CN106058276B - A kind of preparation method of silicon dioxide modified more spherical cavity carbon materials and its application in fuel cell membrane electrode - Google Patents

A kind of preparation method of silicon dioxide modified more spherical cavity carbon materials and its application in fuel cell membrane electrode Download PDF

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CN106058276B
CN106058276B CN201610548972.3A CN201610548972A CN106058276B CN 106058276 B CN106058276 B CN 106058276B CN 201610548972 A CN201610548972 A CN 201610548972A CN 106058276 B CN106058276 B CN 106058276B
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carbon materials
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CN106058276A (en
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杜丽
张嘉熙
高莹
刘丹丹
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South China University of Technology SCUT
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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
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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
    • H01M8/00—Fuel cells; Manufacture thereof
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Abstract

The invention discloses a kind of preparation method of silicon dioxide modified more spherical cavity carbon materials and its applications in fuel cell membrane electrode.This method polymerize using silicon oxide pellets as template, by aniline around the bead, obtains nitrating, silicon dioxide modified more spherical cavity carbon materials after carbonization, etching silicon dioxide bead successively.The size of the spherical cavity of more spherical cavity carbon materials is controllable, while having certain hydrogen reduction electro-chemical activity, therefore can be used as and the relevant material of electro-catalysis.In addition, modification silica can allow more spherical cavity carbon materials to have the performance from humidification.The catalyst that the present invention is prepared using the more spherical cavity carbon materials of silica as carrier loaded Pt, electrocatalysis characteristic is high, performance and stability are good under the low humidity, service life is long, the ideal chose of fuel battery anode catalyst, be indicated above the present invention the more spherical cavity carbon materials of silica can be used as fuel battery anode catalyst carrier material and membrane electrode from the relevant material of being humidified.

Description

The preparation method of a kind of silicon dioxide modified more spherical cavity carbon materials and its in fuel cell membranes Application in electrode
Technical field
The present invention relates to new material technology fields, and in particular to a kind of preparation method of silicon dioxide modified more spherical cavity carbon materials And its application in fuel cell membrane electrode.
Background technology
Fuel cell is a kind of high efficient energy sources profit that the chemical energy being stored in fuel can be directly converted into electric energy Use device.Due to the shortcomings that not discharging the traditional energies Land use systems such as nitrogenous, sulphur atmosphere pollution and particulate matter, simultaneously Also because having the characteristics of high-energy conversion efficiency and Miniaturizable, fuel cell will possess prodigious in following energy market Application prospect.Wherein Proton Exchange Membrane Fuel Cells is particularly held in both hands by the heat of researcher, is applied in recent years portable In the dynamical system of electronic equipment and electric vehicle.Although Proton Exchange Membrane Fuel Cells technology is very ripe, in business Change and is still faced with that cathod catalyst reserves of high cost are few, improve the choosing of anode catalyst antitoxin sexuality and fuel on universal road The lot of challenges such as select.Water is the key factor that Proton Exchange Membrane Fuel Cells maintains proton conductivity in the process of running.Usually Additional substance is needed to soak reaction gas, to keep the conductivity of proton.But this also increases answering for battery simultaneously Polygamy, and increase additional energy expenditure.Therefore developing has from the carrier material and membrane electrode material of moisturization, can be Simplify the operational management of battery system while holding compared with high proton conductivity and reduce operating cost, is to realize proton exchange membrane The inevitable choice of commercializing fuel cells.
Invention content
For overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of silicon dioxide modified more spherical cavity carbon materials The preparation method of material and its application in fuel cell membrane electrode.
The purpose of the present invention is achieved through the following technical solutions.
The basic preparation process of the present invention includes preparing silicon oxide pellets mother liquor, silicon oxide pellets diauxic growth, carbon Precursor polymerize the carbonization and two of the precursor complex, compound that form silicon/carbon dioxide around silicon oxide pellets The processes such as the etching of silica bead, to realize the preparation of more spherical cavity meso-porous carbon materials with self-moistening function.
A kind of silicon dioxide modified more spherical cavity carbon materials (are labeled as SiO2- MSCC) preparation method, steps are as follows：
(1) by L-arginine, hexamethylene, water in molar ratio 1:（50 ~ 150）:（5000 ~ 15000）Mixing, 40 DEG C ~ 80 DEG C of stirring conditions under fully dissolve, obtain mixed liquor A；
(2) under 40 DEG C ~ 80 DEG C stirring conditions, step (1) institute is added with 1 ~ 2 drop/sec of speed in ethyl orthosilicate It obtains in mixed liquor A, the molar ratio of wherein ethyl orthosilicate and L-arginine used in step (1) is（20 ~ 80）：1, continue to stir 12 ~ 24 h are mixed, silicon oxide pellets mother liquor B is obtained；
(3) under 40 DEG C ~ 80 DEG C stirring conditions, by silicon oxide pellets mother liquor B obtained by step (2) and hexamethylene, just Silester and water are 1 in mass ratio:（0.1 ~ 0.8）:（0.08 ~ 0.4）:（ 1 ~ 5）It is made into growth-promoting media, continues to stir 15 ~ 30 h are mixed, silicon dioxide gel C is obtained；
(4) under 40 DEG C ~ 80 DEG C stirring conditions, into step (3) in gained silica dioxide gel C, polyethylene is added The mass ratio of pyrrolidones, wherein polyvinylpyrrolidone and silica dioxide gel C are 1:（60 ~ 120）, obtain mixed liquor D;
(5) pH value of mixed liquor D obtained by step (4) is adjusted to 0 ~ 0.3 with concentrated hydrochloric acid, under lasting stirring in mass ratio Mixed liquor D:Aniline is（15 ~ 30）:1 aniline is added into mixed liquor D, and it is 20 then to instill ammonium persulfate mass fraction The aqueous solution E that wt% ~ 30 wt%, pH are 0 ~ 0.3, the wherein mass ratio of aqueous solution E and aniline are（10 ~ 20）:1, so It keeps 300-1200 revs/min of stir speed (S.S.) to stir 12 ~ 48 h at 0 ~ 15 DEG C afterwards, is then evaporated, you can obtain two Silica/Polyaniline;
(6) silica/Polyaniline for obtaining step (5) under nitrogen atmosphere, with 2 ~ 15 DEG C/min's Heating rate is warming up to 600 DEG C ~ 1000 DEG C, keeps 1 ~ 3 h, is cooled to room temperature, obtains C-N/ silica composites；
(7) the C-N/ silica composites that step (6) obtains are mixed with NaOH solution, is carved at 50 ~ 120 DEG C 0 ~ 4 h of erosion processing obtains silicon dioxide modified more spherical cavity carbon materials, is labeled as by being filtered, washed and dried after cooling SiO2- MSCC materials（MSCC is the abbreviation of multi-spherical cavity carbon）.
Further, the stirring is stirred with 300 ~ 1200 revs/min of stir speed (S.S.).
Further, in the silicon dioxide gel C, a diameter of 20 ~ 50 nm of silicon oxide pellets.
Further, the polyvinylpyrrolidone is one kind in PVP-k10, PVP-k15, PVP-k17 and PVP-k30 Or it is several.
Further, step（5）The temperature being evaporated is 90 DEG C.
Further, step（7）The amount of 25 mL NaOH solutions is corresponded to by C-N/ by 1 g C-N/ silica composites Silica composite is mixed with the NaOH solution of 2 mol/L.
Further, in silicon dioxide modified more spherical cavity carbon materials, a diameter of 10 ~ 40 nm of spherical cavity.
Further, the particle of silicon dioxide modified more spherical cavity carbon materials is directly 100 ~ 200nm.
A kind of silicon dioxide modified more spherical cavity carbon materials made from above-described preparation method are as fuel cell The carrier material of anode catalyst is applied to humidification material in fuel cell membrane electrode.
Further, the preparation method of the anode catalyst（Pt is supported on to silicon dioxide modified more spherical cavity carbon Material preparation Pt/SiO2- MSCC catalyst）It is as follows：
By SiO2- MSCC materials pre-process for use, then sodium citrate is dissolved in ethylene glycol, ultrasound 60 minutes, then The ethylene glycol solution of six hydration chloroplatinic acids is added, stirs 30 minutes, then 1 ~ 12 times of Pt mass of addition is pretreated SiO2- MSCC materials, ultrasound 60 minutes adjust pH of mixed with the KOH/EG solution of 5 wt%>After 9, it is transferred to polytetrafluoroethyl-ne In the reaction kettle in the villages Xi Nei, 6 h are reacted at 120 DEG C；After cooling with the HNO of 10 wt%3Solution adjusts pH<5, cross water after filter It washes, it is dry in vacuum drying chamber, you can to obtain the silicon dioxide modified more spherical cavity carbon material catalyst of Pt/；Six hydration Chloroplatinic acid is 1 with the molar ratio with sodium citrate: 2~2.5.
Further, the SiO2The pretreatment of-MSCC materials is by SiO210 times of SiO are added in-MSCC materials2- 3 h are stirred in the acetone of MSCC quality of materials, are dried in vacuum tank after filtering and washing, and 50 times of SiO are added after dry2-MSCC The HNO of 10 wt% of quality of materials3With H2O2Mixed liquor in, wherein the HNO of 10 wt%3With H2O2Volume ratio is 2:1, at 80 DEG C 8 h of lower reflux, it is dry in vacuum drying chamber after filtration washing, then by the sample after drying in N2The lower 300 DEG C of processing 3 of atmosphere h。
Further, the quality for dissolving the ethylene glycol of sodium citrate is 500 ~ 1000 times of chloroplatinic acid quality.
Further, the time of the drying is 12 h.
Further, the number of the washing is 5 times.
More spherical cavity carbon materials of the present invention can be as desired by the size of adjusting silicon oxide pellets to obtain different rulers Very little spherical cavity structure, simultaneously as large specific surface area, doped with nitrogen and have certain hydrogen reduction electro-chemical activity, Therefore can be used as and the relevant material of electro-catalysis.In addition, modification silica can allow more spherical cavity carbon materials to have the property from humidification Can, the etch period by controlling silicon oxide pellets controls the content of silica to obtain having different degrees of humidification to imitate The material of fruit.The catalyst that the present invention is prepared using the more spherical cavity carbon materials of silica-as carrier loaded Pt, electrocatalysis characteristic Height, performance and stability are good under the low humidity, service life is long, are the ideal choses of fuel battery anode catalyst, thus table The more spherical cavity carbon materials of silica-of the bright present invention can be used as the carrier material of fuel battery anode catalyst and membrane electrode increases certainly Wet relevant material.
Compared with prior art, the invention has the advantages that：
(1) present invention prepares the carbon material SiO with more spherical cavity structures by template of silicon oxide pellets2- MSCC materials Material, has the characteristics that spherical cavity size and dioxide-containing silica are controllable, large specific surface area, in situ to adulterate nitrogen, has certain oxygen also Former activity.
(2) it is of the present invention it is silicon dioxide modified be in-situ modification, with it is rear modification compared to technique used more simply, Convenient, controllability is more preferable.
(3) more spherical cavity carbon materials prepared by the present invention have the performance from humidification, can be used as fuel battery anode catalysis Carrier material and fuel battery anode catalysis layer the humidification material of agent.
（4）Pt/SiO prepared by the present invention2The Pt particles of-MSCC catalyst are uniformly dispersed, and Pt particles are small and uniform.Pt/ SiO2The electrochemistry specific surface area height of-MSCC catalyst, electrochemical catalysis activity are good.Still kept under conditions of compared with low humidity compared with High catalytic activity and stability is good from moisturization.
Description of the drawings
Fig. 1 is SiO2The TEM of-MSCC-4h materials schemes.
Fig. 2 is SiO2The TEM of-MSCC-0h materials schemes.
Fig. 3 is SiO2The EDS of-MSCC-4h materials schemes.
Fig. 4 is SiO2Kong Rong-graph of pore diameter distribution of-MSCC-2h materials.
Fig. 5 is SiO2Isothermal curve figure is desorbed in the nitrogen adsorption of-MSCC-2h materials.
Fig. 6 is SiO2The ORR curve graph of-MSCC-4h catalyst in 0.1 mol/L KOH electrolyte solutions.
Fig. 7 is 15 wt% Pt/SiO2The TEM of-MSCC-2h catalyst schemes.
Fig. 8 is 20 wt%Pt/SiO2The XRD diagram of-MSCC-0h catalyst.
Fig. 9 is 8 wt% Pt/SiO2- MSCC-4h catalyst is in 0.5 mol/L H2SO4The CV figures that electrolyte solution measures.
Figure 10 is 10 wt% Pt/SiO2- MSCC-2h as anode catalyst membrane electrode at 60 DEG C, relative humidity be The performance map tested for a long time under the conditions of 20% etc..
Specific implementation mode
Below by specific embodiment to the SiO of the present invention2- MSCC materials and SiO2- MSCC material load Pt catalyst Preparation is further described.
Embodiment 1
(1) SiO2The preparation of-MSCC-2h materials：
1) it is respectively 82 mg, 2.1 mL and 45 mL to take the amount of L-arginine, hexamethylene and water, under 60 DEG C of stirring conditions Fully dissolving, obtains mixed liquor A；
2) 2.1 mL ethyl orthosilicates are added with 1 drop/sec of speed in mixed liquor A obtained by step 1), keep temperature after 12 h of continuous stirring, obtain silicon oxide pellets mother liquor B；
3) 5 mL hexamethylenes, 4 mL ethyl orthosilicates and 50 are added into silicon oxide pellets mother liquor B obtained by step 2) The growth-promoting media that mL water is made into keeps temperature to continue to stir 15 h, obtains silicon dioxide gel C；
4) 0.8 g PVP-k30 are added, obtain mixed liquor D in gained silica dioxide gel C into step 3);
5) pH value of mixed liquor D obtained by step 4) is adjusted to 0 with concentrated hydrochloric acid, lasting stirring is lower to be added 6.7 into mixed liquor D ML aniline, it is the 0, hydrochloric acid solution containing 13.4 g ammonium persulfates then to instill 67 mL pH value, then keeps 300 at 0 DEG C Rev/min stir speed (S.S.) stir 12 h, be then evaporated at 90 DEG C, obtain silica/Polyaniline;
6) silica/Polyaniline for obtaining step 5) is under nitrogen atmosphere, fast with the heating of 2 DEG C/min Rate is warming up to 600 DEG C, keeps 3 h, is cooled to room temperature, obtains C-N/ silica composites；
7) the C-N/ silica composites for obtaining step 6) correspond to 25 mL by 1 g C-N/ silica composites The amount of NaOH solution is mixed with the NaOH solution of 2 mol/L, 2 h of etching processing at 50 DEG C, it is cooling after by being filtered, washed and It is dry, use SiO2The expression of-MSCC-2h materials has etched the sample of 2 h acquisitions with NaOH solution.
Fig. 4 is SiO2Kong Rong-graph of pore diameter distribution of-MSCC-2h materials, Fig. 4 show SiO2- MSCC-2h materials are in addition to existing Outside a large amount of micropore, in 15 ~ 20 nm ranges there is the pore-size distribution more concentrated, it is small to further demonstrate silica Ball size is to SiO2The influence of spherical cavity size in-MSCC materials.
Fig. 5 is SiO2Isothermal curve figure is desorbed in the nitrogen adsorption of-MSCC-2h materials, and test shows SiO2- MSCC-2h materials Specific surface area be up to 430 m2/g。
(2)SiO2The pretreatment of-MSCC-2h materials：By SiO210 times of SiO are added in-MSCC-2h materials2- MSCC-2h materials 3 h are stirred in the acetone of quality, and 12 h are dried in vacuum tank after filtering and washing 3 times.Then sample is added 50 times after will be dry SiO2The HNO of 10 wt% of-MSCC-2h quality of materials3With H2O2Mixed liquor in（Volume ratio HNO3: H2O2 = 2:1）, 80 Flow back 8 h at DEG C.It is dried in vacuum drying chamber after filtration washing 5 times, then by the sample after drying in N2Lower 300 DEG C of atmosphere Handle 3 h.
(3)Pt/SiO2The preparation of-MSCC-2h catalyst：First 37.7 mg sodium citrates are dissolved in 30 mL ethylene glycol, Ultrasound 60 minutes adds the ethylene glycol solution (20 mg/mL) of 1.33 mL six hydration chloroplatinic acids, stirs 30 minutes, then adds Enter pretreated SiO290 mg of-MSCC-2h materials, ultrasound 60 minutes, with the KOH/EG of 5 wt%（Ethylene glycol）Solution is adjusted It behind pH of mixed=9.5, is transferred in polytetrafluoroethylene (PTFE) in the reaction kettle in village, 6 h is reacted at 120 DEG C.10wt% is used after cooling HNO3Solution adjusts pH=4, is washed 5 times after filtering, dries 12 h in vacuum drying chamber, you can obtain 10wt% Pt/SiO2- MSCC-2h catalyst.
Figure 10 is 10 wt% Pt/SiO2- MSCC-2h catalyst 60 DEG C, relative humidity 20%, hydrogen flowing quantity 300 Under conditions of mL/min and back pressure are 30 psi, the long-time performance test figure of cell membrane-electrode when as anode catalyst.From It is found that 10 wt% Pt/SiO in Figure 102- MSCC-2h catalyst is under lower relative humidity and higher temperature condition, warp The test for crossing 10.5 h is still maintained for up to 850 A/cm2Current density, current density only decayed 8.6%.Show system of the present invention Standby SiO2- MSCC materials have from moisturization, are the ideal choses of fuel cell membrane electrode associated materials.
Embodiment 2
(1) SiO2The preparation of-MSCC-2h materials：
1) it is respectively 82 mg, 4.2 mL and 90 mL to take the amount of L-arginine, hexamethylene and water, under 40 DEG C of stirring conditions Fully dissolving, obtains mixed liquor A；
2) 5.2 mL ethyl orthosilicates are added with 2 drops/sec of speed in mixed liquor A obtained by step 1), keep temperature after 18 h of continuous stirring, obtain silicon oxide pellets mother liquor B；
3) be added in the silicon oxide pellets mother liquor B obtained by the step 2) 45 mL hexamethylenes, 24 mL ethyl orthosilicates and The growth-promoting media that 300 mL water are made into keeps temperature to continue to stir 22.5 h, obtains silicon dioxide gel C；
4) 0.5 g PVP-k10 and 0.5 g PVP-k15 are added, obtain in gained silica dioxide gel C into step 3) Mixed liquor D;
5) pH value of mixed liquor D obtained by step 4) is adjusted to 0.15 with concentrated hydrochloric acid, lasting stirring is lower to be added into mixed liquor D 18.7 mL aniline, it is the 0.15, hydrochloric acid solution containing 70 g ammonium persulfates then to instill 280 mL pH value, then at 7.5 DEG C It keeps 600 revs/min of stir speed (S.S.) to stir 30 h, is then evaporated at 90 DEG C, obtains silica/Polyaniline;
6) silica/Polyaniline for obtaining step 5) under nitrogen atmosphere, with the heating of 9.5 DEG C/min Rate is warming up to 800 DEG C, keeps 2 h, is cooled to room temperature, obtains C-N/ silica composites；
7) the C-N/ silica composites for obtaining step 6) correspond to 25 mL by 1 g C-N/ silica composites The amount of NaOH solution is mixed with the NaOH solution of 2 mol/L, 2 h of etching processing at 85 DEG C, by being filtered, washed after cooling And drying, obtain sample SiO2- MSCC-2h materials.
(2)SiO2The pretreatment of-MSCC-2h materials.By SiO210 times of SiO are added in-MSCC-2h2- MSCC-2h quality of materials Acetone in stir 3 h, after filtering and washing 3 times vacuum tank dry 12 h.Then 50 times of SiO are added in sample after will be dry2- The HNO of 10 wt% of MSCC-2h quality of materials3With H2O2Mixed liquor in（Volume ratio HNO3: H2O2 = 2:1）, in 80 DEG C Flow back 8 h.It is dry in vacuum drying chamber after filtration washing 5 times, then by the sample after drying in N2The lower 300 DEG C of processing of atmosphere 3 h。
(3)Pt/SiO2The preparation of-MSCC catalyst：First 56.5 mg sodium citrates are dissolved in 30 mL ethylene glycol, ultrasound 60 minutes, the ethylene glycol solution (20 mg/mL) of 2.0 mL six hydration chloroplatinic acids is added, stirs 30 minutes, pre- place is then added The SiO managed285 mg of-MSCC-2h materials, ultrasound 60 minutes, after adjusting pH of mixed=10 with the KOH/EG solution of 5 wt%, It is transferred in polytetrafluoroethylene (PTFE) in the reaction kettle in village, 6 h is reacted at 120 DEG C.The HNO of 10wt% is used after cooling3Solution adjusts pH =3.5, it is washed 5 times after filtering, dries 12 h in vacuum drying chamber, you can obtain 15wt% Pt/SiO2- MSCC-2h catalyst.
Fig. 7 is 15 wt% Pt/SiO2The TEM figures of-MSCC-2h catalyst and corresponding Pt particle size distributions figure.By scheming 7 it can be seen that Pt particle heights are evenly dispersed on more spherical cavity carbon carriers, and the diameter of Pt nano particles concentrates on 2 ~ 3.5 Between nm, show that more spherical cavity carbon materials prepared by the present invention are ideal noble metal catalyst carrier materials.
Embodiment 3
(1) SiO2The preparation of-MSCC-4h materials：
1) it is respectively 82 mg, 6.3 mL and 135 mL to take the amount of L-arginine, hexamethylene and water, in 80 DEG C of stirring conditions Lower fully dissolving, obtains mixed liquor A；
2) 8.32 mL ethyl orthosilicates are added with 1.5 drops/sec of speed in mixed liquor A obtained by step 1), keep temperature Degree continues to stir 24 h, obtains silicon oxide pellets mother liquor B；
3) be added in the silicon oxide pellets mother liquor B obtained by the step 2) 120 mL hexamethylenes, 60 mL ethyl orthosilicates and The growth-promoting media that 750 mL water are made into keeps temperature to continue to stir 30 h, obtains silicon dioxide gel C；
4) 0.625 g PVP-k17 and 0.625 g PVP-k30 are added in gained silica dioxide gel C into step 3), Obtain mixed liquor D;
5) pH value of mixed liquor D obtained by step 4) is adjusted to 0.3 with concentrated hydrochloric acid, lasting stirring is lower to be added into mixed liquor D 31.7 mL aniline, it is the 0.3, hydrochloric acid solution containing 190 g ammonium persulfates then to instill 634 mL pH value, then at 15 DEG C It keeps 1200 revs/min of stir speed (S.S.) to stir 48 h, is then evaporated at 90 DEG C, it is compound to obtain silica/polyaniline Object;
6) silica/Polyaniline for obtaining step 5) is under nitrogen atmosphere, fast with the heating of 15 DEG C/min Rate is warming up to 1000 DEG C, keeps 1 h, is cooled to room temperature, obtains C-N/ silica composites；
7) the C-N/ silica composites for obtaining step 6) correspond to 25 mL by 1 g C-N/ silica composites The amount of NaOH solution is mixed with the NaOH solution of 2 mol/L, 4 h of etching processing at 120 DEG C, by being filtered, washed after cooling And drying, obtain sample SiO2- MSCC-4h materials.
Fig. 1, Fig. 3 are the SiO after 4 h of NaOH etching processings2- MSCC materials（It is denoted as SiO2-MSCC-4h）Transmission electron microscope （TEM）Photo and X-ray energy dispersive spectrum（EDS）Figure.It will be seen from figure 1 that material particle size prepared by the present invention exists Between the nm of 100 nm ~ 200, and be evenly distributed in each particle multiple diameters 20 nm or so spherical cavity, this A little spherical cavities are substantially inverted by the shape of silicon oxide pellets, therefore show that the present invention can be by controlling silicon oxide pellets Size further realize SiO2The size of spherical cavity in-MSCC materials.It is removed in the material that as can be seen from Figure 3 prepared by the present invention Contain the SiO that except C, Si and O, prepared by the present invention2- MSCC materials also have the miscellaneous original of electro-chemical activity doped with N and S etc. Son illustrates SiO prepared by the present invention2- MSCC materials can be used as with the relevant material of elctro-catalyst, while the present invention can pass through control The time of NaOH etching processings processed to realize the modification amount of silica on more spherical cavity carbon materials, to make the material prepared have There is moisturization.
Fig. 6 is SiO2Hydrogen reduction of-MSCC-4h the materials in the 0.1 mol/L KOH electrolyte that oxygen is saturated（ORR）It is bent The reaction type of line chart, more spherical cavity carbon material catalytic oxidation-reductions that as can be seen from Figure 6 prepared by the present invention is 4 electron reactions, print Having demonstrate,proved the material of the invention prepared has certain catalytic oxidation-reduction activity, can be used as and the relevant material of electro-catalysis.
(2)SiO2The pretreatment of-MSCC-4h materials：By SiO210 times of SiO are added in-MSCC-4h2- MSCC-4h quality of materials Acetone in stir 3h, after filtering and washing 3 times vacuum tank dry 12h.Then 50 times of SiO are added in sample after will be dry2- The HNO of 10 wt% of MSCC-4h quality of materials3With H2O2Mixed liquor in（Volume ratio HNO3: H2O2 = 2:1）, at 80 DEG C Flow back 8 h.It is dried in vacuum drying chamber after filtration washing 5 times, then by the sample after drying in N2The lower 300 DEG C of processing 3 of atmosphere h。
(3)Pt/SiO2The preparation of-MSCC catalyst：First 30.2 mg sodium citrates are dissolved in 30 mL ethylene glycol, ultrasound 60 minutes, the ethylene glycol solution (20 mg/mL) of 1.06 mL six hydration chloroplatinic acids is added, stirs 30 minutes, is then added pre- Processed SiO292 mg of-MSCC-4h materials, ultrasound 60 minutes adjust pH of mixed=10.5 with the KOH/EG solution of 5 wt% Afterwards, it is transferred in polytetrafluoroethylene (PTFE) in the reaction kettle in village, 6 h is reacted at 120 DEG C.The HNO of 10wt% is used after cooling3Solution tune PH=3 are saved, are washed 5 times after filtering, dry 12 h in vacuum drying chamber, you can obtain 8wt% Pt/SiO2- MSCC-4h is catalyzed Agent.
Fig. 9 is 8 wt% Pt/SiO2The 0.5 mol/L H that-MSCC-4h catalyst is saturated in nitrogen2SO4Electrolyte solution The cyclic voltammetry curve measured（CV）, and compared with business platinum carbon COMPARATIVE CATALYST (20 wt% JM Pt/C).It can be seen that 8 wt% Pt/SiO2The electrochemistry specific surface area of-MSCC-4h catalyst is 2.1 times of 20 wt% JM Pt/C, up to 111 m2/g。 Show SiO prepared by the present invention2- MSCC materials are the ideal carriers for preparing high activity noble metal catalyst.
Embodiment 4
(1) SiO2The preparation of-MSCC-0h materials：
1) it is respectively 82 mg, 6.3 mL and 135 mL to take the amount of L-arginine, hexamethylene and water, in 80 DEG C of stirring conditions Lower fully dissolving, obtains mixed liquor A；
2) 8.32 mL ethyl orthosilicates are added with 2 drops/sec of speed in mixed liquor A obtained by step 1), keep temperature Continue to stir 20 h, obtains silicon oxide pellets mother liquor B；
3) be added in the silicon oxide pellets mother liquor B obtained by the step 2) 120 mL hexamethylenes, 60 mL ethyl orthosilicates and The growth-promoting media that 750 mL water are made into keeps temperature to continue to stir 24 h, obtains silicon dioxide gel C；
4) 0.625 g PVP-k10 and 0.625 g PVP-k30 are added in gained silica dioxide gel C into step 3), Obtain mixed liquor D；
5) pH value of mixed liquor D obtained by step 4) is adjusted to 0.3 with concentrated hydrochloric acid, lasting stirring is lower to be added into mixed liquor D 31.7 mL aniline, it is the 0.3, hydrochloric acid solution containing 190 g ammonium persulfates then to instill 634 mL pH value, then at 10 DEG C It keeps 1200 revs/min of stir speed (S.S.) to stir 24 h, is then evaporated at 90 DEG C, it is compound to obtain silica/polyaniline Object；
6) silica/Polyaniline for obtaining step 5) is under nitrogen atmosphere, fast with the heating of 5 DEG C/min Rate is warming up to 800 DEG C, keeps 1 h, is cooled to room temperature, obtains C-N/ silica composites；
7) the C-N/ silica composites that step 6) obtains, without NaOH etching processings, etch period is 0 h, is obtained To sample SiO2- MSCC-0h materials.
Fig. 2 is SiO2The transmission electron microscope of-MSCC-0h（TEM）Photo.Figure it is seen that material prepared by the present invention For particle size between the nm of 100 nm ~ 200, particle surface and inside are dispersed with SiO2There is not the structure of spherical cavity in bead, This is because etch period is 0, SiO2Bead template does not remove and causes.And these hydrophilic SiO2Bead is but also prepare The material gone out has moisturization.
(2)SiO2The pretreatment of-MSCC-0h materials：By SiO210 times of SiO are added in-MSCC-0h2- MSCC-0h quality of materials Acetone in stir 3h, after filtering and washing 3 times vacuum tank dry 12h.Then 50 times of SiO are added in sample after will be dry2- The HNO of 10 wt% of MSCC-0h quality of materials3With H2O2Mixed liquor in（Volume ratio HNO3: H2O2 = 2:1）, at 80 DEG C Flow back 8 h.It is dried in vacuum drying chamber after filtration washing 5 times, then by the sample after drying in N2The lower 300 DEG C of processing 3 of atmosphere h。
(3)Pt/SiO2The preparation of-MSCC catalyst：First 75 mg sodium citrates are dissolved in 30 mL ethylene glycol, ultrasound 60 Minute, the ethylene glycol solution (20 mg/mL) of 2.65 mL six hydration chloroplatinic acids is added, stirs 30 minutes, pre- place is then added The SiO managed280 mg of-MSCC-0h materials, ultrasound 60 minutes adjust pH of mixed=10.5 with the KOH/EG solution of 5 wt% Afterwards, it is transferred in polytetrafluoroethylene (PTFE) in the reaction kettle in village, 6 h is reacted at 120 DEG C.The HNO of 10wt% is used after cooling3Solution tune PH=3 are saved, are washed 5 times after filtering, dry 12 h in vacuum drying chamber, you can obtain 20 wt% Pt/SiO2- MSCC-0h is catalyzed Agent.
Fig. 8 is that the present invention prepares 20 wt% Pt/SiO2The XRD diagram of-MSCC-0h catalyst.Existing respectively as we know from the figure 39.58 °, 46.36 °, 67.84 °, 81.20 ° and 85.71 ° occur it is corresponding（111）、（200）、（220）、（311）With（222） The diffraction maximum of crystal face, this five crystal faces belong to the feature crystal face of cubic phase Pt, and the diffraction maximum occurred at 23.5 ° in figure is carbon material Peak.Particle size with Scherrer equation calculation Pt is about 3 nm, shows that Pt particle sizes prepared by the present invention are smaller, this hair The carbon material of bright preparation is the ideal carrier for preparing small particle noble metal catalyst.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not limited by the embodiment System.It is any without departing from the spirit and principles of the present invention made by change, modification, replacement, combination, simplification, should be The substitute mode of effect all includes within protection scope of the present invention.

Claims (10)

1. a kind of preparation method of silicon dioxide modified more spherical cavity carbon materials, which is characterized in that steps are as follows：
(1) by L-arginine, hexamethylene, water in molar ratio 1:（50 ~ 150）:（5000 ~ 15000）Mixing, 40 DEG C ~ It is fully dissolved under 80 DEG C of stirring conditions, obtains mixed liquor A；
(2) under 40 DEG C ~ 80 DEG C stirring conditions, ethyl orthosilicate is added with 1 ~ 2 drop/sec of speed obtained by step (1) and is mixed It closes in liquid A, the molar ratio of wherein ethyl orthosilicate and L-arginine used in step (1) is（20 ~ 80）：1, continue stirring 12 ~ 24 h obtain silicon oxide pellets mother liquor B；
(3) under 40 DEG C ~ 80 DEG C stirring conditions, by silicon oxide pellets mother liquor B obtained by step (2) and hexamethylene, positive silicic acid Ethyl ester and water are 1 in mass ratio:（0.1 ~ 0.8）:（0.08 ~ 0.4）:（ 1 ~ 5）It is made into growth-promoting media, continues stirring 15 ~ 30 h obtain silicon dioxide gel C；
(4) under 40 DEG C ~ 80 DEG C stirring conditions, into step (3) in gained silicon dioxide gel C, polyvinyl pyrrole is added The mass ratio of alkanone, wherein polyvinylpyrrolidone and silicon dioxide gel C are 1:（60 ~ 120）, obtain mixed liquor D;
(5) pH value of mixed liquor D obtained by step (4) is adjusted to 0 ~ 0.3 with concentrated hydrochloric acid, is mixed in mass ratio under lasting stirring Liquid D:Aniline is（15 ~ 30）:1 aniline is added into mixed liquor D, and it is 20 wt% then to instill ammonium persulfate mass fraction The aqueous solution E that ~ 30 wt%, pH are 0 ~ 0.3, the wherein mass ratio of aqueous solution E and aniline are（10 ~ 20）:1, then exist It keeps 300-1200 revs/min of stir speed (S.S.) to stir 12 ~ 48 h at 0 ~ 15 DEG C, is then evaporated, you can obtain titanium dioxide Silicon/Polyaniline;
(6) silica/Polyaniline for obtaining step (5) under nitrogen atmosphere, with the heating of 2 ~ 15 DEG C/min Rate is warming up to 600 DEG C ~ 1000 DEG C, keeps 1 ~ 3 h, is cooled to room temperature, obtains C-N/ silica composites；
(7) the C-N/ silica composites that step (6) obtains are mixed with NaOH solution, at 50 ~ 120 DEG C at etching 0 ~ 4 h is managed, by being filtered, washed and dried after cooling, silicon dioxide modified more spherical cavity carbon materials is obtained, is labeled as SiO2- MSCC materials.
2. a kind of preparation method of silicon dioxide modified more spherical cavity carbon materials according to claim 1, which is characterized in that The stirring is stirred with 300 ~ 1200 revs/min of stir speed (S.S.).
3. a kind of preparation method of silicon dioxide modified more spherical cavity carbon materials according to claim 1, which is characterized in that Step（3）In gained silicon dioxide gel C, a diameter of 20 ~ 50 nm of silicon oxide pellets.
4. a kind of preparation method of silicon dioxide modified more spherical cavity carbon materials according to claim 1, which is characterized in that Step（4）The polyvinylpyrrolidone is one or more of PVP-k10, PVP-k15, PVP-k17 and PVP-k30.
5. a kind of preparation method of silicon dioxide modified more spherical cavity carbon materials according to claim 1, which is characterized in that Step（7）In silicon dioxide modified more spherical cavity carbon materials, a diameter of 10 ~ 40 nm of spherical cavity；Silicon dioxide modified is more The particle of spherical cavity carbon material is directly 100 ~ 200nm.
6. a kind of preparation method of silicon dioxide modified more spherical cavity carbon materials according to claim 1, which is characterized in that Step（7）The amount of 25 mL NaOH solutions is corresponded to by C-N/ silica composites and 2 by 1 g C-N/ silica composites The NaOH solution of mol/L mixes.
7. a kind of silicon dioxide modified more spherical cavity carbon materials work made from claim 1-6 any one of them preparation methods It is applied in fuel cell membrane electrode for the carrier material and humidification material of fuel battery anode catalyst.
8. application according to claim 7, which is characterized in that the preparation method of the anode catalyst is as follows：
By SiO2- MSCC materials pre-process for use, then sodium citrate is dissolved in ethylene glycol, and ultrasound 60 minutes adds six It is hydrated the ethylene glycol solution of chloroplatinic acid, stirs 30 minutes, the pretreated SiO of 1 ~ 12 times of Pt mass is then added2-MSCC Material, ultrasound 60 minutes adjust pH of mixed with the KOH/EG solution of 5 wt%>After 9, it is transferred to village in polytetrafluoroethylene (PTFE) In reaction kettle, 6 h are reacted at 120 DEG C；After cooling with the HNO of 10 wt%3Solution adjusts pH<5, it is washed after filtering, true It is dry in empty drying box, you can to obtain the silicon dioxide modified more spherical cavity carbon material catalyst of Pt/；It is described six hydration chloroplatinic acid with Molar ratio with sodium citrate is 1: 2~2.5.
9. application according to claim 8, which is characterized in that the SiO2The pretreatment of-MSCC materials is by SiO2- 10 times of SiO are added in MSCC materials23 h are stirred in the acetone of-MSCC quality of materials, are dried, are done in vacuum tank after filtering and washing 50 times of SiO are added after dry2The HNO of 10 wt% of-MSCC quality of materials3With H2O2Mixed liquor in, wherein the HNO of 10 wt%3With H2O2Volume ratio is 2:1, flow back 8 h at 80 DEG C, dry in vacuum drying chamber after filtration washing, then by the sample after drying Product are in N23 h of the lower 300 DEG C of processing of atmosphere.
10. application according to claim 8, which is characterized in that the quality for dissolving the ethylene glycol of sodium citrate is chloroplatinic acid 500 ~ 1000 times of quality.
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