CN104826625A - Double-layer TiO2/Au porous structure catalyst and preparation method thereof - Google Patents
Double-layer TiO2/Au porous structure catalyst and preparation method thereof Download PDFInfo
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- CN104826625A CN104826625A CN201510167744.7A CN201510167744A CN104826625A CN 104826625 A CN104826625 A CN 104826625A CN 201510167744 A CN201510167744 A CN 201510167744A CN 104826625 A CN104826625 A CN 104826625A
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- tio
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Abstract
The invention relates to a double-layer TiO2/Au porous structure catalyst and a preparation method thereof. The double layer porous structure is taken as nano porous gold (NPG) as a substrate, and a magnetron sputtering method is used for sputtering a TiO2 film on the surface. The preparation method comprises the following steps: placing the NPG film on an electro-conductive glass, placing in a vacuum chamber, employing high purity titanium as a target material, adjusting O2 partial pressure to 0.1-1.5*10<-3>Pa, wherein the sputtering power is 20-50W, substrate temperature is 23 DEG C, and bias voltage is 0--300mV. According to the invention, direct current sputtering is employed for film deposition, deposition time is 5-300s, and the film thickness of the sputtered TiO2 film is 2-20 nanometers. The double-layer porous structure high temperature-resistance catalyst has an internal layer Au possessing good heat stability and an external layer TiO2.
Description
Technical field
The present invention relates in general to catalyst material field, is specifically related to double-deck TiO
2/ Au loose structure Catalysts and its preparation method.
Background technology
Automobile exhaust pollution has accounted for the 65%-80% of atmosphere pollution, and the noxious pollutant of discharge mainly contains carbon monoxide (CO), unburned hydrocarbon (HC), nitrogen oxide (NOx).Desirable removal auto-exhaust catalyst should have the superperformances such as high activity, high selectivity, high thermal stability.For a long time, precious metal catalytic material (Pt, Rh, Pd) is conventional vehicle maintenance service catalysis material, but there is the problems such as catalyst granules is easy to reunion, poisoning, high temperature oxidation resistance is poor, have impact on the service life of catalyst.
Nano-porous gold (NPG), as a kind of novel nano metal material, has the features such as higher specific area, good conductivity and flexible structure be controlled.The catalytic performance of its excellence given by the loose structure of its uniqueness, and being used widely at catalytic fields such as fuel cell, selective catalysis, water electrolysis hydrogen productions, is a kind of new catalytic material.But the outstanding shortcoming of nano-porous gold is that the loose structure of its nanoscale belongs to the unstable structure of thermodynamics, is easy to thermic alligatoring, cause loose structure cracked, disappear, finally cause the catalytic performance of its uniqueness to disappear.Such as, nano-porous gold at room temperature shows good CO catalytic oxidation performance, but removes for the vehicle exhaust under hot environment, then do not show good effect.
The main method improving NPG structure thermal stability modifies precious metal element, such as Pd and Pt.China technological invention patent CN 101997123 A and 101332438 A reports the preparation technology adopting inertia precious metal ion (Pt) decorated nanometer porous gold.But there are the following problems for noble metal decorated nanometer porous gold: (1) is noble metal decorated, easily occur catalysis intoxicating phenomenon, and manufacturing cost is high; (2) thermal stable temperature is not high, just occurs serious hole coarsening phenomenon at 400 DEG C.
The present invention in order to solve this problem of NPG poor heat stability, at the surface sputtering nano-TiO of NPG loose structure
2layer, improves nano-porous gold thermal stability under the high temperature conditions.TiO
2fusing point be 1830 DEG C, there is good high temperature resistant, low temperature resistant stable chemical property.The present invention utilizes magnetically controlled sputter method at NPG surface preparation TiO
2film, makes it still have good catalytic performance under the high temperature conditions.
Summary of the invention
The object of the invention is, in order to overcome above-mentioned some or certain defect of the prior art, to provide a kind of double-deck TiO
2/ Au loose structure Catalysts and its preparation method.
According to an aspect of the present invention, a kind of double-deck TiO is provided
2/ Au loose structure catalyst, comprises Au internal layer and TiO
2outer membrane, catalyst is continuous poriferous structure.
Under preferable case, internal layer Au is nano-porous gold, outer TiO
2film is amorphous state and/or crystalline state nanometer.More preferably in situation, nanocrystalline TiO
2crystallite dimension be 2 ~ 5nm.
Under preferable case, outer TiO
2film thickness is 2 ~ 20nm.
Under preferable case, described catalyst is applicable to remove vehicle exhaust.
According to another aspect of the present invention, one is provided to prepare double-deck TiO
2the method of/Au loose structure catalyst, comprises step: adopt nanoporous gold thin film to be matrix, utilize magnetically controlled sputter method to plate one deck TiO in porous gold surface
2, prepare co-continuous loose structure catalyst.
Under preferable case, the condition of magnetron sputtering is: take Titanium as target, O
2dividing potential drop is 0.1-1.5 × 10
-3pa, sputtering power is 20-50W, and bias voltage is 0 ~-300mV, and sputtering time is 5 ~ 300s.
Under preferable case, also comprise heat treatment step: heat-treat the sample after magnetron sputtering, heat treatment temperature is 100-600 DEG C, and heat treatment time is 5 minutes to 5 hours.Double-deck TiO after Overheating Treatment
2/ Au loose structure catalyst microstructure is more stable.
The double-deck TiO that the present invention prepares
2/ Au loose structure catalyst, it has following characteristics: (1) has good heat endurance, and its serviceability temperature can reach 600 DEG C; (2) owing to adopting the mode of magnetron sputtering plating, TiO is made
2and the adhesion between matrix NPG is good; (3) without the need to modifying noble metal, cost significantly reduces; (4) this process is simple, easy to operate, with short production cycle, is easy to batch production.
Accompanying drawing explanation
The original nanoporous gold thin film SEM collection of illustrative plates of Fig. 1 a embodiment 1;
Fig. 1 b embodiment 1 gained Au and TiO
2double-layer porous structural membrane SEM collection of illustrative plates;
The original nanoporous gold thin film of Fig. 1 c embodiment 1 is SEM collection of illustrative plates after high temperature 400 DEG C is annealed 2 hours; And
Fig. 1 d embodiment 1 gained Au and TiO
2double-layer porous structural membrane is SEM collection of illustrative plates after high temperature 400 DEG C is annealed 2 hours.
Detailed description of the invention
Also by reference to the accompanying drawings the present invention is further elaborated below by specific embodiment, but does not limit the invention.
embodiment 1
Adopt high purity titanium target (purity is 99.995%), the electro-conductive glass matrix being placed with nanoporous gold thin film is installed, passes into Ar gas, regulate O
2dividing potential drop is 1 × 10
-2pa, control sputtering power 20W, bias voltage is-300mV, and base reservoir temperature is 23 DEG C.Adopt d.c. sputtering to carry out thin film deposition, the time is 300s, depositing Ti O on nano-porous gold film surface and inwall
2film.From operating room's sampling, obtain TiO
2the double-layer porous structural membrane of/Au.Accompanying drawing 1a is original nanoporous gold thin film SEM collection of illustrative plates, and continuous print loose structure as seen from the figure, aperture size is about 20nm.After magnetron sputtering, gained Au and TiO
2accompanying drawing 1b is shown in by double-layer porous structural membrane SEM collection of illustrative plates, presents co-continuous loose structure, and internal layer is auri body, and surface and hole wall deposit one deck TiO
2film, thickness is 15nm.The TiO of sputtering
2layer is mainly nanocrystalline structure, and crystallite dimension is 4nm.Original nanoporous gold thin film and prepared TiO
2accompanying drawing 1c and accompanying drawing 1d is shown in respectively by the double-layer porous structural membrane of/Au SEM collection of illustrative plates after 400 DEG C are annealed 2 hours; Contrast finds, original NPG film melts after Overheating Treatment, occurs extensive densification gold thin film (as shown by arrows), and TiO
2the double-layer porous structural membrane of/Au after heat treatment still keeps good continuous cavernous structure, and aperture size remains unchanged.
embodiment 2
Adopt high purity titanium target (purity is 99.995%), the electro-conductive glass matrix being placed with nanoporous gold thin film is installed, passes into Ar gas, regulate O
2dividing potential drop is 1.5 × 10
-3pa, control sputtering power 50W, bias voltage is 0mV, and base reservoir temperature is 23 DEG C.Adopt d.c. sputtering to carry out thin film deposition, the time is 5s, at nano-porous gold membrane pores inwall sputtering sedimentation TiO
2film.From operating room's sampling, obtain TiO
2the double-layer porous structural membrane of/Au.The TiO of sputtering
2layer is mainly non crystalline structure, and thickness is 2nm.Gained TiO
2the double-layer porous structural membrane of/Au still keeps good continuous cavernous structure through high temperature 400 DEG C annealing after 2 hours.
embodiment 3
Adopt high purity titanium target (purity is 99.995%), the electro-conductive glass matrix being placed with nanoporous gold thin film is installed, passes into Ar gas, regulate O
2dividing potential drop is 0.1Pa, and control sputtering power 30W, bias voltage is-100mV, and base reservoir temperature is 23 DEG C.Adopt d.c. sputtering to carry out thin film deposition, the time is 100s, at nano-porous gold membrane pores inwall sputtering sedimentation TiO
2film.From operating room's sampling, obtain TiO
2the double-layer porous structural membrane of/Au.Depositing Ti O on hole wall
2film, thickness is 10nm.The TiO of sputtering
2layer is nano-crystalline and amorphous mixed structure, and wherein nanocrystalline grain size is 2-4nm.Gained TiO
2the double-layer porous structural membrane of/Au still keeps good continuous cavernous structure through high temperature 600 DEG C annealing after 2 hours.
The double-deck TiO that the present invention prepares
2/ Au loose structure catalyst, has good heat endurance, and its serviceability temperature can reach 600 DEG C; Be applicable to the process of vehicle exhaust, also go for other catalytic field.
Claims (8)
1. a double-deck TiO
2/ Au loose structure catalyst, comprises Au internal layer and TiO
2outer membrane, catalyst is continuous poriferous structure.
2. double-deck TiO according to claim 1
2/ Au loose structure catalyst, internal layer Au nano-porous gold, outer TiO
2film is amorphous state and/or crystalline state nanometer.
3. double-deck TiO according to claim 2
2/ Au loose structure catalyst, nanocrystalline TiO
2crystallite dimension be 2 ~ 5nm.
4. double-deck TiO according to claim 1
2/ Au loose structure catalyst, outer TiO
2film thickness is 2 ~ 20nm.
5. double-deck TiO according to claim 1
2/ Au loose structure catalyst, is applicable to remove vehicle exhaust.
6. prepare double-deck TiO for one kind
2the method of/Au loose structure catalyst, comprises step: adopt nanoporous gold thin film to be matrix, utilize magnetically controlled sputter method to plate one deck TiO in porous gold surface
2, prepare co-continuous loose structure catalyst.
7. one according to claim 6 prepares double-deck TiO
2the method of/Au loose structure catalyst, the condition of magnetron sputtering is: take Titanium as target, O
2dividing potential drop is 0.1-1.5 × 10
-3pa, sputtering power is 20-50W, and bias voltage is 0 ~-300mV, and sputtering time is 5 ~ 300s.
8. one according to claim 6 prepares double-deck TiO
2the method of/Au loose structure catalyst, also comprises heat treatment step: heat-treat the sample after magnetron sputtering, and heat treatment temperature is 100-600 DEG C, and heat treatment time is 5 minutes to 5 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105621349A (en) * | 2016-01-05 | 2016-06-01 | 河南师范大学 | Method for synthesizing Au and Ag co-modified TiO2 nanorod array by use of photo-reduction method |
| CN106395739A (en) * | 2015-07-29 | 2017-02-15 | 上海师范大学 | Nano-grade porous tin dioxide film gas sensitive material, and preparation method and application thereof |
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2015
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106395739A (en) * | 2015-07-29 | 2017-02-15 | 上海师范大学 | Nano-grade porous tin dioxide film gas sensitive material, and preparation method and application thereof |
| CN106395739B (en) * | 2015-07-29 | 2018-12-14 | 上海师范大学 | A kind of nanoporous tin dioxide thin film gas sensitive and its preparation method and application |
| CN105621349A (en) * | 2016-01-05 | 2016-06-01 | 河南师范大学 | Method for synthesizing Au and Ag co-modified TiO2 nanorod array by use of photo-reduction method |
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| CN104826625B (en) | 2017-02-01 |
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Inventor after: Chen Aiying Inventor after: Shi Shanshan Inventor after: Wang Jingwen Inventor after: Pan Deng Inventor before: Chen Aiying Inventor before: Shi Shanshan Inventor before: Wang Jingwen Inventor before: Pan Deng |
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