CN105060355B

CN105060355B - Preparation method of ultrafine RuO2 nanoparticles

Info

Publication number: CN105060355B
Application number: CN201510477249.6A
Authority: CN
Inventors: 郑明波; 林子夏; 施毅; 赵斌; 濮琳
Original assignee: Nanjing University
Current assignee: Nanjing University
Priority date: 2015-08-06
Filing date: 2015-08-06
Publication date: 2017-01-18
Anticipated expiration: 2035-08-06
Also published as: CN105060355A

Abstract

The invention provides a preparation method of ultrafine RuO2 nanoparticles. The method includes: mixing a surfactant P123, 1M hydrochloric acid and ethanol according to a mass ratio of 1:0.1-0.3:3-7, then adding 2-2.5 by mass of tetraethyl orthosilicate, and conducting stirring to obtain an initial solution; pouring the initial solution into an evaporation dish, performing standing for 36-48h, hydrolyzing tetraethyl orthosilicate to form silicon dioxide filling soft template gaps; standing ethanol to volatilize so as to obtain a block; annealing the obtained silicon dioxide block; putting the obtained SiO2 template in a culture dish, adding RuCl3's ethanol solution containing 0.38g Ru in per 5-7mL solution to the SiO2 template, i.e. a hard template, conducting annealing at 300-600DEG C in air, performing soaking in excess HF with a concentration of over 8wt%, removing the SiO2 template, conducting cleaning with deionized water, and performing drying, thus obtaining the ultrafine RuO2 nanoparticles.

Description

A kind of ultra-fine ruo2The preparation method of nanoparticle

Technical field

The present invention relates to the field of material technology of ultracapacitor, lithium-air battery is and in particular to a kind of ordered porous knot Structure ruo₂Material and preparation method thereof.

Background technology

ruo₂In ultracapacitor and lithium-air battery field, there iss important and excellent performance.ruo₂As super During the electrode material of capacitor, there is very high ratio electric capacity (768f/g), be optimal electrode of super capacitor material at present One of material.

And during as lithium-air battery electrode material, ruo₂Excellent electro catalytic activity can be shown, can effectively reduce electricity The overvoltage in pond.

If by ruo₂Make nanostructured, the specific surface area of material can be increased, thus increasing connecing of material and electrolyte Contacting surface is amassed.For ultracapacitor, high-specific surface area can effectively increase and compares capacitance；For lithium-air battery, High-specific surface area can improve ruo₂Catalytic effect.Additionally, nanostructured is conducive to transmission in nanostructured for the electrolyte, make Electrolysis liquid energy is goed deep into inside electrode material, thus improving the high rate performance of ultracapacitor or battery.

Use sio at present₂Hard template method prepares ultra-fine ruo₂Nanoparticle yet there are no pertinent literature report.

Content of the invention

Present invention aim at, by ruo₂Material is prepared into ultra-fine the receiving of high-specific surface area (especially having meso-hole structure) Rice corpuscles.

For achieving the above object, the present invention adopts the following technical scheme that a kind of ultra-fine ruo₂Nanoparticle preparation method, its Feature is to comprise the following steps, 1) surfactant p123,1m hydrochloric acid and ethanol are mixed by the mass ratio of 1:0.1-0.3:3-7 Close, adding the tetraethyl orthosilicate stirring that quality is 2-2.5 becomes initial soln；2) evaporation induced self-assembly: initial soln falls Enter in evaporating dish, stand 36～48 hours, the micelle that surfactant is formed, with the volatilization of ethanol, carries out self assembly arrangement shape Become soft template, tetraethyl orthosilicate hydrolyzes to form in the silica-filled space in soft template；Obtain after standing ethanol volatilization Block；3) liquid paraffin of 2～3mm thickness is poured on the block obtaining in evaporating dish, puts into air dry oven and carry out 80-100 DEG C dry, block takes out from evaporating dish, cleans the liquid paraffin on surface with filter paper；In the situation keeping block structure as far as possible Under, remove remaining ethanol；4) the silicon dioxide block obtaining, is annealed, and annealing temperature changes to 900 DEG C from 550 DEG C, obtains To sio₂Average pore size 20nm of template changes to 2nm；Pore volume is from 0.33cm³/ g changes to 0.07cm³/g；5) sio obtaining₂ Template is placed in culture dish, uses rucl₃Ethanol solution, concentration be every 5～7ml solution in contain 0.38g ru, be added drop-wise to sio₂ Template is in hard template, every 500mg hard template, Deca 0.2ml solution, after solution volatilizees completely, continues Deca, repeats 4～5 Secondary, fill rucl in template hole₃；6) the filling rucl obtaining₃Sio₂Template, is annealed with 300～600 DEG C under air, Annealing time 30-120min, makes rucl₃It is oxidized to ruo₂；7) the filling ruo obtaining₂Sio₂Template, is dipped into excessive In the hf of 8wt% concentrations above, 12～24 hours, remove sio₂Template, 8) deionized water is cleaned, repeatedly in air dry oven Middle drying, obtains ultra-fine ruo₂Nanoparticle.

P123, ethanol, the hydrochloric acid of 1m and tetraethyl orthosilicate mass ratio are 1:5:0.2:2.08.

In initial soln, add hydrochloric acid, adjust ph value, the hydrolysis rate of tetraethyl orthosilicate can be controlled.

The process of evaporation induced self-assembly, slower, the structure obtaining is more regular；Solution is poured in evaporating dish, is placed in In the cupboard of atmosphere draught-free, stand 36～48 hours.

For obtaining ultra-fine ruo₂Particle, reduces filling ruo₂And the number of times annealed, or even it is filled only with 1 time；In order to fully sharp With template, repeatable step 5), fill 15～20 times, full by filling as far as possible inside template.

Carry out 2-5 annealing, just drip rucl₃Annealing temperature after solution is 300 DEG C, and last annealing temperature reaches To 400～600 DEG C, total annealing time 30-120min time, react fully, obtain ruo₂Crystal.

By surfactant p123, the mass ratio mixing of 1:0.2:5 pressed by the hydrochloric acid of 1m and ethanol, after fully dissolving, then plus Enter tetraethyl orthosilicate, magneton stirs 10 minutes.

The rucl of Deca every time₃The amount of ethanol solution adds 0.2ml solution for every 500mg hard template, treats that solution volatilizees completely Afterwards, continue Deca, every Deca is once annealed for 4～5 times, and the ru salt being filled in template hole is converted into ruo₂.

Remove sio₂The hf solution that template uses is 10%wt.

Described ultra-fine ruo₂Nanoparticle, replicates mesoporous sio₂The pattern in space, particle size is in 2～20nm.

Beneficial effects of the present invention: the ultra-fine ruo 1) obtaining₂Material has high specific surface area, and particle size is adjustable, knot Structure is stable.2) ruo of nanostructured₂There is more preferable catalysis activity, for preparing the material of ultracapacitor, lithium-air battery Can there is better performance.Obtain ultra-fine ruo₂Nanoparticle.

Brief description

Fig. 1 is the ultra-fine ruo obtaining in embodiment 1₂The transmission electron microscope photo of nanoparticle；

Fig. 2 is the ultra-fine ruo obtaining in embodiment 1₂The x-ray diffraction of nanoparticle；

Fig. 3 is the mesoporous sio obtaining in embodiment 1₂The graph of pore diameter distribution of template.

Specific embodiment

The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to following reality Apply example.

Embodiment 1

1. take 5g p123 and 1ml 1mhcl solution to be dissolved in 25g ethanol, be sufficiently stirred for dissolving, add, 10.4g positive silicic acid second Ester, magneton stirs 10 minutes.

2. above-mentioned solution is poured in the evaporating dish of 6cm, put in cupboard, stand 48 hours.

3. pour the thick liquid paraffin of 2～3mm in evaporating dish into, put it into air dry oven, 90 degree, be dried 12 little When.

4. block is taken out from evaporating dish, clean the liquid paraffin on surface with filter paper.

5., by above-mentioned block, carry out 900 degree of annealing, 2 DEG C/min of heating rate under air, continue 1 hour, be situated between Hole sio₂Template.

6. these hard template are placed in the culture dish of 5cm, rucl3 ethanol solution (every 5-7ml solution of Deca 0.2ml The element of ru containing 0.38g), treat that ethanol volatilizees completely, continue Deca；Deca 5 times repeatedly.

7. rucl will be filled₃Template under air 300 DEG C anneal 1 hour, 1 DEG C/minute of heating rate, make rucl₃Aoxidize To ruo₂

8. soaked 12 hours with 10%hf, remove sio₂, deionized water is cleaned repeatedly, is finally putting into air dry oven 80 Degree is dried, and obtains ultra-fine ruo₂Nanoparticle.

The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with Modify, all should belong to the covering scope of the present invention.

Claims

1. a kind of ultra-fine ruo₂Nanoparticle preparation method, is characterized in that comprising the following steps, 1) by surfactant p123,1m Hydrochloric acid and ethanol are mixed by 1: 0.1-0.3: 3-7 mass ratio, and adding quality is 2-2.5 times of surfactant p123's Tetraethyl orthosilicate stirring becomes initial soln；2) evaporation induced self-assembly: initial soln is poured in evaporating dish, stands 36～48 Hour, the micelle that surfactant is formed, with the volatilization of ethanol, carries out self assembly arrangement form soft template, tetraethyl orthosilicate is sent out Life hydrolyzes to form in the silica-filled space in soft template；Block is obtained after standing ethanol volatilization；3) obtain in evaporating dish The liquid paraffin of 2～3mm thickness is poured on block, puts into air dry oven and carry out 80-100 DEG C of drying, block is from evaporating dish Take out, clean the liquid paraffin on surface with filter paper；In the case of keeping block structure, remove remaining ethanol as far as possible；4) obtain Silicon dioxide block, annealed, annealing temperature changes to 900 DEG C from 550 DEG C, obtains sio₂Average pore size 20nm of template Change to 2nm；Pore volume is from 0.33 cm³/ g changes to 0.07 cm³/g；5) sio obtaining₂Template is placed in culture dish, uses rucl₃Ethanol solution, concentration be every 5～7 ml solution in contain 0.38 g ru, be added drop-wise to sio₂Template is in hard template, Every 500 mg hard template, Deca 0.2 ml solution, after solution volatilizees completely, continues Deca, repeats 4～5 times, in pattern hole Filling rucl in gap₃；6) the filling rucl obtaining₃Sio₂Template, is annealed with 300～600 DEG C under air, annealing time 30-120min, makes rucl₃It is oxidized to ruo₂；7) the filling ruo obtaining₂Sio₂Template, is dipped into excessive more than 8wt% dense In the hf of degree, 12～24 hours, remove sio₂Template, 8) deionized water is cleaned repeatedly, dries, obtain in air dry oven Ultra-fine ruo₂Nanoparticle.

2. ultra-fine ruo according to claim 1₂The preparation method of nanoparticle it is characterised in that: p123, ethanol, 1m Hydrochloric acid and tetraethyl orthosilicate mass ratio are 1: 5: 0.2: 2.08.

3. ultra-fine ruo according to claim 1₂The preparation method of nanoparticle it is characterised in that: in initial soln, plus Enter hydrochloric acid, adjust ph value, the hydrolysis rate of tetraethyl orthosilicate can be controlled.

4. ultra-fine ruo according to claim 1₂The preparation method of nanoparticle it is characterised in that: evaporation induced self-assembly Process, slower, the structure obtaining is more regular；Solution is poured in evaporating dish, is placed in the cupboard of atmosphere draught-free, stand 36 ～48 hours.

5. ultra-fine ruo according to claim 1₂The preparation method of nanoparticle it is characterised in that: by surfactant The hydrochloric acid of p123,1m and ethanol, by 1: 0.2: 5 mass ratio mixing, after fully dissolving, add tetraethyl orthosilicate, magneton Stirring 10 minutes.

6. ultra-fine ruo according to claim 1₂The preparation method of nanoparticle it is characterised in that: the rucl of Deca every time₃ The amount of ethanol solution adds 0.2 ml solution for every 500 mg hard template, after solution volatilizees completely, continues Deca, and every Deca 4～ Once annealed for 5 times, the ru salt being filled in template hole is converted into ruo₂.

7. ultra-fine ruo according to claim 1₂The preparation method of nanoparticle it is characterised in that: remove sio₂Template makes Hf solution is 10 wt %.