Hollow nano carbon microsphere is distributed in dispersant, oleic acid is added dropwise, the surface of hollow nano carbon microsphere is made to live with reference to carboxyl
Property group；
S103：Using hollow nano carbon microsphere as carrier, silver nitrate solution is added in as silver-colored source, ethylene glycol is added dropwise, utilizes citric acid
Solution reduction carries out post-processing to obtain final product after reduction reaction.
2. a kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst according to claim 1
Preparation method, it is characterised in that：In S101, glucose solution is used to prepare hollow nano carbon microsphere using hydro-thermal reaction for raw material；
A concentration of 50~60g/L of the glucose solution；Hydrothermal reaction condition is 10~12h of hydro-thermal under the conditions of 160~180 DEG C.
3. a kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst according to claim 1
Preparation method, it is characterised in that：In S102, dispersant selection absolute ethyl alcohol, hollow nano carbon microsphere ultrasound point in absolute ethyl alcohol
Oleic acid is added dropwise after dissipating 1h, then proceedes to ultrasonic 30min.
4. a kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst according to claim 1
Preparation method, it is characterised in that：In S103, ultrasound after ethylene glycol is added dropwise in hollow nano carbon microsphere and silver nitrate solution mixture
Then citric acid solution is added dropwise in 30min dropwise, continue 5~10min of ultrasound after adding.
5. according to a kind of system of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst described in claim 1
Preparation Method, it is characterised in that：In S103, the silver nitrate solution of addition and the molar ratio of citric acid solution are 1：1.
6. a kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst according to claim 1
Preparation method, it is characterised in that：In S103, using the time of citric acid solution reduction for for 24 hours.
7. a kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst according to claim 1
Preparation method, it is characterised in that：In S103, post processing be by the centrifugation under 8000r/min rotating speeds of reduction reaction product, after
Continue centrifuge washing 5~6 times, dry 12h obtains final product under the conditions of 60~80 DEG C.
8. a kind of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst, it is characterised in that：Using such as power
Profit requires the preparation side of the hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst of 1~7 any one of them
Method is prepared.
9. a kind of application of hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst, it is characterised in that：It will
Hollow nano carbon microsphere load Ag nano particles fuel cell oxygen reduction catalyst is used for catalytic fuel cell as claimed in claim 8
Oxygen reduction reaction.
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