CN108043437A - A kind of preparation method of hollow SiC carrier models Ir-Ru catalyst - Google Patents
A kind of preparation method of hollow SiC carrier models Ir-Ru catalyst Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000002243 precursor Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
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- 239000003513 alkali Substances 0.000 claims description 7
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- 239000003795 chemical substances by application Substances 0.000 claims description 3
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- 235000019441 ethanol Nutrition 0.000 claims description 2
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- MAZOHJVAXBNBPX-UHFFFAOYSA-N ruthenium hydrochloride Chemical compound Cl.[Ru] MAZOHJVAXBNBPX-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
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- 238000004321 preservation Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 2
- 102000010637 Aquaporins Human genes 0.000 description 1
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- 229910003978 SiClx Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
- B01J27/224—Silicon carbide
-
- B01J35/33—
-
- B01J35/397—
-
- B01J35/40—
-
- B01J35/50—
Abstract
The present invention provides a kind of preparation method of hollow SiC carrier models Ir Ru catalyst, including：It prepares nano-carbon powder, prepare SiO2The nano-carbon powder of cladding, the SiC nanospheres for preparing pure hollow-core construction and prepare product.Ir Ru catalyst utilizations greatly improved in method provided by the invention, improve the performance and stability of Ir Ru catalyst, improve the electro-chemical activity specific surface of catalyst, improve catalyst utilization, considerably reduce cost.By the way of batch microwave, the fine controlling reaction temperature of energy, temperature rises uniformly technical solution provided by the invention, reproducible.
Description
Technical field
The present invention relates to new energy and solid electrolyte battery technical fields, and in particular to a kind of solid electrolyte electrolytic cell
With the preparation method of hollow SiC carrier models Ir-Ru catalyst.
Background technology
With the development of economy, energy crisis getting worse, energy problem have become the great difficult problem that the world today faces,
The importance of new energy materials and its Land use systems is increasingly prominent.There are mainly three types of existing water electrolysis hydrogen production technologies：Alkaline water
It is electrolysed (AEC), soild oxide water electrolysis (solid oxide electrolytic cells, SOEC) and solid polymer electricity
Solve matter water electrolysis (SPE).Wherein, SPE water electrolyzers, can be close in high current with its small, efficient, generation hydrogen purity height
The advantages that spending lower longtime running is considered as most promising water electrolysis hydrogen production technology.The technology is public originating from General Electric (U.S.A.)
Take charge of the Proton Exchange Membrane Fuel Cells for space programme exploitation.SPE electrolytic cells are mainly made of two electrodes and thin polymer film,
Polymer film with proton exchange ability usually integrally changes structure with electrode catalyst.In this configuration, use is porous
Gas-diffusion electrode is close to proton exchange membrane both side surface as hydrogen-precipitating electrode and analysis oxygen electrode, electrode.Proton exchange membrane category
Perfluorinated sulfonic acid film type, includes SO3H groups, hydrone are broken down into oxygen and H in anode+, and SO3H is easy to resolve into SO3 -
And H+, H+With water molecules into H3O+, it is hydrogen to reach cathode and chemical combination through film under electric field action.SPE electrolytic cells are not required to
Electrolyte only needs pure water, than alkaline electrolytic bath safety and reliably.There is chemical stability, high matter using SPE as electrolyte
The advantages that sub- conductibility and good gas permeability.Due to higher proton-conducting, SPE electrolytic cells can be operated in higher
Electric current under, so as to increase electrolytic efficiency.And since SPE films are relatively thin, ohmic loss is reduced, also improves the effect of system
Rate.The efficiency of existing SPE electrolytic cells can reach 85% or more.
But since SPE electrolyte has highly acid (pH value is equivalent to 10%H2SO4 solution), catalyst generally use
Liberation of hydrogen is small with analysis oxygen overpotential and the platinum-group noble metals of strong corrosion resistant ability or its oxide, SPE electrolytic cells are also difficult at present
Input is large-scale to be used.In addition, for the SPE electrolysis pool technologies towards photoelectricity, wind-powered electricity generation electrolytic hydrogen production, electrolytic cell is developed
It should inherently consider the working condition directly powered using solar energy, wind energy rather than consider to use commercially available AC power supply,
It must take into consideration the unstability of new energy.Under unstable decomposition voltage, the meeting accelerated ageing of SPE electrolytic cells catalyst loses
Activity, this proposes higher requirement for the durability of catalyst of SPE electrolytic cells.
Based on reducing SPE electrolytic cells cost and improving the target of durability, for existing SPE electrolytic cells oxygen-separating catalyst skill
Art deficiency, the present invention provides a kind of preparation methods of hollow SiC carrier models Ir-Ru catalyst.Using hollow SiC balls conduct
The carrier of Ir-Ru improves the dispersion degree of Ir-Ru, increases operation rate, and then reduces cost；Simultaneously SiC due to chemical property it is steady
Fixed, thermal conductivity factor height, coefficient of thermal expansion is small, wear-resisting property is good, can for a long time stablize in the SPE electrolytic environments of highly acid, inhibits
The loss of Ir-Ru catalyst improves the durability of SPE electrolytic cells.
The content of the invention
It is an object of the invention to provide it is a kind of and meanwhile have the Pt/C of electronic conduction ability and proton conductivity catalysis
The preparation method of agent.
In order to achieve the above object, the present invention provides using following technical proposals：
A kind of preparation method of hollow SiC carrier models Ir-Ru catalyst, the preparation method include the following steps：
(1) nano-carbon powder is prepared；
(2) nano-carbon powder of SiO2 claddings is prepared；
(3) the SiC nanospheres of pure hollow-core construction are prepared；
(4) product is prepared.
Preferably, the step (1) includes the following steps：
A, 20~48h of glucose solution that concentration is 1%~10% is heated in 140~250 DEG C of water heating kettle, to taking out
Filter gained turbid solution is successively with repeatedly washing and the drying of deionized water and absolute ethyl alcohol；
B, the product ultrasonic disperse for taking 50~500nm grain sizes of the above-mentioned drying of 1~5g is water-soluble in 10~500mL sodium hydroxides
In liquid, the water-bath neutral and alkali processing at 90 DEG C filters, washs and dries and to obtain nano-carbon powder.
Preferably, the drying temperature is 30~80 DEG C.
Preferably, the concentration of the sodium hydroxide is 1mol/L~5mol/L.
Preferably, the step (2) includes the following steps：The nano-carbon powder of 1~5g obtained by step (2) is added in concentration is
In the ethanol solution of 1~5% 10~100mL ethyl orthosilicates, 10~500mL of hydrochloric acid of 0.1mol/L~1mol/L is added in,
After being aged 20~30h, centrifugal drying obtains the nano-carbon powder of SiO2 claddings.
Preferably, the step (3) includes the following steps：It is 1 by mass ratio：1：Nano-carbon powder, the Fe of 2 SiO2 claddings
Powder and NaF powder are put into 1~4h of heat preservation in 1100 DEG C under inert atmosphere~1500 DEG C vacuum drying ovens, and 1 is aoxidized at 600~800 DEG C
After~5h with HF clean hollow-core construction SiC nanospheres.
Preferably, the gas flow of the inert atmosphere is 30~200mL/min.
Preferably, the step (4) includes the following steps：By the SiC nanospheres, Ir precursor solutions, Ru of hollow-core construction
Mixture 10~20min of ultrasound of precursor solution, water and ethylene glycol continues 15~25min of ultrasound after adjusting pH value；In inertia
45s~5min is heated under atmosphere, filtering is dried and grinds to obtain hollow SiC carrier models Ir-Ru catalyst.
Preferably, the Ir precursor solutions include the ethylene glycol solution of chloro-iridic acid；The Ru precursor solutions of stating include
The ethylene glycol solution of ruthenium hydrochloride.
Preferably, the mass ratio of hollow SiC nanospheres and Ir-Ru presomas is 1：(1.5~4)；Ir-Ru presomas exist
Concentration in ethylene glycol is 0.012-0.02mol/L；The volume ratio of water and ethylene glycol is 1：6~10.
Preferably, the SiC nanospheres of the hollow-core construction, Ir precursor solutions, Ru precursor solutions, water and ethylene glycol
Ratio is 1：1：1：60：30.
Preferably, the pH value is 10~13.
Preferably, heating described in the step (4) with power be 700~900W, the microwave that temperature is 115~130 DEG C
Heating.
Preferably, it is described to be heated to be intermittent mode heating, often heat 10~30s, 5~15s of interval.
Preferably, the method is further included using pickling and deionization washing removal impurity metal ion.
A kind of catalyst as made from preparation method described in any one of the above embodiments, which is characterized in that the catalyst compares table
Area is 400~500m2/g；The electrochemical reduction area of the catalyst is 63~92m2/g.
Preferably, the Ir-Ru load capacity in the catalyst is 40~60wt, wherein the size of Ir-Ru particles for 2~
4nm。
Compared with the latest prior art, technical solution provided by the invention has the advantages that：
1st, Ir-Ru catalyst utilizations have been significantly increased in preparation method provided by the invention, pass through hollow Nano SiC
Sphere loads Ir-Ru particles, and the aquaporin, electron channel, proton for effectively increasing Ir-Ru particles and electrochemical reaction lead to
The multiphase contact of road, gas passage etc. improves the electro-chemical activity specific surface of catalyst, improves the utilization rate of catalyst,
Cost is greatly reduced.
2nd, the performance and stability of Ir-Ru catalyst can be substantially improved in preparation method provided by the invention.Hollow Nano SiC
Sphere loads Ir-Ru particles, and SiC nano particles can generate synergistic effect with Ir-Ru, and Ir-Ru catalyst is made to have very high oxygen
Reduction catalysts activity, and the hair of dissolving, reunion, electrochemistry the sintering failure procedure of Ir-Ru beaded catalysts can be effectively inhibited
It is raw.
3rd, preparation method of the invention is carried out by the way of batch microwave, the better controlling reaction temperature of energy, Wen Shengjun
It is even, it is reproducible.
4., the hollow SiC carrier models Ir-Ru catalyst for preparing of the present invention, Ir-Ru particle sizes are small, particle diameter distribution is uniform,
And degree of scatter is higher, catalyst performance is preferable and lasts a long time.
Description of the drawings
Fig. 1 is the TEM collection of illustrative plates of single carbon bead template prepared by embodiment 1；
Fig. 2 is SiC carrier XRD spectrums in embodiment 1；
Fig. 3 is single hollow SiC carrier models Ir-Ru catalyst collection of illustrative plates prepared by embodiment 1；
Fig. 4 is the electrolytic cell of hollow SiC carrier models Ir-Ru catalyst and existing Ir-Ru catalyst prepared by embodiment 1
Performance comparison；
Fig. 5 is the electrolytic cell of hollow SiC carrier models Ir-Ru catalyst and existing Ir-Ru catalyst prepared by embodiment 1
Stability compares.
Specific embodiment
Be described in further detail in the following with reference to the drawings and specific embodiments, technical scheme is carried out it is clear,
It is fully described by.
Embodiment 1
First, the preparation of catalyst
1st, 6g glucose is added in 100ml deionized waters, is sufficiently stirred dissolving, be then transferred into 200ml water heating kettles
In, when 140 DEG C of pyroreactions 20 are small, obtained brownish black turbid solution is filtered, washed respectively with deionized water and absolute ethyl alcohol
2 times, it is spare to obtain 2.3g nano carbon microspheres after product drying.
2nd, the above-mentioned nano carbon microspheres of 2.3g are taken, add in 0.5mol sodium hydroxides and 500ml deionized waters, through ultrasonic disperse and by force
After power stirs evenly, in 90 DEG C of water-baths obtaining surface after alkali treatment modifying, suction filtration, washing, drying respectively contains abundant hydroxyl
The nano-carbon powder of base and carboxylic group.
3rd, above-mentioned nano-carbon powder is added in the ethanol water of ethyl orthosilicate [Si (OC2H5) 4, TEOS] (1%), then
0.1mol/L hydrochloric acid is added in, is slowly stirred at a room temperature after a certain period of time, under the action of electrostatic adsorption force, nano-carbon powder surface layer
SiO can be coated2, after being aged 20h, SiO is obtained after centrifugal drying2The nano-carbon powder structure of cladding；
4th, SiO will be obtained after above-mentioned centrifugal drying2The nano-carbon powder structure of cladding presses 1:1:2 ratio adds Fe powder and NaF
Powder mixes, and is placed in graphite crucible, is put into (1100 DEG C) conversions of vacuum drying oven high temperature, and when heat preservation 1 is small, (stream is protected using argon gas
Measure 30mL/min), make the SiO of nano-carbon powder and its surface2Pyroreaction generates SiC.The sample obtained after conversion carries out 700 DEG C
Aoxidize 1 it is small when, remove unreacted C, and clean in HF acid remaining SiO2, obtain the SiC nanometers of pure hollow-core construction
Ball.
5th, by the SiC nanospheres of above-mentioned hollow-core construction, Ir precursor solutions, Ru precursor solutions, water, ethylene glycol according to 1:
1:1:60:30 mixing, ultrasonic 10min, addition lye adjusting pH make to be uniformly mixed in 10, continuation ultrasound 15min.After ultrasound
Mixed liquor be placed in microwave reactor, be stirred to react liquid, be first passed through N2The air in reaction solution is excluded, then in lasting stirring
Under conditions of using microwave radiation make reaction solution heating heating；The power of microwave is controlled as 700W, the control of microwave reaction temperature exists
115 DEG C, catalyst cake is obtained by filtration in reaction time 45s；
6th, by filtration cakes torrefaction, grinding obtains hollow SiC carrier models Ir-Ru catalyst.
2nd, performance test
1st, as shown in Figure 1, the TEM collection of illustrative plates of the nano carbon microsphere obtained for 1 step 1 of embodiment, as seen from the figure, the present invention are closed
Into carbon bead template grain size in 100nm or so.
2nd, as shown in Fig. 2, the XRD spectrum of the SiC nanospheres obtained for 1 step 4 of embodiment.As seen from the figure, positioned at 36 °,
60 ° and 72 ° of peak be carborundum 3 strong peaks, correspond to SiC (111), (220) and (311) crystallographic plane diffraction peak position respectively, with β-
SiC, that is, 3C-SiC spectral lines peak corresponds to.The phase composition of SiC nanospheres be monocrystalline silicon carbide, crystalline form be cubic structure 3C-SiC, carbon
SiClx purity is high.
3rd, as shown in figure 3, for embodiment 1 obtain hollow SiC carrier models Ir-Ru catalyst TEM collection of illustrative plates, with single carbon
Based on bead template, hollow SiC carrier model Ir-Ru catalyst of the grain size in 100nm or so has been prepared.
Hollow SiC carrier models Ir-Ru catalyst obtained above is prepared into membrane electrode respectively, is assembled into electrolytic cell, 80
Electrolysis test is carried out under DEG C normal pressure, electrolysis estimation of stability is electrolytic cell in 80 DEG C, normal pressure, 1A/cm2 and periodic running situation
Lower progress, decomposition voltage is investigated with accumulated running time situation of change, and the result is shown in Fig. 4 and Fig. 5.
It can be seen that from Fig. 4 and Fig. 5, compared with traditional Ir-Ru oxygen-separating catalysts, urged using hollow SiC carrier models Ir-Ru
The electrolysis performance and stability of agent are all improved largely.
Embodiment 2
1st, 6g glucose is added in 100ml deionized waters, is sufficiently stirred dissolving, be then transferred into 200ml water heating kettles
In, when 250 DEG C of pyroreactions 48 are small, obtained brownish black turbid solution is filtered, washed respectively with deionized water and absolute ethyl alcohol
3 times, it is spare to obtain 2.3g nano carbon microspheres after product drying.
2nd, the above-mentioned nano carbon microspheres of 2.3g are taken, add in 0.6mol sodium hydroxides and 500ml deionized waters, through ultrasonic disperse and by force
After power stirs evenly, alkali treatment modifying is distinguished in 90 DEG C of water-baths, obtaining surface after suction filtration, washing, drying contains abundant hydroxyl
The nano-carbon powder of base and carboxylic group.
The 3rd, above-mentioned nano-carbon powder is added in the ethanol water of ethyl orthosilicate [Si (OC2H5) 4, TEOS] (1~5%)
In, 1mol/L hydrochloric acid 500mL are added, are slowly stirred at a room temperature after a certain period of time, under the action of electrostatic adsorption force, nanometer
Carbon dust surface layer can coat SiO2, after being aged 30h, SiO is obtained after centrifugal drying2The nano-carbon powder structure of cladding；
4th, SiO will be obtained after above-mentioned centrifugal drying2The nano-carbon powder structure of cladding presses 1:1:2 ratio adds Fe powder and NaF
Powder mixes, and is placed in graphite crucible, is put into (1500 DEG C) conversions of vacuum drying oven high temperature, and when heat preservation 4 is small, (stream is protected using argon gas
Measure 200mL/min), make the SiO of nano-carbon powder and its surface2Pyroreaction generates SiC.The sample obtained after conversion carries out 700
When DEG C oxidation 5 is small, unreacted C is removed, and cleans in HF acid remaining SiO2, the SiC for obtaining pure hollow-core construction receives
Rice ball.
5th, by the SiC nanospheres of above-mentioned hollow-core construction, Ir precursor solutions, Ru precursor solutions, water, ethylene glycol according to 1:
1:1:60:30 ratio mixing, ultrasonic 20min, addition lye adjusting pH make to be uniformly mixed in 13, continuation ultrasound 25min.It will
Mixed liquor after ultrasound is placed in microwave reactor, is stirred to react liquid, is first passed through N2The air in reaction solution is excluded, is then being held
Make reaction solution heating heating using microwave radiation under conditions of continuous stirring；The power of microwave is controlled as 900W, microwave reaction temperature
At 130 DEG C, catalyst cake is obtained by filtration in reaction time 5min for control；
6th, by filtration cakes torrefaction, grinding obtains hollow SiC carrier models Ir-Ru catalyst.
Embodiment 3
1st, 6g glucose is added in 100ml deionized waters, is sufficiently stirred dissolving, be then transferred into 200ml water heating kettles
In, when 200 DEG C of pyroreactions 36 are small, obtained brownish black turbid solution is filtered, washed respectively with deionized water and absolute ethyl alcohol
3 times, it is spare to obtain 2.3g nano carbon microspheres after product drying.
2nd, the above-mentioned nano carbon microspheres of 2.3g are taken, 2mol sodium hydroxides and 500ml deionized waters are added in, through ultrasonic disperse and strength
After stirring evenly, alkali treatment modifying is distinguished in 90 DEG C of water-baths, obtaining surface after suction filtration, washing, drying contains abundant hydroxyl
With the nano-carbon powder of carboxylic group.
(3) above-mentioned nano-carbon powder is added in the ethanol water of ethyl orthosilicate [Si (OC2H5) 4, TEOS] (1~5%)
In, 0.5mol/L hydrochloric acid 500mL are added, are slowly stirred at a room temperature after a certain period of time, under the action of electrostatic adsorption force, are received
Rice carbon dust surface layer can coat SiO2, after being aged 25h, SiO is obtained after centrifugal drying2The nano-carbon powder structure of cladding；
(4) SiO will be obtained after above-mentioned centrifugal drying2The nano-carbon powder structure of cladding presses 1:1:2 ratio adds Fe powder and NaF
Powder mixes, and is placed in graphite crucible, is put into (1200 DEG C) conversions of vacuum drying oven high temperature, and when heat preservation 3 is small, (stream is protected using argon gas
Measure 100mL/min), make the SiO of nano-carbon powder and its surface2Pyroreaction generates SiC.The sample obtained after conversion carries out 700
When DEG C oxidation 3 is small, unreacted C is removed, and cleans in HF acid remaining SiO2, the SiC for obtaining pure hollow-core construction receives
Rice ball.
(5) by the SiC nanospheres of above-mentioned hollow-core construction, Ir precursor solutions, Ru precursor solutions, water, ethylene glycol according to
1:1:1:60:30 ratio mixing, ultrasonic 15min, addition lye adjusting pH make to be uniformly mixed in 12, continuation ultrasound 20min.
Mixed liquor after ultrasound is placed in microwave reactor, liquid is stirred to react, is first passed through N2Exclude the air in reaction solution, Ran Hou
Make reaction solution heating heating using microwave radiation under conditions of lasting stirring；The power of microwave is controlled as 800W, microwave reaction temperature
At 120 DEG C, catalyst cake is obtained by filtration in reaction time 2min for degree control；
(6) by filtration cakes torrefaction, grinding obtains hollow SiC carrier models Ir-Ru catalyst.
Embodiment 4
(1) 6g glucose is added in 100ml deionized waters, is sufficiently stirred dissolving, be then transferred into 200ml water heating kettles
In, when 160 DEG C of pyroreactions 25 are small, obtained brownish black turbid solution is filtered, washed respectively with deionized water and absolute ethyl alcohol
3 times, it is spare to obtain 2.3g nano carbon microspheres after product drying.
(2) take the above-mentioned nano carbon microspheres of 2.3g, add in 2.5mol sodium hydroxides and 500ml deionized waters, through ultrasonic disperse and
After strong stirring is uniform, in 90 DEG C of water-baths distinguish alkali treatment modifying, filter, washing, drying after obtain surface contain it is abundant
The nano-carbon powder of hydroxyl and carboxylic group.
(3) above-mentioned nano-carbon powder is added in the ethanol water of ethyl orthosilicate [Si (OC2H5) 4, TEOS] (1~5%)
In, 0.6mol/L hydrochloric acid 500mL are added, are slowly stirred at a room temperature after a certain period of time, under the action of electrostatic adsorption force, are received
Rice carbon dust surface layer can coat SiO2, after ageing for 24 hours, SiO is obtained after centrifugal drying2The nano-carbon powder structure of cladding；
(4) SiO will be obtained after above-mentioned centrifugal drying2The nano-carbon powder structure of cladding presses 1:1:2 ratio adds Fe powder and NaF
Powder mixes, and is placed in graphite crucible, is put into (1300 DEG C) conversions of vacuum drying oven high temperature, and when heat preservation 2 is small, (stream is protected using argon gas
Measure 120mL/min), make the SiO of nano-carbon powder and its surface2Pyroreaction generates SiC.The sample obtained after conversion carries out 700
When DEG C oxidation 5 is small, unreacted C is removed, and cleans in HF acid remaining SiO2, the SiC for obtaining pure hollow-core construction receives
Rice ball.
(5) by the SiC nanospheres of above-mentioned hollow-core construction, Ir precursor solutions, Ru precursor solutions, water, ethylene glycol according to
1:1:1:60:30 ratio mixing, ultrasonic 13min, addition lye adjusting pH make to be uniformly mixed in 11, continuation ultrasound 18min.
Mixed liquor after ultrasound is placed in microwave reactor, liquid is stirred to react, is first passed through N2Exclude the air in reaction solution, Ran Hou
Make reaction solution heating heating using microwave radiation under conditions of lasting stirring；The power of microwave is controlled as 750W, microwave reaction temperature
At 125 DEG C, catalyst cake is obtained by filtration in reaction time 3min for degree control；
(6) by filtration cakes torrefaction, grinding obtains hollow SiC carrier models Ir-Ru catalyst.
Embodiment 5
(1) 6g glucose is added in 100ml deionized waters, is sufficiently stirred dissolving, be then transferred into 200ml water heating kettles
In, when 200 DEG C of pyroreactions 36 are small, obtained brownish black turbid solution is filtered, washed respectively with deionized water and absolute ethyl alcohol
2 times, it is spare to obtain 2.3g nano carbon microspheres after product drying.
(2) take the above-mentioned nano carbon microspheres of 2.3g, add in 1.2mol sodium hydroxides and 500ml deionized waters, through ultrasonic disperse and
After strong stirring is uniform, in 90 DEG C of water-baths distinguish alkali treatment modifying, filter, washing, drying after obtain surface contain it is abundant
The nano-carbon powder of hydroxyl and carboxylic group.
(3) above-mentioned nano-carbon powder is added in the ethanol water of ethyl orthosilicate [Si (OC2H5) 4, TEOS] (1~5%)
In, 0.4mol/L hydrochloric acid 50mL are added, are slowly stirred at a room temperature after a certain period of time, under the action of electrostatic adsorption force, are received
Rice carbon dust surface layer can coat SiO2, after being aged 26h, SiO is obtained after centrifugal drying2The nano-carbon powder structure of cladding；
(4) SiO will be obtained after above-mentioned centrifugal drying2The nano-carbon powder structure of cladding presses 1:1:2 ratio adds Fe powder and NaF
Powder mixes, and is placed in graphite crucible, is put into (1150 DEG C) conversions of vacuum drying oven high temperature, and when heat preservation 4 is small, (stream is protected using argon gas
Measure 50mL/min), make the SiO of nano-carbon powder and its surface2Pyroreaction generates SiC.The sample obtained after conversion carries out 700 DEG C
Aoxidize 2.5 it is small when, remove unreacted C, and clean in HF acid remaining SiO2, the SiC for obtaining pure hollow-core construction receives
Rice ball.
(5) by the SiC nanospheres of above-mentioned hollow-core construction, Ir precursor solutions, Ru precursor solutions, water, ethylene glycol according to
1:1:1:60:30 ratio mixing, ultrasonic 16min, addition lye adjusting pH make to be uniformly mixed in 12, continuation ultrasound 23min.
Mixed liquor after ultrasound is placed in microwave reactor, liquid is stirred to react, is first passed through N2Exclude the air in reaction solution, Ran Hou
Make reaction solution heating heating using microwave radiation under conditions of lasting stirring；The power of microwave is controlled as 750W, microwave reaction temperature
At 125 DEG C, catalyst cake is obtained by filtration in reaction time 1min for degree control；
(6) by filtration cakes torrefaction, grinding obtains hollow SiC carrier models Ir-Ru catalyst.
The above embodiments are merely illustrative of the technical solutions of the present invention rather than is limited, the common skill of fields
Art personnel, which should be appreciated that, can be modified or replaced equivalently the specific embodiment of the present invention with reference to above-described embodiment,
These are applying for pending claim protection model without departing from any modification of spirit and scope of the invention or equivalent substitution
Within enclosing.
Claims (17)
1. a kind of preparation method of hollow SiC carrier models Ir-Ru catalyst, which is characterized in that the preparation method includes as follows
Step：
(1) nano-carbon powder is prepared；
(2) SiO is prepared2The nano-carbon powder of cladding；
(3) the SiC nanospheres of pure hollow-core construction are prepared；
(4) product is prepared.
2. preparation method according to claim 1, which is characterized in that the step (1) includes the following steps：
A, 20~48h of glucose solution that concentration is 1%~10% is heated in 140~250 DEG C of water heating kettle, to filtering institute
Turbid solution is obtained successively with repeatedly washing and the drying of deionized water and absolute ethyl alcohol；
B, the product ultrasonic disperse of 50~500nm grain sizes of the above-mentioned drying of 1~5g is taken in 10~500mL sodium hydrate aqueous solutions
In, the water-bath neutral and alkali processing at 90 DEG C filters, washs and dries and to obtain nano-carbon powder.
3. preparation method according to claim 2, which is characterized in that the drying temperature is 30~80 DEG C.
4. preparation method according to claim 2, which is characterized in that the concentration of the sodium hydroxide for 1mol/L~
5mol/L。
5. preparation method according to claim 1, which is characterized in that the step (2) includes the following steps：By step
(2) nano-carbon powder of 1~5g of gained is added in the ethanol solution for 10~100mL ethyl orthosilicates that concentration is 1~5%, is added in
10~500mL of hydrochloric acid of 0.1mol/L~1mol/L, after being aged 20~30h, centrifugal drying obtains SiO2The nano-carbon powder of cladding.
6. preparation method according to claim 1, which is characterized in that the step (3) includes the following steps：By mass ratio
For 1：1：2 SiO2Nano-carbon powder, Fe powder and the NaF powder of cladding are put into 1100 DEG C under inert atmosphere~1500 DEG C vacuum drying ovens
Keep the temperature 1~4h, at 600~800 DEG C aoxidize 1~5h after with HF clean hollow-core construction SiC nanospheres.
7. preparation method according to claim 6, which is characterized in that the gas flow of the inert atmosphere for 30~
200mL/min。
8. preparation method according to claim 1, which is characterized in that the step (4) includes the following steps：By hollow knot
The SiC nanospheres of structure, Ir precursor solutions, Ru precursor solutions, mixture 10~20min of ultrasound of water and ethylene glycol, are adjusted
Continue 15~25min of ultrasound after pH value；45s~5min is heated under an inert atmosphere, and filtering is dried and grind to obtain hollow SiC loads
Build Ir-Ru catalyst.
9. preparation method according to claim 8, which is characterized in that the Ir precursor solutions include the second two of chloro-iridic acid
Alcoholic solution；The Ru precursor solutions of stating include the ethylene glycol solution of ruthenium hydrochloride.
10. preparation method according to claim 8, which is characterized in that hollow SiC nanospheres and Ir-Ru presomas
Mass ratio is 1：(1.5~4)；Concentration of the Ir-Ru presomas in ethylene glycol is 0.012-0.02mol/L；Water and ethylene glycol
Volume ratio is 1：6~10.
11. preparation method according to claim 10, which is characterized in that the SiC nanospheres of the hollow-core construction, Ir forerunner
Liquid solution, Ru precursor solutions, the ratio of water and ethylene glycol are 1：1：1：60：30.
12. preparation method according to claim 8, which is characterized in that the pH value is 10~13.
13. preparation method according to claim 8, which is characterized in that heating described in the step (4) is with power
700~900W, the microwave heating that temperature is 115~130 DEG C.
14. preparation method according to claim 13, which is characterized in that it is described to be heated to be intermittent mode heating, often heat
10~30s, 5~15s of interval.
15. preparation method according to claim 8, which is characterized in that the method is further included using pickling and deionization
Washing removal impurity metal ion.
16. a kind of catalyst as made from claim 1~15 any one of them preparation method, which is characterized in that described to urge
Agent specific surface area is 400~500m2/g；The electrochemical reduction area of the catalyst is 63~92m2/g。
17. catalyst according to claim 16, which is characterized in that Ir-Ru load capacity in the catalyst for 40~
60wt, the wherein size of Ir-Ru particles are 2~4nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108531932A (en) * | 2018-04-11 | 2018-09-14 | 郑州大学 | A kind of hollow carbon sphere encapsulation Ru nano particle electrolysis water catalyst and preparation method thereof |
| CN109036857A (en) * | 2018-09-17 | 2018-12-18 | 张军 | A kind of carbon-based dye-sensitized solar cells is to electrode and preparation method thereof |
| CN111392728A (en) * | 2020-02-28 | 2020-07-10 | 山东天岳先进材料科技有限公司 | Raw material for producing silicon carbide crystal and preparation method and application thereof |
| CN115301262A (en) * | 2022-07-06 | 2022-11-08 | 福州大学 | Composite photocatalyst material with sea urchin ball morphology and preparation method and application thereof |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124538A (en) * | 1964-05-28 | 1978-11-07 | Shell Oil Company | Catalyst comprising Ir or Ir and Ru for hydrazine decomposition |
| JPH08155295A (en) * | 1994-05-31 | 1996-06-18 | Corning Inc | Carbon body and preparation thereof |
| JP2004105920A (en) * | 2002-09-20 | 2004-04-08 | Asahi Kasei Chemicals Corp | Photocatalyst-carrying structural body |
| JP2006176924A (en) * | 2004-12-22 | 2006-07-06 | Japan Atomic Energy Agency | Method for controlling wall thickness of silicon carbide microtube by irradiation under cooling |
| CN1830554A (en) * | 2004-03-10 | 2006-09-13 | 罗姆和哈斯公司 | Modified catalysts and process |
| CN1921194A (en) * | 2006-08-17 | 2007-02-28 | 武汉理工大学 | Proton conducter modified fuel cell catalyst using conductive ceramics as carrier and its preparation |
| CN1927451A (en) * | 2006-09-22 | 2007-03-14 | 中国海洋大学 | Method for preparation of nano powder |
| CN101041437A (en) * | 2007-03-07 | 2007-09-26 | 福州大学 | Raw material formulation and method for low-temperature silicon carbide synthesization |
| CN101428217A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Catalyst selective oxidation reaction of hydrogen gas |
| CN101638796A (en) * | 2009-06-29 | 2010-02-03 | 新奥科技发展有限公司 | Preparation method of anode catalyst for water electrolysis reaction |
| CN101733095A (en) * | 2008-11-12 | 2010-06-16 | 中国科学院大连化学物理研究所 | Catalyst for water electrolysis and preparation and application thereof |
| WO2012126338A1 (en) * | 2011-03-18 | 2012-09-27 | 上海交通大学 | Silicon-carbon composite cathode material for lithium ion battery and preparation method thereof |
| CN103157467A (en) * | 2011-12-14 | 2013-06-19 | 中国科学院大连化学物理研究所 | Ru and / or Ir noble metal oxide and application thereof to oxygen evolution electro-catalysis |
| US20130345048A1 (en) * | 2011-11-30 | 2013-12-26 | University Of Notre Dame Du Lac | Glass catalysts for soot combustion and methods of manufacturing the same |
| CN105236411A (en) * | 2015-10-12 | 2016-01-13 | 湖北朗驰新型材料有限公司 | High-specific surface area nanometer mesoporous silicon carbide hollow ball and preparation method thereof |
| CN106744967A (en) * | 2016-12-01 | 2017-05-31 | 中国科学院理化技术研究所 | A kind of preparation method of silicon carbide powder |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101700495B (en) * | 2009-11-04 | 2011-09-07 | 河北工业大学 | Composite catalyst of silica-coated multi-metal nanoparticles and activated carbon powder and preparation method and application thereof |
-
2017
- 2017-11-09 CN CN201711099848.4A patent/CN108043437B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4124538A (en) * | 1964-05-28 | 1978-11-07 | Shell Oil Company | Catalyst comprising Ir or Ir and Ru for hydrazine decomposition |
| JPH08155295A (en) * | 1994-05-31 | 1996-06-18 | Corning Inc | Carbon body and preparation thereof |
| JP2004105920A (en) * | 2002-09-20 | 2004-04-08 | Asahi Kasei Chemicals Corp | Photocatalyst-carrying structural body |
| CN1830554A (en) * | 2004-03-10 | 2006-09-13 | 罗姆和哈斯公司 | Modified catalysts and process |
| JP2006176924A (en) * | 2004-12-22 | 2006-07-06 | Japan Atomic Energy Agency | Method for controlling wall thickness of silicon carbide microtube by irradiation under cooling |
| CN1921194A (en) * | 2006-08-17 | 2007-02-28 | 武汉理工大学 | Proton conducter modified fuel cell catalyst using conductive ceramics as carrier and its preparation |
| CN1927451A (en) * | 2006-09-22 | 2007-03-14 | 中国海洋大学 | Method for preparation of nano powder |
| CN101041437A (en) * | 2007-03-07 | 2007-09-26 | 福州大学 | Raw material formulation and method for low-temperature silicon carbide synthesization |
| CN101428217A (en) * | 2007-11-07 | 2009-05-13 | 中国石油化工股份有限公司 | Catalyst selective oxidation reaction of hydrogen gas |
| CN101733095A (en) * | 2008-11-12 | 2010-06-16 | 中国科学院大连化学物理研究所 | Catalyst for water electrolysis and preparation and application thereof |
| CN101638796A (en) * | 2009-06-29 | 2010-02-03 | 新奥科技发展有限公司 | Preparation method of anode catalyst for water electrolysis reaction |
| WO2012126338A1 (en) * | 2011-03-18 | 2012-09-27 | 上海交通大学 | Silicon-carbon composite cathode material for lithium ion battery and preparation method thereof |
| US20130345048A1 (en) * | 2011-11-30 | 2013-12-26 | University Of Notre Dame Du Lac | Glass catalysts for soot combustion and methods of manufacturing the same |
| CN103157467A (en) * | 2011-12-14 | 2013-06-19 | 中国科学院大连化学物理研究所 | Ru and / or Ir noble metal oxide and application thereof to oxygen evolution electro-catalysis |
| CN105236411A (en) * | 2015-10-12 | 2016-01-13 | 湖北朗驰新型材料有限公司 | High-specific surface area nanometer mesoporous silicon carbide hollow ball and preparation method thereof |
| CN106744967A (en) * | 2016-12-01 | 2017-05-31 | 中国科学院理化技术研究所 | A kind of preparation method of silicon carbide powder |
Non-Patent Citations (9)
| Title |
|---|
| JUN LI等: "Preparation of hollow mesoporous silica spheres by a sol-gel/emulsion approach", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| JUN LI等: "Preparation of hollow mesoporous silica spheres by a sol-gel/emulsion approach", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 127, no. 1, 31 January 2010 (2010-01-31), pages 67 - 72, XP026734289, DOI: 10.1016/j.micromeso.2009.06.028 * |
| SEONG-CHEOL NOH等: "Synthesis of thermally stable porous SiC hollow spheres and control of the shell thickness", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| SEONG-CHEOL NOH等: "Synthesis of thermally stable porous SiC hollow spheres and control of the shell thickness", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 199, 15 November 2014 (2014-11-15), pages 11 - 17 * |
| 欧阳海波等: "不同纳米结构SiC的光催化性能研究", 《陕西科技大学学报》 * |
| 欧阳海波等: "不同纳米结构SiC的光催化性能研究", 《陕西科技大学学报》, vol. 33, no. 4, 31 August 2015 (2015-08-31), pages 46 * |
| 王海燕: "SPE电解池用新型SiC担载析氧电催化的研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技辑》 * |
| 王海燕: "SPE电解池用新型SiC担载析氧电催化的研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技辑》, 15 June 2010 (2010-06-15), pages 51 - 52 * |
| 赵丽娟等: "RuO2-IrO2-TiO2析氧催化剂的制备工艺", 《电池》, pages 19 - 22 * |
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