CN105252015A - Yolk-eggshell structure Au@ hollow carbon nanosphere composite material and preparation and application thereof - Google Patents
Yolk-eggshell structure Au@ hollow carbon nanosphere composite material and preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a yolk-eggshell structure Au@ hollow carbon nanosphere composite material and preparation and application thereof. A preparation method includes the following steps that sodium citrate is adopted for reducing chlorogoldacid, and nanogold hydrosol is prepared; the nanogold hydrosol, organic monomers, water and a Triton X-100 aqueous solution are stirred and mixed; then, an initiating agent is added into a system to initiate polymerization of the monomers, and precursors are prepared; the organic monomers are composed of aniline and pyrrole; and under the inert atmosphere, the precursors are processed in a high-temperature carbonizing manner so that the yolk-eggshell structure Au@ hollow carbon nanosphere composite material can be prepared. According to the preparation method, the tedious steps that a template is prepared, complicated surface modification is needed and the template is removed are not needed, and preparation is easy and convenient. The specific surface area and the size of the prepared material can be regulated and controlled through the carbonization condition and the concentration of the organic monomers, the specific surface area is high, and the prepared material has a good catalytic effect on nitrobenzene and p-nitrophenol.
Description
Technical field
The invention belongs to field of material technology, be specifically related to a kind of yolk-eggshell structure Au hollow carbon nanosphere composite and Synthesis and applications thereof.
Background technology
Yolk-eggshell structure nanometer composite material, particularly noble metal hollow carbon nanospheres, it is the important advanced material of a class, there is unique nanoshells and the noble metal nano particles of nano-hollow chamber institute load thereof, be with a wide range of applications in fields such as catalysis, the energy, nano-reactor, environment, biological medicines.
Up to now, yolk-eggshell structure noble metal hollow carbon nanospheres adopts template to be prepared usually, specifically comprises the preparation of noble metal nano particles, coated, the carbonization subsequently of substep of protein template layer and carbon source outer shell and the removal of template.But, be difficult to the shortcoming overcome below template ubiquity: the surface modification that (1) needs are complicated: when introducing noble metal yolk core, need surface chemical modification to solve yolk core/template, template/carbon precursor interface compatibility problem; (2) loaded down with trivial details template is needed to remove: the experimental implementation removing hard template is loaded down with trivial details, sometimes even dangerous and contaminated environment (such as etches SiO with HF
2protein template); (3) the one-tenth charcoal of most charcoal shell presoma (being polymer usually) is poor, needs complicated chemical crosslinking; (4) porosity of gained charcoal shell is usually lower, and resistance to mass tranfer is comparatively large, is unfavorable for the Function of noble metal yolk core.These shortcomings seriously hinder base application research and the industrialization process of this kind of nano composite material.
Summary of the invention
For solving the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is the preparation method providing a kind of yolk-eggshell structure Au hollow carbon nanosphere composite.First the method utilizes interfacial polymerization process simply and efficiently, prepares yolk-eggshell structure Au hollow aniline-co-pyrrole copolymer nanosphere; Then directly carbonize, yolk-eggshell structure Au hollow carbon nanosphere composite can be prepared.This method is not only without the need to constructing out yolk-eggshell structure by any hard template, and polymeric shell layer has the conjugated structure of very rigidity, without the need to directly can carbonize the charcoal shell being formed and be rich in micropore through any chemical crosslinking.
Another object of the present invention is to the yolk-eggshell structure Au hollow carbon nanosphere composite providing above-mentioned preparation method to obtain.This composite has the nanosphere pattern of uniformity, and charcoal shell specific area can up to 1145m
2/ g, p-nitrophenyl and p-nitrophenol have good catalytic action.
The yolk-eggshell structure Au hollow carbon nanosphere composite that another object of the present invention is to provide above-mentioned preparation method to obtain is as the application in the catalyst material in p-nitrophenyl and p-nitrophenol reduction.
The object of the invention is achieved through the following technical solutions:
A preparation method for yolk-eggshell structure Au hollow carbon nanosphere composite, comprises the following steps:
(1) adopt trisodium citrate reduction gold chloride, prepare the nm of gold hydrosol;
(2) the nm of gold hydrosol, organic monomer, water and the TritonX-100 aqueous solution that step (1) is obtained are uniformly mixed; Again initator is added trigger monomer polymerization in system, obtained yolk-eggshell structure Au hollow carbon nanosphere composite material precursor; Described organic monomer is aniline and pyrroles;
(3) under an inert atmosphere, the yolk-eggshell structure Au hollow carbon nanosphere composite material precursor that high temperature carbonization treatment step (2) is obtained, obtained described yolk-eggshell structure Au hollow carbon nanosphere composite.
The consumption proportion of the gold chloride described in step (1) and trisodium citrate is preferably 1g:5.79g.
The concrete steps of described step (1) are: be added to the water by gold chloride, and heating is fully dissolved and obtained chlorauric acid solution, then add the obtained nm of gold hydrosol of trisodium citrate aqueous solution reduction.
Described heating-up temperature can be preferably 100 DEG C.
In described chlorauric acid solution, the consumption proportion of gold chloride and water can be preferably 1g:10995mL; Trisodium citrate in described trisodium citrate aqueous solution: the consumption proportion of water can be preferably 1g:100mL.
Initator described in step (2) is preferably ammonium persulfate.
TritonX-100 in gold chloride described in step (1) and the TritonX-100 aqueous solution described in step (2), pyrroles, aniline amount ratio are preferably 0.36g:1g:(4.83 ~ 6.17) mL:(6.33 ~ 8.17) mL;
The mol ratio of the pyrroles described in step (2) and aniline is preferably 1:1;
Initiator amount described in step (2) and pyrroles and the total consumption mol ratio of aniline are preferably 1:1.
The concrete steps of described step (2) are: the nm of gold hydrosol obtained for step (1) is carried out centrifugal, remove supernatant, concentrated, then the TritonX-100 aqueous solution and organic monomer is added, adding water again makes the concentration of pyrroles and aniline in reaction system be 0.07 ~ 0.09mol/L, after stirring at room temperature, ultrasonic, ice bath stir, add pre-cooled initiator solution again, stir rapidly, under ice-water bath condition, leave standstill reaction; Rear filtration under diminished pressure, the obtained yolk-eggshell structure Au hollow carbon nanosphere composite material precursor of washing are reacted.
The described nm of gold hydrosol carry out centrifugal, remove after supernatant concentrated, the impact of simmer down to how much concentration is little, after add water again and regulate, bonding bulk concentration is at 0.07 ~ 0.09mol/L.
Described stirring at room temperature, time that is ultrasonic, ice bath stirring all can be preferably 30min, and the standing reaction time can be preferably 12h.
In the described TritonX-100 aqueous solution, the ratio of TritonX-100 and water can be preferably 1g:100mL; In described initiator solution, the ratio of initator and water can be preferably (0.38 ~ 0.49) g:1mL.
Described initiator solution is cooled to 0 ~ 5 DEG C before addition in advance; Described filtration under diminished pressure, washing are at room temperature filtration under diminished pressure, and wash product with water, until filtrate be neutrality.
High temperature carbonization process described in step (3) is specially: yolk-eggshell structure Au hollow carbon nanosphere composite material precursor is placed in inert atmosphere, is warmed up to 400 ~ 950 DEG C, charing 3h.
Described heating rate can be preferably 2 DEG C/min; Described inert atmosphere is the nitrogen atmosphere of 400mL/min flow velocity.
The yolk-eggshell structure Au hollow carbon nanosphere composite that above-mentioned preparation method obtains.In described composite, gold content is 5 ~ 12%, and gold nanosphere is of a size of 20nm; Described composite outer dia is 102 ~ 186nm, and interior cavity diameters is 38 ~ 91nm, and the micropore canals of shell is of a size of 0.5 ~ 1.3nm, and specific area is 320 ~ 1145m
2/ g.
Application in the catalyst material of the yolk-eggshell structure Au hollow carbon nanosphere composite that above-mentioned preparation method obtains in reducing as p-nitrophenyl and p-nitrophenol.
Compared with prior art, the present invention has the following advantages and beneficial effect:
The synthetic route that the present invention prepares Au hollow nano-sphere has the different of essence from utilizing template: the preparation not needing template, needs complicated surface modification, and the tedious steps such as template removal, simple and convenient.In addition, polymeric shell layer has the conjugated structure of very rigidity, without the need to directly can carbonize the charcoal shell being formed and be rich in micropore through any chemical crosslinking.Prepared material specific surface area and size can be regulated and controled by Carbonization Conditions and organic monomer concentration, and specific area can up to 1145m
2/ g, p-nitrophenyl and p-nitrophenol have good catalytic action.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of yolk-eggshell structure Au hollow carbon nanosphere composite prepared by embodiment 1.
Fig. 2 is the transmission electron microscope photo of yolk-eggshell structure Au hollow carbon nanosphere composite prepared by embodiment 1.
Fig. 3 is the nitrogen adsorption-desorption isotherm of yolk-eggshell structure Au hollow carbon nanosphere composite prepared by embodiment 1.
Fig. 4 is yolk-eggshell structure Au hollow carbon nanosphere composite prepared by embodiment 1 take sodium borohydride as the UV-Vis spectra figure that reducing agent carries out catalytic reduction reaction.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of yolk-eggshell structure Au hollow carbon nanosphere composite is prepared according to following steps:
(1) HAuCl of 0.0216g is taken
4be dissolved in 237.5mL deionized water, join be equipped with aqueduct, reflux condensing tube, vacuum stopper, magneton 500mL three-neck flask in, use magneton vigorous stirring, add hot reflux, be heated to boil, obtain chlorauric acid solution; Take 0.125g trisodium citrate to be dissolved in 12.5mL deionized water and to obtain sodium citrate aqueous solution, then it is disposablely rapidly joined in chlorauric acid solution, continue to add hot reflux 30min, cool to room temperature, obtain the nm of gold hydrosol;
(2) the nm of gold hydrosol prepared by step (1) is carried out centrifugal (11800rpm, centrifugal 30min), remove supernatant, be concentrated into 30 ~ 40mL, add 6mL and prepare the good TritonX-100 solution (0.01g/mL) of constant volume, add deionized water according to real solution amount and make cumulative volume reach 60mL; Add the pyrrole monomer of 0.37mL and the aniline monomer of 0.49mL in the solution, electromagnetic agitation 30min under room temperature; After stirring completes, ultrasonic 30min under room temperature, then be placed in the standing 30min of 0 DEG C of low temperature thermostat bath, ammonium persulfate solution (2.465gAPS is dissolved in 5mL deionized water) is added rapidly and stirs 30s, be placed in 0 DEG C of low temperature thermostat bath reaction; After arrest reaction 12h, suction filtration, spend deionized water product to filtrate colourless (neutrality), the dry 24h of 60 DEG C, vacuum is dry, prepares yolk-eggshell structure Au Hollow Polymeric Nanospheres (i.e. yolk-eggshell structure Au hollow carbon nanosphere composite material precursor);
(3) by the N of yolk-eggshell structure Au hollow carbon nanosphere composite material precursor obtained for step (2) at 400mL/min flow velocity
2under atmosphere protection, rise to 950 DEG C with 2 DEG C/min heating rate, keep 3h, prepare yolk-eggshell structure Au hollow carbon nanosphere composite.
The yolk-eggshell structure Au hollow carbon nanosphere composite prepared by the present embodiment with conducting resinl is fixed on observation platform, be placed in the dry 12h of vacuum drying oven, after metal spraying process, the structure and morphology of the JSM-6330F cold field emission scanning electron microscopic observation sample produced with Jeol Ltd., the stereoscan photograph obtaining yolk-eggshell structure Au hollow carbon nanosphere composite is shown in Fig. 1.As seen from Figure 1, prepared yolk-eggshell structure Au hollow carbon nanosphere compound material ball pattern size is even, and diameter is 154nm.
The yolk-eggshell structure Au hollow carbon nanosphere composite prepared by the present embodiment is fully milled, and gets sample in a small amount afterwards and is placed in absolute ethyl alcohol, ultrasonic disperse.Be placed on copper mesh by sample in a small amount, dry more than 12h at 100 DEG C, the JEM-2010H transmission electron microscope observing sample structure utilizing Jeol Ltd. to produce, the transmission electron microscope photo obtaining sample is shown in Fig. 2.Can be clear that by Fig. 2 in the cavity of yolk-eggshell structure and wrap into nano Au particle, wherein hollow cavity is 71nm, and yolk Au nanosphere size is about 20nm; These ball particles are even, with ESEM see consistent.
The N of the ASAP2020 adsorption instrument working sample produced with Micromeritics company of the U.S.
2adsorption-desorption isothermal.Get yolk-eggshell structure Au hollow carbon nanosphere composite prepared by about 0.05g the present embodiment, test before at 250 DEG C vacuum outgas 6h; Then the specific area S of BTE method calculation sample is utilized
bET, test result is shown in the nitrogen adsorption-desorption isotherm figure of Fig. 3, and lower at relative pressure, adsorbance sharply increases, and illustrates that shell micropore exists, and relative pressure higher position, there is obvious delayed winding, prove the existence of hollow-core construction.
Yolk-eggshell structure Au hollow carbon nanosphere composite gold content prepared by the present embodiment is 12%; Charcoal shell micropore canals is of a size of 0.5 ~ 1.3nm; BET specific surface area is 1145m
2/ g, wherein micropore surface amasss as 891m
2/ g; Total pore volume is 0.77cm
3/ g, wherein Micropore volume and external holes pore volume are respectively 0.42cm
3/ g and 0.35cm
3/ g.
Fig. 4 is yolk-eggshell structure Au hollow carbon nanosphere composite prepared by the present embodiment take sodium borohydride as the UV-Vis spectra figure that reducing agent carries out catalytic reduction reaction.The UV-Vis spectra of Fig. 4 shows, material p-nitrophenyl and p-nitrophenol have good catalytic action.Under room temperature condition, the p-nitrophenol Restore All of 1mL0.11mmol/L can be para-aminophenol after 8min by 0.3mg sample under the effect of enough sodium borohydrides, can be aniline by the nitrobenzene Restore All of 2mL0.11mol/L after 0.2mg sample 20min.
Embodiment 2
A kind of yolk-eggshell structure Au hollow carbon nanosphere composite is prepared according to following steps:
(1) HAuCl of 0.0216g is taken
4be dissolved in 237.5mL deionized water, join be equipped with aqueduct, reflux condensing tube, vacuum stopper, magneton 500mL three-neck flask in, use magneton vigorous stirring, add hot reflux, be heated to boil, obtain chlorauric acid solution; Take 0.125g trisodium citrate to be dissolved in 12.5mL deionized water and to obtain sodium citrate aqueous solution, then it is disposablely rapidly joined in chlorauric acid solution, continue to add hot reflux 30min, cool to room temperature, obtain the nm of gold hydrosol;
(2) the nm of gold hydrosol prepared by step (1) is carried out centrifugal (11800rpm, centrifugal 30min), remove supernatant, be concentrated into 30 ~ 40mL, add 6mL and prepare the good TritonX-100 solution (0.01g/mL) of constant volume, add deionized water according to real solution amount and make cumulative volume reach 60mL; Add the pyrrole monomer of 0.37mL and the aniline monomer of 0.49mL in the solution, electromagnetic agitation 30min under room temperature; After stirring completes, ultrasonic 30min under room temperature, then be placed in the standing 30min of 0 DEG C of low temperature thermostat bath, ammonium persulfate solution (2.465gAPS is dissolved in 5mL deionized water) is added rapidly and stirs 30s, be placed in 0 DEG C of low temperature thermostat bath reaction; After arrest reaction 12h, suction filtration, spend deionized water product to filtrate colourless (neutrality), the dry 24h of 60 DEG C, vacuum is dry, prepares yolk-eggshell structure Au Hollow Polymeric Nanospheres (i.e. yolk-eggshell structure Au hollow carbon nanosphere composite material precursor);
(3) by the N of yolk-eggshell structure Au Hollow Polymeric Nanospheres obtained for step (2) at 400mL/min flow velocity
2under atmosphere protection, rise to 800 DEG C with 2 DEG C/min heating rate, keep 3h, prepare yolk-eggshell structure Au hollow carbon nanosphere composite.
In yolk-eggshell structure Au hollow carbon nanosphere composite prepared by the present embodiment, gold content is 7%; Outer dia is 154nm, and interior cavity diameters is 75nm; Micropore canals is of a size of 0.5 ~ 1.3nm; BET specific surface area is 521m
2/ g, wherein micropore surface amasss as 425m
2/ g; Total pore volume is 0.50cm
3/ g, wherein Micropore volume and external holes pore volume are respectively 0.42cm
3/ g and 0.35cm
3/ g.
Embodiment 3
A kind of yolk-eggshell structure Au hollow carbon nanosphere composite is prepared according to following steps:
(1) HAuCl of 0.0216g is taken
4be dissolved in 237.5mL deionized water, join be equipped with aqueduct, reflux condensing tube, vacuum stopper, magneton 500mL three-neck flask in, use magneton vigorous stirring, add hot reflux, be heated to boil, obtain chlorauric acid solution; Take 0.125g trisodium citrate to be dissolved in 12.5mL deionized water and to obtain sodium citrate aqueous solution, then it is disposablely rapidly joined in chlorauric acid solution, continue to add hot reflux 30min, cool to room temperature, obtain the nm of gold hydrosol;
(2) the nm of gold hydrosol prepared by step (1) is carried out centrifugal (11800rpm, centrifugal 30min), remove supernatant, be concentrated into 30 ~ 40mL, add 6mL and prepare the good TritonX-100 solution (0.01g/mL) of constant volume, add deionized water according to real solution amount and make cumulative volume reach 60mL; Add the pyrrole monomer of 0.37mL and the aniline monomer of 0.49mL in the solution, electromagnetic agitation 30min under room temperature; After stirring completes, ultrasonic 30min under room temperature, then be placed in the standing 30min of 0 DEG C of low temperature thermostat bath, ammonium persulfate solution (2.465gAPS is dissolved in 5mL deionized water) is added rapidly and stirs 30s, be placed in 0 DEG C of low temperature thermostat bath reaction; After arrest reaction 12h, suction filtration, spend deionized water product to filtrate colourless (neutrality), the dry 24h of 60 DEG C, vacuum is dry, prepares yolk-eggshell structure Au Hollow Polymeric Nanospheres (i.e. yolk-eggshell structure Au hollow carbon nanosphere composite material precursor);
(3) by the N of yolk-eggshell structure Au hollow carbon nanosphere composite material precursor obtained for step (2) at 400mL/min flow velocity
2under atmosphere protection, rise to 600 DEG C with 2 DEG C/min heating rate, keep 3h, prepare yolk-eggshell structure Au hollow carbon nanosphere composite.
The gold content of the yolk-eggshell structure Au hollow carbon nanosphere composite prepared by the present embodiment is 6%; Outer dia is 174nm, and interior cavity diameters is 93nm; Micropore canals is of a size of 0.5 ~ 1.3nm; BET specific surface area is 401m
2/ g; Total pore volume is 0.35cm
3/ g.
Embodiment 4
A kind of yolk-eggshell structure Au hollow carbon nanosphere composite is prepared according to following steps:
(1) HAuCl of 0.0216g is taken
4be dissolved in 237.5mL deionized water, join be equipped with aqueduct, reflux condensing tube, vacuum stopper, magneton 500mL three-neck flask in, use magneton vigorous stirring, add hot reflux, be heated to boil, obtain chlorauric acid solution; Take 0.125g trisodium citrate to be dissolved in 12.5mL deionized water and to obtain sodium citrate aqueous solution, then it is disposablely rapidly joined in chlorauric acid solution, continue to add hot reflux 30min, cool to room temperature, obtain the nm of gold hydrosol;
(2) the nm of gold hydrosol prepared by step (1) is carried out centrifugal (11800rpm, centrifugal 30min), remove supernatant, be concentrated into 30 ~ 40mL, add 6mL and prepare the good TritonX-100 solution (0.01g/mL) of constant volume, add deionized water according to real solution amount and make cumulative volume reach 60mL; Add the pyrrole monomer of 0.37mL and the aniline monomer of 0.49mL in the solution, electromagnetic agitation 30min under room temperature; After stirring completes, ultrasonic 30min under room temperature, then be placed in the standing 30min of 0 DEG C of low temperature thermostat bath, ammonium persulfate solution (2.465gAPS is dissolved in 5mL deionized water) is added rapidly and stirs 30s, be placed in 0 DEG C of low temperature thermostat bath reaction; After arrest reaction 12h, suction filtration, spend deionized water product to filtrate colourless (neutrality), the dry 24h of 60 DEG C, vacuum is dry, prepares yolk-eggshell structure Au Hollow Polymeric Nanospheres (i.e. yolk-eggshell structure Au hollow carbon nanosphere composite material precursor);
(3) by the N of yolk-eggshell structure Au hollow carbon nanosphere composite material precursor obtained for step (2) at 400mL/min flow velocity
2under atmosphere protection, rise to 400 DEG C with 2 DEG C/min heating rate, keep 3h, prepare yolk-eggshell structure Au hollow carbon nanosphere composite.
The gold content of the yolk-eggshell structure Au hollow carbon nanosphere composite prepared by the present embodiment is 5%; Outer dia is 186nm, and interior cavity diameters is 91nm; 1.3nm is distributed in micropore canals set of dimensions; BET specific surface area is 320m
2/ g; Total pore volume is 0.25cm
3/ g.
Embodiment 5
A kind of yolk-eggshell structure Au hollow carbon nanosphere composite is prepared according to following steps:
(1) HAuCl of 0.0216g is taken
4be dissolved in 237.5mL deionized water, join be equipped with aqueduct, reflux condensing tube, vacuum stopper, magneton 500mL three-neck flask in, use magneton vigorous stirring, add hot reflux, be heated to boil, obtain chlorauric acid solution; Take 0.125g trisodium citrate to be dissolved in 12.5mL deionized water and to obtain sodium citrate aqueous solution, then it is disposablely rapidly joined in chlorauric acid solution, continue to add hot reflux 30min, cool to room temperature, obtain the nm of gold hydrosol;
(2) the nm of gold hydrosol prepared by step (1) is carried out centrifugal (11800rpm, centrifugal 30min), remove supernatant, be concentrated into 30 ~ 40mL, add 6mL and prepare the good TritonX-100 solution of constant volume, add deionized water according to real solution amount and make cumulative volume reach 60mL; Add the pyrrole monomer of 0.29mL and the aniline monomer of 0.38mL in the solution, electromagnetic agitation 30min under room temperature; After stirring completes, ultrasonic 30min under room temperature, then be placed in the standing 30min of 0 DEG C of low temperature thermostat bath, add disposable for ammonium persulfate (APS) solution (1.9169gAPS is dissolved in 5mL deionized water), rapid stirring 30s, is placed in 0 DEG C of low temperature thermostat bath reaction; After leaving standstill reaction 12h, suction filtration, spend deionized water product to filtrate colourless (neutrality), vacuum 60 DEG C of dry 24h, prepare the Au nanosphere composite (i.e. yolk-eggshell structure Au hollow carbon nanosphere composite material precursor) with yolk-eggshell structure;
(3) by the N of yolk-eggshell structure Au hollow carbon nanosphere composite material precursor obtained for step (2) at 400mL/min flow velocity
2under atmosphere protection, rise to 800 DEG C with 2 DEG C/min heating rate, keep 3h, prepare yolk-eggshell structure Au hollow carbon nanosphere composite.
Yolk-eggshell structure Au hollow carbon nanosphere composite outer dia prepared by the present embodiment is 102nm, and interior cavity diameters is 38nm.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for yolk-eggshell structure Au hollow carbon nanosphere composite, is characterized in that, comprise the following steps:
(1) adopt trisodium citrate reduction gold chloride, prepare the nm of gold hydrosol;
(2) the nm of gold hydrosol, organic monomer, water and the TritonX-100 aqueous solution that step (1) is obtained are uniformly mixed; Again initator is added trigger monomer polymerization in system, obtained yolk-eggshell structure Au hollow carbon nanosphere composite material precursor; Described organic monomer is aniline and pyrroles;
(3) under an inert atmosphere, the yolk-eggshell structure Au hollow carbon nanosphere composite material precursor that high temperature carbonization treatment step (2) is obtained, obtained described yolk-eggshell structure Au hollow carbon nanosphere composite.
2. the preparation method of yolk-eggshell structure Au hollow carbon nanosphere composite according to claim 1, it is characterized in that, the consumption proportion of the gold chloride described in step (1) and trisodium citrate is 1g:5.79g.
3. the preparation method of yolk-eggshell structure Au hollow carbon nanosphere composite according to claim 1, it is characterized in that, the concrete steps of described step (1) are: be added to the water by gold chloride, heating for dissolving obtains chlorauric acid solution, then adds the obtained nm of gold hydrosol of trisodium citrate aqueous solution reduction.
4. the preparation method of yolk-eggshell structure Au hollow carbon nanosphere composite according to claim 1, it is characterized in that, the initator described in step (2) is ammonium persulfate.
5. the preparation method of yolk-eggshell structure Au hollow carbon nanosphere composite according to claim 1, it is characterized in that, the TritonX-100 in the gold chloride described in step (1) and the TritonX-100 aqueous solution described in step (2), pyrroles, aniline amount ratio are 0.36g:1g:(4.83 ~ 6.17) mL:(6.33 ~ 8.17) mL;
The mol ratio of the pyrroles described in step (2) and aniline is 1:1;
Initiator amount described in step (2) and pyrroles and the total consumption mol ratio of aniline are 1:1.
6. the preparation method of yolk-eggshell structure Au hollow carbon nanosphere composite according to claim 1, it is characterized in that, the concrete steps of described step (2) are: the nm of gold hydrosol that step (1) is obtained carries out centrifugal, remove supernatant, concentrated, then the TritonX-100 aqueous solution and organic monomer is added, adding water again makes the concentration of pyrroles and aniline in reaction system be 0.07 ~ 0.09mol/L, through stirring at room temperature, ultrasonic, after ice bath stirs, add pre-cooled initiator solution again, stir, reaction is left standstill under ice-water bath condition, rear filtration under diminished pressure, washing are reacted, obtained yolk-eggshell structure Au hollow carbon nanosphere composite material precursor.
7. the preparation method of yolk-eggshell structure Au hollow carbon nanosphere composite according to claim 6, it is characterized in that, the initiator solution described in step (2) is cooled to 0 ~ 5 DEG C before addition in advance; Described filtration under diminished pressure, washing are at room temperature filtration under diminished pressure, and wash product with water, until filtrate be neutrality.
8. the preparation method of yolk-eggshell structure Au hollow carbon nanosphere composite according to claim 1, it is characterized in that, high temperature carbonization process described in step (3) is specially: yolk-eggshell structure Au hollow carbon nanosphere composite material precursor is placed in inert atmosphere, be warmed up to 400 ~ 950 DEG C, charing 3h.
9. a yolk-eggshell structure Au hollow carbon nanosphere composite, is characterized in that, it is obtained by the preparation method of the yolk-eggshell structure Au hollow carbon nanosphere composite described in any one of claim 1 to 8.
10. the application in the catalyst material of yolk-eggshell structure Au hollow carbon nanosphere composite according to claim 9 in reducing as p-nitrophenyl and p-nitrophenol.
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