CN103949248A - Composite catalyst with titanium dioxide coated gold nanocage structure, as well as preparation method and application of composite catalyst - Google Patents

Composite catalyst with titanium dioxide coated gold nanocage structure, as well as preparation method and application of composite catalyst Download PDF

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CN103949248A
CN103949248A CN201410192847.4A CN201410192847A CN103949248A CN 103949248 A CN103949248 A CN 103949248A CN 201410192847 A CN201410192847 A CN 201410192847A CN 103949248 A CN103949248 A CN 103949248A
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composite catalyst
titanium dioxide
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CN103949248B (en
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张建鹏
吕晓明
杨晓玲
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Shanghai Wending Water Treatment Engineering Co Ltd
SHANGHAI WINNER ENVIRONMENTAL TECHNOLOGIES Co Ltd
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Shanghai Wending Water Treatment Engineering Co Ltd
SHANGHAI WINNER ENVIRONMENTAL TECHNOLOGIES Co Ltd
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Abstract

The invention relates to a composite catalyst with a titanium dioxide coated gold nanocage structure, as well as a preparation method and application of the composirte catalyst. The composite catalyst comprises an inner core and an outer layer, wherein the inner core is a hollow gold nanocage with a particle size being 200-500nm; the outer layer is a nano titanium dioxide coated layer with a thickness being 5-20nm. According to the composite catalyst, a large quantity of gaps are formed in a gold nanocage layer and a TiO2 nanolayer; by virtue of the gaps, the diffusion of reactants and products can be accelerated; the composite catalyst is capable of firmly limiting the reactants in the inner space and enabling the reactants to reach the extremely-high concentration condition, thereby accelerating catalytic reaction; meanwhile, the composite catalyst is high in reaction activity, small in possibility of catalyst poisoning and capable of greatly improving the catalytic performance, so that the composite catalyst can be widely used in a plurality of composite structural materials with oxides-coated metals.

Description

Composite catalyst of a kind of coated by titanium dioxide gold nanometer cage structure and its preparation method and application
Technical field
The present invention relates to inorganic nano material and catalysis organic pollutant degradation technology, particularly, is a kind of Au@TiO 2composite catalyst of nanocages structure (coated by titanium dioxide gold nanometer cage structure) and preparation method thereof and the application in 4-nitrophenol catalytic reduction.
Background technology
Hollow material is owing to having many good character such as density is low, specific area is high, thermal coefficient of expansion is low, index of refraction is low, therefore receive the fervent concern of numerous scientific workers.Wherein, especially deep with the research of nano-hollow ball.The practical technique of nano-hollow ball is ripe and progressively practical gradually, but not spherical hollow structural material is due to its irregular shape and anisotropy thereof, also plays a significant role at aspects such as biomedicine, targeted drug release, stored energies more and more.
Gold nanometer cage structural material is the special non-spherical hollow structural material of a class.It has the physical and chemical performance different from non-hollow metal nano material, especially has good optics and catalytic performance.The Li Zhuan of Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences etc. (CN101758243A) add gold seeds solution in the growth-promoting media of gold chloride, hexa and protective agent composition by seed mediated growth method, successfully make golden nanometer particle grow into for hollow gold nanometer cage under the condition of water, normal temperature.The intelligent grade of the Yang Yun of Yunnan Normal University (CN103604926A) is utilized the biocompatibility that gold nanometer cage material is good, in solution, distributional stability self has the features such as certain color manifests, one-step method has been prepared gold nanometer cage and has been applied to immuno-chromatographic test paper strip, has overcome at present conventional colored marker gold nano particle colloidal sols and has been difficult for the shortcoming of preserving.
Although gold nanometer cage structural material is more and more paid close attention to because its unique character and potential application have obtained people, but it still exists some problems urgently to be resolved hurrily: (1) is as noble metal catalyst, in the time that its long term exposure is in reactant and surrounding environment, thereby as easy as rolling off a log the changing of pattern caused the reduction of its catalytic and stability, and gold nanometer cage obviously also exists this shortcoming; (2) the further functionalization of gold nanometer cage also rarely has research.Noble metal and oxide are compound is the effective ways that address the above problem, if noble metal is compounded to form nucleocapsid structure with oxide, can avoid contacting of noble metal and reactant, stops its distortion to be reunited.In addition, the contact area of noble metal and oxide promotes greatly, and obvious synergy has occurred between the two, and catalytic effect has been played to great facilitation.For this research that forms nucleocapsid structure at precious metal surface composite oxides, have a large amount of patent and bibliographical informations.As (CN103252502A) such as the Qi Jian of State Nanometer Science Center easily mixes the colloidal solution of golden nanometer particle with ethanol/water, then contact with titanium source and carry out hydrothermal crystallizing, gone out hollow Au TiO without template synthesis 2hollow nano-sphere structural material.The people such as Mou are by being coated the hollow SiO of one deck using water-in-oil microemulsion as template on gold nano hollow ball surface 2layer, empirical tests, this catalyst has very high catalytic activity (J.Mater.Chem, 2011,27,789-794) to 4-NP.
But aspheric metal structure is as gold nanometer cage, owing to having edge effect, very difficult at its coated with uniform oxide skin(coating), yet there are no correlative study report.
Summary of the invention
In view of above problem, the object of this invention is to provide composite catalyst of a kind of coated by titanium dioxide gold nanometer cage structure and its preparation method and application.Concrete technical scheme is as follows:
A composite catalyst for coated by titanium dioxide gold nanometer cage structure, described composite catalyst comprises kernel and skin, and described kernel is that particle diameter is the hollow gold nanometer cage of 200～500nm, and described skin is that thickness is the nanometer titanium dioxide-coated layer of 5～20nm.
A preparation method for the composite catalyst of coated by titanium dioxide gold nanometer cage structure, comprises the steps:
(1) ascorbic acid reduction is prepared Cu 2o octahedron: by NaOH solution, CuCl 2h 2after O solution, sodium citrate solution, PVP mix, stir 0.5～1h, drip ascorbic acid, dropwise, mixed solution is slaking 2～3h at 25～60 DEG C, after cooling washing, obtains Cu 2o octahedron;
In described mixed solution, NaOH solution concentration is 0～2mol/L, CuCl 2h 2o solution concentration is 0～10mmol/L, and sodium citrate solution concentration is 0～3.4mmol/L, and PVP molecular weight is 30000～60000, and quality is 0～4g;
(2) the coated TiO of hydro-thermal method 2layer: by step 1) in the Cu that obtains 2o octahedron is distributed in the aqueous solution, with the TiF of 0～0.6mL 4mix, hydro-thermal reaction 0.5～1h at 180～200 DEG C, obtains the Cu of coated by titanium dioxide 2o, that is, and Cu 2o@TiO 2;
Wherein, Cu 2the octahedral quality of O is 0～0.01g, TiF 4solution concentration is 0.01～0.05mol/L;
(3) oxidation-reduction method is prepared Cu 2o@Au@TiO 2: by the Cu obtaining in step (2) 2o@TiO 2be dispersed in the PVP aqueous solution of 0～1wt%, at 30～60 DEG C, add the HAuCl of 0～1.5mL10～20mmol/L 4solution, reaction 1～2h, centrifuge washing obtains product C u 2o@Au@TiO 2;
Above-mentioned Cu 2o@TiO 2quality is 0～0.01g, and PVP molecular weight is 30000～60000, and quality is 0～4g;
(4) soda acid etching method is removed Cu 2o template: the Cu that step (3) is obtained 2o@Au@TiO 2immerse the HNO containing 1wt%PVP 38～14h in solution, centrifuge washing obtains the composite catalyst of described coated by titanium dioxide gold nanometer cage structure, is designated hereinafter simply as Au@TiO 2catalyst;
Above-mentioned Cu 2o@Au@TiO 2quality is 0～0.1g, and PVP molecular weight is 30000～60000, and quality is 0～4g, HNO 3solution concentration is 0.1～0.3mol/L;
Wherein, in step (1)～(4), the content of each reactive component is not all 0.
The application of the composite catalyst of aforementioned coated by titanium dioxide gold nanometer cage structure, for the catalytic reaction to 4-nitrophenol, the reaction time, while being 5～12min, the conversion ratio of 4-nitrophenol exceeded 80%, reaches as high as 100%.
The process of catalytic reaction is specific as follows: by a certain amount of Au@TiO 2catalyst is dispersed in the deionized water of 5～10mL, gets 1mL catalyst solution and joins in the aqueous solution of 24mL containing 4-nitrophenol and sodium borohydride, at room temperature stirs.Every a UV-Vis spectrum of one minute record.After reaction finishes, with deionized water centrifuge washing catalyst.Catalyst recovery is also used it for catalytic reaction for the second time.This process repeats 10 times.Above-mentioned Au@TiO 2catalyst quality is 0～0.1g and is not that 0,4-nitro phenol concentration is 10 -4～10 -5m, sodium borohydride concentration is 0.1～0.5M.
The present invention adopts Au@TiO 2nanocages catalyst, the 4-nitrophenols of degrading in the aqueous solution that contains sodium borohydride, shows significant degradation effect.Advantage of the present invention is:
(1) gold nanometer cage layer and TiO 2in nanometer layer, all have a large amount of spaces, the diffusion of reactant and product has been accelerated in these spaces;
(2) the Au@TiO2 nanocages catalyst that prepared by the present invention, can firmly be limited to inner space by reactant, makes reactant reach high concentration conditions, thereby accelerates catalytic reaction;
(3) Au@TiO 2nanocages catalyst has a lot of corner angle, contains undersaturated chemical valence at the atom of edges and corners, and reactivity is high, and this has greatly improved catalytic performance;
(4) Au layer and TiO 2the synergy of layer can be accelerated the transfer of electric charge, has effectively suppressed catalyst poisoning, has accelerated the transformation of 4-nitrophenol to PAP;
(5) the present invention adopts preparation method from outside to inside, first synthetic TiO 2layer, secondly Au layer is at TiO 2the inner accumulated growth of layer, this method has solved non-spherical structure and has been difficult to coated shortcoming, and can be widely used in the sandwich of many oxide clad metal.
Brief description of the drawings
Fig. 1 is the Au@TiO of embodiment 1 2the stereoscan photograph of nanocages catalyst;
Fig. 2 is the Au@TiO of embodiment 1 2the transmission electron microscope photo of nanocages catalyst;
Fig. 3 is the hollow octahedron of the Au of embodiment 1 and Au@TiO 2the plasma of nanocages catalyst absorbs spectrogram;
Fig. 4 is the Au@TiO of embodiment 1 2nanocages catalyst at room temperature reduces the time dependent uv-visible absorption spectra of 4-nitrophenols;
Fig. 5 is the Au@TiO of embodiment 1 2the comparison of the conversion ratio of the 4-nitrophenols of nanocages catalyst in 10 continuous periodic reactions.
Detailed description of the invention
Further illustrate content of the present invention below in conjunction with embodiment, but these embodiment do not limit the scope of the invention.
Embodiment 1
(1) ascorbic acid reduction is prepared Cu 2o octahedron
Take successively CuCl 2h 2o0.1704g, natrium citricum 0.1g, 3.4g PVP, be dissolved in 100ml deionized water, is stirred to evenly, and then dropwise splashing into concentration is 10mL NaOH solution the continuation stirring of 2mol/L.After 0.5h, 10mL0.6mol/L ascorbic acid is dropwise added to aforementioned solution.Finally, mixed solution is slaking 2.5h at 30 DEG C, naturally cools to room temperature, centrifugal after, with ethanol and deionized water washing 3 times, obtain Cu 2o octahedron.
(2) Cu 2o@TiO 2preparation
Take Cu prepared by 0.01g 2o octahedron is in 25mL deionized water, by the TiF of the 0.02mol/L of itself and 0.6mL 4aqueous solution, uniform stirring 10min.Mixed solution is transferred in 50mL water heating kettle, hydro-thermal 1h at 180 DEG C, naturally cooling rear centrifugal, use ethanol and water washing 3 times, obtain Cu 2o@TiO 2.(3) Cu 2o@Au@TiO 2preparation
Take 0.01g Cu 2o@TiO 2be dispersed in containing in the aqueous solution of 1wt%PVP, solution is heated at 60 DEG C, add the HAuCl of 1.5mL10mmol/L 4the aqueous solution, reaction 1h.Cooling rear centrifugal, water and ethanol washing obtain product C u 3 times 2o@Au@TiO 2.
(4) Au@TiO 2the preparation of catalyst
By the Cu obtaining in (3) 2o@Au@TiO 2add the 0.15mol/L HNO containing 1wt%PVP 3in the aqueous solution, centrifugal after immersion 12h, water and ethanol washing obtain target product Au@TiO for 3 times 2catalyst.
The reduction of model test 4-nitrophenols:
With Au TiO obtained above 2catalyst is catalyst, catalytic reduction degraded 4-nitrophenols.Reaction unit is the conical flask of 50ml, in each deoxidization, degradation reaction, in bottle, all contains the sodium borohydride of 25ml and the aqueous solution of 4-nitrophenols, and wherein the concentration of sodium borohydride is 0.3mol/L, and the initial concentration of 4-nitrophenols is 0.0001mol/L.At room temperature, by Au@TiO 2catalyst, for reaction, after each catalyst uses, all by reaction solution centrifugation, and with deionized water washing, is obtained catalyst dry in order to using next time.Continuous recovery for 10 times used, and the degradable conversion ratio of 4-nitrophenols reaches all up to 95%.
Fig. 1 is the prepared Au@of this embodiment TiO 2the SEM figure of nanocages catalyst.As can be seen from Figure 1, this catalyst is octahedral structure, and from Fig. 1, a damaged structure can be found out its hollow nature.Fig. 2 is the prepared Au@of this embodiment TiO 2the TEM figure of nanocages catalyst.As can be seen from Figure 2 Au nanocages edge is more black, further proves that it is hollow-core construction, has at Au nanocages skin the TiO that one deck is fine and close and be evenly distributed 2.Fig. 3 has compared Au nanocages and Au@TiO 2the plasma resonance absorption spectrogram of nanocages catalyst.As seen from Figure 3, the coated TiO of Au nanocages 2after, due to TiO 2the refraction action of shell, it absorbs limit red shift obviously occurs.Fig. 4 is the prepared Au@of this embodiment TiO 2nanocages catalyst at room temperature reduces the time dependent uv-visible absorption spectra of 4-nitrophenols.As can be seen from Figure 4, along with the growth in reaction time, the absworption peak of 4-NP reduces gradually, and the absworption peak of 4-AP raises gradually, and when reaction arrives 5 minutes, 4-NP is almost reduced completely.Speed constant is 7.78 × 10 -3s -1.Fig. 5 is the prepared Au@of this embodiment TiO 2the comparison of the conversion ratio of the 4-nitrophenols of nanocages catalyst in 10 continuous periodic reactions, as can be seen from Figure 5, after 10 circulations, catalyst is still keeping 95% conversion ratio to the reduction of 4-NP, have good stability.
Comparative example 1
In comparative example 1, will be with Cu 2o template replaces Cu 2o@TiO 2, other condition is with embodiment 1, and preparation Au nanocages is also used it for 4-NP reduction.At room temperature react after 7min, 4-degrading mononitrophenol conversion ratio reaches 90%, and speed constant is 4.50 × 10 -3s -1.Recycle after five times, its transformation efficiency to 4-NP is reduced to 50%.
Visible, Au nanocages and Au@TiO 2nanocages is compared, and has lost TiO 2the protection of layer, catalytic effect reduces, and cyclical stability is relatively poor.
Comparative example 2
In comparative example 2, by the aqueous solution containing PVP, instead of the aqueous solution, other condition is with comparative example 1, and preparation Au nano particle is also used it for 4-NP reduction.At room temperature react after 12min, 4-degrading mononitrophenol conversion ratio reaches 90%, and speed constant is 3.25 × 10 -3s -1.
Visible, Au nano particle is compared with gold nanometer cage, and catalytic effect further reduces, and has verified the impact of cage shape effect on catalytic performance.
Be only preferred embodiment of the present invention in sum, be not used for limiting practical range of the present invention.And all equivalence variations and modification of doing according to the content of the present patent application the scope of the claims, all should be technology category of the present invention.

Claims (5)

1. the composite catalyst of a coated by titanium dioxide gold nanometer cage structure, it is characterized in that, described composite catalyst comprises kernel and skin, and described kernel is that particle diameter is the hollow gold nanometer cage of 200～500nm, and described skin is that thickness is the nanometer titanium dioxide-coated layer of 5～20nm.
2. a preparation method for the composite catalyst of coated by titanium dioxide gold nanometer cage structure, is characterized in that, comprises the steps:
(1) ascorbic acid reduction is prepared Cu 2o octahedron: by NaOH solution, CuCl 2h 2after O solution, sodium citrate solution, PVP mix, stir 0.5～1h, drip ascorbic acid, dropwise, mixed solution is slaking 2～3h at 25～60 DEG C, after cooling washing, obtains Cu 2o octahedron;
In described mixed solution, NaOH solution concentration is 0～2mol/L, CuCl 2h 2o solution concentration is 0～10mmol/L, and sodium citrate solution concentration is 0～3.4mmol/L, and PVP molecular weight is 30000～60000, and quality is 0～4g;
(2) the coated TiO of hydro-thermal method 2layer: by step 1) in the Cu that obtains 2o octahedron is distributed in the aqueous solution, with the TiF of 0～0.6mL 4mix, hydro-thermal reaction 0.5～1h at 180～200 DEG C, obtains the Cu of coated by titanium dioxide 2o, that is, and Cu 2o@TiO 2;
Wherein, Cu 2the octahedral quality of O is 0～0.01g, TiF 4solution concentration is 0.01～0.05mol/L;
(3) oxidation-reduction method is prepared Cu 2o@Au@TiO 2: by the Cu obtaining in step (2) 2o@TiO 2be dispersed in the PVP aqueous solution of 0～1wt%, at 30～60 DEG C, add the HAuCl of 0～1.5mL10～20mmol/L 4solution, reaction 1～2h, centrifuge washing obtains product C u 2o@Au@TiO 2;
Above-mentioned Cu 2o@TiO 2quality is 0～0.01g, and PVP molecular weight is 30000～60000, and quality is 0～4g;
(4) soda acid etching method is removed Cu 2o template: the Cu that step (3) is obtained 2o@Au@TiO 2immerse the HNO containing 1wt%PVP 38～14h in solution, centrifuge washing obtains the composite catalyst of described coated by titanium dioxide gold nanometer cage structure, that is, and Au@TiO 2catalyst;
Above-mentioned Cu 2o@Au@TiO 2quality is 0～0.1g, and PVP molecular weight is 30000～60000, and quality is 0～4g, HNO 3solution concentration is 0.1～0.3mol/L;
Wherein, in step (1)～(4), the content of each reactive component is not all 0.
3. the application of the composite catalyst of coated by titanium dioxide gold nanometer cage structure described in claim 1, is characterized in that, for the catalytic reaction to 4-nitrophenol.
4. application according to claim 3, is characterized in that, the time of described catalytic reaction, while being 5～12min, the conversion ratio of 4-nitrophenol exceeded 80%.
5. according to the application described in claim 3 or 4, it is characterized in that, the process of described catalytic reaction is as follows: the composite catalyst of described coated by titanium dioxide gold nanometer cage structure is dispersed in the deionized water of 5～10mL, getting 1mL solution joins in the aqueous solution of 24mL containing 4-nitrophenol and sodium borohydride, at room temperature stir, every a UV-Vis spectrum of one minute record;
Wherein, the quality of the composite catalyst of described coated by titanium dioxide gold nanometer cage structure is 0～0.1g and is not that 0,4-nitro phenol concentration is 10 -4～10 -5m, sodium borohydride concentration is 0.1～0.5M.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784775A (en) * 2017-01-19 2017-05-31 吉林大学 The Cu of hollow Nano basket structure2O‑CuO‑TiO2The preparation method of composite
CN109358195A (en) * 2018-11-06 2019-02-19 枣庄学院 More empty silica shell nano enzymes of a kind of hollow plation nanocages core-and its preparation method and application
CN110556547A (en) * 2018-05-30 2019-12-10 中国科学院深圳先进技术研究院 Noble metal nano cage catalyst and preparation method and application thereof
CN114684848A (en) * 2022-04-25 2022-07-01 延安大学 Cu2Preparation method of O nanometer quadrangular bipyramid

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CN101758243A (en) * 2010-01-28 2010-06-30 中国科学院长春应用化学研究所 Preparation method of hollow gold nanometer cage
CN101837290A (en) * 2009-03-20 2010-09-22 中国科学院上海硅酸盐研究所 Titanium dioxide gold granular composite mesoporous film material, preparation method and application
CN103252502A (en) * 2012-02-17 2013-08-21 国家纳米科学中心 Hollow core shell structure Au@TiO2 nano-composite material and preparation method thereof

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CN101837290A (en) * 2009-03-20 2010-09-22 中国科学院上海硅酸盐研究所 Titanium dioxide gold granular composite mesoporous film material, preparation method and application
CN101758243A (en) * 2010-01-28 2010-06-30 中国科学院长春应用化学研究所 Preparation method of hollow gold nanometer cage
CN103252502A (en) * 2012-02-17 2013-08-21 国家纳米科学中心 Hollow core shell structure Au@TiO2 nano-composite material and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784775A (en) * 2017-01-19 2017-05-31 吉林大学 The Cu of hollow Nano basket structure2O‑CuO‑TiO2The preparation method of composite
CN106784775B (en) * 2017-01-19 2019-10-18 吉林大学 The Cu of hollow Nano basket structure2O-CuO-TiO2The preparation method of composite material
CN110556547A (en) * 2018-05-30 2019-12-10 中国科学院深圳先进技术研究院 Noble metal nano cage catalyst and preparation method and application thereof
CN109358195A (en) * 2018-11-06 2019-02-19 枣庄学院 More empty silica shell nano enzymes of a kind of hollow plation nanocages core-and its preparation method and application
CN114684848A (en) * 2022-04-25 2022-07-01 延安大学 Cu2Preparation method of O nanometer quadrangular bipyramid

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