CN106058276A - Preparation method of silica-modified multi-spherical-cavity carbon material and application of carbon material to fuel cell membrane electrode - Google Patents

Preparation method of silica-modified multi-spherical-cavity carbon material and application of carbon material to fuel cell membrane electrode Download PDF

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CN106058276A
CN106058276A CN201610548972.3A CN201610548972A CN106058276A CN 106058276 A CN106058276 A CN 106058276A CN 201610548972 A CN201610548972 A CN 201610548972A CN 106058276 A CN106058276 A CN 106058276A
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sio
mscc
silicon dioxide
spherical cavity
carbon material
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CN106058276B (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
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • 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
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04089—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants
    • H01M8/04119—Arrangements for control of reactant parameters, e.g. pressure or concentration of gaseous reactants with simultaneous supply or evacuation of electrolyte; Humidifying or dehumidifying
    • H01M8/04126—Humidifying
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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 preparation method of a silica-modified multi-spherical-cavity carbon material and application of the carbon material to a fuel cell membrane electrode. According to the method, a silica bead is used as a template, aniline is polymerized around the bead, the silica bead is carbonized and etched in sequence, and the nitrogen-doped silica-modified multi-spherical-cavity carbon material is obtained. The size of spherical cavities of the multi-spherical-cavity carbon material is controllable, meanwhile the multi-spherical-cavity carbon material has certain oxygen reduction electrochemical activity, and therefore the carbon material can serve as a material relevant to electro-catalysis. Besides, silica modification enables the multi-spherical-cavity carbon material to have self-humidifying performance. A catalyst prepared from the silica-multi-spherical-cavity carbon material which serves as a carrier carrying Pt is high in electro-catalytic property, good in performance and stability under low humidity and long in service life and is an ideal choice for a fuel cell anode catalyst. It is indicated that the silica-multi-spherical-cavity carbon material can serve as the carrier material of the fuel cell anode catalyst and the material relevant to self-humidifying of the membrane electrode.

Description

The preparation method of a kind of silicon dioxide modified many spherical cavity material with carbon element and at fuel cell membranes Application in electrode
Technical field
The present invention relates to new material technology field, be specifically related to the preparation method of a kind of silicon dioxide modified many spherical cavity material with carbon element And the 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 directly be converted into electric energy Use device.Owing to not discharging the shortcoming of the traditional energy Land use systems such as nitrogenous, the atmosphere pollution of sulfur and particulate matter, simultaneously Also because possessing the feature of high-energy conversion efficiency and Miniaturizable, fuel cell will have the biggest in following energy market Application prospect.Wherein Proton Exchange Membrane Fuel Cells is particularly held in both hands by the heat of research worker, is applied to portable in recent years In the dynamical system of electronic equipment and electric motor car.Although Proton Exchange Membrane Fuel Cells technology is the most ripe, but in business Change and on universal road, be still faced with that cathod catalyst cost height reserves are few, improve anode catalyst mithridatism ability and the choosing of fuel The lot of challenges such as select.Water is the key factor that Proton Exchange Membrane Fuel Cells maintains proton conductivity in running.Generally Need extra material that reacting gas is carried out moistening, to keep the conductivity of proton.But this adds answering of battery the most simultaneously Polygamy, and add extra energy expenditure.Therefore develop and there is the carrier material from moisturization and membrane electrode material, can be Simplify the operational management of battery system while keeping relatively high proton conductivity and reduce operating cost, being to realize PEM The inevitable choice of commercializing fuel cells.
Summary of the invention
In order to overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of silicon dioxide modified many spherical cavity carbon material The preparation method of material and the application in fuel cell membrane electrode thereof.
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 solution, silicon oxide pellets diauxic growth, carbon Precursor be polymerized around silicon oxide pellets formation the precursor complex of silicon/carbon dioxide, the carbonization of complex and two The processes such as the etching of silicon oxide bead, thus realize the preparation with many spherical cavity meso-porous carbon material of self-moistening function.
A kind of silicon dioxide modified many spherical cavity material with carbon element (is labeled as SiO2-MSCC) preparation method, step is as follows:
(1) by L-arginine, hexamethylene, your ratio 1 of hydromassage: (50 ~ 150): (5000 ~ 15000) mixing, 40 DEG C ~ Fully dissolve under 80 DEG C of stirring conditions, obtain mixed liquor A；
(2) under 40 DEG C ~ 80 DEG C stirring conditions, tetraethyl orthosilicate is added step (1) gained with the speed of 1 ~ 2 drop/sec and mixes Closing in liquid A, wherein the mol ratio of L-arginine used is (20 ~ 80) to tetraethyl orthosilicate with step (1): 1, continues stirring 12 ~ 24 h, obtain silicon oxide pellets mother solution B；
(3) under 40 DEG C ~ 80 DEG C stirring conditions, by step (2) gained silicon oxide pellets mother solution B and hexamethylene, positive silicic acid Ethyl ester and water are 1 in mass ratio: (0.1 ~ 0.8): (0.08 ~ 0.4): (1 ~ 5) is made into growth-promoting media, continue stirring 15 ~ 30 h, obtain silicon dioxide gel C；
(4), under 40 DEG C ~ 80 DEG C stirring conditions, in step (3) in gained silica dioxide gel C, polyvinyl pyrrole is added Alkanone, wherein polyvinylpyrrolidone is 1 with the mass ratio of silica dioxide gel C: (60 ~ 120), obtains mixed liquor D;
(5) the pH value concentrated hydrochloric acid of step (4) gained mixed liquor D is adjusted to 0 ~ 0.3, continuously stirred under mix in mass ratio Liquid D: aniline is (15 ~ 30): 1 adds aniline in mixed liquor D, and then instilling Ammonium persulfate. mass fraction is 20 wt% ~ 30 wt%, pH are the aqueous solution E of 0 ~ 0.3, and wherein aqueous solution E is (10 ~ 20) with the mass ratio of aniline: 1, then exists Keep stir speed (S.S.) stirring 12 ~ 48 h of 300-1200 rev/min at 0 ~ 15 DEG C, be evaporated subsequently, i.e. can get titanium dioxide Silicon/Polyaniline;
(6) silicon dioxide/Polyaniline step (5) obtained is under nitrogen atmosphere, with the intensification of 2 ~ 15 DEG C/min Ramp, to 600 DEG C ~ 1000 DEG C, keeps 1 ~ 3 h, is cooled to room temperature, obtains C-N/ silica composite；
(7) the C-N/ silica composite that step (6) obtains is mixed with NaOH solution, at 50 ~ 120 DEG C at etching Reason 0 ~ 4 h, through being filtered, washed and dried after cooling, obtains silicon dioxide modified many spherical cavity material with carbon element, is labeled as SiO2- The MSCC material abbreviation of multi-spherical cavity carbon (MSCC be).
Further, described stirring is to stir with the stir speed (S.S.) of 300 ~ 1200 revs/min.
Further, in described silicon dioxide gel C, a diameter of 20 ~ 50 nm of silicon oxide pellets.
Further, the one during described polyvinylpyrrolidone is PVP-k10, PVP-k15, PVP-k17 and PVP-k30 Or it is several.
Further, the temperature being evaporated described in step (5) is 90 DEG C.
Further, step (7) presses the amount of the corresponding 25 mL NaOH solution of 1 g C-N/ silica composite by C-N/ The NaOH solution mixing of silica composite and 2 mol/L.
Further, in described silicon dioxide modified many spherical cavity material with carbon element, a diameter of 10 ~ 40 nm of spherical cavity.
Further, the granule of described silicon dioxide modified many spherical cavity material with carbon element is directly 100 ~ 200nm.
A kind of silicon dioxide modified many spherical cavity material with carbon element prepared by above-described preparation method is as fuel cell The carrier material of anode catalyst and humidification materials application are in fuel cell membrane electrode.
Further, the preparation method of described anode catalyst (will be supported on silicon dioxide modified many spherical cavity carbon by Pt Pt/SiO prepared by material2-MSCC catalyst) as follows:
By SiO2It is stand-by that-MSCC material carries out pretreatment, then is dissolved in ethylene glycol by sodium citrate, ultrasonic 60 minutes, adds The ethylene glycol solution of six hydration chloroplatinic acids, stirs 30 minutes, is subsequently adding the pretreated SiO of 1 ~ 12 times of Pt mass2- MSCC material, ultrasonic 60 minutes, regulates pH of mixed with the KOH/EG solution of 5 wt% > after 9, it is transferred in politef In the reactor in village, react 6 h at 120 DEG C；After cooling with the HNO of 10 wt%3Solution regulation pH < 5, washes after filtration, Vacuum drying oven is dried, i.e. can get many spherical cavity material with carbon element catalyst silicon dioxide modified for Pt/；Described six hydration chlorine platinum Acid is 1: 2 ~ 2.5 with the mol ratio with sodium citrate.
Further, described SiO2The pretreatment of-MSCC material, is by SiO2-MSCC material adds 10 times of SiO2- The acetone of MSCC quality of materials stirs 3 h, is dried at vacuum tank after filtering and washing, 50 times of SiO of dried addition2-MSCC The HNO of 10 wt% of quality of materials3With H2O2Mixed liquor in, the wherein HNO of 10 wt%3With H2O2Volume ratio is 2:1, at 80 DEG C Lower backflow 8 h, is dried after filtration washing, then by dried sample at N in vacuum drying oven2Lower 300 DEG C of atmosphere processes 3 h。
Further, quality is chloroplatinic acid quality 500 ~ 1000 times of the ethylene glycol of dissolving sodium citrate.
Further, the described dry time is 12 h.
Further, the number of times of described washing is 5 times.
Many spherical cavity material with carbon element of the present invention can be as desired by the size of regulation silicon oxide pellets to obtain different chi Very little spherical cavity structure, simultaneously as specific surface area is big, have certain hydrogen reduction electro-chemical activity doped with nitrogen element, Therefore can be used as the material relevant to electro-catalysis.Many spherical cavity material with carbon element can be allowed to have the property from humidification additionally, modify silicon dioxide Can, obtain having, by controlling the content of the etch period control silicon dioxide of silicon oxide pellets, the effect that is humidified in various degree The material of fruit.The catalyst that the present invention is prepared using silicon dioxide-many spherical cavity material with carbon element as carrier loaded Pt, electrocatalysis characteristic High, under the low humidity performance and good stability, service life long, be the ideal chose of fuel battery anode catalyst, thus table The silicon dioxide of the bright present invention-many spherical cavity material with carbon element can increase certainly as the carrier material of fuel battery anode catalyst and membrane electrode The material that wetting phase closes.
Compared with prior art, present invention have the advantage that
(1) present invention prepares the material with carbon element SiO with many spherical cavity structure with silicon oxide pellets for template2-MSCC material, Having spherical cavity size and the controlled feature of dioxide-containing silica, specific surface area is big, in situ doping nitrogen, has certain hydrogen reduction and lives Property.
(2) of the present invention silicon dioxide modified for in-situ modification, compared with rear modification technique used simpler, Convenient, controllability is more preferable.
(3) the many spherical cavity material with carbon element prepared by the present invention has the performance from humidification, can be used as fuel battery anode catalysis The carrier material of agent and fuel battery anode catalysis layer humidification material.
(4) Pt/SiO prepared by the present invention2The Pt granule of-MSCC catalyst is uniformly dispersed, and Pt granule is little and homogeneous.Pt/ SiO2The electrochemistry specific surface area of-MSCC catalyst is high, electrochemical catalysis activity is good.Still keep relatively under conditions of relatively low humidity High catalysis activity and stability are good from moisturization.
Accompanying drawing explanation
Fig. 1 is SiO2The TEM figure of-MSCC-4h material.
Fig. 2 is SiO2The TEM figure of-MSCC-0h material.
Fig. 3 is SiO2The EDS figure of-MSCC-4h material.
Fig. 4 is SiO2Pore volume-the graph of pore diameter distribution of-MSCC-2h material.
Fig. 5 is SiO2The nitrogen adsorption desorption isothermal curve figure of-MSCC-2h material.
Fig. 6 is SiO2-MSCC-4h catalyst ORR curve chart in 0.1 mol/L KOH electrolyte solution.
Fig. 7 is 15 wt% Pt/SiO2The TEM figure of-MSCC-2h catalyst.
Fig. 8 is 20 wt%Pt/SiO2The XRD figure of-MSCC-0h catalyst.
Fig. 9 is 8 wt% Pt/SiO2-MSCC-4h catalyst is at 0.5 mol/L H2SO4The CV figure that electrolyte solution records.
Figure 10 is 10 wt% Pt/SiO2-MSCC-2h as the membrane electrode of anode catalyst at 60 DEG C, relative humidity be The performance map of long-time test under the conditions of 20% grade.
Detailed description of the invention
Below by the specific embodiment SiO to the present invention2-MSCC material and SiO2-MSCC material load Pt catalyst Preparation is further described.
Embodiment 1
(1) SiO2The preparation of-MSCC-2h material:
1) amount taking L-arginine, hexamethylene and water is respectively 82 mg, 2.1 mL and 45 mL, under 60 DEG C of stirring conditions fully Dissolve, obtain mixed liquor A；
2) 2.1 mL tetraethyl orthosilicates are added step 1 with the speed of 1 drop/sec) in gained mixed liquor A, keep temperature to continue to stir Mix 12 h, obtain silicon oxide pellets mother solution B；
3) toward step 2) gained silicon oxide pellets mother solution B adds with 5 mL hexamethylene, 4 mL tetraethyl orthosilicates and 50 mL water The growth-promoting media being made into, keeps temperature to continue stirring 15 h, obtains silicon dioxide gel C；
4) toward step 3) in gained silica dioxide gel C, add 0.8 g PVP-k30, obtain mixed liquor D;
5) by step 4) the pH value concentrated hydrochloric acid of gained mixed liquor D is adjusted to 0, continuously stirred lower adds 6.7 mL in mixed liquor D Aniline, then instill 67 mL pH value be 0, hydrochloric acid solution containing 13.4 g Ammonium persulfate .s, then keep at 0 DEG C 300 turns/ Minute stir speed (S.S.) stir 12 h, be then evaporated at 90 DEG C, obtain silicon dioxide/Polyaniline;
6) by step 5) silicon dioxide/Polyaniline of obtaining under nitrogen atmosphere, with the heating rate liter of 2 DEG C/min Temperature, to 600 DEG C, keeps 3 h, is cooled to room temperature, obtain C-N/ silica composite；
7) by step 6) the C-N/ silica composite that obtains, by corresponding 25 mL of 1 g C-N/ silica composite The amount of NaOH solution mixes with the NaOH solution of 2 mol/L, etching processing 2 h at 50 DEG C, after cooling through filtration, washing and It is dried, uses SiO2-MSCC-2h material expression NaOH solution has etched the sample that 2 h obtain.
Fig. 4 is SiO2Pore volume-the graph of pore diameter distribution of-MSCC-2h material, Fig. 4 shows SiO2-MSCC-2h material is except existing Outside substantial amounts of micropore, there is, in 15 ~ 20 nm scopes, the pore-size distribution more concentrated, further demonstrate silicon dioxide little Ball size is to SiO2The impact of spherical cavity size in-MSCC material.
Fig. 5 is SiO2The nitrogen adsorption desorption isothermal curve figure of-MSCC-2h material, test shows SiO2-MSCC-2h material Specific surface area be up to 430 m2/g。
(2)SiO2The pretreatment of-MSCC-2h material: by SiO2-MSCC-2h material adds 10 times of SiO2-MSCC-2h material The acetone of quality stirs 3 h, after filtering and wash 3 times, is dried 12 h at vacuum tank.Then dried sample is added 50 times SiO2The HNO of 10 wt% of-MSCC-2h quality of materials3With H2O2Mixed liquor in (volume ratio HNO3: H2O2 =2:1), 80 Reflux at DEG C 8 h.It is dried at vacuum drying oven, then by dried sample at N after filtration washing 5 times2Lower 300 DEG C of atmosphere Process 3 h.
(3)Pt/SiO2The preparation of-MSCC-2h catalyst: first 37.7 mg sodium citrates are dissolved in 30 mL ethylene glycol, Ultrasonic 60 minutes, add 1.33 mL six and be hydrated the ethylene glycol solution (20 mg/mL) of chloroplatinic acid, stir 30 minutes, then add Enter pretreated SiO2-MSCC-2h material 90 mg, ultrasonic 60 minutes, with the KOH/EG(ethylene glycol of 5 wt%) solution regulation Behind pH of mixed=9.5, it is transferred to, in politef in the reactor in village, react 6 h at 120 DEG C.Use 10wt% after cooling HNO3Solution regulation pH=4, wash 5 times after filtration, are dried 12 h at vacuum drying oven, i.e. can get 10wt% Pt/SiO2- MSCC-2h catalyst.
Figure 10 is 10 wt% Pt/SiO2-MSCC-2h catalyst 60 DEG C, relative humidity be 20%, hydrogen flowing quantity be 300 Under conditions of mL/min and back pressure are 30 psi, as the long-time performance test figure of cell membrane-electrode during anode catalyst.From Figure 10 understands, 10 wt% Pt/SiO2-MSCC-2h catalyst under relatively low relative humidity and higher temperature conditions, warp The test crossing 10.5 h is still maintained for up to 850 A/cm2Electric current density, electric current density has only decayed 8.6%.Show system of the present invention Standby SiO2-MSCC material has from moisturization, is the ideal chose of fuel cell membrane electrode associated materials.
Embodiment 2
(1) SiO2The preparation of-MSCC-2h material:
1) amount taking L-arginine, hexamethylene and water is respectively 82 mg, 4.2 mL and 90 mL, under 40 DEG C of stirring conditions fully Dissolve, obtain mixed liquor A；
2) 5.2 mL tetraethyl orthosilicates are added step 1 with the speed of 2 drops/sec) in gained mixed liquor A, keep temperature to continue to stir Mix 18 h, obtain silicon oxide pellets mother solution B；
3) toward step 2) gained silicon oxide pellets mother solution B adds with 45 mL hexamethylene, 24 mL tetraethyl orthosilicates and 300 The growth-promoting media that mL water is made into, keeps temperature to continue stirring 22.5 h, obtains silicon dioxide gel C；
4) toward step 3) in gained silica dioxide gel C, add 0.5 g PVP-k10 and 0.5 g PVP-k15, mixed Liquid D;
5) by step 4) the pH value concentrated hydrochloric acid of gained mixed liquor D is adjusted to 0.15, continuously stirred lower adds 18.7 in mixed liquor D ML aniline, then instill 280 mL pH value be 0.15, hydrochloric acid solution containing 70 g Ammonium persulfate .s, then keep at 7.5 DEG C The stir speed (S.S.) of 600 revs/min stirs 30 h, is then evaporated at 90 DEG C, obtains silicon dioxide/Polyaniline;
6) by step 5) silicon dioxide/Polyaniline of obtaining under nitrogen atmosphere, with the heating rate of 9.5 DEG C/min It is warming up to 800 DEG C, keeps 2 h, be cooled to room temperature, obtain C-N/ silica composite；
7) by step 6) the C-N/ silica composite that obtains, by the corresponding 25 mL NaOH of 1 g C-N/ silica composite The amount of solution mixes with the NaOH solution of 2 mol/L, etching processing 2 h at 85 DEG C, through filtering, washing and do after cooling Dry, obtain sample SiO2-MSCC-2h material.
(2)SiO2The pretreatment of-MSCC-2h material.By SiO2-MSCC-2h adds 10 times of SiO2-MSCC-2h quality of materials Acetone in stir 3 h, be dried 12 h at vacuum tank after filtering and wash 3 times.Then dried sample is added 50 times of SiO2- The HNO of 10 wt% of MSCC-2h quality of materials3With H2O2Mixed liquor in (volume ratio HNO3: H2O2 =2:1), in 80 DEG C Reflux 8 h.It is dried in vacuum drying oven after filtration washing 5 times, then by dried sample at N2The lower 300 DEG C of process of atmosphere 3 h。
(3)Pt/SiO2The preparation of-MSCC catalyst: first 56.5 mg sodium citrates are dissolved in 30 mL ethylene glycol, ultrasonic 60 minutes, add 2.0 mL six and be hydrated the ethylene glycol solution (20 mg/mL) of chloroplatinic acid, stir 30 minutes, be subsequently adding pre-place The SiO managed2-MSCC-2h material 85 mg, ultrasonic 60 minutes, after regulating pH of mixed=10 with the KOH/EG solution of 5 wt%, It is transferred to, in politef in the reactor in village, react 6 h at 120 DEG C.After cooling with the HNO of 10wt%3Solution regulation pH =3.5, wash 5 times after filtration, be dried 12 h at vacuum drying oven, i.e. can get 15wt% Pt/SiO2-MSCC-2h catalyst.
Fig. 7 is 15 wt% Pt/SiO2The TEM figure of-MSCC-2h catalyst and corresponding Pt particle size distribution figure.By scheming 7 can be seen that Pt particle height is evenly dispersed on many spherical cavity carbon carrier, and the diameter of Pt nano-particle concentrates on 2 ~ 3.5 Between nm, show that many spherical cavity material with carbon element prepared by the present invention is preferable noble metal catalyst carrier material.
Embodiment 3
(1) SiO2The preparation of-MSCC-4h material:
1) amount taking L-arginine, hexamethylene and water is respectively 82 mg, 6.3 mL and 135 mL, fills under 80 DEG C of stirring conditions Divide and dissolve, obtain mixed liquor A；
2) 8.32 mL tetraethyl orthosilicates are added step 1 with the speed of 1.5 drops/sec) in gained mixed liquor A, keep temperature to continue Continuous stirring 24 h, obtain silicon oxide pellets mother solution B；
3) toward step 2) gained silicon oxide pellets mother solution B adds with 120 mL hexamethylene, 60 mL tetraethyl orthosilicates and 750 The growth-promoting media that mL water is made into, keeps temperature to continue stirring 30 h, obtains silicon dioxide gel C；
4) toward step 3) in gained silica dioxide gel C, add 0.625 g PVP-k17 and 0.625 g PVP-k30, obtain Mixed liquor D;
5) by step 4) the pH value concentrated hydrochloric acid of gained mixed liquor D is adjusted to 0.3, continuously stirred lower adds 31.7 in mixed liquor D ML aniline, then instill 634 mL pH value be 0.3, hydrochloric acid solution containing 190 g Ammonium persulfate .s, then keep at 15 DEG C The stir speed (S.S.) of 1200 revs/min stirs 48 h, is then evaporated at 90 DEG C, obtains silicon dioxide/Polyaniline;
6) by step 5) silicon dioxide/Polyaniline of obtaining under nitrogen atmosphere, with the heating rate liter of 15 DEG C/min Temperature, to 1000 DEG C, keeps 1 h, is cooled to room temperature, obtain C-N/ silica composite；
7) by step 6) the C-N/ silica composite that obtains, by the corresponding 25 mL NaOH of 1 g C-N/ silica composite The amount of solution mixes with the NaOH solution of 2 mol/L, etching processing 4 h at 120 DEG C, through filtering, washing and do after cooling Dry, obtain sample SiO2-MSCC-4h material.
Fig. 1, Fig. 3 are the SiO after NaOH etching processing 4 h2-MSCC material (is designated as SiO2-MSCC-4h) transmission electron microscope (TEM) photo and X-ray energy dispersion spectrum (EDS) figure.It will be seen from figure 1 that material particle size prepared by the present invention exists Between 100 nm ~ 200 nm, and in each granule, it is evenly distributed multiple diameter spherical cavity at about 20 nm, this The shape reverse of silicon oxide pellets is turned over by a little spherical cavity substantially, therefore shows that the present invention can be by controlling silicon oxide pellets Size realize SiO further2The size of spherical cavity in-MSCC material.The material that as can be seen from Figure 3 prepared by the present invention removes Outside containing C, Si and O, SiO prepared by the present invention2-MSCC material also has the miscellaneous former of electro-chemical activity doped with N and S etc. Son, illustrates SiO prepared by the present invention2-MSCC material can be used as the material relevant to eelctro-catalyst, and the present invention can be by control simultaneously The time of NaOH etching processing processed is to realize the modification amount of silicon dioxide on many spherical cavity material with carbon element, so that the material tool prepared There is moisturization.
Fig. 6 is SiO2The hydrogen reduction (ORR) in the saturated 0.1 mol/L KOH electrolyte of the oxygen of-MSCC-4h material is bent Line chart, the response type of many spherical cavity material with carbon element catalytic oxidation-reduction that as can be seen from Figure 6 prepared by the present invention is 4 electron reactions, print Demonstrate,prove material prepared by the present invention and there is certain catalytic oxidation-reduction activity, can be used as the material relevant to electro-catalysis.
(2)SiO2The pretreatment of-MSCC-4h material: by SiO2-MSCC-4h adds 10 times of SiO2-MSCC-4h quality of materials Acetone in stir 3h, be dried 12h at vacuum tank after filtering and wash 3 times.Then dried sample is added 50 times of SiO2- The HNO of 10 wt% of MSCC-4h quality of materials3With H2O2Mixed liquor in (volume ratio HNO3: H2O2 =2:1), at 80 DEG C Reflux 8 h.It is dried at vacuum drying oven, then by dried sample at N after filtration washing 5 times2Lower 300 DEG C of atmosphere processes 3 h。
(3)Pt/SiO2The preparation of-MSCC catalyst: first 30.2 mg sodium citrates are dissolved in 30 mL ethylene glycol, ultrasonic 60 minutes, add 1.06 mL six and be hydrated the ethylene glycol solution (20 mg/mL) of chloroplatinic acid, stir 30 minutes, be subsequently adding pre- The SiO processed2-MSCC-4h material 92 mg, ultrasonic 60 minutes, regulates pH of mixed=10.5 with the KOH/EG solution of 5 wt% After, it is transferred to, in politef in the reactor in village, react 6 h at 120 DEG C.After cooling with the HNO of 10wt%3Solution is adjusted Joint pH=3, wash 5 times after filtration, are dried 12 h at vacuum drying oven, i.e. can get 8wt% Pt/SiO2-MSCC-4h is catalyzed Agent.
Fig. 9 is 8 wt% Pt/SiO2-MSCC-4h catalyst is at the saturated 0.5 mol/L H of nitrogen2SO4Electrolyte solution The cyclic voltammetry curve (CV) recorded, and contrast with business platinum C catalyst contrast (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, reaches 111 m2/g。 Show SiO prepared by the present invention2-MSCC material is the ideal carrier preparing high activity noble metal catalyst.
Embodiment 4
(1) SiO2The preparation of-MSCC-0h material:
1) amount taking L-arginine, hexamethylene and water is respectively 82 mg, 6.3 mL and 135 mL, fills under 80 DEG C of stirring conditions Divide and dissolve, obtain mixed liquor A；
2) 8.32 mL tetraethyl orthosilicates are added step 1 with the speed of 2 drops/sec) in gained mixed liquor A, keep temperature to continue Stir 20 h, obtain silicon oxide pellets mother solution B；
3) toward step 2) gained silicon oxide pellets mother solution B adds with 120 mL hexamethylene, 60 mL tetraethyl orthosilicates and 750 The growth-promoting media that mL water is made into, keeps temperature to continue stirring 24 h, obtains silicon dioxide gel C；
4) toward step 3) in gained silica dioxide gel C, add 0.625 g PVP-k10 and 0.625 g PVP-k30, obtain Mixed liquor D；
5) by step 4) the pH value concentrated hydrochloric acid of gained mixed liquor D is adjusted to 0.3, continuously stirred lower adds 31.7 in mixed liquor D ML aniline, then instill 634 mL pH value be 0.3, hydrochloric acid solution containing 190 g Ammonium persulfate .s, then keep at 10 DEG C The stir speed (S.S.) of 1200 revs/min stirs 24 h, is then evaporated at 90 DEG C, obtains silicon dioxide/Polyaniline；
6) by step 5) silicon dioxide/Polyaniline of obtaining under nitrogen atmosphere, with the heating rate liter of 5 DEG C/min Temperature, to 800 DEG C, keeps 1 h, is cooled to room temperature, obtain C-N/ silica composite；
7) step 6) the C-N/ silica composite that obtains, do not carry out NaOH etching processing, etch period is 0 h, obtains sample Product SiO2-MSCC-0h material.
Fig. 2 is SiO2Transmission electron microscope (TEM) photo of-MSCC-0h.Figure it is seen that material prepared by the present invention Particle size is between 100 nm ~ 200 nm, and particle surface and inside are dispersed with SiO2, there is not the structure of spherical cavity in bead, This is owing to etch period is 0, SiO2Bead template is not removed and causes.And these hydrophilic SiO2Bead also makes preparation The material gone out has moisturization.
(2)SiO2The pretreatment of-MSCC-0h material: by SiO2-MSCC-0h adds 10 times of SiO2-MSCC-0h quality of materials Acetone in stir 3h, be dried 12h at vacuum tank after filtering and wash 3 times.Then dried sample is added 50 times of SiO2- The HNO of 10 wt% of MSCC-0h quality of materials3With H2O2Mixed liquor in (volume ratio HNO3: H2O2 =2:1), at 80 DEG C Reflux 8 h.It is dried at vacuum drying oven, then by dried sample at N after filtration washing 5 times2Lower 300 DEG C of atmosphere processes 3 h。
(3)Pt/SiO2The preparation of-MSCC catalyst: first 75 mg sodium citrates are dissolved in 30 mL ethylene glycol, ultrasonic 60 Minute, add 2.65 mL six and be hydrated the ethylene glycol solution (20 mg/mL) of chloroplatinic acid, stir 30 minutes, be subsequently adding pre-place The SiO managed2-MSCC-0h material 80 mg, ultrasonic 60 minutes, regulates pH of mixed=10.5 with the KOH/EG solution of 5 wt% After, it is transferred to, in politef in the reactor in village, react 6 h at 120 DEG C.After cooling with the HNO of 10wt%3Solution is adjusted Joint pH=3, wash 5 times after filtration, are dried 12 h at vacuum drying oven, i.e. can get 20 wt% Pt/SiO2-MSCC-0h is catalyzed Agent.
Fig. 8 is that the present invention prepares 20 wt% Pt/SiO2The XRD figure of-MSCC-0h catalyst.Existing respectively as we know from the figure 39.58 °, 46.36 °, 67.84 °, 81.20 ° and 85.71 ° occur in that (111), (200), (220), (311) and (222) of correspondence The diffraction maximum of crystal face, these five crystal faces belong to the feature crystal face of Emission in Cubic Pt, and in figure, the diffraction maximums 23.5 ° of appearance are material with carbon element Peak.It is about 3 nm by the particle size of Scherrer Equation for Calculating Pt, shows that Pt particle size prepared by the present invention is less, this The material with carbon element of bright preparation is the ideal carrier preparing small particle noble metal catalyst.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not limited by described embodiment System.The change made under any spirit without departing from the present invention and principle, modify, replace, combine, simplify, all should be The substitute mode of effect, within all comprising protection scope of the present invention.

Claims (10)

1. the preparation method of silicon dioxide modified many spherical cavity material with carbon element, it is characterised in that step is as follows:
(1) by L-arginine, hexamethylene, your ratio 1 of hydromassage: (50 ~ 150): (5000 ~ 15000) mixing, 40 DEG C ~ Fully dissolve under 80 DEG C of stirring conditions, obtain mixed liquor A；
(2) under 40 DEG C ~ 80 DEG C stirring conditions, tetraethyl orthosilicate is added step (1) gained with the speed of 1 ~ 2 drop/sec and mixes Closing in liquid A, wherein the mol ratio of L-arginine used is (20 ~ 80) to tetraethyl orthosilicate with step (1): 1, continues stirring 12 ~ 24 h, obtain silicon oxide pellets mother solution B；
(3) under 40 DEG C ~ 80 DEG C stirring conditions, by step (2) gained silicon oxide pellets mother solution B and hexamethylene, positive silicic acid Ethyl ester and water are 1 in mass ratio: (0.1 ~ 0.8): (0.08 ~ 0.4): (1 ~ 5) is made into growth-promoting media, continue stirring 15 ~ 30 h, obtain silicon dioxide gel C；
(4), under 40 DEG C ~ 80 DEG C stirring conditions, in step (3) in gained silica dioxide gel C, polyvinyl pyrrole is added Alkanone, wherein polyvinylpyrrolidone is 1 with the mass ratio of silica dioxide gel C: (60 ~ 120), obtains mixed liquor D;
(5) the pH value concentrated hydrochloric acid of step (4) gained mixed liquor D is adjusted to 0 ~ 0.3, continuously stirred under mix in mass ratio Liquid D: aniline is (15 ~ 30): 1 adds aniline in mixed liquor D, and then instilling Ammonium persulfate. mass fraction is 20 wt% ~ 30 wt%, pH are the aqueous solution E of 0 ~ 0.3, and wherein aqueous solution E is (10 ~ 20) with the mass ratio of aniline: 1, then exists Keep stir speed (S.S.) stirring 12 ~ 48 h of 300-1200 rev/min at 0 ~ 15 DEG C, be evaporated subsequently, i.e. can get titanium dioxide Silicon/Polyaniline;
(6) silicon dioxide/Polyaniline step (5) obtained is under nitrogen atmosphere, with the intensification of 2 ~ 15 DEG C/min Ramp, to 600 DEG C ~ 1000 DEG C, keeps 1 ~ 3 h, is cooled to room temperature, obtains C-N/ silica composite；
(7) the C-N/ silica composite that step (6) obtains is mixed with NaOH solution, at 50 ~ 120 DEG C at etching Reason 0 ~ 4 h, through being filtered, washed and dried after cooling, obtains silicon dioxide modified many spherical cavity material with carbon element, is labeled as SiO2- MSCC material.
The preparation method of a kind of silicon dioxide modified many spherical cavity material with carbon element the most according to claim 1, its feature exists In, described stirring is to stir with the stir speed (S.S.) of 300 ~ 1200 revs/min.
The preparation method of a kind of silicon dioxide modified many spherical cavity material with carbon element the most according to claim 1, it is characterised in that In step (3) gained silicon dioxide gel C, a diameter of 20 ~ 50 nm of silicon oxide pellets.
The preparation method of a kind of silicon dioxide modified many spherical cavity material with carbon element the most according to claim 1, it is characterised in that Step (4) described polyvinylpyrrolidone is one or more in PVP-k10, PVP-k15, PVP-k17 and PVP-k30.
The preparation method of a kind of silicon dioxide modified many spherical cavity material with carbon element the most according to claim 1, it is characterised in that In the described silicon dioxide modified many spherical cavity material with carbon element of step (7), a diameter of 10 ~ 40 nm of spherical cavity；Silicon dioxide modified many The granule of spherical cavity material with carbon element is directly 100 ~ 200nm.
The preparation method of a kind of silicon dioxide modified many spherical cavity material with carbon element the most according to claim 1, it is characterised in that Step (7) presses the amount of the corresponding 25 mL NaOH solution of 1 g C-N/ silica composite by C-N/ silica composite and 2 The NaOH solution mixing of mol/L.
7. a kind of silicon dioxide modified many spherical cavity material with carbon element prepared by the preparation method described in any one of claim 1-6 is made Carrier material and humidification materials application for fuel battery anode catalyst are in fuel cell membrane electrode.
Application the most according to claim 7, it is characterised in that the preparation method of described anode catalyst is as follows:
By SiO2It is stand-by that-MSCC material carries out pretreatment, then is dissolved in ethylene glycol by sodium citrate, ultrasonic 60 minutes, adds six The ethylene glycol solution of hydration chloroplatinic acid, stirs 30 minutes, is subsequently adding the pretreated SiO of 1 ~ 12 times of Pt mass2-MSCC Material, ultrasonic 60 minutes, regulates pH of mixed with the KOH/EG solution of 5 wt% > after 9, it is transferred to village in politef In reactor, react 6 h at 120 DEG C；After cooling with the HNO of 10 wt%3Solution regulation pH < 5, washes after filtration, very Empty drying baker is dried, i.e. can get many spherical cavity material with carbon element catalyst silicon dioxide modified for Pt/；Described six hydration chloroplatinic acids with It is 1: 2 ~ 2.5 with the mol ratio of sodium citrate.
Application the most according to claim 8, it is characterised in that described SiO2The pretreatment of-MSCC material, is by SiO2- MSCC material adds 10 times of SiO2The acetone of-MSCC quality of materials stirs 3 h, is dried at vacuum tank after filtering and washing, dry 50 times of SiO are added after dry2The HNO of 10 wt% of-MSCC quality of materials3With H2O2Mixed liquor in, the wherein HNO of 10 wt%3With H2O2Volume ratio is 2:1, and reflux at 80 DEG C 8 h, is dried, then by dried sample after filtration washing in vacuum drying oven Product are at N2Lower 300 DEG C of atmosphere processes 3 h.
Application the most according to claim 8, it is characterised in that the quality of the ethylene glycol dissolving sodium citrate is chloroplatinic acid 500 ~ 1000 times of quality.
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