CN110436440A - A kind of hollow ordered mesoporous carbon nanospheres of noble metal and the preparation method and application thereof - Google Patents
A kind of hollow ordered mesoporous carbon nanospheres of noble metal and the preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to field of material technology, a kind of hollow ordered mesoporous carbon nanospheres of noble metal and the preparation method and application thereof are disclosed.For the preparation method by " reactive interface assisted self assembling ", design synthesizes the noble metal@SiO of reactive hollow cavity template-surface chemical functional group containing aldehyde radical a kind of2Core-shell nanospheres, covalent bond is formed with the phenolic group reaction in-situ of resol in self assembling process using the aldehyde radical on its surface, thus greatly enhance the interaction force in shell source and hollow cavity template, and then polymer coating can be realized in noble metal SiO2The uniform package of nanometer ball surface.By carbonization reaction and removal SiO2After template, the hollow ordered mesoporous carbon nanospheres of noble metal are just obtained.Its shell has many advantages, such as that duct arranged regular is orderly, pore size is big, pore-size distribution is narrow, can be used for chemical catalysis, antibacterial, the fields such as electro-catalysis.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of hollow ordered mesoporous carbon nanospheres of noble metal and its system
Preparation Method and application.
Background technique
The hollow carbon nanospheres of yolk-eggshell structure nanometer composite material, especially noble metal are a kind of important advanced
Material.The noble metal nano particles that there is unique nanoshells and its nano-hollow chamber to be loaded for they, can play hollow carbon
The synergistic effect advantage of nanosphere and noble metal nano particles, the hollow carbon nanospheres of noble metal the energy, catalysis, biological medicine,
The fields such as environment, nano-reactor are with a wide range of applications, and are the popular research fields of material subject.
Shell structurre is the important component of yolk-eggshell structure nanometer composite material, is to influence such material property
Key factor.Therefore, the shell structurre of advanced design is the core of noble metal@hollow nano-sphere high performance research work.
Currently, the shell of the hollow carbon nanospheres of noble metal is usually that (standard) is non-porous, and pore structure is mainly derived from non-carbon element in charcoal
Removal during change and a small amount of micropore formed, cause the porosity of spherical carbon skeleton lower, resistance to mass tranfer is larger, limits
The performance boost of such material and application extension.
In recent years, people are transformed shell structurre design, are synthesized using technology paths such as template, super cross-linking methods
The hollow carbon nanospheres of noble metal with porous crust structure.Studies have shown that constructing reasonable porous knot in nanosphere shell
Structure can provide sufficient surface product space not only for the dispersion of active material, can also enter hollow cavity and work for guest molecule
Property noble metal nano particles contact and efficiently transmission path is provided, be thus obviously improved the performance of material.Therefore, these are high
The yolk-eggshell nanospheres of porosity non-porous nano ball more quasi- than tradition shows more excellent fast transport reactive material
Performance shows wide application prospect in the fields such as catalysis, adsorbing separation.
However, noble metal hollow carbon nanosphere shell still remains three big faults of construction urgently to be resolved: (1) hole at present
Road arrangement is mixed and disorderly unordered.Compared to unordered hole, regular orderly duct is more conducive to the transmission and hole surface benefit of molecular/ionic
With.(2) aperture is smaller.Currently, the pore structure of noble metal hollow carbon nanosphere shell is generally less than the micropore group of 2nm by aperture
At reactive material resistance to mass tranfer with higher in the channel of such small-bore, especially transporting and separating in macromolecular
The application of aspect is unfavorable for the Function of noble metal yolk core.(3) pore-size distribution is wide.In general, wide pore-size distribution be difficult to compared with
It is accurately that yolk-eggshell structure is associated with performance.Obviously, these disadvantages hinder this kind of nano combined material to a certain extent
The applied basic research of material and industrialization process.Therefore, how in noble metal hollow carbon nanosphere shell ordered mesoporous is constructed
(aperture is between 2nm and 50nm) structure is still urgently to be resolved in the design of yolk-eggshell structure nanometer composite material structure
The problem of.
Summary of the invention
In order to overcome the deficiencies in the prior art, the primary purpose of the present invention is that it is hollow to provide a kind of noble metal@
The preparation method of ordered mesoporous carbon nanospheres, this method belong to simple and efficient " reactive interface assisted self assembling " method.
Another object of the present invention is to provide the hollow ordered mesoporous carbon nanometers of noble metal@that the above method is prepared
Ball.
A further object of the present invention is to provide the hollow ordered mesoporous carbon nanospheres of above-mentioned noble metal catalysis, antibacterial and
Application in fuel cell.
The purpose of the invention is achieved by the following technical solution:
A kind of preparation method of the hollow ordered mesoporous carbon nanospheres of noble metal, including following operating procedure:
(1) by precious metal simple substance solution, organic solvent, ammonium hydroxide obtains mixed solution after ethyl orthosilicate is mixed；
(2) 3- aminopropyl triethoxysilane, organic solvent and aldehydes are sequentially added into mixed solution obtained by step (1)
Substance is stirred to react, and purifying is dried to obtain sample 1 after the reaction was completed；
(3) it is stirred to react after mixing alkaline solution, formalin, aqueous surfactant solution with phenol organic matter,
Obtain mixed solution；
(4) it after mixing the aqueous solution of sample 1 obtained by step (2) with mixed solution obtained by step (3), is stirred anti-
It answers, then carries out hydro-thermal reaction again, purifying is dried to obtain sample 2 after reaction；
(5) under nitrogen protection, sample 2 obtained by step (4) is carbonized；
(6) sample 2 after charing obtained by step (5) is added in HF solution and is stirred, then purify drying, obtained described
The hollow ordered mesoporous carbon nanospheres of noble metal.
The solvent of step (1) the precious metal simple substance solution is water or organic solvent；Wherein, the precious metal simple substance is
At least one of Au, Ag, Pt etc.；The organic solvent is at least one of ethyl alcohol and isopropanol.
Precious metal salt is restored to obtain by step (1) described precious metal simple substance preferably by reducing agent, the precious metal salt
For HAuCl4、AgNO3、H2PtCl6At least one of Deng, the reducing agent is sodium citrate, ethylene glycol, NaBH4In extremely
Few one kind.
Step (1) organic solvent is at least one of ethyl alcohol and isopropanol.
In step (1) the precious metal simple substance solution concentration of precious metal simple substance be 1~350mg/mL, preferably 1~
130mg/mL。
The mass volume ratio of step (1) precious metal simple substance and ethyl orthosilicate be 5~1100mg/mL, preferably 7~
30mg/mL。
The volume ratio of organic solvent, ammonium hydroxide and ethyl orthosilicate described in step (1) is (8-200): (0.5-10):
(0.5-5), preferably 19:0.8:1.6.
Mixing time described in step (1) is 1-10h；
Organic solvent described in step (2) is preferably ethyl alcohol, and the aldehyde material is preferably glyoxal；
The volume ratio of 3- aminopropyl triethoxysilane, organic solvent and aldehyde material described in step (2) be 0.05~
0.5:50~200:0.5~5, preferably 0.15:100:2.
Mixing time described in step (2) is 0.5-10h, and whipping temp is 40-120 DEG C.
Alkaline solution described in step (3) be sodium hydrate aqueous solution, potassium hydroxide aqueous solution, calcium hydroxide aqueous solution and
At least one of baryta water；The aqueous surfactant solution is at least one in F127 and P123 aqueous solution
Kind, the phenol organic matter is phenol, at least one of biphenol and naphthols.
The concentration of step (3) described alkaline solution is 0.1-1.0mol/L, and the concentration of formalin is 37wt.%-
40wt.%, the concentration of aqueous surfactant solution are 0.01-0.02g/mL；
The quality volume of step (3) alkaline solution, formalin, aqueous surfactant solution and phenol organic matter
Than for (15-20) mL:(2-3) mL:(60-70) mL:(0.6-0.65) g.
Step (3) is described to be stirred to react, for 100-1000rpm, 8~15h to be stirred at 50~80 DEG C with rate；
The concentration of sample 2 is 0.001-0.0005g/mL in the aqueous solution of step (4) sample 2；
The aqueous solution of step (4) sample 2 and the volume ratio of mixed solution are 150-500:20-80.
Step (4) temperature being stirred to react is 50~75 DEG C, and the reaction time is 6~12h.
The temperature of step (4) described hydro-thermal reaction is 100-300 DEG C, reaction time 1-48h.
Step (5) carbonization temperature is 300-1200 DEG C, carbonization time 1-10h.When temperature is at 600 DEG C or less,
Heating rate be 1 DEG C/min, temperature 600 DEG C the above are when, heating rate be 5 DEG C/min；
The concentration of HF solution described in step (6) is 20-60wt.%.
Step (6) mixing time is 8-48h.
Purifying described in step (2) (4) and (6) is centrifuge washing 1~3 time, centrifugation rate 1000-20000rpm, often
Secondary centrifugation time is 1-20min.
A kind of hollow ordered mesoporous carbon ball of noble metal@being prepared according to the above method.
The hollow ordered mesoporous carbon ball of noble metal@, which is that the golden@with chemical catalysis active nano gold yolk core is hollow, to be had
It sequence mesoporous carbon nanospheres, the hollow ordered mesoporous carbon nanospheres of silver with antibacterial activity nano silver yolk core and is urged with electricity
Change the hollow ordered mesoporous carbon nanospheres of platinum of active nano platinum yolk core.
Application of the above-mentioned hollow ordered mesoporous carbon ball of noble metal@in catalysis, antibacterial and fuel cell.
The mechanism of invention are as follows:
The present invention is with the noble metal@SiO of surface chemical functional group containing aldehyde radical2Core-shell nanospheres as hollow cavity template,
Covalent bond is formed with the phenolic group reaction in-situ of resol in self assembling process using the aldehyde radical on its surface, thus greatly
Ground enhances the interaction force in shell source and hollow cavity template, and then polymer coating can be realized in noble metal SiO2It receives
Rice ball surface uniformly coats, and forms uniform and firm core-shell structure copolymer interface, obtains the carbon shell structurre with ordered mesostructure.
By carbonization reaction and removal SiO2After template, a kind of completely new hollow ordered mesoporous carbon nanospheres of noble metal are just obtained.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
(1) present invention design synthesizes novel reactive hollow cavity template, uses efficient " reactive interface auxiliary
The method of self assembly " realizes polymer coating in noble metal@SiO2The uniform package of nanometer ball surface.
(2) the noble metal@SiO that the present invention synthesizes2The shell duct arranged regular of nanosphere is orderly, pore size is big and hole
Diameter narrowly distributing；
(3) ordered mesoporous shell prepared by the present invention can provide quick transfer passages for reactant or product, greatly
Ground reduces resistance to mass tranfer, is very beneficial for the Function of noble metal yolk core, and then promote material property；
(4) the height monodisperse of noble metal nano particles not only may be implemented in yolk-eggshell structure prepared by the present invention, prevents
Only reunite and fall off and cause high concentration heavy metal pollution and rapid failure, and also help noble metal nano ball separation and
Recycling.
Detailed description of the invention
Fig. 1 is 1 gained Au@SiO of embodiment2Scanning electron microscopic picture (a), the 1 hollow mesoporous carbon nanometer of gained Au@of embodiment
The scanning electron microscopic picture (b) of ball, the transmission electron microscope picture (c) and embodiment 3 of the hollow mesoporous carbon nanospheres of 2 gained Ag of embodiment
The transmission electron microscope picture (d) of the hollow mesoporous carbon nanospheres of gained Pt.
Fig. 2 is the low angle X-ray diffraction map (a) and embodiment of the hollow ordered mesoporous carbon nanospheres of 1 gained Au of embodiment
The low angle X-ray diffraction map (b) of the hollow ordered mesoporous carbon nanospheres of 2 gained Ag.
Fig. 3 is 1 gained Au of embodiment orderly catalytic reduction performance of the hollow carbon nanospheres for nitrobenzene and nitrophenol
Scheme (a), inhibitory effect figure (b) and embodiment of the hollow ordered mesoporous carbon nanospheres of 2 gained Ag of embodiment to Escherichia coli Growth
The electrocatalysis characteristic figure (c) of the 3 hollow orderly carbon nanospheres of gained Pt@.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
The preparation of the hollow ordered mesoporous carbon nanospheres of embodiment 1Au
A kind of preparation method of the hollow ordered mesoporous carbon nanospheres of Au the following steps are included:
(1) by 0.125g sodium citrate, 0.0216g HAuCl4It is dissolved in and is heated to boiling in 237.5mL deionized water and flow back
30min, then weigh 0.0042g PVP and be dissolved in 1mL deionized water, it is added in the above-mentioned mixed liquor to flow back, is stirred at room temperature
For 24 hours, it is centrifugated nano-Au solution, centrifugal speed 11800rpm after reaction, each centrifugation time is 20min, centrifugation
It is that nanogold can be obtained in neutrality to supernatant liquor, gained nanogold is dispersed in 6mL water；
(2) ethyl orthosilicate of 1.6mL is dissolved in and obtains the ethyl orthosilicate that volume fraction is 8.42% after 19mL ethyl alcohol
Ethanol solution, then take nanometer gold solution obtained by 6mL step (1), 0.8mL mass fraction is that the ammonium hydroxide of 20%-25% is molten
Three kinds of solution are added in three-neck flask by liquid, and stirring 5h mixes to obtain Au@SiO2Solution；
(3) in the resulting Au@SiO of step (2)2Solution in sequentially add 0.15mL 3- aminopropyl triethoxysilane,
100mL ethyl alcohol and 2mL glutaraldehyde, are stirred to react 2h at 80 DEG C, post-treated Au@SiO2-CHO；
(4) by 0.61g phenol, the NaOH aqueous solution of 15mL 0.1mol/L, 2.1mL 37wt.% formalin is 70
After being stirred to react 0.5h at DEG C with 330-350rpm, the aqueous solution for the F127 that 65mL concentration is 0.015g/mL is added.Gained is mixed
It closes liquid and 13h is stirred with 330-350rpm at 65 DEG C, it is molten that resol-F127 compound can be obtained after reaction
Liquid.
(5) by the resulting Au@SiO of step (3)2- CHO is dissolved in the Au@for obtaining that concentration is 0.002g/mL in 150mL water
SiO2Then-CHO aqueous solution is mixed with the resulting resol-F127 complex solution of 40mL step (4), at 65 DEG C
It after lower reaction 6h, is added in water heating kettle, hydro-thermal reaction is for 24 hours at 130 DEG C.It is post-treated to obtain solid product；
(6) under nitrogen protection, sample step (5) obtained high-temperature process 3h at 800 DEG C, obtains core-shell structure
Au@SiO2@ordered mesoporous carbon nanospheres.Wherein, when temperature is at 600 DEG C, heating rate is 1 DEG C/min, and temperature is at 600 DEG C
When above, heating rate is 5 DEG C/min；
(7) by Au@SiO2@ordered mesoporous carbon nanospheres stir for 24 hours in 40wt.%HF, and post-treated to obtain Au hollow
Ordered mesoporous carbon nanospheres；
It is seen using FEI Tecnai G2 transmission electron microscope (TEM) and JSM-6330F scanning electron microscope (SEM)
The microstructure of gained sample is examined, Fig. 1 (a) is 1 gained Au@SiO of embodiment2Scanning electron microscopic picture, Fig. 1 (b) be Au@it is hollow
The scanning electron microscopic picture of ordered mesoporous carbon nanospheres.Scanning electron microscopic picture shows the hollow ordered mesoporous carbon nanospheres of Au in regular
Spherical shape, and size distribution it is uniform.Au SiO is measured using nano measure software auxiliary2With modified Au@SiO2-CHO
Particle size, the two particle diameter distribution is kept substantially unanimously, and average-size is 118nm.Au@SiO2The hollow ordered mesoporous of@
Carbon nanospheres are uniformly distributed, and its partial size is 168nm.From Fig. 1 (b) it is found that removing SiO by HF2The Au@obtained afterwards is hollow to be had
The uniform particle size of sequence mesoporous carbon nanospheres remains 166nm.Spread out using the III type X-ray of D/max-A that Japanese Rigaku is produced
Instrument measurement XRD spectrum is penetrated, scanning range is 10 °~90 °, and voltage and current is respectively 40kV and 26mA.Fig. 2 (a) is embodiment 1
The low angle X-ray diffraction map of the hollow ordered mesoporous carbon nanospheres of gained Au.As seen from the figure, the hollow ordered mesoporous carbon nanometer of Au@
There is diffraction maximum in 2 θ=0.94 ° of low angle X-ray diffraction map of ball, shows that the hollow ordered mesoporous carbon nanospheres of Au have very
Orderly central hole structure.Utilize the N for the ASAP2020 adsorption instrument measurement sample that Micromeritics company, the U.S. produces2Absorption-is de-
Attached thermoisopleth calculates specific surface area S using BET methodBET, it is 0.990 lower N according to relative pressure2Adsorption volume calculates total pore volume
Vt.The specific surface area of the hollow ordered mesoporous carbon nanospheres of Au is 475m2/ g, Kong Rongwei 0.31cm3/ g, mesopore pore size is in 3.4nm
There are single distributions at place.
The hollow ordered mesoporous carbon nanospheres of Au are tested for the catalysis reduction characteristic of nitrobenzene and nitrophenol.First will
4- nitrophenol is made into the aqueous solution that concentration is 0.767g/L, and the 4mL solution is taken to be placed in heating mantle, and the another concentration that is added is
6.67g/L brand-new NaBH4The two is mixed magnetic agitation by solution 100mL, and the hollow ordered mesoporous carbon of 10mg 3%Au@is added and receives
Rice sphere catalyst, control reaction temperature are 30 DEG C, weigh appropriate reaction solution during the reaction and are placed in quartz colorimetric utensil, with purple
Outside-visible spectrum is analyzed.(specific test method reference literature-Zhao Jingjing has the conjunction of core-shell structure gold C catalyst
At and in nitro compound reduction reaction application [D] Shanghai Normal University, 2015.).Fig. 3 (a) is 1 gained of embodiment
Orderly catalytic reduction performance figure of the hollow carbon nanospheres for nitrobenzene and nitrophenol of Au.Au@is empty as the result is shown for test data
The catalytic performance of heart ordered mesoporous carbon nanospheres p-nitrophenyl keeps balancing in 5 minutes, the hollow ordered mesoporous carbon nanospheres of Au
The catalytic performance of p-nitrophenol extends at any time and gradually weakens.
The preparation of the hollow ordered mesoporous carbon ball of embodiment 2Ag@
A kind of preparation method of the hollow ordered mesoporous carbon ball of Ag@the following steps are included:
(1) 50g PVP, 375mL ethylene glycol, 2g AgNO are taken3Three-neck flask is added, mechanical stirring obtains under 115 DEG C of oil baths
A large amount of acetone (about 1800mL) is added after natural cooling in silver sol, and it is colourless for staticly settling 7~8h to supernatant.It removes colourless
Supernatant is diluted with 500mL ethyl alcohol, is centrifuged (revolving speed 11500rpm, 15min), centrifugation bottom of the tube nano silver is isolated, by upper layer
Continue to be centrifuged containing Nano silver solution, be repeated 3 times.After the completion of centrifugation, by gained containing Nano silver solution with ethyl alcohol eccentric cleaning 3 times
(revolving speed 11500rpm, 15min), finally disperses gained silver in 10mL ethyl alcohol and obtains the ethanol solution of nano silver；
(2) 1.2mL ethyl orthosilicate is dissolved in 19mL isopropanol, then takes the second of nano silver obtained by 10mL step (1)
Alcoholic solution, 180mL isopropanol, 5mL ammonium hydroxide three kinds of solution are added in three-neck flask, 40 DEG C of stirring 2h, and post-processing obtains Ag@
SiO2Solution；
(3) in the resulting Ag@SiO of step (2)20.15mL 3- aminopropyl triethoxysilane is sequentially added in solution,
100mL ethyl alcohol and 2mL glutaraldehyde, are stirred to react 2h at 80 DEG C, post-treated Ag@SiO2-CHO；
(4) by 0.61g phenol, the NaOH aqueous solution of 15mL 0.1mol/L, 2.1mL 37wt.% formalin is 70
After being stirred to react 0.5h at DEG C with 330-350rpm, the aqueous solution for the F127 that 65mL concentration is 0.015g/mL is added.Gained is mixed
It closes liquid and 13h is stirred with 330-350rpm at 65 DEG C, it is molten that resol-F127 compound can be obtained after reaction
Liquid.
(5) by the resulting Ag@SiO of step (3)2- CHO is dissolved in the Ag@for obtaining that concentration is 0.002g/mL in 150mL water
SiO2Then-CHO aqueous solution is mixed with the resulting resol-F127 complex solution of 40mL step (4), at 65 DEG C
It after lower reaction 6h, is added in water heating kettle, hydro-thermal reaction is for 24 hours at 130 DEG C.It is post-treated to obtain solid product；
(6) under nitrogen protection, sample step (5) obtained high-temperature process 3h at 800 DEG C, obtains core-shell structure
Ag@SiO2@ordered mesoporous carbon nanospheres.Wherein, when temperature is at 600 DEG C, heating rate be 1 DEG C/min, temperature 600 DEG C with
When upper, heating rate is 5 DEG C/min；
(7) by Ag@SiO2@ordered mesoporous carbon nanospheres stir in 40wt.%HF~for 24 hours, it is post-treated to respectively obtain
The hollow ordered mesoporous carbon nanospheres of Ag.
It is seen using FEI Tecnai G2 transmission electron microscope (TEM) and JSM-6330F scanning electron microscope (SEM)
The microstructure for examining sample measures Ag SiO using nano measure software auxiliary2With modified Ag@SiO2The grain of-CHO
Sub- size, the two particle diameter distribution are kept substantially unanimously, and average-size is 118nm.Ag@SiO2The hollow ordered mesoporous carbon of@is received
Rice ball is uniformly distributed, and its partial size is 166nm.Fig. 1 (c) is the transmission electron microscope of the hollow mesoporous carbon nanospheres of 2 gained Ag of embodiment
Picture.Transmission electron microscope picture shows that the hollow ordered mesoporous carbon nanospheres of Ag are in regular spherical shape, and size distribution is uniform.By
HF removes SiO2The uniform particle size of the hollow ordered mesoporous carbon nanospheres of the Au obtained afterwards remains 166nm.Utilize Japan
The III type X-ray diffractometer of D/max-A that Rigaku is produced measures XRD spectrum, and scanning range is 10 °~90 °, voltage and current difference
For 40kV and 26mA.Fig. 2 (b) is the low angle X-ray diffraction map of the hollow ordered mesoporous carbon nanospheres of 2 gained Ag of embodiment.By
Figure shows that the hollow ordered mesoporous carbon nanospheres of Ag have very well ordered mesoporous knot it is found that there is diffraction maximum in 2 θ=0.94 °
Structure.Utilize the N for the ASAP2020 adsorption instrument measurement sample that Micromeritics company, the U.S. produces2Adsorption-desorption isothermal, benefit
Specific surface area S is calculated with BET methodBET, it is 0.990 lower N according to relative pressure2Adsorption volume calculates total pore volume Vt.Ag@is hollow
The specific surface area of ordered mesoporous carbon nanospheres is 476m2/ g, Kong Rongwei 0.31cm3/ g, there are single at 3.2nm for mesopore pore size
Distribution.
The hollow ordered mesoporous carbon nanospheres composite material of Ag is tested for the inhibiting effect of Escherichia coli.With taking collarium to take
A ring strain Escherichia coli out is transplanted in the test tube equipped with 6mL fluid nutrient medium, is cultivated for 24 hours at 30 DEG C, to obtain large intestine
Bacillus Liquid Culture dilution.The hollow ordered mesoporous carbon nanospheres composite material of 0.1g Ag is taken, the Plondrel of 4.5mL is added to
In hydrochlorate buffer solution (0.03mol/L), the culture dilution of Escherichia coli obtained by 0.5mL is added, 30 DEG C are placed in after mixing
4h is cultivated in constant incubator.Fig. 3 (b) is the hollow ordered mesoporous carbon nanospheres of 2 gained Ag of embodiment to Escherichia coli Growth
Inhibitory effect figure.As seen from the figure, the hollow ordered mesoporous carbon nanospheres composite material of Ag is placed in equipped with Escherichia coli dilution
Test tube in, the Escherichia coli directly contacted with the hollow ordered mesoporous carbon nanospheres composite material of Ag are killed immediately, formed
Apparent antibacterial ring size, illustrates that the hollow ordered mesoporous carbon nanospheres composite material of Ag has apparent inhibiting effect to Escherichia coli.
The preparation of the hollow ordered mesoporous carbon ball of embodiment 3Pt@
A kind of preparation method of the hollow ordered mesoporous carbon ball of Pt@the following steps are included:
(1) by 4mL 7.723 × 10-3mol·L-1H2PtCl6, 51.4mg PVP, 35.2mg NaBH4With deionization moisture
Jia Ru not be in three-neck flask, Hybrid Heating is to 50 DEG C, then deionized water is slowly added dropwise, and stirs 15h after being added dropwise to complete, and obtains Pt nanometers
Particle.It is respectively then centrifuged 15min at revolving speed 14000rpm and 3000rpm respectively, is stored in the deionized water of 6mL, obtains
The aqueous solution of nano platinum particle.
(2) ethyl orthosilicate of 1.6mL is dissolved in and obtains the ethyl orthosilicate that volume fraction is 8.42% after 19mL ethyl alcohol
Ethanol solution, then take the aqueous solution of nano platinum particle obtained by 6mL step (1), three kinds of solution are added three by 0.8mL ammonium hydroxide
In neck flask, 12h is stirred at room temperature, obtains Pt@SiO2Nanosphere solution；
(3) in the resulting Pt@SiO of step (2)20.15mL 3- aminopropyl triethoxysilane is sequentially added in solution,
100mL ethyl alcohol and 2mL glutaraldehyde, are stirred to react 2h at 80 DEG C, post-treated Pt@SiO2-CHO；
(4) by 0.61g phenol, the NaOH aqueous solution of 15mL 0.1mol/L, 2.1mL 37wt.% formalin is 70
After being stirred to react 0.5h at DEG C with 330-350rpm, the aqueous solution for the F127 that 65mL concentration is 0.015g/mL is added.Gained is mixed
It closes liquid and 13h is stirred with 330-350rpm at 65 DEG C, it is molten that resol-F127 compound can be obtained after reaction
Liquid.
(5) by the resulting Pt@SiO of step (3)2- CHO is dissolved in the Pt@for obtaining that concentration is 0.002g/mL in 150mL water
SiO2Then-CHO aqueous solution is mixed with the resulting resol-F127 complex solution of 40mL step (4), at 65 DEG C
It after lower reaction 6h, is added in water heating kettle, hydro-thermal reaction is for 24 hours at 130 DEG C.It is post-treated to obtain solid product；
(6) under nitrogen protection, the sample upper step obtained high-temperature process 3h at 800 DEG C obtains core-shell structure Pt@
SiO2@ordered mesoporous carbon nanospheres.Wherein, when temperature is at 600 DEG C, heating rate is 1 DEG C/min, and temperature is at 600 DEG C or more
When, heating rate is 5 DEG C/min；
(7) by Pt@SiO2@ordered mesoporous carbon nanospheres stir for 24 hours in 40wt.%HF, post-treated to respectively obtain Pt
Hollow ordered mesoporous carbon nanospheres.
It is seen using FEI Tecnai G2 transmission electron microscope (TEM) and JSM-6330F scanning electron microscope (SEM)
The microstructure of sample is examined, Fig. 1 (d) is the transmission electron microscope picture of the hollow mesoporous carbon nanospheres of 3 gained Pt of embodiment.Transmission electricity
Mirror picture shows that the hollow ordered mesoporous carbon nanospheres of Pt are in regular spherical shape.Pt is measured using nano measure software auxiliary
SiO2With modified Pt@SiO2The particle size of-CHO, the two particle diameter distribution are kept substantially unanimously, and average-size is
116nm。Pt@SiO2The hollow ordered mesoporous carbon nanospheres of@are uniformly distributed, and its partial size is 167nm.SiO is removed by HF2Afterwards
To the hollow ordered mesoporous carbon nanospheres of Pt scanning electron microscopic picture it is similar to scan image in embodiment 1, gained particle size
Uniformly remain 166nm.XRD spectrum, scanning range are measured using the III type X-ray diffractometer of D/max-A that Japanese Rigaku is produced
It is 10 °~90 °, voltage and current is respectively 40kV and 26mA.The low angle X-ray diffraction of the hollow ordered mesoporous carbon nanospheres of Pt
Map is consistent substantially with low angle X-ray diffraction map in embodiment 2, diffraction maximum occurs in 2 θ=0.94 °, shows that Pt@is empty
Heart ordered mesoporous carbon nanospheres have very well ordered central hole structure.The ASAP produced using Micromeritics company, the U.S.
The N of 2020 adsorption instruments measurement sample2Adsorption-desorption isothermal calculates specific surface area S using BET methodBET, according to relative pressure
For 0.990 lower N2Adsorption volume calculates total pore volume Vt.The specific surface area of the hollow ordered mesoporous carbon nanospheres of Pt is 478m2/ g, hole
Holding is 0.36cm3/ g, there are single distributions at 3.4nm for mesopore pore size.
Test the electrocatalytic hydrogen evolution performance of the hollow ordered mesoporous carbon nanospheres of Pt.Fig. 3 (c) is that 3 gained Pt@of embodiment is empty
The electrocatalysis characteristic figure of the orderly carbon nanospheres of the heart.Pt electrode has optimal electrochemical catalysis Hydrogen Evolution Performance, confirms after tested,
The electrocatalysis characteristic and Pt electrode of the hollow ordered mesoporous carbon nanospheres of Pt are close, show the hollow ordered mesoporous carbon nanospheres tool of Pt
Standby excellent electrocatalysis characteristic.
The preparation of the hollow ordered mesoporous carbon ball of embodiment 4Au@
The present embodiment difference from example 1 is that, in step (2) additional amount of nanometer gold solution be 4mL, ammonia
The mass fraction of water is 25-28wt%, additional amount 0.6mL.
It is seen using FEI Tecnai G2 transmission electron microscope (TEM) and JSM-6330F scanning electron microscope (SEM)
The microstructure of sample is examined, scanning electron microscope (SEM) photograph obtained by the present embodiment is consistent substantially with embodiment 1, and scanning electron microscopic picture is shown
The hollow ordered mesoporous carbon nanospheres of Au are in regular spherical shape, and size distribution is uniform.Utilize nano measure software auxiliary quantity
Au@SiO out2With modified Au@SiO2The particle size of-CHO, the two particle diameter distribution are kept substantially unanimously, and average-size is equal
For 118nm.Au@SiO2The hollow ordered mesoporous carbon nanospheres of@are uniformly distributed, and its partial size is 168nm.SiO is removed by HF2Afterwards
The scanning electron microscopic picture of the hollow ordered mesoporous carbon nanospheres of obtained Au is consistent substantially with embodiment 1, uniform particle size
Remain 166nm.XRD spectrum is measured using the III type X-ray diffractometer of D/max-A that Japanese Rigaku is produced, scanning range is 10 °
~90 °, voltage and current is respectively 40kV and 26mA.The low angle X of the hollow ordered mesoporous carbon nanospheres of Au obtained by the present embodiment is penetrated
Ray diffraction diagram spectrum is consistent substantially with embodiment 1, diffraction maximum is occurred in 2 θ=0.94 °, is shown that the hollow ordered mesoporous carbon of Au@is received
Rice ball has very well ordered central hole structure.Sample is measured using the ASAP2020 adsorption instrument that Micromeritics company, the U.S. produces
The N of product2Adsorption-desorption isothermal calculates specific surface area S using BET methodBET, it is 0.990 lower N according to relative pressure2Adsorbent
Product calculates total pore volume Vt.The specific surface area of the hollow ordered mesoporous carbon nanospheres of Au is 480m2/ g, Kong Rongwei 0.36cm3/ g, mesoporous
There are single distributions at 3.8nm in aperture.
The preparation of the hollow ordered mesoporous carbon ball of embodiment 5Pt@
The present embodiment and embodiment 3 the difference is that, the carbonization temperature of sample is 700 DEG C in step (6).
It is seen using FEI Tecnai G2 transmission electron microscope (TEM) and JSM-6330F scanning electron microscope (SEM)
The microstructure of sample is examined, transmission electron microscope picture obtained by the present embodiment is consistent substantially with embodiment 3, and transmission electron microscope picture is shown
The hollow ordered mesoporous carbon nanospheres of Pt are in regular spherical shape, and size distribution is uniform.Utilize nano measure software auxiliary quantity
Pt@SiO out2With modified Pt@SiO2The particle size of-CHO, the two particle diameter distribution are kept substantially unanimously, and average-size is equal
For 116nm.Pt@SiO2The hollow ordered mesoporous carbon nanospheres of@are uniformly distributed, and its partial size is 163nm.SiO is removed by HF2Afterwards
The uniform particle size of the hollow ordered mesoporous carbon nanospheres of obtained Pt remains 162nm.The D/ produced using Japanese Rigaku
III type X-ray diffractometer of max-A measure XRD spectrum, scanning range be 10 °~90 °, voltage and current be respectively 40kV and
26mA.The low angle X-ray diffraction map of the hollow ordered mesoporous carbon nanospheres of Pt obtained by the present embodiment is penetrated with angle X low in embodiment 2
Ray diffraction diagram spectrum is consistent substantially, diffraction maximum is occurred in 2 θ=0.94 °, is shown that the hollow ordered mesoporous carbon nanospheres of Pt have
Very well ordered central hole structure.Utilize the N for the ASAP2020 adsorption instrument measurement sample that Micromeritics company, the U.S. produces2It inhales
Attached-desorption isotherm calculates specific surface area S using BET methodBET, it is 0.990 lower N according to relative pressure2Adsorption volume calculates
Total pore volume Vt.The specific surface area of the hollow ordered mesoporous carbon nanospheres of Pt is 473m2/ g, Kong Rongwei 0.32cm3/ g, mesopore pore size exist
There are single distributions at 3.1nm.
The preparation of the hollow ordered mesoporous carbon ball of embodiment 6Au@
The present embodiment is difference from example 1 is that the carbonization time of step (6) is 2h.
It is seen using FEI Tecnai G2 transmission electron microscope (TEM) and JSM-6330F scanning electron microscope (SEM)
The microstructure of sample is examined, scanning electron microscope (SEM) photograph obtained by the present embodiment is consistent substantially with embodiment 1, and scanning electron microscopic picture is shown
The hollow ordered mesoporous carbon nanospheres of Au are in regular spherical shape, and size is distributed uniform utilization nano measure software auxiliary quantity
The particle size of Au@SiO2 and modified Au@SiO2-CHO, the two particle diameter distribution are kept substantially unanimously out, average-size
It is 118nm.The hollow ordered mesoporous carbon nanospheres of Au SiO2 are uniformly distributed, and its partial size is 168nm.SiO2 is removed by HF
The uniform particle size of the hollow ordered mesoporous carbon nanospheres of the Au obtained afterwards remains 166nm.The D/ produced using Japanese Rigaku
III type X-ray diffractometer of max-A measure XRD spectrum, scanning range be 10 °~90 °, voltage and current be respectively 40kV and
26mA.The low angle X-ray diffraction map of the hollow ordered mesoporous carbon nanospheres of Au obtained by the present embodiment is similar to Example 1, in 2 θ
=0.94 ° there is diffraction maximum, shows that the hollow ordered mesoporous carbon nanospheres of Au have very well ordered central hole structure.Utilize the U.S.
The N for the ASAP2020 adsorption instrument measurement sample that Micromeritics company produces2Adsorption-desorption isothermal utilizes BET method meter
Specific surface area SBET is calculated, is 0.990 lower N according to relative pressure2Adsorption volume calculates total pore volume Vt.The hollow ordered mesoporous carbon of Au@
The specific surface area of nanosphere is 470m2/ g, Kong Rongwei 0.31cm3/ g, there are single distributions at 3.4nm for mesopore pore size.
The preparation of the hollow ordered mesoporous carbon ball of embodiment 7Au@
The present embodiment difference from example 1 is that, in step (2) mass fraction of ammonium hydroxide be 25-28wt%, add
Entering amount is 0.6mL；Carbonization time is 2h in step (6)
It is seen using FEI Tecnai G2 transmission electron microscope (TEM) and JSM-6330F scanning electron microscope (SEM)
Examine the microstructure of sample.Scanning electron microscope (SEM) photograph obtained by the present embodiment is consistent substantially with embodiment 1, and scanning electron microscopic picture is shown
The hollow ordered mesoporous carbon nanospheres of Au are in regular spherical shape, and size distribution is uniform.Utilize nano measure software auxiliary quantity
The particle size of Au@SiO2 and modified Au@SiO2-CHO, the two particle diameter distribution are kept substantially unanimously out, average-size
It is 118nm.The hollow ordered mesoporous carbon nanospheres of Au SiO2 are uniformly distributed, and its partial size is 168nm.SiO2 is removed by HF
The uniform particle size of the hollow ordered mesoporous carbon nanospheres of the Au obtained afterwards remains 166nm.The D/ produced using Japanese Rigaku
III type X-ray diffractometer of max-A measure XRD spectrum, scanning range be 10 °~90 °, voltage and current be respectively 40kV and
26mA.The low angle X-ray diffraction map and embodiment 1 of the hollow ordered mesoporous carbon nanospheres of Au obtained by the present embodiment are kept substantially
Unanimously, there is diffraction maximum in 2 θ=0.94 ° of low angle X-ray diffraction map of the hollow ordered mesoporous carbon nanospheres of Au, shows Au sky
Heart ordered mesoporous carbon nanospheres have very well ordered central hole structure.It is produced using Micromeritics company, the U.S.
The N of ASAP2020 adsorption instrument measurement sample2Adsorption-desorption isothermal calculates specific surface area S using BET methodBET, according to opposite
Pressure is 0.990 lower N2Adsorption volume calculates total pore volume Vt.The specific surface area of the hollow ordered mesoporous carbon nanospheres of Au is 472m2/
G, Kong Rongwei 0.30cm3/ g, there are single distributions at 3.5nm for mesopore pore size.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the hollow ordered mesoporous carbon nanospheres of noble metal, which is characterized in that including following operating procedure:
(1) by precious metal simple substance solution, organic solvent, ammonium hydroxide obtains mixed solution after ethyl orthosilicate is mixed；
(2) 3- aminopropyl triethoxysilane, organic solvent and aldehydes are sequentially added into mixed solution obtained by step (1)
Matter is stirred to react, and purifying is dried to obtain sample 1 after the reaction was completed；
(3) it is stirred to react, obtains after mixing alkaline solution, formalin, aqueous surfactant solution with phenol organic matter
Mixed solution；
(4) it after mixing the aqueous solution of sample 1 obtained by step (2) with mixed solution obtained by step (3), is stirred to react, so
Carry out hydro-thermal reaction again afterwards, purifying is dried to obtain sample 2 after reaction；
(5) under nitrogen protection, sample 2 obtained by step (4) is carbonized；
(6) sample 2 after charing obtained by step (5) is added in HF solution and is stirred, then purify drying, obtained described expensive
The hollow ordered mesoporous carbon nanospheres of metal.
2. the preparation method of the hollow ordered mesoporous carbon nanospheres of noble metal according to claim 1, it is characterised in that:
The solvent of step (1) the precious metal simple substance solution is water or organic solvent；Wherein the precious metal simple substance be Au, Ag,
At least one of Pt；The organic solvent is at least one of ethyl alcohol and isopropanol.
3. the preparation method of the hollow ordered mesoporous carbon nanospheres of noble metal according to claim 1, it is characterised in that:
Step (1) organic solvent is at least one of ethyl alcohol and isopropanol；
The concentration of precious metal simple substance is 1~350mg/mL in step (1) the precious metal simple substance solution；
The mass volume ratio of step (1) precious metal simple substance and ethyl orthosilicate is 5~1100mg/mL；
The volume ratio of organic solvent, ammonium hydroxide and ethyl orthosilicate described in step (1) is (8-200): (0.5-10): (0.5-5).
4. the preparation method of the hollow ordered mesoporous carbon nanospheres of noble metal according to claim 1, it is characterised in that:
Organic solvent described in step (2) is ethyl alcohol, and the aldehyde material is glyoxal；
The volume ratio of 3- aminopropyl triethoxysilane, organic solvent and aldehyde material described in step (2) is 0.05~0.5:
50~200:0.5~5.
5. the preparation method of the hollow ordered mesoporous carbon nanospheres of noble metal according to claim 1, it is characterised in that:
Alkaline solution described in step (3) is sodium hydrate aqueous solution, potassium hydroxide aqueous solution, calcium hydroxide aqueous solution and hydrogen-oxygen
Change at least one of barium aqueous solution；The aqueous surfactant solution is at least one of F127 and P123 aqueous solution；Institute
Stating phenol organic matter is phenol, at least one of biphenol and naphthols.
6. the preparation method of the hollow ordered mesoporous carbon nanospheres of noble metal according to claim 1, it is characterised in that:
The concentration of step (3) described alkaline solution is 0.1-1.0mol/L, and the concentration of formalin is 37wt.%-
40wt.%, the concentration of aqueous surfactant solution are 0.01-0.02g/mL；
Step (3) alkaline solution, formalin, aqueous surfactant solution and phenol organic matter mass volume ratio be
(15-20) mL:(2-3) mL:(60-70) mL:(0.6-0.65) g.
7. the preparation method of the hollow ordered mesoporous carbon nanospheres of noble metal according to claim 1, it is characterised in that:
The concentration of sample 2 is 0.001-0.0005g/mL in the aqueous solution of step (4) sample 2；
The aqueous solution of step (4) sample 2 and the volume ratio of mixed solution are 150-500:20-80；
The concentration of HF solution described in step (6) is 20-60wt.%.
8. the preparation method of the hollow ordered mesoporous carbon nanospheres of noble metal according to claim 1, it is characterised in that:
Mixing time described in step (1) is 1-10h；Mixing time described in step (2) is 0.5-10h, whipping temp 40-
120℃；Step (3) is described to be stirred to react, for 100-1000rpm, 8~15h to be stirred at 50~80 DEG C with rate；
Step (4) temperature being stirred to react is 50~75 DEG C, and the reaction time is 6~12h；Step (4) described hydro-thermal reaction
Temperature be 100-300 DEG C, reaction time 1-48h；Step (5) carbonization temperature is 300-1200 DEG C, and carbonization time is
1-10h；Step (6) mixing time is 8-48h.
9. a kind of hollow ordered mesoporous carbon ball of noble metal@that the method for any one according to claim 1~8 is prepared.
10. application of the hollow ordered mesoporous carbon ball of noble metal@in catalysis, antibacterial and fuel cell according to claim 9.
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